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.

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)

Influence of anionic and cationic polyelectrolytes on the conductivity and morphology of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films

Energy Technology Data Exchange (ETDEWEB)

Valtakari, Dimitar, E-mail: dimitar.valtakari@abo.fi [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland); Bollström, Roger [Omya International AG, CH 4665 Oftringen (Switzerland); Toivakka, Martti; Saarinen, Jarkko J. [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland)

2015-09-01

Conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) strongly depends on the film morphology, which can be altered by the presence of polyelectrolytes. Aqueous dispersion of PEDOT:PSS was studied with anionic sodium polyacrylate (PA) and cationic poly(dimethyldiallylammonium chloride) (pDADMAC) polyelectrolytes that are typically used in papermaking as retention aids and dispersing agents in the paper pigment coating formulations. Spin-coated PEDOT:PSS films on a PA coated glass formed non-uniform layers with lowered conductivity compared to the reference PEDOT:PSS films on a clean glass substrate. On contrary, spin-coated PEDOT:PSS on a pDADMAC coated glass formed uniform layers with good conductivity. These results point out the importance of surface chemistry when using renewable and recyclable paper-based substrates with the PEDOT:PSS films. - Highlights: • PEDOT:PSS polymer was studied in the presence of polyelectrolytes. • Uniform layers of PEDOT:PSS and polyelectrolytes were spin-coated on glass. • Cationic polyelectrolyte was found to be more susceptible to humidity. • Cationic polyelectrolyte improves the conductivity of PEDOT:PSS. • PEDOT:PSS forms non-uniform layers on anionic polyelectrolyte coated glass.

Influence of anionic and cationic polyelectrolytes on the conductivity and morphology of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films

International Nuclear Information System (INIS)

Valtakari, Dimitar; Bollström, Roger; Toivakka, Martti; Saarinen, Jarkko J.

2015-01-01

Conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) strongly depends on the film morphology, which can be altered by the presence of polyelectrolytes. Aqueous dispersion of PEDOT:PSS was studied with anionic sodium polyacrylate (PA) and cationic poly(dimethyldiallylammonium chloride) (pDADMAC) polyelectrolytes that are typically used in papermaking as retention aids and dispersing agents in the paper pigment coating formulations. Spin-coated PEDOT:PSS films on a PA coated glass formed non-uniform layers with lowered conductivity compared to the reference PEDOT:PSS films on a clean glass substrate. On contrary, spin-coated PEDOT:PSS on a pDADMAC coated glass formed uniform layers with good conductivity. These results point out the importance of surface chemistry when using renewable and recyclable paper-based substrates with the PEDOT:PSS films. - Highlights: • PEDOT:PSS polymer was studied in the presence of polyelectrolytes. • Uniform layers of PEDOT:PSS and polyelectrolytes were spin-coated on glass. • Cationic polyelectrolyte was found to be more susceptible to humidity. • Cationic polyelectrolyte improves the conductivity of PEDOT:PSS. • PEDOT:PSS forms non-uniform layers on anionic polyelectrolyte coated glass

Small angle neutron scattering study of polyelectrolyte brushes grafted to well-defined gold nanoparticle interfaces.

Science.gov (United States)

Jia, Haidong; Grillo, Isabelle; Titmuss, Simon

2010-05-18

Small angle neutron scattering (SANS) has been used to study the conformations, and response to added salt, of a polyelectrolyte layer grafted to the interfaces of well-defined gold nanoparticles. The polyelectrolyte layer is prepared at a constant coverage by grafting thiol-functionalized polystyrene (M(w) = 53k) to gold nanoparticles of well-defined interfacial curvature (R(c) = 26.5 nm) followed by a soft-sulfonation of 38% of the segments to sodium polystyrene sulfonate (NaPSS). The SANS profiles can be fit by Fermi-Dirac distributions that are consistent with a Gaussian distribution but are better described by a parabolic distribution plus an exponential tail, particularly in the high salt regime. These distributions are consistent with the predictions and measurements for osmotic and salted brushes at interfaces of low curvature. When the concentration of added salt exceeds the concentration of counterions inside the brush, there is a salt-induced deswelling, but even at the highest salt concentration the brush remains significantly swollen due to a short-ranged excluded volume interaction. This is responsible for the observed resistance to aggregation of these comparatively high concentration polyelectrolyte stabilized gold nanoparticle dispersions even in the presence of a high concentration of added salt.

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...

Polyelectrolyte bundles

Energy Technology Data Exchange (ETDEWEB)

Limbach, H J; Sayar, M; Holm, C [Max-Planck-Institut fuer Polymerforschung, Ackermannweg 10, 55128 Mainz (Germany)

2004-06-09

Using extensive molecular dynamics simulations we study the behaviour of polyelectrolytes with hydrophobic side chains, which are known to form cylindrical micelles in aqueous solution. We investigate the stability of such bundles with respect to hydrophobicity, the strength of the electrostatic interaction and the bundle size. We show that for the parameter range relevant for sulfonated poly(para-phenylenes) (PPP) one finds a stable finite bundle size. In a more generic model we also show the influence of the length of the precursor oligomer on the stability of the bundles. We also point out that our model has close similarities to DNA solutions with added condensing agents, hinting at the possibility that the size of DNA aggregates is, under certain circumstances, thermodynamically limited.

Polyelectrolyte bundles

International Nuclear Information System (INIS)

Limbach, H J; Sayar, M; Holm, C

2004-01-01

Using extensive molecular dynamics simulations we study the behaviour of polyelectrolytes with hydrophobic side chains, which are known to form cylindrical micelles in aqueous solution. We investigate the stability of such bundles with respect to hydrophobicity, the strength of the electrostatic interaction and the bundle size. We show that for the parameter range relevant for sulfonated poly(para-phenylenes) (PPP) one finds a stable finite bundle size. In a more generic model we also show the influence of the length of the precursor oligomer on the stability of the bundles. We also point out that our model has close similarities to DNA solutions with added condensing agents, hinting at the possibility that the size of DNA aggregates is, under certain circumstances, thermodynamically limited

Polyelectrolyte bundles

Science.gov (United States)

Limbach, H. J.; Sayar, M.; Holm, C.

2004-06-01

Using extensive Molecular Dynamics simulations we study the behavior of polyelectrolytes with hydrophobic side chains, which are known to form cylindrical micelles in aqueous solution. We investigate the stability of such bundles with respect to hydrophobicity, the strength of the electrostatic interaction, and the bundle size. We show that for the parameter range relevant for sulfonated poly-para-phenylenes (PPP) one finds a stable finite bundle size. In a more generic model we also show the influence of the length of the precursor oligomer on the stability of the bundles. We also point out that our model has close similarities to DNA solutions with added condensing agents, hinting to the possibility that the size of DNA aggregates is under certain circumstances thermodynamically limited.

Influence of Hydrophobicity on Polyelectrolyte Complexation

Energy Technology Data Exchange (ETDEWEB)

Sadman, Kazi [Department; amp, Engineering, Northwestern University, Evanston, Illinois 60208, United States; Wang, Qifeng [Department; amp, Engineering, Northwestern University, Evanston, Illinois 60208, United States; Chen, Yaoyao [Department; amp, Engineering, Northwestern University, Evanston, Illinois 60208, United States; Keshavarz, Bavand [Department; Jiang, Zhang [X-ray; Shull, Kenneth R. [Department; amp, Engineering, Northwestern University, Evanston, Illinois 60208, United States

2017-11-16

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) with methyl, ethyl and propyl substituents– thereby increasing the hydrophobicity with increasing side chain length– and complexing them with a common anionic polyelectrolyte, poly(styrene sulfonate). The mechanical 1 ACS Paragon Plus Environment behavior of these complexes is compared to the more hydrophilic system of poly(styrene sulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling-modulus master curves that are quantified in this work. The rheological behavior of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.

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.

Characterization for Soil Fixation by Polyelectrolyte Complex

International Nuclear Information System (INIS)

Choi, Yong Suk; Kwon, Sang Woon; Yang, Heeman; Lee, Kune Woo; Seo, Bumkyoung; Moon, Jei Kwon

2014-01-01

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

Molecular dynamics simulation of the response of bi-disperse polyelectrolyte brushes to external electric fields

International Nuclear Information System (INIS)

Zhang Fen; Ding Huan-Da; Duan Chao; Tong Chao-Hui; Zhao Shuang-Liang

2017-01-01

Langevin dynamics simulations have been performed to investigate the response of bi-disperse and strong polyacid chains grafted on an electrode to electric fields generated by opposite surface charges on the polyelectrolyte (PE)-grafted electrode and a second parallel electrode. Simulation results clearly show that, under a negative external electric field, the longer grafted PE chains are more strongly stretched than the shorter ones in terms of the relative change in their respective brush heights. Whereas under a positive external electric field, the grafted shorter chains collapse more significantly than the longer ones. It was found that, under a positive external electric field, the magnitude of the total electric force acting on one shorter PE chain is larger than that on one longer PE chain, or vice versa. The effects of smeared and discrete charge distributions of grafted PE chains on the response of PE brushes to external electric fields were also examined. (paper)

Study of polyelectrolytes for Los Alamos National Laboratory. Final report

International Nuclear Information System (INIS)

Labonne, N.

1994-11-01

To assess the safety of a potential radioactive waste repository, analysis of the fluid solution containing low levels of activity need to be performed. In some cases, the radioactivity would be so weak (3--30 pCi/L) that the solution must be concentrated for measurement. For this purpose, Los Alamos National Laboratory scientists are synthesizing some water soluble polyelectrolytes, which, because they are strong complexing agents for inorganic cations, can concentrate the radioelements in solution. To assist in characterization of these polyelectrolytes, the author has performed experiments to determine physico-chemical constants, such as pKa values and stability constants. The complexation constants between both polyelectrolytes and europium were determined by two methods: solvent extraction and ion exchange. Results are presented

Obtaining and characterization of thin films polyelectrolyte with gold nanoparticles

International Nuclear Information System (INIS)

Popiolski, Tatiane M.; Crespo, Janaina S.; Silva, Renato B.

2011-01-01

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

Species dispersal rates alter diversity and ecosystem stability in pond metacommunities.

Science.gov (United States)

Howeth, Jennifer G; Leibold, Mathew A

2010-09-01

Metacommunity theory suggests that relationships between diversity and ecosystem stability can be determined by the rate of species dispersal among local communities. The predicted relationships, however, may depend upon the relative strength of local environmental processes and disturbance. Here we evaluate the role of dispersal frequency and local predation perturbations in affecting patterns of diversity and stability in pond plankton metacommunities. Pond metacommunities were composed of three mesocosm communities: one of the three communities maintained constant "press" predation from a selective predator, bluegill sunfish (Lepomis macrochirus); the second community maintained "press" conditions without predation; and the third community experienced recurrent "pulsed" predation from bluegill sunfish. The triads of pond communities were connected at either no, low (0.7%/d), or high (20%/d) planktonic dispersal. Richness and composition of zooplankton and stability of plankton biomass and ecosystem productivity were measured at local and regional spatial scales. Dispersal significantly affected diversity such that local and regional biotas at the low dispersal rate maintained the greatest number of species. The unimodal local dispersal-diversity relationship was predator-dependent, however, as selective press predation excluded species regardless of dispersal. Further, there was no effect of dispersal on beta diversity because predation generated local conditions that selected for distinct community assemblages. Spatial and temporal ecosystem stability responded to dispersal frequency but not predation. Low dispersal destabilized the spatial stability of producer biomass but stabilized temporal ecosystem productivity. The results indicate that selective predation can prevent species augmentation from mass effects but has no apparent influence on stability. Dispersal rates, in contrast, can have significant effects on both species diversity and ecosystem

Scaling Theory of Polyelectrolyte Nanogels

International Nuclear Information System (INIS)

Qu Li-Jian

2017-01-01

The present paper develops the scaling theory of polyelectrolyte nanogels in dilute and semidilute solutions. The dependencies of the nanogel dimension on branching topology, charge fraction, subchain length, segment number, solution concentration are obtained. For a single polyelectrolyte nanogel in salt free solution, the nanogel may be swelled by the Coulombic repulsion (the so-called polyelectrolyte regime) or the osmotic counterion pressure (the so-called osmotic regime). Characteristics and boundaries between different regimes of a single polyelectrolyte nanogel are summarized. In dilute solution, the nanogels in polyelectrolyte regime will distribute orderly with the increase of concentration. While the nanogels in osmotic regime will always distribute randomly. Different concentration dependencies of the size of a nanogel in polyelectrolyte regime and in osmotic regime are also explored. (paper)

Dispersion and stabilization of cochleate nanoparticles.

Science.gov (United States)

Bozó, Tamás; Wacha, András; Mihály, Judith; Bóta, Attila; Kellermayer, Miklós S Z

2017-08-01

Cochleates, calcium-stabilized membrane rolls of nanoscale diameter, promise a unique and efficient way of delivering lipid-soluble drugs, proteins or nucleic acids into biological systems because they protect the encapsulated material against enzymatic or chemical degradation. Self-aggregation, which typically arises during production and storage is a major obstacle that has so far precluded the development of an efficient cochleate-based drug-delivery system. Here we show that citric acid, added transiently in a narrow concentration range, effectively disperses cochleate aggregates, stabilizes the disperse state for long-term storage and preserves the canonical ultrastructure and topological characteristics of cochleate nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Studies on dispersive stabilization of porous media flows

Energy Technology Data Exchange (ETDEWEB)

Daripa, Prabir, E-mail: prabir.daripa@math.tamu.edu; Gin, Craig [Department of Mathematics, Texas A& M University, College Station, Texas 77843 (United States)

2016-08-15

Motivated by a need to improve the performance of chemical enhanced oil recovery (EOR) processes, we investigate dispersive effects on the linear stability of three-layer porous media flow models of EOR for two different types of interfaces: permeable and impermeable interfaces. Results presented are relevant for the design of smarter interfaces in the available parameter space of capillary number, Peclet number, longitudinal and transverse dispersion, and the viscous profile of the middle layer. The stabilization capacity of each of these two interfaces is explored numerically and conditions for complete dispersive stabilization are identified for each of these two types of interfaces. Key results obtained are (i) three-layer porous media flows with permeable interfaces can be almost completely stabilized by diffusion if the optimal viscous profile is chosen, (ii) flows with impermeable interfaces can also be almost completely stabilized for short time, but become more unstable at later times because diffusion flattens out the basic viscous profile, (iii) diffusion stabilizes short waves more than long waves which leads to a “turning point” Peclet number at which short and long waves have the same growth rate, and (iv) mechanical dispersion further stabilizes flows with permeable interfaces but in some cases has a destabilizing effect for flows with impermeable interfaces, which is a surprising result. These results are then used to give a comparison of the two types of interfaces. It is found that for most values of the flow parameters, permeable interfaces suppress flow instability more than impermeable interfaces.

Scaling Theory of Polyelectrolyte Nanogels

Science.gov (United States)

Qu, Li-Jian

2017-08-01

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

Insight into the electrical properties and chain conformation of spherical polyelectrolyte brushes by dielectric spectroscopy

Science.gov (United States)

Guo, Xiaoxia; Zhao, Kongshuang

2017-02-01

We report here a dielectric study on three kinds of anionic spherical polyelectrolyte brush (SPBs, consisting of a polystyrene (PS) core and three different poly (acrylic acid) chains grafted onto the core) suspensions over a frequency ranging from 40 Hz to 110 MHz. The relaxation behavior of the SPB suspensions shows significant changes in the brush-layer properties when the mass fraction of SPBs and the pH of the suspensions change. Two definite relaxations related to the interfacial polarization are observed around 100 kHz and 10 MHz. A single-layer spherical-shell model is applied to describe the SPB suspensions wherein the suspended SPB is modeled as a spherical-shell composite particle in which an insulated PS sphere is surrounded by a conducting ion-permeable shell (the polyelectrolyte chain layer). We developed the curve-fitting procedure to analyze the dielectric spectrum in order to obtain the dielectric properties of the components of the SPBs, especially the properties of the polyelectrolyte brush. Based on this method and model, the permittivity and conductivity of the brush layer, ζ potential, etc are calculated. The ordered orientation of the water molecules in the layer leads to an additional electrical dipole moment; increasing pH causes the brush layer to swell. In addition, the repulsive force between the SPB particles are evaluated using the brush-layer thickness, which is obtained by fitting dielectric spectra, combined with relative theoretical formulas. Increasing PH values or SPB concentration would improve the stability of the SPBs dispersion.

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.

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

Science.gov (United States)

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

2009-05-01

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

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

Stability studies of colloidal silica dispersions in binary solvent mixtures

International Nuclear Information System (INIS)

Bean, Keith Howard

1997-01-01

A series of monodispersed colloidal silica dispersions, of varying radii, has been prepared. These particles are hydrophilic in nature due to the presence of surface silanol groups. Some of the particles have been rendered hydrophobic by terminally grafting n-alkyl (C 18 ) chains to the surface. The stability of dispersions of these various particles has been studied in binary mixtures of liquids, namely (i) ethanol and cyclohexane, and (ii) benzene and n-heptane. The ethanol - cyclohexane systems have been studied using a variety of techniques. Adsorption excess isotherms have been established and electrophoretic mobility measurements have been made. The predicted stability of the dispersions from D.V.L.O. calculations is compared to the observed stability. The hydrophilic silica particles behave as predicted by the calculations, with the zeta potential decreasing and the van der Waals attraction increasing with increasing cyclohexane concentration. The hydrophobic particles behave differently than expected, and the stability as a function of solvent mixture composition does not show a uniform trend. The effect of varying the coverage of C 18 chains on the surface and the effect of trace water in the systems has also been investigated. Organophilic silica dispersions in benzene - n-heptane solvent mixtures show weak aggregation and phase separation into a diffuse 'gas-like' phase and a more concentrated 'liquid-like' phase, analogous to molecular condensation processes. Calculations of the van der Waals potential as a function of solvent mixture composition show good agreement with the observed stability. Determination of the number of particles in each phase at equilibrium allows the energy of flocculation to be determined using a simple thermodynamic relationship. Finally, the addition of an AB block copolymer to organophilic silica particles in benzene n-heptane solvent mixtures has been shown to have a marked effect on the dispersion stability. This stability

Accelerated Physical Stability Testing of Amorphous Dispersions.

Science.gov (United States)

Mehta, Mehak; Suryanarayanan, Raj

2016-08-01

The goal was to develop an accelerated physical stability testing method of amorphous dispersions. Water sorption is known to cause plasticization and may accelerate drug crystallization. In an earlier investigation, it was observed that both the increase in mobility and decrease in stability in amorphous dispersions was explained by the "plasticization" effect of water (Mehta et al. Mol. Pharmaceutics 2016, 13 (4), 1339-1346). In this work, the influence of water concentration (up to 1.8% w/w) on the correlation between mobility and crystallization in felodipine dispersions was investigated. With an increase in water content, the α-relaxation time as well as the time for 1% w/w felodipine crystallization decreased. The relaxation times of the systems, obtained with different water concentration, overlapped when the temperature was scaled (Tg/T). The temperature dependencies of the α-relaxation time as well as the crystallization time were unaffected by the water concentration. Thus, the value of the coupling coefficient, up to a water concentration of 1.8% w/w, was approximately constant. Based on these findings, the use of "water sorption" is proposed to build predictive models for crystallization in slow crystallizing dispersions.

Glucose Oxidase Adsorption on Sequential Adsorbed Polyelectrolyte Films Studied by Spectroscopic Techniques

Science.gov (United States)

Tristán, Ferdinando; Solís, Araceli; Palestino, Gabriela; Gergely, Csilla; Cuisinier, Frédéric; Pérez, Elías

2005-04-01

The adsorption of Glucose Oxidase (GOX) on layers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) deposited on Sequentially Adsorbed Polyelectrolyte Films (SAPFs) were studied by three different spectroscopic techniques. These techniques are: Optical Wave Light Spectroscopy (OWLS) to measure surface density; Fluorescence Resonance Energy Transfer (FRET) to verify the adsorption of GOX on the surface; and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection mode (FTIR-HATR) to inspect local structure of polyelectrolytes and GOX. Two positive and two negative polyelectrolytes are used: Cationic poly(ethyleneimine) (PEI) and poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrene sulfonate) (PSS) and poly(acrylic acid) (PAA). These spectroscopic techniques do not require any labeling for GOX or SAPFs, specifically GOX and PSS are naturally fluorescent and are used as a couple donor-acceptor for the FRET technique. The SAPFs are formed by a (PEI)-(PSS/PAH)2 film followed by (PAA/PAH)n bilayers. GOX is finally deposited on top of SAPFs at different values of n (n=1..5). Our results show that GOX is adsorbed on positive ended SAPFs forming a monolayer. Contrary, GOX adsorption is not observed on negative ended film polyelectrolyte. GOX stability was tested adding a positive and a negative polyelectrolyte after GOX adsorption. Protein is partially removed by PAH and PAA, with lesser force by PAA.

Stabilization of liquid crystal dispersions with acrylamide copolymers

Energy Technology Data Exchange (ETDEWEB)

Park, S.J.; Kim, M.H.; Lee, J.R. [Korea Research Institute of Chemical Technology, Taejon (Korea, Republic of)

1999-03-01

The effects of hydrophobic moieties(styrene and methyl methacrylate) on the stability of a liquid crystal(LC, E-7)-in-water dispersion stabilized by copolymers of hydrophilic acrylamide with hydrophobic monomers have been studied in terms of nematic curvilinear aligned phase(NCAP) system. It was observed that the preferential adsorption hydrophobic moieties onto LC droplet surface resulted in steric stabilization of the dispersion, due to increasing the interfacial tension of LC and reducing the LC droplet size. According to the interfacial tension, coalescence time, and sedimented layer thickness measurements, it was proposed that the presence of hydrophobic moieties allows to form the apolar microenvironment in the round of LC droplet and finally reduces the anchoring effect between LC and the polymeric wall. 16 refs., 10 figs.

Stability of anionic polymers in presence of multivalent cations

International Nuclear Information System (INIS)

Sabbagh, Imad

1997-01-01

This research thesis aimed at studying the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. For this purpose, the author more particularly studied specific interactions between anionic poly-electrolytes and multivalent cations. After a recall of properties of neutral polymers and poly-electrolytes in solution, the author evokes interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. The next part presents various experimental spectroscopic and electrochemical techniques and results of the characterization of the used products. Spectroscopic techniques allow ion-polymer interactions at the atomic scale to be studied, and electrochemical techniques allow the behaviour of small ions to be studied. The author then discusses the main differences of solubility between poly-electrolytes containing sulphonate or sulphate groups and those containing carboxylate groups. A model is then developed to generalise phase diagrams of a poly-electrolyte with respect to the chemical affinity of its functional group with ions of opposite sign. The author then addresses the behaviour of a non charged polyacrylic acid in various saline solutions, and presents a phase diagram model [fr

Ionically Paired Layer-by-Layer Hydrogels: Water and Polyelectrolyte Uptake Controlled by Deposition Time

Directory of Open Access Journals (Sweden)

Victor Selin

2018-01-01

Full Text Available Despite intense recent interest in weakly bound nonlinear (“exponential” multilayers, the underlying structure-property relationships of these films are still poorly understood. This study explores the effect of time used for deposition of individual layers of nonlinearly growing layer-by-layer (LbL films composed of poly(methacrylic acid (PMAA and quaternized poly-2-(dimethylaminoethyl methacrylate (QPC on film internal structure, swelling, and stability in salt solution, as well as the rate of penetration of invading polyelectrolyte chains. Thicknesses of dry and swollen films were measured by spectroscopic ellipsometry, film internal structure—by neutron reflectometry (NR, and degree of PMAA ionization—by Fourier-transform infrared spectroscopy (FTIR. The results suggest that longer deposition times resulted in thicker films with higher degrees of swelling (up to swelling ratio as high as 4 compared to dry film thickness and stronger film intermixing. The stronger intermixed films were more swollen in water, exhibited lower stability in salt solutions, and supported a faster penetration rate of invading polyelectrolyte chains. These results can be useful in designing polyelectrolyte nanoassemblies for biomedical applications, such as drug delivery coatings for medical implants or tissue engineering matrices.

Multiple Linear Regression Modeling To Predict the Stability of Polymer-Drug Solid Dispersions: Comparison of the Effects of Polymers and Manufacturing Methods on Solid Dispersion Stability.

Science.gov (United States)

Fridgeirsdottir, Gudrun A; Harris, Robert J; Dryden, Ian L; Fischer, Peter M; Roberts, Clive J

2018-03-29

Solid dispersions can be a successful way to enhance the bioavailability of poorly soluble drugs. Here 60 solid dispersion formulations were produced using ten chemically diverse, neutral, poorly soluble drugs, three commonly used polymers, and two manufacturing techniques, spray-drying and melt extrusion. Each formulation underwent a six-month stability study at accelerated conditions, 40 °C and 75% relative humidity (RH). Significant differences in times to crystallization (onset of crystallization) were observed between both the different polymers and the two processing methods. Stability from zero days to over one year was observed. The extensive experimental data set obtained from this stability study was used to build multiple linear regression models to correlate physicochemical properties of the active pharmaceutical ingredients (API) with the stability data. The purpose of these models is to indicate which combination of processing method and polymer carrier is most likely to give a stable solid dispersion. Six quantitative mathematical multiple linear regression-based models were produced based on selection of the most influential independent physical and chemical parameters from a set of 33 possible factors, one model for each combination of polymer and processing method, with good predictability of stability. Three general rules are proposed from these models for the formulation development of suitably stable solid dispersions. Namely, increased stability is correlated with increased glass transition temperature ( T g ) of solid dispersions, as well as decreased number of H-bond donors and increased molecular flexibility (such as rotatable bonds and ring count) of the drug molecule.

Dispersion stability of nanoparticles in ecotoxicological investigations: the need for adequate measurement tools

Energy Technology Data Exchange (ETDEWEB)

Tantra, Ratna, E-mail: ratna.tantra@npl.co.uk; Jing Shingheng; Pichaimuthu, Sivaraman K. [National Physical Laboratory (United Kingdom); Walker, Nicholas [University of Exeter, School of Biosciences (United Kingdom); Noble, James [National Physical Laboratory (United Kingdom); Hackley, Vincent A. [National Institute of Standards and Technology (United States)

2011-09-15

One of the main challenges in nanoecotoxicological investigations is in the selection of the most suitable measurement methods and protocols for nanoparticle characterisation. Several parameters have been identified as being important as they govern nanotoxicological activity, with some parameters being better defined than others. For example, as a parameter, there is some ambiguity as to how to measure dispersion stability in the context of ecotoxicological investigations; indeed, there is disagreement over which are the best methods to measure nanoparticle dispersion stability. The purpose of this article is to use various commercially available tools to measure dispersion stability and to understand the information given by each tool. In this study, CeO{sub 2} was dispersed in two different types of media: de-ionised water and electrolyte-containing fish medium. The DLS mean particle size of freshly dispersed sample in DI water was {approx}200 nm in diameter. A visual sedimentation experiment showed that nanoparticle dispersion made in the fish medium was less stable compared to corresponding dispersion in de-ionised water. Stability of these dispersions was monitored using various techniques, for a period of 3 days. Our findings have shown that dispersion stability can be suitably assessed by monitoring: (a) surface charge, (b) sedimentation events and (c) presence of agglomerates, through time. The majority of techniques employed here (zeta potential, particle size via DLS, fluorescence and UV-Vis spectroscopy and SEM) were shown to provide useful, complementary information on dispersion stability. Nanoparticle Tracking Analysis (NTA) provides useful, quantitative information on the concentration of nanoparticles in suspension, but is limited by its inability to accurately track the motion of large agglomerates found in the fish medium.

Dispersion stability of nanoparticles in ecotoxicological investigations: the need for adequate measurement tools

International Nuclear Information System (INIS)

Tantra, Ratna; Jing Shingheng; Pichaimuthu, Sivaraman K.; Walker, Nicholas; Noble, James; Hackley, Vincent A.

2011-01-01

One of the main challenges in nanoecotoxicological investigations is in the selection of the most suitable measurement methods and protocols for nanoparticle characterisation. Several parameters have been identified as being important as they govern nanotoxicological activity, with some parameters being better defined than others. For example, as a parameter, there is some ambiguity as to how to measure dispersion stability in the context of ecotoxicological investigations; indeed, there is disagreement over which are the best methods to measure nanoparticle dispersion stability. The purpose of this article is to use various commercially available tools to measure dispersion stability and to understand the information given by each tool. In this study, CeO 2 was dispersed in two different types of media: de-ionised water and electrolyte-containing fish medium. The DLS mean particle size of freshly dispersed sample in DI water was ∼200 nm in diameter. A visual sedimentation experiment showed that nanoparticle dispersion made in the fish medium was less stable compared to corresponding dispersion in de-ionised water. Stability of these dispersions was monitored using various techniques, for a period of 3 days. Our findings have shown that dispersion stability can be suitably assessed by monitoring: (a) surface charge, (b) sedimentation events and (c) presence of agglomerates, through time. The majority of techniques employed here (zeta potential, particle size via DLS, fluorescence and UV–Vis spectroscopy and SEM) were shown to provide useful, complementary information on dispersion stability. Nanoparticle Tracking Analysis (NTA) provides useful, quantitative information on the concentration of nanoparticles in suspension, but is limited by its inability to accurately track the motion of large agglomerates found in the fish medium.

Empirical correlations to estimate agglomerate size and deposition during injection of a polyelectrolyte-modified Fe0 nanoparticle at high particle concentration in saturated sand.

Science.gov (United States)

Phenrat, Tanapon; Kim, Hye-Jin; Fagerlund, Fritjof; Illangasekare, Tissa; Lowry, Gregory V

2010-11-25

Controlled emplacement of polyelectrolyte-modified nanoscale zerovalent iron (NZVI) particles at high particle concentration (1-10 g/L) is needed for effective in situ subsurface remediation using NZVI. Deep bed filtration theory cannot be used to estimate the transport and deposition of concentrated polyelectrolyte-modified NZVI dispersions (>0.03 g/L) because particles agglomerate during transport which violates a fundamental assumption of the theory. Here we develop two empirical correlations for estimating the deposition and transport of concentrated polyelectrolyte-modified NZVI dispersions in saturated porous media when NZVI agglomeration in porous media is assumed to reach steady state quickly. The first correlation determines the apparent stable agglomerate size formed during NZVI transport in porous media for a fixed hydrogeochemical condition. The second correlation estimates the attachment efficiency (sticking coefficient) of the stable agglomerates. Both correlations are described using dimensionless numbers derived from parameters affecting deposition and agglomeration in porous media. The exponents for the dimensionless numbers are determined from statistical analysis of breakthrough data for polyelectrolyte-modified NZVI dispersions collected in laboratory scale column experiments for a range of ionic strength (1, 10, and 50mM Na(+) and 0.25, 1, and 1.25 mM Ca(2+)), approach velocity (0.8 to 55 × 10(-4)m/s), average collector sizes (d(50)=99 μm, 300 μm, and 880 μm), and polyelectrolyte surface modifier properties. Attachment efficiency depended on approach velocity and was inversely related to collector size, which is contrary to that predicted from classic filtration models. High ionic strength, the presence of divalent cations, lower extended adsorbed polyelectrolyte layer thickness, decreased approach velocity, and a larger collector size promoted NZVI agglomeration and deposition and thus limited its mobility in porous media. These effects

Immobilization of Superoxide Dismutase on Polyelectrolyte-Functionalized Titania Nanosheets.

Science.gov (United States)

Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan

2018-02-16

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

Carrier-inside-carrier: polyelectrolyte microcapsules as reservoir for drug-loaded liposomes.

Science.gov (United States)

Maniti, Ofelia; Rebaud, Samuel; Sarkis, Joe; Jia, Yi; Zhao, Jie; Marcillat, Olivier; Granjon, Thierry; Blum, Loïc; Li, Junbai; Girard-Egrot, Agnès

2015-01-01

Conventional liposomes have a short life-time in blood, unless they are protected by a polymer envelope, most often polyethylene glycol. However, these stabilizing polymers frequently interfere with cellular uptake, impede liposome-membrane fusion and inhibit escape of liposome content from endosomes. To overcome such drawbacks, polymer-based systems as carriers for liposomes are currently developed. Conforming to this approach, we propose a new and convenient method for embedding small size liposomes, 30-100 nm, inside porous calcium carbonate microparticles. These microparticles served as templates for deposition of various polyelectrolytes to form a protective shell. The carbonate particles were then dissolved to yield hollow polyelectrolyte microcapsules. The main advantage of using this method for liposome encapsulation is that carbonate particles can serve as a sacrificial template for deposition of virtually any polyelectrolyte. By carefully choosing the shell composition, bioavailability of the liposomes and of the encapsulated drug can be modulated to respond to biological requirements and to improve drug delivery to the cytoplasm and avoid endosomal escape.

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).

Ionic Conductivity of Polyelectrolyte Hydrogels.

Science.gov (United States)

Lee, Chen-Jung; Wu, Haiyan; Hu, Yang; Young, Megan; Wang, Huifeng; Lynch, Dylan; Xu, Fujian; Cong, Hongbo; Cheng, Gang

2018-02-14

Polyelectrolytes have many important functions in both living organisms and man-made applications. One key property of polyelectrolytes is the ionic conductivity due to their porous networks that allow the transport of water and small molecular solutes. Among polyelectrolytes, zwitterionic polymers have attracted huge attention for applications that involve ion transport in a polyelectrolyte matrix; however, it is still unclear how the functional groups of zwitterionic polymer side chains affect their ion transport and swelling properties. In this study, zwitterionic poly(carboxybetaine acrylamide), poly(2-methacryloyloxyethyl phosphorylcholine), and poly(sulfobetaine methacrylate) hydrogels were synthesized and their ionic conductivity was studied and compared to cationic, anionic, and nonionic hydrogels. The change of the ionic conductivity of zwitterionic and nonionic hydrogels in different saline solutions was investigated in detail. Zwitterionic hydrogels showed much higher ionic conductivity than that of the widely used nonionic poly(ethylene glycol) methyl ether methacrylate hydrogel in all tested solutions. For both cationic and anionic hydrogels, the presence of mobile counterions led to high ionic conductivity in low salt solutions; however, the ionic conductivity of zwitterionic hydrogels surpassed that of cationic and ionic hydrogels in high salt solutions. Cationic and anionic hydrogels showed much higher water content than that of zwitterionic hydrogels in deionized water; however, the cationic hydrogels shrank significantly with increasing saline concentration. This work provides insight into the effects of polyelectrolyte side chains on ion transport. This can guide us in choosing better polyelectrolytes for a broad spectrum of applications, including bioelectronics, neural implants, battery, and so on.

Surface functionalization of microwave plasma-synthesized silica nanoparticles for enhancing the stability of dispersions

Science.gov (United States)

Sehlleier, Yee Hwa; Abdali, Ali; Schnurre, Sophie Marie; Wiggers, Hartmut; Schulz, Christof

2014-08-01

Gas phase-synthesized silica nanoparticles were functionalized with three different silane coupling agents (SCAs) including amine, amine/phosphonate and octyltriethoxy functional groups and the stability of dispersions in polar and non-polar dispersing media such as water, ethanol, methanol, chloroform, benzene, and toluene was studied. Fourier transform infrared spectroscopy showed that all three SCAs are chemically attached to the surface of silica nanoparticles. Amine-functionalized particles using steric dispersion stabilization alone showed limited stability. Thus, an additional SCA with sufficiently long hydrocarbon chains and strong positively charged phosphonate groups was introduced in order to achieve electrosteric stabilization. Steric stabilization was successful with hydrophobic octyltriethoxy-functionalized silica nanoparticles in non-polar solvents. The results from dynamic light scattering measurements showed that in dispersions of amine/phosphonate- and octyltriethoxy-functionalized silica particles are dispersed on a primary particle level. Stable dispersions were successfully prepared from initially agglomerated nanoparticles synthesized in a microwave plasma reactor by designing the surface functionalization.

[Effect of stability and dissolution of realgar nano-particles using solid dispersion technology].

Science.gov (United States)

Guo, Teng; Shi, Feng; Yang, Gang; Feng, Nian-Ping

2013-09-01

To improve the stability and dissolution of realgar nano-particles by solid dispersion. Using polyethylene glycol 6000 and poloxamer-188 as carriers, the solid dispersions were prepare by melting method. XRD, microscopic inspection were used to determine the status of realgar nano-particles in solid dispersions. The content and stability test of As(2)0(3) were determined by DDC-Ag method. Hydride generation atomic absorption spectrometry was used to determine the content of Arsenic and investigated the in vitro dissolution behavior of solid dispersions. The results of XRD and microscopic inspection showed that realgar nano-particles in solid dispersions were amorphous. The dissolution amount and rate of Arsenic from realgar nano-particles of all solid dispersions were increased significantly, the reunion of realgar nano-particles and content of As(2)0(3) were reduced for the formation of solid dispersions. The solid dispersion of realgar nano-particles with poloxamer-188 as carriers could obviously improve stability, dissolution and solubility.

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.

Dynamic force spectroscopy of oppositely charged polyelectrolyte brushes

NARCIS (Netherlands)

Spruijt, E.; Cohen Stuart, M.A.; Gucht, van der J.

2010-01-01

Ion pairing is the main driving force in the formation of polyelectrolyte complexes, which find widespread use in micellar assemblies, drug carriers, and coatings. In this paper we examine the actual ion pairing forces in a polyelectrolyte complex between two oppositely charged polyelectrolyte

Polyelectrolyte brushes at the air/water interface

International Nuclear Information System (INIS)

Matsuoka, Hideki

2005-01-01

The nanostructure of amphiphilic diblock copolymer monolayer on water surface was investigated by in situ X-ray and neutron reflectivity. The diblock copolymers used have a long hydrophobic chain and a polyelectrolyte chain as a hydrophilic block. The monolayer was found not to have a simple double layer structure (hydrophobic layer / hydrophilic (carpet) layer) but to have a three layer structure consisting of hydrophobic layer, hydrophilic dense carpet layer, and polyelectrolyte brush layer when the polyelectrolyte block is long enough and the surface pressure (i.e. brush density) is high enough. The transition from carpet only to carpet/brush double layer structure in hydrophilic layer was observed as a function of polyelectrolyte chain length, the surface pressure. When the hydrophilic chain is a weak polyelectrolyte, the monolayer first expanded and then shrunk with increasing salt concentration in the subphase. For the strongly ionic polyelectrolyte, the monolayer structure was not affected by salt addition up to ∼0.2 M. These observations can be explained by a balance of the charged state of the brush chain, an electrostatic repulsion between brush chains and salt concentration in the brush layer

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

Stabilization of aqueous dispersions of poly(methacrylic acid)-coated iron oxide nanoparticles by double hydrophilic block polyelectrolyte poly(ethylene oxide)-block-poly(N-methyl-2-vinylpyridinium iodide)

Czech Academy of Sciences Publication Activity Database

Wozniak, E.; Špírková, Milena; Šlouf, Miroslav; Garamus, V. M.; Šafaříková, Miroslava; Šafařík, Ivo; Štěpánek, M.

2017-01-01

Roč. 514, 5 February (2017), s. 32-37 ISSN 0927-7757 R&D Projects: GA TA ČR(CZ) TE01020118; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 ; RVO:60077344 Keywords : superparamagnetic iron oxide nanoparticles * polyelectrolytes * SAXS Subject RIV: CD - Macromolecular Chemistry; CD - Macromolecular Chemistry (BC-A) OBOR OECD: Polymer science; Polymer science (BC-A) Impact factor: 2.714, year: 2016

Advances in polyelectrolyte multilayer nanofilms as tunable drug delivery systems

Science.gov (United States)

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

2009-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Vögele, Martin [Institute for Computational Physics, University of Stuttgart, Stuttgart (Germany); Department of Theoretical Biophysics, Max Planck Institute of Biophysics, Frankfurt a. M. (Germany); Holm, Christian; Smiatek, Jens, E-mail: smiatek@icp.uni-stuttgart.de [Institute for Computational Physics, University of Stuttgart, Stuttgart (Germany)

2015-12-28

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

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

International Nuclear Information System (INIS)

Vögele, Martin; Holm, Christian; Smiatek, Jens

2015-01-01

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

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...

Annealed star-branched polyelectrolytes in solution

NARCIS (Netherlands)

Klein Wolterink, J.; Male, van J.; Cohen Stuart, M.A.; Koopal, L.K.; Zhulina, E.B.; Borisov, O.V.

2002-01-01

Equilibrium conformations of annealed star-branched polyelectrolytes (polyacids) are calculated with a numerical self-consistent-field (SCF) model. From the calculations we obtain also the size and charge of annealed polyelectrolyte stars as a function of the number of arms, pH, and the ionic

Development of antibacterial paper coated with sodium hyaluronate stabilized curcumin-Ag nanohybrid and chitosan via polyelectrolyte complexation for medical applications

Science.gov (United States)

Rao Kummara, Madhusudana; Kumar, Anuj; Soo, Han Sung

2017-11-01

Sodium hyaluronate (HA) stabilized curcumin-Ag (Cur-Ag) hybrid nanoparticles were prepared in the water-ethanol mixture under constant mechanical stirring condition. The obtained HA stabilized Cur-Ag hybrid nanoparticles were characterized by fourier transform infrared spectroscopy, UV-visible spectroscopy, and x-ray diffraction to confirm the formation and structural interactions. The obtained Cur-Ag hybrid nanoparticles showed spherical shape with their size range 5-12 nm that was increased with the increasing a amount of silver ions as confirmed by transmission electron microscopic analysis. Further, a fibrous cellulose filter paper was impregnated with these hybrid nanoparticles and chitosan (CS) as biopolymer via polyelectrolyte complexation. The morphological analysis confirmed the uniform distribution of hybrid nanoparticle system onto the cellulose fibers of the fibrous filter paper. As per disc diffusion method, the Cur-Ag hybrid nanoparticles impregnated CS-coated filter paper exhibited excellent antibacterial properties against gram-negative Escherichia coli (E.coli) bacteria compared to HA stabilized Cur only. Moreover, as prepared hybrid nanoparticles impregnated biocomposite system is eco-friendly with efficient antibacterial property and have good potential to be used in medical applications.

Bulk heterojunction organic photovoltaic based on polythiophene-polyelectrolyte carbon nanotube composites

Energy Technology Data Exchange (ETDEWEB)

Reyes-Reyes, M. [Instituto de Investigacion en Comunicacion Optica, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, San Luis Potosi (Mexico); Lopez-Sandoval, R. [Advanced Materials Department, IPICYT, Camino a la Presa San Jose 2055, Col. Lomas 4a. Seccion, San Luis Potosi 78216 (Mexico); Liu, J.; Carroll, D.L. [Center for Nanotechnology and Molecular Materials, Wake Forest University, Winston-Salem, NC (United States)

2007-09-22

It is shown that carbon nanotubes can be used to enhance carrier mobility for efficient removal of the charges in thin film polymer-conjugated/fullerene photovoltaic devices. The fabricated photovoltaic devices consist of poly(3-octylthiophene) (P3OT) polymer blended with undoped multiwalled carbon nanotubes (MWNTs) and carbon nanotubes doped with nitrogen (CNx-MWNTs). Nanophase formation and dispersion problems associated with the use of carbon nanotubes in polymer devices were addressed through the generation of functional groups and electrostatic attaching of the polyelectrolyte poly(dimethyldiallylamine) chloride (PDDA) in both MWNTs and CNx-MWNT systems. The resultant nanophase was highly dispersed allowing for excellent bulk heterojunction formation. Our results indicate that CNx-MWNTs enhance the efficiency of P3OT solar cells in comparison with MWNTs. (author)

Stability of anionic polymers in presence of multivalent cations

International Nuclear Information System (INIS)

Sabbagh, Imad

1997-01-01

The objectives of this research thesis were to study the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. After a recall of the properties of neutral polymers and of poly-electrolytes in solution, the author evokes the interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. Then, he presents different experimental techniques (scattering techniques and electrochemical techniques) and the results obtained when characterizing the used compounds. In the next part, the author discusses the basic differences of solubility between poly-electrolytes with sulfonate or sulfate groups and those with carboxylate groups. A simple model, inspired by the electrostatic model, allows poly-electrolyte phase diagram to be generalised with respect to the chemical affinity of its functional group with ions of opposed sign. The author then reports the study of the behaviour of non-charged poly-acrylic acid in various saline solutions, and then checks the behaviour of this acid within an intermediate range of dissociation level. The poly-acrylic acid structure and the distribution of ions before de-mixing are studied by X-ray and neutron scattering. The author finally tries to understand what is going on when multivalent cations are replaced by positively charged nano-metric particles (dendrimers) [fr

Stability of Bragg grating solitons in a cubic-quintic nonlinear medium with dispersive reflectivity

International Nuclear Information System (INIS)

Dasanayaka, Sahan; Atai, Javid

2010-01-01

We investigate the existence and stability of Bragg grating solitons in a cubic-quintic medium with dispersive reflectivity. It is found that the model supports two disjoint families of solitons. One family can be viewed as the generalization of the Bragg grating solitons in Kerr nonlinearity with dispersive reflectivity. On the other hand, the quintic nonlinearity is dominant in the other family. Stability regions are identified by means of systematic numerical stability analysis. In the case of the first family, the size of the stability region increases up to moderate values of dispersive reflectivity. However for the second family (i.e. region where quintic nonlinearity dominates), the size of the stability region increases even for strong dispersive reflectivity. For all values of m, there exists a subset of the unstable solitons belonging to the first family for which the instability development leads to deformation and subsequent splitting of the soliton into two moving solitons with different amplitudes and velocities.

The Stabilization of Amorphous Zopiclone in an Amorphous Solid Dispersion.

Science.gov (United States)

Milne, Marnus; Liebenberg, Wilna; Aucamp, Marique

2015-10-01

Zopiclone is a poorly soluble psychotherapeutic agent. The aim of this study was to prepare and characterize an amorphous form of zopiclone as well as the characterization and performance of a stable amorphous solid dispersion. The amorphous form was prepared by the well-known method of quench-cooling of the melt. The solid dispersion was prepared by a solvent evaporation method of zopiclone, polyvinylpyrrolidone-25 (PVP-25), and methanol, followed by freeze-drying. The physico-chemical properties and stability of amorphous zopiclone and the solid dispersion was studied using differential scanning calorimetry (DSC), infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), hot-stage microscopy (HSM), X-ray diffractometry (XRD), solubility, and dissolution studies. The zopiclone amorphous solid-state form was determined to be a fragile glass; it was concluded that the stability of the amorphous form is influenced by both temperature and water. Exposure of amorphous zopiclone to moisture results in rapid transformation of the amorphous form to the crystalline dihydrated form. In comparison, the amorphous solid dispersion proved to be more stable with increased aqueous solubility.

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

Science.gov (United States)

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Surface Modification of Multiwall Carbon Nanotubes with Cationic Conjugated Polyelectrolytes: Fundamental Interactions and Intercalation into Conductive Poly(methyl-methacrylate) Composites

KAUST Repository

Ezzeddine, Alaa

2015-05-22

This research investigates the modification and dispersion and of pristine multiwalled carbon nanotubes (MWCNTs) through a simple solution mixing technique based on noncovalent interactions between poly(phenylene ethynylene) based conjugated polyelectrolytes functionalized with cationic imidazolium solubilizing groups (PIM-2 and PIM-4) and MWCNTs. Spectroscopic studies demonstrated the ability of PIMs to strongly interact with and efficiently disperse MWCNTs in different solvents mainly due to π-interactions between the PIMs and MWCNTs. Transmission electron microscopy and atomic force microscopy revealed the coating of the polyelectrolytes on the walls of the nanotubes. Scanning electron microscopy (SEM) studies confirm the homogenous dispersion of PIM modified MWCNTs in poly(methyl methacrylate) (PMMA) matrix. The addition of 1 wt% PIM modified MWCNTs to the matrix has led to a significant decrease in DC resistivity of the composite (13 orders of magnitude). The increase in electrical conductivity and the improvement in thermal and mechanical properties of the membranes containing the PIM modified MWCNTs is ascribed to the formation of MWCNTs networks and cross-linking sites that provided channels for the electrons to move in throughout the matrix and reinforced the interface between MWCNTs and PMMA.

Aqueous suspensions of {alpha}Al{sub 2}O{sub 3}/SiC mixed systems

Energy Technology Data Exchange (ETDEWEB)

Pagnoux, C.; Baklouti, S.; Chartier, T.; Baumard, J.F. [ENSCI, Limoges (France). LMCTS

1997-12-31

The preparation of aqueous {alpha}-Al{sub 2}O{sub 3}, {alpha}-SiO{sub 2} and {alpha}-SiC suspensions with polyelectrolytes, respectively the NH{sub 4}{sup +} salt of polymethacrylic acid (PMA-NH{sub 4}{sup +}) and acidic form polyethylene imine (PEI-H{sup +}) is investigated. It is based on the adsorption of these polyelectrolytes which in turn depends mainly on the nature of the polyelectrolyte, and the charge density which develops on the powder surface in water. Good dispersion and stability of dispersions are then obtained through electrostatic and steric stabilization. As an application, the preparation of an Al{sub 2}O{sub 3}-SiC aqueous mixed slurry was investigated as a preliminary step for processing of Al{sub 2}O{sub 3}/SiC nanocomposites. (orig.) 2 refs.

Dissecting the structure of surface stabilizer on the dispersion of inorganic nanoparticles in aqueous medium

Energy Technology Data Exchange (ETDEWEB)

Ding, Yong; Yu, Zongzhi; Zheng, Junping, E-mail: jpzheng@tju.edu.cn [Tianjin University, Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering (China)

2017-03-15

Dispersing inorganic nanoparticles in aqueous solutions is a key requirement for a great variety of products and processes, including carriers in drug delivery or fillers in polymers. To be highly functional in the final product, inorganic particles are required to be finely dispersed in nanoscale. In this study, silica was selected as a representative inorganic particle. Surface stabilizers with different chain length and charged group were designed to reveal the influence of electrostatic and van der Waals forces between silica and stabilizer on the dispersion of silica particles in aqueous medium. Results showed surface stabilizer with longer alkyl chain and charged group exerted best ability to deaggregate silica, leading to a hydrodynamic size of 51.1 nm. Surface stabilizer designing with rational structure is a promising solution for deagglomerating and reducing process time and energy. Giving the designability and adaptability of surface stabilizer, this method is of potential for dispersion of other inorganic nanoparticles.

Dissecting the structure of surface stabilizer on the dispersion of inorganic nanoparticles in aqueous medium

Science.gov (United States)

Ding, Yong; Yu, Zongzhi; Zheng, Junping

2017-03-01

Dispersing inorganic nanoparticles in aqueous solutions is a key requirement for a great variety of products and processes, including carriers in drug delivery or fillers in polymers. To be highly functional in the final product, inorganic particles are required to be finely dispersed in nanoscale. In this study, silica was selected as a representative inorganic particle. Surface stabilizers with different chain length and charged group were designed to reveal the influence of electrostatic and van der Waals forces between silica and stabilizer on the dispersion of silica particles in aqueous medium. Results showed surface stabilizer with longer alkyl chain and charged group exerted best ability to deaggregate silica, leading to a hydrodynamic size of 51.1 nm. Surface stabilizer designing with rational structure is a promising solution for deagglomerating and reducing process time and energy. Giving the designability and adaptability of surface stabilizer, this method is of potential for dispersion of other inorganic nanoparticles.

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.

A Molecular-Level View of the Physical Stability of Amorphous Solid Dispersions

Science.gov (United States)

Yuan, Xiaoda

Many pharmaceutical compounds being developed in recent years are poorly soluble in water. This has led to insufficient oral bioavailability of many compounds in vitro. The amorphous formulation is one of the promising techniques to increase the oral bioavailability of these poorly water-soluble compounds. However, an amorphous drug substance is inherently unstable because it is a high energy form. In order to increase the physical stability, the amorphous drug is often formulated with a suitable polymer to form an amorphous solid dispersion. Previous research has suggested that the formation of an intimately mixed drug-polymer mixture contributes to the stabilization of the amorphous drug compound. The goal of this research is to better understand the role of miscibility, molecular interactions and mobility on the physical stability of amorphous solid dispersions. Methods were developed to detect different degrees of miscibility on nanometer scale and to quantify the extent of hydrogen-bonding interactions between the drug and the polymer. Miscibility, hydrogen-bonding interactions and molecular mobility were correlated with physical stability during a six-month period using three model systems. Overall, this research provides molecular-level insights into many factors that govern the physical stability of amorphous solid dispersions which can lead to a more effective design of stable amorphous formulations.

Polysaccharides for stabilization of lipid particles

International Nuclear Information System (INIS)

Lionzo, Maria I.Z.; Silveira, Nadya P. Da; Muniz, Edvani Curti

2011-01-01

The main goal of this paper was to investigate the impact of different amounts of polyelectrolytes on the size, surface charge and rigidity of the bilayers of multilamellar liposomes. For this purpose, composite liposomes were developed containing chitosan and chondroitin sulfate. The use of a second polyelectrolyte, chondroitin sulfate, for the coating of the liposomes was applied in order to modulate their surface charge, maintaining the stability given by the presence of chitosan. Light and X-rays small angle scattering were the main techniques applied. Zeta-potential values were used to determine the charge density and the amount of adsorbed polyelectrolytes on the liposomes. (author)

Dispersion and Stabilization of Photocatalytic TiO2 Nanoparticles in Aqueous Suspension for Coatings Applications

Directory of Open Access Journals (Sweden)

Siti Hajar Othman

2012-01-01

Full Text Available To produce titanium dioxide (TiO2 nanoparticle coatings, it is desirable that the nanoparticles are dispersed into a liquid solution and remain stable for a certain period of time. Controlling the dispersion and aggregation of the nanoparticles is crucial to exploit the advantages of the nanometer-sized TiO2 particles. In this work, TiO2 nanoparticles were dispersed and stabilized in aqueous suspensions using two common dispersants which were polyacrylic acid (PAA and ammonium polymethacrylate (Darvan C. The effect of parameters such as ultrasonication amplitude and type and amount of dispersants on the dispersibility and stability of the TiO2 aqueous suspensions were examined. Rupture followed by erosion was determined to be the main break up mechanisms when ultrasonication was employed. The addition of dispersant was found to produce more dispersed and more stabilized aqueous suspension. 3 wt.% of PAA with average molecular weight (Mw of 2000 g/mol (PAA 2000 was determined to produce the best and most stable dispersion. The suspensions were then coated on quartz glass, whereby the photocatalytic activity of the coatings was studied via the degradation of formaldehyde gas under UV light. The coatings were demonstrated to be photocatalytically active.

Formation of Polyelectrolyte Complex Colloid Particles between Chitosan and Pectin with Different Degree of Esterification

Science.gov (United States)

Wang, Hui; Sun, Hongyuan; He, Jieyu

2017-12-01

The effects of degree of esterification, pectin/chitosan ratio and pH on the formation of polyelectrolyte complex colloid particles between chitosan (CS) and pectin (PE) were investigated. Low methoxyl pectin (LPE) was achieved by de-esterifying high methoxyl pectin (HPE) with pectin methyl esterase. Turbidity titration and colorimetric method was used to determine the stability of complex colloid particles. The structure and morphology of complex particles were characterized by FTIR and TEM. When pectin solution was dropped into chitosan solution, complex colloidal dispersion was stable as PE/CS mass ratio was no more than 3:2. Colloidal particles of HPE-CS complex coagulated at larger ratio of PE/CS than LPE-CS. The maximum complex occurred at pH 6.1 for HPE-CS and pH 5.7 for LPE-CS, and decreasing pH leaded to the dissociation of complex particles. Electrostatic interactions between carboxyl groups on pectin and amino groups on chitosan were confirmed by FTIR. Colloidal particle sizes ranged from about 100 nm to 400 nm with spherical shape.

Aggregation of superparamagnetic iron oxide nanoparticles in dilute aqueous dispersions: Effect of coating by double-hydrophilic block polyelectrolyte

Czech Academy of Sciences Publication Activity Database

Hajduová, J.; Uchman, M.; Šafařík, Ivo; Šafaříková, Miroslava; Šlouf, Miroslav; Pispas, S.; Štěpánek, M.

2015-01-01

Roč. 483, oct (2015), s. 1-7 ISSN 0927-7757 R&D Projects: GA TA ČR(CZ) TE01020118 Institutional support: RVO:67179843 ; RVO:61389013 Keywords : magnetic nanoparticles * block polyelectrolytes * aggregation * small-angle light scattering Subject RIV: CD - Macromolecular Chemistry; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 2.760, year: 2015

Oxidative Stability of Dispersions Prepared from Purified Marine Phospholipid and the Role of α-Tocopherol

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

2012-01-01

, respectively, during 32 days of storage at 2 °C. Nonenzymatic browning was investigated through measurement of Strecker aldehydes, color changes, and pyrrole content. Dispersions containing α-tocopherol or higher levels of purified marine PL showed a lower increment of volatiles after 32 days storage......The objective of this study was to investigate the oxidative stability of dispersions prepared from different levels of purified marine phospholipid (PL) obtained by acetone precipitation, with particular focus on the interaction between α-tocopherol and PL in dispersions. This also included...... the investigation of nonenzymatic browning in purified marine PL dispersions. Dispersions were prepared by high-pressure homogenizer. The oxidative and hydrolytic stabilities of dispersions were investigated by determination of hydroperoxides, secondary volatile oxidation products, and free fatty acids...

UV stabilization of wood by nano metal oxides dispersed in propylene glycol.

Science.gov (United States)

Nair, Sreeja; Nagarajappa, Giridhar B; Pandey, Krishna K

2018-06-01

Nanoparticles of some of the metal oxides are known to have high UV protective efficiency. The UV filtering efficiency of nanoparticles invariably depends on their size and stability in the dispersion. In the present work, a stable dispersion of nanoparticles of three metal oxides, zinc oxide (ZnO), cerium oxide (CeO 2 ) and titanium dioxide (TiO 2 ), was prepared in propylene glycol (PG) using ultrasonication. The method is easy and useful as no additional surfactant or dispersant is needed. The particle size and its distribution was confirmed by Scanning Electron Microscopy and Dynamic Light Scattering. The stability of dispersion was assessed by UV-visible absorption spectroscopy. The UV stability of wood surfaces of Wrightia tinctoria coated with nanodispersions of ZnO, CeO 2 and TiO 2 was evaluated under laboratory conditions in an accelerated weathering tester. Changes in the colour and FTIR spectra of exposed specimens were measured periodically. Rapid colour darkening (yellowing) was observed in uncoated and PG coated specimens. In contrast, nanodispersion coated specimens prevented photo-yellowing considerably with significant reduction in colour changes examined by CIE L*, a*, b* and ΔE*. Increase in concentration of nanoparticles in the dispersion imparted higher resistance to UV induced degradation. However, increased concentration of nanoparticles reduced the transparency of the coating. FTIR analysis indicated rapid degradation of lignin in uncoated and PG coated specimens due to UV exposure. Coating of wood surfaces with nanodispersions restricted lignin degradation. The study also demonstrates the potential of propylene glycol as a dispersant for developing stable and efficient UV protective nanodispersions for wood coating. Copyright © 2018 Elsevier B.V. All rights reserved.

Surfactive stabilization of multi-walled carbon nanotube dispersions with dissolved humic substances

Energy Technology Data Exchange (ETDEWEB)

Chappell, Mark A. [Environmental Laboratory, Engineering Research and Development Center, US Army Corps of Engineers, 3909 Halls Ferry Road, Vicksburg, MS 39180 (United States)], E-mail: mark.a.chappell@usace.army.mil; George, Aaron J.; Dontsova, Katerina M.; Porter, Beth E. [SpecPro, Inc., 4815 Bradford Drive, Suite 201, Huntsville, AL 35805 (United States); Price, Cynthia L. [Environmental Laboratory, Engineering Research and Development Center, US Army Corps of Engineers, 3909 Halls Ferry Road, Vicksburg, MS 39180 (United States); Zhou Pingheng; Morikawa, Eizi [J. Bennett Johnston Sr. Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States); Kennedy, Alan J.; Steevens, Jeffery A. [Environmental Laboratory, Engineering Research and Development Center, US Army Corps of Engineers, 3909 Halls Ferry Road, Vicksburg, MS 39180 (United States)

2009-04-15

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L{sup -1} added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment. - Suspensions of multi-walled carbon nanotubes are stabilized by relatively low concentrations of dissolved humic substances in solution through surfactive mechanisms.

Surfactive stabilization of multi-walled carbon nanotube dispersions with dissolved humic substances

International Nuclear Information System (INIS)

Chappell, Mark A.; George, Aaron J.; Dontsova, Katerina M.; Porter, Beth E.; Price, Cynthia L.; Zhou Pingheng; Morikawa, Eizi; Kennedy, Alan J.; Steevens, Jeffery A.

2009-01-01

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L -1 added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment. - Suspensions of multi-walled carbon nanotubes are stabilized by relatively low concentrations of dissolved humic substances in solution through surfactive mechanisms

[Inclusion of proteins into polyelectrolyte microcapsules by coprecipitation and adsorption].

Science.gov (United States)

Kochetkova, O Iu; Kazakova, L I; Moshkov, D A; Vinokurov, M G; Shabarchina, L I

2013-01-01

In present study microcapsules composed of synthetic (PSS and PAA) and biodegradable (DS and PAr) polyelectrolytes on calcium carbonate microparticles were obtained. The ultrastructural organization of biodegradable microcapsules was studied using transmission electron microscopy. The envelope of such capsules consisting of six polyelectrolyte layers is already well-formed, having the average thickness of 44 ± 3.0 nm, and their internal polyelectrolyte matrix is sparser compared to the synthetic microcapsules. Spectroscopy was employed to evaluate the efficiency of incorporation of FITC-labeled BSA into synthetic microcapsules by adsorption, depending on the number of polyelectrolyte layers. It was shown that the maximal amount of protein incorporated into the capsules with 6 or 7 polyelectrolyte layers (4 and 2 pg/capsule, correspondingly). As a result we conclude that, in comparison with co-precipitation, the use of adsorption allows to completely avoid the loss of protein upon encapsulation.

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.

Layer-by-Layer Assembly of Fluorine-Free Polyelectrolyte-Surfactant Complexes for the Fabrication of Self-Healing Superhydrophobic Films.

Science.gov (United States)

Wu, Mengchun; An, Ni; Li, Yang; Sun, Junqi

2016-11-29

Fluorine-free self-healing superhydrophobic films are of significance for practical applications because of their extended service life and cost-effective and eco-friendly preparation process. In this study, we report the fabrication of fluorine-free self-healing superhydrophobic films by layer-by-layer (LbL) assembly of poly(sodium 4-styrenesulfonate) (PSS)-1-octadecylamine (ODA) complexes (PSS-ODA) and poly(allylamine hydrochloride) (PAH)-sodium dodecyl sulfonate (SDS) (PAH-SDS) complexes. The wettability of the LbL-assembled PSS-ODA/PAH-SDS films depends on the film structure and can be tailored by changing the NaCl concentration in aqueous dispersions of PSS-ODA complexes and the number of film deposition cycles. The freshly prepared PSS-ODA/PAH-SDS film with micro- and nanoscaled hierarchical structures is hydrophilic and gradually changes to superhydrophobic in air because the polyelectrolyte-complexed ODA and SDS surfactants tend to migrate to the film surface to cover the film with hydrophobic alkyl chains to lower its surface energy. The large amount of ODA and SDS surfactants loaded in the superhydrophobic PSS-ODA/PAH-SDS films and the autonomic migration of these surfactants to the film surface endow the resultant superhydrophobic films with an excellent self-healing ability to restore the damaged superhydrophobicity. The self-healing superhydrophobic PSS-ODA/PAH-SDS films are mechanically robust and can be deposited on various flat and nonflat substrates. The LbL assembly of oppositely charged polyelectrolyte-surfactant complexes provides a new way for the fabrication of fluorine-free self-healing superhydrophobic films with satisfactory mechanical stability, enhanced reliability, and extended service life.

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

International Nuclear Information System (INIS)

Steitz, R.; Leiner, V.; Tauer, K.; Khrenov, V.; Klitzing, R. 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 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.)

Water-resistive humidity sensor prepared by printing process using polyelectrolyte ink derived from new monomer.

Science.gov (United States)

Kim, Min-Ji; Gong, Myoung-Seon

2012-03-21

A simple strategy was developed based on a new monomer containing both photocurable function and ammonium salt, N-(2-cinnamoyloxy)ethyl-N-(2-(methacryloyloxy)ethyl)-N,N-dimethyl ammonium bromide (CMDAB) to obtain photocurable polyelectrolyte ink and stable humidity-sensitive membranes by printing process. Humidity-sensitive membranes are photocrosslinked polyelectrolytes obtained from copolymers of [2-(methacryloyloxy)ethyl] dimethyl propyl ammonium bromide (MEPAB), CMDAB and MMA. A flexible gold electrode/polyimide was pretreated with 2-(mercaptoethyl) cinnamamide (MEC) containing a thiol-coupling agent for the purpose of anchoring the humidity-sensitive polyelectrolyte to the gold electrode. The sensors using screen printing methods reduced the deflection of sensor characteristics showing humidity precision ±1%RH. The photocured copolymer MEPAB/CMDAB/MMA = 63/7/30 show good sensitivity (0.0586 logΩ/%RH) changing resistance approximately four orders of magnitude with relative humidity varying from 20% to 95% and fast response and recovery time. The resultant sensors showed acceptable linearity (Y = -0.04X + 7.0, R(2) = -0.9900) and small hysteresis. The reliability including water resistance and a long-term stability were estimated for the application of the flexible humidity sensor prepared by screen printing process.

Surface colonized silver nano particles over chitosan poly-electrolyte micro-spheres and their multi-functional behavior

Science.gov (United States)

Prakash, B.; Asha, S.; Nimrodh Ananth, A.; Vanithakumari, G.; Okram, G. S.; Jose, Sujin P.; Jothi Rajan, M. A.

2018-02-01

Chitosan/tripolyphosphate polyelectrolyte (TPP) microspheres, decorated and surface functionalized with silver nanoparticles (NPs) of average diameter of 15 nm, were synthesized following a simple two-step procedure. These Ag NP-functionalized polyelectrolyte microspheres (Ag-CSPMs) are found to be biocompatible and enhancing the reactive oxygen species in curcumin with excellent anti-bacterial activity for selected Gram-positive and negative bacterial strains, making them much attractive relative to bare surface counterparts; the well-stabilized silver NPs do not form any agglomerations on the surface of the chitosan microspheres. They also show excellent cytotoxic behavior towards MCF7 cell lines, showing a half-maximal inhibitory concentration (IC50) of 32 μg ml-1. Therefore, Ag-CSPMs exhibit multi-functional ability having potential towards theranostics applications.

Cell Permeating Nano-Complexes of Amphiphilic Polyelectrolytes Enhance Solubility, Stability, and Anti-Cancer Efficacy of Curcumin.

Science.gov (United States)

Fatima, Munazza T; Chanchal, Abhishek; Yavvari, Prabhu S; Bhagat, Somnath D; Gujrati, Mansi; Mishra, Ram K; Srivastava, Aasheesh

2016-07-11

Many hydrophobic drugs encounter severe bioavailability issues owing to their low aqueous solubility and limited cellular uptake. We have designed a series of amphiphilic polyaspartamide polyelectrolytes (PEs) that solubilize such hydrophobic drugs in aqueous medium and enhance their cellular uptake. These PEs were synthesized through controlled (∼20 mol %) derivatization of polysuccinimide (PSI) precursor polymer with hydrophobic amines (of varying alkyl chain lengths, viz. hexyl, octyl, dodecyl, and oleyl), while the remaining succinimide residues of PSI were opened using a protonable and hydrophilic amine, 2-(2-amino-ethyl amino) ethanol (AE). Curcumin (Cur) was employed as a representative hydrophobic drug to explore the drug-delivery potential of the resulting PEs. Unprecedented enhancement in the aqueous solubility of Cur was achieved by employing these PEs through a rather simple protocol. In the case of PEs containing oleyl/dodecyl residues, up to >65000× increment in the solubility of Cur in aqueous medium could be achieved without requiring any organic solvent at all. The resulting suspensions were physically and chemically stable for at least 2 weeks. Stable nanosized polyelectrolyte complexes (PECs) with average hydrodynamic diameters (DH) of 150-170 nm (without Cur) and 220-270 nm (after Cur loading) were obtained by using submolar sodium polyaspartate (SPA) counter polyelectrolyte. The zeta potential of these PECs ranged from +36 to +43 mV. The PEC-formation significantly improved the cytocompatibility of the PEs while affording reconstitutable nanoformulations having up to 40 wt % drug-loading. The Cur-loaded PECs were readily internalized by mammalian cells (HEK-293T, MDA-MB-231, and U2OS), majorly through clathrin-mediated endocytosis (CME). Cellular uptake of Cur was directly correlated with the length of the alkyl chain present in the PECs. Further, the PECs significantly improved nuclear transport of Cur in cancer cells, resulting in their

Encapsulation of Phase Change Materials Using Layer-by-Layer Assembled Polyelectrolytes

Directory of Open Access Journals (Sweden)

Qiangying Yi

2015-01-01

Full Text Available Phase change materials absorb the thermal energy when changing their phases (e.g., solid-to-liquid at constant temperatures to achieve the latent heat storage. The major drawbacks such as limited thermal conductivity and leakage prevent the PCMs from wide application in desired areas. In this work, an environmentally friendly and low cost approach, layer-by-layer (LbL assembly technique, was applied to build up ultrathin shells to encapsulate the PCMs and therefore to regulate their changes in volume when the phase change occurs. Generally, the oppositely charged strong polyelectrolytes Poly(diallyldimethylammonium chloride (PDADMAC and Poly(4-styrenesulfonic acid sodium salt (PSS were employed to fabricate multilayer shells on emulsified octadecane droplets using either bovine serum albumin (BSA or sodium dodecyl sulfate (SDS as surfactant. Specifically, using BSA as the surfactant, polyelectrolyte encapsulated octadecane spheres in size of ∼500 nm were obtained, with good shell integrity, high octadecane content (91.3% by mass, and good thermal stability after cycles of thermal treatments.

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

Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers.

Science.gov (United States)

Fares, Hadi M; Schlenoff, Joseph B

2017-10-18

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

Complexation Behavior of Polyelectrolytes and Polyampholytes

KAUST Repository

Nair, Arun Kumar Narayanan; Jimenez, Arturo Martinez; Sun, Shuyu

2017-01-01

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.

Complexation Behavior of Polyelectrolytes and Polyampholytes

KAUST Repository

Nair, Arun Kumar Narayanan

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.

Unique coexistence of dispersion stability and nanoparticle chemisorption in alkylamine/alkylacid encapsulated silver nanocolloids.

Science.gov (United States)

Aoshima, Keisuke; Hirakawa, Yuya; Togashi, Takanari; Kurihara, Masato; Arai, Shunto; Hasegawa, Tatsuo

2018-04-17

Surface encapsulation of metal nanoparticles (NPs) is fundamental to achieve sufficient dispersion stability of metal nanocolloids, or metal nanoink. However, the feature is incompatible with surface reactive nature of the metal NPs, although these features are both essential to realizing the functional applications into printed electronics technologies. Here we show that two different kinds of encapsulation for silver NPs (AgNPs) by alkylamine and alkylacid together are the key to achieve unique compatibility between the high dispersion stability as dense nanoclolloids and the AgNP chemisorption printing on activated patterned polymer surfaces. Advanced confocal dynamic light scattering study reveals that an additive trace amount of oleic acid is the critical parameter for controlling the dispersion and coagulative (or surface-reactive) characteristics of the silver nanocolloids. The composition of the disperse media is also important for obtaining highly concentrated but low-viscosity silver nanocolloids that show very stable dispersion. The results demonstrate that the high-resolution AgNP chemisorption printing is possible only by using unique silver nanocolloids composed of an exceptional balance of ligand formulation and dispersant composition.

Both solubility and chemical stability of curcumin are enhanced by solid dispersion in cellulose derivative matrices.

Science.gov (United States)

Li, Bin; Konecke, Stephanie; Wegiel, Lindsay A; Taylor, Lynne S; Edgar, Kevin J

2013-10-15

Amorphous solid dispersions (ASD) of curcumin (Cur) in cellulose derivative matrices, hydroxypropylmethylcellulose acetate succinate (HPMCAS), carboxymethylcellulose acetate butyrate (CMCAB), and cellulose acetate adipate propionate (CAAdP) were prepared in order to investigate the structure-property relationship and identify polymer properties necessary to effectively increase Cur aqueous solution concentration. XRD results indicated that all investigated solid dispersions were amorphous, even at a 9:1 Cur:polymer ratio. Both stability against crystallization and Cur solution concentration from these ASDs were significantly higher than those from physical mixtures and crystalline Cur. Remarkably, curcumin was also stabilized against chemical degradation in solution. Chemical stabilization was polymer-dependent, with stabilization in CAAdP>CMCAB>HPMCAS>PVP, while matrices enhanced solution concentration as PVP>HPMCAS>CMCAB≈CAAdP. HPMCAS/Cur dispersions have useful combinations of pH-triggered release profile, chemical stabilization, and strong enhancement of Cur solution concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Superhydrophilic Polyelectrolyte Brush Layers with Imparted Anti-Icing Properties

DEFF Research Database (Denmark)

Chernyy, Sergey; Järn, Mikael; Shimizu, Kyoko

2014-01-01

. 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...

Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

International Nuclear Information System (INIS)

Voisin, David

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 polyelectrolyte-surfactant particle in the region of the CAC, and just beyond, contains many polyelectrolyte chains, held together essentially by micelle bridges. These particles, however, remain net positively charged, and therefore stable. At the other end of the binding range of the surfactant, so many internal micelles are present that the polymer-surfactant particles are now net negatively charged. Indeed binding stops since no further micelles can be accommodated. Again, the particles are stable. However, there exists a range of surfactant concentrations, lying within the range referred to above, where the net charge is reduced sufficiently that the polymer-surfactant particles will flocculate to form much larger structures. The onset of this second range might be termed the 'critical flocculation concentration' (CFC), and the end, the 'critical stabilisation concentration' (CSC). In this work, the CFC and the CSC have been determined for mixtures of

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)

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

Effect of preparation methods on dispersion stability and electrochemical performance of graphene sheets

International Nuclear Information System (INIS)

Chen, Li; Li, Na; Zhang, Mingxia; Li, Pinnan; Lin, Zhengping

2017-01-01

Chemical exfoliation is one of the most important strategies for preparing graphene. The aggregation of graphene sheets severely prevents graphene from exhibiting excellent properties. However, there are no attempts to investigate the effect of preparation methods on the dispersity of graphene sheets. In this study, three chemical exfoliation methods, including Hummers method, modified Hummers method, and improved method, were used to prepare graphene sheets. The influence of preparation methods on the structure, dispersion stability in organic solvents, and electrochemical properties of graphene sheets were investigated. Fourier transform infrared microscopy, Raman spectra, transmission electron microscopy, and UV–vis spectrophotometry were employed to analyze the structure of the as-prepared graphene sheets. The results showed that graphene prepared by improved method exhibits excellent dispersity and stability in organic solvents without any additional stabilizer or modifier, which is attributed to the completely exfoliation and regular structure. Moreover, cyclic voltammetric and electrochemical impedance spectroscopy measurements showed that graphene prepared by improved method exhibits superior electrochemical properties than that prepared by the other two methods. - Graphical abstract: Graphene oxides with different oxidation degree were obtained via three methods, and then graphene with different crystal structures were created by chemical reduction of exfoliated graphene oxides. - Highlights: • Graphene oxides with different oxidation degree were obtained via three oxidation methods. • The influence of oxidation methods on microstructure of graphene was investigated. • The effect of oxidation methods on dispersion stability of graphene was investigated. • The effect of oxidation methods on electrochemical properties of graphene was discussed.

Effect of preparation methods on dispersion stability and electrochemical performance of graphene sheets

Energy Technology Data Exchange (ETDEWEB)

Chen, Li, E-mail: chenli1981@lut.cn; Li, Na; Zhang, Mingxia; Li, Pinnan; Lin, Zhengping

2017-05-15

Chemical exfoliation is one of the most important strategies for preparing graphene. The aggregation of graphene sheets severely prevents graphene from exhibiting excellent properties. However, there are no attempts to investigate the effect of preparation methods on the dispersity of graphene sheets. In this study, three chemical exfoliation methods, including Hummers method, modified Hummers method, and improved method, were used to prepare graphene sheets. The influence of preparation methods on the structure, dispersion stability in organic solvents, and electrochemical properties of graphene sheets were investigated. Fourier transform infrared microscopy, Raman spectra, transmission electron microscopy, and UV–vis spectrophotometry were employed to analyze the structure of the as-prepared graphene sheets. The results showed that graphene prepared by improved method exhibits excellent dispersity and stability in organic solvents without any additional stabilizer or modifier, which is attributed to the completely exfoliation and regular structure. Moreover, cyclic voltammetric and electrochemical impedance spectroscopy measurements showed that graphene prepared by improved method exhibits superior electrochemical properties than that prepared by the other two methods. - Graphical abstract: Graphene oxides with different oxidation degree were obtained via three methods, and then graphene with different crystal structures were created by chemical reduction of exfoliated graphene oxides. - Highlights: • Graphene oxides with different oxidation degree were obtained via three oxidation methods. • The influence of oxidation methods on microstructure of graphene was investigated. • The effect of oxidation methods on dispersion stability of graphene was investigated. • The effect of oxidation methods on electrochemical properties of graphene was discussed.

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

Science.gov (United States)

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

2007-09-11

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

Optimizing Glassy Polymer Network Morphology for Nano-particle Dispersion, Stabilization and Performance

Science.gov (United States)

2016-10-03

viscosity and stabilization of MWCNTs within rheological regimes which inhibit re-agglomeration to aid in post processing stabilization of dispersion state...polypropylene- clay nanocomposites subjected to laser pulse heating Bartolucci, Stephen, Supan, Karen, Wiggins, Jeffrey, LaBeaud, Lawrence, Warrender...addition, concurrent chain extension reactions advance prepolymer molecular weights to desired viscosities in less than 2 minutes of mean residence

Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

International Nuclear Information System (INIS)

Zielińska, Katarzyna; Leeuwen, Herman P. van

2014-01-01

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

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

Science.gov (United States)

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

2015-06-17

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

Horseradish peroxidase-nanoclay hybrid particles of high functional and colloidal stability.

Science.gov (United States)

Pavlovic, Marko; Rouster, Paul; Somosi, Zoltan; Szilagyi, Istvan

2018-08-15

Highly stable dispersions of enzyme-clay nanohybrids of excellent horseradish peroxidase activity were developed. Layered double hydroxide nanoclay was synthesized and functionalized with heparin polyelectrolyte to immobilize the horseradish peroxidase enzyme. The formation of a saturated heparin layer on the platelets led to charge inversion of the positively charged bare nanoclay and to highly stable aqueous dispersions. Great affinity of the enzyme to the surface modified platelets resulted in strong horseradish peroxidase adsorption through electrostatic and hydrophobic interactions as well as hydrogen bonding network and prevented enzyme leakage from the obtained material. The enzyme kept its functional integrity upon immobilization and showed excellent activity in decomposition of hydrogen peroxide and oxidation of an aromatic compound in the test reactions. In addition, remarkable long term functional stability of the enzyme-nanoclay hybrid was observed making the developed colloidal system a promising antioxidant candidate in biomedical treatments and industrial processes. Copyright © 2018 Elsevier Inc. All rights reserved.

Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films

Science.gov (United States)

Ball, Vincent

2012-01-01

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

Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

Energy Technology Data Exchange (ETDEWEB)

Voisin, David

2002-07-01

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

A basic insight into the stability and manufacturing aspects of solid dispersions

Directory of Open Access Journals (Sweden)

Jishnu Vijay

2012-01-01

Full Text Available The development of a bioavailable dosage form is the most challenging task for the researchers. In the arena of advanced drug delivery systems, the solid dispersion techniques seem to be a promising system for the development of an optimized, bioavailable formulation of Class 2 drugs. The methods of formulation of solid dispersion have been summarized. This article is an effort to define a solid dispersion and its classification. The prospective of the stability of solid dispersion has also been discussed. Moreover, the major techniques that have been used so far such as the fusion/melting method, solvent evaporation method, hot melt extrusion method, supercritical fluid methods, have also been detailed.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

Science.gov (United States)

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

2010-07-27

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

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.

Amorphous Solid Dispersion of Epigallocatechin Gallate for Enhanced Physical Stability and Controlled Release

Directory of Open Access Journals (Sweden)

Yizheng Cao

2017-11-01

Full Text Available Epigallocatechin gallate (EGCG has been recognized as the most prominent green tea extract due to its healthy influences. The high instability and low bioavailability, however, strongly limit its utilization in food and drug industries. This work, for the first time, develops amorphous solid dispersion of EGCG to enhance its bioavailability and physical stability. Four commonly used polymeric excipients are found to be compatible with EGCG in water-dioxane mixtures via a stepwise mixing method aided by vigorous mechanical interference. The dispersions are successfully generated by lyophilization. The physical stability of the dispersions is significantly improved compared to pure amorphous EGCG in stress condition (elevated temperature and relative humidity and simulated gastrointestinal tract environment. From the drug release tests, one of the dispersions, EGCG-Soluplus® 50:50 (w/w shows a dissolution profile that only 50% EGCG is released in the first 20 min, and the remains are slowly released in 24 h. This sustained release profile may open up new possibilities to increase EGCG bioavailability via extending its elimination time in plasma.

Amorphous Solid Dispersion of Epigallocatechin Gallate for Enhanced Physical Stability and Controlled Release.

Science.gov (United States)

Cao, Yizheng; Teng, Jing; Selbo, Jon

2017-11-09

Epigallocatechin gallate (EGCG) has been recognized as the most prominent green tea extract due to its healthy influences. The high instability and low bioavailability, however, strongly limit its utilization in food and drug industries. This work, for the first time, develops amorphous solid dispersion of EGCG to enhance its bioavailability and physical stability. Four commonly used polymeric excipients are found to be compatible with EGCG in water-dioxane mixtures via a stepwise mixing method aided by vigorous mechanical interference. The dispersions are successfully generated by lyophilization. The physical stability of the dispersions is significantly improved compared to pure amorphous EGCG in stress condition (elevated temperature and relative humidity) and simulated gastrointestinal tract environment. From the drug release tests, one of the dispersions, EGCG-Soluplus ® 50:50 ( w / w ) shows a dissolution profile that only 50% EGCG is released in the first 20 min, and the remains are slowly released in 24 h. This sustained release profile may open up new possibilities to increase EGCG bioavailability via extending its elimination time in plasma.

Microencapsulation of Ginger Volatile Oil Based on Gelatin/Sodium Alginate Polyelectrolyte Complex.

Science.gov (United States)

Wang, Lixia; Yang, Shiwei; Cao, Jinli; Zhao, Shaohua; Wang, Wuwei

2016-01-01

The coacervation between gelatin and sodium alginate for ginger volatile oil (GVO) microencapsulation as functions of mass ratio, pH and concentration of wall material and core material load was evaluated. The microencapsulation was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and thermal gravimetric analysis (TGA). SEM and FT-IR studies indicated the formation of polyelectrolyte complexation between gelatin and sodium alginate and successful encapsulation of GVO into the microcapsules. Thermal property study showed that the crosslinked microparticles exhibited higher thermal stability than the neat GVO, gelatin, and sodium alginate. The stability of microencapsulation of GVO in a simulated gastric and an intestinal situation in vitro was also studied. The stability results indicated that the release of GVO from microcapsules was much higher in simulated intestinal fluid, compared with that in simulated-gastric fluid.

Surface and permeability properties of membranes from polyelectrolyte complexes and polyelectrolyte surfactant complexes

Czech Academy of Sciences Publication Activity Database

Schwarz, H. H.; Lukáš, Jaromír; Richau, K.

2003-01-01

Roč. 218, 1-2 (2003), s. 1-9 ISSN 0376-7388 R&D Projects: GA AV ČR KSK4050111 Keywords : polyelectrolyte complex membranes * pervaporation * dehydration of organics Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.081, year: 2003

Polyelectrolyte functionalized gold nanoparticles-reduced graphene oxide nanohybrid for electrochemical determination of aminophenol isomers

International Nuclear Information System (INIS)

Li, Xinchun; Zhong, Anni; Wei, Shanshan; Luo, Xiaoli; Liang, Yanjin; Zhu, Qiao

2015-01-01

A green chemical method for preparation of gold nanoparticles-reduced graphene oxide nanocomposite is described. This can be readily accomplished through a two-step chemical reduction scheme by using poly(diallyldimethylammonium chloride), a cationic polyelectrolyte as a common reducer. Polyelectrolyte here also serves to stabilize gold nanoparticles and is beneficial to electrical communication, leading to the formation of well-characteristic nanohybrid. The prepared nanomaterial showed remarkable electrocatalytic ability as a result of the rational conjunction of graphene and gold nanoparticles, which was demonstrated by direct electrochemical determination of three aminophenol isomers on a modified glassy carbon electrode. Effective peak separation of three isomers was achieved due to the favorable electron-transfer network perfectly assembled on the electrode surface, thus enabling the simultaneous assay of multiple components featuring analogous chemical structure without chromatographic separation. The modified electrode was further used to detect para-aminophenol in paracetamol tablets. The present method is simple, eco-friendly and holds potential for electroanalytical and biosensing applications

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.

Layer-by-layer modification of high surface curvature nanoparticles with weak polyelectrolytes using a multiphase solvent precipitation process.

Science.gov (United States)

Nagaraja, Ashvin T; You, Yil-Hwan; Choi, Jeong-Wan; Hwang, Jin-Ha; Meissner, Kenith E; McShane, Michael J

2016-03-15

The layer-by-layer modification of ≈5 nm mercaptocarboxylic acid stabilized gold nanoparticles was studied in an effort to illustrate effective means to overcome practical issues in handling and performing surface modification of such extremely small materials. To accomplish this, each layer deposition cycle was separated into a multi-step process wherein solution pH was controlled in two distinct phases of polyelectrolyte adsorption and centrifugation. Additionally, a solvent precipitation step was introduced to make processing more amenable by concentrating the sample and exchanging solution pH before ultracentrifugation. The pH-dependent assembly on gold nanoparticles was assessed after each layer deposition cycle by monitoring the plasmon peak absorbance location, surface charge, and the percentage of nanoparticles recovered. The selection of solution pH during the adsorption phase was found to be a critical parameter to enhance particle recovery and maximize surface charge when coating with weak polyelectrolytes. One bilayer was deposited with a high yield and the modified particles exhibited enhanced colloidal stability across a broad pH range and increased ionic strength. These findings support the adoption of this multi-step processing approach as an effective and generalizable approach to improve stability of high surface curvature particles. Copyright © 2015 Elsevier Inc. All rights reserved.

Tribological behavior of in situ Ag nanoparticles/polyelectrolyte composite molecular deposition films

International Nuclear Information System (INIS)

Guo Yanbao; Wang Deguo; Liu Shuhai

2010-01-01

Multilayer polyelectrolyte films containing silver ions were obtained by molecular deposition method on a glass plate or a quartz substrate. The in situ Ag nanoparticles were synthesized in the multilayer polyelectrolyte films which were put into fresh NaBH 4 aqueous solution. The structure and surface morphology of composite molecular deposition films were observed by UV-vis spectrophotometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Tribological characteristic was investigated by AFM and micro-tribometer. It was found that the in situ Ag nanoparticles/polyelectrolyte composite molecular deposition films have lower coefficient of friction and higher anti-wear life than pure polyelectrolyte molecular deposition films.

Solution dynamics of synthetic and natural polyelectrolytes

Science.gov (United States)

Krause, Wendy E.

Polyelectrolytes are abundant in nature and essential to life, and used extensively in industry. This work discussed two polyelectrolytes: sodium poly(2-acrylamido-2-methylpropanesulfonate) (NaPAMS), synthetic polyelectrolyte, and sodium hyaluronate (NaHA), a glycosaminoglycan. Rheological data of NaPAMS solutions of variable chain length and concentration were reported. A strong dependence of viscosity eta on chain length: eta ˜ M2.4 was found. The comparison of the rheological data with two proposed scaling theories (Dobrynin 1995, Witten 1987) forces the conclusion that neither theory is correct. A possible interpretation of the viscosity data falling between the predictions of the two scaling theories is that some chain rigidity may persist beyond the correlation length. A sample model for the conductivity of semidilute polyelectrolytes with no added salt was presented. The model correctly describes the logarithmic decrease of specific conductance observed for many polyelectrolytes at low concentration (below ca. 10-2M), and is in good agreement with data from NaPAMS solutions. NaHA in phosphate buffered saline behaves as a typical polyelectrolyte in the high-salt limit, as Newtonian viscosities are observed over a wide range of shear rates. There is no evidence of intermolecular hydrogen bonding causing gel formation in NaHA solutions without protein present. The viscosity of 3 mg/mL NaHA was measured in the presence of the selected anti-inflammatory agents. Of the seven additives investigated only (D)-penicillamine significantly altered the rheology of HA. (D)-Penicillamine dramatically reduced the viscosity of HA, probably by disrupting intramolecular hydrogen bonding. The plasma proteins albumin and gamma-globulins bind to HA in solution to form a weak reversible gel. The rheology and osmotic pressure of the simple model for synovial fluid, consisting of 3mg/mL NaHA, 11 mg/mL albumin, and 7 mg/mL gamma-globulins in phosphate buffered saline, were studied

Screening effects in a polyelectrolyte brush: self-consistent-field theory

NARCIS (Netherlands)

Zhulina, E.B.; Klein Wolterink, J.; Borisov, O.V.

2000-01-01

We have developed an analytical self-consistent-field (SCF) theory describing conformations of weakly charged polyelectrolyte chains tethered to the solid-liquid interface and immersed in a solution of low molecular weight salt. Depending on the density of grafting of the polyelectrolytes to the

Habitat stability affects dispersal and the ability to track climate change

DEFF Research Database (Denmark)

Hof, Christian; Brändle, Martin; Dehling, D. Matthias

2012-01-01

Habitat persistence should influence dispersal ability, selecting for stronger dispersal in habitats of lower temporal stability. As standing (lentic) freshwater habitats are on average less persistent over time than running (lotic) habitats, lentic species should show higher dispersal abilities ...... that lentic species track climatic changes more rapidly than lotic species. These results are consistent with the proposed hypothesis that habitat persistence affects the evolution of dispersal....... than lotic species. Assuming that climate is an important determinant of species distributions, we hypothesize that lentic species should have distributions that are closer to equilibrium with current climate, and should more rapidly track climatic changes. We tested these hypotheses using datasets...... from 1988 and 2006 containing all European dragon- and damselfly species. Bioclimatic envelope models showed that lentic species were closer to climatic equilibrium than lotic species. Furthermore, the models over-predicted lotic species ranges more strongly than lentic species ranges, indicating...

Debundling of single-walled carbon nanotubes by using natural polyelectrolytes

International Nuclear Information System (INIS)

Liu Yangqiao; Gao Lian; Zheng Shan; Wang Yan; Sun Jing; Kajiura, Hisashi; Li Yongming; Noda, Kazuhiro

2007-01-01

Natural polyelectrolytes (NPs), including sodium lignosulfonate, humic acid and so forth, are reported for the first time to solubilize single-walled carbon nanotubes (SWNTs) in water through a noncovalent interaction. A variety of methods, including transmission electron microscopy (TEM), visible-near-infrared (vis-NIR) spectra, Raman spectra and zeta potential measurements, were used to characterize the NP-dispersed SWNT solutions. It is found that the SWNTs can be exfoliated into thin bundles or individual tubes, even at NP concentrations as low as 0.15 mg ml -1 . Their high performance is attributed to the abundance of aromatic groups and ionized groups in the NP molecules. This method of solubilization opens the way for exploiting new natural materials as SWNT solubilizers and may find applications in nanocomposites, self-assembly, and so forth

Debundling of single-walled carbon nanotubes by using natural polyelectrolytes

Energy Technology Data Exchange (ETDEWEB)

Liu Yangqiao [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Gao Lian [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Zheng Shan [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Wang Yan [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Sun Jing [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Kajiura, Hisashi [Materials Laboratories, Sony Corporation, Atsugi Tec. No. 2, 4-16-1 Okata Atsugi, Kanagawa 243-0021 (Japan); Li Yongming [Materials Laboratories, Sony Corporation, Atsugi Tec. No. 2, 4-16-1 Okata Atsugi, Kanagawa 243-0021 (Japan); Noda, Kazuhiro [Materials Laboratories, Sony Corporation, Atsugi Tec. No. 2, 4-16-1 Okata Atsugi, Kanagawa 243-0021 (Japan)

2007-09-12

Natural polyelectrolytes (NPs), including sodium lignosulfonate, humic acid and so forth, are reported for the first time to solubilize single-walled carbon nanotubes (SWNTs) in water through a noncovalent interaction. A variety of methods, including transmission electron microscopy (TEM), visible-near-infrared (vis-NIR) spectra, Raman spectra and zeta potential measurements, were used to characterize the NP-dispersed SWNT solutions. It is found that the SWNTs can be exfoliated into thin bundles or individual tubes, even at NP concentrations as low as 0.15 mg ml{sup -1}. Their high performance is attributed to the abundance of aromatic groups and ionized groups in the NP molecules. This method of solubilization opens the way for exploiting new natural materials as SWNT solubilizers and may find applications in nanocomposites, self-assembly, and so forth.

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.

Microparticles Containing Curcumin Solid Dispersion: Stability, Bioavailability and Anti-Inflammatory Activity.

Science.gov (United States)

Teixeira, C C C; Mendonça, L M; Bergamaschi, M M; Queiroz, R H C; Souza, G E P; Antunes, L M G; Freitas, L A P

2016-04-01

This work aimed at improving the solubility of curcumin by the preparation of spray-dried ternary solid dispersions containing Gelucire®50/13-Aerosil® and quantifying the resulting in vivo oral bioavailability and anti-inflammatory activity. The solid dispersion containing 40% of curcumin was characterised by calorimetry, infrared spectroscopy and X-ray powder diffraction. The solubility and dissolution rate of curcumin in aqueous HCl or phosphate buffer improved up to 3600- and 7.3-fold, respectively. Accelerated stability test demonstrated that the solid dispersion was stable for 9 months. The pharmacokinetic study showed a 5.5-fold increase in curcumin in rat blood plasma when compared to unprocessed curcumin. The solid dispersion also provided enhanced anti-inflammatory activity in rat paw oedema. Finally, the solid dispersion proposed here is a promising way to enhance curcumin bioavailability at an industrial pharmaceutical perspective, since its preparation applies the spray drying, which is an easy to scale up technique. The findings herein stimulate further in vivo evaluations and clinical tests as a cancer and Alzheimer chemoprevention agent.

The processing of polyelectrolyte-covered magnetite nanoparticles in the form of nanostructured thin films

International Nuclear Information System (INIS)

Marangoni, Valéria S.; Martins, Marccus Victor A.; Souza, José A.; Oliveira, Osvaldo N.; Zucolotto, Valtencir; Crespilho, Frank N.

2012-01-01

Magnetic nanoparticles are promising for a variety of applications, such as biomedical devices, spin electronics, magnetic data storage media, to name a few. However, these goals may only be reached if stable and organized structures are fabricated. In this article, we report on a single-step synthetic route with the coprecipitation method, in which iron oxide magnetic nanoparticles (Fe 3 O 4 NPs) were stabilized in aqueous media using the poly(diallyldimethylammonium chloride) (PDAC) polyelectrolyte. The Fe 3 O 4 NPs had a diameter of ca. 5 nm, according to transmission electron microscopy (TEM) images, being arranged in an inverse spinel structure typical of magnetite. An investigation with infrared spectroscopy indicated that the mechanisms of stabilization in the polymer matrix were based on the interaction between quaternary amide groups from PDAC and the nanoparticle surface. The Fe 3 O 4 -PDAC NPs exhibited considerable magnetic susceptibility, with a monotonic increase in the magnetization with decreasing temperature. These Fe 3 O 4 -PDAC NPs were immobilized in layer-by-layer (LbL) films, being alternated with layers of poly(vinylsulfonic acid) (PVS). The LbL films were much rougher than typical films made with polyelectrolytes, and Fe 3 O 4 -PDAC NPs have been responsible for the high electrocatalytic activity toward H 2 O 2 reduction, with an overpotential shift of 0.69 V. Overall, the stability, magnetic properties and film-forming ability indicate that the Fe 3 O 4 -PDAC NPs may be used for nanoelectronics and bioelectrochemical devices requiring reversible and magnetic redox materials.

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

Science.gov (United States)

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

2016-08-01

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

Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media

International Nuclear Information System (INIS)

Kamiya, Hidehiro; Iijima, Motoyuki

2010-01-01

Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids. (topical review)

Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media

Directory of Open Access Journals (Sweden)

Hidehiro Kamiya and Motoyuki Iijima

2010-01-01

Full Text Available Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM. Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids.

Bioresorbable polyelectrolytes for smuggling drugs into cells.

Science.gov (United States)

Jaganathan, Sripriya

2016-06-01

There is ample evidence that biodegradable polyelectrolyte nanocapsules are multifunctional vehicles which can smuggle drugs into cells, and release them upon endogenous activation. A large number of endogenous stimuli have already been tested in vitro, and in vivo research is escalating. Thus, the interest in the design of intelligent polyelectrolyte multilayer (PEM) drug delivery systems is clear. The need of the hour is a systematic translation of PEM-based drug delivery systems from the lab to clinical studies. Reviews on multifarious stimuli that can trigger the release of drugs from such systems already exist. This review summarizes the available literature, with emphasis on the recent progress in PEM-based drug delivery systems that are receptive in the presence of endogenous stimuli, including enzymes, glucose, glutathione, pH, and temperature, and addresses different active and passive drug targeting strategies. Insights into the current knowledge on the diversified endogenous approaches and methodological challenges may bring inspiration to resolve issues that currently bottleneck the successful implementation of polyelectrolytes into the catalog of third-generation drug delivery systems.

Preparation and properties of high storage stability polyester polyol dispersion for two-component waterborne polyurethane coating

Science.gov (United States)

Hao, H.; Hu, J. Q.; Wang, F.; Tu, W. P.

2017-01-01

A new type of polyester polyol dispersion with good storage stability was prepared based on a hydrophilic monomer 5-sodium sulfodimethyl isophthalate (5-SIPM), and frequently-used monomers such as neopentyl glycol (NPG), dimethyl terephthalate (DMT), dimethyl phthalate (DMP) and trimethylolpropane (TMP) by the transpolycondensation and polycondensation method. The polyester polyol dispersion was characterized by FTIR and GPC. The proper content of these monomers were determined by the performance of polyester dispersion: the content of TMP was 15wt%, the content of NPG was 7.5wt% and the hydrophilic monomer 5-SIPM content was 5wt%. Two-component waterborne polyurethane (2K-WPU) coatings were prepared by Bayhydur® XP2487/1 and polyester polyol dispersions, which were stored before and after at 40 ° for 6 weeks, the prepared films have no differences in drying time, adhesion, pencil hardness, gloss and chemical resistance, the result also reveals that the polyester polyol dispersion have excellent storage stability resistance.

Stabilization of liquid crystal dispersion by nonionic surfactant/acrylamide copolymer containing hydrophobic moieties

Energy Technology Data Exchange (ETDEWEB)

Park, S.J.; Kim, M.H.; Lee, J.R. [Korea Research Institute of Chemical Technology, Taejon (Korea)

1999-07-01

The effect of nonionic surfactant (H(OCH){sub 2}-OC{sub 6}H{sub 4}-C{sub 9}H{sub 19}, NP-8) and acrylamide copolymer containing nonylphenyl groups as hydrophobic moieties on the stabilization of liquid crystal (LC)-in-water dispersion has been studied. According to cloud point and adsorption measurements, the hydrophobically strong interaction between NP-8 and the nonylphenol moieties is formed. And the addition of surfactant increases the stability of LC dispersion and improve the electrooptical properties of the nematic curvilinear aligned phase (NCAP) composite film. It is due to the presence of surfactant which allows the formation of nonpolar microenvironment in the round of LC droplet and finally reduces the anchoring effect between LC and the polymeric wall. 21 refs., 8 figs.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

Science.gov (United States)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes — polyacrylic and polymethacrylic acids — are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions.

Surfactant-assisted dispersion of carbon nanotubes: mechanism of stabilization and biocompatibility of the surfactant

Science.gov (United States)

Singh, Raman Preet; Jain, Sanyog; Ramarao, Poduri

2013-10-01

Nanoparticles (NPs) are thermodynamically unstable system and tend to aggregate to reduce free energy. The aggregation property of NPs results in inhomogeneous exposure of cells to NPs resulting in variable cellular responses. Several types of surfactants are used to stabilize NP dispersions and obtain homogenous dispersions. However, the effects of these surfactants, per se, on cellular responses are not completely known. The present study investigated the application of Pluronic F68 (PF68) for obtaining stable dispersion of NPs using carbon nanotubes as model NPs. PF68-stabilized NP suspensions are stable for long durations and do not show signs of aggregation or settling during storage or after autoclaving. The polyethylene oxide blocks in PF68 provide steric hindrance between adjacent NPs leading to stable NP dispersions. Further, PF68 is biocompatible in nature and does not affect integrity of mitochondria, lysosomes, DNA, and nuclei. Also, PF68 neither induce free radical or cytokine production nor does it interfere with cellular uptake mechanisms. The results of the present study suggest that PF68-assisted dispersion of NPs produced suspensions, which are stable after autoclaving. Further, PF68 does not interfere with normal physiological functions suggesting its application in nanomedicine and nanotoxicity evaluation.

Surfactant-assisted dispersion of carbon nanotubes: mechanism of stabilization and biocompatibility of the surfactant

International Nuclear Information System (INIS)

Singh, Raman Preet; Jain, Sanyog; Ramarao, Poduri

2013-01-01

Nanoparticles (NPs) are thermodynamically unstable system and tend to aggregate to reduce free energy. The aggregation property of NPs results in inhomogeneous exposure of cells to NPs resulting in variable cellular responses. Several types of surfactants are used to stabilize NP dispersions and obtain homogenous dispersions. However, the effects of these surfactants, per se, on cellular responses are not completely known. The present study investigated the application of Pluronic F68 (PF68) for obtaining stable dispersion of NPs using carbon nanotubes as model NPs. PF68-stabilized NP suspensions are stable for long durations and do not show signs of aggregation or settling during storage or after autoclaving. The polyethylene oxide blocks in PF68 provide steric hindrance between adjacent NPs leading to stable NP dispersions. Further, PF68 is biocompatible in nature and does not affect integrity of mitochondria, lysosomes, DNA, and nuclei. Also, PF68 neither induce free radical or cytokine production nor does it interfere with cellular uptake mechanisms. The results of the present study suggest that PF68-assisted dispersion of NPs produced suspensions, which are stable after autoclaving. Further, PF68 does not interfere with normal physiological functions suggesting its application in nanomedicine and nanotoxicity evaluation

Surfactant-assisted dispersion of carbon nanotubes: mechanism of stabilization and biocompatibility of the surfactant

Energy Technology Data Exchange (ETDEWEB)

Singh, Raman Preet, E-mail: ramanpreetsingh@hotmail.com [Evalueserve SEZ (Gurgaon) Pvt. Ltd. (India); Jain, Sanyog [National Institute of Pharmaceutical Education and Research, Centre for Pharmaceutical Nanotechnology, Department of Pharmaceutics (India); Ramarao, Poduri, E-mail: ramaraop@yahoo.com [Central University of Punjab, School of Basic and Applied Sciences (India)

2013-10-15

Nanoparticles (NPs) are thermodynamically unstable system and tend to aggregate to reduce free energy. The aggregation property of NPs results in inhomogeneous exposure of cells to NPs resulting in variable cellular responses. Several types of surfactants are used to stabilize NP dispersions and obtain homogenous dispersions. However, the effects of these surfactants, per se, on cellular responses are not completely known. The present study investigated the application of Pluronic F68 (PF68) for obtaining stable dispersion of NPs using carbon nanotubes as model NPs. PF68-stabilized NP suspensions are stable for long durations and do not show signs of aggregation or settling during storage or after autoclaving. The polyethylene oxide blocks in PF68 provide steric hindrance between adjacent NPs leading to stable NP dispersions. Further, PF68 is biocompatible in nature and does not affect integrity of mitochondria, lysosomes, DNA, and nuclei. Also, PF68 neither induce free radical or cytokine production nor does it interfere with cellular uptake mechanisms. The results of the present study suggest that PF68-assisted dispersion of NPs produced suspensions, which are stable after autoclaving. Further, PF68 does not interfere with normal physiological functions suggesting its application in nanomedicine and nanotoxicity evaluation.

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).

Polysaccharides for stabilization of lipid particles; Polissacarideos na estabilizacao de particulas lipidicas

Energy Technology Data Exchange (ETDEWEB)

Lionzo, Maria I.Z.; Silveira, Nadya P. Da, E-mail: nadya@iq.ufrgs.br [Universidade Federal do Rio Grande do Sul - UFRGS, Campus do Vale, Porto Alegre, RS (Brazil); Muniz, Edvani Curti [Departamento de Quimica, Universidade Estadual de Maringa, PR (Brazil)

2011-07-01

The main goal of this paper was to investigate the impact of different amounts of polyelectrolytes on the size, surface charge and rigidity of the bilayers of multilamellar liposomes. For this purpose, composite liposomes were developed containing chitosan and chondroitin sulfate. The use of a second polyelectrolyte, chondroitin sulfate, for the coating of the liposomes was applied in order to modulate their surface charge, maintaining the stability given by the presence of chitosan. Light and X-rays small angle scattering were the main techniques applied. Zeta-potential values were used to determine the charge density and the amount of adsorbed polyelectrolytes on the liposomes. (author)

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.

Polyelectrolyte microcapsules for sustained delivery of water-soluble drugs

International Nuclear Information System (INIS)

Anandhakumar, S.; Debapriya, M.; Nagaraja, V.; Raichur, Ashok M.

2011-01-01

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 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.

Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory.

Science.gov (United States)

Shew, Chwen-Yang; Do, Changwoo; Hong, Kunlun; Liu, Yun; Porcar, Lionel; Smith, Gregory S; Chen, Wei-Ren

2012-07-14

We present small angle neutron scattering (SANS) measurements of deuterium oxide (D(2)O) solutions of linear and star sodium poly(styrene sulfonate) (NaPSS) as a function of polyelectrolyte concentration. Emphasis is on understanding the dependence of their SANS coherent scattering cross section I(Q) on the molecular architecture of single polyelectrolyte. The key finding is that for a given concentration, star polyelectrolytes exhibit more pronounced characteristic peaks in I(Q), and the position of the first peak occurs at a smaller Q compared to their linear counterparts. Based on a model of integral equation theory, we first compare the SANS experimental I(Q) of salt-free polyelectrolyte solutions with that predicted theoretically. Having seen their satisfactory qualitative agreement, the dependence of counterion association behavior on polyelectrolyte geometry and concentration is further explored. Our predictions reveal that the ionic environment of polyelectrolyte exhibits a strong dependence on polyelectrolyte geometry at lower polyelectrolyte concentration. However, when both linear and star polyelectrolytes exceed their overlap concentrations, the spatial distribution of counterion is found to be essentially insensitive to polyelectrolyte geometry due to the steric effect.

Does stability in local community composition depend on temporal variation in rates of dispersal and connectivity?

Science.gov (United States)

Valanko, Sebastian; Norkko, Joanna; Norkko, Alf

2015-04-01

In ecology understanding variation in connectivity is central for how biodiversity is maintained. Field studies on dispersal and temporal dynamics in community regulating processes are, however, rare. We test the short-term temporal stability in community composition in a soft-sediment benthic community by determining among-sampling interval similarity in community composition. We relate stability to in situ measures of connectivity (wind, wave, current energy) and rates of dispersal (quantified in different trap types). Waves were an important predictor of when local community taxa are most likely to disperse in different trap-types, suggesting that wave energy is important for connectivity in a region. Community composition at the site was variable and changed stochastically over time. We found changes in community composition (occurrence, abundance, dominance) to be greater at times when connectivity and rates of dispersal were low. In response to periods of lower connectedness dominant taxa in the local community only exhibited change in their relative abundance. In contrast, locally less abundant taxa varied in both their presence, as well as in relative abundance. Constancy in connectivity and rates of dispersal promotes community stability and persistence, suggesting that local community composition will be impacted by changes in the spatial extent over which immigration and emigration operates in the region. Few empirical studies have actually measured dispersal directly in a multi-species context to demonstrate the role it plays in maintaining local community structure. Even though our study does not evaluate coexistence over demographic time scales, it importantly demonstrates that dispersal is not only important in initial recruitment or following a disturbance, but also key in maintaining local community composition.

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

Science.gov (United States)

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

2018-06-01

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

Localized in situ polymerization on graphene surfaces for stabilized graphene dispersions.

Science.gov (United States)

Das, Sriya; Wajid, Ahmed S; Shelburne, John L; Liao, Yen-Chih; Green, Micah J

2011-06-01

We demonstrate a novel in situ polymerization technique to develop localized polymer coatings on the surface of dispersed pristine graphene sheets. Graphene sheets show great promise as strong, conductive fillers in polymer nanocomposites; however, difficulties in dispersion quality and interfacial strength between filler and matrix have been a persistent problem for graphene-based nanocomposites, particularly for pristine graphene. With this in mind, a physisorbed polymer layer is used to stabilize graphene sheets in solution. To create this protective layer, we formed an organic microenvironment around dispersed graphene sheets in surfactant solutions, and created a nylon 6, 10 or nylon 6, 6 coating via interfacial polymerization. Technique lies at the intersection of emulsion and admicellar polymerization; a similar technique was originally developed to protect luminescent properties of carbon nanotubes in solution. These coated graphene dispersions are aggregation-resistant and may be reversibly redispersed in water even after freeze-drying. The coated graphene holds promise for a number of applications, including multifunctional graphene-polymer nanocomposites. © 2011 American Chemical Society

Stability of nano-metric colloidal dispersions of titanium: effect of surface complexation

International Nuclear Information System (INIS)

Peyre, Veronique

1996-01-01

This research thesis reports the study of the adsorption of small organic molecules at the surface of nano-particles of mineral oxides (zirconia), and of its effects on the stability of the colloidal dispersion. Adsorption has been quantified by adsorption isotherms and surface titrations. Processes and mechanisms are thus discussed with respect to pH. The influence of various protecting molecules (acetyl acetone, but also acetic acid, citric acid and diethanolamine) has been studied, and notably highlighted the role of the outer face of the complexing agent in the assessment of reactions between particles which govern the compression and re-dispersability properties of protected dispersions. This study is performed by osmotic pressure measurements and by X-ray diffusion at small angles, completed by statistical mechanics calculations [fr

Physical stability of API/polymer-blend amorphous solid dispersions.

Science.gov (United States)

Lehmkemper, Kristin; Kyeremateng, Samuel O; Bartels, Mareike; Degenhardt, Matthias; Sadowski, Gabriele

2018-03-01

The preparation of amorphous solid dispersions (ASDs) is a well-established strategy for formulating active pharmaceutical ingredients by embedding them in excipients, usually amorphous polymers. Different polymers can be combined for designing ASDs with desired properties like an optimized dissolution behavior. One important criterion for the development of ASD compositions is the physical stability. In this work, the physical stability of API/polymer-blend ASDs was investigated by thermodynamic modeling and stability studies. Amorphous naproxen (NAP) and acetaminophen (APAP) were embedded in blends of hydroxypropyl methylcellulose acetate succinate (HPMCAS) and either poly(vinylpyrrolidone) (PVP) or poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA64). Parameters for modeling the API solubility in the blends and the glass-transition temperature curves of the water-free systems with Perturbed-Chain Statistical Associating Fluid Theory and Kwei equation, respectively, were correlated to experimental data. The phase behavior for standardized storage conditions (0%, 60% and 75% relative humidity (RH)) was predicted and compared to six months-long stability studies. According to modeling and experimental results, the physical stability was reduced with increasing HPMCAS content and increasing RH. This trend was observed for all investigated systems, with both APIs (NAP and APAP) and both polymer blends (PVP/HPMCAS and PVPVA64/HPMCAS). PC-SAFT and the Kwei equation turned out to be suitable tools for modeling and predicting the physical stability of the investigated API/polymer-blends ASDs. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-Assembled Polyelectrolyte Nanoparticles as Fluorophore-Free Contrast Agents for Multicolor Optical Imaging

Directory of Open Access Journals (Sweden)

Da Hye Shin

2015-03-01

Full Text Available In this work, we describe the fabrication of self-assembled polyelectrolyte nanoparticles that provide a multicolor optical imaging modality. Poly(γ-glutamic acid(γ-PGA formed self-assembled nanoparticles through electrostatic interactions with two different cationic polymers: poly(L-lysine(PLL and chitosan. The self-assembled γ-PGA/PLL and γ-PGA/chitosan nanoparticles were crosslinked by glutaraldehyde. Crosslinking of the ionic self-assembled nanoparticles with glutaraldehyde not only stabilized the nanoparticles but also generated a strong autofluorescence signal. Fluorescent Schiff base bonds (C=N and double bonds (C=C were generated simultaneously by crosslinking of the amine moiety of the cationic polyelectrolytes with monomeric glutaraldehyde or with polymeric glutaraldehyde. The unique optical properties of the nanoparticles that resulted from the crosslinking by glutaraldehyde were analyzed using UV/Vis and fluorescence spectroscopy. We observed that the fluorescence intensity of the nanoparticles could be regulated by adjusting the crosslinker concentration and the reaction time. The nanoparticles also exhibited high performance in the labeling and monitoring of therapeutic immune cells (macrophages and dendritic cells. These self-assembled nanoparticles are expected to be a promising multicolor optical imaging contrast agent for the labeling, detection, and monitoring of cells.

ENCAPSULATION OF ANTITUBERCULAR DRUGS BY BIOPOLYMERS AND POLYELECTROLYTE MULTILAYERS

Directory of Open Access Journals (Sweden)

B. H. Mussabayeva

2017-01-01

Full Text Available The problem of drug-resistant tuberculosis treatment is complex and urgent: the standardof treatment includes the oral administration of six names of antibiotics, i.e. up totwenty tablets a day by the patient. This causes severe side effects, including those appeareddue to the formation of toxic products of drug interactions in the body. Therefore, itis important that some drugs dissolve in a stomach, and others – in the intestine, which willlead to increased bioavailability, reduced dosage and toxicity. The development of targeteddelivery systems for drugs with controlled release, targeted delivery and minimization ofside effects are of interest. One of the promising methods is polyelectrolytic multilayersand the technology of creating such layers by a step-by-step adsorption of heterogeneouslycharged polyelectrolytes.The aim of this article is the microencapsulation of anti-tuberculousdrugs into biopolymers coated with polyelectrolytic multilayers, and the solubilitystudy of microcapsules at pH values simulating various parts of the gastrointestinal tract.Materials and methods. Drugs as isoniazide, pyrazinamide, moxifloxacin, and biopolymers:gellan, pectin and sodium alginate, chitosan and dextran sulfate, as well as EudragitS are used to prepare microcapsules. The obtained microcapsules are studied by a methodof scanning electron microscopy. Quantitative determination of the effectiveness of the inclusionof drugs in microcapsules was carried out using pharmacopoeial methods.Results and discussion. The inclusion efficiency rises with an increase of biopolymer concentration. The inclusion efficiency increases in the row isoniazide polyelectrolytic multilayers is shown.At pH = 7.4, the degree of release of the drugs from microcapsules without applied multilayersfor 12 hours was

Dispersing and stabilizing effect of nonaqueous media with different acid-base functions when preparing process suspensions

International Nuclear Information System (INIS)

Koshevar, V.D.; Rat'ko, A.I.; Mironenko, I.N.

1999-01-01

Dispersing and stabilizing effect of organic liquids related to the Lewis acids and baser is studied when preparing the suspensions of certain minerals and metal oxides, beryllium oxide, in particular. Practical recommendations are provided for the choice of dispersing media to produce stable suspensions

Passivation of Titanium Oxide in Polyethylene Matrices using Polyelectrolytes as Titanium Dioxide Surface Coating

Directory of Open Access Journals (Sweden)

Javier Vallejo-Montesinos

2017-05-01

Full Text Available One of the major challenges of the polyolefins nowadays is the ability of those to resist weathering conditions, specially the photodegradation process that suffer any polyolefin. A common way to prevent this, is the use of hindered amine light stabilizers (HALS are employed. An alternative route to avoid photodegradation is using polyelectrolites as coating of fillers such as metal oxides. Composites of polyethylene were made using titanium dioxide (TiO2 as a filler with polyelectrolytes (polyethylenimine and sodium polystyrene sulfonate attached to its surface, to passivate its photocatalytic activity. We exposed the samples to ultraviolet-visible (UV-Vis light to observe the effect of radiation on the degradation of coated samples, compared to those without the polyelectrolyte coating. From the experimental results, we found that polyethylenimine has a similar carbonyl signal area to the sample coated with hindered amine light stabilizers (HALS while sodium polystyrene sulfonate exhibit more degradation than the HALS coated samples, but it passivates the photocatalytic effect when compared with the non-coated TiO2 samples. Also, using AFM measurements, we confirmed that the chemical nature of polyethylenimine causes the TiO2 avoid the migration to the surface during the extrusion process, inhibiting the photodegradation process and softening the sample. On this basis, we found that polyethylenimine is a good choice for reducing the degradation caused by TiO2 when it is exposed to UV-Vis light.

Polyelectrolyte determination in drinking water

African Journals Online (AJOL)

try as there are no readily available methods for the determination of residual polyelectrolyte concentration. This study aims at ... quate, making the need to quantify them more critical (Fielding,. 1999). ... decisions and actions are sometimes required in the environ- ... were conducted on both distilled and real water systems.

Polyelectrolytes-promoted Forward Osmosis Processes

KAUST Repository

Ge, Q.C.; Ling, M.M.; Amy, Gary L.; Chung, T.S.

2012-01-01

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 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.

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.

Influence of solvent composition on the miscibility and physical stability of naproxen/PVP K 25 solid dispersions prepared by cosolvent spray-drying.

Science.gov (United States)

Paudel, Amrit; Van den Mooter, Guy

2012-01-01

To investigate the influence of solvent properties on the phase behavior and physical stability of spray-dried solid dispersions containing naproxen and PVP K 25 prepared from binary cosolvent systems containing methanol, acetone and dichloromethane. The viscosity, polymer globular size and evaporation rate of the spray-drying feed solutions were characterized. The solid dispersions were prepared by spray-drying drug-polymer solutions in binary solvent blends containing different proportions of each solvent. The phase behavior was investigated with mDSC, pXRD, FT-IR and TGA. Further, physical stability of solid dispersions was assessed by analyzing after storage at 75% RH. The solid dispersions prepared from solvent/anti-solvent mixture showed better miscibility and physical stability over those prepared from the mixtures of good solvents. Thus, solid dispersions prepared from dichloromethane-acetone exhibited the best physicochemical attributes followed by those prepared from methanol-acetone. FT-IR analysis revealed differential drug-polymer interaction in solid dispersions prepared from various solvent blends, upon the exposure to elevated humidity. Spray-drying from a cocktail of good solvent and anti-solvent with narrower volatility difference produces solid dispersions with better miscibility and physical stability resulting from the simultaneous effect on the polymer conformation and better dispersivity of drug.

Tailored adhesion behavior of polyelectrolyte thin films deposited on plasma-treated poly(dimethylsiloxane) for functionalized membranes

Energy Technology Data Exchange (ETDEWEB)

Bassil, Joelle, E-mail: joelle.bassil@univ-lorraine.fr [Institut Jean Lamour (IJL), UMR CNRS 7198, Université de Lorraine, Parc de Saurupt CS50840, 54011 Nancy (France); Alem, Halima, E-mail: halima.alem@univ-lorraine.fr [Institut Jean Lamour (IJL), UMR CNRS 7198, Université de Lorraine, Parc de Saurupt CS50840, 54011 Nancy (France); Henrion, Gérard, E-mail: gerard.henrion@univ-lorraine.fr [Institut Jean Lamour (IJL), UMR CNRS 7198, Université de Lorraine, Parc de Saurupt CS50840, 54011 Nancy (France); Roizard, Denis, E-mail: denis.roizard@univ-lorraine.fr [Laboratoire Réactions et Génie des Procédés (LRGP), UMR CNRS 7274, ENSIC, Université de Lorraine, 1 rue Grandville, 54011 Nancy (France)

2016-04-30

Graphical abstract: - Highlights: • The surface of PDMS membrane was first modified by Ar/O{sub 2} plasma to increase its surface energy. • Subsequently, a homogeneous multilayer of the well-known couple of polyelectrolyte PDADMAC/PSS was deposited on the plasma treated PDMS. • The relation between the parameters of the modification processes and the morphology, wettability, structure and adhesion of the polyelectrolytes layers based PDMS membranes is investigated and enlightened. - Abstract: Completely homogenous films formed via the layer-by-layer assembly of poly(diallyldimethylammonium chloride) (PDADMAC) and the poly(styrene sulfonate) were successfully obtained on plasma-treated poly(dimethylsiloxane) (PDMS) substrates. To modify the hydrophobicity of the PDMS surface, a cold plasma treatment was previously applied to the membrane, which led to the creation of hydrophilic groups on the surface of the membrane. PDMS wettability and surface morphology were successfully correlated with the plasma parameters. A combination of contact angle measurements, scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis was used to demonstrate that homogeneous and hydrophilic surfaces could be achieved on PDMS cold-plasma-treated membranes. The stability of the assembled PEL layer on the PDMS was evaluated using a combination of pull-off testing and X-ray photoelectron spectroscopy (XPS), which confirmed the relevance of a plasma pre-treatment as the adhesion of the polyelectrolyte multilayers was greatly enhanced when the deposition was completed on an activated PDMS surface at 80 W for 5 min.

Salt-induced aggregation of stiff polyelectrolytes

International Nuclear Information System (INIS)

Fazli, Hossein; Mohammadinejad, Sarah; Golestanian, Ramin

2009-01-01

Molecular dynamics simulation techniques are used to study the process of aggregation of highly charged stiff polyelectrolytes due to the presence of multivalent salt. The dominant kinetic mode of aggregation is found to be the case of one end of one polyelectrolyte meeting others at right angles, and the kinetic pathway to bundle formation is found to be similar to that of flocculation dynamics of colloids as described by Smoluchowski. The aggregation process is found to favor the formation of finite bundles of 10-11 filaments at long times. Comparing the distribution of the cluster sizes with the Smoluchowski formula suggests that the energy barrier for the aggregation process is negligible. Also, the formation of long-lived metastable structures with similarities to the raft-like structures of actin filaments is observed within a range of salt concentration.

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

Science.gov (United States)

Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

2017-08-22

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

The annual averaged atmospheric dispersion factor and deposition factor according to methods of atmospheric stability classification

Energy Technology Data Exchange (ETDEWEB)

Jeong, Hae Sun; Jeong, Hyo Joon; Kim, Eun Han; Han, Moon Hee; Hwang, Won Tae [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2016-09-15

This study analyzes the differences in the annual averaged atmospheric dispersion factor and ground deposition factor produced using two classification methods of atmospheric stability, which are based on a vertical temperature difference and the standard deviation of horizontal wind direction fluctuation. Daedeok and Wolsong nuclear sites were chosen for an assessment, and the meteorological data at 10 m were applied to the evaluation of atmospheric stability. The XOQDOQ software program was used to calculate atmospheric dispersion factors and ground deposition factors. The calculated distances were chosen at 400 m, 800 m, 1,200 m, 1,600 m, 2,400 m, and 3,200 m away from the radioactive material release points. All of the atmospheric dispersion factors generated using the atmospheric stability based on the vertical temperature difference were shown to be higher than those from the standard deviation of horizontal wind direction fluctuation. On the other hand, the ground deposition factors were shown to be same regardless of the classification method, as they were based on the graph obtained from empirical data presented in the Nuclear Regulatory Commission's Regulatory Guide 1.111, which is unrelated to the atmospheric stability for the ground level release. These results are based on the meteorological data collected over the course of one year at the specified sites; however, the classification method of atmospheric stability using the vertical temperature difference is expected to be more conservative.

Limiting law excess sum rule for polyelectrolytes.

Science.gov (United States)

Landy, Jonathan; Lee, YongJin; Jho, YongSeok

2013-11-01

We revisit the mean-field limiting law screening excess sum rule that holds for rodlike polyelectrolytes. We present an efficient derivation of this law that clarifies its region of applicability: The law holds in the limit of small polymer radius, measured relative to the Debye screening length. From the limiting law, we determine the individual ion excess values for single-salt electrolytes. We also consider the mean-field excess sum away from the limiting region, and we relate this quantity to the osmotic pressure of a dilute polyelectrolyte solution. Finally, we consider numerical simulations of many-body polymer-electrolyte solutions. We conclude that the limiting law often accurately describes the screening of physical charged polymers of interest, such as extended DNA.

Charge correlation effects on ionization of weak polyelectrolytes

International Nuclear Information System (INIS)

Panagiotopoulos, A Z

2009-01-01

Ionization curves of weak polyelectrolytes were obtained as a function of the charge coupling strength from Monte Carlo simulations. In contrast to many earlier studies, the present work treats counterions explicitly, thus allowing the investigation of charge correlation effects at strong couplings. For conditions representing typical weak polyelectrolytes in water near room temperature, ionization is suppressed because of interactions between nearby dissociated groups, as also seen in prior work. A novel finding here is that, for stronger couplings, relevant for non-aqueous environments in the absence of added salt, the opposite behavior is observed-ionization is enhanced relative to the behavior of the isolated groups due to ion-counterion correlation effects. The fraction of dissociated groups as a function of position along the chain also behaves non-monotonically. Dissociation is highest near the ends of the chains for aqueous polyelectrolytes and highest at the chain middle segments for non-aqueous environments. At intermediate coupling strengths, dissociable groups appear to behave in a nearly ideal fashion, even though chain dimensions still show strong expansion effects due to ionization. These findings provide physical insights on the impact of competition between acid/base chemical equilibrium and electrostatic attractions in ionizable systems.

Modification of Bacterial Cellulose Biofilms with Xylan Polyelectrolytes.

Science.gov (United States)

Santos, Sara M; Carbajo, José M; Gómez, Nuria; Ladero, Miguel; Villar, Juan C

2017-11-28

The effect of the addition of two [4-butyltrimethylammonium]-xylan chloride polyelectrolytes (BTMAXs) on bacterial cellulose (BC) was evaluated. The first strategy was to add the polyelectrolytes to the culture medium together with a cell suspension of the bacterium. After one week of cultivation, the films were collected and purified. The second approach consisted of obtaining a purified and homogenized BC, to which the polyelectrolytes were added subsequently. The films were characterized in terms of tear and burst indexes, optical properties, surface free energy, static contact angle, Gurley porosity, SEM, X-ray diffraction and AFM. Although there are small differences in mechanical and optical properties between the nanocomposites and control films, the films obtained by BC synthesis in the presence of BTMAXs were remarkably less opaque, rougher, and had a much lower specular gloss. The surface free energy depends on the BTMAXs addition method. The crystallinity of the composites is lower than that of the control material, with a higher reduction of this parameter in the composites obtained by adding the BTMAXs to the culture medium. In view of these results, it can be concluded that BC-BTMAX composites are a promising new material, for example, for paper restoration.

Evaluation and enhancement of physical stability of semi-solid dispersions containing piroxicam into hard gelatin capsules.

Science.gov (United States)

Karataş, Ayşegül; Bekmezci, Serife

2013-01-01

The aim of the study was to investigate the physical stability of the semi-solid dispersions into the hard gelatine capsules prepared with Gelucire 44/14, Labrasol and different additives such as microcrystalline cellulose (MCC), mannitol and lactose (alpha-monohydrate) used for enhancing the stability of the formulations. The master dispersion prepared with only Gelucire 44/14 (20% w/w) and Labrasol (80% w/w) was stored in a refrigerator (5 +/- 3 degrees C), while the modified dispersions with the additives (2% w/w) were kept in a climatic chamber (25 +/- 2 degrees C / 60 +/- 5% RH) for 12 months. Dissolution tests of the semi-solid dispersions were performed in media with different pH's immediatly after preparation and after 3, 6 and 12 months of storage. FTIR and DSC studies were also carried out at the same time points. The ideal storage condition for the master dispersion was found to be at 5 degrees C. The addition of MCC, mannitol and lactose (alpha-monohydrate) to the original dispersion afforded a solidification effect on the formulation at room temperature and showed the same dissolution behavior (not less than 85% of piroxicam within 30 min in pH 1.2, 4.5 and 6.8; and water) with the master. The dispersion including lactose was stable at 25 degrees C for 12 months. However, the ideal period of storage for the modified dispersions including MCC and mannitol was 6 months at 25 degrees C. FTIR and DSC results both confirmed the amorphous state of piroxicam in all semi-solid dispersions under storage conditions for 12 months.

Influence of network topology on the swelling of polyelectrolyte nanogels

OpenAIRE

Rizzi, Leandro G.; Levin, Yan

2016-01-01

It is well-known that the swelling behavior of ionic nanogels depends on their cross-link density, however it is unclear how different topologies should affect the response of the polyelectrolyte network. Here we perform Monte Carlo simulations to obtain the equilibrium properties of ionic nanogels as a function of salt concentration $C_s$ and the fraction $f$ of ionizable groups in a polyelectrolyte network formed by cross-links of functionality $z$. Our results indicate that the network wit...

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

Energy Technology Data Exchange (ETDEWEB)

Liu, Jiang; Wu, Wen-Jie; Fang, Fang [Fudan University, Department of Chemistry (China); Zorin, Nikolay A. [Russian Academy of Sciences, Institute of Basic Biological Problems (Russian Federation); Chen, Meng; Qian, Dong-Jin, E-mail: djqian@fudan.edu.cn [Fudan University, Department of Chemistry (China)

2016-08-15

Immobilization of active enzymes on the surfaces of electrodes and nanomaterials is important in the fields of bioscience, and biotechnology. In this study, we investigated electrocatalytic properties of the interconversion of protons and hydrogen by means of hydrogenase (H{sub 2}ase)-functionalized carbon nanotube polyelectrolyte composites. Multiwalled carbon nanotube polyelectrolytes (MWNT-PEs) were synthesized through a diazonium and an addition reaction with poly(4-vinylpyridine) (P4VP), followed by another addition reaction with either methyl iodide (CH{sub 3}I) or N-methyl-N′-benzyl bromide bipyridinium (VBenBr) to produce MWNT-P4VPMe or MWNT-P4VPBenV polyelectrolytes, respectively. The MWNT-PE@H{sub 2}ase bio-nanocomposites were then prepared by means of MWNT-PEs as substrates to bind with H{sub 2}ase. The redox current density of the MWNT-PE@H{sub 2}ase-modified electrodes increased with a decrease in pH values of the Ar-saturated electrolyte solution owing to the catalytic reduction of protons (H{sub 2} production); further, it increased with the increasing pH values of the H{sub 2}-saturated solution owing to the catalytic oxidation of hydrogen. The reversible color change between blue-colored and colorless viologen (catalyzed by the MWNT-PE@H{sub 2}ase bio-nanocomposites) suggested that they may be developed as nano-biosensors for molecular H{sub 2}. The as-synthesized bio-nanocomposites showed strong long-term stability and high bioactivity.Graphical Abstract.

Effect of sodium dodecylbenzene sulfonate on the dispersion stability of ceramic glaze suspension

Energy Technology Data Exchange (ETDEWEB)

Satchawan, Suphapan; Naksata, Wimol; Rattanakawin, Chairoj; Thiansem, Sakdiphon; Arqueropanyo, Orn-anong [Chiang Mai University, Chiang Mai (Thailand); Panya, Preecha [Kamphaengphet Rajabhat University, Kamphaengphet (Thailand); Sooksamiti, Ponlayuth [The Office of Primary Industries and Mines Region 3, Chiang Mai (Thailand); Scales, Peter J. [The University of Melbourne, Parkville Victoria (Australia)

2014-06-15

Sodium dodecylbenzene sulfonate (SDBS) was used to render the stability of ceramic glaze dispersion which is composed of limestone, feldspar, quartz, kaolin and ferric oxide. The measured zeta potential showed negative values for the systems in deionized water and 0.001 M MgCl{sub 2} media at pH above 2, but a positive value was observed in 0.1M MgCl{sub 2} at pH higher than 6.7. Adsorption of SDBS in aqueous suspensions of ceramic glaze in deionized water and in 0.001 M MgCl{sub 2}, within the concentration range studied, followed both the Langmuir and Freundlich isotherms, but the Freundlich isotherm was more favored. Adsorption of SDBS in 0.1M MgCl{sub 2} corresponded to the Freundlich isotherm. From dispersion stability investigation, SDBS could render the suspension in deionized water and in 0.001 mM MgCl{sub 2} more than in 0.1 mM MgCl{sub 2}.

Effect of sodium dodecylbenzene sulfonate on the dispersion stability of ceramic glaze suspension

International Nuclear Information System (INIS)

Satchawan, Suphapan; Naksata, Wimol; Rattanakawin, Chairoj; Thiansem, Sakdiphon; Arqueropanyo, Orn-anong; Panya, Preecha; Sooksamiti, Ponlayuth; Scales, Peter J.

2014-01-01

Sodium dodecylbenzene sulfonate (SDBS) was used to render the stability of ceramic glaze dispersion which is composed of limestone, feldspar, quartz, kaolin and ferric oxide. The measured zeta potential showed negative values for the systems in deionized water and 0.001 M MgCl 2 media at pH above 2, but a positive value was observed in 0.1M MgCl 2 at pH higher than 6.7. Adsorption of SDBS in aqueous suspensions of ceramic glaze in deionized water and in 0.001 M MgCl 2 , within the concentration range studied, followed both the Langmuir and Freundlich isotherms, but the Freundlich isotherm was more favored. Adsorption of SDBS in 0.1M MgCl 2 corresponded to the Freundlich isotherm. From dispersion stability investigation, SDBS could render the suspension in deionized water and in 0.001 mM MgCl 2 more than in 0.1 mM MgCl 2

A Study On Dispersion Stability Of Nickel Nanoparticles Synthesized By Wire Explosion In Liquid Media

Directory of Open Access Journals (Sweden)

Kim C.K.

2015-06-01

Full Text Available In this study, nickel nanoparticles were synthesized in ethanol using portable pulsed wire evaporation, which is a one-step physical method. From transmission electron microscopy images, it was found that the Ni nanoparticles exhibited a spherical shape with an average diameter of 7.3 nm. To prevent aggregation of the nickel nanoparticles, a polymer surfactant was added into the ethanol before the synthesis of nickel nanoparticles, and adsorbed on the freshly synthesized nickel nanoparticles during the wire explosion. The dispersion stability of the prepared nickel nanofluids was investigated by zeta-potential analyzer and Turbiscan optical analyzer. As a result, the optimum concentration of polymer surfactant to be added was suggested for the maximized dispersion stability of the nickel nanofluids.

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.

Synthesis and characterization of polypyrrole doped with anionic spherical polyelectrolyte brushes

Directory of Open Access Journals (Sweden)

N. Su

2012-09-01

Full Text Available The procedures for the synthesis of polypyrrole (PPy doped with anionic spherical polyelectrolyte brushes (ASPB (PPy/ASPB nanocomposite by means of in situ chemical oxidative polymerization were presented. Fourier transform infrared spectroscopy (FTIR and Raman spectroscopic analysis suggested the bonding structure of PPy/ASPB nanocomposite. Scanning electron microscopy (SEM was used to confirm the morphologies of samples. The crystallographic structure, chemical nature and thermal stability of conducting polymers were analyzed by X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS and Thermo-gravimetric analysis (TGA respectively. Investigation of the electrical conductivity at room temperature showed that the electrical conductivity of PPy/ASPB nanocomposite was 20 S/cm, which was higher than that of PPy (3.6 S/cm.

Phase stability of oxide dispersion-strengthened ferritic steels in neutron irradiation

International Nuclear Information System (INIS)

Yamashita, S.; Oka, K.; Ohnuki, S.; Akasaka, N.; Ukai, S.

2002-01-01

Oxide dispersion-strengthened ferritic steels were irradiated by neutrons up to 21 dpa and studied by microstructural observation and microchemical analysis. The original high dislocation density did not change after neutron irradiation, indicating that the dispersed oxide particles have high stability under neutron irradiation. However, there is potential for recoil resolution of the oxide particles due to ballistic ejection at high dose. From the microchemical analysis, it was implied that some of the complex oxides have a double-layer structure, such that TiO 2 occupied the core region and Y 2 O 3 the outer layer. Such a structure may be more stable than the simple mono-oxides. Under high-temperature irradiation, Laves phase was the predominant precipitate occurring at grain boundaries α phase and χ phase were not observed in this study

Coarse-Grained Modeling of Polyelectrolyte Solutions

Science.gov (United States)

Denton, Alan R.; May, Sylvio

2014-03-01

Ionic mixtures, such as electrolyte and polyelectrolyte solutions, have attracted much attention recently for their rich and challenging combination of electrostatic and non-electrostatic interparticle forces and their practical importance, from battery technologies to biological systems. Hydration of ions in aqueous solutions is known to entail ion-specific effects, including variable solubility of organic molecules, as manifested in the classic Hofmeister series for salting-in and salting-out of proteins. The physical mechanism by which the solvent (water) mediates effective interactions between ions, however, is still poorly understood. Starting from a microscopic model of a polyelectrolyte solution, we apply a perturbation theory to derive a coarse-grained model of ions interacting through both long-range electrostatic and short-range solvent-induced pair potentials. Taking these effective interactions as input to molecular dynamics simulations, we calculate structural and thermodynamic properties of aqueous ionic solutions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Aggregation of flexible polyelectrolytes: Phase diagram and dynamics.

Science.gov (United States)

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

2017-10-14

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

Modification of Bacterial Cellulose Biofilms with Xylan Polyelectrolytes

Directory of Open Access Journals (Sweden)

Sara M. Santos

2017-11-01

Full Text Available The effect of the addition of two [4-butyltrimethylammonium]-xylan chloride polyelectrolytes (BTMAXs on bacterial cellulose (BC was evaluated. The first strategy was to add the polyelectrolytes to the culture medium together with a cell suspension of the bacterium. After one week of cultivation, the films were collected and purified. The second approach consisted of obtaining a purified and homogenized BC, to which the polyelectrolytes were added subsequently. The films were characterized in terms of tear and burst indexes, optical properties, surface free energy, static contact angle, Gurley porosity, SEM, X-ray diffraction and AFM. Although there are small differences in mechanical and optical properties between the nanocomposites and control films, the films obtained by BC synthesis in the presence of BTMAXs were remarkably less opaque, rougher, and had a much lower specular gloss. The surface free energy depends on the BTMAXs addition method. The crystallinity of the composites is lower than that of the control material, with a higher reduction of this parameter in the composites obtained by adding the BTMAXs to the culture medium. In view of these results, it can be concluded that BC–BTMAX composites are a promising new material, for example, for paper restoration.

Structure of ordered polyelectrolyte films from atomic-force microscopy and X-ray reflectivity data

International Nuclear Information System (INIS)

Belyaev, V.V.; Tolstikhina, A.L.; Stepina, N.D.; Kayushina, R.L.

1998-01-01

The possible application of atomic-force microscopy and X-ray reflectometry methods to structural studies of polyelectrolyte films obtained due to alternating adsorption of oppositely charged polyanion [sodium polysterenesulfonate (PSS)] and polycation [poly(allylamine) hydrochloride (PAA)] layers on solid substrates has been considered. The atomic-force microscopy study has revealed the characteristic features of the surface topography of samples consisting of different numbers of polyelectrolyte layers deposited from solutions characterized by different ionic strength values. It is shown that the shape of the reflectivity curves obtained from thin polyelectrolyte films depends on their surface structure

Surface analysis monitoring of polyelectrolyte deposition on Ba0.5Sr0.5TiO3 thin films

International Nuclear Information System (INIS)

Morales-Cruz, Angel L.; Fachini, Estevao R.; Miranda, Felix A.; Cabrera, Carlos R.

2007-01-01

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

Preparation of silver colloid and enhancement of dispersion stability in organic solvent

International Nuclear Information System (INIS)

Kim, Ki Young; Choi, Young Tai; Seo, Dae Jong; Park, Seung Bin

2004-01-01

Silver colloid of nanometer size was prepared in liquid phase by a reduction method. AgNO 3 , FeSO 4 .7H 2 O, and Na 3 C 6 H 5 O 7 .2H 2 O were used as silver precursor, reducing agent and dispersing agent, respectively. As precursor concentration was decreased or the concentration of dispersing agent was increased, the prepared particle size was decreased from 180 nm to 20 nm. Apparently, the particle size seemed to be decreased with the increase of stirring rate, but it was confirmed by TEM that the size of primary particle remained the same. This result indicates that the uniformity of precursor concentration in the reactor affects the particle size and the stirring rate should be kept higher than the critical value to prevent the agglomeration of particles. In order to make the dispersion stability of the prepared silver colloid maintained even in non-polar organic solvent, electrodialysis technique was applied. As ionic species in colloidal solution were removed by electrodialysis, the dispersability of the colloid in the organic solvent of long carbon chain was confirmed to be increased

Multiscale patterning of nanocomposite polyelectrolyte/nanoparticle films using inkjet printing and AFM scratching

International Nuclear Information System (INIS)

Leigh, S J; Bowen, J; Preece, J A

2015-01-01

The fabrication of structured polymer/nanoparticle composite films through a combination of additive, subtractive and self-assembly methodologies is investigated. Consumer grade inkjet printing hardware is employed to deposit cationic polyelectrolytes on (i) hydrophilic and (ii) hydrophobised glass substrates. The hydrophobisation process controls the spreading of the droplets and hence the lateral size of printed features. The printed cationic polyelectrolyte regions are used as a template to direct the self-assembly of negatively charged gold nanoparticles onto the surface. Micro-scale features are created in the polyelectrolyte/nanoparticle films using AFM scratching to selectively displace material. The effect of substrate wettability on film morphology is discussed. (paper)

Effects of various surfactants on the dispersion stability and electrical conductivity of surface modified graphene

Energy Technology Data Exchange (ETDEWEB)

Uddin, Md. Elias [WCU Program, Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Kuila, Tapas [Surface Engineering and Tribology, CSIR – Central Mechanical Engineering Research Institute, Durgapur 721 302 (India); Nayak, Ganesh Chandra [Department of Applied Chemistry, ISM Dhanbad, Dhanbad 826 004, Jharkhand (India); Kim, Nam Hoon [Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Ku, Bon-Cheol [Institute of Advanced Composite Materials, Korea Institute of Science and Technology, Dunsan-ri, Bongdong-eup, Wanju-gun, Jeollabuk-do 864-9 (Korea, Republic of); Lee, Joong Hee, E-mail: jhl@chonbuk.ac.kr [WCU Program, Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of)

2013-06-15

Highlights: ► Water dispersible graphene has been prepared using ionic and non-ionic surfactants. ► XPS and FTIR spectra analysis confirm surface modification and reduction of GO. ► The highest water dispersibility is observed in the graphene modified with of SDBS. ► The best properties of modified graphene is achieved with GO/surfactant ratio of two. -- Abstract: Ionic and non-ionic surfactant functionalized, water dispersible graphene were prepared to investigate the effects on the dispersion stability and electrical conductivity of graphene. In this study, sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfate and 4-(1,1,3,3-tetramethylbutyl) phenyl-polyethylene glycol (Triton X-100) were used as ionic and non-ionic surfactants. The effects of surfactant concentrations on the dispersibility and electrical conductivity of the surface modified graphene were investigated. The dispersion stability of SDBS functionalized graphene (SDBS-G) was found to be best in water at 1.5 mg ml{sup −1}. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analysis indicate that the presence of surfactants does not prevent the reduction of graphene oxide (GO). These measurements also demonstrated that the surfactants were present on the surface of graphene, resulting in the formation of functionalized graphene. The thickness of different functionalized graphene was measured by Atomic force microscopy and varied significantly with different surfactants. The thermal properties of the functionalized graphene were also found to be dependent on the nature of the surfactants. The electrical conductivity of SDBS-G (108 S m{sup −1}) was comparatively higher than SDS and Triton X-100 functionalized graphene.

Investigation of polyelectrolytes by total reflection x-ray fluorescence spectrometry

International Nuclear Information System (INIS)

Varga, I.; Nagy, M.

2000-01-01

Water soluble polyelectrolyte samples containing mono-, bi- and trivalent metal ions were investigated without any pretreatment. Acid digestion of linear polymers may lead to a product insoluble in water so the digestion has to be avoided. The aim of this paper was the determination of analytical characteristics and limitations of the total reflection x-ray fluorescence (TXRF) analysis for poly (vinylalcohol-vinylsulphate) salts and poly (acrylic acid, acrylamide) copolymers containing the following cations: K + , Cs + , Ba 2+ , Cu 2+ and La 3+ . On the basis of our results efficiency of ion-exchange during preparation of polyelectrolytes and stoichiometry of the end-product were determined. TXRF results were compared with data gained by inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements except in the case of Cs + which has poor sensitivity in ICP-AES. Good agreement was found between the results of the two techniques and calculations from titrimetric data. Concentration of Li + and Mg 2+ in polymer samples was measured by ICP-AES. In majority of cases film-like dry residues of aqueous solutions of polyelectrolytes can be characterized by homogeneous spatial distribution of metal ions within the organic matrix. This is because the migration of the ions is hindered during drying process. Determination of metals in polyelectrolyte films by TXRF is quite ideal as model for analysis of plant, animal or human tissues which is a frequent task in environmental and inorganic biomedical analytical chemistry. (author)

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

Biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres for controlled drug release.

Science.gov (United States)

Du, Pengcheng; Zeng, Jin; Mu, Bin; Liu, Peng

2013-05-06

Well-defined biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres have been accomplished via the layer-by-layer (LbL) self-assembly technique. The hybrid shell was fabricated by the electrostatic interaction between the polyelectrolyte cation, chitosan (CS), and the hybrid anion, citrate modified ferroferric oxide nanoparticles (Fe3O4-CA), onto the uniform polystyrene sulfonate microsphere templates. Then the magnetic hybrid core/shell composite particles were modified with a linear, functional poly(ethylene glycol) (PEG) monoterminated with a biotargeting molecule (folic acid (FA)). Afterward the dual targeting hybrid hollow microspheres were obtained after etching the templates by dialysis. The dual targeting hybrid hollow microspheres exhibit exciting pH response and stability in high salt-concentration media. Their pH-dependent controlled release of the drug molecule (anticancer drug, doxorubicin (DOX)) was also investigated in different human body fluids. As expected, the cell viability of the HepG2 cells which decreased more rapidly was treated by the FA modified hybrid hollow microspheres rather than the unmodified one in the in vitro study. The dual-targeting hybrid hollow microspheres demonstrate selective killing of the tumor cells. The precise magnetic and molecular targeting properties and pH-dependent controlled release offers promise for cancer treatment.

QM/MM-MD simulations of conjugated polyelectrolytes

DEFF Research Database (Denmark)

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

2014-01-01

A methodological development is reported for the study of luminescence properties of conjugated polyelectrolytes, encompassing systems in which dihedral rotational barriers are easily overcome at room temperature. The components of the model include (i) a molecular mechanics (MM) force field desc...

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

Science.gov (United States)

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

2007-10-01

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

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

Science.gov (United States)

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

2018-01-01

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

Polyelectrolyte complex formation and stability when mixing polyanions and polycations in salted media: A model study related to the case of body fluids

Czech Academy of Sciences Publication Activity Database

Etrych, Tomáš; Leclercq, L.; Boustta, M.; Vert, M.

2005-01-01

Roč. 25, 1-2 (2005), s. 281-288 ISSN 0928-0987 EU Projects: European Commission(XE) 512087 - GIANT Institutional research plan: CEZ:AV0Z40500505 Keywords : polyelectrolyte complex * selectivity * light scattering Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.347, year: 2005

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

Salt dependence of compression normal forces of quenched polyelectrolyte brushes

Science.gov (United States)

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

2001-03-01

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

A molecular-thermodynamic model for polyelectrolyte solutions

Energy Technology Data Exchange (ETDEWEB)

Jiang, J.; Liu, H.; Hu, Y. [Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237 (China); Prausnitz, J.M. [Department of Chemical Engineering, University of California, Berkeley, and Chemical Sciences Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 (United States)

1998-01-01

Polyelectrolyte solutions are modeled as freely tangent-jointed, charged hard-sphere chains and corresponding counterions in a continuum medium with permitivity {var_epsilon}. By adopting the sticky-point model, the Helmholtz function for polyelectrolyte solutions is derived through the r-particle cavity-correlation function (CCF) for chains of sticky, charged hard spheres. The r-CCF is approximated by a product of effective nearest-neighbor two-particle CCFs; these are determined from the hypernetted-chain and mean-spherical closures (HNC/MSA) inside and outside the hard core, respectively, for the integral equation theory for electrolytes. The colligative properties are given as explicit functions of a scaling parameter {Gamma} that can be estimated by a simple iteration procedure. Osmotic pressures, osmotic coefficients, and activity coefficients are calculated for model solutions with various chain lengths. They are in good agreement with molecular simulation and experimental results. {copyright} {ital 1998 American Institute of Physics.}

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

Science.gov (United States)

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

2016-04-26

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

Kaolinite and Silica Dispersions in Low-Salinity Environments: Impact on a Water-in-Crude Oil Emulsion Stability

Directory of Open Access Journals (Sweden)

Vladimir Alvarado

2011-10-01

Full Text Available This research aims at providing evidence of particle suspension contributions to emulsion stability, which has been cited as a contributing factor in crude oil recovery by low-salinity waterflooding. Kaolinite and silica particle dispersions were characterized as functions of brine salinity. A reference aqueous phase, representing reservoir brine, was used and then diluted with distilled water to obtain brines at 10 and 100 times lower Total Dissolved Solid (TDS. Scanning Electron Microscope (SEM and X-ray Diffraction (XRD were used to examine at the morphology and composition of clays. The zeta potential and particle size distribution were also measured. Emulsions were prepared by mixing a crude oil with brine, with and without dispersed particles to investigate emulsion stability. The clay zeta potential as a function of pH was used to investigate the effect of particle charge on emulsion stability. The stability was determined through bottle tests and optical microscopy. Results show that both kaolinite and silica promote emulsion stability. Also, kaolinite, roughly 1 mm in size, stabilizes emulsions better than larger clay particles. Silica particles of larger size (5 µm yielded more stable emulsions than smaller silica particles do. Test results show that clay particles with zero point of charge (ZPC at low pH become less effective at stabilizing emulsions, while silica stabilizes emulsions better at ZPC. These result shed light on emulsion stabilization in low-salinity waterflooding.

Dispersion stability of 1-octanethiol coated Cu nanoparticles in a 1-octanol solvent for the application of nanoink

Energy Technology Data Exchange (ETDEWEB)

Cho, Danee [Department of Materials Engineering, Hanyang University, Ansan 426-791 (Korea, Republic of); Baik, Jong-Hwan [Lean on Tech., Guri 471-854 (Korea, Republic of); Choi, Da-hyun [Department of Materials Engineering, Hanyang University, Ansan 426-791 (Korea, Republic of); Lee, Caroline Sunyong, E-mail: sunyonglee@hanyang.ac.kr [Department of Materials Engineering, Hanyang University, Ansan 426-791 (Korea, Republic of)

2014-08-01

Conductive ink with Copper nanoparticles (Cu NPs) has various advantages compared with conventional ink, such as good electrical conductivity and low cost. However, it suffers through easily oxidization problem, leading to an unstable electrical conductivity, which decreases over time. Therefore, it is important to prevent (or least minimize) oxidation of the Cu NPs. In this study, Cu NPs with diameter of 50 nm were coated with 1-octanethiol (CH₃(CH₂)₇SH) in a high-vacuum condition (5.33 × 10⁻⁴ Pa). The coating conditions were systematically varied to investigate the effect on the coating thicknesses. Coated Cu NPs were dispersed in 1-octanol to form the conductive ink, and the dispersion behavior was studied as a function of the thickness of the 1-octanethiol coating. The thickness of the coating layer was characterized using transmission electron microscopy and X-ray spectroscopy analysis, and was found to be 3 nm, 6 nm, and 10 nm. The dispersion stability of the inks was characterized by Turbiscan dispersion stability and viscosity measurements, and it was found that the copper nanoink formed using Cu NPs with a 6-nm-thick coating exhibited the most stable dispersion properties.

Dispersion stability of 1-octanethiol coated Cu nanoparticles in a 1-octanol solvent for the application of nanoink

International Nuclear Information System (INIS)

Cho, Danee; Baik, Jong-Hwan; Choi, Da-hyun; Lee, Caroline Sunyong

2014-01-01

Conductive ink with Copper nanoparticles (Cu NPs) has various advantages compared with conventional ink, such as good electrical conductivity and low cost. However, it suffers through easily oxidization problem, leading to an unstable electrical conductivity, which decreases over time. Therefore, it is important to prevent (or least minimize) oxidation of the Cu NPs. In this study, Cu NPs with diameter of 50 nm were coated with 1-octanethiol (CH 3 (CH 2 ) 7 SH) in a high-vacuum condition (5.33 × 10 −4 Pa). The coating conditions were systematically varied to investigate the effect on the coating thicknesses. Coated Cu NPs were dispersed in 1-octanol to form the conductive ink, and the dispersion behavior was studied as a function of the thickness of the 1-octanethiol coating. The thickness of the coating layer was characterized using transmission electron microscopy and X-ray spectroscopy analysis, and was found to be 3 nm, 6 nm, and 10 nm. The dispersion stability of the inks was characterized by Turbiscan dispersion stability and viscosity measurements, and it was found that the copper nanoink formed using Cu NPs with a 6-nm-thick coating exhibited the most stable dispersion properties.

Lipophilic polyelectrolyte gel derived from phosphonium borate can absorb a wide range of organic solvents.

Science.gov (United States)

Sunaga, Sokuro; Kokado, Kenta; Sada, Kazuki

2018-01-24

Herein, we demonstrate a polyelectrolyte gel which can absorb a wide range of organic solvents from dimethylsulfoxide (DMSO, permittivity: ε = 47.0) to tetrahydrofuran (ε = 5.6). The gel consists of polystyrene chains with small amounts (∼5 mol%) of lipophilic electrolytes derived from triphenylphosphonium tetraaryl borate. The swelling ability of the polyelectrolyte gel was higher than that of the alkyl ammonium tetraaryl borate previously reported by us, and this is attributed to the higher compatibility with organic solvents, as well as the higher dissociating ability, of the triphenyl phosphonium salt. The role of the ionic moieties was additionally confirmed by post modification of the polyelectrolyte gel via a conventional Wittig reaction, resulting in a nonionic gel. Our findings introduced here will lead to a clear-cut molecular design for polyelectrolyte gels which absorb all solvents.

Polyelectrolyte-mediated bridging interactions: columnar macromolecular phases

International Nuclear Information System (INIS)

Licer, Matjaz; Podgornik, Rudolf

2010-01-01

We present a mean-field theory for charged polymer chains in an external electrostatic field in the weak and strong coupling limits. We apply the theory to describe the statistical mechanics of flexible polyelectrolyte chains in a hexagonal columnar lattice of stiff cylindrical macroions, such as DNA, in a bathing solution of a uni-univalent salt (e.g. NaCl). The salt effects are first described in the Debye-Hueckel framework. This yields the macroion electrostatic field in the screened Coulomb form, which we take to represent the mean field into which the chains are immersed. We introduce the Green's function for the polyelectrolyte chains and derive the corresponding Edwards equation which we solve numerically in the Wigner-Seitz cylindrical cell using the ground state dominance ansatz. The solutions indicate the presence of polyelectrolyte bridging, which results in a like-charge attraction between stiff macroions. Then we reformulate the Edwards theory for the strong coupling case and use the standard Poisson-Boltzmann picture to describe the salt solution. We begin with the free energy which we minimize to obtain the Euler-Lagrange equations. The solutions yield self-consistently determined monomer density and electrostatic fields. We furthermore calculate the free energy density as well as the total osmotic pressure in the system. We again show that bridging implicates like-charge attractions of entropic origin between stiff cylindrical macroions. By analyzing the osmotic pressure we demonstrate that, in certain parts of the parameter space, a phase transition occurs between two phases of the same hexagonal symmetry.

Effect of dispersing and stabilizing additives on rheological characteristics of the upgraded brown coal water mixture

International Nuclear Information System (INIS)

Umar, Datin Fatia; Muta'alim; Usui, Hiromoto; Komoda, Yoshiyuki

2009-01-01

Upgraded brown coal water mixture (UBCWM) preparation by using an Indonesian upgraded coal produced by upgraded brown coal (UBC) process, was carried out to study the effect of dispersing and stabilizing additives on rheological behavior of the UBCWM. Three kinds of anionic dispersing additives, naphthalene sulfonic formaldehyde condensate (NSF), poly (meth) acrylate (PMA) and poly styrene sulfonic acid (PSS) and three kinds of stabilizing additives, carboxyl methyl cellulose (CMC), rhansam gum (S-194) and gellan gum (S-60) were used in this study. Results indicate that the addition of NSF 0.3 wt.% together with S-194 0.01 wt.% is effective in preparing UBCWM with good slurryability and stability, based on its rheological characteristics with the apparent viscosity at shear rate of 100 s - 1 and yield stress at zero point of shear rate. The rheological behavior of all of the UBCWM that prepared, exhibits non-Newtonian Bingham plastic. From the economical point of view, the price of S-194 is expensive. On the other hand, CMC is cheap and abundant. Therefore, the addition of CMC 0.01 wt.% together with NSF 0.3 wt.% is also effective in preparing UBCWM with good fluidity and stability. (author)

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.

The effect of guanidinium functionalization on the structural properties and anion affinity of polyelectrolyte multilayers

NARCIS (Netherlands)

Cao, Zheng; Gordiichuk, Pavlo; Loos, Katja; Sudhölter, Ernst Jan Robert; Smet, Louis

2015-01-01

Poly(allylamine hydrochloride) (PAH) is chemically functionalized with guanidinium (Gu) moieties in water at room temperature. The resulting PAH-Gu is used to prepare polyelectrolyte multilayers (PEMs) with poly(sodium 4-styrene sulfonate) (PSS) via layer-by-layer deposition. The polyelectrolyte

Influence of solvent evaporation rate and formulation factors on solid dispersion physical stability.

Science.gov (United States)

Wu, Jian X; Yang, Mingshi; Berg, Frans van den; Pajander, Jari; Rades, Thomas; Rantanen, Jukka

2011-12-18

New chemical entities (NCEs) often show poor water solubility necessitating solid dispersion formulation. The aim of the current study is to employ design of experiments in investigating the influence of one critical process factor (solvent evaporation rate) and two formulation factors (PVP:piroxicam ratio (PVP:PRX) and PVP molecular weight (P(MW))) on the physical stability of PRX solid dispersion prepared by the solvent evaporation method. The results showed the rank order of an increase in factors contributing to a decrease in the extent of PRX nucleation being evaporation rate>PVP:PRX>P(MW). The same rank order was found for the decrease in the extent of PRX crystal growth in PVP matrices from day 0 up to day 12. However, after 12days the rank became PVP:PRX>evaporation rate>P(MW). The effects of an increase in evaporation rate and PVP:PRX ratio in stabilizing PRX were of the same order of magnitude, while the effect from P(MW) was much smaller. The findings were confirmed by XRPD. FT-IR showed that PRX recrystallization in the PVP matrix followed Ostwald's step rule, and an increase in the three factors all led to increased hydrogen bonding interaction between PRX and PVP. The present study showed the applicability of the Quality by Design approach in solid dispersion research, and highlights the need for multifactorial analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Influence of network topology on the swelling of polyelectrolyte nanogels.

Science.gov (United States)

Rizzi, L G; Levin, Y

2016-03-21

It is well-known that the swelling behavior of ionic nanogels depends on their cross-link density; however, it is unclear how different topologies should affect the response of the polyelectrolyte network. Here we perform Monte Carlo simulations to obtain the equilibrium properties of ionic nanogels as a function of salt concentration Cs and the fraction f of ionizable groups in a polyelectrolyte network formed by cross-links of functionality z. Our results indicate that the network with cross-links of low connectivity result in nanogel particles with higher swelling ratios. We also confirm a de-swelling effect of salt on nanogel particles.

The phase stability and toughening effect of 3Y-TZP dispersed in the lanthanum zirconate ceramics

International Nuclear Information System (INIS)

Wang, Yanfei; Xiao, Ping

2014-01-01

The low fracture toughness of lanthanum zirconate (La 2 Zr 2 O 7 , LZ) greatly impedes its wide application as thermal barrier coatings (TBC). The 3 mol% Y 2 O 3 -stabilized tetragonal zirconia polycrystals (3Y-TZP) have been introduced to toughen the brittle LZ ceramics. The dispersive 3Y-TZP undergoes a simultaneous t–m transformation upon cooling below a critical volume fraction x of 3Y-TZP, above which its tetragonal phases can however be preserved. The different stabilities of 3Y-TZP second phases arise from a variation of residual tensile stress within them. The fracture toughness has been greatly improved by dispersing the tetragonal particulates (t-3YSZ) in the LZ matrix and the primary toughening mechanisms are phase transformations of the dispersive second phases and the residual compressive stress within the matrix. An anticipated increase of fracture toughness from the ferroelastic toughening and the residual compressive stress toughening highlights the great potentials to improve coating durability by depositing t′-3YSZ/LZ composite TBCs by the industrial non-equilibrium route

Multilayer films of cationic graphene-polyelectrolytes and anionic graphene-polyelectrolytes fabricated using layer-by-layer self-assembly

International Nuclear Information System (INIS)

Rani, Adila; Oh, Kyoung Ah; Koo, Hyeyoung; Lee, Hyung jung; Park, Min

2011-01-01

Extremely thin sheets of carbon atoms called graphene have been predicted to possess excellent thermal properties, electrical conductivity, and mechanical stiffness. To harness such properties in composite materials for multifunctional applications, one would require the incorporation of graphene. In this study, new thin film composites were created using layer-by-layer (LBL) assembly of polymer-coated graphitic nanoplatelets. The positive and negative polyelectrolytes used to cover graphene sheets were poly allylamine hydrochloride (PAH) and poly sodium 4-styrenesulfonate (PSS). The synthesized poly allylamine hydrochloride-graphene (PAH-G) and poly sodium 4-styrenesulfonate-gaphene (PSS-G) were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and thermo gravimetric analysis (TGA). The multilayer films created by spontaneous sequential adsorption of PAH-G and PSS-G were characterized by ultra violet spectroscopy (UV-vis), scanning electron microscopy (SEM), and AFM. The electrical conductivity of the graphene/polyelectrolyte multilayer film composites measured by the four-point probe method was 0.2 S cm -1 , which was sufficient for the construction of advanced electro-optical devices and sensors.

A comparison of short-term dispersion estimates resulting from various atmospheric stability classification methods

International Nuclear Information System (INIS)

Mitchell, A.E. Jr.

1982-01-01

Four methods of classifying atmospheric stability class are applied at four sites to make short-term (1-h) dispersion estimates from a ground-level source based on a model consistent with U.S. Nuclear Regulatory Commission practice. The classification methods include vertical temperature gradient, standard deviation of horizontal wind direction fluctuations (sigma theta), Pasquill-Turner, and modified sigma theta which accounts for meander. Results indicate that modified sigma theta yields reasonable dispersion estimates compared to those produced using methods of vertical temperature gradient and Pasquill-Turner, and can be considered as a potential economic alternative in establishing onsite monitoring programs. (author)

Surface Modification of Carbon Nanotubes with Conjugated Polyelectrolytes: Fundamental Interactions and Applications in Composite Materials, Nanofibers, Electronics, and Photovoltaics

KAUST Repository

Ezzeddine, Alaa

2015-10-01

Ever since their discovery, Carbon nanotubes (CNTs) have been renowned to be potential candidates for a variety of applications. Nevertheless, the difficulties accompanied with their dispersion and poor solubility in various solvents have hindered CNTs potential applications. As a result, studies have been developed to address the dispersion problem. The solution is in modifying the surfaces of the nanotubes covalently or non-covalently with a desired dispersant. Various materials have been employed for this purpose out of which polymers are the most common. Non-covalent functionalization of CNTs via polymer wrapping represents an attractive method to obtain a stable and homogenous CNTs dispersion. This method is able to change the surface properties of the nanotubes without destroying their intrinsic structure and preserving their properties. This thesis explores and studies the surface modification and solublization of pristine single and multiwalled carbon nanotubes via a simple solution mixing technique through non-covalent interactions of CNTs with various anionic and cationic conjugated polyelectrolytes (CPEs). The work includes studying the interaction of various poly(phenylene ethynylene) electrolytes with MWCNTs and an imidazolium functionalized poly(3-hexylthiophene) with SWCNTs. Our work here focuses on the noncovalent modifications of carbon nanotubes using novel CPEs in order to use these resulting CPE/CNT complexes in various applications. Upon modifying the CNTs with the CPEs, the resulting CPE/CNT complex has been proven to be easily dispersed in various organic and aqueous solution with excellent homogeneity and stability for several months. This complex was then used as a nanofiller and was dispersed in another polymer matrix (poly(methyl methacrylate), PMMA). The PMMA/CPE/CNT composite materials were cast or electrospun depending on their desired application. The presence of the CPE modified CNTs in the polymer matrix has been proven to enhance

Improving the stability of coal slurries: Quarterly progress report for the period September 15, 1987-December 15, 1987

Energy Technology Data Exchange (ETDEWEB)

Fogler, H.S.

1987-01-01

Gum tragacanth, GT changes the conformation on the negative surface of sulfate polystyrene latex particles as the amount of charge in GT alters with pH. Also, it had been indicated that the polygalacturonic acid, PGUA which constitutes the core of GT molecules is responsible for the conformational change. In order to find how this conformational change is related to the adsorption affinity between the surface and the polyelectrolyte, the positively charged amidine polystyrene latex particles were employed. The stability study showed that the PGUA can also stabilize the positively charged particles and that the stability of the amidine latex is virtually independent of pH whereas the stability of the sulfate latex is dependent on pH. The adsorption study indicated that this independence of stability on pH for the amidine latex is due to the fact that the strong adsorption affinity between the positive surface and the negative polyelectrolyte gives the similar conformation regardless of pH. 6 refs., 8 figs., 2 tabs.

Modeling competitive substitution in a polyelectrolyte complex

International Nuclear Information System (INIS)

Peng, B.; Muthukumar, M.

2015-01-01

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

Electrostatic self-assembly in polyelectrolyte-neutral block copolymers and oppositely charged surfactant solutions

International Nuclear Information System (INIS)

Berret, J.-F.Jean-Francois; Oberdisse, Julian

2004-01-01

We report on small-angle neutron scattering (SANS) of colloidal complexes resulting from the electrostatic self-assembly of polyelectrolyte-neutral copolymers and oppositely charged surfactants. The polymers are double hydrophilic block copolymers of low molecular weight (between 5000 and 50 000 g/mol). One block is a polyelectrolyte chain, which can be either positively or negatively charged, whereas the second block is neutral and in good solvent conditions. In aqueous solutions, surfactants with an opposite charge to that of the polyelectrolyte interact strongly with these copolymers. The two species associate into stable 100 nm-colloidal complexes which exhibit a core-shell microstructure. For different polymer/surfactant couples, we have shown that the core is constituted from densely packed surfactant micelles connected by the polyelectrolyte chains. The outer part of the complex is a corona formed by the neutral soluble chains. Using a model of aggregation based on a Monte-Carlo algorithm, we have simulated the internal structure of the aggregates. The model assumes spherical cages containing one to several hundreds of micelles in a closely packed state. The agreement between the model and the data is remarkable

Solid dispersions of Myricetin with enhanced solubility: Formulation, characterization and crystal structure of stability-impeding Myricetin monohydrate crystals

Science.gov (United States)

Mureşan-Pop, M.; Pop, M. M.; Borodi, G.; Todea, M.; Nagy-Simon, T.; Simon, S.

2017-08-01

Three solid dispersion forms of Myricetin combined with the Polyvinylpyrrolidone were successfully prepared by spray drying method, and characterized by X-ray powder diffraction, thermal analysis, infrared spectroscopy and optical microscopy. Zeta potential measurements provided indications on solid dispersions stability in aqueous suspension related to their storage at elevated temperature and relative humidity, which depends on the Myricetin load. By increase of Myricetin load, the stability of the solid dispersion is impeded due to growth of Myricetin monohydrate crystals. The amorphous dispersions with 10% and 50% Myricetin load are stable and, compared to pure Myricetin, their aqueous solubility is enhanced by a factor of 47 and 13, respectively. The dispersion with 80% Myricetin load is unstable on storage, and this behavior acts in conjunction with the development of Myricetin monohydrate crystals. Single-crystal X-ray diffraction results obtained for Myricetin monohydrate reveal a structure of an infinite 2D network of hydrogen-bonded molecules involving all six hydroxyl groups of Myricetin. The water molecules are positioned in between the infinite chains, and contribute via H-bonds to robust crystal packing. The calculated needle-like morphology of monohydrate form is in agreement with the optical microscopy results. The study shows that the solid amorphous dispersions with up to 50% Myricetin load are a viable option for achieving substantial solubility improvement of Myricetin, and supports their potential use in pharmaceutical applications.

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

Dispersion stability of a ceramic glaze achieved through ionic surfactant adsorption.

Science.gov (United States)

Panya, Preecha; Arquero, Orn-anong; Franks, George V; Wanless, Erica J

2004-11-01

The adsorption of cetylpyridinium chloride (CPC) and sodium dodecylbenzenesulfonate (SDBS) onto a ceramic glaze mixture composed of limestone, feldspar, quartz, and kaolin has been investigated. Both adsorption isotherms and the average particle zeta potential have been studied in order to understand the suspension stability as a function of pH, ionic strength, and surfactant concentration. The adsorption of small amounts of cationic CPC onto the primarily negatively charged surfaces of the particles at pH 7 and 9 results in strong attraction and flocculation due to hydrophobic interactions. At higher surfactant concentrations a zeta potential of more than +60 mV results from the bilayered adsorbed surfactant, providing stability at salt concentrations dispersion or hydrophobic interactions, the magnitude of the negative zeta potential increases slightly. At pH 9 this increase is enough to promote stability with an average zeta potential of more than -55 mV, whereas at pH 7 the zeta potential is lower at about -45 mV. The stability of suspensions at pH 7 is additionally due to steric repulsion caused by the adsorption of thick layers of neutrally charged Ca(DBS)2 complexes created when the surfactant interacts with dissolved calcium ions from the calcium carbonate component.

Bacteriophage enzymes for the prevention and treatment of bacterial infections: Stability and stabilization of the enzyme lysing Streptococcus pyogenes cells

Energy Technology Data Exchange (ETDEWEB)

Klyachko, N. L.; Dmitrieva, N. F.; Eshchina, A. S.; Ignatenko, O. V.; Filatova, L. Y.; Rainina, Evguenia I.; Kazarov, A. K.; Levashov, A. V.

2008-06-01

Recombinant, phage associated lytic enzyme Ply C capable to lyse streptococci of groups A and C was stabilized in the variety of the micelles containing compositions to improve the stability of the enzyme for further application in medicine. It was shown that, in the micellar polyelectrolyte composition M16, the enzyme retained its activity for 2 months; while in a buffer solution under the same conditions ((pH 6.3, room temperature), it completely lost its activity in 2 days

Conformations and solution properties of star-branched polyelectrolytes

NARCIS (Netherlands)

Borisov, O.V.; Zhulina, E.B.; Leermakers, F.A.M.; Ballauff, M.; Muller, A.H.E.

2011-01-01

Aqueous solutions of star-like polyelectrolytes (PEs) exhibit distinctive features that originate from the topological complexity of branched macromolecules. In a salt-free solution of branched PEs, mobile counterions preferentially localize in the intramolecular volume of branched macroions.

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.

Layer-by-layer polyelectrolyte films for contact electric energy harvesting

International Nuclear Information System (INIS)

Guo, X D; Helseth, L E

2015-01-01

We report how self-assembly of polyelectrolyte thin films alters the contact electrification of polyimide polymer films used in contact based triboelectric energy harvesting systems. Polyimide films of the same size do produce a very small current when brought into contact. However, by covering one of the polyimide films with a polyelectrolyte thin film terminated by positively charged poly(allylamine hydrochloride) (PAH), the current is reversed and a much larger current and voltage are generated upon contact with the other polyimide film. A similar increase in contact current is not seen for polyelectrolyte thin films terminated by the negatively charged poly(sodium 4-styrenesulfonate). The PAH-terminated Kapton films are used to create an energy harvesting system providing a voltage of about 60 V and a current of 10 μA. At an average power of 11 μW for a load resistance of 100 MΩ, the energy harvester is able to power several light emitting diodes. Further studies on the contact electrification of the polyelectrolyte demonstrate that nanostructuring of the polymer surface using reactive ion etching does not give rise to polarity reversal. This is explained as hidden pockets of charge not accessible to PAH molecules, but which become accessible when the polymer is put under stress. Although the current originating for a PAH-terminated multilayer film does initially have the opposite sign to that of bare polyimide, it is found that the polarity will switch after subjecting it to a periodical mechanical force. Characteristic changes in current signatures associated with the switch are found, and are interpreted as mechanical interpenetration of the charged layers. (paper)

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.

Weak polyelectrolyte complexation driven by associative charging

Science.gov (United States)

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

2018-03-01

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

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

Science.gov (United States)

Ubbink, Job; Khokhlov, Alexei R

2004-03-15

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

Polyelectrolyte hydrogels and methods of their preparation

International Nuclear Information System (INIS)

Ward, J.A.

1981-01-01

This invention relates to polyelectrolyte polymers which are water insoluble but water swellable, and methods for producing them. More particularly, it relates to cross-linked, random copolymers comprised of an acrylate salt and acrylamide and methods of producing them by means of a controlled dose and controlled intensity of ionizing radiation. (author)

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

Science.gov (United States)

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

2017-11-01

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

Impact of the self-assembly of multilayer polyelectrolyte functionalized gold nanorods and its application to biosensing

International Nuclear Information System (INIS)

Li Xin; Qian Jun; He Sailing

2008-01-01

Multilayered polyelectrolyte functionalized gold nanorods (GNRs) are reported for the conjugation of and sensitive detection of bio-molecules. Multilayered polyelectrolyte functionalized GNRs can significantly improve the biocompatibility of cetyltrimethylammonium bromide (CTAB) coated GNRs in a bio-environment and can diminish the toxicity induced by CTAB. Biotin, bovine serum albumin (BSA)-biotin and streptavidin are conjugated to polyelectrolyte functionalized GNRs, and the conjugates can serve as a platform for many biotin-streptavidin-based biological applications. Through the robust self-assembly effect of GNRs, biotin-conjugated GNRs are also utilized as a very sensitive probe for the detection of a small amount of streptavidin

Polyelectrolyte Complex Optimization for Macrophage Delivery of Redox Enzyme Nanoparticles

Science.gov (United States)

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

2011-01-01

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

Effect of highly dispersed yttria addition on thermal stability of hydroxyapatite

International Nuclear Information System (INIS)

Parente, P.; Savoini, B.; Ferrari, B.; Monge, M.A.; Pareja, R.; Sanchez-Herencia, A.J.

2013-01-01

The capability of the colloidal method to produce yttria (Y 2 O 3 ) dispersed hydroxyapatite (HA) has been investigated as an alternative method to the conventional method of mechanical mixing and sintering for developing HA-based materials that could exhibit controllable and enhanced functional properties. A water based colloidal route to produce HA materials with highly dispersed Y 2 O 3 has been applied, and the effect of 10 wt.% Y 2 O 3 addition to HA investigated by thermal analysis, X-ray diffraction and Fourier transform infrared spectroscopy. These measurements evidence a remarkable effect of this Y 2 O 3 addition on decomposition mechanisms of synthetic HA. Results show that incorporation of Y 2 O 3 as dispersed second phase is beneficial because it hinders the decomposition mechanisms of HA into calcium phosphates. This retardation will allow the control of the sintering conditions for developing HA implants with improved properties. Besides, substitution of Ca 2+ with Y 3+ ions appears to promote the formation of OH − vacancies, which could improve the conductive properties of HA favorable to osseointegration. - Highlights: ► We reveal the influence of Y 2 O 3 on thermal stability of hydroxyapatite. ► Incorporation of Y 2 O 3 delays decomposition of hydroxyapatite to calcium phosphates. ► Addition of Y 2 O 3 enables sintering conditions more favorable to the densification.

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.

Serum Proteins Enhance Dispersion Stability and Influence the Cytotoxicity and Dosimetry of ZnO Nanoparticles in Suspension and Adherent Cancer Cell Models

Science.gov (United States)

Anders, Catherine B.; Chess, Jordan J.; Wingett, Denise G.; Punnoose, Alex

2015-11-01

Agglomeration and sedimentation of nanoparticles (NPs) within biological solutions is a major limitation in their use in many downstream applications. It has been proposed that serum proteins associate with the NP surface to form a protein corona that limits agglomeration and sedimentation. Here, we investigate the effect of fetal bovine serum (FBS) proteins on the dispersion stability, dosimetry, and NP-induced cytotoxicity of cationic zinc oxide nanoparticles (nZnO) synthesized via forced hydrolysis with a core size of 10 nm. Two different in vitro cell culture models, suspension and adherent, were evaluated by comparing a phosphate buffered saline (PBS) nZnO dispersion (nZnO/PBS) and an FBS-stabilized PBS nZnO dispersion (nZnO - FBS/PBS). Surface interactions of FBS on nZnO were analyzed via spectroscopic and optical techniques. Fourier transformed infrared spectroscopy (FTIR) confirmed the adsorption of negatively charged protein components on the cationic nZnO surface through the disappearance of surfaced-adsorbed carboxyl functional groups and the subsequent detection of vibrational modes associated with the protein backbone of FBS-associated proteins. Further confirmation of these interactions was noted in the isoelectric point shift of the nZnO from the characteristic pH of 9.5 to a pH of 6.1. In nZnO - FBS/PBS dispersions, the FBS reduced agglomeration and sedimentation behaviors to impart long-term improvements (>24 h) to the nZnO dispersion stability. Furthermore, mathematical dosimetry models indicate that nZnO - FBS/PBS dispersions had consistent NP deposition patterns over time unlike unstable nZnO/PBS dispersions. In suspension cell models, the stable nZnO - FBS/PBS dispersion resulted in a ~33 % increase in the NP-induced cytotoxicity for both Jurkat leukemic and Hut-78 lymphoma cancer cells. In contrast, the nZnO - FBS/PBS dispersion resulted in 49 and 71 % reductions in the cytotoxicity observed towards the adherent breast (T-47D) and prostate

Serum Proteins Enhance Dispersion Stability and Influence the Cytotoxicity and Dosimetry of ZnO Nanoparticles in Suspension and Adherent Cancer Cell Models.

Science.gov (United States)

Anders, Catherine B; Chess, Jordan J; Wingett, Denise G; Punnoose, Alex

2015-12-01

Agglomeration and sedimentation of nanoparticles (NPs) within biological solutions is a major limitation in their use in many downstream applications. It has been proposed that serum proteins associate with the NP surface to form a protein corona that limits agglomeration and sedimentation. Here, we investigate the effect of fetal bovine serum (FBS) proteins on the dispersion stability, dosimetry, and NP-induced cytotoxicity of cationic zinc oxide nanoparticles (nZnO) synthesized via forced hydrolysis with a core size of 10 nm. Two different in vitro cell culture models, suspension and adherent, were evaluated by comparing a phosphate buffered saline (PBS) nZnO dispersion (nZnO/PBS) and an FBS-stabilized PBS nZnO dispersion (nZnO - FBS/PBS). Surface interactions of FBS on nZnO were analyzed via spectroscopic and optical techniques. Fourier transformed infrared spectroscopy (FTIR) confirmed the adsorption of negatively charged protein components on the cationic nZnO surface through the disappearance of surfaced-adsorbed carboxyl functional groups and the subsequent detection of vibrational modes associated with the protein backbone of FBS-associated proteins. Further confirmation of these interactions was noted in the isoelectric point shift of the nZnO from the characteristic pH of 9.5 to a pH of 6.1. In nZnO - FBS/PBS dispersions, the FBS reduced agglomeration and sedimentation behaviors to impart long-term improvements (>24 h) to the nZnO dispersion stability. Furthermore, mathematical dosimetry models indicate that nZnO - FBS/PBS dispersions had consistent NP deposition patterns over time unlike unstable nZnO/PBS dispersions. In suspension cell models, the stable nZnO - FBS/PBS dispersion resulted in a ~33 % increase in the NP-induced cytotoxicity for both Jurkat leukemic and Hut-78 lymphoma cancer cells. In contrast, the nZnO - FBS/PBS dispersion resulted in 49 and 71 % reductions in the cytotoxicity observed towards the adherent breast (T-47D) and prostate

On the calculation of the structure of charge-stabilized colloidal dispersions using density-dependent potentials

International Nuclear Information System (INIS)

Castañeda-Priego, R; Lobaskin, V; Mixteco-Sánchez, J C; Rojas-Ochoa, L F; Linse, P

2012-01-01

The structure of charge-stabilized colloidal dispersions has been studied through a one-component model using a Yukawa potential with density-dependent parameters examined with integral equation theory and Monte Carlo simulations. Partial thermodynamic consistency was guaranteed by considering the osmotic pressure of the dispersion from the approximate mean-field renormalized jellium and Poisson-Boltzmann cell models. The colloidal structures could be accurately described by the Ornstein-Zernike equation with the Rogers-Young closure by using the osmotic pressure from the renormalized jellium model. Although we explicitly show that the correct effective pair-potential obtained from the inverse Monte Carlo method deviates from the Yukawa shape, the osmotic pressure constraint allows us to have a good description of the colloidal structure without losing information on the system thermodynamics. Our findings are corroborated by primitive model simulations of salt-free colloidal dispersions. (paper)

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.

Entrapment of curcumin into monoolein-based liquid crystalline nanoparticle dispersion for enhancement of stability and anticancer activity

Science.gov (United States)

Baskaran, Rengarajan; Madheswaran, Thiagarajan; Sundaramoorthy, Pasupathi; Kim, Hwan Mook; Yoo, Bong Kyu

2014-01-01

Despite the promising anticancer potential of curcumin, its therapeutic application has been limited, owing to its poor solubility, bioavailability, and chemical fragility. Therefore, various formulation approaches have been attempted to address these problems. In this study, we entrapped curcumin into monoolein (MO)-based liquid crystalline nanoparticles (LCNs) and evaluated the physicochemical properties and anticancer activity of the LCN dispersion. The results revealed that particles in the curcumin-loaded LCN dispersion were discrete and monodispersed, and that the entrapment efficiency was almost 100%. The stability of curcumin in the dispersion was surprisingly enhanced (about 75% of the curcumin survived after 45 days of storage at 40°C), and the in vitro release of curcumin was sustained (10% or less over 15 days). Fluorescence-activated cell sorting (FACS) analysis using a human colon cancer cell line (HCT116) exhibited 99.1% fluorescence gating for 5 μM curcumin-loaded LCN dispersion compared to 1.36% for the same concentration of the drug in dimethyl sulfoxide (DMSO), indicating markedly enhanced cellular uptake. Consistent with the enhanced cellular uptake of curcumin-loaded LCNs, anticancer activity and cell cycle studies demonstrated apoptosis induction when the cells were treated with the LCN dispersion; however, there was neither noticeable cell death nor significant changes in the cell cycle for the same concentration of the drug in DMSO. In conclusion, entrapping curcumin into MO-based LCNs may provide, in the future, a strategy for overcoming the hurdles associated with both the stability and cellular uptake issues of the drug in the treatment of various cancers. PMID:25061290

Structural characterization of the phospholipid stabilizer layer at the solid-liquid interface of dispersed triglyceride nanocrystals with small-angle x-ray and neutron scattering

Science.gov (United States)

Schmiele, Martin; Schindler, Torben; Unruh, Tobias; Busch, Sebastian; Morhenn, Humphrey; Westermann, Martin; Steiniger, Frank; Radulescu, Aurel; Lindner, Peter; Schweins, Ralf; Boesecke, Peter

2013-06-01

Dispersions of crystalline nanoparticles with at least one sufficiently large unit cell dimension can give rise to Bragg reflections in the small-angle scattering range. If the nanocrystals possess only a small number of unit cells along these particular crystallographic directions, the corresponding Bragg reflections will be broadened. In a previous study of phospholipid stabilized dispersions of β-tripalmitin platelets [Unruh, J. Appl. Crystallogr.JACGAR0021-889810.1107/S0021889807044378 40, 1008 (2007)], the x-ray powder pattern simulation analysis (XPPSA) was developed. The XPPSA method facilitates the interpretation of the rather complicated small-angle x-ray scattering (SAXS) curves of such dispersions of nanocrystals. The XPPSA method yields the distribution function of the platelet thicknesses and facilitates a structural characterization of the phospholipid stabilizer layer at the solid-liquid interface between the nanocrystals and the dispersion medium from the shape of the broadened 001 Bragg reflection. In this contribution an improved and extended version of the XPPSA method is presented. The SAXS and small-angle neutron scattering patterns of dilute phospholipid stabilized tripalmitin dispersions can be reproduced on the basis of a consistent simulation model for the particles and their phospholipid stabilizer layer on an absolute scale. The results indicate a surprisingly flat arrangement of the phospholipid molecules in the stabilizer layer with a total thickness of only 12 Å. The stabilizer layer can be modeled by an inner shell for the fatty acid chains and an outer shell including the head groups and additional water. The experiments support a dense packing of the phospholipid molecules on the nanocrystal surfaces rather than isolated phospholipid domains.

Partial molar volume of anionic polyelectrolytes in aqueous solution.

Science.gov (United States)

Salamanca, Constain; Contreras, Martín; Gamboa, Consuelo

2007-05-15

In this work the partial molar volumes (V) of different anionic polyelectrolytes and hydrophobically modified polyelectrolytes (PHM) were measured. Polymers like polymaleic acid-co-styrene, polymaleic acid-co-1-olefin, polymaleic acid-co-vinyl-2-pyrrolidone, and polyacrylic acid (abbreviated as MAS-n, PA-n-K2, AMVP, and PAA, respectively) were employed. These materials were investigated by density measurements in highly dilute aqueous solutions. The molar volume results allow us to discuss the effect of the carboxylic groups and the contributions from the comonomeric principal chain. The PAA presents the smaller V, while the largest V value was for AMVP. The V of PHM shows a linear relationship with the number of methylene groups in the lateral chain. It is found that the magnitude of the contribution per methylene group decreases as the hydrophobic character of the environment increases.

Interaction between two parallel plates covered with a polyelectrolyte brush layer in an electrolyte solution.

Science.gov (United States)

Ohshima, Hiroyuki

An approximate analytic expression is derived for the interaction energy between two parallel plates covered with a polyelectrolyte brush layer in an electrolyte solution. The interaction energy has three components: electrostatic interaction energy between two brush layers before and after their contact, steric interaction energy between two brush layers after their contact, and the van der Waals interaction energy between the cores of the plates. It is shown that these three components are of the same order of magnitude and contribute equally to the total interaction energy between two polyelectrolyte-coated plates in an electrolyte solution. On the basis of Derjaguin's approximation, an approximate expression for the interaction energy between two spherical particles covered with polyelectrolyte brush layers is also derived.

Tuning smart microgel swelling and responsive behavior through strong and weak polyelectrolyte pair assembly.

Science.gov (United States)

Costa, Eunice; Lloyd, Margaret M; Chopko, Caroline; Aguiar-Ricardo, Ana; Hammond, Paula T

2012-07-03

The layer-by-layer (LbL) assembly of polyelectrolyte pairs on temperature and pH-sensitive cross-linked poly(N-isopropylacrylamide)-co-(methacrylic acid), poly(NIPAAm-co-MAA), microgels enabled a fine-tuning of the gel swelling and responsive behavior according to the mobility of the assembled polyelectrolyte (PE) pair and the composition of the outermost layer. Microbeads with well-defined morphology were initially prepared by synthesis in supercritical carbon dioxide. Upon LbL assembly of polyelectrolytes, interactions between the multilayers and the soft porous microgel led to differences in swelling and thermoresponsive behavior. For the weak PE pairs, namely poly(L-lysine)/poly(L-glutamic acid) and poly(allylamine hydrochloride)/poly(acrylic acid), polycation-terminated microgels were less swollen and more thermoresponsive than native microgel, whereas polyanion-terminated microgels were more swollen and not significantly responsive to temperature, in a quasi-reversible process with consecutive PE assembly. For the strong PE pair, poly(diallyldimethylammonium chloride)/poly(sodium styrene sulfonate), the differences among polycation and polyanion-terminated microgels are not sustained after the first PE bilayer due to extensive ionic cross-linking between the polyelectrolytes. The tendencies across the explored systems became less noteworthy in solutions with larger ionic strength due to overall charge shielding of the polyelectrolytes and microgel. ATR FT-IR studies correlated the swelling and responsive behavior after LbL assembly on the microgels with the extent of H-bonding and alternating charge distribution within the gel. Thus, the proposed LbL strategy may be a simple and flexible way to engineer smart microgels in terms of size, surface chemistry, overall charge and permeability.

Synthesis, Characterization, and Applications of Magnetic Nanoparticles Featuring Polyzwitterionic Coatings

Directory of Open Access Journals (Sweden)

Philip Biehl

2018-01-01

Full Text Available Throughout the last decades, magnetic nanoparticles (MNP have gained tremendous interest in different fields of applications like biomedicine (e.g., magnetic resonance imaging (MRI, drug delivery, hyperthermia, but also more technical applications (e.g., catalysis, waste water treatment have been pursued. Different surfactants and polymers are extensively used for surface coating of MNP to passivate the surface and avoid or decrease agglomeration, decrease or modulate biomolecule absorption, and in most cases increase dispersion stability. For this purpose, electrostatic or steric repulsion can be exploited and, in that regard, surface charge is the most important (hybrid particle property. Therefore, polyelectrolytes are of great interest for nanoparticle coating, as they are able to stabilize the particles in dispersion by electrostatic repulsion due to their high charge densities. In this review article, we focus on polyzwitterions as a subclass of polyelectrolytes and their use as coating materials for MNP. In the context of biomedical applications, polyzwitterions are widely used as they exhibit antifouling properties and thus can lead to minimized protein adsorption and also long circulation times.

Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

Directory of Open Access Journals (Sweden)

Qing-Xi Wu

2014-12-01

Full Text Available 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.

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

2014-12-19

Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

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

Radiation Stability of Nanoclusters in Nano-structured Oxide Dispersion Strengthened (ODS) Steels

International Nuclear Information System (INIS)

Certain, Alicia G.; Kuchibhatla, Satyanarayana; Shutthanandan, V.; Allen, T. R.

2013-01-01

Nanostructured oxide dispersion strengthened (ODS) steels are considered candidates for nuclear fission and fusion applications at high temperature and dose. The complex oxide nanoclusters in these alloys provide high-temperature strength and are expected to afford better radiation resistance. Proton, heavy ion, and neutron irradiations have been performed to evaluate cluster stability in 14YWT and 9CrODS steel under a range of irradiation conditions. Energy-filtered transmission electron microscopy and atom probe tomography were used in this work to analyze the evolution of the oxide population.

Melt dispersion of thermoplastic polystyrene in polymer polyols

NARCIS (Netherlands)

2009-01-01

Polystyrene is dispersed into a polyol via a mechanical dispersion process. A stabilizer is present to stabilize the dispersed polymer particles. The stabilizer includes a copolymer of (1) from 10 to 70% by weight of a branched polyol which has a molecular weight of from 4000 to 20,000, from 0.2 to

Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

OpenAIRE

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...

Reversibility and Relaxation Behavior of Polyelectrolyte Complex Micelle Formation

NARCIS (Netherlands)

Lindhoud, Saskia; Norde, Willem; Stuart, Martien A. Cohen

2009-01-01

In this study, the formation and disintegration of polyelectrolyte complex micelles is studied by dynamic light scattering titrations with the aim to assess the extent to which these complexes equilibrate. Also, the time evolution of samples at fixed (electroneutral) composition was followed to

Complexation behavior of oppositely charged polyelectrolytes: Effect of charge distribution

International Nuclear Information System (INIS)

Zhao, Mingtian; Li, Baohui; Zhou, Jihan; Su, Cuicui; Niu, Lin; Liang, Dehai

2015-01-01

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) 5 /(KGKG) 5 , (EEGG) 5 /(KKGG) 5 , and (EEGG) 5 /(KGKG) 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 of the apparent weight

Stability of casein micelles in milk

Science.gov (United States)

Tuinier, R.; de Kruif, C. G.

2002-07-01

Casein micelles in milk are proteinaceous colloidal particles and are essential for the production of flocculated and gelled products such as yogurt, cheese, and ice-cream. The colloidal stability of casein micelles is described here by a calculation of the pair potential, containing the essential contributions of brush repulsion, electrostatic repulsion, and van der Waals attraction. The parameters required are taken from the literature. The results are expressed by the second osmotic virial coefficient and are quite consistent with experimental findings. It appears that the stability is mainly attributable to a steric layer of κ-casein, which can be described as a salted polyelectrolyte brush.

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

Science.gov (United States)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity

Polyelectrolyte Complex Inclusive Biohybrid Microgels for Tailoring Delivery of Copigmented Anthocyanins.

Science.gov (United States)

Tan, Chen; B Celli, Giovana; Lee, Michelle; Licker, Jonathan; Abbaspourrad, Alireza

2018-05-14

This study fabricated a novel biohybrid microgel containing polysaccharide-based polyelectrolyte complexes (PECs) for anthocyanins. Herein, anthocyanins were encapsulated into PECs composed of chondroitin sulfate and chitosan, followed by incorporation into alginate microgels using emulsification/internal gelation method. We demonstrated that PECs incorporation strongly affected the properties of microgels, dependent on the polysaccharide concentration and pH in which they were fabricated. The dense internal network surrounded by an alginate shell was clearly visualized in cross-sectioned PECs-microgels. Stability studies carried out under varying ionic strength and pH conditions demonstrated the stimuli-responsiveness of the PECs-microgels. Additionally, the presence of PECs conferred microgels with high rigidity during freeze-drying and excellent reconstitution capacity upon rehydration. These observations were attributed to the modulation of electrostatic and hydrogen-bonding cross-linking between PECs and the alginate gel matrix and suggest the PECs inclusive microgels hold promise as delivery vehicles for the controlled release of hydrophilic bioactive compounds.

Formation of nano-hydroxyapatite crystal in situ in chitosan-pectin polyelectrolyte complex network

International Nuclear Information System (INIS)

Li Junjie; Zhu Dunwan; Yin Jianwei; Liu Yuxi; Yao Fanglian; Yao Kangde

2010-01-01

Hydroxyapatite (HA)/polysaccharide composites have been widely used in bone tissue engineering due to their chemical similarity to natural bone. Polymer matrix-mediated synthesis of nano-hydroxyapatite is one of the simplest models for biomimetic. In this article, the nano-hydroxyapatite/chitosan-pectin (nHCP) composites were prepared through in situ mineralization of hydroxyapatite in chitosan-pectin polyelectrolyte complex (PEC) network. The formation processes of nHCP were investigated by X-ray diffraction (XRD) analysis. The interactions between nHA crystal and chitosan-pectin PEC networks were studied using Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). The morphology and structure of nHA crystal were characterized by XRD and Transmission Electron Microscope (TEM). Results suggested that the interfacial interactions between nano-hydroxyapatite crystal and chitosan-pectin PEC network assist the site specific nucleation and growth of nHA nanoparticles. The nHA crystals grow along the c-axis. In this process, pH value is the main factor to control the nucleation and growth of nHA crystal in chitosan-pectin PEC networks, because both the interactions' strength between nHA crystal and chitosan-pectin and diffusion rate of inorganic ions depend on the pH value of the reaction system. Apart from the pH value, the chitosan/pectin ratio and [Ca 2+ ] also take important effects on the formation of nHA crystal. An effective way to control the size of nHA crystal is to adjust the content of pectin and [Ca 2+ ]. It is interesting that the Zeta potential of nHCP composites is about - 30 mV when the chitosan/pectin ratio ≤ 1:1, and the dispersion solution of nHCP composites has higher stability, which provides the possibility to prepare 3D porous scaffolds with nHCP for bone tissue engineering.

Formation of nano-hydroxyapatite crystal in situ in chitosan-pectin polyelectrolyte complex network

Energy Technology Data Exchange (ETDEWEB)

Li Junjie [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Research Institute of Polymeric Materials, Tianjin University, Tianjin, 300072 (China); Zhu Dunwan [Institute of Biomedical Engineering, Chinese Academy of Medical Sciences and Peking Union Medical College, Tianjin, 300072 (China); Yin Jianwei; Liu Yuxi [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Yao Fanglian, E-mail: yaofanglian@tju.edu.cn [Department of Polymer Science and Key Laboratory of Systems Bioengineering of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 (China); Yao Kangde [Research Institute of Polymeric Materials, Tianjin University, Tianjin, 300072 (China)

2010-07-20

Hydroxyapatite (HA)/polysaccharide composites have been widely used in bone tissue engineering due to their chemical similarity to natural bone. Polymer matrix-mediated synthesis of nano-hydroxyapatite is one of the simplest models for biomimetic. In this article, the nano-hydroxyapatite/chitosan-pectin (nHCP) composites were prepared through in situ mineralization of hydroxyapatite in chitosan-pectin polyelectrolyte complex (PEC) network. The formation processes of nHCP were investigated by X-ray diffraction (XRD) analysis. The interactions between nHA crystal and chitosan-pectin PEC networks were studied using Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). The morphology and structure of nHA crystal were characterized by XRD and Transmission Electron Microscope (TEM). Results suggested that the interfacial interactions between nano-hydroxyapatite crystal and chitosan-pectin PEC network assist the site specific nucleation and growth of nHA nanoparticles. The nHA crystals grow along the c-axis. In this process, pH value is the main factor to control the nucleation and growth of nHA crystal in chitosan-pectin PEC networks, because both the interactions' strength between nHA crystal and chitosan-pectin and diffusion rate of inorganic ions depend on the pH value of the reaction system. Apart from the pH value, the chitosan/pectin ratio and [Ca{sup 2+}] also take important effects on the formation of nHA crystal. An effective way to control the size of nHA crystal is to adjust the content of pectin and [Ca{sup 2+}]. It is interesting that the Zeta potential of nHCP composites is about - 30 mV when the chitosan/pectin ratio {<=} 1:1, and the dispersion solution of nHCP composites has higher stability, which provides the possibility to prepare 3D porous scaffolds with nHCP for bone tissue engineering.

Use of solid dispersions to increase stability of dithranol in topical formulations

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Marilene Estanqueiro

2014-09-01

Full Text Available The present study was planned to improve the stability of dithranol using solid dispersions (SD. Two different SD at a 1:9 ratio of dithranol/excipient were prepared: one of them using glyceryl behenate as excipient and the other using a mixture of argan oil with stearic acid (1:8 ratio as excipient. Pure dithranol and SD of dithranol were incorporated in an oil-in-water cream and in a hydrophobic ointment in a drug/dermatological base ratio of 1:10. The physical and mechanical properties of semisolid formulations incorporating the pure drug and the developed SD were evaluated through rheological and textural analysis. To evaluate the stability, L*a*b* color space parameters of SD and semisolid formulations, and pH of hydrophilic formulations were determined at defined times, during one month. Each sample was stored at different conditions namely, light exposure (room temperature, high temperature exposition (37 °C (protected from light and protected from light (room temperature. Despite higher values of firmness and adhesiveness, hydrophobic ointment exhibited the best rheological features compared to the oil-in-water cream, namely a shear-thinning behavior and high thixotropy. These formulations have also presented more stability, with minor changes in L*a*b* color space parameters. The results of this study indicate that is possible to conclude that the developed SD contributed to the increased stability of dithranol.

Acid–base interaction between carbon black and polyurethane molecules with different amine values: Dispersion stability of carbon black suspension for use in lithium ion battery cathodes

International Nuclear Information System (INIS)

Kil, Ki Chun; Kim, Gu Yeon; Cho, Chae-Woong; Lim, Myung Duk; Kim, Kijun; Jeong, Kyung-Min; Lee, Jinuk; Paik, Ungyu

2013-01-01

The dispersion properties of carbon black (CB) slurries as well as the accompanying electrochemical properties of Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 (NCM) electrodes were investigated by controlling the amine value of polyurethane-based dispersants. The increase in amine value of dispersants leads to an increase in adsorption level on CB surface due to a strong acid/base interaction between dispersants and CB particles, providing the improvement of steric repulsion between particles at the solid–liquid interface. This results in the enhancement of the dispersion stability of CB and the related microstructure of the electrodes. Electrochemical experiments indicated that the rate capabilities and cycle performance of the electrodes are in good agreement with dispersion properties of CB slurries. However, it was found that the excessive addition of the dispersant was deleterious to electrochemical properties because the non-adsorbed dispersants act as an electronic conduction barrier between solid phases. Therefore, it is suggested that the amine value of dispersant and tailored amount of dispersant addition can be key roles for obtaining the optimized dispersion stability of CB and the corresponding excellent electrochemical properties of the cathode

Effect of highly dispersed yttria addition on thermal stability of hydroxyapatite

Energy Technology Data Exchange (ETDEWEB)

Parente, P., E-mail: pparente@icv.csic.es [Instituto de Ceramica y Vidrio, CSIC, C/Kelsen 5, Madrid 28049 (Spain); Savoini, B. [Departamento de Fisica, Universidad Carlos III de Madrid, Avda. Universidad 30, Leganes 28911 (Spain); Ferrari, B. [Instituto de Ceramica y Vidrio, CSIC, C/Kelsen 5, Madrid 28049 (Spain); Monge, M.A.; Pareja, R. [Departamento de Fisica, Universidad Carlos III de Madrid, Avda. Universidad 30, Leganes 28911 (Spain); Sanchez-Herencia, A.J. [Instituto de Ceramica y Vidrio, CSIC, C/Kelsen 5, Madrid 28049 (Spain)

2013-03-01

The capability of the colloidal method to produce yttria (Y{sub 2}O{sub 3}) dispersed hydroxyapatite (HA) has been investigated as an alternative method to the conventional method of mechanical mixing and sintering for developing HA-based materials that could exhibit controllable and enhanced functional properties. A water based colloidal route to produce HA materials with highly dispersed Y{sub 2}O{sub 3} has been applied, and the effect of 10 wt.% Y{sub 2}O{sub 3} addition to HA investigated by thermal analysis, X-ray diffraction and Fourier transform infrared spectroscopy. These measurements evidence a remarkable effect of this Y{sub 2}O{sub 3} addition on decomposition mechanisms of synthetic HA. Results show that incorporation of Y{sub 2}O{sub 3} as dispersed second phase is beneficial because it hinders the decomposition mechanisms of HA into calcium phosphates. This retardation will allow the control of the sintering conditions for developing HA implants with improved properties. Besides, substitution of Ca{sup 2+} with Y{sup 3+} ions appears to promote the formation of OH{sup -} vacancies, which could improve the conductive properties of HA favorable to osseointegration. - Highlights: Black-Right-Pointing-Pointer We reveal the influence of Y{sub 2}O{sub 3} on thermal stability of hydroxyapatite. Black-Right-Pointing-Pointer Incorporation of Y{sub 2}O{sub 3} delays decomposition of hydroxyapatite to calcium phosphates. Black-Right-Pointing-Pointer Addition of Y{sub 2}O{sub 3} enables sintering conditions more favorable to the densification.

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

Science.gov (United States)

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

2002-03-01

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

Stabilization of the Peregrine soliton and Kuznetsov-Ma breathers by means of nonlinearity and dispersion management

Science.gov (United States)

Cuevas-Maraver, J.; Malomed, Boris A.; Kevrekidis, P. G.; Frantzeskakis, D. J.

2018-04-01

We demonstrate a possibility to make rogue waves (RWs) in the form of the Peregrine soliton (PS) and Kuznetsov-Ma breathers (KMBs) effectively stable objects, with the help of properly defined dispersion or nonlinearity management applied to the continuous-wave (CW) background supporting the RWs. In particular, it is found that either management scheme, if applied along the longitudinal coordinate, making the underlying nonlinear Schrödinger equation (NLSE) self-defocusing in the course of disappearance of the PS, indeed stabilizes the global solution with respect to the modulational instability of the background. In the process, additional excitations are generated, namely, dispersive shock waves and, in some cases, also a pair of slowly separating dark solitons. Further, the nonlinearity-management format, which makes the NLSE defocusing outside of a finite domain in the transverse direction, enables the stabilization of the KMBs, in the form of confined oscillating states. On the other hand, a nonlinearity-management format applied periodically along the propagation direction, creates expanding patterns featuring multiplication of KMBs through their cascading fission.

Experimental and Numerical Investigation of Effect of Air Stability on Exhaled Air Dispersion

DEFF Research Database (Denmark)

Xu, Chunwen; Gong, Guangcai; Nielsen, Peter Vilhelm

2014-01-01

studies. As the thermal stratification under displacement ventilation blocks the vertical movement of exhaled air, the exhaled contaminant may be trapped between temperature stratifications. As the dispersion of contaminant is closely related to the health of human indoors, the temperature structure...... was used for experimental study, and a numerical person was built to simulate the manikin. The velocity, temperature and concentration of tracer gas in exhaled air are affected by air stability to different degrees. The similarity of this effect among these parameters can also be observed through numerical...

Polyelectrolyte Complex Nanoparticles of Poly(ethyleneimine and Poly(acrylic acid: Preparation and Applications

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Martin Müller

2011-04-01

Full Text Available In this contribution we outline polyelectrolyte (PEL complex (PEC nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine (PEI and poly(acrylic acid (PAC. It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter of spherical PEI/PAC nanoparticles, in the range between 80–1,000 nm, in a defined way. Finally, applications of dispersed PEI/PAC particles as additives for the paper making process, as well as for drug delivery, are outlined. PEI/PAC nanoparticles mixed directly on model cellulose film showed a higher adsorption level applying the mixing order 1. PAC 2. PEI compared to 1. PEI 2. PAC. Surface bound PEI/PAC nanoparticles were found to release a model drug compound and to stay immobilized due to the contact with the aqueous release medium.

Influence of dispersing additives and blend composition on stability of marine high-viscosity fuels

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Т. Н. Митусова

2017-12-01

Full Text Available The article offers a definition of the stability of marine high-viscosity fuel from the point of view of the colloid-chemical concept of oil dispersed systems. The necessity and importance of the inclusion in the current regulatory requirements of this quality parameter of high-viscosity marine fuel is indicated. The objects of the research are high-viscosity marine fuels, the basic components of which are heavy oil residues: fuel oil that is the atmospheric residue of oil refining and viscosity breaking residue that is the product of light thermal cracking of fuel oil. As a thinning agent or distillate component, a light gas oil was taken from the catalytic cracking unit. The stability of the obtained samples was determined through the xylene equivalent index, which characterizes the stability of marine high-viscosity fuel to lamination during storage, transportation and operation processes. To improve performance, the resulting base compositions of high-viscosity marine fuels were modified by introducing small concentrations (0.05 % by weight of stabilizing additives based on oxyethylated amines of domestic origin and alkyl naphthalenes of foreign origin.

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

Science.gov (United States)

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

2017-10-01

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

Studies of Electrolytic Conductivity of Some Polyelectrolyte Solutions: Importance of the Dielectric Friction Effect at High Dilution

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Anis Ghazouani

2013-01-01

Full Text Available We present a general description of conductivity behavior of highly charged strong polyelectrolytes in dilute aqueous solutions taking into account the translational dielectric friction on the moving polyions modeled as chains of charged spheres successively bounded and surrounded by solvent molecules. A general formal limiting expression of the equivalent conductivity of these polyelectrolytes is presented in order to distinguish between two concentration regimes and to evaluate the relative interdependence between the ionic condensation effect and the dielectric friction effect, in the range of very dilute solutions for which the stretched conformation is favored. This approach is illustrated by the limiting behaviors of three polyelectrolytes (sodium heparinate, sodium chondroitin sulfate, and sodium polystyrene sulphonate characterized by different chain lengths and by different discontinuous charge distributions.

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

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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.

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

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. Copyright © 2011 Wiley Periodicals, Inc.

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

Science.gov (United States)

Manning, Gerald S

2018-05-23

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

Dispersion stability and thermophysical properties of environmentally friendly graphite oil–based nanofluids used in machining

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Yu Su

2016-01-01

Full Text Available As environmentally friendly cutting fluids, vegetable-based oil and ester oil are being more and more widely used in metal cutting industry. However, their cooling and lubricating properties are required to be further improved in order to meet more cooling and lubricating challenges in high-efficiency machining. Nanofluids with enhanced heat carrying and lubricating capabilities seem to give a promising solution. In this article, graphite oil–based nanofluids with LB2000 vegetable-based oil and PriEco6000 unsaturated polyol ester as base fluids were prepared by ultrasonically assisted two-step method, and their dispersion stability and thermophysical properties such as viscosity and thermal conductivity were experimentally and theoretically investigated at different ultrasonication times. The results indicate that graphite-PriEco6000 nanofluid showed better dispersion stability, higher viscosity, and thermal conductivity than graphite-LB2000 nanofluid, which made it more suitable for application in high-efficiency machining as coolant and lubricant. The theoretical classical models showed good agreement with the thermal conductivity values of graphite oil–based nanofluids measured experimentally. However, the deviation between the experimental values of viscosity and the theoretical models was relatively big. New empirical correlations were proposed for predicting the viscosity of graphite oil–based nanofluids at various ultrasonication times.

Red blood cells and polyelectrolyte multilayer capsules: natural carriers versus polymer-based drug delivery vehicles.

Science.gov (United States)

Kolesnikova, Tatiana A; Skirtach, Andre G; Möhwald, Helmuth

2013-01-01

Red blood cells (RBCs) and lipid-based carriers on the one hand and polymeric capsules on the other hand represent two of the most widely used carriers in drug delivery. Each class of these carriers has its own set of properties, specificity and advantages. Thorough comparative studies of such systems are reported here for the first time. In this review, RBCs are described in comparison with synthetic polymeric drug delivery vehicles using polyelectrolyte multilayer capsules as an example. Lipid-based composition of the shell in the former case is particularly attractive due to their inherent biocompatibility and flexibility of the carriers. On the other hand, synthetic approaches to fabrication of polyelectrolyte multilayer capsules permit manipulation of the permeability of their shell as well as tuning their composition, mechanical properties, release methods and targeting. In conclusion, properties of RBCs and polyelectrolyte multilayer capsules are reported here highlighting similarities and differences in their preparation and applications. In addition, their advantages and disadvantages are discussed.

Building a road map for tailoring multilayer polyelectrolyte films

International Nuclear Information System (INIS)

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

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos, and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other

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

Science.gov (United States)

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

1984-01-01

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

Chitosan/lecithin liposomal nanovesicles as an oral insulin delivery system.

Science.gov (United States)

Al-Remawi, Mayyas; Elsayed, Amani; Maghrabi, Ibrahim; Hamaidi, Mohammad; Jaber, Nisrein

2017-05-01

In the present work, insulin-chitosan polyelectrolyte complexes associated to lecithin liposomes were investigated as a new carrier for oral delivery of insulin. The preparation was characterized in terms of particle size, zeta potential and encapsulation efficiency. Surface tension measurements revealed that insulin-chitosan polyelectrolyte complexes have some degree of hydrophobicity and should be added to lecithin liposomal dispersion and not the vice versa to prevent their adsorption on the surface. Stability of insulin was enhanced when it was associated to liposomes. Significant reduction of blood glucose levels was noticed after oral administration of liposomal preparation to streptozotocin diabetic rats compared to control. The hypoglycemic activity was more prolonged compared to subcutaneously administered insulin.

Dispersion of Pt Nanoparticle-Doped Reduced Graphene Oxide Using Aniline as a Stabilizer

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Hyoung-Joon Jin

2012-12-01

Full Text Available In this study, a simple one-step method was developed to load small-sized Pt nanoparticles (3.1 ± 0.3 nm in large quantities (50 wt % on aniline-functionalized and reduced graphene oxide (r-fGO. In the process, an ethylene glycol solution and aniline-functionalized moiety play the roles of reducing agent and stabilizer for the Pt nanoparticles, respectively, without damaging the graphite structures of the r-fGO. The Pt nanoparticles loading on the surface of r-fGO with uniform dispersion have a great effect on the electrical conductivity.

Electrospinning polyelectrolyte complexes: pH-responsive fibers.

Science.gov (United States)

Boas, Mor; Gradys, Arkadiusz; Vasilyev, Gleb; Burman, Michael; Zussman, Eyal

2015-03-07

Fibers were electrospun from a solution comprised of oppositely charged polyelectrolytes, in efforts to achieve highly confined macromolecular packaging. A stoichiometric ratio of poly(allylamine hydrochloride) and poly(acrylic acid) solution was mixed in an ethanol-water co-solvent. Differential scanning calorimetry (DSC) analysis of electrospun fibers demonstrated no indication of glass transition, Tg. Infrared spectroscopy (FTIR) analysis of the fibers as a function of temperature, demonstrated an amidation process at lower temperature compared to cast film. Polarized FTIR indicated a preference of the functional groups to be perpendicular to the fiber axis. These results imply formation of mixed phase fibers with enhanced conditions for intermolecular interactions, due to the highly aligned and confined assembly of the macromolecules. The tunable intermolecular interactions between the functional groups of the polyelectrolytes, impact pH-driven, reversible swelling-deswelling of the fibers. The degree of ionization of PAA at pH 5.5 and pH 1.8 varied from 85% to 18%, correspondingly, causing transformation of ionic interactions to hydrogen bonding between the functional groups. The chemical change led to a massive water diffusion of 500% by weight and to a marked increase of 400% in fiber diameter, at a rate of 0.50 μm s(-1). These results allow for manipulation and tailoring of key fiber properties for tissue engineering, membranes, and artificial muscle applications.

The characteristic and dispersion stability of nanocellulose produced by mixed acid hydrolysis and ultrasonic assistance.

Science.gov (United States)

Niu, Fuge; Li, Mengya; Huang, Qi; Zhang, Xiuzhen; Pan, Weichun; Yang, Jiansheng; Li, Jianrong

2017-06-01

Axiolitic shape nanocellulose particles were prepared using a combined mixed acid hydrolysis and ultrasonic treatment. The crystallinity, morphology and stability properties of cellulose were characterized to investigate the mechanism of nanocellulose formation and stability. It was found the hydrodynamic radius decreased from 205nm to 89nm, and the crystallinity index of the nanocellulose increased from 62.90% to 72.31% with an increase in hydrolysis time from 2 to 10h. Sulfate esters and sulfonate group were present in the nanocellulose, and released more COH groups after hydrolysis. The ζ-potential of cellulose decreased from -11.5 to -43.8mV after 10h of hydrolysis. These results illustrated the amorphous characteristic of cellulose was removed after acid hydrolysis and ultrasonic treatment. The higher ζ-potential and relatively small cellulose particles caused a more stable suspension, suggesting that electrostatic interactions played an important role in maintaining the stability and dispersibility of the nanocellulose particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of gelation of inner dispersed phase on stability of (w1/o/w2) multiple emulsions

NARCIS (Netherlands)

Oppermann, A.K.L.; Renssen, M.; Schuch, A.; Stieger, M.A.; Scholten, E.

2015-01-01

The use of water-in-oil-in-water (w1/o/w2) multiple emulsions offers a method for the reduction of oil in foods. In this study we investigated the influence of osmotic pressure tailoring and gelation of the inner dispersed w1 water droplets on the stability and yield of multiple emulsions. Yield is

Entrapment of curcumin into monoolein-based liquid crystalline nanoparticle dispersion for enhancement of stability and anticancer activity

Directory of Open Access Journals (Sweden)

Baskaran R

2014-06-01

Full Text Available Rengarajan Baskaran,1 Thiagarajan Madheswaran,2 Pasupathi Sundaramoorthy,1 Hwan Mook Kim,1 Bong Kyu Yoo1 1College of Pharmacy, Gachon University, Incheon, South Korea; 2College of Pharmacy Yeungnam University, Gyeongsan, South Korea Abstract: Despite the promising anticancer potential of curcumin, its therapeutic application has been limited, owing to its poor solubility, bioavailability, and chemical fragility. Therefore, various formulation approaches have been attempted to address these problems. In this study, we entrapped curcumin into monoolein (MO-based liquid crystalline nanoparticles (LCNs and evaluated the physicochemical properties and anticancer activity of the LCN dispersion. The results revealed that particles in the curcumin-loaded LCN dispersion were discrete and monodispersed, and that the entrapment efficiency was almost 100%. The stability of curcumin in the dispersion was surprisingly enhanced (about 75% of the curcumin survived after 45 days of storage at 40°C, and the in vitro release of curcumin was sustained (10% or less over 15 days. Fluorescence-activated cell sorting (FACS analysis using a human colon cancer cell line (HCT116 exhibited 99.1% fluorescence gating for 5 µM curcumin-loaded LCN dispersion compared to 1.36% for the same concentration of the drug in dimethyl sulfoxide (DMSO, indicating markedly enhanced cellular uptake. Consistent with the enhanced cellular uptake of curcumin-loaded LCNs, anticancer activity and cell cycle studies demonstrated apoptosis induction when the cells were treated with the LCN dispersion; however, there was neither noticeable cell death nor significant changes in the cell cycle for the same concentration of the drug in DMSO. In conclusion, entrapping curcumin into MO-based LCNs may provide, in the future, a strategy for overcoming the hurdles associated with both the stability and cellular uptake issues of the drug in the treatment of various cancers. Keywords: liquid

Influence of water-soluble conjugated/non-conjugated polyelectrolytes on electrodeposition of nanostructured MnO{sub 2} film for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Kim, Eun-Kyung; Shrestha, Nabeen K. [Department of Chemistry, Hanyang University, Seoul 133-791 (Korea, Republic of); Lee, Wonjoo [Department of Chemistry, Hanyang University, Seoul 133-791 (Korea, Republic of); Department of Defense Ammunitions, Daeduk College, Daejeon 305-715 (Korea, Republic of); Cai, Gangri, E-mail: caigangri@naver.com [Department of Applied Chemistry, TianJin University of Technology, Tianjin 300384 (China); Department of Chemistry, Hanyang University, Seoul 133-791 (Korea, Republic of); Han, Sung-Hwan, E-mail: shhan@hanyang.ac.kr [Department of Chemistry, Hanyang University, Seoul 133-791 (Korea, Republic of)

2015-04-01

Manganese dioxide (MnO{sub 2}) thin films are deposited electrochemically on an indium–tin-oxide (ITO) electrode using aqueous bath in presence of conjugated water soluble sulfonated polyaniline (SPAN) or a non-conjugated polyacrylic acid (PAA) polyelectrolyte surfactant. The surface morphology and nature of the electrodeposited MnO{sub 2} films are found to be influenced strongly by the amount and type of polyelectrolyte in the deposition bath. Increasing the SPAN concentration, a porous structure resulting from the reduction of voids between the MnO{sub 2} nano-flakes is obtained. In contrast, by increasing the PAA concentration, dense and spherical MnO{sub 2} nanostructures have been deposited. These results may be caused by initiation of different kinetics and orientation of nucleation of MnO{sub 2} deposits on ITO surface in presence of different types of polyelectrolytes. Cyclic voltammetry study of these films shows the supercapacitor behavior. The porous MnO{sub 2} films grown from the SPAN containing electrolyte demonstrates a specific capacitance of 368.53 F/g at scan rate of 10 mV/s, which is approximately 10 times higher (i.e., 30.29 F/g) than that of the spherical MnO{sub 2} dense films grown from PAA containing electrolyte. - Highlights: • Conjugated/non-conjugated polyelectrolytes were used in deposition of MnO{sub 2}. • The two kinds of MnO{sub 2} film showed entirely different morphology. • Conjugated polyelectrolyte worked as template and also affected the growth rate. • Non-conducting polyelectrolyte could work as template but hindered MnO{sub 2} growth. • The specific capacitance of MnO{sub 2}–S was 10 times higher than MnO{sub 2}–P.

Aqueous dispersion of red clay-based ceramic powder with the addition of starch

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Maria Victoria Alcantar Umaran

2013-04-01

Full Text Available The optimum dispersion and rheological properties of red clay-based ceramic suspension loaded with unary and binary starch were investigated in aqueous medium. The aqueous ceramic suspension was prepared consisting of red clay, quartz, feldspar, and distilled water. Using a polyelectrolyte dispersant (Darvan 821A, the ternary ceramic powder was initially optimized to give the smallest average particle size at 0.8 wt. (% dispersant dosage as supported by sedimentation test. This resulted into an optimum high solid loading of 55 wt. (%. The addition of either unary or binary starches to the optimized ceramic slurry increased the viscosity but maintained an acceptable fluidity. The mechanism of such viscosity increase was found to be due to an adsorption of starch granules onto ceramic surfaces causing tolerable agglomeration. Correspondingly, the rheological evaluations showed that the flow behaviors of all starch-loaded ceramic slurries can be described using Herschel-Bulkley model. The parameters from this model indicated that all ceramic slurries loaded with starch are shear thinning that is required for direct casting process.

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

Science.gov (United States)

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

2016-12-01

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

Layer-by-Layer Assembly of Polyelectrolyte Multilayer onto PET Fabric for Highly Tunable Dyeing with Water Soluble Dyestuffs

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Shili Xiao

2017-12-01

Full Text Available Poly(ethyleneterephthalate (PET is a multi-purpose and widely used synthetic polymer in many industrial fields because of its remarkable advantages such as low cost, light weight, high toughness and resistance to chemicals, and high abrasion resistance. However, PET suffers from poor dyeability due to its non-polar nature, benzene ring structure as well as high crystallinity. In this study, PET fabrics were firstly treated with an alkaline solution to produce carboxylic acid functional groups on the surface of the PET fabric, and then was modified by polyelectrolyte polymer through the electrostatic layer-by-layer self-assembly technology. The polyelectrolyte multilayer-deposited PET fabric was characterized using scanning electron microscopy SEM, contact angle, Fourier transform infrared (FTIR and X-ray photoelectron spectroscopy (XPS. The dyeability of PET fabrics before and after surface modification was systematically investigated. It showed that the dye-uptake of the polyelectrolyte multilayer-deposited PET fabric has been enhanced compared to that of the pristine PET fabric. In addition, its dyeability is strongly dependent on the surface property of the polyelectrolyte multilayer-deposited PET fabric and the properties of dyestuffs.

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

Science.gov (United States)

Nejati Moshtaghin, Mahboubeh

The focus of this thesis is to achieve a better understanding of the newly discovered surfactant-polyelectrolyte complex coacervate (SPCC) systems induced by fluoroalcohol/acid as well as short chain aliphatic alcohol; and to elucidate their applications in extraction and enrichment of proteins and enzyme. We have discovered that fluoroalcohols and --acids induce complex coacervation and phase separation in the aqueous mixtures of oppositely charged anionic polyelectrolytes; specifically, sodium salts of polyacrylic acid and polymethacrylic acid and cationic surfactant (cetyltrimethylammonium bromide, CTAB) over a broad range of concentrations of mole fractions of the oppositely charged amphiphiles. Accordingly, these new classes of coacervators will significantly broaden the scope and facilitate engineering of new coacervate phases. Toward these goals, we have inspected the formation of surfactant-polyelectrolyte complex coacervates in the presence of fluoroalcohols namely hexafluoroisopropanol (HFIP) and Trifluoroethanol (TFE). Furthermore, the extent of coacervation as a function of concentrations the system components, and charge ratios of the oppositely charged amphiphiles has been investigated. Polyelectrolytes are considered to be milder reagents, as compared to surfactants, regarding proteins denaturation. This highlights the importance of a detailed investigation of the efficiency of our coacervate systems for extraction and preconcentration of proteins and enzymes, especially, when the biological activity of the extracted proteins needs to be maintained based on the objectives mentioned above, the results of the investigations have been organized in four chapters. In Chapter II, the phase behavior of the FA-SPCC will be investigated. The objective is to examine the phase behavior and phase properties with respect to the extent of coacervation in different solution conditions. In particular, the effects of different solution variables such as concentration

Enzyme-polyelectrolyte complexes in water-ethanol mixtures: negatively charged groups artificially introduced into alpha-chymotrypsin provide additional activation and stabilization effects.

Science.gov (United States)

Kudryashova, E V; Gladilin, A K; Vakurov, A V; Heitz, F; Levashov, A V; Mozhaev, V V

1997-07-20

Formation of noncovalent complexes between alpha-chymotrypsin (CT) and a polyelectrolyte, polybrene (PB), has been shown to produce two major effects on enzymatic reactions in binary mixtures of polar organic cosolvents with water. (i) At moderate concentrations of organic cosolvents (10% to 30% v/v), enzymatic activity of CT is higher than in aqueous solutions, and this activation effect is more significant for CT in complex with PB (5- to 7-fold) than for free enzyme (1.5- to 2.5-fold). (ii) The range of cosolvent concentrations that the enzyme tolerates without complete loss of catalytic activity is much broader. For enhancement of enzyme stability in the complex with the polycation, the number of negatively charged groups in the protein has been artificially increased by using chemical modification with pyromellitic and succinic anhydrides. Additional activation effect at moderate concentrations of ethanol and enhanced resistance of the enzyme toward inactivation at high concentrations of the organic solvent have been observed for the modified preparations of CT in the complex with PB as compared with an analogous complex of the native enzyme. Structural changes behind alterations in enzyme activity in water-ethanol mixtures have been studied by the method of circular dichroism (CD). Protein conformation of all CT preparations has not changed significantly up to 30% v/v of ethanol where activation effects in enzymatic catalysis were most pronounced. At higher concentrations of ethanol, structural changes in the protein have been observed for different forms of CT that were well correlated with a decrease in enzymatic activity. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 267-277, 1997.

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

Energy Technology Data Exchange (ETDEWEB)

Talukdar, Hrishikesh [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati 781035, Assam (India); Kundu, Sarathi, E-mail: sarathi.kundu@gmail.com [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati 781035, Assam (India); Basu, Saibal [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

2016-09-30

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

IPEC Gels for Remediating Soils Contaminated as Result of Nuclear and Industrial Activities

International Nuclear Information System (INIS)

Mikheykin, S.V.; Anciferova, E.Yu.; Simonov, V.P.; Zezin, A.B.; Rogacheva, V.B.; Bolusheva, T.N.

2006-01-01

Under International Scientific and Technological Center (ISTC, Moscow) Project no. 1567 the Moscow research team in collaboration with Los Alamos National Laboratory developed and tested new kind of inter-polyelectrolyte complexes with micro-gel (IPECs) for soil surface stabilization, prevention of radioactive contamination distribution with wind and water streams and for site remediation using mixtures of new water-soluble polymers with seeding grasses. Evidently, the most important factor responsible for the effectiveness of a polymeric aggregator is the ratio of the size of poly-complex particles to that of dispersion particles being aggregated. The particle size of IPEC produced of a pair of linear oppositely charged poly-electrolytes is usually fractions of a micron. Such a particle can fix only small aggregates (∼10 μm and less). One of the ways of improving poly-complex aggregators is to use loose cross-linked poly-electrolytic gels as an IPEC component. When generating/dispersing these poly-electrolytic gels, particles of specified sizes can be produced. These poly-electrolytic micro-gels introduced into soil save moisture, what is important for arid sites. Wind erosion was studied as a function of soil physical-chemical properties and the air stream velocity. A laboratory wind tunnel instrumented to follow the process on a real-time basis was used for our study. Polymer-treated samples show a high wind erosion resistance in the wind velocity range up to 40 m/s. The micro-gel dispersion MGD-2 was injected in combination with MLA-1 in the experiments with water flow - water erosion resistance. With an increase in the water-polymer solution application rate from 2.0 to 4.0 l/m 2 the soil resistance to eroding water streams with velocity of 55 cm/s (2.0 l/m 2 ) and at 70.0 cm/s with 4.0 l/m 2 . Based on the classification of soils by erosion resistance, soils eroded with a water stream 1 cm high at a velocity of 50 cm/s are considered to be highly erosion

Melt dispersion of thermoplastic polystyrene in polymer polyols

OpenAIRE

2009-01-01

Polystyrene is dispersed into a polyol via a mechanical dispersion process. A stabilizer is present to stabilize the dispersed polymer particles. The stabilizer includes a copolymer of (1) from 10 to 70% by weight of a branched polyol which has a molecular weight of from 4000 to 20,000, from 0.2 to about 1.2 polymerizable ethylenically unsaturated groups per molecule and from about 3 to about 8 hydroxyl groups per molecule with (2) from 30 to 90% by weight of styrene or a mixture of styrene a...

Insulin-egg yolk dispersions in self microemulsifying system.

Science.gov (United States)

Singnurkar, P S; Gidwani, S K

2008-11-01

Formulation of insulin into a microemulsion very often presents a physicochemical instability during their preparation and storage. In order to overcome this lack of stability and facilitate the handling of these colloidal systems, stabilization of insulin in presence of hydrophobic components of a microemulsion appears as the most promising strategy. The present paper reports the use of egg yolk for stabilization of insulin in self microemulsifying dispersions. Insulin loaded egg yolk self microemulsifying dispersions were prepared by lyophilization followed by dispersion into self microemulsifying vehicle. The physicochemical characterization of selfmicroemulsifying dispersions includes such as insulin encapsulation efficiency, in vitro stability of insulin in presence of proteolytic enzymes and in vitro release. The biological activity of insulin from the dispersion was estimated by enzyme-linked immunosorbant assay and in vivo using Wistar diabetic rats. The particle size ranged 1.023±0.316 μm in diameter and insulin encapsulation efficiency was 98.2±0.9 %. Insulin hydrophobic self microemulsifying dispersions suppressed insulin release in pH 7.4 phosphate buffer and shown to protect insulin from enzymatic degradation in vitro in presence of chymotripsin. Egg yolk encapsulated insulin was bioactive, demonstrated through both in vivo and in vitro.

Low-shear rheology and sedimentation stability of coal-oil dispersions

Energy Technology Data Exchange (ETDEWEB)

Rutter, P. R.; Davies, J. M.; Jones, T. E.R.

1984-10-15

Stable coal-oil mixtures can be prepared by grinding coal particles in fuel oil. These products have been prepared by the British Petroleum Company plc and are referred to as Coal-Oil Dispersions (COD). One of the major problems associated with the production of DOD is the rapid assessment of the length of time the coal particles are likely to remain in suspension under a particular set of storage conditions. This paper describes a number of measurements of the low-shear rheology and sedimentation stability of a series of CODs prepared by grinding two types of coal in two different fuel oils. The results suggest that two types of COD are possible. One type exhibits complex rheological properties at low shear rates and does not produce a coal sediment, even after prolonged storage at 80/sup 0/C under dynamic conditions. The other exhibits near Newtonian behaviour and appears to form a sedimented layer of coal during storage.

Facile hydrothermal method for synthesizing nitrogen-doped graphene nanoplatelets using aqueous ammonia: dispersion, stability in solvents and thermophysical performances

Science.gov (United States)

Shafiah Shazali, Siti; Amiri, Ahmad; Zubir, Mohd. Nashrul Mohd; Rozali, Shaifulazuar; Zakuan Zabri, Mohd; Sabri, Mohd Faizul Mohd

2018-03-01

A simple and green approach has been developed to synthesize nitrogen-doped graphene nanoplatelets (N-doped GNPs) for mass production with a very high stability in different solvents e.g. water, ethylene glycol, methanol, ethanol, and 1-hexanol. The strategy is based on mild oxidation of GNPs using hydrogen peroxide and doping with nitrogen using hydrothermal process. The modification of N-doped GNPs was demonstrated by FTIR, TGA, XPS, Raman spectroscopy and high resolution-transmission electron microscope (HRTEM). Further study was carried out by using N-doped GNPs as an additive to prepare different colloidal dispersions. Water-based N-doped GNPs, methanol-based N-doped GNPs, ethanol-based N-doped GNPs, ethylene-glycol based N-doped GNPs and 1-hexanol-based N-doped GNPs dispersions at 0.01 wt.% shown great colloidal stabilities, indicating 17%, 29%, 33%, 18%, and 43% sedimentations after a 15-days period, respectively. The thermophysical properties e.g., viscosity and thermal conductivity of water-based N-doped GNP nanofluids were also evaluated for different weight concentrations of 0.100, 0.075, 0.050, and 0.025 wt.%. Through this, it is found that the obtained dispersions have great potential to be used as working fluids for industrial thermal systems.

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

Science.gov (United States)

Carnal, Fabrice; Stoll, Serge

2011-01-01

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

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.

Enhanced Cycling Stability of Lithium–Sulfur batteries by Electrostatic-Interaction

International Nuclear Information System (INIS)

Ma, Zhaoling; Huang, Xiaobing; Jiang, Qianqian; Huo, Jia; Wang, Shuangyin

2015-01-01

Highlights: • Electrostatic interaction is utilized to hinder the shuttling of polysulfides. • Directly functionalizing SG can better prolong the cycle life of Li–S batteries. • SG/PDDA showed significantly improved capacity retention. - Abstract: Lithiums–sulfur battery is considered as one of the most promising energy storage devices to replace the current Li ion batteries because of its high theoretical capacity of 1675 mA h g −1 . However, the poor cycle stability hinders the further development of this battery system. In order to improve the stability of Li–S batteries, the diffusion of polysulfides from electrodes into electrolyte should be suppressed. Herein, we utilize a positively charged polyelectrolyte to functionalize the electrode materials with the aim to hamper the polysulfides dissolution via electrostatic interaction between strong positively charged polyelectrolyte and negatively charged polysulfides anion. The effect of the functionalization quantity of poly(diallyl dimethylammonium) chloride (PDDA) and functionalization sequence on cycling performances is investigated in detail. It is found that the sulfur–graphene composite (SG) directly functionalized with 10 times PDDA exhibited best cycling stability. At a discharge current density of 0.2 C, much higher capacity retention was realized on the functionalized electrodes than the unfunctionalized (81% vs. 47.3%) after 120 cycles. The as-observed results demonstrate that the electrostatic interaction can effectively prolong the cycling life of Li–S batteries, which provides a new promising strategy for improving the electrochemical performance of Li–S batteries.

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

Science.gov (United States)

Kremer, Kurt

1996-03-01

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

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.

Preparation of Acrylamide-based Anionic Polyelectrolytes for Soil Establishment

Directory of Open Access Journals (Sweden)

Ahmad Rabiee

2012-12-01

Full Text Available Synthetic water soluble acrylamide-based polymers have wide range of ap-plications  in  the  feld  of  soil  establishment  and  non-desertifcation.  In  this research, the acrylamide-based anionic polyelectrolytes were prepared by  solution polymerization. The polymerization was carried out using AIBN as a radical initiator and at different degrees of anionic charges ranging between 10% and 30% using sodium hydroxide as hydrolyzing agents. The chemical structure of the  synthetic polymers was studied and confrmed by FTIR technique. The charge density on polymer backbone was determined by titration method. The rheological behavior of polymer solutions was evaluated by Brookfeld viscometer. The results show that the viscosity decreases with increasing the shear rate of solutions. Molecular weights of samples were measured by laser light scattering analyzer. The morphology of the polymer was studied by SEM and the EDX was used for elemental analysis determination. The anionic polymers with 10-30% negative charges were mixed with clay in order to evaluate the soil establishment. The results show that an anionic polyelectro-lyte can make soil particles more cohesive and improve soil physical properties.

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

Science.gov (United States)

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

2007-03-27

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

RECG maintains plastid and mitochondrial genome stability by suppressing extensive recombination between short dispersed repeats.

Directory of Open Access Journals (Sweden)

Masaki Odahara

2015-03-01

Full Text Available Maintenance of plastid and mitochondrial genome stability is crucial for photosynthesis and respiration, respectively. Recently, we have reported that RECA1 maintains mitochondrial genome stability by suppressing gross rearrangements induced by aberrant recombination between short dispersed repeats in the moss Physcomitrella patens. In this study, we studied a newly identified P. patens homolog of bacterial RecG helicase, RECG, some of which is localized in both plastid and mitochondrial nucleoids. RECG partially complements recG deficiency in Escherichia coli cells. A knockout (KO mutation of RECG caused characteristic phenotypes including growth delay and developmental and mitochondrial defects, which are similar to those of the RECA1 KO mutant. The RECG KO cells showed heterogeneity in these phenotypes. Analyses of RECG KO plants showed that mitochondrial genome was destabilized due to a recombination between 8-79 bp repeats and the pattern of the recombination partly differed from that observed in the RECA1 KO mutants. The mitochondrial DNA (mtDNA instability was greater in severe phenotypic RECG KO cells than that in mild phenotypic ones. This result suggests that mitochondrial genomic instability is responsible for the defective phenotypes of RECG KO plants. Some of the induced recombination caused efficient genomic rearrangements in RECG KO mitochondria. Such loci were sometimes associated with a decrease in the levels of normal mtDNA and significant decrease in the number of transcripts derived from the loci. In addition, the RECG KO mutation caused remarkable plastid abnormalities and induced recombination between short repeats (12-63 bp in the plastid DNA. These results suggest that RECG plays a role in the maintenance of both plastid and mitochondrial genome stability by suppressing aberrant recombination between dispersed short repeats; this role is crucial for plastid and mitochondrial functions.

Release of polyanions from polyelectrolyte complexes by selective degradation of the polycation

Czech Academy of Sciences Publication Activity Database

Etrych, Tomáš; Boustta, M.; Leclercq, L.; Vert, M.

2006-01-01

Roč. 21, č. 2 (2006), s. 89-105 ISSN 0883-9115 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyelectrolyte complex * enzymatic degradation * hydrolytic degradation Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.925, year: 2006

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

International Nuclear Information System (INIS)

Qin Haixia; Liu Jiyang; Chen Chaogui; Wang Jiahi; Wang Erkang

2012-01-01

Highlights: ► An electrochemical aptasensor for selective detection of peptide is constructed. ► This aptasensor is based on grapheme multilayer via layer-by-layer assembly. ► 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 −1 and a wide detection range from 1 to 265 ng mL −1 .

Kinetics of electrically and chemically induced swelling in polyelectrolyte gels

Science.gov (United States)

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

1990-09-01

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

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

Science.gov (United States)

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

2013-07-16

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

Electrostatic Swelling and Conformational Variation Observed in High-Generation Polyelectrolyte Dendrimers

International Nuclear Information System (INIS)

Butler, Paul D.; Chen, Wei-Ren; Herwig, Kenneth W.; Hong, Kunlun; Liu, Yun; Porcar, L.; Shew, Chwen-Yang; Smith, Gregory Scott; Chen, Hsin-Lung; Chen, Chun-Yu; Li, Xin; Liu, Emily

2010-01-01

A coordinated study combining small angle neutron scattering (SANS) and small angle x-ray scattering (SAXS) measurements was conducted to investigate the structural characteristics of aqueous (D2O) generation 7 and 8 (G7 and G8) PAMAM dendrimer solutions as a function of molecular protonation at room temperature. The change in intra-molecular conformation was clearly exhibited in the data analysis by separating the variation in the inter-molecular correlation. Our results unambiguously demonstrate an increased molecular size and evolved intra-molecular density profile upon increasing the molecular protonation. This is contrary to the existing understanding that in higher generation polyelectrolyte dendrimers, steric crowding stiffens the local motion of dendrimer segments exploring additional available intra-dendrimer volume and therefore inhibits the electrostatic swelling. Our observation is relevant to elucidation of the general microscopic picture of polyelectrolyte dendrimer structure, as well as the development of dendrimer-based packages with based on the stimuli-responsive principle.

Colloidal Stability of Gold Nanoparticles Coated with Multithiol-Poly(ethylene glycol) Ligands: Importance of Structural Constraints of the Sulfur Anchoring Groups

Science.gov (United States)

2013-08-13

order: monothiol < flexible dithiol < constrained dithiol < disulfide. The present study indicates that the colloidal stability of thiolated ligand...protein/ polymer - negatively charged AuNP) and hydrophobic adsorption (hydrophobic protein pockets - AuNP).1, 20 Each mechanism will also be...colloidal stability has been significantly improved by preparing a relatively thicker shell with polymers or polyelectrolytes such as poly(N-vinyl-2

Stability and generalization in seed dispersal networks: a case study of frugivorous fish in Neotropical wetlands.

Science.gov (United States)

Correa, Sandra Bibiana; Arujo, Joisiane K; Penha, Jerry; Nunes da Cunha, Catia; Bobier, Karen E; Anderson, Jill T

2016-08-31

When species within guilds perform similar ecological roles, functional redundancy can buffer ecosystems against species loss. Using data on the frequency of interactions between fish and fruit, we assessed whether co-occurring frugivores provide redundant seed dispersal services in three species-rich Neotropical wetlands. Our study revealed that frugivorous fishes have generalized diets; however, large-bodied fishes had greater seed dispersal breadth than small species, in some cases, providing seed dispersal services not achieved by smaller fish species. As overfishing disproportionately affects big fishes, the extirpation of these species could cause larger secondary extinctions of plant species than the loss of small specialist frugivores. To evaluate the consequences of frugivore specialization for network stability, we extracted data from 39 published seed dispersal networks of frugivorous birds, mammals and fish (our networks) across ecosystems. Our analysis of interaction frequencies revealed low frugivore specialization and lower nestedness than analyses based on binary data (presence-absence of interactions). In that case, ecosystems may be resilient to loss of any given frugivore. However, robustness to frugivore extinction declines with specialization, such that networks composed primarily of specialist frugivores are highly susceptible to the loss of generalists. In contrast with analyses of binary data, recently developed algorithms capable of modelling interaction strengths provide opportunities to enhance our understanding of complex ecological networks by accounting for heterogeneity of frugivore-fruit interactions. © 2016 The Author(s).

Dynamics of complexation of a charged dendrimer by linear polyelectrolyte: Computer modelling

NARCIS (Netherlands)

Lyulin, S.V.; Darinskii, A.A.; Lyulin, A.V.

2007-01-01

Brownian-dynamics simulations have been performed for complexes formed by a charged dendrimer and a long oppositely charged linear polyelectrolyte when overcharging phenomenon is always observed. After a complex formation the orientational mobility of the individual dendrimer bonds, the fluctuations

A magnetic relaxation study on anisotropic reorientation in aqueous polyelectrolyte solutions

International Nuclear Information System (INIS)

Mulder, C.W.R.

1984-01-01

The present thesis proposes a study on anisotropic reorientation of aqueous polyelectrolyte solutions. In particular, it is directed to the question to what extent information may be obtained on anisotropic reorientation by nuclear magnetic relaxation experiments. The polymethacrylic acid/water system has been chosen as probe system. (Auth.)

Structure and Stability of Molecular Crystals with Many-Body Dispersion-Inclusive Density Functional Tight Binding.

Science.gov (United States)

Mortazavi, Majid; Brandenburg, Jan Gerit; Maurer, Reinhard J; Tkatchenko, Alexandre

2018-01-18

Accurate prediction of structure and stability of molecular crystals is crucial in materials science and requires reliable modeling of long-range dispersion interactions. Semiempirical electronic structure methods are computationally more efficient than their ab initio counterparts, allowing structure sampling with significant speedups. We combine the Tkatchenko-Scheffler van der Waals method (TS) and the many-body dispersion method (MBD) with third-order density functional tight-binding (DFTB3) via a charge population-based method. We find an overall good performance for the X23 benchmark database of molecular crystals, despite an underestimation of crystal volume that can be traced to the DFTB parametrization. We achieve accurate lattice energy predictions with DFT+MBD energetics on top of vdW-inclusive DFTB3 structures, resulting in a speedup of up to 3000 times compared with a full DFT treatment. This suggests that vdW-inclusive DFTB3 can serve as a viable structural prescreening tool in crystal structure prediction.

Preparation and electrochemical properties of gold nanoparticles containing carbon nanotubes-polyelectrolyte multilayer thin films

International Nuclear Information System (INIS)

Yu Aimin; Zhang Xing; Zhang Haili; Han, Deyan; Knight, Allan R.

2011-01-01

Highlights: → Gold nanoparticles containing carbon nanotubes-polyelectrolyte multilayer thin films were prepared via layer-by-layer self-assembly technique. → The electron transfer behaviour of the hybrid thin films were investigated using an electrochemical probe. → The resulting thin films exhibited an electrocatalytic activity towards the oxidation of nitric oxide. - Abstract: Multi-walled carbon nanotubes (MWCNT)/polyelectrolyte (PE) hybrid thin films were fabricated by alternatively depositing negatively charged MWCNT and positively charged (diallyldimethylammonium chloride) (PDDA) via layer-by-layer (LbL) assembly technique. The stepwise growth of the multilayer films of MWCNT and PDDA was characterized by UV-vis spectroscopy. Scanning electron microscopy (SEM) images indicated that the MWCNT were uniformly embedded in the film to form a network and the coverage density of MWCNT increased with layer number. Au nanoparticles (NPs) could be further adsorbed onto the film to form PE/MWCNT/Au NPs composite films. The electron transfer behaviour of multilayer films with different compositions were studied by cyclic voltammetry using [Fe(CN) 6 ] 3-/4- as an electrochemical probe. The results indicated that the incorporation of MWCNT and Au NPs not only greatly improved the electronic conductivity of pure polyelectrolyte films, but also provided excellent electrocatalytic activity towards the oxidation of nitric oxide (NO).

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

Science.gov (United States)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-03-01

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

Electrochemical metal speciation in natural and model polyelectrolyte systems

OpenAIRE

Hoop, van den, M.A.G.T.

1994-01-01

The purpose of the research described in this thesis was to examine the applicability of electro-analytical techniques in obtaining information on the speciation of metals, i.e. their distribution over different physico-chemical forms, in aquatic systems containing charged macromolecules. In chapter 1 a general introduction is given to (i) metal speciation in aquatic systems, (ii) (bio)polyelectrolytes and their counterion distributions and (iii) electrochemical ...

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

Science.gov (United States)

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Polythiophene-based conjugated polyelectrolyte: Optical properties and association behavior in solution

Czech Academy of Sciences Publication Activity Database

Urbánek, P.; di Martino, A.; Gladyš, S.; Kuřitka, I.; Minařík, A.; Pavlova, Ewa; Bondarev, D.

2015-01-01

Roč. 202, April (2015), s. 16-24 ISSN 0379-6779 R&D Projects: GA TA ČR(CZ) TE01020118; GA ČR GAP108/12/1143 Institutional support: RVO:61389013 Keywords : polyelectrolyte * conjugated polymer * UV–vis spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.299, year: 2015

Effect of enzyme location on activity and stability of trypsin and urease immobilized on porous membranes by using layer-by-layer self-assembly of polyelectrolyte

OpenAIRE

Guedidi, Sadika; Yürekli, Yılmaz; Deratani, André; Déjardin, Philippe; Innocent, Christophe; Altınkaya, Sacide; Roudesli, Sadok; Yemenicioğlu, Ahmet

2010-01-01

The layer-by-layer (LbL) self-assembly of polyelectrolyte is one of the simplest ways to immobilize enzyme on membrane. In this paper, the immobilization of trypsin (TRY) and urease (URE) on polyacrylonitrile based membranes using the LbL assembly technique was presented. The studied systems consisted in bilayered assemblies with the enzyme layer as the outer layer and trilayered assemblies with the enzyme layer as the inner sandwiched layer. The membrane pore size was chosen so that the smal...

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

Science.gov (United States)

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

2015-01-08

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

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

Science.gov (United States)

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

2018-01-24

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

Effect of Graphene-EC on Ag NW-Based Transparent Film Heaters: Optimizing the Stability and Heat Dispersion of Films.

Science.gov (United States)

Cao, Minghui; Wang, Minqiang; Li, Le; Qiu, Hengwei; Yang, Zhi

2018-01-10

To optimize the performance of silver nanowire (Ag NW) film heaters and explore the effect of graphene on a film, we introduced poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) and graphene modified with ethyl cellulose (graphene-EC) into the film. The high-quality and well-dispersed graphene-EC was synthesized from graphene obtained by electrochemical exfoliation as a precursor. The transparent film heaters were fabricated via spin-coating. With the assistance of graphene-EC, the stability of film heaters was greatly improved, and the conductivity was optimized by adjusting the Ag NW concentration. The film heaters exhibited a fast and accurate response to voltage, accompanied by excellent environmental endurance, and there was no significant performance degradation after being operated for a long period of time. These results indicate that graphene-EC plays a crucial role in optimizing film stability and heat dispersion in the film. The Ag NW/PEDOT:PSS-doped graphene-EC film heaters show a great potential in low-cost indium-tin-oxide-free flexible transparent electrodes, heating systems, and transparent film heaters.

Polyelectrolyte multilayer film-assisted formation of zero-valent iron nanoparticles onto polymer nanofibrous mats

International Nuclear Information System (INIS)

Xiao Shili; Shi Xiangyang; Wu Siqi; Shen Mingwu; Guo Rui; Wang Shanyuan

2009-01-01

A facile approach that combines the electrospinning technique and layer-by-layer (LbL) assembly method has been developed to synthesize and immobilize zero-valent iron nanoparticles (ZVI NPs) onto the surface of nanofibers for potential environmental applications. In this approach, negatively charged cellulose acetate (CA) nanofibers fabricated by electrospinning CA solution were modified with bilayers composed of positively charged poly(diallyl-dimethyl-ammoniumchloride) (PDADMAC) and negatively charged poly(acrylic acid) (PAA) through electrostatic LbL assembly approach to form composite nanofibrous mats. The composite nanofibrous mats were immersed into the ferrous iron solution to allow Fe(II) ions to complex with the free carboxyl groups of PAA, and then ZVI NPs were immobilized onto the composite nanofibrous mats instantly by reducing the ferrous cations. Combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and thermogravimetry analysis demonstrated that the ZVI NPs are successfully synthesized and uniformly distributed into the polyelectrolyte (PE) multilayer films assembled onto the CA nanofibers. The present approach to synthesis ZVI NPs opens a new avenue to fabricating various materials with high surface area for environmental, catalytic, and sensing applications.

Aqueous Dispersions of Silica Stabilized with Oleic Acid Obtained by Green Chemistry.

Science.gov (United States)

Nistor, Cristina Lavinia; Ianchis, Raluca; Ghiurea, Marius; Nicolae, Cristian-Andi; Spataru, Catalin-Ilie; Culita, Daniela Cristina; Pandele Cusu, Jeanina; Fruth, Victor; Oancea, Florin; Donescu, Dan

2016-01-05

The present study describes for the first time the synthesis of silica nanoparticles starting from sodium silicate and oleic acid (OLA). The interactions between OLA and sodium silicate require an optimal OLA/OLANa molar ratio able to generate vesicles that can stabilize silica particles obtained by the sol-gel process of sodium silicate. The optimal molar ratio of OLA/OLANa can be ensured by a proper selection of OLA and respectively of sodium silicate concentration. The titration of sodium silicate with OLA revealed a stabilization phenomenon of silica/OLA vesicles and the dependence between their average size and reagent's molar ratio. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) measurements emphasized the successful synthesis of silica nanoparticles starting from renewable materials, in mild condition of green chemistry. By grafting octadecyltrimethoxysilane on the initial silica particles, an increased interaction between silica particles and the OLA/OLANa complex was achieved. This interaction between the oleyl and octadecyl chains resulted in the formation of stable gel-like aqueous systems. Subsequently, olive oil and an oleophylic red dye were solubilized in these stable aqueous systems. This great dispersing capacity of oleosoluble compounds opens new perspectives for future green chemistry applications. After the removal of water and of the organic chains by thermal treatment, mesoporous silica was obtained.

Hydrogen bond network relaxation in aqueous polyelectrolyte solutions: the effect of temperature

International Nuclear Information System (INIS)

Sarti, S; Bordi, F; Truzzolillo, D

2012-01-01

Dielectric spectroscopy data over the range 100 MHz-40 GHz allow for a reliable analysis of two of the major relaxation phenomena for polyelectrolytes (PE) in water. Within this range, the dielectric relaxation of pure water is dominated by a near-Debye process at ν = 18.5 GHz corresponding to a relaxation time of τ = 8.4 ps at 25 °C. This mode is commonly attributed to the cooperative relaxation specific to liquids forming a hydrogen bond network (HBN) and arising from long range H-bond-mediated dipole-dipole interactions. The presence of charged polymers in water partially modifies the dielectric characteristics of the orientational water molecule relaxation due to a change of the dielectric constant of water surrounding the charges on the polyion chain. We report experimental results on the effect of the presence of a standard flexible polyelectrolyte (sodium polyacrylate) on the HBN relaxation in water for different temperatures, showing that the HBN relaxation time does not change by increasing the polyelectrolyte density in water, even if relatively high concentrations are reached (0.02 monomol l -1 ≤ C ≤ 0.4 monomol l -1 ). We also find that the effect of PE addition on the HBN relaxation is not even a broadening of its distribution, rather a decrease of the spectral weight that goes beyond the pure volume fraction effect. This extra decrease is larger at low T and less evident at high T, supporting the idea that the correlation length of the water is less affected by the presence of charged flexible chains at high temperatures. (paper)

Investigation of polyelectrolyte desorption by single molecule force spectroscopy

International Nuclear Information System (INIS)

Friedsam, C; Seitz, M; Gaub, H E

2004-01-01

Single molecule force spectroscopy has evolved into a powerful method for the investigation of intra- and intermolecular interactions at the level of individual molecules. Many examples, including the investigation of the dynamic properties of complex biological systems as well as the properties of covalent bonds or intermolecular transitions within individual polymers, are reported in the literature. The technique has recently been extended to the systematic investigation of desorption processes of individual polyelectrolyte molecules adsorbed on generic surfaces. The stable covalent attachment of polyelectrolyte molecules to the AFM-tip provides the possibility of performing long-term measurements with the same set of molecules and therefore allows the in situ observation of the impact of environmental changes on the adsorption behaviour of individual molecules. Different types of interactions, e.g. electrostatic or hydrophobic interactions, that determine the adsorption process could be identified and characterized. The experiments provided valuable details that help to understand the nature and the properties of non-covalent interactions, which is helpful with regard to biological systems as well as for technical applications. Apart from this, desorption experiments can be utilized to characterize the properties of surfaces or polymer coatings. Therefore they represent a versatile tool that can be further developed in terms of various aspects

Molecular Dynamics Simulation of Salt Diffusion in Polyelectrolyte Assemblies.

Science.gov (United States)

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

2018-06-05

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

Aspectos da Reologia e da Estabilidade de Suspensões Cerâmicas. Parte III: Mecanismo de Estabilização Eletroestérica de Suspensões com Alumina Aspects of Rheology and Stability of Ceramic Suspensions. Part III: Electrosteric Stabilization Mechanism of Alumina Suspensions

Directory of Open Access Journals (Sweden)

F. S. Ortega

1997-08-01

deflocculants used to afford such dispersion mechanism cover a specific kind of polymer, named polyelectrolytes, which are macromolecules that are ionizable in solution. The study of how the polyelectrolytes behave is justified due to the large use of this polymeric product in the ceramic industry. Polyacrylic acid (PAA and polymethacrylic acid (PMAA are examples of polyelectrolytes that are widely used in the processing of alumina based materials. The medium pH and ion concentration are strengthened, and the importance of the ionic strength is emphasized. As a practical application, the stability of alumina-PMAA system is presented. The viscosity and dispersion behaviour of the suspension are also reported. This study is concluded presenting results concerning the effect of molecular weigth on the suspension viscosity, and shows that it is not enough to select a polymer considering just its class. It is fundamental to specify the average molecular weight of the selected polymer.

Colloidal micro- and nano-particles as templates for polyelectrolyte multilayer capsules.

Science.gov (United States)

Parakhonskiy, Bogdan V; Yashchenok, Alexey M; Konrad, Manfred; Skirtach, Andre G

2014-05-01

Colloidal particles play an important role in various areas of material and pharmaceutical sciences, biotechnology, and biomedicine. In this overview we describe micro- and nano-particles used for the preparation of polyelectrolyte multilayer capsules and as drug delivery vehicles. An essential feature of polyelectrolyte multilayer capsule preparations is the ability to adsorb polymeric layers onto colloidal particles or templates followed by dissolution of these templates. The choice of the template is determined by various physico-chemical conditions: solvent needed for dissolution, porosity, aggregation tendency, as well as release of materials from capsules. Historically, the first templates were based on melamine formaldehyde, later evolving towards more elaborate materials such as silica and calcium carbonate. Their advantages and disadvantages are discussed here in comparison to non-particulate templates such as red blood cells. Further steps in this area include development of anisotropic particles, which themselves can serve as delivery carriers. We provide insights into application of particles as drug delivery carriers in comparison to microcapsules templated on them. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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

2017-11-29

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

SANS observations on weakly flocculated dispersions

DEFF Research Database (Denmark)

Mischenko, N.; Ourieva, G.; Mortensen, K.

1997-01-01

Structural changes occurring in colloidal dispersions of poly-(methyl metacrylate) (PMMA) particles, sterically stabilized with poly-(12-hydroxystearic acid) (PHSA), while varying the solvent quality, temperature and shear rate, are investigated by small-angle neutron scattering (SANS......). For a moderately concentrated dispersion in a marginal solvent the transition on cooling from the effective stability to a weak attraction is monitored, The degree of attraction is determined in the framework of the sticky spheres model (SSM), SANS and rheological results are correlated....

Improving the Efficiency of a Coagulation-Flocculation Wastewater Treatment of the Semiconductor Industry through Zeta Potential Measurements

Directory of Open Access Journals (Sweden)

Eduardo Alberto López-Maldonado

2014-01-01

Full Text Available Efficiency of coagulation-flocculation process used for semiconductor wastewater treatment was improved by selecting suitable conditions (pH, polyelectrolyte type, and concentration through zeta potential measurements. Under this scenario the zeta potential, ζ, is the right parameter that allows studying and predicting the interactions at the molecular level between the contaminants in the wastewater and polyelectrolytes used for coagulation-flocculation. Additionally, this parameter is a key factor for assessing the efficiency of coagulation-flocculation processes based on the optimum dosages and windows for polyelectrolytes coagulation-flocculation effectiveness. In this paper, strategic pH variations allowed the prediction of the dosage of polyelectrolyte on wastewater from real electroplating baths, including the isoelectric point (IEP of the dispersions of water and commercial polyelectrolytes used in typical semiconductor industries. The results showed that there is a difference between polyelectrolyte demand required for the removal of suspended solids, turbidity, and organic matter from wastewater (23.4 mg/L and 67 mg/L, resp.. It was also concluded that the dose of polyelectrolytes and coagulation-flocculation window to achieve compliance with national and international regulations as EPA in USA and SEMARNAT in Mexico is influenced by the physicochemical characteristics of the dispersions and treatment conditions (pH and polyelectrolyte dosing strategy.

Polyelectrolyte Complex Based Interfacial Drug Delivery System with Controlled Loading and Improved Release Performance for Bone Therapeutics

Directory of Open Access Journals (Sweden)

David Vehlow

2016-03-01

Full Text Available An improved interfacial drug delivery system (DDS based on polyelectrolyte complex (PEC coatings with controlled drug loading and improved release performance was elaborated. The cationic homopolypeptide poly(l-lysine (PLL was complexed with a mixture of two cellulose sulfates (CS of low and high degree of substitution, so that the CS and PLL solution have around equal molar charged units. As drugs the antibiotic rifampicin (RIF and the bisphosphonate risedronate (RIS were integrated. As an important advantage over previous PEC systems this one can be centrifuged, the supernatant discarded, the dense pellet phase (coacervate separated, and again redispersed in fresh water phase. This behavior has three benefits: (i Access to the loading capacity of the drug, since the concentration of the free drug can be measured by spectroscopy; (ii lower initial burst and higher residual amount of drug due to removal of unbound drug and (iii complete adhesive stability due to the removal of polyelectrolytes (PEL excess component. It was found that the pH value and ionic strength strongly affected drug content and release of RIS and RIF. At the clinically relevant implant material (Ti40Nb similar PEC adhesive and drug release properties compared to the model substrate were found. Unloaded PEC coatings at Ti40Nb showed a similar number and morphology of above cultivated human mesenchymal stem cells (hMSC compared to uncoated Ti40Nb and resulted in considerable production of bone mineral. RIS loaded PEC coatings showed similar effects after 24 h but resulted in reduced number and unhealthy appearance of hMSC after 48 h due to cell toxicity of RIS.

Self-consistent field theory of protein adsorption in a non-Gaussian polyelectrolyte brush

NARCIS (Netherlands)

Biesheuvel, P.M.; Leermakers, F.A.M.; Stuart, M.A.C.

2006-01-01

To describe adsorption of globular protein molecules in a polyelectrolyte brush we use the strong-stretching approximation of the Edwards self-consistent field equation, combined with corrections for a non-Gaussian brush. To describe chemical potentials in this mixture of (globular) species of

Investigating the effect of moisture protection on solid-state stability and dissolution of fenofibrate and ketoconazole solid dispersions using PXRD, HSDSC and Raman microscopy.

Science.gov (United States)

Kanaujia, Parijat; Lau, Grace; Ng, Wai Kiong; Widjaja, Effendi; Schreyer, Martin; Hanefeld, Andrea; Fischbach, Matthias; Saal, Christoph; Maio, Mario; Tan, Reginald B H

2011-09-01

Enhanced dissolution of poorly soluble active pharmaceutical ingredients (APIs) in amorphous solid dispersions often diminishes during storage due to moisture-induced re-crystallization. This study aims to investigate the influence of moisture protection on solid-state stability and dissolution profiles of melt-extruded fenofibrate (FF) and ketoconazole (KC) solid dispersions. Samples were kept in open, closed and Activ-vials(®) to control the moisture uptake under accelerated conditions. During 13-week storage, changes in API crystallinity were quantified using powder X-ray diffraction (PXRD) (Rietveld analysis) and high sensitivity differential scanning calorimetry (HSDSC) and compared with any change in dissolution profiles. Trace crystallinity was observed by Raman microscopy, which otherwise was undetected by PXRD and HSDSC. Results showed that while moisture protection was ineffective in preventing the re-crystallization of amorphous FF, KC remained X-ray amorphous despite 5% moisture uptake. Regardless of the degree of crystallinity increase in FF, the enhanced dissolution properties were similarly diminished. Moisture uptake above 10% in KC samples also led to re-crystallization and significant decrease in dissolution rates. In conclusion, eliminating moisture sorption may not be sufficient in ensuring the stability of solid dispersions. Analytical quantification of API crystallinity is crucial in detecting subtle increase in crystallinity that can diminish the enhanced dissolution properties of solid dispersions.

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.

Aqueous Dispersions of Silica Stabilized with Oleic Acid Obtained by Green Chemistry

Directory of Open Access Journals (Sweden)

Cristina Lavinia Nistor

2016-01-01

Full Text Available The present study describes for the first time the synthesis of silica nanoparticles starting from sodium silicate and oleic acid (OLA. The interactions between OLA and sodium silicate require an optimal OLA/OLANa molar ratio able to generate vesicles that can stabilize silica particles obtained by the sol-gel process of sodium silicate. The optimal molar ratio of OLA/OLANa can be ensured by a proper selection of OLA and respectively of sodium silicate concentration. The titration of sodium silicate with OLA revealed a stabilization phenomenon of silica/OLA vesicles and the dependence between their average size and reagent’s molar ratio. Dynamic light scattering (DLS and scanning electron microscopy (SEM measurements emphasized the successful synthesis of silica nanoparticles starting from renewable materials, in mild condition of green chemistry. By grafting octadecyltrimethoxysilane on the initial silica particles, an increased interaction between silica particles and the OLA/OLANa complex was achieved. This interaction between the oleyl and octadecyl chains resulted in the formation of stable gel-like aqueous systems. Subsequently, olive oil and an oleophylic red dye were solubilized in these stable aqueous systems. This great dispersing capacity of oleosoluble compounds opens new perspectives for future green chemistry applications. After the removal of water and of the organic chains by thermal treatment, mesoporous silica was obtained.

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

NARCIS (Netherlands)

Ubbink, J.; Khokhlov, A.R.

2004-01-01

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the

Evaluation on the stability of Hg in ABS disk CRM during measurements by wavelength dispersive X-ray fluorescence spectrometry.

Science.gov (United States)

Ohata, Masaki; Kidokoro, Toshihiro; Hioki, Akiharu

2012-01-01

The stability of Hg in an acrylonitrile-butadiene-styrene disk certified reference material (ABS disk CRM, NMIJ CRM 8116-a) during measurements by wavelength dispersion X-ray fluorescence (WD-XRF) analysis was evaluated in this study. The XRF intensities of Hg (L(α)) and Pb (L(α)) as well as the XRF intensity ratios of Hg (L(α))/Pb (L(α)) observed under different X-ray tube current conditions as well as their irradiation time were examined to evaluate the stability of Hg in the ABS disk CRM. The observed XRF intensities and the XRF intensity ratios for up to 32 h of measurements under 80 mA of X-ray tube current condition were constant, even though the surface of the ABS disk CRM was charred by the X-ray irradiation with high current for a long time. Moreover, the measurements on Hg and Pb in the charred disks by an energy dispersive XRF (ED-XRF) spectrometer showed constant XRF intensity ratios of Hg (L(α))/Pb (L(α)). From these results, Hg in the ABS disk CRM was evaluated to be sufficiently stable for XRF analysis.

The interplay of nanointerface curvature and calcium binding in weak polyelectrolyte-coated nanoparticles.

Science.gov (United States)

Nap, Rikkert J; Gonzalez Solveyra, Estefania; Szleifer, Igal

2018-05-01

When engineering nanomaterials for application in biological systems, it is important to understand how multivalent ions, such as calcium, affect the structural and chemical properties of polymer-modified nanoconstructs. In this work, a recently developed molecular theory was employed to study the effect of surface curvature on the calcium-induced collapse of end-tethered weak polyelectrolytes. In particular, we focused on cylindrical and spherical nanoparticles coated with poly(acrylic acid) in the presence of different amounts of Ca2+ ions. We describe the structural changes that grafted polyelectrolytes undergo as a function of calcium concentration, surface curvature, and morphology. The polymer layers collapse in aqueous solutions that contain sufficient amounts of Ca2+ ions. This collapse, due to the formation of calcium bridges, is not only controlled by the calcium ion concentration but also strongly influenced by the curvature of the tethering surface. The transition from a swollen to a collapsed layer as a function of calcium concentration broadens and shifts to lower amounts of calcium ions as a function of the radius of cylindrical and spherical nanoparticles. The results show how the interplay between calcium binding and surface curvature governs the structural and functional properties of the polymer molecules. This would directly impact the fate of weak polyelectrolyte-coated nanoparticles in biological environments, in which calcium levels are tightly regulated. Understanding such interplay would also contribute to the rational design and optimization of smart interfaces with applications in, e.g., salt-sensitive and ion-responsive materials and devices.

Interaction between two polyelectrolyte brushes.

Science.gov (United States)

Kumar, N Arun; Seidel, Christian

2007-08-01

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

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

International Nuclear Information System (INIS)

Jiang, Hao; Adidharma, Hertanto

2014-01-01

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

Behaviour of human mesenchymal stem cells on a polyelectrolyte-modified HEMA hydrogel for silk-based ligament tissue engineering.

Science.gov (United States)

Bosetti, M; Boccafoschi, F; Calarco, A; Leigheb, M; Gatti, S; Piffanelli, V; Peluso, G; Cannas, M

2008-01-01

The aim of this study was to design a functional bio-engineered material to be used as scaffold for autologous mesenchymal stem cells in ligament tissue engineering. Polyelectrolyte modified HEMA hydrogel (HEMA-co-METAC), applied as coating on silk fibroin fibres, has been formulated in order to take advantage of the biocompatibility of the polyelectrolyte by increasing its mechanical properties with silk fibres. Human bone marrow mesenchymal stem cells behaviour on such reinforced polyelectrolyte has been studied by evaluating cell morphology, cell number, attachment, spreading and proliferation together with collagen matrix production and its mRNA expression. Silk fibroin fibres matrices with HEMA-co-METAC coating exhibited acceptable mechanical behaviour compared to the natural ligament, good human mesenchymal stem cell adhesion and with mRNA expression studies higher levels of collagen types I and III expression when compared to control cells on polystyrene. These data indicate high expression of mRNA for proteins responsible for the functional characteristics of the ligaments and suggest a potential for use of this biomaterial in ligament tissue-engineering applications.

Smaller Counter Cation for Higher Transconductance in Anionic Conjugated Polyelectrolytes

KAUST Repository

Schmidt, Martina M.

2017-12-11

Conjugated polyelectrolytes (CPEs) are a focus of research because combine their inherent electrical conductivity and the ability to interact with ions in aqueous solutions or biological systems. However, it is still not understood to what degree the counter ion in CPEs influences the properties of the CPE itself and the performance of electronic transducers. In order to investigate this, three different conjugated polyelectrolytes, poly(6-(thiophen-3-yl)hexane-1-sulfonate)s (PTHS−X+), are synthesized, which have the same polythiophene backbone but different X+ counter ions: the bulky tetrabutylammonium (TBA+), tetraethylammonium (TEA+), and the smallest tetramethylammonium (TMA+). At the interface with biological systems, thin CPE films have to be stable in an aqueous environment and should allow the inward and outward flow of ions from the electrolyte. Since the studied PTHS−X+ have different solubilities in water, the optical properties of pristine PTHS−X+ as well as of crosslinked PTHS−X+ via UV–vis absorption spectroscopy are investigated additionally. PTHS−TMA+ exhibits better aggregation, fast interdiffusion of ions, and fast recovery from the oxidized state. Additionally, spectroelectrochemical and cyclic voltammetric as well as electrochemical capacitance investigations show that PTHS−TMA+ can be oxidized to a higher degree. This leads to a better performance of PTHS−TMA+-based organic electrochemical transistors.

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.

Polyelectrolyte microparticles for enhancing anode performance in an air–cathode μ-Liter microbial fuel cell

International Nuclear Information System (INIS)

Chen, Yan-Yu; Wang, Hsiang-Yu

2015-01-01

Highlights: • Microparticles with high consistency and surface area per volume are fabricated. • P(DADMAC) microparticles facilitate microorganism accumulation and charge transfer. • Microbes in microparticles are capable of proliferation and electricity generation. • Microparticles increase limiting current/power output to more than 200% of biofilm. • Microparticles decrease the anode charge-transfer resistance to 44% of biofilm. - Abstract: Microbial fuel cell (MFC) is considered an environmentally friendly energy source because it generates electrical power by digesting organic substrates in the wastewater. However, it is still challenging for MFC to become an economically affordable and highly efficient energy source due to its relatively low power output and coulombic efficiency. The aim of this study is to increase the performance of anode by using polyelectrolyte microparticles to facilitate the accumulation of microorganisms and the collection of electrons. The polyelectrolyte microparticle is subjected to microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and continuous electricity generation in an air–cathode μ-Liter MFC (μMFC) to validate its biocompatibility, ability in retaining redox species, reduced electron transfer resistance, and sustained energy generation. During the 168-hour operation, microorganisms proliferate inside the microparticle and generate around 250% power output and 200% limiting current of those from microorganism biofilm. The polyelectrolyte microparticle also decreased charge-transfer resistance of anode electrode in air–cathode μMFC by 56% compared with biofilm.

Dispersion of nanoparticulate suspensions using self-assembled surfactant aggregates

Science.gov (United States)

Singh, Pankaj Kumar

The dispersion of particles is critical for several industrial applications such as paints, inks, coatings, and cosmetics. Several emerging applications such as abrasives for precision polishing, and drug delivery systems are increasingly relying on nanoparticulates to achieve the desired performance. In the case of nanoparticles, the dispersion becomes more challenging because of the lack of fundamental understanding of dispersant adsorption and interparticle force prediction. Additionally, many of these processes use severe processing environments such as high normal forces (>100 mN/m), high shear forces (>10,000 s -1), and high ionic strengths (>0.1 M). Under such processing conditions, traditionally used dispersants based on electrostatics, and steric force repulsion mechanism may not be adequate. Hence, the development of optimally performing dispersants requires a fundamental understanding of the dispersion mechanism at the atomic/molecular scale. This study explores the use of self-assembled surfactant aggregates at the solid-liquid interface for dispersing nanoparticles in severe processing environments. Surfactant molecules can provide a feasible alternative to polymeric or inorganic dispersants for stabilizing ultrafine particles. The barrier to aggregation in the presence of surfactant molecules was measured using atomic force microscopy. The barrier heights correlated to suspension stability. To understand the mechanism for nanoparticulate suspension stability in the presence of surfactant films, the interface was characterized using zeta potential, contact angle, adsorption, and FT-IR (adsorbed surfactant film structure measurements). The effect of solution conditions such as pH and ionic strength on the suspension stability, and the self-assembled surfactant films was also investigated. It was determined that a transition from a random to an ordered orientation of the surfactant molecules at the interface was responsible for stability of

Structural hierarchy in flow-aligned hexagonally self-organized microphases with parallel polyelectrolytic structures

NARCIS (Netherlands)

Ruotsalainen, T; Torkkeli, M; Serimaa, R; Makela, T; Maki-Ontto, R; Ruokolainen, J; ten Brinke, G; Ikkala, O; Mäkelä, Tapio; Mäki-Ontto, Riikka

2003-01-01

We report a novel structural hierarchy where a flow-aligned hexagonal self-organized structure is combined with a polyelectrolytic self-organization on a smaller length scale and where the two structures are mutually parallel. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is selected with

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

Science.gov (United States)

Hoda, Nazish; Kumar, Satish

2007-12-01

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

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

Science.gov (United States)

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

2014-11-26

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

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

Science.gov (United States)

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

2012-08-31

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

Thickness and morphology of polyelectrolyte coatings on silica surfaces before and after protein exposure studied by atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Haselberg, Rob, E-mail: r.haselberg@vu.nl [Biomolecular Analysis, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (Netherlands); AIMMS Division of BioMolecular Analysis, VU University Amsterdam, de Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Flesch, Frits M. [Biomolecular Analysis, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (Netherlands); Boerke, Arjan [Department of Biochemistry and Cell Biology, Utrecht University, Yalelaan 2, 3508 TD Utrecht (Netherlands); Somsen, Govert W. [Biomolecular Analysis, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (Netherlands); AIMMS Division of BioMolecular Analysis, VU University Amsterdam, de Boelelaan 1083, 1081 HV Amsterdam (Netherlands)

2013-05-24

Graphical abstract: -- Highlights: •Atomic force microscopy is used to characterize polyelectrolyte coatings. •Coating procedure leads to nm-thick layers on a silica surface. •Polyelectrolyte coatings effectively prevent protein adsorption. •AFM provides the high resolution to investigate these thin films. •AFM results support earlier findings obtained with capillary electrophoresis. -- Abstract: Analyte–wall interaction is a significant problem in capillary electrophoresis (CE) as it may compromise separation efficiencies and migration time repeatability. In CE, self-assembled polyelectrolyte multilayer films of Polybrene (PB) and dextran sulfate (DS) or poly(vinylsulfonic acid) (PVS) have been used to coat the capillary inner wall and thereby prevent analyte adsorption. In this study, atomic force microscopy (AFM) was employed to investigate the layer thickness and surface morphology of monolayer (PB), bilayer, (PB-DS and PB-PVS), and trilayer (PB-DS-PB and PB-PVS-PB) coatings on glass surfaces. AFM nanoshaving experiments providing height distributions demonstrated that the coating procedures led to average layer thicknesses between 1 nm (PB) and 5 nm (PB-DS-PB), suggesting the individual polyelectrolytes adhere flat on the silica surface. Investigation of the surface morphology of the different coatings by AFM revealed that the PB coating does not completely cover the silica surface, whereas full coverage was observed for the trilayer coatings. The DS-containing coatings appeared on average 1 nm thicker than the corresponding PVS-containing coatings, which could be attributed to the molecular structure of the anionic polymers applied. Upon exposure to the basic protein cytochrome c, AFM measurements showed an increase of the layer thickness for bare (3.1 nm) and PB-DS-coated (4.6 nm) silica, indicating substantial protein adsorption. In contrast, a very small or no increase of the layer thickness was observed for the PB and PB-DS-PB coatings

Study of the stability of the nanometer-sized oxides dispersed in ODS steels under ion irradiations

International Nuclear Information System (INIS)

Lescoat, M.-L.

2012-01-01

Oxide Dispersion Strengthened (ODS) Ferritic-Martensitic (FM) alloys are expected to play an important role as cladding materials in Generation IV sodium fast reactors operating in extreme temperature (400-500 C) and irradiation conditions (up to 200 dpa). Since nano-oxides give ODS steels their high temperature strength, the stability of these particles is an important issue. The present study evaluates the radiation response of nano-oxides by the use of in-situ and ex-situ ion irradiations performed on both Fe18Cr1W0,4Ti +0,3 Y 2 O 3 and Fe18Cr1W0,4Ti + 0.3 MgO ODS steels. In particular, the results showed that Y-Ti-O nano-oxides are quite stable under very high irradiation dose, namely 219 dpa at 500 C, and that the oxide interfacial structures are likely playing an important role on the behavior under irradiation (oxide stability and point defect recombination. (author) [fr

Microwave Irradiation Effect on the Dispersion and Thermal Stability of RGO Nanosheets within a Polystyrene Matrix

Directory of Open Access Journals (Sweden)

Edreese H. Alsharaeh

2014-07-01

Full Text Available Polystyrene-reduced graphene oxide (PSTY/RGO composites were prepared via the in situ bulk polymerization method using two different preparation techniques. The general approach is to use microwave irradiation (MWI to enhance the exfoliation and the dispersion of RGO nanosheets within the PSTY matrix. In the first approach, a mixture of GO and styrene monomers (STY were polymerized using a bulk polymerization method facilitated by microwave irradiation (MWI to obtain R-(GO-PSTY composites. In the second approach, a mixture of RGO and STY monomers were polymerized using a bulk polymerization method to obtain RGO-(PSTY composites. The two composites were characterized by FTIR, 1H-NMR, XRD, SEM, HRTEM, TGA and DSC. The results indicate that the composite obtained using the first approach, which involved MWI, had a better morphology and dispersion with enhanced thermal stability, compared with the composites prepared without MWI. Moreover, DSC results showed that the Tg value of the composites after loading the RGO significantly increased by 24.6 °C compared to the neat polystyrene.

A Method for Suppression of Active Metal Leaching during the Direct Synthesis of H{sub 2}O{sub 2} by Using Polyelectrolyte Multilayers

Energy Technology Data Exchange (ETDEWEB)

Chung, Young-Min [Kunsan National University, Kunsan (Korea, Republic of)

2015-04-15

In this study, two types of catalysts were prepared via conventional metal supporting method and encapsulation of metal nanoparticles in the polyelectrolyte multilayers constructed on support. The resulting catalysts were applied to the direct synthesis of hydrogen peroxide, and the effect of catalyst preparation method on the catalyst life as well as hydrogen peroxide productivity was investigated. The catalytic activity was strongly dependent upon the acid strength of support regardless of the catalyst preparation methods and HBEA (SAR=25) with strong acidity was superior to other supports to promote the reaction. In the case of metal supported catalyst, while hydrogen peroxide productivity was higher than that of polyelectrolyte multilayered counterpart, the reaction performance was sharply decreased during catalyst recycling due to the metal leaching. On the other hand, construction of polyelectrolyte multilayers on support weakened the influence of acid support on the reaction medium and therefore resulted in the decrease of catalytic activity and the increase of hydrogen peroxide decomposition as well. It is noted, however, that the catalytic activity was maintained after 5 recycles, which suggests that the introduction of polyelectrolyte multilayers on the support is very effective to suppress the unfavorable metal leaching phenomenon during a reaction.

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…

Ion binding by humic and fulvic acids: A computational procedure based on functional site heterogeneity and the physical chemistry of polyelectrolyte solutions

International Nuclear Information System (INIS)

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

1988-04-01

Ion binding equilibria for humic and fulvic acids are examined from the point of view of functional site heterogeneity and the physical chemistry of polyelectrolyte solutions. A detailed explanation of the potentiometric properties of synthetic polyelectrolytes and ion-exchange gels is presented first to provide the basis for a parallel consideration of the potentiometric properties exhibited by humic and fulvic acids. The treatment is then extended to account for functional site heterogeneity. Sample results are presented for analysis of the ion-binding reactions of a standard soil fulvic acid (Armadale Horizons Bh) with this approach to test its capability for anticipation of metal ion removal from solution. The ultimate refined model is shown to be adaptable, after appropriate consideration of the heterogeneity and polyelectrolyte factors, to programming already available for the consideration of ion binding by inorganics in natural waters. (orig.)

Formation and dielectric properties of polyelectrolyte multilayers studied by a silicon-on-insulator based thin film resistor.

Science.gov (United States)

Neff, Petra A; Wunderlich, Bernhard K; Klitzing, Regine V; Bausch, Andreas R

2007-03-27

The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator based thin film resistor which is sensitive to variations of the surface potential. The buildup of the PEMs at the silicon oxide surface of the device can be observed in real time as defined potential shifts. The influence of polymer charge density is studied using the strong polyanion poly(styrene sulfonate), PSS, combined with the statistical copolymer poly(diallyl-dimethyl-ammoniumchloride-stat-N-methyl-N-vinylacetamide), P(DADMAC-stat-NMVA), at various degrees of charge (DC). The multilayer formation stops after a few deposition steps for a DC below 75%. We show that the threshold of surface charge compensation corresponds to the threshold of multilayer formation. However, no reversion of the preceding surface charge was observed. Screening of polyelectrolyte charges by mobile ions within the polymer film leads to a decrease of the potential shifts with the number of layers deposited. This decrease is much slower for PEMs consisting of P(DADMAC-stat-NMVA) and PSS as compared to PEMs consisting of poly(allylamine-hydrochloride), PAH, and PSS. From this, significant differences in the dielectric constants of the polyelectrolyte films and in the concentration of mobile ions within the films can be derived.

Cyclodextrin-grafted barium titanate nanoparticles for improved dispersion and stabilization in water-based systems

Energy Technology Data Exchange (ETDEWEB)

Serra-Gómez, R. [Universidad de Navarra, Departamento de Química y Edafología (Spain); Martinez-Tarifa, J. M. [Universidad Carlos III de Madrid, Departamento de Ingeniería Eléctrica (Spain); González-Benito, J. [Universidad Carlos III de Madrid, Departamento de Ciencia e Ingeniería de Materiales e Ingeniería Química, IQMAAB (Spain); González-Gaitano, G., E-mail: gaitano@unav.es [Universidad de Navarra, Departamento de Química y Edafología (Spain)

2016-01-15

Ceramic nanoparticles with piezoelectric properties, such as BaTiO{sub 3} (BT), constitute a promising approach in the fields of nanocomposite materials and biomaterials. In the latter case, to be successful in their preparation, the drawback of their fast aggregation and practically null stability in water has to be overcome. The objective of this investigation has been the surface functionalization of BaTiO{sub 3} nanoparticles with cyclodextrins (CDs) as a way to break the aggregation and improve the stability of the nanoparticles in water solution, preventing and minimizing their fast precipitation. As a secondary goal, we have achieved extra-functionality of the nanoparticles, bestowed from the hydrophobic cavity of the macrocycle, which is able to lodge guest molecules that can form inclusion complexes with the oligosaccharide. The nanoparticle functionalization has been fully tracked and characterized, and the cytotoxicity of the modified nanoparticles with fibroblasts and pre-osteoblasts cell lines has been assessed with excellent results in a wide range of concentrations. The modified nanoparticles were found to be suitable for the easy preparation of nanocomposite hydrogels, via dispersion in hydrophilic polymers of typical use in biomedical applications (PEG, Pluronics, and PEO), and further processed in the form of films via water casting, showing very good results in terms of homogeneity in the dispersion of the filler. Likewise, as examples of application and with the aim of exploring a different range of nanocomposites, rhodamine B was included in the macrocycles as a model molecule, and films prepared from a thermoplastic matrix (EVA) via high-energy ball milling have been tested by impedance spectroscopy to discuss their dielectric properties, which indicated that even small modifications in the surface of the nanoparticles generate a different kind of interaction with the polymeric matrix. The CD-modified nanoparticles are thus suitable for easy

Characterization of swollen structure of high-density polyelectrolyte brushes in salt solution by neutron reflectivity

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, Motoyasu; Takahara, Atsushi [Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Terayama, Yuki [Graduate School of Engineering, Kyushu University (Japan); Hino, Masahiro [Reactor Research Institute, Kyoto University (Japan); Ishihara, Kazuhiko, E-mail: takahara@cstf.kyushu-u.ac.j [Graduate School of Engineering, University of Tokyo (Japan)

2009-08-01

Zwitterionic and cationic polyelectrolyte brushes on quartz substrate were prepared by surface-initiated atom transfer radical polymerization of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (METAC), respectively. The effects of ionic strength on brush structure and surface properties of densely grafted polyelectrolyte brushes were analysed by neutron reflectivity (NR) measurements. NR at poly(METAC)/D{sub 2}O and poly(MPC)/D{sub 2}O interface revealed that the grafted polymer chains were fairly extended from the substrate surface, while the thickness reduction of poly(METAC) brush was observed in 5.6 M NaCl/D{sub 2}O solution due to the screening of the repulsive interaction between polycations by hydrated salt ions. Interestingly, no structural change was observed in poly(MPC) brush even in a salt solution probably due to the unique interaction properties of phosphorylcholine units.

dispersion characteristics of settleable and dissolvable pollutants in ...

African Journals Online (AJOL)

The implication of this in waste stabilization pond design was also discussed. KEYWORDS: Dispersion, settleable pollutants, waste stabilization ponds. INTRODUCTION. A waste ...... and Soil Pollution 52, 237-245. Agunwamba, J. C., 1991.

Wang-Landau Reaction Ensemble Method: Simulation of Weak Polyelectrolytes and General Acid-Base Reactions.

Science.gov (United States)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-02-14

We present a novel method for the study of weak polyelectrolytes and general acid-base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang-Landau sampling method. Deprotonation and protonation reactions are simulated explicitly with the help of the reaction ensemble method, while the accurate sampling of the corresponding phase space is achieved by the Wang-Landau approach. The combination of both techniques provides a sufficient statistical accuracy such that meaningful estimates for the density of states and the partition sum can be obtained. With regard to these estimates, several thermodynamic observables like the heat capacity or reaction free energies can be calculated. We demonstrate that the computation times for the calculation of titration curves with a high statistical accuracy can be significantly decreased when compared to the original reaction ensemble method. The applicability of our approach is validated by the study of weak polyelectrolytes and their thermodynamic properties.

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

Science.gov (United States)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Birefringent dispersive FDTD subgridding scheme

OpenAIRE

De Deckere, B; Van Londersele, Arne; De Zutter, Daniël; Vande Ginste, Dries

2016-01-01

A novel 2D finite difference time domain (FDTD) subgridding method is proposed, only subject to the Courant limit of the coarse grid. By making mu or epsilon inside the subgrid dispersive, unconditional stability is induced at the cost of a sparse, implicit set of update equations. By only adding dispersion along preferential directions, it is possible to dramatically reduce the rank of the matrix equation that needs to be solved.

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

Science.gov (United States)

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

2010-04-01

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

Gd-functionalised Au nanoparticles as targeted contrast agents in MRI: relaxivity enhancement by polyelectrolyte coating.

Science.gov (United States)

Warsi, Muhammad Farooq; Adams, Ralph W; Duckett, Simon B; Chechik, Victor

2010-01-21

Monolayer-protected, Gd(3+)-functionalised gold nanoparticles with enhanced spin-lattice relaxivity (r(1)) were prepared; adsorption of polyelectrolytes on these materials further increased r(1) and ligand exchange with a biotin-derivatised disulfide led to a prototype avidin-targeted contrast agent.

Thermodynamic study of aqueous solutions of polyelectrolytes of low and medium charge density without added salt by direct measurement of osmotic pressure

Energy Technology Data Exchange (ETDEWEB)

Nagy, Miklos, E-mail: miklosnagy@chem.elte.h [Institute of Chemistry, Department of Physical Chemistry, Laboratory for Colloid and Supermolecular Structures, L. Eoetvoes University, P.O. Box 32 H-1518 Budapest 112 (Hungary)

2010-03-15

A special block osmometer has been constructed and applied to a systematic study of poly (vinyl alcohol and vinyl sulphate ester) (PVS) sodium salts in dilute and moderately concentrated salt free aqueous solutions. In order to avoid surely ionic contamination all parts of the equipment that can contact with the polyelectrolyte solutions were made of different kinds of plastics and glass. The pressure range spans from (50 to 1.3 . 10{sup 5}) Pa. The measuring system was found to be appropriate for determination of the molar mass of water soluble polymers, too. Above a certain analytical density of dissociable groups (ADDG) an ion size dependent transition was observed on the reduced osmotic pressure vs. concentration curves. The analysis of the osmotic pressure data has clearly revealed that the dependence of the degree of dissociation on ADDG calculated at zero polyelectrolyte concentration contradicts to 'ion condensation' theory. With increasing polyelectrolyte concentration the degree of dissociation decreased rather steeply but at very low concentrations sharp maximums appeared due either to the change in conformation of these charged macromolecules, or formation of dynamic clusters induced by salting out of neutral parts of the macromolecules by the ionized groups. The applicability of the scaling concept as well as the many possible ways of characterization of non-ideality of polyelectrolyte solutions will be discussed in detail.

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

A linearized dispersion relation for orthorhombic pseudo-acoustic modeling

KAUST Repository

Song, Xiaolei; Alkhalifah, Tariq Ali

2012-01-01

Wavefield extrapolation in acoustic orthorhombic anisotropic media suffers from wave-mode coupling and stability limitations in the parameter range. We introduce a linearized form of the dispersion relation for acoustic orthorhombic media to model acoustic wavefields. We apply the lowrank approximation approach to handle the corresponding space-wavenumber mixed-domain operator. Numerical experiments show that the proposed wavefield extrapolator is accurate and practically free of dispersions. Further, there is no coupling of qSv and qP waves, because we use the analytical dispersion relation. No constraints on Thomsen's parameters are required for stability. The linearized expression may provide useful application for parameter estimation in orthorhombic media.

A linearized dispersion relation for orthorhombic pseudo-acoustic modeling

KAUST Repository

Song, Xiaolei

2012-11-04

Wavefield extrapolation in acoustic orthorhombic anisotropic media suffers from wave-mode coupling and stability limitations in the parameter range. We introduce a linearized form of the dispersion relation for acoustic orthorhombic media to model acoustic wavefields. We apply the lowrank approximation approach to handle the corresponding space-wavenumber mixed-domain operator. Numerical experiments show that the proposed wavefield extrapolator is accurate and practically free of dispersions. Further, there is no coupling of qSv and qP waves, because we use the analytical dispersion relation. No constraints on Thomsen\\'s parameters are required for stability. The linearized expression may provide useful application for parameter estimation in orthorhombic media.

Repulsive interactions between two polyelectrolyte networks

Science.gov (United States)

Erbas, Aykut; Olvera de La Cruz, Monica; Olvera Group Collaboration

Surfaces formed by charged polymeric species are highly_abundant in both synthetic and biological systems, for which maintaining_an optimum contact distance and a pressure balance is paramount. We investigate interactions between surfaces of two same-charged and_highly swollen polyelectrolyte gels, using extensive molecular dynamic_simulations and minimal analytical methods. The external-pressure_responses of the gels and the polymer-free ionic solvent layer separating_two surfaces are considered. Simulations confirmed that the surfaces are_held apart by osmotic pressure resulting from excess charges diffusing out_of the network. Both the solvent layer and pressure dependence are well_described by an analytical model based on the Poisson -Boltzmann solution for low and moderate electrostatic strengths. Our results can be of great importance for systems where charged gels or gel-like structures interact in various solvents, including systems encapsulated by gels and microgels in confinement.

Longitudinal stability of the diurnal rhythm of intraocular pressure in subjects with healthy eyes, ocular hypertension and pigment dispersion syndrome.

Science.gov (United States)

Huchzermeyer, Cord; Reulbach, Udo; Horn, Folkert; Lämmer, Robert; Mardin, Christian Y; Jünemann, Anselm G M

2014-10-15

The diurnal fluctuation of intraocular pressure may be relevant in glaucoma. The aim of this study was to find out whether the timing of diurnal fluctuation is stable over the years. Long-term IOP data from the Erlangen Glaucoma Registry, consisting of several annual extended diurnal IOP profiles for each patient, was retrospectively analyzed. Normal subjects, patients with ocular hypertension and with pigment dispersion syndrome were included because these subjects had not been treated with antiglaucomatous medications at the time of data acquisition. A cosine curve was fitted to the IOP data and the stability of individual rhythms over the years was tested using the Rayleigh test. To compare the peak times among groups, means were calculated only from subjects with a significant Rayleigh test. Of the fifty-two eligible subjects, a total of 364 extended diurnal IOP profiles measured in a sitting position had been collected over a period of 114 ± 39 months. The Rayleigh test indicated intraindividual stability of phase timing only in 19 subjects (36%). In subjects with pigment dispersions syndrome, peak IOP occurred on average two hours and seven minutes later during the day compared with subjects without this condition (p = 0.05). Fitting of cosine curves to the clinical IOP profiles was generally feasible, although careful interpretation is warranted due to lack of measurements in supine position and between midnight and 7 am. The interesting observation of a phase lag in eyes with pigment dispersion syndrome warrants confirmation and exploration in future prospective studies. The analysis of the IOP data showed no stable individual rhythm in the long term in a majority of patients.

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

Science.gov (United States)

Wang, Dongrui; Wang, Xiaogong

2011-03-01

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

Application of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride polyelectrolyte complexes for structuring of polluted soil of Semipalatinsk nuclear test site

International Nuclear Information System (INIS)

Sabantseva, T.; Bashenova, A.; Orazzhanova, L.K.; Yashkarova, M.G.; Bimendina, L.A.

2002-01-01

The present communication is devoted to investigation of structuring efficiency of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride (PAA-PDMDAACI) polyelectrolyte complexes. The granulometric analysis of selected soil samples before and after the treatment of aqueous solution of PAA, PDMDAACI and PAA-PDMDAACI complexes at different molar ratio of polymer components and polymer concentrations was carried out. Analysis shows that nonstoichiometric polyelectrolyte complex [PAA]:[PDMDAACI]=3:1 possesses the best structuring effect. But this result is worse than in the case using of [PAA]:[polyethylene glycol]=1:1 inter-polymer complex

Large Scale Simulation of Hydrogen Dispersion by a Stabilized Balancing Domain Decomposition Method

Directory of Open Access Journals (Sweden)

Qing-He Yao

2014-01-01

Full Text Available The dispersion behaviour of leaking hydrogen in a partially open space is simulated by a balancing domain decomposition method in this work. An analogy of the Boussinesq approximation is employed to describe the connection between the flow field and the concentration field. The linear systems of Navier-Stokes equations and the convection diffusion equation are symmetrized by a pressure stabilized Lagrange-Galerkin method, and thus a balancing domain decomposition method is enabled to solve the interface problem of the domain decomposition system. Numerical results are validated by comparing with the experimental data and available numerical results. The dilution effect of ventilation is investigated, especially at the doors, where flow pattern is complicated and oscillations appear in the past research reported by other researchers. The transient behaviour of hydrogen and the process of accumulation in the partially open space are discussed, and more details are revealed by large scale computation.

Polyelectrolytes processing at pilot scale level by electron beam irradiation

International Nuclear Information System (INIS)

Martin, D.; Cirstea, E.; Craciun, G.; Ighigeanu, D.; Marin, Gheorghe G.

2002-01-01

Three years of research, combined with engineering activities, have culminated in the development of a new method of electron beam processing applicable up to the pilot scale level, namely, the polyelectrolytes (acrylamide - acrylic acid copolymers) electron beam processing. This new radiation processing method has been achieved by bilateral co-operation between the National Institute for Laser, Plasma and Radiation Physics (NILPRP) and the Electrical Design and Research Institute, EDRI - Bucharest. The polyelectrolytes electron beam (EB) processing was put in operation at EDRI, where, recently, an industrial electron accelerator of 2 MeV and 20 kW, manufactured by Institute of Nuclear Physics, Novosibirsk, Russia was installed in a specially designed irradiation facility. Automatic start-up via computer control makes it compatible with industrial processing. According to the first conclusions, which resulted from our experimental research with regard to acrylamide - acrylic acid copolymers production by EB irradiation, the proper physical and chemical characteristics can be well controlled by chemical composition to be treated and by suitable adjustment of absorbed dose and absorbed dose rate. So, it was possible to obtain a very large area of characteristics and therefore a large area of applications. The conversion coefficient is very high (> 98%) and concentration of the residual monomer is under 0.05%. The tests applied to some wastewaters from the vegetable oil plants demonstrated that the fatty substances, matters in suspension, chemical oxygen demand and biological oxygen demand over 5 days were much reduced, in comparison with classical treatment. Also, sedimentation time was around four times smaller and sediment volume was 60% smaller than the values obtained in case of classical treatment. The necessary EB absorbed dose for the acrylamide - acrylic acid aqueous solution polymerization, established by optimization of chemical composition and irradiation

Macrostructure of smectite-water systems. Influence of anionic poly-electrolytes on the organisation of montmorillonite suspensions

International Nuclear Information System (INIS)

Morvan, Mikel

1993-01-01

In its first part, this research thesis reports a bibliographical study which aimed at highlighting the main aspects of smectite swelling, discusses the organisation of smectite suspension, and briefly presents the knowledge on clay-polymer mixtures. Then, the author describes the method he used to characterise clay suspensions (relaxation, MNR, osmometric techniques, small-angle X-ray diffraction), and theoretical elements required to interpret results. He addresses more particularly the organisation of smectite-water systems with either a natural smectite (montmorillonite) or a synthetic one (laponite) which have different geometries. The last part addresses the interactions between a montmorillonite suspension and sodium polyacrylates. The author, based on the use of small-angle X-ray diffraction and the measurement of the polyelectrolyte osmotic pressure, proposes a new interpretation of the action mechanism of an anionic polyelectrolyte of low molecular mass within a montmorillonite suspension

Key factors for UV curable pigment dispersions

International Nuclear Information System (INIS)

Magny, B.; Pezron, E.; Ciceron, P.H.; Askienazy, A.

1999-01-01

UV oligomers with good pigment dispersion are needed to allow good formulation flexibility and possibility to apply thinner films. Pigment dispersion mainly depends on three phenomena: the wetting of agglomerates, the breakage of agglomerates by mechanical stress and the stabilization of smaller agglomerates and primary particles against flocculation. It has been shown that oligomers with low viscosity and low surface tension induce a good pigment wetting. Examples of monomers and oligomers for good pigment dispersion are given

Stability of dispersions in polar organic media. I. Electrostatic stabilization

NARCIS (Netherlands)

Rooy, N. de; Bruyn, P.L. de; Overbeek, J.Th.G.

Electrostatically stabilized sols of silver, silver iodide, α-goethite, and copper phthalocyanine in methanol, ethanol, isopropanol, and acetone have been prepared and characterized. Coagulation concentrations with electrolytes of various charge numbers have been determined in water, in organic

The role of minor alloying elements on the stability and dispersion of yttria nanoclusters in nanostructured ferritic alloys: An ab initio study

International Nuclear Information System (INIS)

Murali, D.; Panigrahi, B.K.; Valsakumar, M.C.; Chandra, Sharat; Sundar, C.S.; Raj, Baldev

2010-01-01

Nanostructured ferritic alloys derive their strength from the dispersion of oxide nanoclusters in the ferritic matrix. We have explored the relative role of minor alloying elements like Ti and Zr on the stability of nanoclusters of vacancy-Y-Ti-O by density functional theory calculations and shown that the binding energy of these clusters increases when we replace Ti with Zr. This could imply faster nucleation of the nanoclusters which, in turn, may lead to finer dispersion of nanoclusters resulting in improved performance of ferritic alloys. Further, we show a core/shell structure for these nanoclusters in which the core is enriched in Y, O, Ti while the shell is enriched in Cr.

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

Science.gov (United States)

Wei, Qingrong; Ai, Hua; Gu, Zhongwei

2011-06-15

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

Polyelectrolyte flocculation of grain stillage for improved clarification and water recovery within bioethanol production facilities.

Science.gov (United States)

Menkhaus, Todd J; Anderson, Jason; Lane, Samuel; Waddell, Evan

2010-04-01

Polyelectrolytes were investigated for flocculation of a corn whole stillage stream to improve solid-liquid clarification operations and reduce downstream utility requirements for evaporation and drying within a bioethanol process. Despite a negative zeta potential for the stillage solids, an anionic polyelectrolyte was found to provide the best flocculation. At the optimal dosage of 1.1mg polymer/g dry suspended solids, an anionic flocculant provided a clarified stream with only 0.15% w/w suspended solids (equivalent to a total dissolved solid to total suspended solid ratio greater than 40, and a viscosity reduction of 39% compared to an unflocculated "clarified" stream). The resulting solids cake had greater than 40% w/w solids, and more than 80% water recovery was found in the clarified stream. Addition of flocculant improved filtration flux by six fold and/or would allow for up to a 4-times higher flow rate if using a decanting centrifuge for clarification of corn stillage. Copyright 2009 Elsevier Ltd. All rights reserved.

Ductile polyelectrolyte macromolecule-complexed zinc phosphate conversion crystal pre-coatings and topcoatings embodying a laminate

Science.gov (United States)

Sugama, Toshifumi; Kukacka, Lawrence E.; Carciello, Neal R.

1987-01-01

This invention relates to a precoat, laminate, and method for ductile coatings on steel and non-ferrous metals which comprises applying a zinc phosphating coating solution modified by a solid polyelectrolyte selected from polyacrylic acid (PAA), polymethacrylic acid (PMA), polyitaconic acid (PIA), and poly-L-glutamic acid. The contacting of the resin with the phosphating solution is made for a period of up to 20 hours at about 80.degree. C. The polyelectrolyte or the precoat is present in about 0.5-5.0% by weight of the total precoat composition and after application, the precoat base is dried for up to 5 hours at about 150.degree. C. to desiccate. Also, a laminate may be formed where polyurethane (PU) is applied as an elastomeric topcoating or polyfuran resin is applied as a glassy topcoating. It has been found that the use of PAA at a molecular weight of about 2.times.10.sup.5 gave improved ductility modulus effect.

Computer simulations of dendrimer-polyelectrolyte complexes.

Science.gov (United States)

Pandav, Gunja; Ganesan, Venkat

2014-08-28

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

Formulation of disperse systems science and technology

CERN Document Server

Tadros, Tharwat F

2014-01-01

This book presents comprehensively the science and technology behind the formulation of disperse systems like emulsions, suspensions, foams and others. Starting with a general introduction, the book covers a broad range of topics like the role of different classes of surfactants, stability of disperse systems, formulation of different dispersions, evaluation of formulations and many more. Many examples are included, too. Written by the experienced author and editor Tharwart Tadros, this book is indispensable for every scientist working in the field.

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

Science.gov (United States)

Palo, Emilia; Salomäki, Mikko; Lastusaari, Mika

2017-12-15

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

Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

Science.gov (United States)

Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

2015-03-25

Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

Statistical Physics of Colloidal Dispersions.

Science.gov (United States)

Canessa, E.

Available from UMI in association with The British Library. Requires signed TDF. This thesis is concerned with the equilibrium statistical mechanics of colloidal dispersions which represent useful model systems for the study of condensed matter physics; namely, charge stabilized colloidal dispersions and polymer stabilized colloidal dispersions. A one-component macroparticle approach is adopted in order to treat the macroscopic and microscopic properties of these systems in a simple and comprehensive manner. The thesis opens with the description of the nature of the colloidal state before reviewing some basic definitions and theory in Chapter II. In Chapter III a variational theory of phase equilibria based on the Gibbs-Bogolyobov inequality is applied to sterically stabilized colloidal dispersions. Hard spheres are chosen as the reference system for the disordered phases while an Einstein model is used for the ordered phases. The new choice of pair potential, taken for mathematical convenience, is a superposition of two Yukawa functions. By matching a double Yukawa potential to the van der Waals attractive potential at different temperatures and introducing a purely temperature dependent coefficient to the repulsive part, a rich variety of observed phase separation phenomena is qualitatively described. The behaviour of the potential is found to be consistent with a small decrease of the polymer layer thickness with increasing temperature. Using the same concept of a collapse transition the non-monotonic second virial coefficient is also explained and quantified. It is shown that a reduction of the effective macroparticle diameter with increasing temperature can only be partially examined from the point of view of a (binary-) polymer solution theory. This chapter concludes with the description of the observed, reversible, depletion flocculation behaviour. This is accomplished by using the variational formalism and by invoking the double Yukawa potential to allow

Charge inversion of dendrimers in complexes with linear polyelectrolytes in the solutions with low pH

NARCIS (Netherlands)

Larin, S.V.; Lyulin, S.V.; Lyulin, A.V.; Darinskii, A.A.

2009-01-01

Complexes of fully ionized third-generation dendrimers with oppositely charged linear polyelectrolyte chains are studied by the Brownian dynamics method. A freely jointed model of a dendrimer and a linear chain is used. Electrostatic interactions are considered within the Debye-Hückel approximation

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

International Nuclear Information System (INIS)

Piotrowski, Marek; Szczepanowicz, Krzysztof; Jantas, Danuta; Leśkiewicz, Monika; Lasoń, Władysław; Warszyński, Piotr

2013-01-01

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 2 O 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

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

Science.gov (United States)

Li, Hao; Chen, Guang; Das, Siddhartha

2016-11-01

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

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.

Structure and stability of acrolein and allyl alcohol networks on Ag(111) from density functional theory based calculations with dispersion corrections

Science.gov (United States)

Ferullo, Ricardo M.; Branda, Maria Marta; Illas, Francesc

2013-11-01

The interaction of acrolein and allyl alcohol with the Ag(111) surface has been studied by means of periodic density functional theory based calculations including explicitly dispersion terms. Different coverage values have been explored going from isolated adsorbed molecules to isolated dimers, interacting dimers or ordered overlayers. The inclusion of the dispersion terms largely affects the calculated values of the adsorption energy and also the distance between adsorbed molecule and the metallic surface but much less the adsorbate-adsorbate interactions. Owing to the large dipole moment of acrolein, the present calculations predict that at high coverage this molecule forms a stable extensive two-dimensional network on the surface, caused by the alignment of the adsorbate dipoles. For the case of allyl alcohol, dimers and complex networks exhibit similar stability.

THE STUDYING OF COLLOIDAL-CHEMICAL PROPERTIES OF CLAY MINERALS DISPERSIONS

Directory of Open Access Journals (Sweden)

A. F. Tymchuk

2015-02-01

Full Text Available The element structure is studied, the microscopic analysis of fine-dispersed min­eral systems (ground sediments of a mouth of the river Danube is carried out. The sedimentation process of clay minerals dispersions in solutions of surfactants and macromolecular substances is studied. Concentration intervals of stabilization of investigating dispersions were defined.

Two-relaxation-time lattice Boltzmann method for the anisotropic dispersive Henry problem

Science.gov (United States)

Servan-Camas, Borja; Tsai, Frank T.-C.

2010-02-01

This study develops a lattice Boltzmann method (LBM) with a two-relaxation-time collision operator (TRT) to cope with anisotropic heterogeneous hydraulic conductivity and anisotropic velocity-dependent hydrodynamic dispersion in the saltwater intrusion problem. The directional-speed-of-sound technique is further developed to address anisotropic hydraulic conductivity and dispersion tensors. Forcing terms are introduced in the LBM to correct numerical errors that arise during the recovery procedure and to describe the sink/source terms in the flow and transport equations. In order to facilitate the LBM implementation, the forcing terms are combined with the equilibrium distribution functions (EDFs) to create pseudo-EDFs. This study performs linear stability analysis and derives LBM stability domains to solve the anisotropic advection-dispersion equation. The stability domains are used to select the time step at which the lattice Boltzmann method provides stable solutions to the numerical examples. The LBM was implemented for the anisotropic dispersive Henry problem with high ratios of longitudinal to transverse dispersivities, and the results compared well to the solutions in the work of Abarca et al. (2007).

Use of multiple dispersal pathways facilitates amphibian persistence in stream networks

Science.gov (United States)

Campbell, Grant E.H.; Nichols, J.D.; Lowe, W.H.; Fagan, W.F.

2010-01-01

Although populations of amphibians are declining worldwide, there is no evidence that salamanders occupying small streams are experiencing enigmatic declines, and populations of these species seem stable. Theory predicts that dispersal through multiple pathways can stabilize populations, preventing extinction in habitat networks. However, empirical data to support this prediction are absent for most species, especially those at risk of decline. Our mark-recapture study of stream salamanders reveals both a strong upstream bias in dispersal and a surprisingly high rate of overland dispersal to adjacent headwater streams. This evidence of route-dependent variation in dispersal rates suggests a spatial mechanism for population stability in headwater-stream salamanders. Our results link the movement behavior of stream salamanders to network topology, and they underscore the importance of identifying and protecting critical dispersal pathways when addressing region-wide population declines.

Use of multiple dispersal pathways facilitates amphibian persistence in stream networks.

Science.gov (United States)

Campbell Grant, Evan H; Nichols, James D; Lowe, Winsor H; Fagan, William F

2010-04-13

Although populations of amphibians are declining worldwide, there is no evidence that salamanders occupying small streams are experiencing enigmatic declines, and populations of these species seem stable. Theory predicts that dispersal through multiple pathways can stabilize populations, preventing extinction in habitat networks. However, empirical data to support this prediction are absent for most species, especially those at risk of decline. Our mark-recapture study of stream salamanders reveals both a strong upstream bias in dispersal and a surprisingly high rate of overland dispersal to adjacent headwater streams. This evidence of route-dependent variation in dispersal rates suggests a spatial mechanism for population stability in headwater-stream salamanders. Our results link the movement behavior of stream salamanders to network topology, and they underscore the importance of identifying and protecting critical dispersal pathways when addressing region-wide population declines.

Dispersions of Carbon nanotubes in Polymer Matrices

Science.gov (United States)

Wise, Kristopher Eric (Inventor); Park, Cheol (Inventor); Siochi, Emilie J. (Inventor); Harrison, Joycelyn S. (Inventor); Lillehei, Peter T. (Inventor); Lowther, Sharon E. (Inventor)

2010-01-01

Dispersions of carbon nanotubes exhibiting long term stability are based on a polymer matrix having moieties therein which are capable of a donor-acceptor complexation with carbon nanotubes. The carbon nanotubes are introduced into the polymer matrix and separated therein by standard means. Nanocomposites produced from these dispersions are useful in the fabrication of structures, e.g., lightweight aerospace structures.

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.

Phase Transition of Poly(acrylic acid-co-N-isopropylacrylamide) Core-shell Nanogels

Science.gov (United States)

Liu, Xiao-bing; Zhou, Jian-feng; Ye, Xiao-dong

2012-08-01

A series of poly(acrylic acid) macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and characterized by 1H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly(potassium acrylate) macro-RAFT agents as the electrosteric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.

The synthesis and the electric-responsiveness of hydrogels entrapping natural polyelectrolyte

International Nuclear Information System (INIS)

Sutani, Kouichi; Kaetsu, Isao; Uchida, Kumao

2001-01-01

A mixture of vinyl monomer, a natural polyelectrolyte--hyaluronic acid--and crosslinker was polymerized and crosslinked to entrap the natural polymer into the synthetic gel. The controlled release of the model drug from the obtained gel was studied under the on-off switching of electric field. It was proved that electric-responsive drug releases were possible using hyaluronic acid entrapping gel and the electro-responsiveness was greatly affected by various factors such as degree of swelling, crosslinking density, kind and composition of vinyl monomer and crosslinkers

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).

Preparation and analysis of multilayer composites based on polyelectrolyte complexes

Energy Technology Data Exchange (ETDEWEB)

Petrova, V. A. [Russian Academy of Sciences, Institute of Macromolecular Compounds (Russian Federation); Orekhov, A. S. [Russian Academy of Sciences, Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics” (Russian Federation); Chernyakov, D. D. [St. Petersburg State Chemical Pharmaceutical Academy (Russian Federation); Baklagina, Yu. G. [Russian Academy of Sciences, Institute of Macromolecular Compounds (Russian Federation); Romanov, D. P. [Russian Academy of Sciences, Grebenshchikov Institute of Silicate Chemistry (Russian Federation); Kononova, S. V. [Russian Academy of Sciences, Institute of Macromolecular Compounds (Russian Federation); Volod’ko, A. V.; Ermak, I. M. [Russian Academy of Sciences, Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch (Russian Federation); Klechkovskaya, V. V., E-mail: klechvv@ns.crys.ras.ru [Russian Academy of Sciences, Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics” (Russian Federation); Skorik, Yu. A., E-mail: yury-skorik@mail.ru [Russian Academy of Sciences, Institute of Macromolecular Compounds (Russian Federation)

2016-11-15

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan–hyaluronic acid, chitosan–alginic acid, and chitosan–carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Adsorption of molecular brushes with polyelectrolyte backbones onto oppositely charged surfaces: A self-consistent field theory

NARCIS (Netherlands)

Feuz, L.; Leermakers, F.A.M.; Textor, M.; Borisov, O.V.

2008-01-01

The two-gradient version of the Scheutjens¿Fleer self-consistent field (SF-SCF) theory is employed to model the interaction between a molecular bottle brush with a polyelectrolyte backbone and neutral hydrophilic side chains and an oppositely charged surface. Our system mimics graft-copolymers with

Poly-electrolyte fuel cell membrane based on crosslinked polytetrafluoroethylene by radiation-grafting

International Nuclear Information System (INIS)

Ichizuri, Shogo; Asano, Saneto; Li, Jingye

2004-01-01

Poly-electrolyte fuel cell (PEFC) membranes based on crosslinked Polytetrafluoroethylene (RX-PTFE) have been fabricated by radiation-grafting with reactive styrene monomers using γ-ray irradiation in air at room temperature / electron beam irradiation under N 2 gas atmosphere at room temperature. The characteristic properties of obtained materials have been measured by DSC, TGA and FT-IR spectroscopy, and so on. Ion exchange capacity of sulfonated crosslinked PTFE has been achieved 2.8meq/g. (author)

Use of marker ion and cationic surfactant plastic membrane electrode for potentiometric titration of cationic polyelectrolytes.

Science.gov (United States)

Masadome, Takashi; Imato, Toshihiko

2003-07-04

A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to stearyltrimethylammonium (STA) ion is applied to the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by potentiometric titration, using a potassium poly (vinyl sulfate) (PVSK) solution as a titrant. The end-point of the titration is detected as the potential change of the plasticized PVC membrane electrode caused by decrease in the concentration of STA ion added to the sample solution as a marker ion due to the ion association reaction between the STA ion and PVSK. The effects of the concentration of STA ion, coexisting electrolytes in the sample solution and pH of the sample on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2x10(-5) to 4x10(-4) N for Cat-floc, glycol chitosan, and methylglycol chitosan.

Polyelectrolyte-coated nanocapsules containing undecylenic acid: Synthesis, biocompatibility and neuroprotective properties.

Science.gov (United States)

Piotrowski, Marek; Jantas, Danuta; Szczepanowicz, Krzysztof; Łukasiewicz, Sylwia; Lasoń, Władysław; Warszyński, Piotr

2015-11-01

The main objectives of the present study were to investigate the biocompatibility of polyelectrolyte-coated nanocapsules and to evaluate the neuroprotective action of the nanoencapsulated water-insoluble neuroprotective drug-undecylenic acid (UDA), in vitro. Core-shell nanocapsules were synthesized using nanoemulsification and the layer-by-layer (LbL) technique (by saturation method). The average size of synthesized nanocapsules was around 80 nm and the concentration was 2.5 × 10(10) particles/ml. Their zeta potential values ranged from less than -30 mV for the ones with external polyanion layers through -4 mV for the PEG-ylated layers to more than 30 mV for the polycation layers. Biocompatibility of synthesized nanocarriers was evaluated in the SH-SY5Y human neuroblastoma cell line using cell viability/toxicity assays (MTT reduction, LDH release). The results obtained showed that synthesized nanocapsules coated with PLL and PGA (also PEG-ylated) were non-toxic to SH-SY5Y cells, therefore, they were used as nanocarriers for UDA. Moreover, studies with ROD/FITC-labeled polyelectrolytes demonstrated approximately 20% cellular uptake of synthetized nanocapsules. Further studies showed that nanoencapsulated form of UDA was biocompatible and protected SH-SY5Y cells against the staurosporine-induced damage in lower concentrations than those of the same drug added directly to the culture medium. These data suggest that designed nanocapsules might serve as novel, promising delivery systems for neuroprotective agents. Copyright © 2015 Elsevier B.V. All rights reserved.

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

International Nuclear Information System (INIS)

Carballo, R.R.; Campodall' Orto, V.; Hurst, J.A.; Spiaggi, A.; Bonazzola, C.; Rezzano, I.N.

2008-01-01

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

New method for fabrication of loaded micro- and nanocontainers: emulsion encapsulation by polyelectrolyte layer-by-layer deposition on the liquid core.

Science.gov (United States)

Grigoriev, D O; Bukreeva, T; Möhwald, H; Shchukin, D G

2008-02-05

A novel approach to the emulsion encapsulation was developed by combining the advantages of direct encapsulation of a liquid colloidal core with the accuracy and multifunctionality of layer-by-layer polyelectrolyte deposition. Experimental data obtained for the model oil-in-water emulsion confirm unambiguously the alternating PE assembly in the capsule shell as well as the maintenance of the liquid colloidal core. Two different mechanisms of capsule destruction upon interaction with the solid substrate were observed and qualitatively explained. The proposed method can be easily generalized to the preparation of oil-filled capsules in various oil/water/polyelectrolyte systems important in the field of pharmacy, medicine, and food industry.

Influence of corona structure on binding of an ionic surfactant in oppositely charged amphiphilic polyelectrolyte micelles

Czech Academy of Sciences Publication Activity Database

Delisavva, F.; Uchman, M.; Škvarla, J.; Wozniak, E.; Pavlova, Ewa; Šlouf, Miroslav; Garamus, V. M.; Procházka, K.; Štěpánek, M.

2016-01-01

Roč. 32, č. 16 (2016), s. 4059-4065 ISSN 0743-7463 R&D Projects: GA TA ČR(CZ) TE01020118; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : amphiphilic polymers * polyelectrolyte * corona structure Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.833, year: 2016

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

Science.gov (United States)

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

2017-08-01

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

A constraint on the velocity dispersion of the missing mass in the solar neighborhood

International Nuclear Information System (INIS)

Nakamura, Takashi

1978-01-01

The stability of an N-component stellar disk with finite thickness is examined with the gas dynamical approximation. The dispersion relation for marginal stability is obtained. This dispersion relation for N = 2 is applied to the missing mass problem in the solar neighborhood, where two components represent the observed mass component and the missing mass component in the solar neighborhood. From the requirement that the Galactic disk should be locally stable, it is found that the velocity dispersion of the missing mass component should be greater than about 25km/sec. The stability of an infinitesimally thin disk is also investigated and compared with the disk of finite thickness. (auth.)

Application of original assemblies of polyelectrolytes, urease and electrodeposited polyaniline as sensitive films of potentiometric urea biosensors

International Nuclear Information System (INIS)

Buron, Cédric C.; Quinart, Mélanie; Vrlinic, Tjasa; Yunus, Sami; Glinel, Karine; Jonas, Alain M.; Lakard, Boris

2014-01-01

Highlights: • Elaboration of original polymer materials using self-assembly and electrochemistry. • In situ monitoring of the growth of the polymer materials. • Development of urea electrochemical sensors using a home-made mini-potentiostat. - Abstract: Original assemblies were prepared for use as sensitive films of potentiometric enzyme urea sensors, and compared to identify the more efficient structure with respect to stability. These films included electrodeposited polyaniline, used as transducer, urease, used as catalyst, and biocompatible polyelectrolytes, used as a matrix to preserve the integrity of the enzyme in the sensitive film. Two kinds of assemblies were done: the first one consisted in the adsorption of urease onto a polyaniline film followed by the adsorption of a chitosan-carboxymethylpullulan multilayer film, while the second one consisted in the adsorption of a urease-chitosan multilayer film onto an electrodeposited polyaniline film. The morphological features and growth of these assemblies were characterized by scanning electron microscopy and quartz crystal microbalance, respectively. This allowed us to demonstrate that the assemblies are successfully formed onto the electrodes of the sensors. The potentiometric responses of both assemblies were then measured as a function of urea concentration using a home-made portable potentiostat. The electrochemical response of resulting sensors was fast and sensitive for both types of assemblies, but the stability in time was much better for the films obtained from alternative adsorption of urease and chitosan onto a layer of urease adsorbed over electrodeposited polyaniline

Condensation of Counterions Gives Rise to Contraction Transitions in a One-Dimensional Polyelectrolyte Gel

Directory of Open Access Journals (Sweden)

Gerald S. Manning

2018-04-01

Full Text Available The equilibrium volume of a polyelectrolyte gel results from a balance between the tendency to swell caused by outbound polymer/counterion diffusion along with Coulomb interactions on the one hand; and, on the other, the elastic resilience of the cross-linked polymer network. Direct Coulomb forces contribute both to non-ideality of the equilibrated Donnan osmotic pressure, but also to stretching of the network. To isolate the effect of polyelectrolyte expansion, we have analyzed a “one-dimensional” version of a gel, a linear chain of charged beads connected by Hooke’s law springs. As in the range of weak Coulomb strengths previously studied, the springs are significantly stretched by the repulsive interactions among the beads even when the Coulomb strength is strong enough to cause condensation of counterions. There is a quasi-abrupt transition from a stretched state to a partially collapsed state in a transition range between weak and strong Coulomb strengths. Fluctuations between stretched and contracted conformations occur within the transition range. As the solvent quality decreases past the transition range, a progressive collapse can result if the condensed counterions strengthen the spring constant.

Combination of adsorption by porous CaCO3 microparticles and encapsulation by polyelectrolyte multilayer films for sustained drug delivery.

Science.gov (United States)

Wang, Chaoyang; He, Chengyi; Tong, Zhen; Liu, Xinxing; Ren, Biye; Zeng, Fang

2006-02-03

Combination of adsorption by porous CaCO(3) microparticles and encapsulation by polyelectrolyte multilayers via the layer-by-layer (LbL) self-assembly was proposed for sustained drug release. Firstly, porous calcium carbonate microparticles with an average diameter of 5 microm were prepared for loading a model drug, ibuprofen (IBU). Adsorption of IBU into the pores was characterized by ultraviolet (UV), infrared (IR), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) experiment and X-ray diffraction (XRD). The adsorbed IBU amount Gamma was 45.1mg/g for one-time adsorption and increased with increasing adsorption times. Finally, multilayer films of protamine sulfate (PRO) and sodium poly(styrene sulfonate) (PSS) were formed on the IBU-loaded CaCO(3) microparticles by the layer-by-layer self-assembly. Amorphous IBU loaded in the pores of the CaCO(3) microparticles had a rapider release in the gastric fluid and a slower release in the intestinal fluid, compared with the bare IBU crystals. Polyelectrolyte multilayers assembled on the drug-loaded particles by the LbL reduced the release rate in both fluids. In this work, polymer/inorganic hybrid core-shell microcapsules were fabricated for controlled release of poorly water-soluble drugs. The porous inorganic particles are useful to load drugs in amorphous state and the polyelectrolyte multilayer films coated on the particle assuage the initial burst release.

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

Science.gov (United States)

Eleftheriou, E.; Karatasos, K.

2012-10-01

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

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

Science.gov (United States)

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

2008-07-01

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

Thermal analysis of polyaniline poly(N-vinylpyrrolidone)-stabilized dispersions

Czech Academy of Sciences Publication Activity Database

Peřinka, N.; Držková, M.; Hajná, Milena; Jašúrek, B.; Šulcová, P.; Syrový, T.; Kaplanová, M.; Stejskal, Jaroslav

2014-01-01

Roč. 116, č. 2 (2014), s. 589-595 ISSN 1388-6150 R&D Projects: GA TA ČR TE01020022 Institutional support: RVO:61389013 Keywords : polyaniline * poly(N-vinylpyrrolidone) * dispersion Subject RIV: CG - Electrochemistry Impact factor: 2.042, year: 2014

Highly-correlated charges in polyelectrolyte gels

Science.gov (United States)

Sing, Charles; Zwanikken, Johannes; Olvera de La Cruz, Monica

2013-03-01

Polyelectrolyte gels are ubiquitous in polymer physics due to their attractive combination of structural and chemical features that permit the realization of ``environmentally responsive'' systems. The conventional conceptual picture of the volume response of these systems is based on a competition between osmotic and elastic effects. We elaborate on this fundamental understanding by including ion correlations through the use of liquid-state integral equation theory. This allows for a statistical mechanical representation of the state of the system that not only surpasses traditional Poisson-Boltzmann theories but also renders structural features in a highly accurate fashion. In particular, the local ion structure is elucidated, allowing for detailed articulation of charge inversion and condensation effects in the context of gel swelling. The inclusion of correlations has a number of ramifications that become apparent, with enhanced gel collapse and excluded volume competitions that give rise to novel and ion-dependent reentrant swelling effects. We expect this rigorous theory to prove instructive in understanding any number of gelated structures, such as chromosomes or designed synthetic materials for drug delivery.

Polyelectrolyte Complex Nanoparticles of Poly(ethyleneimine) and Poly(acrylic acid): Preparation and Applications

OpenAIRE

Martin Müller; Bernd Keßler; Sebastian Poeschla; Bernhard Torger; Johanna Fröhlich

2011-01-01

In this contribution we outline polyelectrolyte (PEL) complex (PEC) nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAC). It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter) of spherica...

1H NMR analysis of long-chain-branched strong polyelectrolytes obtained by vinyl/divinyl monomer copolymerization in aqueous medium

Czech Academy of Sciences Publication Activity Database

Podešva, Jiří; Spěváček, Jiří; Kratochvíl, Pavel; Netopilík, Miloš

2013-01-01

Roč. 18, č. 7 (2013), s. 557-565 ISSN 1023-666X Institutional support: RVO:61389013 Keywords : long-chain branching * NMR * polyelectrolytes Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.487, year: 2013

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

DEFF Research Database (Denmark)

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

2000-01-01

outlined in the Odijk-Skolnick-Fixman theory, in which the behavior of charged polymers is described only in terms of increasing local rigidity and excluded volume effects. Moreover, the Monte Carlo data are found to be in very good agreement with experimental scattering measurements with equilibrium......We present a systematic Monte Carlo study of the scattering function S(q) of semiflexible polyelectrolytes at infinite dilution, in solutions with different concentrations of added salt. In the spirit of a theoretical description of polyelectrolytes in terms of the equivalent parameters, namely......, persistence length and excluded volume interactions, we used a modified wormlike chain model, in which the monomers are represented by charged hard spheres placed at distance a. The electrostatic interactions are approximated by a Debye-Huckel potential. We show that the scattering function is quantitatively...

Dispersion for the preparation of an injectable radiopharmaceutical scanning agent

International Nuclear Information System (INIS)

Wolfangel, R.G.

1976-01-01

The invention deals with the preparation of a dispersion of a tin (II) sulphur colloid in an aqueous solution with additions of a stabilizing agent. Labelled with sup(99m)Tc, the dispersion can be used as an injectable radiopharmaceutical scanning agent. (VJ) [de

Analysis of site-specific dispersion conditions

International Nuclear Information System (INIS)

Paesler-Sauer, J.

1989-03-01

This report presents an analysis of atmospheric dispersion conditions in the environs of nuclear power stations in the Federal Republic of Germany. The analysis is based on meteorological data measured on the power station sites (KFUe = nuclear reactor remote control records) and by neighbouring stations operated by the German Weather Service. The data are series of hourly mean values of wind and temperature gradient or stability class over the period of one or more years. The aim of the data analysis is to find types of dispersion conditions characterized by the flow field and stratification, and to assess the feasibility of calculating these quantities in the case of an emergency. Influences of terrain structures in the environs of the site are considered. The annual frequencies of types of dispersion situations are assessed, the capability to recognize the dispersion situation from meteorological data measured on the site and the applicability of dispersion models are discussed. (orig.) [de

Dynamically formed hydrous zirconium (IV) oxide-polyelectrolyte membranes. III: Poly(acrylic acid) and substituted poly(acrylic acid) homo, co and terpolymer membranes

International Nuclear Information System (INIS)

Van Reenen, A.J.; Sanderson, R.D.

1989-01-01

A series of acrylic acid and substituted acrylic acid homo, co and terpolymers was synthesised. These polymers were used as polyelectrolytes in dynamically formed hydrous zirconium (iv) oxide-polyelectrolyte membranes. Substitution of the acrylic acid α-hydrogen was done to increase the number of carboxylic acid groups per monomer unit and to change the acid strength of acrylic acid carboxylic acid group. None of these changes improved the salt rejection of these membranes over that of commercially used poly(acrylic acid). Improvement in rejection was found when a hydrophobic comonomer, vinyl acetate, was used in conjunction with acrylic acid in a copolymer dynamic membrane. 16 refs., 6 figs., 1 tab

Evaluating the atmospheric dispersion characteristics of Suez Canal area

International Nuclear Information System (INIS)

Aly, A.I.M.; Sabek, G.; Abd El-Aal, M.; El-Ghamry, M.

1988-01-01

The atmospheric dispersion characteristics of Suez Canal area were determined for subsequent estimation of the environmental impacts of transporting radioactive or hazardous material through the Suez Canal and for the study of environmental pollution resulting from fossil power plants. The atmospheric stability classes were determined at three stations: Port Said, Ismailia and Port Tawfiek (Suez). For achieving this purpose, a computer program was developed through which the atmospheric stability classes A - F and insolation were determined by combining the measured meteorological parameters and the sun elevation which was calculated by another developed computer program with the help of astronomical tables. The results show that the most frequent stability class at Port-Said and Suez is stability class D (neutral condition), whereas at Ismailia area the moderately stable class F, which is the inversion condition with unfavourable dispersion characteristics, is prevailing. The determination of the frequency of stability classes will make it possible to calculate the concentration of a pollutant at a given distance from the source and therefore will be used in dose assessment

Colloid remediation in groundwater by polyelectrolyte capture

International Nuclear Information System (INIS)

Nuttall, H.E.; Rao, S.; Jain, R.

1992-01-01

This paper describes an ongoing study to characterize groundwater colloids, to understand the geochemical factors affecting colloid transport in groundwater, and to develop an in-situ colloid remediation process. The colloids and suspended particulate matter used in this study were collected from a perched aquifer site that has radiation levels several hundred times the natural background and where previous researchers have measured and reported the presence of radiocolloids containing plutonium and americium. At this site, radionuclides have spread over several kilometers. Inorganic colloids collected from water samples are characterized with respect to concentration, mineralogy, size distribution, electrophoretic mobility (zeta potential), and radioactivity levels. Presented are the methods used to investigate the physiochemical factors affecting colloid transport and the preliminary analytical results. Included below are a description of a colloid transport model and the corresponding computational code, water analyses, characterization of the inorganic colloids, and a conceptual description of a process for in-situ colloid remediation using the phenomenon of polyelectrolyte capture

Stable Nafion-functionalized graphene dispersions for transparent conducting films

International Nuclear Information System (INIS)

Liu Yangqiao; Gao Lian; Sun Jing; Wang Yan; Zhang Jing

2009-01-01

Nafion was used for the first time to aid in preparing stable graphene dispersions in mixed water/ethanol (1:1) solvents via the reduction of graphite oxide using hydrazine. The dispersion was characterized by ultraviolet-visible (UV-vis) spectra, transmission electron microscopy, zeta potential analysis, etc. It was found that for Nafion-to-graphene ratios higher than 5:1, graphene solutions with concentrations up to 1 mg ml -1 and stabilities of over three months were obtained. It was proposed that the Nafion adsorbed onto the graphene by the hydrophobic interaction of its fluoro-backbones with the graphene layer and imparted stability by an electrosteric mechanism. Furthermore, transparent and conductive films were prepared using these highly stable Nafion-stabilized graphene dispersions. The prepared Nafion-graphene films possess smooth and homogeneous surfaces and the sheet resistance was as low as 30 kΩ/sq for a transmittance of 80% at 550 nm, which was much lower than for other graphene films obtained by chemical reduction. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed the p-doping of the graphene by Nafion. It was expected that this p-doping effect, as well as the high dispersing ability of Nafion for graphene and the connection of the sp 2 domains by residual Nafion combined to produce good properties of the Nafion-graphene films.

Preparation and tribological behavior of Cu-nanoparticle polyelectrolyte multilayers obtained by spin-assisted layer-by-layer assembly

International Nuclear Information System (INIS)

Yang Guangbin; Geng Zhengang; Ma Hongxia; Wu Zhishen; Zhang Pingyu

2009-01-01

Polyelectrolyte multilayers (PEMs) fabricated by spin-assisted layer-by-layer assembly technique were used as nanoreactors for in-situ synthesis Cu nanoparticles. Chemical reaction within the PEMs was initiated by a reaction cycle in which Cu 2+ was absorbed into the polymer-coated substrate and then reduced in NaBH 4 solutions. Repeating the above process resulted in an increase in density of the nanoparticles and further growth in the dimension of the particles initially formed. So, different Cu-nanoparticle polyelectrolyte multilayers were formed in the process. The friction and wear properties of Cu-nanoparticle PEMs formed by different reaction cycles were investigated on a microtribometer against a stainless steel ball. The PEMs reinforced with Cu nanoparticles, prepared under the best preparation conditions, possess good tribological behavior, because of the weakened adhesion between the PEMs and the substrate and decreased mobility of the polymeric chains in the presence of excessive Cu nanoparticles generated at larger reaction cycles

Insulin-egg yolk dispersions in self microemulsifying system

OpenAIRE

Singnurkar P; Gidwani S

2008-01-01

Formulation of insulin into a microemulsion very often presents a physicochemical instability during their preparation and storage. In order to overcome this lack of stability and facilitate the handling of these colloidal systems, stabilization of insulin in presence of hydrophobic components of a microemulsion appears as the most promising strategy. The present paper reports the use of egg yolk for stabilization of insulin in self microemulsifying dispersions. Insulin loaded egg yolk self m...

Relaxation Behavior by Time-Salt and Time-Temperature Superpositions of Polyelectrolyte Complexes from Coacervate to Precipitate

Directory of Open Access Journals (Sweden)

Samim Ali

2018-01-01

Full Text Available Complexation between anionic and cationic polyelectrolytes results in solid-like precipitates or liquid-like coacervate depending on the added salt in the aqueous medium. However, the boundary between these polymer-rich phases is quite broad and the associated changes in the polymer relaxation in the complexes across the transition regime are poorly understood. In this work, the relaxation dynamics of complexes across this transition is probed over a wide timescale by measuring viscoelastic spectra and zero-shear viscosities at varying temperatures and salt concentrations for two different salt types. We find that the complexes exhibit time-temperature superposition (TTS at all salt concentrations, while the range of overlapped-frequencies for time-temperature-salt superposition (TTSS strongly depends on the salt concentration (Cs and gradually shifts to higher frequencies as Cs is decreased. The sticky-Rouse model describes the relaxation behavior at all Cs. However, collective relaxation of polyelectrolyte complexes gradually approaches a rubbery regime and eventually exhibits a gel-like response as Cs is decreased and limits the validity of TTSS.

Synthesis and Characterization of Fe3O4 Magnetic Nanoparticles Coated with Carboxymethyl Chitosan Grafted Sodium Methacrylate

Directory of Open Access Journals (Sweden)

S. Asgari

2014-01-01

Full Text Available N-sodium acrylate-O-carboxymethyl chitosan [CMCH-g-PAA(Na] bound Fe3O4 nanoparticles were developed as a novel magnetic nanoparticles with an ionic structure that can be potentially used in many fields. CMCH-g-PAA (Na was obtained by grafting of sodium polyacrylate on O-carboxymethyl chitosan, which is an amphiphilic polyelectrolyte with the biocompatibility and biodegradability properties. According to the great interest for improving the stability of Fe3O4 nanoparticles, CMCH-g-PAA (Na was used as a stabilizer to prepare a well dispersed suspension of magnetic nanoparticle According to the results,the presence of CMCH-g-PAA(Na could eliminate agglomeration of magnetic nanoparticles without destroying the superparamagnetic  properties

Stabilization of silica nanoparticles dispersions by surface modification with silicon derivative of thiacalix[4]arene

Energy Technology Data Exchange (ETDEWEB)

Gorbachuk, Vladimir V.; Ziatdinova, Ramilia V. [Kazan Federal University, A.M. Butlerov’ Chemical Institute (Russian Federation); Evtugyn, Vladimir G. [Kazan Federal University, Interdisciplinary Centre for Analytical Microscopy (Russian Federation); Stoikov, Ivan I., E-mail: ivan.stoikov@mail.ru [Kazan Federal University, A.M. Butlerov’ Chemical Institute (Russian Federation)

2015-03-15

For the first time, silica nanopowder functionalized with thiacalixarene derivatives was synthesized by ultrasonication of nanoparticles (diameter 23.7 ± 2.4 nm) with organosilicon derivative of thiacalixarene in glacial acetic acid. The protocol resulted in the formation of colloidal solution of low-disperse (polydispersity index of 0.11) submicron-sized (diameter 192.5 nm) clusters of nanoparticles according to the dynamic light scattering data. As defined by scanning electron microscopy (SEM), mean diameter of thiacalixarene-functionalized nanoparticles is equal to 25.5 ± 2.5 nm and the shape is close to spherical. SEM images confirm low aggregation of thiacalixarene-modified nanoparticle compared to initial silica nanopowder (mean diameter of aggregates 330 and 429 nm, correspondingly). According to the thermogravimetry/differential scanning calorimetry and elemental analysis of the nanoparticles obtained, 5 % of the powder mass was related to thiacalixarene units. The effect of thiacalixarene functionalization of silica nanoparticles on linear polydimethylsiloxane (PDMS)—silica dispersions was modeled to achieve high resistance toward liquid media required for similar sol–gel prepared PDMS-based materials applied for solid-phase microextraction. In such a manner, the influence of thiacalixarene-modified nanofiller on thermal stability and resistance against polar organic solvents was estimated. Similarity of decomposition temperature of both thiacalixarene-functionalized nanoparticles and non-functionalized silica nanoparticles was found. Swelling/solubility behavior observed was related to partial dissolution of PDMS/silica (10 % mixture) in alcohols. Thiacalixarene-functionalized silica particles exerted significantly higher resistance of PDMS/silica composites toward alcohol solvents.

Stabilization of silica nanoparticles dispersions by surface modification with silicon derivative of thiacalix[4]arene

International Nuclear Information System (INIS)

Gorbachuk, Vladimir V.; Ziatdinova, Ramilia V.; Evtugyn, Vladimir G.; Stoikov, Ivan I.

2015-01-01

For the first time, silica nanopowder functionalized with thiacalixarene derivatives was synthesized by ultrasonication of nanoparticles (diameter 23.7 ± 2.4 nm) with organosilicon derivative of thiacalixarene in glacial acetic acid. The protocol resulted in the formation of colloidal solution of low-disperse (polydispersity index of 0.11) submicron-sized (diameter 192.5 nm) clusters of nanoparticles according to the dynamic light scattering data. As defined by scanning electron microscopy (SEM), mean diameter of thiacalixarene-functionalized nanoparticles is equal to 25.5 ± 2.5 nm and the shape is close to spherical. SEM images confirm low aggregation of thiacalixarene-modified nanoparticle compared to initial silica nanopowder (mean diameter of aggregates 330 and 429 nm, correspondingly). According to the thermogravimetry/differential scanning calorimetry and elemental analysis of the nanoparticles obtained, 5 % of the powder mass was related to thiacalixarene units. The effect of thiacalixarene functionalization of silica nanoparticles on linear polydimethylsiloxane (PDMS)—silica dispersions was modeled to achieve high resistance toward liquid media required for similar sol–gel prepared PDMS-based materials applied for solid-phase microextraction. In such a manner, the influence of thiacalixarene-modified nanofiller on thermal stability and resistance against polar organic solvents was estimated. Similarity of decomposition temperature of both thiacalixarene-functionalized nanoparticles and non-functionalized silica nanoparticles was found. Swelling/solubility behavior observed was related to partial dissolution of PDMS/silica (10 % mixture) in alcohols. Thiacalixarene-functionalized silica particles exerted significantly higher resistance of PDMS/silica composites toward alcohol solvents

Preparation and study of properties of dispersed graphene oxide

Directory of Open Access Journals (Sweden)

Evgeniya Seliverstova

2015-09-01

Full Text Available Ability of graphene oxide to form stable dispersion in organic solvents was studied in this work. As it was shown, sonication of graphene leads to the decreas of the particle size. Stability of prepared graphene dispersions was studied upon measurements of distribution of number of the particles via size and change of optical density of the solutions with time. It was found that graphene oxide forms a more stable dispersion in tetrahydrofuran and dimethylformamide than in chloroform and acetone.

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

Science.gov (United States)

Wasupalli, Geeta Kumari; Verma, Devendra

2018-03-16

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

Quenched polyelectrolytes with hydrophobicity independent from chemical charge fraction: A SANS and SAXS study

Directory of Open Access Journals (Sweden)

Souha Ben Mahmoud

2017-11-01

Full Text Available We investigate by SANS and SAXS the structure of semidilute aqueous hydrophobic quenched polyelectrolyte solutions, in which we can vary independently the hydrophobicity and the chemical/electrostatic charge fraction (above the Manning condensation threshold 36%. Such a de-correlation is the original point of the work, reached using statistical tri-copolymers poly(acrylamide-co-styrene-co-2-acrylamido-2-methylpropane-sodium sulfonate, poly(AMx-co-STy-co-AMPSz. The hydrophobicity is brought by ST, the chemical electrostatic charge by AMPS and solubility without charge by AM. We consider that although these copolymers have chemical structure different from partially sulfonated polystyrene sulfonate, PS-co-SSNa, made of two monomers, one charged, one hydrophobic, they have however vicinal behavior. The variation of chemical charge, has no strong consequence on the structure properties which is in agreement with the fact that it is always larger than the Manning threshold. The dependence of q∗ with AM content shows that AM reduces hydrophobicity. The similarity with PS-co-SSNa, for which pearl necklace-like conformations were directly measured by SANS (form factor using ZAC method, suggests that pearl necklace conformations are also adopted by these tri-copolymers and that this behavior could be so generalized to a much larger range of synthetic hydrophobic polyelectrolytes using simple copolymerization.

Layer-by-layer polyelectrolyte-polyester hybrid microcapsules for encapsulation and delivery of hydrophobic drugs.

Science.gov (United States)

Luo, Rongcong; Venkatraman, Subbu S; Neu, Björn

2013-07-08

A two-step process is developed to form layer-by-layer (LbL) polyelectrolyte microcapsules, which are able to encapsulate and deliver hydrophobic drugs. Spherical porous calcium carbonate (CaCO3) microparticles were used as templates and coated with a poly(lactic acid-co-glycolic acid) (PLGA) layer containing hydrophobic compounds via an in situ precipitation gelling process. PLGA layers that precipitated from N-methyl-2-pyrrolidone (NMP) had a lower loading and smoother surface than those precipitated from acetone. The difference may be due to different viscosities and solvent exchange dynamics. In the second step, the successful coating of multilayer polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) onto the PLGA coated CaCO3 microparticles was confirmed with AFM and ζ-potential studies. The release of a model hydrophobic drug, ibuprofen, from these hybrid microcapsules with different numbers of PAH/PSS layers was investigated. It was found that the release of ibuprofen decreases with increasing layer numbers demonstrating the possibility to control the release of ibuprofen with these novel hybrid microcapsules. Besides loading of hydrophobic drugs, the interior of these microcapsules can also be loaded with hydrophilic compounds and functional nanoparticles as demonstrated by loading with Fe3O4 nanoparticles, forming magnetically responsive dual drug releasing carriers.

Enhanced thermal conductivity of nano-SiC dispersed water based ...

Indian Academy of Sciences (India)

Silicon carbide (SiC) nanoparticle dispersed water based nanofluids were prepared using up to 0.1 vol% of nanoparticles. Use of suitable stirring routine ensured uniformity and stability of dispersion. Thermal conductivity ratio of nanofluid measured using transient hot wire device shows a significant increase of up to 12% ...

Rheology and stability kinetics of bare silicon nanoparticle inks for low-cost direct printing

International Nuclear Information System (INIS)

More, Priyesh V.; Jeong, Sunho; Seo, Yeong-Hui; Ryu, Beyong-Hwan; Choi, Youngmin; Kim, Seong Jip; Nahm, Sahn

2013-01-01

Highly dispersed and stable silicon nanoparticles ink is formulated for its application in direct printing or printable electronics. These dispersions are prepared from free-standing silicon nanoparticles which are not capped with any organic ligand, making it suitable for electronic applications. Silicon nanoparticles dispersions are prepared by suspending the nanoparticles in benzonitrile or ethanol by using polypropylene glycol (PPG) as a binder. All the samples show typical shear thinning behavior while the dispersion samples show low viscosities signifying good quality dispersion. Such thinning behavior favors in fabrication of dense films with spin-coating or patterns with drop casting. The dispersion stability is monitored by turbiscan measurements showing good stability for one week. A low-cost direct printing method for dispersion samples is also demonstrated to obtain micro-sized patterns. Low electrical resistivity of resulting patterns, adjustable viscosity and good stability makes these silicon nanoparticles dispersions highly applicable for direct printing process

Rheology and stability kinetics of bare silicon nanoparticle inks for low-cost direct printing

Energy Technology Data Exchange (ETDEWEB)

More, Priyesh V.; Jeong, Sunho; Seo, Yeong-Hui; Ryu, Beyong-Hwan; Choi, Youngmin [Advanced Materials Division, Korea Research Institute of Chemical Technology 141 Gajeong-ro, Yuseong-gu, Daejeon 305-600 (Korea, Republic of); Kim, Seong Jip [Advanced Materials Division, Korea Research Institute of Chemical Technology 141 Gajeong-ro, Yuseong-gu, Daejeon 305-600 Korea and Department of Materials Science and Engineering, Korea University 5-1 Anam-Dong, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Nahm, Sahn [Department of Materials Science and Engineering, Korea University 5-1 Anam-Dong, Seongbuk-gu, Seoul 136-701 (Korea, Republic of)

2013-12-16

Highly dispersed and stable silicon nanoparticles ink is formulated for its application in direct printing or printable electronics. These dispersions are prepared from free-standing silicon nanoparticles which are not capped with any organic ligand, making it suitable for electronic applications. Silicon nanoparticles dispersions are prepared by suspending the nanoparticles in benzonitrile or ethanol by using polypropylene glycol (PPG) as a binder. All the samples show typical shear thinning behavior while the dispersion samples show low viscosities signifying good quality dispersion. Such thinning behavior favors in fabrication of dense films with spin-coating or patterns with drop casting. The dispersion stability is monitored by turbiscan measurements showing good stability for one week. A low-cost direct printing method for dispersion samples is also demonstrated to obtain micro-sized patterns. Low electrical resistivity of resulting patterns, adjustable viscosity and good stability makes these silicon nanoparticles dispersions highly applicable for direct printing process.

Conformation and arrangement of polyelectrolytes in semi-diluted solution. A study by small angle neutrons scattering; Conformation et arrangement des polyelectrolytes en solution semi-diluee. Etude par diffusion des neutrons aux petits angles

Energy Technology Data Exchange (ETDEWEB)

Spiteri, M N

1997-03-25

Polyelectrolytes have particular physical and chemical properties and can thus be used for instance for petroleum production. Some of their microscopic properties have been studied in this work. With the particular zero average contrast technique, the small angle neutron scattering allows to directly know the form factors in semi-diluted solutions of polyelectrolytes where the chains are mixed. Another measure leads to the crystal structure. The electrostatic screen effects when salt is added in aqueous solutions of completely charged PSSNa solutions (f=1) (sodium polystyrene sulfonate) are studied. It seems that the chains take a vermiform conformation. Their persistence length varies as I{sup -1/3} (I is the ionic force). The hydrophobicity effects in partially charged PSSNa solutions (f<1) are given too. They lead to a progressive collapse of the chains when their charge rates decrease. The screen and condensation effects when the charge rate f of the PSSNa (f>f(Manning)) varies in a polar solvent (DMSO) are studied. The vermiform chains have the same persistence length (for each f) which varies as I{sup -1/4}. Lastly, the f variation effects in the case of a weakly charged hydrophilic poly-ion (f

Microwave stability at transition

International Nuclear Information System (INIS)

Holt, J.A.; Colestock, P.L.

1995-05-01

The question of microwave stability at transition is revisited using a Vlasov approach retaining higher order terms in the particle dynamics near the transition energy. A dispersion relation is derived which can be solved numerically for the complex frequency in terms of the longitudinal impedance and other beam parameters. Stability near transition is examined and compared with simulation results

A novel pulsed drug-delivery system: polyelectrolyte layer-by-layer coating of chitosan–alginate microgels

Directory of Open Access Journals (Sweden)

Zhou GC

2013-02-01

Full Text Available Guichen Zhou,1,2,* Ying Lu,1,* He Zhang,1,* Yan Chen,1 Yuan Yu,1 Jing Gao,1 Duxin Sun,3 Guoqing Zhang,2 Hao Zou,1 Yanqiang Zhong1 1Department of Pharmaceutical Science, Second Military Medical University, Shanghai, People's Republic of China; 2Department of Pharmacy, East Hospital of Hepatobiliary Surgery, Shanghai, People's Republic of China; 3Department of Pharmaceutical Sciences, University of Michigan, Ann Arbor, MI, USA*These authors contributed equally to this workPurpose: The aim of this report was to introduce a novel “core-membrane” microgel drug-delivery device for spontaneously pulsed release without any external trigger.Methods: The microgel core was prepared with alginate and chitosan. The semipermeable membrane outside the microgel was made of polyelectrolytes including polycation poly(allylamine hydrochloride and sodium polystyrene sulfonate. The drug release of this novel system was governed by the swelling pressure of the core and the rupture of the outer membrane.Results: The size of the core-membrane microgel drug-delivery device was 452.90 ± 2.71 µm. The surface charge depended on the layer-by-layer coating of polyelectrolytes, with zeta potential of 38.6 ± 1.4 mV. The confocal microscope exhibited the layer-by-layer outer membrane and inner core. The in vitro release profile showed that the content release remained low during the first 2.67 hours. After this lag time, the cumulative release increased to 80% in the next 0.95 hours, which suggested a pulsed drug release. The in vivo drug release in mice showed that the outer membrane was ruptured at approximately 3 to 4 hours, as drug was explosively released.Conclusion: These data suggest that the encapsulated substance in the core-membrane microgel delivery device can achieve a massive drug release after outer membrane rupture. This device was an effective system for pulsed drug delivery.Keywords: polyelectrolyte, chitosan–alginate, microgels, layer-by-layer, pulsed

Swelling of biological and semiflexible polyelectrolytes.

Science.gov (United States)

Dobrynin, Andrey V; Carrillo, Jan-Michael Y

2009-10-21

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

In vitro characterization of a novel polymeric system for preparation of amorphous solid drug dispersions.

Science.gov (United States)

Mahmoudi, Zahra N; Upadhye, Sampada B; Ferrizzi, David; Rajabi-Siahboomi, Ali R

2014-07-01

Preparation of amorphous solid dispersions using polymers is a commonly used formulation strategy for enhancing the solubility of poorly water-soluble drugs. However, often a single polymer may not bring about a significant enhancement in solubility or amorphous stability of a poorly water-soluble drug. This study describes application of a unique and novel binary polymeric blend in preparation of solid dispersions. The objective of this study was to investigate amorphous solid dispersions of glipizide, a BCS class II model drug, in a binary polymeric system of polyvinyl acetate phthalate (PVAP) and hypromellose (hydroxypropyl methylcellulose, HPMC). The solid dispersions were prepared using two different solvent methods: rotary evaporation (rotavap) and fluid bed drug layering on sugar spheres. The performance and physical stability of the dispersions were evaluated with non-sink dissolution testing, powder X-ray diffraction (PXRD), and modulated differential scanning calorimetry (mDSC). PXRD analysis demonstrated an amorphous state for glipizide, and mDSC showed no evidence of phase separation. Non-sink dissolution testing in pH 7.5 phosphate buffer indicated more than twofold increase in apparent solubility of the drug with PVAP-HPMC system. The glipizide solid dispersions demonstrated a high glass transition temperature (Tg) and acceptable chemical and physical stability during the stability period irrespective of the manufacturing process. In conclusion, the polymeric blend of PVAP-HPMC offers a unique formulation approach for developing amorphous solid dispersions with the flexibility towards the use of these polymers in different ratios and combined quantities depending on drug properties.

Polyelectrolyte-complex nanostructured fibrous scaffolds for tissue engineering

International Nuclear Information System (INIS)

Verma, Devendra; Katti, Kalpana S.; Katti, Dinesh R.

2009-01-01

In the current work, polyelectrolyte complex (PEC) fibrous scaffolds for tissue engineering have been synthesized and a mechanism of their formation has been investigated. The scaffolds are synthesized using polygalacturonic acid and chitosan using the freeze drying methodology. Highly interconnected pores of sizes in the range of 5-20 μm are observed in the scaffolds. The thickness of the fibers was found to be in the range of 1-2 μm. Individual fibers have a nanogranular structure as observed using AFM imaging. In these scaffolds, PEC nanoparticles assemble together at the interface of ice crystals during freeze drying process. Further investigation shows that the freezing temperature and concentration have a remarkable effect on structure of scaffolds. Biocompatibility studies show that scaffold containing chitosan, polygalacturonic acid and hydroxyapatite promotes cell adhesion and proliferation. On the other hand, cells on scaffolds fabricated without hydroxyapatite nanoparticles showed poor adhesion.

Cellular immobilization within microfluidic microenvironments: dielectrophoresis with polyelectrolyte multilayers.

Science.gov (United States)

Forry, Samuel P; Reyes, Darwin R; Gaitan, Michael; Locascio, Laurie E

2006-10-25

The development of biomimetic microenvironments will improve cell culture techniques by enabling in vitro cell cultures that mimic in vivo behavior; however, experimental control over attachment, cellular position, or intercellular distances within such microenvironments remains challenging. We report here the rapid and controllable immobilization of suspended mammalian cells within microfabricated environments using a combination of electronic (dielectrophoresis, DEP) and chemical (polyelectrolyte multilayers, PEMS) forces. While cellular position within the microsystem is rapidly patterned via intermittent DEP trapping, persistent adhesion after removal of electronic forces is enabled by surface treatment with PEMS that are amenable to cellular attachment. In contrast to DEP trapping alone, persistent adhesion enables the soluble microenvironment to be systematically varied, facilitating the use of soluble probes of cell state and enabling cellular characterization in response to various soluble stimuli.

Estimating plume dispersion: a comparison of several sigma schemes

International Nuclear Information System (INIS)

Irwin, J.S.

1983-01-01

The lateral and vertical Gaussian plume dispersion parameters are estimated and compared with field tracer data collected at 11 sites. The dispersion parameter schemes used in this analysis include Cramer's scheme, suggested for tall stack dispersion estimates, Draxler's scheme, suggested for elevated and surface releases, Pasquill's scheme, suggested for interim use in dispersion estimates, and the Pasquill--Gifford scheme using Turner's technique for assigning stability categories. The schemes suggested by Cramer, Draxler and Pasquill estimate the dispersion parameters using onsite measurements of the vertical and lateral wind-velocity variances at the effective release height. The performances of these schemes in estimating the dispersion parameters are compared with that of the Pasquill--Gifford scheme, using the Prairie Grass and Karlsruhe data. For these two experiments, the estimates of the dispersion parameters using Draxler's scheme correlate better with the measurements than did estimates using the Pasquill--Gifford scheme. Comparison of the dispersion parameter estimates with the measurement suggests that Draxler's scheme for characterizing the dispersion results in the smallest mean fractional error in the estimated dispersion parameters and the smallest variance of the fractional errors

Monitoring layer-by-layer assembly of polyelectrolyte multi-layers using high-order cladding mode in long-period fiber gratings

Czech Academy of Sciences Publication Activity Database

Tian, F.; Kaňka, Jiří; Li, X.; Du, H.

-, č. 196 (2014), s. 475-479 ISSN 0925-4005 R&D Projects: GA MŠk(CZ) LH11038 Institutional support: RVO:67985882 Keywords : Layer-by-layer assembly * Polyelectrolyte * Cladding mode Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 4.097, year: 2014

Dispersions of silica nanoparticles in ionic liquids investigated with advanced rheology

International Nuclear Information System (INIS)

Wittmar, Alexandra; Ruiz-Abad, David; Ulbricht, Mathias

2012-01-01

The colloidal stabilities of dispersions of unmodified and surface-functionalized SiO 2 nanoparticles in hydrophobic and hydrophilic imidazolium-based ionic liquids were studied with advanced rheology at three temperatures (25, 100, and 200 °C). The rheological behavior of the dispersions was strongly affected by the ionic liquids hydrophilicity, by the nanoparticles surface, by the concentration of the nanoparticles in the dispersion as well as by the temperature. The unmodified hydrophilic nanoparticles showed a better compatibility with the hydrophilic ionic liquid. The SiO 2 surface functionalization with hydrophobic groups clearly improved the colloidal stability of the dispersions in the hydrophobic ionic liquid. The temperature increase was found to lead to a destabilization in all studied systems, especially at higher concentrations. The results of this study imply that ionic liquids with tailored properties could be used in absorbers directly after reactors for gas-phase synthesis of nanoparticles or/and as solvents for their further surface functionalization without agglomeration or aggregation.

Theory of polyelectrolytes in solvents.

Science.gov (United States)

Chitanvis, Shirish M

2003-12-01

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

Phase behaviour and structure of stable complexes of oppositely charged polyelectrolytes

Science.gov (United States)

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

2009-03-01

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

Modification of polyelectrolyte microcapsules into a container for the low molecular weight compounds

Science.gov (United States)

Goryacheva, O. A.; Gao, H.; Sukhorukov, G. B.

2018-04-01

Polyelectrolyte microcapsules are one of the most successful developments in the direction of target drug delivery. Nevertheless, to encapsulate low molecular weight compounds and to deliver the targeted drugs it is necessary to modify the surface of the microcapsules. Silica nanostructures obtained as result of hydrolysis of (3-Aminopropyl)- triethoxysilane (APTES) were used for the modification of the microcapsules. This material shows no toxic effect on cells and is capable of biodegradation. Amino-groups in the structure of APTES make it possible for further direct bioconjugation.

Nasal inserts containing ondansetron hydrochloride based on Chitosan–gellan gum polyelectrolyte complex: In vitro–in vivo studies

Energy Technology Data Exchange (ETDEWEB)

Sonje, Ashish G.; Mahajan, Hitendra S., E-mail: hsmahajan@rediffmail.com

2016-07-01

The aim of this study was the production of ondansetron hydrochloride loaded lyophilized insert for nasal delivery. The nasal insert was prepared by the lyophilisation technique using Chitosan–gellan gum polyelectrolyte complex as the polymer matrix. The ondansetron loaded inserts were evaluated with respect to water uptake, bioadhesion, drug release kinetic study, ex vivo permeation study, and in vivo study. Lyophilised nasal inserts were characterized by differential scanning calorimetry, scanning electron microscopy and X-ray diffraction study. Scanning electron microscopy confirmed the porous sponge like structure of inserts whereas release kinetic model revealed that drug release followed non-fickian case II diffusion. The nasal delivery showed improved bioavailability as compared to oral delivery. In conclusion, the ondansetron containing nasal inserts based on Chitosan–gellan gum complex with potential muco-adhesive potential is suitable for nasal delivery. - Highlights: • Chitosan–gellan gum polyelectrolyte complex based inserts have been prepared. • The synthesized polymer complex demonstrated important insert properties. • No toxicity was observed toward nasal mucosa. • In vivo study demonstrates the enhancement of bioavailability.

Chemosensors and biosensors based on polyelectrolyte microcapsules containing fluorescent dyes and enzymes.

Science.gov (United States)

Kazakova, Lyubov I; Shabarchina, Lyudmila I; Anastasova, Salzitsa; Pavlov, Anton M; Vadgama, Pankaj; Skirtach, Andre G; Sukhorukov, Gleb B

2013-02-01

The concept of enzyme-assisted substrate sensing based on use of fluorescent markers to detect the products of enzymatic reaction has been investigated by fabrication of micron-scale polyelectrolyte capsules containing enzymes and dyes in one entity. Microcapsules approximately 5 μm in size entrap glucose oxidase or lactate oxidase, with peroxidase, together with the corresponding markers Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (Ru(dpp)) complex and dihydrorhodamine 123 (DHR123), which are sensitive to oxygen and hydrogen peroxide, respectively. These capsules are produced by co-precipitation of calcium carbonate particles with the enzyme followed by layer-by-layer assembly of polyelectrolytes over the surface of the particles and incorporation of the dye in the capsule interior or in the multilayer shell. After dissolution of the calcium carbonate the enzymes and dyes remain in the multilayer capsules. In this study we produced enzyme-containing microcapsules sensitive to glucose and lactate. Calibration curves based on fluorescence intensity of Ru(dpp) and DHR123 were linearly dependent on substrate concentration, enabling reliable sensing in the millimolar range. The main advantages of using these capsules with optical recording is the possibility of building single capsule-based sensors. The response from individual capsules was observed by confocal microscopy as increasing fluorescence intensity of the capsule on addition of lactate at millimolar concentrations. Because internalization of the micron-sized multi-component capsules was feasible, they could be further optimized for in-situ intracellular sensing and metabolite monitoring on the basis of fluorescence reporting.

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.

Statics and dynamics in spherical poly-electrolytes

International Nuclear Information System (INIS)

Belloni, Luc

1987-01-01

Statics and dynamics of globular poly-electrolytes are studied in the framework of the primitive model. All particle, poly-ions and ions, are taken explicitly into account and are considered as charged hard-spheres. In the first part A, the equilibrium and structural properties are calculated with the hyper-netted chain integral equation. The strong accumulation of counterions near the poly-ion surface is studied in terms of condensation. In the large charge regime, the primitive model leads to a liquid-gas like phase separation. The theoretical scattering spectra improve the results of the classical one-component model. Specific applications are presented for micellar solutions. Some improvements of the HNC equation are discussed. In the second part B, the diffusional modes are calculated with the multi-component Smoluchowski equation or with the normal modes macroscopic theory. The non-instantaneous diffusion of ions decreases the velocity of macromolecules, especially at low salinity. The hydrodynamic interactions in concentrated solutions are studied with the screened Navier-Stokes equation. Lastly, the ionic relaxation around colloids is discussed qualitatively. (author) [fr

Clozapine-carboxylic acid plasticized co-amorphous dispersions: Preparation, characterization and solution stability evaluation

Directory of Open Access Journals (Sweden)

Ali Ahmed Mahmoud Abdelhaleem

2015-06-01

Full Text Available This study addressed the possibility of forming of co-amorphous systems between clozapine (CZ and various carboxylic acid plasticizers (CAPs. The aim was to improve the solubility and oral bioavailability of clozapine. Co-amorphous dispersions were prepared using modified solvent evaporation methodology at drug/plasticizer stoichiometric ratios of 1:1, 1:1.5 and 1:2. Solid state characterization was performed using differential scanning calorimetry, X-ray diffraction and infra red spectroscopy. Highly soluble homogeneous co-amorphous dispersions were formed between clozapine and CAPs via hydrogen bonding. The co-amorphous dispersions formed with tartaric acid (1:2 showed the highest dissolution percentage (> 95 % in 20 minutes compared to pure crystalline CZ (56 %. Highly stable solutions were obtained from co-amorphous CZ-citric and CZ-tartaric acid at 1:1.5 molar ratio. The prepared dispersions suggest the possibility of peroral or sublingual administration of highly soluble clozapine at a reduced dose with the great chance to bypass the first pass metabolism.

Highly Dispersed Nickel-Containing Mesoporous Silica with Superior Stability in Carbon Dioxide Reforming of Methane: The Effect of Anchoring

Directory of Open Access Journals (Sweden)

Wenjia Cai

2014-03-01

Full Text Available A series of nickel-containing mesoporous silica samples (Ni-SiO2 with different nickel content (3.1%–13.2% were synthesized by the evaporation-induced self-assembly method. Their catalytic activity was tested in carbon dioxide reforming of methane. The characterization results revealed that the catalysts, e.g., 6.7%Ni-SiO2, with highly dispersed small nickel particles, exhibited excellent catalytic activity and long-term stability. The metallic nickel particle size was significantly affected by the metal anchoring effect between metallic nickel particles and unreduced nickel ions in the silica matrix. A strong anchoring effect was suggested to account for the remaining of small Ni particle size and the improved catalytic performance.

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

Directory of Open Access Journals (Sweden)

Sergio P. Campana-Filho

2009-01-01

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

The influence of screening of the polyion electrostatic potential on the counterion dynamics in polyelectrolyte solutions

Science.gov (United States)

Schipper, F. J. M.; Hollander, J. G.; Leyte, J. C.

1998-10-01

The self-diffusion coefficient of tetra-methylammonium counterion in solutions of polymethacrylic acid in 0953-8984/10/41/004/img1 has been measured over a broad polyion concentration range at a constant degree of neutralization and at different ratios of added monovalent or bivalent salt to polyions. A maximum counterion self-diffusion coefficient was observed as a function of polyion concentration. The value of the self-diffusion coefficient at the maximum did not depend on the valency of the added salt. The maximum was found at lower polymer concentrations and with a higher value, when the ratio of added salt to polyions was increased, as predicted by the Poisson-Boltzmann-Smoluchowski equation in the cylindrical cell model for polyelectrolytes. At higher polyion concentrations a maximum counterion self-diffusion coefficient against the ratio of added salt and polyions was observed, which has not been reported before. Upon increasing this ratio the electrostatic potential of the polyelectrolyte gets screened, leading to an increase of the counterion self-diffusion coefficient. Concentration effects of the added salt on the other hand ultimately lead to a decrease of the counterion self-diffusion coefficient, which explains the occurrence of a maximum.

Dispersion and transport of atmospheric pollutants

International Nuclear Information System (INIS)

Cieslik, S.

1991-01-01

This paper presents the physical mechanisms that govern the dispersion and transport of air pollutant; the influence of the state of the 'carrying fluid', i.e. the role of meteorology; and finally, outlines the different techniques of assessing the process. Aspects of physical mechanisms and meteorology covered include: fate of an air pollutant; turbulence and dispersion; transport; wind speed and direction; atmospheric stability; and the role of atmospheric water. Assessment techniques covered are: concentrations measurements; modelling meteorological observations; and tracer releases. It is concluded that the only way to reduce air pollution is to pollute less. 10 refs., 12 figs., 2 tabs

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

Science.gov (United States)

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes

Directory of Open Access Journals (Sweden)

AYAZ HASSAN

2018-04-01

Full Text Available ABSTRACT Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC anodes are revised for the following catalyst systems: (1 a carbon supported PtMo electrocatalyst submitted to heat treatments; (2 Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C; (3 ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4 Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Effect of screening on the transport of polyelectrolytes through nanopores

Science.gov (United States)

Oukhaled, G.; Bacri, L.; Mathé, J.; Pelta, J.; Auvray, L.

2008-05-01

We study the transport of dextran sulfate molecules (Mw=8000 Da) through a bacterial α-hemolysin channel inserted into a bilayer lipid membrane submitted to an external electric field. We detect the current blockades induced by the molecules threading through one pore and vary the ionic strength in an unexplored range starting at 10-3 M. In the conditions of the experiment, the polyelectrolyte molecules enter the pore only if the Debye screening length is smaller than the pore radius in agreement with theory. We also observe that large potentials favour the passage of the molecules. The distribution of blockade durations suggests that a complex process governs the kinetics of the molecules. The dwelling time increases sharply as the Debye length increases and approaches the pore radius.

Stability and precipitation of diverse nanoparticles

Science.gov (United States)

Desai, Chintal

Nanotechnology is a rapidly growing industry that is exploiting the novel characteristics of materials manufactured at the nanoscale. Carbon based nanomaterials such as Carbon Nanotubes (CNTs) and Detonation Nanodiamond (DND) possess unique properties and find a wide range of industrial applications. With the advent of mass production of such materials, there is a possibility of contamination of water resources. Depending on the surface properties and structures, they might aggregate and settle down, or be dispersed and transported by the water. Therefore, there is a need to develop an understanding of the fate of such materials in aqueous media. The understanding and effect of solution chemistry is a key to predicting their deposition, transport, reactivity, and bioavailability in aquatic environments. The colloidal behavior of organic dispersed CNTs and water dispersed DNDs is investigated. The aggregation behavior of these two colloidal systems is quite different from that of hydrophilic, water soluble functionalized CNTs (F-CNTs). The values of the Fuchs stability ratio or the critical coagulant concentration are determined experimentally using time-resolved dynamic light scattering and are used to predict the stability of such systems. It is found that the aggregation behavior of the organic dispersed, antisolvent precipitated system does not follow the conventional Derjaguin--Landau--Verwey-- Overbeek (DLVO) theory. But they stabilize in the long term, which is attributed to the supersaturation generated by different solubility of a solute in the solvent/antisolvent. Based on particle size distribution, zeta potential as well as the aggregation kinetics, the water dispersed DNDs are found to be relatively stable in aqueous solutions, but aggregate rapidly in presence of mono and divalent salts. Also, the formation of carboxylic groups on the DND surface does not alter colloidal behavior as dramatically as it does for other nanocarbons especially carbon

Sustainable steric stabilization of colloidal titania nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Elbasuney, Sherif, E-mail: sherif_basuney2000@yahoo.com

2017-07-01

Graphical abstract: Controlled surface properties of titania nanoparticles via surface modification, flocculation from aqueous phase (a), stabilization in aqueous phase (b), extraction to organic phase (c). - Highlights: • Complete change in surface properties of titania nanoparticles from hydrophilic to hydrophobic. • Harvesting the formulated nanoparticles from the aqueous phase to the organic phase. • Exclusive surface modification in the reactor during nanoparticle synthesis. • Sustainable stabilization of titania nanoparticles in aqueous media with polar polymeric dispersant. - Abstract: A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180–240 °C to ensure DDSA ring opening

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.

RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

Science.gov (United States)

2016-01-01

We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles. PMID:27708458

Small angle neutron scattering in polyelectrolyte solutions: investigation of polymethacrylic acid solutions by contrast variation method

International Nuclear Information System (INIS)

Glavata, D.; Pleshtil, I.; Kunchenko, A.B.; Ostanevich, Yu.M.

1982-01-01

Neutron experiments performed by the contrast (background) variation method allows to understand better the role that hydration plays in the study of macromolecules and to draw the connection between the excess scattering amplitude of hydrated molecule with its partial volume. The observed dependence of the compensation point on the degree of neutralization apparently plays an important role in the investigation of polyelectrolytes of biological origin

Evaluation of polyelectrolyte complex-based scaffolds for mesenchymal stem cell therapy in cardiac ischemia treatment

OpenAIRE

Ceccaldi, Caroline; Bushkalova, Raya; Alfarano, Chiara; Lairez, Olivier; Calise, Denis; Bourin, Philippe; Frugier, Céline; Rouzaud-Laborde, Charlotte; Cussac, Daniel; Parini, Angelo; Sallerin, Brigitte; Girod Fullana, Sophie

2014-01-01

Three-dimensional (3D) scaffolds hold great potential for stem cell-based therapies. Indeed, recent results have shown that biomimetic scaffolds may enhance cell survival and promote an increase in the concentration of therapeutic cells at the injury site. The aim of this work was to engineer an original polymeric scaffold based on the respective beneficial effects of alginate and chitosan. Formulations were made from various alginate/chitosan ratios to form opposite-charge polyelectrolyte co...

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....

Characterization during storage and dissolution of Solid dispersions containing furosemide and hydroxypropyl methylcellulose

DEFF Research Database (Denmark)

Nielsen, Line Hagner; Rades, T.; Müllertz, A.

2013-01-01

Solid dispersions containing furosemide and various amounts of hydroxypropyl methylcellulose (HPMC) were prepared by spray drying to investigate if the physical stability of amorphous furosemide during storage and dissolution could be improved by formulating the drug as a solid dispersion. All...

Graphene Inks with Cellulosic Dispersants: Development and Applications for Printed Electronics

Science.gov (United States)

Secor, Ethan Benjamin

Graphene offers promising opportunities for applications in printed and flexible electronic devices due to its high electrical and thermal conductivity, mechanical flexibility and strength, and chemical and environmental stability. However, scalable production and processing of graphene presents a critical technological challenge preventing the application of graphene for flexible electronic interconnects, electrochemical energy storage, and chemically robust electrical contacts. In this thesis, a promising and versatile platform for the production, patterning, and application of graphene inks is presented based on cellulosic dispersants. Graphene is produced from flake graphite using scalable liquid-phase exfoliation methods, using the polymers ethyl cellulose and nitrocellulose as multifunctional dispersing agents. These cellulose derivatives offer high colloidal stability and broadly tunable rheology for graphene dispersions, providing an effective and tunable platform for graphene ink development. Thermal or photonic annealing decomposes the polymer dispersant to yield high conductivity, flexible graphene patterns for various electronics applications. In particular, the chemical stability of graphene enables robust electrical contacts for ceramic, metallic, organic and electrolytic materials, validating the diverse applicability of graphene in printed electronics. Overall, the strategy for graphene ink design presented here offers a simple, efficient, and versatile method for integrating graphene in a wide range of printed devices and systems, providing both fundamental insight for nanomaterial ink development and realistic opportunities for practical applications.

A study of the physical properties of lamellar liquid-crystalline dispersions

NARCIS (Netherlands)

Pas, Johannes Cornelis van de

1993-01-01

Important questions addressed in this thesis are (i) which are the factors governing the physical stability of these dispersions and (ii) what is the relation between the chemical composition of the surfactant and the physical stability of these systems as a function of electrolyte type and

Nonaqueous Dispersion Formed by an Emulsion Solvent Evaporation Method Using Block-Random Copolymer Surfactant Synthesized by RAFT Polymerization.

Science.gov (United States)

Ezaki, Naofumi; Watanabe, Yoshifumi; Mori, Hideharu

2015-10-27

As surfactants for preparation of nonaqueous microcapsule dispersions by the emulsion solvent evaporation method, three copolymers composed of stearyl methacrylate (SMA) and glycidyl methacrylate (GMA) with different monomer sequences (i.e., random, block, and block-random) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Despite having the same comonomer composition, the copolymers exhibited different functionality as surfactants for creating emulsions with respective dispersed and continuous phases consisting of methanol and isoparaffin solvent. The optimal monomer sequence for the surfactant was determined based on the droplet sizes and the stabilities of the emulsions created using these copolymers. The block-random copolymer led to an emulsion with better stability than obtained using the random copolymer and a smaller droplet size than achieved with the block copolymer. Modification of the epoxy group of the GMA unit by diethanolamine (DEA) further decreased the droplet size, leading to higher stability of the emulsion. The DEA-modified block-random copolymer gave rise to nonaqueous microcapsule dispersions after evaporation of methanol from the emulsions containing colored dyes in their dispersed phases. These dispersions exhibited high stability, and the particle sizes were small enough for application to the inkjet printing process.

The effect of conformational transition of gelatin-polysaccharide polyelectrolyte complex on its functional properties

Directory of Open Access Journals (Sweden)

Tomáš Valenta

2017-01-01

Full Text Available The blends of gelatin and shear-thinning hydrocolloids (guar gum, kappa-carrageenan and xanthan gum were examined to determine the effect of the conformational change on the functional properties of the solutions. The polyelectrolyte complexes of 0.5% gelatin/0.5% polysaccharide in 70 mM KCl or 70 mM NaCl were investigated by the laboratory rheometer and conductivity meter in the temperature range 25 - 45 °C. The rheological data were fitted by the power-law and Herschel-Bulkley model to obtain the flow parameters. The functional properties of the samples were substantially affected by the conformational change of the polysaccharide, as well as by the type of the hydrocolloid and salt solution. There was an evident change of viscosity and conductivity of the solutions upon heating, corresponding to the helix-coil transition of the polysaccharide at temperature about 35 °C. The type of the salt solvent had an effect on the gelation properties of the samples. Gelatin/kappa-carrageenan blend in NaCl provided a gel of high consistency at ambient temperature (20 - 25 °C, whereas the blend in KCl did not gel in the studied temperature range. The potential stability of the blends was determined by zeta-potential analysis. The low values of ζ-potential indicate that the gelatin/polysaccharide blends are electrically unstable systems which tend to coagulate. The mixtures of gelatin/polysaccharide electrostatic complexes may have a great potential in many food applications.

Amphiphilic Fluorinated Block Copolymer Synthesized by RAFT Polymerization for Graphene Dispersions

Directory of Open Access Journals (Sweden)

Hyang Moo Lee

2016-03-01

Full Text Available Despite the superior properties of graphene, the strong π–π interactions among pristine graphenes yielding massive aggregation impede industrial applications. For non-covalent functionalization of highly-ordered pyrolytic graphite (HOPG, poly(2,2,2-trifluoroethyl methacrylate-block-poly(4-vinyl pyridine (PTFEMA-b-PVP block copolymers were prepared by reversible addition-fragmentation chain transfer (RAFT polymerization and used as polymeric dispersants in liquid phase exfoliation assisted by ultrasonication. The HOPG graphene concentrations were found to be 0.260–0.385 mg/mL in methanolic graphene dispersions stabilized with 10 wt % (relative to HOPG PTFEMA-b-PVP block copolymers after one week. Raman and atomic force microscopy (AFM analyses revealed that HOPG could not be completely exfoliated during the sonication. However, on-line turbidity results confirmed that the dispersion stability of HOPG in the presence of the block copolymer lasted for one week and that longer PTFEMA and PVP blocks led to better graphene dispersibility. Force–distance (F–d analyses of AFM showed that PVP block is a good graphene-philic block while PTFEMA is methanol-philic.

Sustainable steric stabilization of colloidal titania nanoparticles

Science.gov (United States)

Elbasuney, Sherif

2017-07-01

A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This

Plasma treatment of diamond nanoparticles for dispersion improvement in water

International Nuclear Information System (INIS)

Yu Qingsong; Kim, Young Jo; Ma, Hongbin

2006-01-01

Low-temperature plasmas of methane and oxygen mixtures were used to treat diamond nanoparticles to modify their surface characteristics and thus improve their dispersion capability in water. It was found that the plasma treatment significantly reduced water contact angle of diamond nanoparticles and thus rendered the nanoparticles with strong water affinity for dispersion enhancement in polar media such as water. Surface analysis using Fourier transform infrared spectroscopy confirmed that polar groups were imparted on nanoparticle surfaces. As a result, improved suspension stability was observed with plasma treated nanoparticles when dispersed in water

Consequences of Urban Stability Conditions for Computational Fluid Dynamics Simulations of Urban Dispersion

Energy Technology Data Exchange (ETDEWEB)

Lundquist, J K; Chan, S T

2005-11-30

The validity of omitting stability considerations when simulating transport and dispersion in the urban environment is explored using observations from the Joint URBAN 2003 field experiment and computational fluid dynamics simulations of that experiment. Four releases of sulfur hexafluoride, during two daytime and two nighttime intensive observing periods, are simulated using the building-resolving computational fluid dynamics model, FEM3MP to solve the Reynolds Averaged Navier-Stokes equations with two options of turbulence parameterizations. One option omits stability effects but has a superior turbulence parameterization using a non-linear eddy viscosity (NEV) approach, while the other considers buoyancy effects with a simple linear eddy viscosity (LEV) approach for turbulence parameterization. Model performance metrics are calculated by comparison with observed winds and tracer data in the downtown area, and with observed winds and turbulence kinetic energy (TKE) profiles at a location immediately downwind of the central business district (CBD) in the area we label as the urban shadow. Model predictions of winds, concentrations, profiles of wind speed, wind direction, and friction velocity are generally consistent with and compare reasonably well with the field observations. Simulations using the NEV turbulence parameterization generally exhibit better agreement with observations. To further explore this assumption of a neutrally-stable atmosphere within the urban area, TKE budget profiles slightly downwind of the urban wake region in the 'urban shadow' are examined. Dissipation and shear production are the largest terms which may be calculated directly. The advection of TKE is calculated as a residual; as would be expected downwind of an urban area, the advection of TKE produced within the urban area is a very large term. Buoyancy effects may be neglected in favor of advection, shear production, and dissipation. For three of the IOPs, buoyancy

Dispersion Analysis of the ADI-FDTD and S-FDTD Methods

OpenAIRE

KUŞAF, Mehmet; ÖZTOPRAK, Abdullah Y.

2014-01-01

Numerical dispersion performances of ADI-FDTD and S-FDTD methods have been compared. It has been shown that for time steps below the stability limits of the S-FDTD method it has much better dispersion performance compared with the ADI-FDTD method and that the S-FDTD method can be usefully employed for space increments in the order of l/25 to l/50.

Biooxidation of 2-phenylethanol to phenylacetic acid by whole-cell Gluconobacter oxydans biocatalyst immobilized in polyelectrolyte complex capsules

Czech Academy of Sciences Publication Activity Database

Bertóková, A.; Vikartovská, A.; Bučko, M.; Gemeiner, P.; Tkáč, J.; Chorvát, D.; Štefuca, V.; Neděla, Vilém

2015-01-01

Roč. 33, č. 2 (2015), s. 111-120 ISSN 1024-2422 R&D Projects: GA ČR(CZ) GA14-22777S Institutional support: RVO:68081731 Keywords : Gluconobacter oxydans * natural flavors * phenylacetic acid * immobilized whole-cell biocatalyst * polyelectrolyte complex capsules * environmental scanning electron microscopy Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 0.892, year: 2015

Characterization of size, surface charge, and agglomeration state of nanoparticle dispersions for toxicological studies

International Nuclear Information System (INIS)

Jiang Jingkun; Oberdoerster, Guenter; Biswas, Pratim

2009-01-01

Characterizing the state of nanoparticles (such as size, surface charge, and degree of agglomeration) in aqueous suspensions and understanding the parameters that affect this state are imperative for toxicity investigations. In this study, the role of important factors such as solution ionic strength, pH, and particle surface chemistry that control nanoparticle dispersion was examined. The size and zeta potential of four TiO 2 and three quantum dot samples dispersed in different solutions (including one physiological medium) were characterized. For 15 nm TiO 2 dispersions, the increase of ionic strength from 0.001 M to 0.1 M led to a 50-fold increase in the hydrodynamic diameter, and the variation of pH resulted in significant change of particle surface charge and the hydrodynamic size. It was shown that both adsorbing multiply charged ions (e.g., pyrophosphate ions) onto the TiO 2 nanoparticle surface and coating quantum dot nanocrystals with polymers (e.g., polyethylene glycol) suppressed agglomeration and stabilized the dispersions. DLVO theory was used to qualitatively understand nanoparticle dispersion stability. A methodology using different ultrasonication techniques (bath and probe) was developed to distinguish agglomerates from aggregates (strong bonds), and to estimate the extent of particle agglomeration. Probe ultrasonication performed better than bath ultrasonication in dispersing TiO 2 agglomerates when the stabilizing agent sodium pyrophosphate was used. Commercially available Degussa P25 and in-house synthesized TiO 2 nanoparticles were used to demonstrate identification of aggregated and agglomerated samples.