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Sample records for interfacial polyelectrolyte complexation

  1. Interfacial tension of polyelectrolyte complex coacervate phases.

    SciTech Connect

    Qin, Jian; Priftis, Dimitrios; Farina, R; Perry, Sarah L.; Leon, Lorraine F.; Whitmer, Jonathan; Hoffmann, Kyle; Tirrell, Matthew; de Pablo, Juan J.

    2014-06-01

    We consider polyelectrolyte solutions which, under suitable conditions, phase separate into a liquid-like coacervate phase and a coexisting supernatant phase that exhibit an extremely low interfacial tension. Such interfacial tension provides the basis for most coacervate-based applications, but little is known about it, including its dependence on molecular weight, charge density, and salt concentration. By combining a Debye-Huckel treatment for electrostatic interactions with the Cahn-Hilliard theory, we derive explicit expressions for this interfacial tension. In the absence of added salts, we find that the interfacial tension scales as N-3/2(eta/eta(c)-1)(3/2) near the critical point of the demixing transition, and that it scales as eta(1/2) far away from it, where N is the chain length and eta measures the electrostatic interaction strength as a function of temperature, dielectric constant, and charge density of the polyelectrolytes. For the case with added salts, we find that the interfacial tension scales with the salt concentration psi as N-1/4(1-psi/psi(c))(3/2) near the critical salt concentration psi(c). Our predictions are shown to be in quantitative agreement with experiments and provide a means to design new materials based on polyelectrolyte complexation.

  2. One-Step Generation of Multifunctional Polyelectrolyte Microcapsules via Nanoscale Interfacial Complexation in Emulsion (NICE).

    PubMed

    Kim, Miju; Yeo, Seon Ju; Highley, Christopher B; Burdick, Jason A; Yoo, Pil J; Doh, Junsang; Lee, Daeyeon

    2015-08-25

    Polyelectrolyte microcapsules represent versatile stimuli-responsive structures that enable the encapsulation, protection, and release of active agents. Their conventional preparation methods, however, tend to be time-consuming, yield low encapsulation efficiency, and seldom allow for the dual incorporation of hydrophilic and hydrophobic materials, limiting their widespread utilization. In this work, we present a method to fabricate stimuli-responsive polyelectrolyte microcapsules in one step based on nanoscale interfacial complexation in emulsions (NICE) followed by spontaneous droplet hatching. NICE microcapsules can incorporate both hydrophilic and hydrophobic materials and also can be induced to trigger the release of encapsulated materials by changes in the solution pH or ionic strength. We also show that NICE microcapsules can be functionalized with nanomaterials to exhibit useful functionality, such as response to a magnetic field and disassembly in response to light. NICE represents a potentially transformative method to prepare multifunctional nanoengineered polyelectrolyte microcapsules for various applications such as drug delivery and cell mimicry.

  3. Composite Scaffold of Poly(Vinyl Alcohol) and Interfacial Polyelectrolyte Complexation Fibers for Controlled Biomolecule Delivery

    PubMed Central

    Cutiongco, Marie Francene A.; Choo, Royden K. T.; Shen, Nathaniel J. X.; Chua, Bryan M. X.; Sju, Ervi; Choo, Amanda W. L.; Le Visage, Catherine; Yim, Evelyn K. F.

    2015-01-01

    Controlled delivery of hydrophilic proteins is an important therapeutic strategy. However, widely used methods for protein delivery suffer from low incorporation efficiency and loss of bioactivity. The versatile interfacial polyelectrolyte complexation (IPC) fibers have the capacity for precise spatiotemporal release and protection of protein, growth factor, and cell bioactivity. Yet its weak mechanical properties limit its application and translation into a viable clinical solution. To overcome this limitation, IPC fibers can be incorporated into polymeric scaffolds such as the biocompatible poly(vinyl alcohol) hydrogel (PVA). Therefore, we explored the use of a composite scaffold of PVA and IPC fibers for controlled biomolecule release. We first observed that the permeability of biomolecules through PVA films were dependent on molecular weight. Next, IPC fibers were incorporated in between layers of PVA to produce PVA–IPC composite scaffolds with different IPC fiber orientation. The composite scaffold demonstrated excellent mechanical properties and efficient biomolecule incorporation. The rate of biomolecule release from PVA–IPC composite grafts exhibited dependence on molecular weight, with lysozyme showing near-linear release for 1 month. Angiogenic factors were also incorporated into the PVA–IPC grafts, as a potential biomedical application of the composite graft. While vascular endothelial growth factor only showed a maximum cumulative release of 3%, the smaller PEGylated-QK peptide showed maximum release of 33%. Notably, the released angiogenic biomolecules induced endothelial cell activity thus indicating retention of bioactivity. We also observed lack of significant macrophage response against PVA–IPC grafts in a rabbit model. Showing permeability, mechanical strength, precise temporal growth factor release, and bioinertness, PVA–IPC fibers composite scaffolds are excellent scaffolds for controlled biomolecule delivery in soft tissue

  4. Composite scaffold of poly(vinyl alcohol) and interfacial polyelectrolyte complexation fibers for controlled biomolecule delivery.

    PubMed

    Cutiongco, Marie Francene A; Choo, Royden K T; Shen, Nathaniel J X; Chua, Bryan M X; Sju, Ervi; Choo, Amanda W L; Le Visage, Catherine; Yim, Evelyn K F

    2015-01-01

    Controlled delivery of hydrophilic proteins is an important therapeutic strategy. However, widely used methods for protein delivery suffer from low incorporation efficiency and loss of bioactivity. The versatile interfacial polyelectrolyte complexation (IPC) fibers have the capacity for precise spatiotemporal release and protection of protein, growth factor, and cell bioactivity. Yet its weak mechanical properties limit its application and translation into a viable clinical solution. To overcome this limitation, IPC fibers can be incorporated into polymeric scaffolds such as the biocompatible poly(vinyl alcohol) hydrogel (PVA). Therefore, we explored the use of a composite scaffold of PVA and IPC fibers for controlled biomolecule release. We first observed that the permeability of biomolecules through PVA films were dependent on molecular weight. Next, IPC fibers were incorporated in between layers of PVA to produce PVA-IPC composite scaffolds with different IPC fiber orientation. The composite scaffold demonstrated excellent mechanical properties and efficient biomolecule incorporation. The rate of biomolecule release from PVA-IPC composite grafts exhibited dependence on molecular weight, with lysozyme showing near-linear release for 1 month. Angiogenic factors were also incorporated into the PVA-IPC grafts, as a potential biomedical application of the composite graft. While vascular endothelial growth factor only showed a maximum cumulative release of 3%, the smaller PEGylated-QK peptide showed maximum release of 33%. Notably, the released angiogenic biomolecules induced endothelial cell activity thus indicating retention of bioactivity. We also observed lack of significant macrophage response against PVA-IPC grafts in a rabbit model. Showing permeability, mechanical strength, precise temporal growth factor release, and bioinertness, PVA-IPC fibers composite scaffolds are excellent scaffolds for controlled biomolecule delivery in soft tissue engineering.

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

    PubMed Central

    Vehlow, David; Schmidt, Romy; Gebert, Annett; Siebert, Maximilian; Lips, Katrin Susanne; Müller, Martin

    2016-01-01

    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.

  6. Composite pullulan-dextran polysaccharide scaffold with interfacial polyelectrolyte complexation fibers: a platform with enhanced cell interaction and spatial distribution.

    PubMed

    Cutiongco, Marie Francene Arnobit; Tan, Ming Hao; Ng, Martin Yoke Kuang; Le Visage, Catherine; Yim, Evelyn King Fai

    2014-10-01

    Hydrogels are highly preferred in soft tissue engineering because they recapitulate the hydrated extracellular matrix. Naturally derived polysaccharides, like pullulan and dextran, are attractive materials with which to form hydrophilic polymeric networks due to their non-immunogenic and non-antigenic properties. However, their inherent hydrophilicity prevents adherent cell growth. In this study, we modified pullulan-dextran scaffolds with interfacial polyelectrolyte complexation (IPC) fibers to improve their ability to support adherent cell growth. We showed that the pullulan-dextran-IPC fiber composite scaffold laden with extracellular matrix protein has improved cell adhesion and proliferation compared to the plain polysaccharide scaffold. We also demonstrated the zero-order release kinetics of the biologics bovine serum albumin and vascular endothelial growth factor (VEGF) incorporated in the composite scaffold. Lastly, we showed that the VEGF released from the composite scaffold retained its capacity to stimulate endothelial cell growth. The incorporation of IPC fibers in the pullulan-dextran hydrogel scaffold improved its functionality and biological activity, thus enhancing its potential in tissue engineering applications.

  7. Biosensors from conjugated polyelectrolyte complexes

    PubMed Central

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

    2002-01-01

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

  8. Biosensors from conjugated polyelectrolyte complexes.

    PubMed

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

    2002-01-08

    A charge neutral complex (CNC) was formed in aqueous solution by combining an orange light emitting anionic conjugated polyelectrolyte and a saturated cationic polyelectrolyte at a 1:1 ratio (per repeat unit). Photoluminescence (PL) from the CNC can be quenched by both the negatively charged dinitrophenol (DNP) derivative, (DNP-BS(-)), and positively charged methyl viologen (MV(2+)). Use of the CNC minimizes nonspecific interactions (which modify the PL) between conjugated polyelectrolytes and biopolymers. Quenching of the PL from the CNC by the DNP derivative and specific unquenching on addition of anti-DNP antibody (anti-DNP IgG) were observed. Thus, biosensing of the anti-DNP IgG was demonstrated.

  9. Saloplastics: processing compact polyelectrolyte complexes.

    PubMed

    Schaaf, Pierre; Schlenoff, Joseph B

    2015-04-17

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

  10. Patterned Microstructure Fabrication: Polyelectrolyte Complexes vs Polyelectrolyte Multilayers

    PubMed Central

    Gai, Meiyu; Frueh, Johannes; Kudryavtseva, Valeriya L.; Mao, Rui; Kiryukhin, Maxim V.; Sukhorukov, Gleb B.

    2016-01-01

    Polyelectrolyte complexes (PEC) are formed by mixing the solutions of oppositely charged polyelectrolytes, which were hitherto deemed “impossible” to process, since they are infusible and brittle when dry. Here, we describe the process of fabricating free-standing micro-patterned PEC films containing array of hollow or filled microchambers by one-step casting with small applied pressure and a PDMS mould. These structures are compared with polyelectrolyte multilayers (PEM) thin films having array of hollow microchambers produced from a layer-by-layer self-assembly of the same polyelectrolytes on the same PDMS moulds. PEM microchambers “cap” and “wall” thickness depend on the number of PEM bilayers, while the “cap” and “wall” of the PEC microchambers can be tuned by varying the applied pressure and the type of patterned mould. The proposed PEC production process omits layering approaches currently employed for PEMs, reducing the production time from ~2 days down to 2 hours. The error-free structured PEC area was found to be significantly larger compared to the currently-employed microcontact printing for PEMs. The sensitivity of PEC chambers towards aqueous environments was found to be higher compared to those composed of PEM. PMID:27830831

  11. Field theoretic simulations of the interfacial properties of complex coacervates

    NASA Astrophysics Data System (ADS)

    Riggleman, Robert; Fredrickson, Glenn

    2011-03-01

    Many biological processes and emerging technologies, such as wet adhesives and biosensors, rely on the association between oppositely charged polyelectrolytes. Such association is driven not only by the electrostatic interactions between the polyelectrolytes, but there is also a substantial entropy gain associated with counterion release upon complexation. In some cases, the association between oppositely charged polymers can lead to a solid precipitate while others can result in a fluid phase rich in polyelectrolytes (coacervate phase) coexisting with a polyelectrolyte-dilute solvent phase. For many of the applications seeking to exploit coacervation, characterization of the interface between the solvent phase and the coacervate is of paramount importance. In this talk, we will present the results of field-theoretic simulations for a coarse-grained polyelectrolyte model that exhibits complex coacervation. Our simulations sample the fully-fluctuating fields in three-dimensions and provide a detailed characterization of the interface between the solvent and the coacervate phase for symmetric polyelectrolytes (where both the polycations and the polyanions carry identical charge densities) as a function of salt concentration and strength of the electrostatic fields. Finally, we characterize the interfacial properties for a select set of asymmetric conditions.

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

    PubMed

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

    2016-02-16

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

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

    PubMed Central

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

    2016-01-01

    It is well known that polyelectrolyte complexes and coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to mainly electrostatic attraction between the oppositely charged polymers. Here, we report the first (to the best of our knowledge) complexation and coacervation of two positively charged polyelectrolytes, which provides a new paradigm for engineering strong, self-healing interactions between polyelectrolytes underwater and a new marine mussel-inspired underwater adhesion mechanism. Unlike the conventional complex coacervate, the like-charged coacervate is aggregated by strong short-range cation–π interactions by overcoming repulsive electrostatic interactions. The resultant phase of the like-charged coacervate comprises a thin and fragile polyelectrolyte framework and round and regular pores, implying a strong electrostatic correlation among the polyelectrolyte frameworks. The like-charged coacervate possesses a very low interfacial tension, which enables this highly positively charged coacervate to be applied to capture, carry, or encapsulate anionic biomolecules and particles with a broad range of applications. PMID:26831090

  14. Solution-processed pH-neutral conjugated polyelectrolyte improves interfacial contact in organic solar cells.

    PubMed

    Zhou, Huiqiong; Zhang, Yuan; Mai, Cheng-Kang; Seifter, Jason; Nguyen, Thuc-Quyen; Bazan, Guillermo C; Heeger, Alan J

    2015-01-27

    The intrinsic acidic nature of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole-transporting layer (HTL) induces interfacial protonation and limits the device performance in organic solar cells based on basic pyridylthiadiazole units. By utilizing a pH neutral, water/alcohol soluble conjugated polyelectrolyte CPE-K as the HTL in p-DTS(PTTh2)2:PC71BM solar cells, a 60% enhancement in PCE has been obtained with an increased V(bi), reduced R(s), and improved charge extraction. These effects originate from the elimination of interfacial protonation and energy barrier compared with the PEDOT:PSS HTL.

  15. Modeling competitive substitution in a polyelectrolyte complex

    SciTech Connect

    Peng, B.; Muthukumar, M.

    2015-12-28

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

  16. Modeling competitive substitution in a polyelectrolyte complex

    NASA Astrophysics Data System (ADS)

    Peng, B.; Muthukumar, M.

    2015-12-01

    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.

  17. Tracer Diffusion of Polyelectrolytes in a Complex Medium

    NASA Astrophysics Data System (ADS)

    Ma, J.; Bruggink, J. L.; Yu, H.

    1997-03-01

    The issue of translational polyelectrolyte diffusion in a complex medium is of both fundamental and practical interest. In our study we examine the diffusion in a gelatin gel as a function of molecular weight and polyelectrolytes concentration. Fractionated, monodisperse gelatin is used as a model matrix. The diffusion of poly(styrene sulfonate) (PSS) and poly (2-acrylamido-2-methylpropane sulfonate) (PAMPS), both in the form of sodium salts, have been studied using fluorescence recovery after photobleaching (FRAP) and dynamic light scattering (DLS) techniques. A series of molecular weights of the two polyelectrolytes and the gelatin have been labeled with fluorescent dyes so that diffusion of each component can be studied individually. By correlating the diffusion of the polyelectrolyte and gelatin, we gain insight into the interactions between the polyelectrolytes and the matrix.

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

    PubMed

    Ou, Zhaoyang; Muthukumar, M

    2006-04-21

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

  19. Theory of polyelectrolyte adsorption on heterogeneously charged surfaces applied to soluble protein-polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    de Vries, R.; Weinbreck, F.; de Kruif, C. G.

    2003-03-01

    Existing theoretical approaches to polymer adsorption on heterogeneous surfaces are applied to the problems of polyelectrolyte and polyampholyte adsorption on randomly charged surfaces. Also, analytical estimates are developed for the critical pH at which weakly charged polyelectrolytes and globular proteins start forming soluble complexes. Below a critical salt concentration, soluble complexes form "on the wrong side" of the protein isoelectric point due to the heterogeneity of the protein surface charge distribution. The analytical estimates are consistent with experimental data on soluble complexes in mixtures of gum arabic and whey protein isolate.

  20. Effect of polyelectrolyte-surfactant complexation on Marangoni transport at a liquid-liquid interface.

    PubMed

    Dunér, Gunnar; Kim, Michelle; Tilton, Robert D; Garoff, Stephen; Przybycien, Todd M

    2016-04-01

    Complexation of surfactants and oppositely charged polyelectrolytes is expected to alter Marangoni transport at a fluid interface compared to either single component system due to altered interfacial tension isotherms and mass transfer rates as well as adsorption irreversibility effects. We investigate Marangoni transport at the oil/water interface by passing mixtures of the anionic surfactant sodium dodecyl sulfate (SDS) and cationic polyelectrolyte poly(3-(2-methylpropionamide)propyl) trimethylammonium chloride-acrylamide (poly[AM-MAPTAC]), or rinsing solutions, over an oil/water interface in a radial, stagnation point flow. The displacements of adsorbed tracer particles are recorded through optical microscopy. The net displacement, defined as the sum of the displacements occurring during the adsorption and desorption stages of one application and rinsing cycle, is up to 10 times greater for complexing surfactant/polymer mixtures compared to either single component system. The enhanced net displacement is largely determined by the enhanced transport upon adsorption, while the reverse displacement that would normally occur upon rinsing is partially suppressed by partially irreversible polymer adsorption at the oil/water interface. In addition to effects of complexation on interfacial tension gradient induced flow, complexation effects on the bulk, and possibly interfacial, viscosity also influence the interfacial transport. Copyright © 2016 Elsevier Inc. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Farina, Robert M.

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

  2. Structural study of coacervation in protein-polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

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

  3. Complex coacervation of supercharged proteins with polyelectrolytes.

    PubMed

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

    2016-04-21

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

  4. Interfacial rheology in complex flow

    NASA Astrophysics Data System (ADS)

    Martin, Jeffrey; Hudson, Steven

    2009-03-01

    Multiphase liquid systems are omnipresent in and essential to everyday life, e.g. foods, pharmaceutics, cosmetics, paints, oil recovery, etc. The morphology and stability of such systems depend on dynamic interfacial properties and processes. Typical methods utilized to measure such interfacial properties often employ drops that are much larger and flows that are much simpler than those encountered in typical processing applications. A microfluidic approach is utilized to measure dynamic structure and kinetics in multiphase systems with drop sizes comparable to those encountered in applications and flow complexity that is easily adjustable. The internal circulation and deformation of an aqueous droplet in clear mineral oil is measured using particle tracers and a detailed shape analysis, which is capable of measuring sub-micron deviations in drop shape. Deformation dynamics, detailed drop shape, interfacial tension, and internal circulation patterns and velocities are measured in Poiseuille and transient elongational flows. Flow kinematics are adjusted by varying the microchannel geometry, relative drop size, and drop height. The effects of confinement on interfacial dynamics and circulation patterns and velocities are also explored.

  5. Dynamic Ordering Transitions of Liquid Crystals Driven by Interfacial Complexes Formed Between Polyanions and Amphiphilic Polyamines

    PubMed Central

    Kinsinger, Michael I.; Buck, Maren E.; Campos, Fernando

    2011-01-01

    We report the design of an amphiphilic polyamine based on poly(2-alkenyl azlactone) (polymer 1) that strongly couples the formation of polyelectrolyte complexes at aqueous/liquid crystal (LC) interfaces to ordering transitions in the LC. We demonstrate that the addition of a strong anionic polyelectrolyte to aqueous solutions in contact with polymer 1-laden LC interfaces (prepared by Langmuir-Schaefer transfer of monolayers of polymer 1 onto micrometer-thick films of nematic LC) triggers ordering transitions in the LCs. We further demonstrate that changes in the ordering of the LCs (i) are driven by electrostatic interactions between the polyelectrolytes, (ii) involve multivalent interactions between the polyelectrolytes, and (iii) are triggered by reorganization of the hydrophobic side chains of amphiphilic polymer 1 upon formation of the interfacial complexes. The results presented in this paper lead us to conclude that ordering transitions in LCs can be used to provide insights into the structure and dynamics of interfacial complexes formed between polyelectrolytes. PMID:18991416

  6. A molecular simulation study on salt response of polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    Antila, Hanne; van Tassel, Paul; Sammalkorpi, Maria

    2015-03-01

    In aqueous solutions, oppositely charged polymers, polyelectrolytes (PEs) form complexes which are known to be sensitive to added salt with responses ranging from shrinking to full destabilization of the complex. As a specific application of PE complexes, the complex formation of DNA with polycations has been demonstrated to be an effective means of transfecting genetic material in gene therapy. We use all-atom molecular dynamics and coarse-grained Monte Carlo simulations to investigate the effect of excess salt on DNA-polycation complex stability. The detailed all-atom simulations demonstrate the mechanism of polycation and ion species specific salt-driven dissociation involving charge reversal. More generally, other possible mechanisms of salt driven dissociation exist as well. The coarse grained approach, which describes the PE complex as oppositely charged, rigid rods and ions as hard spheres, provides a more complete understanding of PE interactions in salt, and suggests possible mechanisms leading to repulsion between the oppositely charged polyelectrolytes.

  7. Triazine-based Polyelectrolyte as an Efficient Cathode Interfacial Material for Polymer Solar Cells.

    PubMed

    Chakravarthi, Nallan; Aryal, Um Kanta; Gunasekar, Kumarasamy; Park, Ho-Yeol; Gal, Yeong-Soon; Cho, Young-Rae; Yoo, Seong Il; Song, Myungkwan; Jin, Sung-Ho

    2017-07-26

    A novel polyelectrolyte containing triazine (TAZ) and benzodithiophene (BDT) scaffolds with polar phosphine oxide (P═O) and quaternary ammonium ions as pendant groups, respectively, in the polymer backbone (PBTAZPOBr) was synthesized to use it as a cathode interfacial layer (CIL) for polymer solar cell (PSC) application. Owing to the high electron affinity of the TAZ unit and P═O group, PBTAZPOBr could behave as an effective electron transport material. Due to the polar quaternary ammonium and P═O groups, the interfacial dipole moment created by PBTAZPOBr substantially reduced the work function of the metal cathode to afford better energy alignment in the device, thus enabling electron extraction and reducing recombination of excitons at the photoactive layer/cathode interface. Consequently, the PSC devices based on the poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl]:[6,6]-phenyl-C71-butyric acid methyl ester (PTB7:PC71BM) system with PBTAZPOBr as CIL displayed simultaneously enhanced open-circuit voltage, short-circuit current density, and fill factor, whereas the power conversion efficiency increased from 5.42% to 8.04% compared to that of the pristine Al device. The outstanding performance of PBTAZPOBr is attributed not only to the polar pendant groups of BDT unit but also to the TAZ unit linked with the P═O group of PBTAZPOBr, demonstrating that functionalized TAZ building blocks are very promising cathode interfacial materials (CIMs). The design strategy proposed in this work will be helpful to develop more efficient CIMs for high performance PSCs in the future.

  8. Molecular and structural basis of low interfacial energy of complex coacervates in water.

    PubMed

    Jho, YongSeok; Yoo, Hee Young; Lin, Yanxian; Han, Songi; Hwang, Dong Soo

    2017-01-01

    Complex coacervate refers to a phase-separated fluid, typically of two oppositely charged polyelectrolytes in solution, representing a complex fluid system that has been shown to be of essential interest to biological systems, as well as for soft materials processing owing to the expectation of superior underwater coating or adhesion properties. The significance and interest in complex coacervate fluids critically rely on its low interfacial tension with respect to water that, in turn, facilitates the wetting of macromolecular or material surfaces under aqueous conditions, provided there is attractive interaction between the polyelectrolyte constituents and the surface. However, the molecular and structural bases of these properties remain unclear. Recent studies propose that the formation of water-filled and bifluidic sponge-like nanostructured network, driven by the tuning of electrostatic interactions between the polyelectrolyte constituents or their complexes may be a common feature of complex coacervate fluids that display low fluid viscosity and low interfacial tension, but more studies are needed to verify the generality of these observations. In this review, we summarize representative studies of interfacial tension and ultrastructures of complex coacervate fluids. We highlight that a consensus property of the complex coacervate fluid is the observation of high or even bulk-like water dynamics within the dense complex coacervate phase that is consistent with a low cohesive energy fluid. Our own studies on this subject are enabled by the application of magnetic resonance relaxometry methods relying on spin labels tethered to polyelectrolyte constituents or added as spin labeled probe molecules that partition into the dense versus the equilibrium coacervate phase, permitting the extraction of information on local polymer dynamics, polymer packing and local water dynamics. We conclude with a snapshot of our current perspective on the molecular and structural

  9. Study of polyelectrolyte complexes of chitosan and sulfoethyl cellulose

    SciTech Connect

    Baklagina, Yu. G. Kononova, S. V.; Petrova, V. A.; Kruchinina, E. V.; Nud'ga, L. A.; Romanov, D. P.; Klechkovskaya, V. V.; Orekhov, A. S.; Bogomazov, A. V.; Arkhipov, S. N.

    2013-03-15

    The complexing of polycation chitosan and polyanion sulphoethyl cellulose during the formation of polyelectrolyte simplex membranes using the layer-by-layer deposition of a solution of one polyion on a gel-like film of another one has been studied. The structural characteristics of the multilayer composites and their components have been analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray microanalysis. A technique is proposed for studying the structure of surface layers of thin polymer films (15-20 {mu}m) using a portable DIFREI-401 diffractometer. It is shown that the sequence of layer deposition during the formation of membrane films does not affect their structural characteristics. The interaction between positively charged chitosan groups (-NH{sub 3}{sup +}) and negatively charged sulfoethyl cellulose groups (-SO{sub 3}{sup -}) during the growth of polyelectrolyte complexes results in a packing of chitosan chains in the multilayer film.

  10. Linear Viscoelasticity and Swelling of Polyelectrolyte Complex Coacervates

    NASA Astrophysics Data System (ADS)

    Hamad, Fawzi; Colby, Ralph

    2012-02-01

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

  11. Sequestration of Methylene Blue into Polyelectrolyte Complex Coacervates.

    PubMed

    Zhao, Mengmeng; Zacharia, Nicole S

    2016-08-01

    Polyelectrolyte complex coacervation is a process that has been proposed as a model for protocell formation due to its ability to compartmentalize chemicals in solution without a membrane. During the liquid-liquid phase separation that results in water rich and polyelectrolyte rich phases, small molecules present in solution selectively partition to one phase over the other. This sequestration is based on relative affinities. Here, a study of the sequestration of methylene blue (MB) into the complex coacervate phase of three pairs of synthetic polyelectrolytes is presented; branched polyethylene imine with polyacrylic acid, polyvinyl sulfonate, or poly(4-styrenesulfonic acid). These materials are characterized with UV-vis, zeta potential measurements, and dynamic light scattering. The branched polyethylene imine/poly(4-styrenesulfonic acid) system is shown to have a significantly higher sequestration capacity for the MB as compared to either of the other two systems, based on π-π interactions which are not possible in the other systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Mechanical enhancement of nanofibrous scaffolds through polyelectrolyte complexation

    NASA Astrophysics Data System (ADS)

    Xu, Jia; Cai, Ning; Xu, Weixiu; Xue, Yanan; Wang, Zelong; Dai, Qin; Yu, Faquan

    2013-01-01

    Optimization of mechanical properties is required in applications of tissue-engineered scaffolds. In this study, a polyelectrolyte complexation approach is proposed to improve the mechanical properties of the nanofibrous scaffolds. Through an electrospun chitosan/gelatin (CG) model system, it is demonstrated that the storage modulus of CG nanofiber-based complex membranes is over 103-fold higher than that of neat chitosan or gelatin membranes. Further, an annealing process was found to promote the conjugation of the oppositely charged polymers and thus the tensile modulus of CG membranes is 1.9-fold elevated. When the molar ratio of aminoglucoside units in chitosan to carboxyl units in gelatin is 1:1, the complex nanofiber-based membranes (CG2) display the highest mechanical strength. In addition, the complex membranes reveal an excellent swelling capacity. By comparing the CG membranes electrospun with cast, it is deduced that the complexation is one of the main contributing factors to the improvement in mechanical properties. FTIR and DSC analyses confirm that more molecular interactions took place in the complexation. SEM observation clearly displays the electrospinnability of the complex. Therefore, polyelectrolyte complexation is an effective strategy for enhancing mechanical properties of nanofibrous scaffolds. These mechanically enhanced chitosan/gelatin nanofibrous membranes have wider applications than wound dressing.

  13. Using jet mixing to prepare polyelectrolyte complexes: complex properties and their interaction with silicon oxide surfaces.

    PubMed

    Ankerfors, Caroline; Ondaral, Sedat; Wågberg, Lars; Odberg, Lars

    2010-11-01

    The influence of mixing procedure on the properties of polyelectrolyte complexes (PECs) was investigated using two complexation techniques, polyelectrolyte titration and jet mixing, the latter being a new method for PEC preparation. For the low-molecular-weight polyelectrolytes polyacrylic acid (PAA) and polyallyl amine hydrochloride (PAH), shorter mixing times produced smaller PECs, whereas for higher molecular weights of the same polyelectrolytes, PEC size first decreased with decreasing mixing time to a certain level, after which it started increasing again. This pattern was likely due to the diffusion-controlled formation of "pre-complexes", which, in the case of low-molecular-weight polymers, occurs sufficiently quickly to form stable complexes; when polyelectrolytes are larger, however, non-equilibrium pre-complexes, more prone to aggregation, are formed. Comparing the techniques revealed that jet mixing produced smaller complexes, allowing PEC size to be controlled by mixing time, which was not the case with polyelectrolyte titration. Higher polyelectrolyte concentration during jet mixing led to the formation of larger PECs. It was also demonstrated that PEC size could be changed after preparation: increasing the pH of the PEC dispersion led to an irreversible increase in PEC size, whereas lowering the pH did not influence PEC size. The adsorption behavior of PECs formed from weak polyelectrolytes on model substrates was studied using QCM-D, SPAR, and AFM imaging; the results indicated that increasing the pH increased the amount of PECs adsorbed to model surfaces. However, the amount of PECs adsorbed to the model surfaces was low compared with other systems in all studied cases. Copyright 2010 Elsevier Inc. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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-averaged molar

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

    NASA Astrophysics Data System (ADS)

    Tirrell, Matthew

    2012-02-01

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

  16. Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

    NASA Astrophysics Data System (ADS)

    Riggleman, Robert A.; Kumar, Rajeev; Fredrickson, Glenn H.

    2012-01-01

    Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field-theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

  17. Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

    SciTech Connect

    Kumar, Rajeev

    2012-01-01

    Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

  18. Investigation of the interfacial tension of complex coacervates using field-theoretic simulations.

    PubMed

    Riggleman, Robert A; Kumar, Rajeev; Fredrickson, Glenn H

    2012-01-14

    Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field-theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

  19. Compact Polyelectrolyte Complexes: “Saloplastic” Candidates for Biomaterials

    PubMed Central

    2009-01-01

    Precipitates of polyelectrolyte complexes were transformed into rugged shapes suitable for bioimplants by ultracentrifugation in the presence of high salt concentration. Salt ions dope the complex, creating a softer material with viscous fluid-like properties. Complexes that were compacted under the centrifugal field (CoPECs) were made from poly(diallyldimethyl ammonium), PDADMA, as polycation, and poly(styrene sulfonate), PSS, or poly(methacrylic acid), PMAA, as polyanion. Dynamic mechanical testing revealed a rubbery plateau at lower frequencies for PSS/PDADMA with moduli that decreased with increasing salt concentration, as internal ion pair cross-links were broken. CoPECs had significantly lower modulii compared to similar polyelectrolyte complexes prepared by the “multilayering” method. The difference in mechanical properties was ascribed to higher water content (located in micropores) for the former and, more importantly, to their nonstoichiometric polymer composition. The modulus of PMAA/PDADMA CoPECs, under physiological conditions, demonstrated dynamic mechanical properties that were close to those of the nucleus pulposus in an intervertebral disk. PMID:19835412

  20. Understanding and Controlling Transitions in Polyelectrolyte Complex Materials

    NASA Astrophysics Data System (ADS)

    Perry, Sarah; Chang, Li-Wei; Liu, Yalin; Momani, Brian; Velez, Jon; Winter, H. Henning

    Polyelectrolyte complexation can be used in the self-assembly of a wide range of responsive soft materials ranging from dehydrated thin film and bulk solids to dense, polymer-rich liquid complex coacervates, and more complex hierarchical structures such as micelles and hydrogels. This responsivity can include swelling and dissolution, or liquid-to-solid transitions, typically as a function of ionic strength and/or pH. The patterning or presentation of charges and other chemical functionalities represents a powerful strategy for the design and manipulation of this type of responsiveness and the corresponding material properties. We utilize polypeptides and polypeptide derivatives as a model platform for the study of sequence and patterning effects on materials self-assembly. We also utilize rheology to understand the nature of the solid-to-liquid transition that has been observed in some systems. The goal of this systematic investigation of the effects of charge patterning is to elucidate design rules that facilitate the tailored creation of materials based on polyelectrolyte complexation with defined properties for a wide range of applications.

  1. Preparation and analysis of multilayer composites based on polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.; Baklagina, Yu. G.; Romanov, D. P.; Kononova, S. V.; Volod'ko, A. V.; Ermak, I. M.; Klechkovskaya, V. V.; Skorik, Yu. A.

    2016-11-01

    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.

  2. Electrophoretic separation of proteins via complexation with a polyelectrolyte

    NASA Astrophysics Data System (ADS)

    Baskin, E. M.; Shklovskii, B. I.; Zilberstein, G. V.

    2003-01-01

    We suggest to augment standard isoelectric focusing for separation of proteins in a gradient of pH by a similar focusing in the presence of a strongly charged polyelectrolyte (PE). Proteins which have the same isoelectric point but different “hidden” charges of both signs in this point make complexes with PE, which focus in different pH. This is a result of charge inversion of such proteins by adsorbed PE molecules, which is sensitive to the hidden charge. Hence, the hidden charge is a new separation parameter.

  3. Kinetic Analysis of Nanoparticulate Polyelectrolyte Complex Interactions with Endothelial Cells

    PubMed Central

    Hartig, Sean M.; Greene, Rachel; Carlesso, Gianluca; Higginbotham, James N.; Khan, Wasif N.; Prokop, Ales; Davidson, Jeffrey M.

    2007-01-01

    A non-toxic, nanoparticulate polyelectrolyte complex (PEC) drug delivery system was formulated to maintain suitable physicochemical properties at physiological pH. Toxicity, binding, and internalization were evaluated in relevant microvascular endothelial cells. PEC were non-toxic, as indicated by cell proliferation studies and propidium iodide staining. Inhibitor studies revealed that PEC were bound, in part, via heparan sulfate proteoglycans and internalized through macropinocytosis. A novel, flow cytometric, Scatchard protocol was established and showed that PEC, in the absence of surface modification, bind cells non-specifically with positive cooperativity, as seen by graphical transformations. PMID:17560645

  4. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes

    NASA Astrophysics Data System (ADS)

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-01

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

  5. Self-assembly and molecular "recognition" phenomena in solutions of (bio)polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    Izumrudov, V. A.

    2008-04-01

    Recently published data on polyelectrolyte complexes formed by both oppositely charged synthetic polyions and natural polyelectrolytes (proteins, enzymes, nucleic acids) are summarised. The properties of these complexes and the phase behaviour of their solutions is shown to obey the general trends found in the studies of cooperative interpolyelectrolyte interactions. The principles of functioning of polyelectrolyte complexes that underlie the self-assembly of complexes in solution and determine the ability of complexes to retain stability over a specified broad range of external conditions and then to quickly and reversibly respond with high sensitivity to a change in the environment by changing their molecular characteristics and phase state are considered. The successful use of the results of fundamental research of (bio)polyelectrolyte complexes for the solution of topical problems of biotechnology, materials science and medicine are demonstrated.

  6. Ionic content and permeability of polyelectrolyte multilayers and complexes

    NASA Astrophysics Data System (ADS)

    Ghostine, Ramy A.

    . After the assembly of about a dozen layers, positive sites begin to accrue in the multilayer. The buildup mechanism is highly asymmetric with respect to the layer number, thus a new model profile for PEMU was employed. The critical impact of asymmetric growth on various properties of multilayers is also discussed. Thickness change, surface roughness, mechanical properties and ionic content of PEMUs were also studied in another part of this dissertation. The effect of salt annealing on these properties was investigated by the use of radiolabeling technique and atomic force microscopy. It was determined that salt annealing causes the polymer mobility in the multilayer to increase, reducing the amount of extrinsic charges and decreasing the surface roughness of the multilayer. The incorporation of 2nd generation fibroblast growth factor was studied in another chapter of this dissertation. FGF-1 is an important protein used in the wound healing process. The addition of FGF into films of PEMU was successful after modifying the ionic content of these films. It was shown that treating PSS terminated PEMU films with 10 mM PSS at high salt concentration would remove all positive extrinsic charges from the multilayer and add extra PSS chains in the bulk of the film. The addition of extra PSS depends on the salt concentration used during the PSS treatment. The highest amount of incorporated FGF was 58 mug cm-2. The release of FGF in phosphate buffer saline solution was also tracked for 30 days period. A total of 13 mug cm-2 of FGF were released from (PDADMA/PSS) 10 when treated with PSS at 1.5 M NaCl. Doping constants and diffusion coefficients for an extruded, stoichiometric, dense polyelectrolyte complex, exPEC, were determined for a Hofmeister series of anions in the last part of this dissertation. Both parameters describe the extent and speed to which a complex may be doped, where they followed a Hofmeister ordering and covered a wide range of response. Doping and undoping

  7. Polyelectrolyte Complex Optimization for Macrophage Delivery of Redox Enzyme Nanoparticles

    PubMed Central

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

    2011-01-01

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

  8. Bicontinuous Fluid Structure with Low Cohesive Energy: Molecular Basis for Exceptionally Low Interfacial Tension of Complex Coacervate Fluids.

    PubMed

    Huang, Kuo-Ying; Yoo, Hee Young; Jho, YongSeok; Han, Songi; Hwang, Dong Soo

    2016-05-24

    An exceptionally low interfacial tension of a dense fluid of concentrated polyelectrolyte complexes, phase-separated from a biphasic fluid known as complex coacervates, represents a unique and highly sought-after materials property that inspires novel applications from superior coating to wet adhesion. Despite extensive studies and broad interest, the molecular and structural bases for the unique properties of complex coacervates are unclear. Here, a microphase-separated complex coacervate fluid generated by mixing a recombinant mussel foot protein-1 (mfp-1) as the polycation and hyaluronic acid (HA) as the polyanion at stoichiometric ratios was macroscopically phase-separated into a dense complex coacervate and a dilute supernatant phase to enable separate characterization of the two fluid phases. Surprisingly, despite up to 4 orders of magnitude differing density of the polyelectrolytes, the diffusivity of water in these two phases was found to be indistinguishable. The presence of unbound, bulk-like, water in the dense fluid can be reconciled with a water population that is only weakly perturbed by the polyelectrolyte interface and network. This hypothesis was experimentally validated by cryo-TEM of the macroscopically phase-separated dense complex coacervate phase that was found to be a bicontinuous and biphasic nanostructured network, in which one of the phases was confirmed by staining techniques to be water and the other polyelectrolyte complexes. We conclude that a weak cohesive energy between water-water and water-polyelectrolytes manifests itself in a bicontinuous network, and is responsible for the exceptionally low interfacial energy of this complex fluid phase with respect to virtually any surface within an aqueous medium.

  9. Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

    PubMed

    Mocchiutti, Paulina; Schnell, Carla N; Rossi, Gerardo D; Peresin, María S; Zanuttini, Miguel A; Galván, María V

    2016-10-05

    Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper.

  10. Preparation and characterization modified chitosan by polyelectrolyte complexation

    NASA Astrophysics Data System (ADS)

    Zuhannisa, Nugraheni, Prihati Sih; Budhijanto, Wiratni; Kusumastuti, Yuni

    2017-03-01

    The polyelectrolyte complexes (PECs) of chitosan with various polysaccharides such as alginate, carrageenan, Arabic gum, carboxymethylcellulose (CMC), pectin, and glucomannan were prepared and characterized. The complexation was performed by addition of polysaccharide solution as crosslinking agent into chitosan solution (0.01% and 2 %) under magnetic stirring. The size of the obtained modified chitosan was analyzed by Particle Size Analyzer (PSA). The turbidity and pH were measured to observe the stability of the modified chitosan during the storage. The stability of the complexes was investigated at room temperature (37°C) for 3 weeks. The existence of glucomannan and arabic gum resulted PECs when it reacted with the chitosan solution using ratio 1:1. The changed crosslinker resulted a hydrogel after it blended. The obtained PECs could be affected by the ratio between chitosan and polysaccharide and the molecular weight of both polymers. The crosslinker concentration gave a significantly influenced the obtained particle size at the chitosan concentration 0.01 % and 2%.

  11. The structure and interaction mechanism of a polyelectrolyte complex: a dissipative particle dynamics study.

    PubMed

    Meneses-Juárez, Efrain; Márquez-Beltrán, César; Rivas-Silva, Juan Francisco; Pal, Umapada; González-Melchor, Minerva

    2015-08-07

    The mechanism of complex formation of two oppositely charged linear polyelectrolytes dispersed in a solvent is investigated by using dissipative particle dynamics (DPD) simulation. In the polyelectrolyte solution, the size of the cationic polyelectrolyte remains constant while the size of the anionic chain increases. We analyze the influence of the anionic polyelectrolyte size and salt effect (ionic strength) on the conformational changes of the chains during complex formation. The behavior of the radial distribution function, the end-to-end distance and the radius of gyration of each polyelectrolyte is examined. These results showed that the effectiveness of complex formation is strongly influenced by the process of counterion release from the polyelectrolyte chains. The radius of gyration of the complex is estimated using the Fox-Flory equation for a wormlike polymer in a theta solvent. The addition of salts in the medium accelerates the complex formation process, affecting its radius of gyration. Depending on the ratio of chain lengths a compact complex or a loosely bound elongated structure can be formed.

  12. Wrap-and-Strip Technology of Protein-Polyelectrolyte Complex for Biomedical Application.

    PubMed

    Shiraki, Kentaro; Kurinomaru, Takaaki; Tomita, Shunsuke

    2016-01-01

    A polyelectrolyte is a polymer composed of repeating units of an electrolyte group that enables reversible complex formation with proteins in aqueous solutions. This review introduces "wrap-and-strip" technology of protein-polyelectrolyte complex (PPC) by noncovalent interaction. Storage: protein is stabilized against physical and chemical stresses. Enrichment: precipitation through PPC can be used as an enrichment method without irreversible unfolding. Catalytic activity switch: a complementary charged pair of polyelectrolytes functions as a reversible enzyme activity switch. Hyperactivation: a specific combination of a polyelectrolyte and substrate enhances enzyme activity by one order of magnitude compared with an enzyme alone. Stabilization: PPC increases protein stability against chemical and physical stresses, such as covalently modified polyethylene glycosylated protein. Simple PPC-based technology can expand the applicable fields of soluble proteins in aqueous solutions.

  13. Interfacial energy of polypeptide complex coacervates measured via capillary adhesion.

    PubMed

    Priftis, Dimitrios; Farina, Robert; Tirrell, Matthew

    2012-06-12

    A systematic study of the interfacial energy (γ) of polypeptide complex coacervates in aqueous solution was performed using a surface forces apparatus (SFA). Poly(L-lysine hydrochloride) (PLys) and poly(L-glutamic acid sodium salt) (PGA) were investigated as a model pair of oppositely charged weak polyelectrolytes. These two synthetic polypeptides of natural amino acids have identical backbones and differ only in their charged side groups. All experiments were conducted using equal chain lengths of PLys and PGA in order to isolate and highlight effects of the interactions of the charged groups during complexation. Complex coacervates resulted from mixing very dilute aqueous salt solutions of PLys and PGA. Two phases in equilibrium evolved under the conditions used: a dense polymer-rich coacervate phase and a dilute polymer-deficient aqueous phase. Capillary adhesion, associated with a coacervate meniscus bridge between two mica surfaces, was measured upon the separation of the two surfaces. This adhesion enabled the determination of the γ at the aqueous/coacervate phase interface. Important experimental factors affecting these measurements were varied and are discussed, including the compression force (1.3-35.9 mN/m) and separation speed (2.4-33.2 nm/s). Physical parameters of the system, such as the salt concentration (100-600 mM) and polypeptide chain length (N = 30, 200, and 400) were also studied. The γ of these polypeptide coacervates was separately found to decrease with both increasing salt concentration and decreasing polypeptide chain length. In most of the above cases, γ measurements were found to be very low, <1 mJ/m(2). Biocompatible complex coacervates with low γ have a strong potential for applications in surface coatings, adhesives, and the encapsulation of a wide range of materials.

  14. Characterization of novel lactoferrin loaded capsules prepared with polyelectrolyte complexes.

    PubMed

    Wu, Qing-Xi; Zhang, Qi-Lei; Lin, Dong-Qiang; Yao, Shan-Jing

    2013-10-15

    Novel capsules loaded with lactoferrin (LF) were prepared using polyelectrolyte complexes that were formed by water soluble chitosan (WSC), sodium cellulose sulfate (NaCS) and sodium polyphosphate (PPS). Normal chitosan (soluble in acidic conditions) was chosen as a control to prepare similar capsules with NaCS and PPS. (1)H NMR and FTIR spectra analysis showed that WSC was in a form of chitosan hydrochloride which can be directly dissolved and protonated in acid-free water. SEM results showed that the capsules had a typical wall-capsule structure with a regular spherical shape and an average diameter of 1.97 mm. TGA studies revealed that the thermal stability of the capsules were enhanced and the moisture content of the drug-free/loaded capsules were 6.3% and 3.2%. SDS-PAGE results showed that the primary structures of the processed LF in the capsules were unchanged. Drug loading (LE%) and encapsulation efficiency (EE%) analysis showed that the capsules had a higher LE% (45.6%) and EE% (70.7%) than that of the control. In vitro release studies showed that the capsules had a regular and sustainable release profiles in simulated colonic fluid. All of these results indicated that the capsules prepared could be used as a candidate protein drug carrier for colon. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Lyophilized Chitosan/xanthan Polyelectrolyte Complex Based Mucoadhesive Inserts for Nasal Delivery of Promethazine Hydrochloride

    PubMed Central

    G Dehghan, Mohamed Hassan; Marzuka, Marzuka

    2014-01-01

    The objective of this investigation was the development of chitosan/xanthan polyelectrolyte complex based mucoadhesive nasal insert of promethazine hydrochloride a drug used in the treatment of motion sickness. A 32 factorial design was applied for preparing chitosan/xanthan polyelectrolyte complex and to study the effect of independent variables i.e. concentration of xanthan [X1] and concentration of chitosan [X2] on various responses i.e. viscosity of polyelectrolyte complex solution, water uptake of nasal inserts (at pH 2, 5.5, 7.4), bioadhesion potential of nasal inserts and in-vitro drug release at Q6h through nasal inserts. FTIR and DSC analysis were carried out to confirm complex formation and on loaded and unloaded nasal insert to investigate any drug excipient interaction. The nasal inserts were also characterized by powder X-ray diffractometry (PXRD) and Scanning electron microscopy (SEM) and for ex-vivo permeation studies. The results show that higher amount of xanthan in polyelectrolyte complexes with respect to higher amount of chitosan retarded in-vitro drug release. The water uptake behaviour of nasal insert was strongly influenced by pH of the medium and by polycation/ polyanion concentration. The investigation verifies the formation of polyelectrolyte complexes formation between chitosan and xanthan at pH values in the vicinity of pKa intervals of the two polymers and confirms their potential for the nasal delivery of promethazine hydrochloride. PMID:25276178

  16. Underwater contact adhesion and microarchitecture in polyelectrolyte complexes actuated by solvent exchange

    NASA Astrophysics Data System (ADS)

    Zhao, Qiang; Lee, Dong Woog; Ahn, B. Kollbe; Seo, Sungbaek; Kaufman, Yair; Israelachvili, Jacob N.; Waite, J. Herbert

    2016-04-01

    Polyelectrolyte complexation is critical to the formation and properties of many biological and polymeric materials, and is typically initiated by aqueous mixing followed by fluid-fluid phase separation, such as coacervation. Yet little to nothing is known about how coacervates evolve into intricate solid microarchitectures. Inspired by the chemical features of the cement proteins of the sandcastle worm, here we report a versatile and strong wet-contact microporous adhesive resulting from polyelectrolyte complexation triggered by solvent exchange. After premixing a catechol-functionalized weak polyanion with a polycation in dimethyl sulphoxide (DMSO), the solution was applied underwater to various substrates whereupon electrostatic complexation, phase inversion, and rapid setting were simultaneously actuated by water-DMSO solvent exchange. Spatial and temporal coordination of complexation, inversion and setting fostered rapid (~25 s) and robust underwater contact adhesion (Wad >= 2 J m-2) of complexed catecholic polyelectrolytes to all tested surfaces including plastics, glasses, metals and biological materials.

  17. Polyelectrolyte complex/PVA membranes for diffusion dialysis.

    PubMed

    Wang, Cong; Wu, Cuiming; Wu, Yonghui; Gu, Jingjing; Xu, Tongwen

    2013-10-15

    Polyelectrolyte complexes (PECs)/polyvinyl alcohol (PVA) membranes are prepared from PVA, anion exchange and cation exchange multisilicon copolymers, which contain plenty of functional groups of OH, N(+)(CH3)3/Si(OCH3)3, and SO3Na/Si(OCH3)3, respectively. The OH and Si(OCH3)3 groups can undertake sol-gel reaction to form crosslinking structure, while the N(+)(CH3)3 and SO3Na groups can be combined through electrostatic interaction. The PECs/PVA membranes exhibit improved thermal stability, swelling resistance and flexibility as compared with single anion or cation exchange hybrid membranes. The PECs/PVA membranes have the water uptakes (WR) of 25.3-70.4%, initial decomposition temperatures (IDTs) of 246-285°C, tensile strength of 23.1-33.8 MPa, and elongation at break of 3.5-13.1%. The membranes can be potentially applied for both acid and alkali recovery through diffusion dialysis (DD) process. The separation factor (S) for HCl/FeCl2 mixture can reach up to 89.9, which is about five times higher than that of commercial DF-120 membrane (18.5 at 25°C). The dialysis coefficients of NaOH (UOH) are in the range of 0.014-0.019 m/h, around 7-9 times higher than the value of commercial SPPO membrane (0.002 m/h at 25°C). The membranes also show potential usefulness for industrial acidic and alkali wastes treatment.

  18. Polyelectrolyte complex of carboxymethyl gum katira-chitosan: Preparation and characterization.

    PubMed

    Minkal; Ahuja, Munish; Bhatt, D C

    2017-08-26

    In the present study polyelectrolyte complex between carboxymethyl gum katira and chitosan were prepared and evaluated for drug delivery using ofloxacin as model drug. The carboxymethyl gum katira-chitosan polyelectrolyte complex was characterized by FTIR, DSC, TGA, DTG, XRD and SEM. The influence of concentration of CMGK/CH and drug loading (%) on yield (%) and drug entrapment (%) was studied using response surface methodology. The result of the study revealed that increasing the relative proportion of CMGK/CH in carboxymethyl gum katira-chitosan polyelectrolyte complex decreases the % yield and increases the % drug entrapment. The optimal calculated parameters were polymer ratio (CMGK/CH) 2.13 and drug loading 50 (%w/w). The optimized batch of carboxymethyl gum katira-chitosan polyelectrolyte complex had yield of 69.04%, entrapment efficiency of ofloxacin 84.86%. Further, the optimized batch of carboxymethyl gum katira-chitosan polyelectrolyte complex releases ofloxacin 84.32% following Higuchi's square-root kinetics. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Hypromellose-graft-chitosan and Its Polyelectrolyte Complex as Novel Systems for Sustained Drug Delivery.

    PubMed

    Lai, Wing-Fu; Shum, Ho Cheung

    2015-05-20

    Polyelectrolyte complexes formed between chitosan (CS) and anionic polymers have attracted increasing interest in drug delivery. In this study, CS is copolymerized with hypromellose via a coupling reagent-mediated approach to form a water-soluble, nontoxic CS derivative, namely hypromellose-graft-CS (HC), which is subsequently complexed with carboxymethylcellulose (CMC) to generate a polyampholytic hydrogel. When compared with conventional CS, HC is highly water-soluble across a wide pH range, and has a substantially higher pH buffering capacity to provide a pH-stable environment for delivery of drugs. In addition, the polyelectrolyte complex of HC exhibits a drug encapsulation efficiency of over 90% in all drugs tested, which is 1-2 fold higher than the efficiency attainable by the polyelectrolyte complex of conventional CS, with a 2-3 fold longer duration of sustained drug release. Our results indicate that as a novel polymer, HC has excellent promise for future pharmaceutical applications.

  20. Polyelectrolyte Complexes: A Review of their Applicability in Drug Delivery Technology

    PubMed Central

    Lankalapalli, S.; Kolapalli, V. R. M.

    2009-01-01

    Over the past several years, great advances have been made towards novel drug delivery systems. The phenomena of interpolymer interactions and formation of polyelectrolyte complexes have been the focus of intensive fundamental and applied research. Interpolyelectrolyte complexes combine unique physicochemical properties with high biocompatibility. Studies have been carried out on many different polymer blends and types. Such combinations may possess unique properties that are different from those of individual component. The present review emphasizes on the applicability of polyelectrolyte complexes in drug delivery technology. PMID:20502564

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

    PubMed Central

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-01-01

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail. PMID:25532565

  2. Interfacial Structure, Dynamics, and Transport of Polyelectrolyte Membrane Materials for Fuel Cells

    NASA Astrophysics Data System (ADS)

    Soles, Christopher; Page, K.; Eastman, S.; Kim, S.; Kang, S.; Dura, J.; National Institute of Standards; Technology; Polymers Divison Team; NIST Collaboration

    2011-03-01

    Polymer electrolyte membranes (PEM) fuel cells show promise for a wide range of applications both in the transportation sector and for stationary power production due to their high charge density and low operating temperatures. While the structure and transport of bulk PEMs have been studied extensively, little is known about these materials at interfaces and under confinement, as they exist within the membrane electrode assembly (MEA). Using neutron/ x-ray reflectivity and polarization-modulation infrared reflection-absorption spectroscopy, we have studied the polymer-substrate interfacial structure, swelling, and water transport as function of humidity, surface chemistry, and film thickness. The interfacial structure is highly dependent upon the substrate surface chemistry and the swelling/water diffusivity are suppressed when the PEM is confined to a thin film. This new information will enable researchers to more accurately model the performance of the MEA as current simulations typically rely on bulk property values to predict water and proton transport under these conditions.

  3. Surface-induced rearrangement of polyelectrolyte complexes: influence of complex composition on adsorbed layer properties.

    PubMed

    Ondaral, Sedat; Ankerfors, Caroline; Odberg, Lars; Wågberg, Lars

    2010-09-21

    The adsorption characteristics of two different types of polyelectrolyte complexes (PECs), prepared by mixing poly(allylamine hydrochloride) and poly(acrylic acid) in a confined impinging jet (CIJ) mixer, have been investigated with the aid of stagnation point adsorption reflectometry (SPAR), a quartz crystal microbalance with dissipation (QCM-D), and atomic force microscopy (AFM) using SiO(2) surfaces. The two sets of PEC were prepared by combining high molecular mass PAH/PAA (PEC-A) and low molecular mass PAH/PAA (PEC-B). The PEC-A showed a higher adsorption to the SiO(2) surfaces than the PEC-B. The adsorption of the PEC-A also showed a larger change in the dissipation (ΔD), according to the QCM-D measurements, suggesting that the adsorbed layer of these complexes had a relatively lower viscosity and a lower shear modulus. Complementary investigations of the adsorbed layer using AFM imaging showed that the adsorbed layer of PEC-A was significantly different from that of PEC-B and that the changes in properties with adsorption time were very different for the two types of PECs. The PEC-A complexes showed a coalescence into larger block of complexes on the SiO(2) surface, but this was not detected with the PEC-B. The size determinations of the complexes in solution showed that they were very stable over time, and it was therefore concluded that the coalescence of the complexes was induced by the interaction between the complexes and the surface. The results also indicated that polyelectrolytes can migrate between the different complexes adsorbed to the surface. The results also give indications that the preparation of PEC-B leads to the formation of two different types of polyelectrolyte complexes differing in the amount of polymer in the complexes; i.e., two populations of complexes were formed with similar sizes but with totally different adsorption structures at the solid-liquid interface.

  4. Self-assembled amorphous drug-polyelectrolyte nanoparticle complex with enhanced dissolution rate and saturation solubility.

    PubMed

    Cheow, Wean Sin; Hadinoto, Kunn

    2012-02-01

    The dissolution rate and solubility of poorly soluble drugs can be enhanced by formulating them into stable amorphous nanoparticle complex (nanoplex). For this purpose, a highly sustainable self-assembly drug-polyelectrolyte complexation process is developed, with ciprofloxacin and dextran sulfate as the drug and polyelectrolyte models, respectively. The nanoplex are prepared by mixing two aqueous salt solutions - one containing the drug and the other containing the oppositely charged polyelectrolyte. The nanoplex suspension is transformed into stable dry-powder form by freeze-drying. The effects of drug concentration, drug-to-polyelectrolyte charge ratio, and salt concentration on the complexation efficiency, yield, drug loading, and nanoplex morphology are examined. The dissolution rates and solubility of the nanoplex are characterized and compared to raw drug crystals. Nearly spherical amorphous nanoplex having fairly uniform sizes in the range of 200-400 nm and 80% drug loading are successfully produced at ≥80% complexation efficiency and yield. The complexation efficiency is governed by the drug concentration and its ratio to the salt concentration. The nanoplex powders exhibit approximately twice higher dissolution rate and solubility than raw drug crystals and remain stable after one-month storage. Overall, amorphous nanoplex represent a promising bioavailability-enhanced formulation of poorly soluble drugs owed to their superior characteristics and ease of preparation. Copyright © 2011 Elsevier Inc. All rights reserved.

  5. Novel surfactant-selective membrane electrode based on polyelectrolyte-surfactant complex.

    PubMed

    Zorin, Ivan; Scherbinina, Tatiana; Fetin, Petr; Makarov, Ivan; Bilibin, Alexander

    2014-12-01

    Novel class of active ionophores for surfactant selective electrodes is proposed. PVC membrane doped with polyelectrolyte-surfactant stoichiometric complex is used for ion-selective electrode construction responsive to cetyltrimethyl ammonium bromide and related surfactants. New ionophore is quite stable and completely insoluble in aqueous media in wide range of pH. The electrode displays nearly Nernstian slope in CTAB concentration range 10(-6)-10(-3)M. Polyelectrolyte platform allows to design wide range of different ionophores responsive to cationic organic substances. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Structural and optical behavior of thin films of protein (BSA)-Polyelectrolyte (PAA, PSS) complexes

    NASA Astrophysics Data System (ADS)

    Talukdar, Hrishikesh; Kundu, Sarathi

    2017-05-01

    Optical behaviors of protein (BSA) in the presence of negatively charged polyelectrolytes (PAA and PSS) in thin film confirmation are studied using UV-Vis and photoluminescence spectroscopy. The out-of-plane structures and in-plane surface morphologies of the thin films of protein-polyelectrolyte complexes (PPC) are investigated using X-ray reflectivity (XRR) and Atomic force microscopy (AFM) respectively. It is found that although the out-of-plane structure and surface morphology of PPC is nearly same as in pure polyelectrolyte but a larger red-shift of ≈ 23 nm is obtained in optical emissions from the thin films of PPC in comparison with that of the pure protein and PPC solutions. Mechanism is proposed for such larger red-shift from the thin film of PPC.

  7. Highly sensitive and fast responsive fiber-optic modal interferometric pH sensor based on polyelectrolyte complex and polyelectrolyte self-assembled nanocoating.

    PubMed

    Yin, Mingjie; Gu, Bobo; Zhao, Qiang; Qian, Jinwen; Zhang, Aping; An, Quanfu; He, Sailing

    2011-04-01

    A new fiber-optic pH sensor is demonstrated by coating negatively charged polyelectrolyte complex (PEC(-)) nanoparticles, made of sodium carboxymethyl cellulose and poly(diallyldimethylammonium chloride) (PDDA), and positively charged PDDA on the surface of a thin-core fiber modal interferometer (TCFMI) with a layer-by-layer (LbL) electrostatic self-assembly method. The fabricated TCFMI pH sensor has different transmission dip wavelengths under different pH values and shows high sensitivities of 0.6 nm/pH unit and -0.85 nm/pH unit for acidic and alkaline solutions, respectively, and short response time of 30-50 s. The LbL electrostatic self-assembly process of a PEC(-)/PDDA multilayer is traced by quartz crystal microbalance and shows a fast thickness growth. Atomic force microscopy shows the root mean square (RMS) surface roughness of electrostatic self-assembly nanocoating of polyelectrolyte complex/polyelectrolyte is much higher than that of polyelectrolyte/polyelectrolyte due to the larger size of PEC(-) colloidal nanoparticles. The enhanced RMS surface roughness and thickness of the nanocoating can shorten the response time and raise the sensitivity of the TCFMI pH sensor, respectively. In addition, the TCFMI pH sensor has highly reversible performance and good durability.

  8. Effects of chain rigidity on the adsorption of a polyelectrolyte chain on mixed lipid monolayer: a Monte Carlo study.

    PubMed

    Duan, Xiaozheng; Ding, Mingming; Zhang, Ran; Li, Liangyi; Shi, Tongfei; An, Lijia; Huang, Qingrong; Xu, Wen-Sheng

    2015-05-14

    We apply Monte Carlo simulation to explore the adsorption of a positively charged polyelectrolyte on a lipid monolayer membrane, composed of electronically neutral, monovalent anionic and mulvitalent anionic phospholipids. We systematically assess the influence of various factors, including the intrinsic rigidity of the polyelectrolyte chain, the bead charge density of the polyelectrolyte, and the ionic strength of the saline solution, on the interfacial structural properties of the polyelectrolyte/monolayer complex. The enhancement of the polyelectrolyte chain intrinsic rigidity reduces the polyelectrolyte conformational entropy loss and the energy gains in electrostatic interaction, but elevates the segregated anionic lipid demixing entropy loss. This energy-entropy competition results in a nonmonotonic dependence of the polyelectrolyte/monolayer association strength on the degree of chain rigidity. The semiflexible polyelectrolyte, i.e., the one with an intermediate degree of chain rigidity, is shown to associate onto the ternary membane below a higher critical ionic concentration. In this ionic concentration regime, the semiflexible polyelectrolyte binds onto the monolayer more firmly than the pancake-like flexible one and exhibits a stretched conformation. When the chain is very rigid, the polyelectrolyte with bead charge density Zb = +1 exhibits a larger tail and tends to dissociate from the membrane, whereas the one with Zb = +2 can still bind onto the membrane in a bridge-like conformation. Our results imply that chain intrinsic rigidity serves as an efficient molecular factor for tailoring the adsorption/desorption transition and interfacial structure of the polyelectrolyte/monolayer complex.

  9. The chitosan-gelatin (bio)polyelectrolyte complexes formation in an acidic medium.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Kuchina, Yuliya A; Sokolan, Nina I

    2016-03-15

    The interaction of cationic polysaccharide chitosan and gelatin accompanied by the stoichiometric (bio)polyelectrolyte complexes formation has been studied by the methods of capillary viscometry, UV and FTIR spectroscopy and dispersion of light scattering. Complexes were formed in the aqueous phase, with pH being less than the isoelectric point of gelatin (pIgel). The particle size of the disperse phase increases along with the growth of the relative viscosity in comparison with sols of the individual components-polysaccharide and gelatin. Possible models and mechanism of (bio)polyelectrolyte complexes formation have been discussed. It was shown that the complex formation takes place not only due to the hydrogen bonds, but also due to the electrostatic interactions between the positively charged amino-groups of chitosan and negatively charged amino acid residues (glutamic Glu and aspartic Asp acids) of gelatin. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2016-11-20

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

  11. Delivery of functional polyelectrolytes from complexes induced by salt addition: impact of the initial binding strength.

    PubMed

    Rondon, Céline; Argillier, Jean-François; Leal-Calderon, Fernando

    2014-12-15

    This paper focuses on polyelectrolyte complexes (PECs) soft nanoparticles and how dissociation occurs upon salt addition. The system is composed of a strong polyanion (polystyrene sulfonate, PSS) and a weak polycation (poly(allylamine) hydrochloride, PAH) in large excess. Soft nanoparticles were obtained by pouring a PSS solution into a PAH one under constant stirring. As the charge density of PAH chain depends on the pH of the polyelectrolyte solution, PEC particles exhibit distinct behaviors under salt addition depending on the pH of the continuous phase. At pH=5.5, PAH chains are fully charged and the addition of salt produces particle aggregation followed by sedimentation. Conversely, at pH=10 where PAH is only partially charged, the addition of salt drives a progressive disentanglement of the two polyelectrolytes, as revealed by both viscosimetric and spectroscopic measurements. At sufficiently high ionic strength, the two electrolytes are fully dissociated. Our results emphasize differences in behavior (binding reversibility) between strongly and weakly bound polyelectrolytes of opposite charge upon addition of salt. We discuss the potential use of these systems as stimulus responsive materials for the delivery of scale nucleation inhibitors in application around petroleum recovery. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. Polyelectrolyte Complex Hydrogels: Self-assembly and the Influence of Charged and Neutral Blocks

    NASA Astrophysics Data System (ADS)

    Srivastava, Samanvaya; Goldfeld, David; Levi, Adam; Mao, Jun; Chen, Wei; Tirrell, Matthew

    Polyelectrolyte complexes (PEC) form when oppositely charged polyelectrolyte chains spontaneously associate and phase separate in aqueous mediums. Bulk phase separation of the PECs can be evaded by combining one or both of the polyelectrolytes with a neutral polymer, thus engineering pathways for self-assembled PEC micelles and hydrogels. The PEC domains in these assemblies can encapsulate therapeutics as well as genetic materials and thus have tremendous potential in drug delivery and tissue engineering applications. We will present insights on the equilibrium structure and self-assembly kinetics of PEC hydrogels with large-scale ordering of the nanoscale PEC domains through detailed structure characterization and rheology studies of self-assembled materials comprising of functionalized polyallyl glycidyl ethers (PAGE) connected to either single poly(ethylene glycol) (PEG) chain to form diblock copolymers or as functionalized end-groups on a triblock copolymer with a PEG midblock. The effect of key parameters such as polymer concentration, polymer block lengths, salt, ionic strength, and degree of charge mismatch on the equilibrium materials properties will be discussed, with a special emphasis on the structure-defining role of the charged blocks and the structure-directing role of neutral blocks. Additionally, interesting similarities, and differences between structures and dynamics of hydrogels comprising diblock and corresponding triblock polyelectrolytes, respectively, will be discussed.

  13. Chitosan Based Polyelectrolyte Complexes as Potential Carrier Materials in Drug Delivery Systems

    PubMed Central

    Hamman, Josias H.

    2010-01-01

    Chitosan has been the subject of interest for its use as a polymeric drug carrier material in dosage form design due to its appealing properties such as biocompatibility, biodegradability, low toxicity and relatively low production cost from abundant natural sources. However, one drawback of using this natural polysaccharide in modified release dosage forms for oral administration is its fast dissolution rate in the stomach. Since chitosan is positively charged at low pH values (below its pKa value), it spontaneously associates with negatively charged polyions in solution to form polyelectrolyte complexes. These chitosan based polyelectrolyte complexes exhibit favourable physicochemical properties with preservation of chitosan’s biocompatible characteristics. These complexes are therefore good candidate excipient materials for the design of different types of dosage forms. It is the aim of this review to describe complexation of chitosan with selected natural and synthetic polyanions and to indicate some of the factors that influence the formation and stability of these polyelectrolyte complexes. Furthermore, recent investigations into the use of these complexes as excipients in drug delivery systems such as nano- and microparticles, beads, fibers, sponges and matrix type tablets are briefly described. PMID:20479980

  14. Formation and properties of positively charged colloids based on polyelectrolyte complexes of biopolymers.

    PubMed

    Schatz, Christophe; Lucas, Jean-Michel; Viton, Christophe; Domard, Alain; Pichot, Christian; Delair, Thierry

    2004-08-31

    Formation of colloids based on polyelectrolyte complexes (PECs) was mainly studied with synthetic polyelectrolytes. In this study, we describe the elaboration of positively charged PEC particles at a submicrometer level obtained by the complexation between two charged polysaccharides, chitosan as polycation and dextran sulfate (DS) as polyanion. The complexes were elaborated by dropwise addition of default amounts of DS to excess chitosan. Quasi-elastic light scattering was used to investigate in detail the influence of the characteristics of components (chain length, degree of acetylation) and parameters linked to the reaction of complexation (molar mixing ratio, ionic strength, concentration in polymer) on the sizes and polydispersity of colloids. Chain length of chitosan is the major parameter affecting the dimensions of the complexes, high molar mass chitosans leading to the largest particles. Variations of hydrodynamic diameters of PECs with the molar mass of chitosan are consistent with a mechanism of particle formation through the segregation of the neutral and then hydrophobic blocks of the polyelectrolyte complexed segments. Resulting particles display probably a structure constituted by a neutral core surrounded by a chitosan shell ensuring the colloidal stabilization. Such a structure was evidenced by measurements of electrophoretic mobilities revealing that the positive charge of particles was decreasing with pH, in relation with the neutralization of excess glucosamine hydrochloride moieties.

  15. Inhibition of atherosclerosis-promoting microRNAs via targeted polyelectrolyte complex micelles

    PubMed Central

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

    2015-01-01

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

  16. Inkjet ink spreading on polyelectrolyte multilayers deposited on pigment coated paper.

    PubMed

    Mielonen, Katriina; Geydt, Pavel; Österberg, Monika; Johansson, Leena-Sisko; Backfolk, Kaj

    2015-01-15

    Mechanisms of inkjet ink spreading and absorption on a coated paper have been studied using a polyelectrolyte multilayering technique. By applying alternating sequences of cationic and anionic polyelectrolyte layers on a mineral coated paper, the role of the interfacial chemistry was evaluated. The polyelectrolyte multilayer was created to imitate a thin resin-like liquid-absorptive layer and to clarify the role of the charge of the protruding polyelectrolyte layer on ink spreading and colorant fixation. The formation of a thin polyelectrolyte layer and coating coverage was confirmed by X-ray photoelectron spectroscopy (XPS). A submolecular mechanical imaging of the polyelectrolyte complexes with an atomic force microscope (AFM) revealed differences in modulus and different nanosize agglomerates were identified which were ascribed to polyion complexes. The polyelectrolyte coatings significantly affect the solid-liquid interaction and particularly the ink spreading revealed as intercolor bleeding and wicking. The interfacial interaction between the ink and the applied polyelectrolyte layers showed differences between dye- and pigment-based colorants, which could be emphasized by the polyelectrolyte chemistry.

  17. Underwater contact adhesion and microarchitecture in polyelectrolyte complexes actuated by solvent exchange

    PubMed Central

    Seo, Sungbaek; Kaufman, Yair; Israelachvili, Jacob N.; Waite, J. Herbert

    2016-01-01

    Polyelectrolyte complexation is critical to the formation and properties of many biological and polymeric materials, and is typically initiated by aqueous mixing1 followed by fluid–fluid phase separation, such as coacervation2–5. Yet little to nothing is known about how coacervates evolve into intricate solid microarchitectures. Inspired by the chemical features of the cement proteins of the sandcastle worm, here we report a versatile and strong wet-contact microporous adhesive resulting from polyelectrolyte complexation triggered by solvent exchange. After premixing a catechol-functionalized weak polyanion with a polycation in dimethyl sulphoxide (DMSO), the solution was applied underwater to various substrates whereupon electrostatic complexation, phase inversion, and rapid setting were simultaneously actuated by water–DMSO solvent exchange. Spatial and temporal coordination of complexation, inversion and setting fostered rapid (~25 s) and robust underwater contact adhesion (Wad ≥ 2 J m−2) of complexed catecholic polyelectrolytes to all tested surfaces including plastics, glasses, metals and biological materials. PMID:26779881

  18. Low molecular weight chitosan-insulin polyelectrolyte complex: characterization and stability studies.

    PubMed

    Al-Kurdi, Zakieh I; Chowdhry, Babur Z; Leharne, Stephen A; Al Omari, Mahmoud M H; Badwan, Adnan A

    2015-03-30

    The aim of the work reported herein was to investigate the effect of various low molecular weight chitosans (LMWCs) on the stability of insulin using USP HPLC methods. Insulin was found to be stable in a polyelectrolyte complex (PEC) consisting of insulin and LMWC in the presence of a Tris-buffer at pH 6.5. In the presence of LMWC, the stability of insulin increased with decreasing molecular weight of LMWC; 13 kDa LMWC was the most efficient molecular weight for enhancing the physical and chemical stability of insulin. Solubilization of insulin-LMWC polyelectrolyte complex (I-LMWC PEC) in a reverse micelle (RM) system, administered to diabetic rats, results in an oral delivery system for insulin with acceptable bioactivity.

  19. Low Molecular Weight Chitosan–Insulin Polyelectrolyte Complex: Characterization and Stability Studies

    PubMed Central

    Al-Kurdi, Zakieh I.; Chowdhry, Babur Z.; Leharne, Stephen A.; Al Omari, Mahmoud M. H.; Badwan, Adnan A.

    2015-01-01

    The aim of the work reported herein was to investigate the effect of various low molecular weight chitosans (LMWCs) on the stability of insulin using USP HPLC methods. Insulin was found to be stable in a polyelectrolyte complex (PEC) consisting of insulin and LMWC in the presence of a Tris-buffer at pH 6.5. In the presence of LMWC, the stability of insulin increased with decreasing molecular weight of LMWC; 13 kDa LMWC was the most efficient molecular weight for enhancing the physical and chemical stability of insulin. Solubilization of insulin-LMWC polyelectrolyte complex (I-LMWC PEC) in a reverse micelle (RM) system, administered to diabetic rats, results in an oral delivery system for insulin with acceptable bioactivity. PMID:25830681

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

    NASA Astrophysics Data System (ADS)

    Delaney, Kris T.; Fredrickson, Glenn H.

    2017-06-01

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

  1. Chitosan/Chondroitin Sulfate Membranes Produced by Polyelectrolyte Complexation for Cartilage Engineering.

    PubMed

    Rodrigues, Mariana N; Oliveira, Mariana B; Costa, Rui R; Mano, João F

    2016-06-13

    Membranes made of chitosan (CHT) and chondroitin sulfate (CS) are herein presented using a polyelectrolyte complexation sedimentation/evaporation method. The membranes present high roughness and heterogeneous morphology induced by salt crystals. Exposing the membranes to different salt concentrations induces saloplastic behavior, as shown by an increasing water absorption and decreasing stiffness while exposed to increasing concentrations of salt. Establishing contact between two parts of a cut membrane leads to their self-adhesion and maintenance of their stretching ability. The membranes sustain the adhesion of ATDC5 prechondrocyte cells, inducing their rearrangement in cellular aggregates typical of chondrogenesis, and the expression of cartilage markers. Impregnated TGF-β3 remains loaded after 14 days of incubation, releasing only 1.2% of its total loaded mass. CHT/CS polyelectrolyte membranes are here shown as suitable candidates for the biomedical field, namely, for cartilage regeneration.

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

    PubMed

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

    2014-11-26

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

  3. Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes.

    PubMed

    Lehmann, Pit; Symietz, Christian; Brezesinski, Gerald; Krass, Henning; Kurth, Dirk G

    2005-06-21

    A detailed analysis of a metallosupramolecular polyelectrolyte-amphiphile complex (PAC) at the air-water interface is presented. Langmuir isotherms, Brewster angle microscopy, and X-ray reflectance and diffraction methods are employed to investigate the structure of the Langmuir monolayers. The PAC is self-assembled from 1,3-bis[4'-oxa-(2,2':6',2' '-terpyridinyl)]propane, iron acetate, and dihexadecyl phosphate (DHP). Spreading the PAC at the air-water interface results in a monolayer that consists of two strata. DHP forms a monolayer at the top of the interface, while the metallosupramolecular polyelectrolyte is immersed in the aqueous subphase. Both strata are coupled to each other through electrostatic interactions. The monolayers can be transferred onto solid substrates, resulting in well-ordered multilayers. Such multilayers are model systems for well-ordered metal ions in two dimensions.

  4. Enzyme-polyelectrolyte complex: Salt effects on the reaction of urease with polyallylamine

    NASA Astrophysics Data System (ADS)

    Tikhonenko, S. A.; Saburova, E. A.; Durdenko, E. N.; Sukhorukov, B. I.

    2009-10-01

    The effects of inorganic mono- and divalent salts of different types on how the cation polyelectrolyte polyallylamine hydrochloride (PAA) binds with the oligomer enzyme urease were studied. It was shown that in solutions of the monovalent salts NaCl, KCl, and NH4Cl, polyelectrolyte-protein complexes formed by electrostatic interactions, which decreased monotonically as the salt concentrations increased according to the classic law of statistical physics, correlating the Debye radius with the ionic strength of the solution. In solutions of the divalent salts Na2SO4 and (NH4)2SO4, the efficiency of the formation of the polyelectrolyte-protein complexes changed abruptly (the enzyme was drastically activated) at low salt concentrations (˜0.6-0.8 mM), which was not consistent with the classic theory of charge interactions in solutions with different ionic strengths. Turbidimetric titration at different salt concentrations in the given range revealed a high aggregative ability for sulfates and low ability for chlorides. It was concluded that the anomalies in the concentration dependence of the enzyme activity and aggregative ability were related to the formation of stable bonds PAA to the divalent SO{4/2-} anion, which increased drastically when the ratio of anion concentration to the number of positively charged PAA monomers in solution reached 1: 2.

  5. Polyelectrolyte complexes based on (quaternized) poly[(2-dimethylamino)ethyl methacrylate]: behavior in contact with blood.

    PubMed

    Yancheva, Elena; Paneva, Dilyana; Danchev, Dobri; Mespouille, Laetitia; Dubois, Philippe; Manolova, Nevena; Rashkov, Iliya

    2007-07-09

    Polyelectrolyte complexes (PECs) between (quaternized) poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) and (crosslinked) N-carboxyethylchitosan (CECh) or poly(2-acrylamido-2-methylpropane sodium sulfonate) (PAMPSNa) were prepared and characterized in terms of their stability, equilibrium water content, and surface morphology. The evaluation of the behavior of the studied PECs in contact with blood revealed that the (crosslinked) CECh/(quaternized) PDMAEMA complexes had lost the inherent PDMAEMA cytotoxicity but still preserved haemostatic activity. In contrast, the complex formation between (quaternized) PDMAEMA and PAMPSNa allowed the preparation of materials with improved blood compatibility.

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

    PubMed

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

    2015-12-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

  9. Complexes of xylan and synthetic polyelectrolytes. Characterization and adsorption onto high quality unbleached fibres.

    PubMed

    Mocchiutti, Paulina; Galván, María V; Peresin, María S; Schnell, Carla N; Zanuttini, Miguel A

    2015-02-13

    In this work, polyelectrolyte complexes (PECs) were formed by adding polyacrylic acid (PAA) or 4-O-methylglucuronoxylan (Xyl) on poly(allylamine hydrochloride) (PAH) solutions, at different ionic strength and neutral pH. Turbidity curves, charge densities of the cationic complexes determined by polyelectrolyte titration method, and z-potential values showed clear differences between both complexes. Stirring favourably reverses the effects of sedimentation of Xyl/PAH complexes, as demonstrated by colloidal stability tests. Adsorption studies on silica surfaces, performed by Quartz Crystal Microbalance with Dissipation (QCM-D) showed that PAA/PAH adsorbed complexes layers were rigid, while the corresponding Xyl/PAH layers were viscoelastic. Despite the different conformations, both complexes were adsorbed as spherical particles, as observed by Atomic Force Microscopy (AFM). Adsorption isotherms performed on fibre suspensions showed that the ionic strength of the liquid medium determines the amount of PEC retained. Finally, it was found that the papermaking properties were significantly increased due to the addition of these PECs.

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

    NASA Astrophysics Data System (ADS)

    Goswami, Monojoy; Sumpter, Bobby

    2014-03-01

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

  11. Thermodynamics of interfacial changes in a protein-protein complex.

    PubMed

    Das, Amit; Chakrabarti, Jaydeb; Ghosh, Mahua

    2014-03-04

    Recent experiments with biomacromolecular complexes suggest that structural modifications at the interfaces are vital for stability of the complexes and the functions of the biomacromolecules. Although several qualitative aspects about such interfaces are known from structural data, quantification of the interfacial changes is lacking. In this work, we study the thermodynamic changes at the interface in the complex between an enzyme, Nuclease A (NucA), and a specific inhibitor protein, NuiA. We calculate the conformational free energy and conformational entropy costs from histograms of the dihedral angles generated from all-atom molecular dynamics simulations on the complex and the free proteins. We extract the conformational thermodynamic parameters for changes in the tertiary structure of NuiA. We show that the binding is dominated by the interfacial changes, where the basic residues of NucA and acidic residues of NuiA are highly ordered and stabilized via strong electrostatic interactions. Our results correlate well with known information from structural studies. The tight interfacial structure is reflected in the significant changes in the structure and dynamics of the water molecules at the enzyme-inhibitor interface. The interfacial water molecules contribute significantly to the entropy loss for the overall complexation.

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

    PubMed Central

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

    2016-01-01

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

  13. Effects of salt on intermolecular polyelectrolyte complexes formation between cationic microgel and polyanion.

    PubMed

    Ogawa, Kazuyoshi

    2015-12-01

    The study of interpolyelectrolyte complex (IPEC) formation between cationic microgel and polyanion was presented. The size and molecular weight of cationic microgel are much larger than those of linear anionic polyelectrolyte. The resulting IPEC was divided by dynamic light scattering (DLS), static light scattering (SLS), and turbidity or spectrometry; (i) water-soluble intra-particle complexes consisting of one microgel to which linear polyelectrolytes bind; (ii) complex coacervates (inter-particle complexes composed of aggregated intra-particle complexes); and (iii) insoluble amorphous precipitates. These types depended on not only the mixing ratio of polyanion to cationic microgel but also salt concentration. This trend was discussed from IPEC's composition, thermodynamics of IPEC formation and the salt effect on intermolecular interactions which were expected in IPEC formation. The results obtained from the use of microgel in IPEC's study suggested that not only electrostatic interaction but also hydrophobic interaction play an important role in the aggregation or association of IPEC. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  15. Quasielastic and electrophoretic light scattering studies of polyelectrolyte-micelle complexes

    NASA Astrophysics Data System (ADS)

    Rigsbee, Daniel R.; Dubin, Paul L.

    1991-06-01

    The aqueous system comprised of poly(dimethylammonium chloride) (a strongly cationic polymer) and a mixture of sodium dodecyl sulfate and Triton X-100 (anionic/nonionic mixed micelles) forms polyelectrolyte-micelle complexes. At suitable micelle compositions and ionic strengths, soluble complexes are formed, which may be studied by a variety of solution techniques, including quasielastic light scattering. In this report, the authors examine the influence of polymer molecular weight and micelle composition on the nature of these complexes. Multiangle measurements were made with two different instruments (hence different procedures for extracting apparent size distributions from measured autocorrelation curves). At the concentrations employed, multipolymer complexes appear to form. The QELS data, taken in conjunction with limited electrophoretic light scattering results, suggest that the main determinant of the extent of higher-order aggregation are those factors influencing the net charge of a 'primary' i.e. intrapolymer complex, with molecular weight per se playing a secondary role.

  16. Perfluoro-alcohol-induced complex coacervates of polyelectrolyte-surfactant mixtures: phase behavior and analysis.

    PubMed

    Nejati, Mahboubeh M; Khaledi, Morteza G

    2015-05-26

    Perfluorinated alcohols and acids such as hexafluoroisopropanol (HFIP), trifluoroethanol, trifluoroacetic acid, pentafluoropropionic acid, and heptafluorobutyric acid induce coacervation and phase separation in aqueous solutions of a wide variety of individual and mixed amphiphiles [ Khaledi Langmuir 2013 , 29 , 2458 ]. This paper focuses on HFIP-induced complex coacervate formation in the mixtures of anionic polyelectrolytes, such as sodium salt of poly(methacrylic acid) (PMA) or poly(acrylic acid) (PAA) and cationic surfactants of alkyltrimethylammonium bromides. In purely aqueous media and over a wide concentration range, mixtures of PMA and CTAB form the catanionic complex (CTA(+)PM(-)) that is insoluble in water (white precipitate). Upon addition of a small percentage of HFIP, the mixture goes through phase transition and formation of two distinctly clear liquid phases. The phase diagram for the HFIP-PMA-CTAB coacervate system was studied. The coacervate volume was determined as a function of system variables such as charge ratio as well as total and individual concentrations of the system components. These results, combined with the chemical composition analysis of the separated aqueous top-phase and coacervate bottom-phase, shed light on the coacervation mechanism. The results suggest that exchange of counterions and ion-pair formation play critical roles in the coacervation process. This process facilitated by HFIP through solvation of the head groups and dehydration of the hydrophobic moieties of the catanionic complex. Because of the presence of HFIP, coacervation occurs over a wide range of concentrations and charge ratios of the oppositely charged polyelectrolyte and surfactant.

  17. Polyelectrolyte complexes stabilize and controllably release vascular endothelial growth factor.

    PubMed

    Huang, Min; Vitharana, Samadhi N; Peek, Laura J; Coop, Tina; Berkland, Cory

    2007-05-01

    Angiogenesis has long been a desired therapeutic approach to improve clinical outcomes of conditions typified by ischemia. Vascular endothelial growth factor (VEGF) has demonstrated the ability to generate new blood vessels in vivo, but trials using intravenous delivery have not yet produced clinical success. Localized, sustained delivery of VEGF has been proven necessary to generate blood vessels as demonstrated by implantable, controlled release devices. Ultimately, nanoparticles delivered by intravenous injection may be designed to accumulate in target tissues and sustain the local VEGF concentration; however, injectable nanosuspensions that control the release of stabilized VEGF must first be developed. In this study, we utilize the heparin binding domain of VEGF to bind the polyanion dextran sulfate, resulting in an enhanced thermal stability of VEGF. Coacervation of the VEGF-bound dextran sulfate with selected polycations (chitosan, polyethylenimine, or poly-L-lysine) produced nanoparticles approximately 250 nm in diameter with high VEGF encapsulation efficiency (50-85%). Release of VEGF from these formulations persisted for >10 days and maintained high VEGF activity as determined by ELISA and a mitogenic bioassay. Chitosan-dextran sulfate complexes were preferred because of their biodegradability, desirable particle size ( approximately 250 nm), entrapment efficiency ( approximately 85%), controlled release (near linear for 10 days), and mitogenic activity.

  18. Nonequilibrium Interfacial Tension in Simple and Complex Fluids

    NASA Astrophysics Data System (ADS)

    Truzzolillo, Domenico; Mora, Serge; Dupas, Christelle; Cipelletti, Luca

    2016-10-01

    Interfacial tension between immiscible phases is a well-known phenomenon, which manifests itself in everyday life, from the shape of droplets and foam bubbles to the capillary rise of sap in plants or the locomotion of insects on a water surface. More than a century ago, Korteweg generalized this notion by arguing that stresses at the interface between two miscible fluids act transiently as an effective, nonequilibrium interfacial tension, before homogenization is eventually reached. In spite of its relevance in fields as diverse as geosciences, polymer physics, multiphase flows, and fluid removal, experiments and theoretical works on the interfacial tension of miscible systems are still scarce, and mostly restricted to molecular fluids. This leaves crucial questions unanswered, concerning the very existence of the effective interfacial tension, its stabilizing or destabilizing character, and its dependence on the fluid's composition and concentration gradients. We present an extensive set of measurements on miscible complex fluids that demonstrate the existence and the stabilizing character of the effective interfacial tension, unveil new regimes beyond Korteweg's predictions, and quantify its dependence on the nature of the fluids and the composition gradient at the interface. We introduce a simple yet general model that rationalizes nonequilibrium interfacial stresses to arbitrary mixtures, beyond Korteweg's small gradient regime, and show that the model captures remarkably well both our new measurements and literature data on molecular and polymer fluids. Finally, we briefly discuss the relevance of our model to a variety of interface-driven problems, from phase separation to fracture, which are not adequately captured by current approaches based on the assumption of small gradients.

  19. Photoluminescence of water-soluble CdSe/ZnS nanoparticles in complexes with cationic and anionic polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Strekal', N.; Kulakovich, O.; Belyaev, A.; Stsiapura, V.; Maskevich, S.

    2008-01-01

    The data on the influence of polyelectrolytes on the photon emission probability of water-soluble CdSe/ZnS nanoparticles are obtained. The decrease in the photoluminescence quantum yield of nanoparticles occurring upon their transfer to aqueous solutions from toluene (in the course of solubilization) depends on the ionic nature of an agent applied for the replacement of trioctylphosphine oxide residues on the surface of nanoparticles. It turns out that such a cationic modifying agent as cysteamine leads to an insignificant (˜10%) decrease in the photoluminescence quantum yield of nanoparticles. The use of such an anionic agent as mercaptoacetic acid causes a significant (˜80%) decrease in the quantum yield and the average decay time of photoluminescence. For nanoparticles modified by mercaptoacetic acid (anionic nanoparticles), this decrease is partially compensated if these particles interact with polyelectrolytes whose backbone is oppositely charged (cationic polyelectrolytes), such as polyallylamine and polydiallyldimethylammonium chloride. In this case, the photoluminescence quantum yield shows a reverse increase by 40%, remaining the same within a matter of months or longer. In contrast to this, cationic nanoparticles, only slightly quenched by cysteamine at the stage of solubilization, are appreciably degraded in complexes with anionic polyelectrolytes in solutions and upon immobilization of complexes on a substrate, so that their photoluminescence quantum yield irreversible decreases to zero within a few days. Possible mechanisms of the effects observed are discussed and their consideration in polyelectrolyte-based molecular lithography.

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

    SciTech Connect

    Vögele, Martin; Holm, Christian; Smiatek, Jens

    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.

  1. Interaction and complex formation between catalase and cationic polyelectrolytes: chitosan and Eudragit E100.

    PubMed

    Boeris, Valeria; Romanini, Diana; Farruggia, Beatriz; Picó, Guillemo

    2009-08-01

    Interactions between catalase and the cationic polyelectrolytes: chitosan and Eudragit E100 have been investigated owing to their scientific and technological importance. These interactions have been characterized by turbidimetry, circular dichroism and fluorescence spectroscopy. It was found that the catalase conformation does not change significantly during the chain entanglements between the protein and the polyelectrolytes. The effects of pH, ionic strength and anions which modify the water structure were evaluated on the polymer-protein complex formation. A net coulombic interaction force between them was found since the insoluble complex formation decreased after the NaCl addition. Both polymers were found to precipitate around 80% of the protein in solution. No modification of the tertiary and secondary protein structure or the enzymatic activity was observed when the precipitate was dissolved by changing the pH of the medium. Chitosan and Eudragit E100 proved to be a useful framework to isolate catalase or proteins with a slightly acid isoelectrical pH by means of precipitation.

  2. Assessment of DNA complexation onto polyelectrolyte-coated magnetic silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Dávila-Ibáñez, Ana B.; Buurma, Niklaas J.; Salgueiriño, Verónica

    2013-05-01

    The polyelectrolyte-DNA complexation method to form magnetoplexes using silica-coated iron oxide magnetic nanoparticles as inorganic substrates is an attractive and promising process in view of the potential applications including magnetofection, DNA extraction and purification, and directed assembly of nanostructures. Herein, we present a systematic physico-chemical study that provides clear evidence of the type of interactions established, reflects the importance of the DNA length, the nanoparticle size and the ionic strength, and permits the identification of the parameters controlling both the stability and the type of magnetoplexes formed. This information can be used to develop targeted systems with properties optimized for the various proposed applications of magnetoplexes.The polyelectrolyte-DNA complexation method to form magnetoplexes using silica-coated iron oxide magnetic nanoparticles as inorganic substrates is an attractive and promising process in view of the potential applications including magnetofection, DNA extraction and purification, and directed assembly of nanostructures. Herein, we present a systematic physico-chemical study that provides clear evidence of the type of interactions established, reflects the importance of the DNA length, the nanoparticle size and the ionic strength, and permits the identification of the parameters controlling both the stability and the type of magnetoplexes formed. This information can be used to develop targeted systems with properties optimized for the various proposed applications of magnetoplexes. Electronic supplementary information (ESI) available: Experimental, description of ITC experiments, Fig. S1-S4, and Tables S1-S3. See DOI: 10.1039/c3nr34358h

  3. Intelligent colloidal hybrids via reversible pH-induced complexation of polyelectrolyte and silica nanoparticles.

    PubMed

    Mori, Hideharu; Müller, Axel H E; Klee, Joachim E

    2003-04-02

    We present novel intelligent colloidal polymer/silica nanocomposites, in which the complexation of cationic silica nanoparticles and a weak anionic polyelectrolyte can be manipulated simply by pH change through a hydrogen-bonding interaction and ionic complexation caused by hydrogen-transfer interactions between the constituents. Special silica particles which have nanometer size (diameter approximately 3.0 nm) and two independent proton-accepting sites were developed in this study. Both the silica and poly(acrylic acid) form transparent colloidal solutions in water, while a white turbid dispersion was obtained just after mixing the two solutions due to the complexation. The pH-induced association-dissociation behavior was confirmed by the turbidity and potentiometric titration measurements. The assembled structures of the hybrids were visualized by scanning force microscopy.

  4. The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes

    SciTech Connect

    Perry, Sarah L.; Li, Yue; Priftis, Dimitrios; Leon, Lorraine; Tirrell, Matthew

    2014-06-01

    Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specific interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.

  5. Interpolymer complexation: comparisons of bulk and interfacial structures.

    PubMed

    Cattoz, Beatrice; de Vos, Wiebe M; Cosgrove, Terence; Crossman, Martin; Espidel, Youssef; Prescott, Stuart W

    2015-04-14

    The interactions between the strong polyelectrolyte sodium poly(styrenesulfonate), NaPSS, and the neutral polymer poly(vinylpyrrolidone), PVP, were investigated in bulk and at the silica/solution interface using a combination of diffusion nuclear magnetic resonance spectroscopy (NMR), small-angle neutron scattering (SANS), solvent relaxation NMR, and ellipsometry. We show for the first time that complex formation occurs between NaPSS and PVP in solution; the complexes formed were shown not to be influenced by pH variation, whereas increasing the ionic strength increases the complexation of NaPSS but does not influence the PVP directly. The complexes formed contained a large proportion of NaPSS. Study of these interactions at the silica interface demonstrated that complexes also form at the nanoparticle interface where PVP is added in the system prior to NaPSS. For a constant PVP concentration and varying NaPSS concentration, the system remains stable until NaPSS is added in excess, which leads to depletion flocculation. Surface complex formation using the layer-by-layer technique was also reported at a planar silica interface.

  6. Interfacial behavior in polyelectrolyte blends: hybrid liquid-state integral equation and self-consistent field theory study.

    PubMed

    Sing, Charles E; Zwanikken, Jos W; Olvera de la Cruz, Monica

    2013-10-18

    Polyelectrolytes and electrolyte solutions are known to demonstrate a rich array of phase behaviors due to the effects of long-ranged interactions inherent in Coulombic attractions and repulsions. While there is a wealth of literature examining these materials to provide some physical insight into their thermodynamics, all of these methods make strong approximations with regards to the nature of the ionic component. In this investigation we develop a hybrid liquid-state integral equation and self-consistent field theory numerical theory, and systematically demonstrate the ramifications on local ion structure on the overall thermodynamics of segregated polymer blends. We show effects on phase separation such as suppression due to hard sphere interactions and enhancement due to ion cohesion that are not described using traditional Poisson-Boltzmann mean-field theory.

  7. Charged pullulan derivatives for the development of nanocarriers by polyelectrolyte complexation.

    PubMed

    Dionísio, M; Braz, L; Corvo, M; Lourenço, J P; Grenha, A; Rosa da Costa, A M

    2016-05-01

    Pullulan, a neutral polysaccharide, was chemically modified in order to obtain two charged derivatives: reaction with SO3(.)DMF complex afforded a sulfate derivative (SP), while reaction with glycidyltrimethylammonium chloride gave a quaternary ammonium salt (AP). The presence of the charged groups was confirmed by FTIR. Assessment of the positions where the reaction took place was based on (1)H- and (13)C NMR (COSY, HSQC-TOCSY, HSQC-DEPT, and HMBC) experiments. Estimation of the degree of substitution (DS) was made from elemental analysis data, and further confirmed by NMR peak areas in the case of AP. These new derivatives showed the capability to condense with each other, forming nanoparticles with the ability to associate a model protein (BSA) and displaying adequate size for drug delivery applications, therefore making them good candidates for the production of pullulan-based nanocarriers by polyelectrolyte complexation.

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

    PubMed

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

    2016-09-12

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

  9. Chitosan-poly(acrylic acid) polyelectrolyte complex membranes: preparation, characterization and permeability studies.

    PubMed

    de Oliveira, H C L; Fonseca, J L C; Pereira, M R

    2008-01-01

    Polyelectrolyte complex (PEC) membranes were obtained by mixing solutions of two polymers of opposite charges, chitosan (Chi) and poly(acrylic acid) PAA. Three membranes were obtained: one made of pure chitosan and two membranes with chitosan mixed with PAA at a ratio of 95:5 (one prepared using PAA solution in 3.5% formic acid, named ChiPAA3.5, and another one using a PAA solution in 10% formic acid, named ChiPAA10). The membranes were characterized by swelling experiments, FT-IR spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), mechanical properties and permeability studies in relation to a drug model (sodium sulphamerazine). The calculation of degree of ionization showed that the lower the formic acid concentration was, the higher the PAA dissociation degree. Polyelectrolyte complex formation was characterized by FT-IR. Water uptake results showed that PEC membranes were more hydrophilic than pure chitosan, ChiPAA3.5 being the most. Morphological analysis by SEM and AFM showed that PAA addition changed the membranes morphology, especially for ChiPAA3.5. Mechanical properties indicated that PEC membranes were more rigid than pure chitosan membranes and that the morphology has an influence on tensile strength values. Permeability values decreased with complex formation and were lower for ChiPAA10 than ChiPAA3.5. However, as drug concentration was increased, the difference between the two complex membranes disappeared. The results were discussed considering the drug-membrane interactions. Diffusion coefficient values indicated that ChiPAA3.5 had a higher drug retention capacity than ChiPAA10.

  10. Electrostatics of Rigid Polyelectrolytes

    SciTech Connect

    Wong, G.C.L.

    2009-06-04

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

  11. Ion Environments in Mn(2+)-Doped Polyelectrolyte Complexes: Dilute Magnetic Saloplastics.

    PubMed

    Abhyankar, Nandita; Ghoussoub, Yara E; Wang, Qifeng; Dalal, Naresh S; Schlenoff, Joseph B

    2016-07-14

    Amorphous hydrated complexes of the polyelectrolytes poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium) were doped with the spin-5/2 ion Mn(2+). X-band electron paramagnetic resonance (EPR) measurements of the Mn(2+) spins within these stoichiometric polyelectrolyte complexes (PECs) revealed an octahedral coordination environment, similar to that observed in aqueous solutions of Mn(2+). This octahedral symmetry of the [Mn(H2O)6](2+) complexes, observed in fully hydrated PECs, is somewhat distorted because of the wide range of ion pairs possible with the sulfonate group on PSS. As the Mn(2+) concentration was increased, the linewidths broadened, indicating the dominance of dipolar broadening over exchange narrowing in determining the linewidths; that is, any exchange narrowing was masked by the large dipolar broadening. The calculated linewidths were used to estimate the strengths of the dipolar interactions, and hence the distances between the Mn(2+) spins, on the basis of a simple model of regularly spaced spins. The distances calculated by this method were roughly comparable to the geometric average distances calculated on the basis of the Mn(2+) concentrations and densities of the doped PEC samples. From a comparison of their EPR spectra, the ion environments in the doped, fully hydrated PECs were found to be similar to those in hydrated classical ion exchange resins. EPR spectra before and after drying of the PECs indicate the replacement of octahedrally coordinated water by oxide anions from the polyanion chain and the corresponding loss of the symmetric environment of Mn(2+) ions.

  12. Characterization of self-assembled polyelectrolyte complex nanoparticles formed from chitosan and pectin.

    PubMed

    Birch, Nathan P; Schiffman, Jessica D

    2014-04-01

    Chronic wounds continue to be a global healthcare concern. Thus, the development of new nanoparticle-based therapies that treat multiple symptoms of these "non-healing" wounds without encouraging antibiotic resistance is imperative. One potential solution is to use chitosan, a naturally antimicrobial polycation, which can spontaneously form polyelectrolyte complexes when mixed with a polyanion in appropriate aqueous conditions. The requirement of at least two different polymers opens up the opportunity for us to form chitosan complexes with an additional functional polyanion. In this study, chitosan:pectin (CS:Pec) nanoparticles were synthesized using an aqueous spontaneous ionic gelation method. Systematically, a number of parameters, polymer concentration, addition order, mass ratio, and solution pH, were explored and their effect on nanoparticle formation was determined. The size and surface charge of the particles were characterized, as well as their morphology using transmission electron microscopy. The effect of polymer concentration and addition order on the nanoparticles was found to be similar to that of other chitosan:polyanion complexes. The mass ratio was tuned to create nanoparticles with a chitosan shell and a controllable positive zeta potential. The particles were stable in a pH range from 3.5 to 6.0 and lost stability after 14 days of storage in aqueous media. Due to the high positive surface charge of the particles, the innate properties of the polysaccharides used, and the harmless disassociation of the polyelectrolytes, we suggest that the development of these CS:Pec nanoparticles offers great promise as a chronic wound healing platform.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  15. New 2-in-1 polyelectrolyte step-by-step film buildup without solution alternation: from PEDOT-PSS to polyelectrolyte complexes.

    PubMed

    de Saint-Aubin, Christine; Hemmerlé, Joseph; Boulmedais, Fouzia; Vallat, Marie-France; Nardin, Michel; Schaaf, Pierre

    2012-06-12

    Although never emphasized and increasingly used in organic electronics, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) layer-by-layer (lbl) film construction violates the alternation of polyanion and polycation rule stated as a prerequisit for a step-by-step film buildup. To demonstrate that this alternation is not always necessary, we studied the step-by-step construction of films using a single solution containing polycation/polyanion complexes. We investigated four different systems: PEDOT-PSS, bPEI-PSS (branched poly(ethylene imine)-poly(sodium 4-styrene sulfonate)), PDADMA-PSS (poly(diallyl dimethyl ammonium)-PSS), and PAH-PSS (poly(allylamine hydrochloride)-PSS). The film buildup obtained by spin-coating or dipping-and-drying process was monitored by ellipsometry, UV-vis-NIR spectrophotometry, and quartz-crystal microbalance. The surface morphology of the films was characterized by atomic force microscopy in tapping mode. After an initial transient regime, the different films have a linear buildup with the number of deposition steps. It appears that, when the particles composed of polyanion-polycation complex and complex aggregates in solution are more or less liquid (case of PEDOT-PSS and bPEI-PSS), our method leads to smooth films (roughness on the order of 1-2 nm). On the other hand, when these complexes are more or less solid particles (case of PDADMA-PSS and PAH-PSS), the resulting films are much rougher (typically 10 nm). Polycation/polyanion molar ratios in monomer unit of the liquid, rinsing, and drying steps are key parameters governing the film buildup process with an optimal polycation/polyanion molar ratio leading to the fastest film growth. This new and general lbl method, designated as 2-in-1 method, allows obtaining regular and controlled film buildup with a single liquid containing polyelectrolyte complexes and opens a new route for surface functionalization with polyelectrolytes.

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

    NASA Astrophysics Data System (ADS)

    Barati Ghahfarokhi, Reza

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

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

    SciTech Connect

    Uchiyama, Hirotaka; Christian, S.D.; Tucker, E.E.; Scamehorn, J.F. )

    1994-03-15

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

  18. Potential of mean force and transient states in polyelectrolyte pair complexation.

    PubMed

    Xu, Xiao; Kanduč, Matej; Wu, Jianzhong; Dzubiella, Joachim

    2016-07-21

    The pair association between two polyelectrolytes (PEs) of the same size but opposite charge is systematically studied in terms of the potential of mean force (PMF) along their center-of-mass reaction coordinate via coarse-grained, implicit-solvent, explicit-salt computer simulations. The focus is set on the onset and the intermediate transient stages of complexation. At conditions above the counterion-condensation threshold, the PE association process exhibits a distinct sliding-rod-like behavior where the polymer chains approach each other by first stretching out at a critical distance close to their contour length, then "shaking hand" and sliding along each other in a parallel fashion, before eventually folding into a neutral complex. The essential part of the PMF for highly charged PEs can be very well described by a simple theory based on sliding charged "Debye-Hückel" rods with renormalized charges in addition to an explicit entropy contribution owing to the release of condensed counterions. Interestingly, at the onset of complex formation, the mean force between the PE chains is found to be discontinuous, reflecting a bimodal structural behavior that arises from the coexistence of interconnected-rod and isolated-coil states. These two microstates of the PE complex are balanced by subtle counterion release effects and separated by a free-energy barrier due to unfavorable stretching entropy.

  19. Potential of mean force and transient states in polyelectrolyte pair complexation

    NASA Astrophysics Data System (ADS)

    Xu, Xiao; Kanduč, Matej; Wu, Jianzhong; Dzubiella, Joachim

    2016-07-01

    The pair association between two polyelectrolytes (PEs) of the same size but opposite charge is systematically studied in terms of the potential of mean force (PMF) along their center-of-mass reaction coordinate via coarse-grained, implicit-solvent, explicit-salt computer simulations. The focus is set on the onset and the intermediate transient stages of complexation. At conditions above the counterion-condensation threshold, the PE association process exhibits a distinct sliding-rod-like behavior where the polymer chains approach each other by first stretching out at a critical distance close to their contour length, then "shaking hand" and sliding along each other in a parallel fashion, before eventually folding into a neutral complex. The essential part of the PMF for highly charged PEs can be very well described by a simple theory based on sliding charged "Debye-Hückel" rods with renormalized charges in addition to an explicit entropy contribution owing to the release of condensed counterions. Interestingly, at the onset of complex formation, the mean force between the PE chains is found to be discontinuous, reflecting a bimodal structural behavior that arises from the coexistence of interconnected-rod and isolated-coil states. These two microstates of the PE complex are balanced by subtle counterion release effects and separated by a free-energy barrier due to unfavorable stretching entropy.

  20. Enhancement of sustained and controlled protein release using polyelectrolyte complex-loaded injectable and thermosensitive hydrogel.

    PubMed

    Park, Mi-Ran; Chun, Changju; Cho, Chong-Su; Song, Soo-Chang

    2010-10-01

    In this study, we aimed at developing controlled and sustained protein release formulations using a combination system of polyelectrolyte complexes (PECs) and thermosensitive poly(organophosphazene) hydrogels as an injectable gel-depot system. In the protein-loaded hydrogel system, the loaded proteins were released rapidly through diffusion regardless of viscosities and mass loss of the gels because of the small hydrodynamic size of the proteins. To suppress protein diffusion and increase protein size, we induced PECs between negatively charged proteins (BSA, gelatin-type B 75 bloom, α-amylase, and hGH) and polycations (protamine, polyethylenimine, poly-l-lysine, and poly-l-arginine (PLA)) via an electrostatic interaction and loaded the PECs into the hydrogels. The formations of PECs were affected by molecular weight, pI (or pK(a)), and types of amine group of the used polycations. Unlike other polycations, PLA formed a large uniform complex with BSA, and the PLA/protein complex-loaded hydrogel showed the slowest protein release behavior. In the PEC-loaded hydrogel system, the protein release could also be controlled by viscosities of the gel and weight ratios of polycations and proteins, although the activities of the proteins were decreased in proportion to the PLA amounts. These results suggest that the PEC-loaded injectable and thermosensitive poly(organophosphazene) hydrogel has considerable potential for creating a sustained protein delivery system by using the PEC via electrostatic interaction. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. Influence of structural features of carrageenan on the formation of polyelectrolyte complexes with chitosan.

    PubMed

    Volod'ko, A V; Davydova, V N; Glazunov, V P; Likhatskaya, G N; Yermak, I M

    2016-03-01

    The polyelectrolyte complexes (PEC) of carrageenans (CG)-κ-, κ/β-, λ-and x-CG with chitosan were obtained. The formation of PEC was detected by Fourier-transform infrared (FTIR) spectroscopy and by centrifugation in a Percoll gradient. The influence of the structural peculiarities of CG on its interaction with chitosan was studied. The results of centrifugation showed that x-CG with a high degree of sulphation (SD) was completely bound to chitosan, unlike low SD κ-CG and κ/β-CG. Binding constant values showed there was a high affinity of CG for chitosan. CG with flexible macromolecule conformation and high SD exhibited the greatest binding affinity for chitosan. The full-atomic 3D-structures of the PEC κ-CG: chitosan in solution have been obtained by the experiments in silico for the first time. The amino groups of chitosan make the largest contribution to the energy of the complex formation by means of hydrogen and ionic bonds. The most probable complexes have stoichiometries of 1:1 and 1:1.5.

  2. Hydrophilic drug encapsulation in shell-core microcarriers by two stage polyelectrolyte complexation method.

    PubMed

    Dalmoro, Annalisa; Sitenkov, Alexander Y; Cascone, Sara; Lamberti, Gaetano; Barba, Anna Angela; Moustafine, Rouslan I

    2017-02-25

    In this study a protocol exploiting the combination of the ultrasonic atomization and the complexation between polyelectrolytes was developed to efficiently encapsulate a hydrophilic chemotherapeutic agent essentially used in the treatment of colon cancer, 5-fluorouracil, in enteric shell-core alginate-based microcarriers. The atomization assisted by ultrasound allowed to obtain small droplets by supplying low energy and avoiding drug degradation. In particular microcarriers were produced in a home-made apparatus where both the core (composed of alginate, drug, and Pluronic F127) and shell (composed of only alginate) feed were separately sent to the coaxial ultrasonic atomizer where they were nebulized and placed in contact with the complexation bulk. With the aim to obtain microstructured particles of alginate encapsulating 5-fluorouracil, different formulations of the first complexation bulk were tested; at last an emulsion made of a calcium chloride aqueous solution and dichloromethane allowed to reach an encapsulation efficiency of about 50%. This result can be considered very interesting considering that in literature similar techniques gave 5-fluorouracil encapsulation efficiencies of about 10%. Since a single complexation stage was not able to assure microcarriers gastroresistance, the formulation of a second complexation bulk was evaluated. The solution of cationic and pH-insoluble Eudragit® RS 100 in dichloromethane was chosen as bulk of second-stage complexation obtaining good enteric properties of shell-core microcarriers, i.e. a 5-FU cumulative release at pH 1 (simulating gastric pH) lower than 35%. The formation of interpolyelectrolyte complex (IPEC) between countercharged polymers and the chemical stability of 5-FU in microcarriers were confirmed by FTIR analysis, the presence of an amorphous dispersion of 5-FU in prepared microparticles was also confirmed by DSC. Finally, shell-core enteric coated microcarriers encapsulating 5-fluorouracil were used

  3. Interfacial Polymerization on Dynamic Complex Colloids: Creating Stabilized Janus Droplets.

    PubMed

    He, Yuan; Savagatrup, Suchol; Zarzar, Lauren D; Swager, Timothy M

    2017-03-01

    Complex emulsions, including Janus droplets, are becoming increasingly important in pharmaceuticals and medical diagnostics, the fabrication of microcapsules for drug delivery, chemical sensing, E-paper display technologies, and optics. Because fluid Janus droplets are often sensitive to external perturbation, such as unexpected changes in the concentration of the surfactants or surface-active biomolecules in the environment, stabilizing their morphology is critical for many real-world applications. To endow Janus droplets with resistance to external chemical perturbations, we demonstrate a general and robust method of creating polymeric hemispherical shells via interfacial free-radical polymerization on the Janus droplets. The polymeric hemispherical shells were characterized by optical and fluorescence microscopy, scanning electron microscopy, and confocal laser scanning microscopy. By comparing phase diagrams of a regular Janus droplet and a Janus droplet with the hemispherical shell, we show that the formation of the hemispherical shell nearly doubles the range of the Janus morphology and maintains the Janus morphology upon a certain degree of external perturbation (e.g., adding hydrocarbon-water or fluorocarbon-water surfactants). We attribute the increased stability of the Janus droplets to (1) the surfactant nature of polymeric shell formed and (2) increase in interfacial tension between hydrocarbon and fluorocarbon due to polymer shell formation. This finding opens the door of utilizing these stabilized Janus droplets in a demanding environment.

  4. Preparation and chemical and biological characterization of a pectin/chitosan polyelectrolyte complex scaffold for possible bone tissue engineering applications.

    PubMed

    Coimbra, P; Ferreira, P; de Sousa, H C; Batista, P; Rodrigues, M A; Correia, I J; Gil, M H

    2011-01-01

    In this work, porous scaffolds obtained from the freeze-drying of pectin/chitosan polyelectrolyte complexes were prepared and characterized by FTIR, SEM and weight loss studies. Additionally, the cytotoxicity of the prepared scaffolds was evaluated in vitro, using human osteoblast cells. The results obtained showed that cells adhered to scaffolds and proliferated. The study also confirmed that the degradation by-products of pectin/chitosan scaffold are noncytotoxic.

  5. Microfabricated photocrosslinkable polyelectrolyte-complex of chitosan and methacrylated gellan gum

    PubMed Central

    Coutinho, Daniela F.; Sant, Shilpa; Shakiba, Mojdeh; Wang, Ben; Gomes, Manuela E.; Neves, Nuno M.; Reis, Rui L.

    2012-01-01

    Chitosan (CHT) based polyelectrolyte complexes (PECs) have been receiving great attention for tissue engineering approaches. These hydrogels are held together by ionic forces and can be disrupted by changes in physiological conditions. In this study, we present a new class of CHT-based PEC hydrogels amenable to stabilization by chemical crosslinking. The photocrosslinkable anionic methacrylated gellan gum (MeGG) was complexed with cationic CHT and exposed to light, forming a PEC hydrogel. The chemical characterization of the photocrosslinkable PEC hydrogel by Fourier transform infrared spectroscopy (FTIR) revealed absorption peaks specific to the raw polymers. A significantly higher swelling ratio was observed for the PEC hydrogel with higher CHT content. The molecular interactions between both polysaccharides were evaluated chemically and microscopically, indicating the diffusion of CHT to the interior of the hydrogel. We hypothesized that the addition of MeGG to CHT solution first leads to a membrane formation around MeGG. Then, migration of CHT inside the MeGG hydrogel occurs to balance the electrostatic charges. The photocrosslinkable feature of MeGG further allowed the formation of cell-laden microscale hydrogel units with different shapes and sizes. Overall, this system is potentially useful for a variety of applications including the replication of microscale features of tissues for modular tissue engineering. PMID:23293429

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  7. Effect of charge balance and dosage of polyelectrolyte complexes on the shear resistance of mineral floc strength and reversibility.

    PubMed

    Korhonen, Markus H J; Rojas, Orlando J; Laine, Janne

    2015-06-15

    We evaluated the effect of polyelectrolyte complexes (PEC) with varying balance of charges on the flocculation of precipitated calcium carbonate (PCC) particles. PECs composed of polyacrylamides carrying opposite charges (A-PAM and C-PAM) were investigated in terms of PCC floc shear resistance and re-flocculation effects. Light transmission was used in real time to monitor the dynamics of flocculation under shear fields. Compared to the single polyelectrolytes, PECs greatly enhanced particle re-flocculation while minor differences in shear resistance were observed. Shear resistance and re-flocculation depended strongly on the molecular weight and charge ratio of the PEC components. In order to achieve floc stability and re-flocculation conditions a minimum concentration of charge-asymmetric PEC should be applied.

  8. Bathroom greywater recycling using polyelectrolyte-complex bilayer membrane: Advanced study of membrane structure and treatment efficiency.

    PubMed

    Oh, K S; Poh, P E; Chong, M N; Chan, E S; Lau, E V; Saint, C P

    2016-09-05

    Polyelectrolyte-complex bilayer membrane (PCBM) was fabricated using biodegradable chitosan and alginate polymers for subsequent application in the treatment of bathroom greywater. In this study, the properties of PCBMs were studied and it was found that the formation of polyelectrolyte network reduced the molecular weight cut-off (MWCO) from 242kDa in chitosan membrane to 2.71kDa in PCBM. The decrease in MWCO of PCBM results in better greywater treatment efficiency, subsequently demonstrated in a greywater filtration study where treated greywater effluent met the household reclaimed water standard of <2 NTU turbidity and <30ppm total suspended solids (TSS). In addition, a further 20% improvement in chemical oxygen demand (COD) removal was achieved as compared to a single layer chitosan membrane. Results from this study show that the biodegradable PCBM is a potential membrane material in producing clean treated greywater for non-potable applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Evaluation of polyelectrolyte complex-based scaffolds for mesenchymal stem cell therapy in cardiac ischemia treatment.

    PubMed

    Ceccaldi, Caroline; Bushkalova, Raya; Alfarano, Chiara; Lairez, Olivier; Calise, Denis; Bourin, Philippe; Frugier, Celine; Rouzaud-Laborde, Charlotte; Cussac, Daniel; Parini, Angelo; Sallerin, Brigitte; Fullana, Sophie Girod

    2014-02-01

    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 complexes (PECs). After freeze-drying, the resultant matrices presented a highly interconnected porous microstructure and mechanical properties suitable for cell culture. In vitro evaluation demonstrated their compatibility with mesenchymal stell cell (MSC) proliferation and their ability to maintain paracrine activity. Finally, the in vivo performance of seeded 3D PEC scaffolds with a polymeric ratio of 40/60 was evaluated after an acute myocardial infarction provoked in a rat model. Evaluation of cardiac function showed a significant increase in the ejection fraction, improved neovascularization, attenuated fibrosis as well as less left ventricular dilatation as compared to an animal control group. These results provide evidence that 3D PEC scaffolds prepared from alginate and chitosan offer an efficient environment for 3D culturing of MSCs and represent an innovative solution for tissue engineering.

  10. Mucoadhesive Nanostructured Polyelectrolyte Complexes as Potential Carrier to Improve Zidovudine Permeability.

    PubMed

    Pedreiro, Liliane Neves; Stringhetti, Beatriz; Cury, Ferreira; Gremião, Maria Palmira Daflon

    2016-02-01

    Mucoadhesive drug delivery systems have been widely investigated as a strategic to allow the raising of intestinal residence time of drugs and the intimate contact with the intestinal mucosa, both factors that increase the local concentration gradient. Zidovudine (AZT) mucoadhesive nanostructured polyelectrolyte complexes were obtained by chitosan (CS)-hypromellose phthalate (HP) interactions in order to favor the permeability through biological membranes and the AZT absorption. Particle size and morphology analyses showed the obtaining of nanoparticulate delivery systems, with AZT loaded about of 65%. The characterization by DSC, X-ray diffraction and FTIR showed a new crystalline structure formed in which the drug remained molecularly dispersed, without changing this structure. The reduced release rates in the simulated gastric medium and the control of release rates in simulated intestinal medium of AZT were demonstrated by in vitro release studies. The nanoparticles liquid uptake ability associated to the mucoadhesiveness by electronic interaction between the particles and mucus revealed that the drug delivery system developed in this work is a promising approach to improve the permeation of this drug throughout the intestinal mucosa.

  11. Structural evolution of polyelectrolyte-complex-core micelles and ordered-phase bulk materials

    NASA Astrophysics Data System (ADS)

    Tirrell, Matthew; Krogstad, Daniel; Kramer, Edward

    2015-03-01

    The kinetics of formation and structural evolution of novel polyelectrolyte complex materials formed by the assembly of water-soluble di- and tri-block copolymers, with one neutral block and one block either cationic or anionic, have been investigated. The mechanism and speed of the assembly process, and the organization of these domains, were probed using dynamic mechanical spectroscopy and small angle X-ray scattering (SAXS). SAXS revealed that the equilibrium morphologies of both the di-block copolymer and the tri-block copolymer materials were generally qualitatively the same with some apparent quantitative differences in phase boundaries, possibly attributable to lack of full equilibration. Slow kinetics and difficulties in reaching equilibrium phase structures, especially in tri-block materials, is a principal message of this article. Detailed analysis of the SAXS data revealed that the tri-block copolymer materials formed ordered phases via a nucleation and growth pathway and that the addition of small amounts (~20%) of corresponding di-block copolymers increased the rate of structure formation and enhanced several key physical properties. This work was supported by the U.S. Department of Energy Office of Science Program in Basic Energy Sciences, Materials Sciences and Engineering Division.

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

    PubMed

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

    2016-11-01

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

  13. Polyelectrolyte complexes as prospective carriers for the oral delivery of protein therapeutics.

    PubMed

    Bourganis, Vassilis; Karamanidou, Theodora; Kammona, Olga; Kiparissides, Costas

    2017-02-01

    The oral administration of protein therapeutics is hindered by the multitude of barriers confronted by these molecules along the gastrointestinal tract (i.e., acidic environment, proteolytic degradation, mucosal barrier, etc.). Their unique properties (e.g., high molecular weight, hydrophilicity, charge, etc.) and labile structure are mainly responsible for their instability in the harsh conditions along the gastrointestinal tract (GIT) and dictate the employment of alternative routes for their administration (e.g., parenteral). The association of proteins with colloidal carriers represents an interesting approach to overcome the aforementioned issues. However, certain requirements, such as stability in the GIT, stimuli-responsiveness, protection of the encapsulated biomolecule from enzymatic degradation and permeability of the mucosa, have to be met in order to efficiently deliver the sensitive payload to the intended site of action, thus resulting in enhanced bioavailability. The formation of colloidal polyelectrolyte complexes (PECs) seems to be a promising strategy towards this direction, and the present review aims to provide an insight into PECs (e.g., preparation methods, characteristics) along with their advantages and drawbacks as drug delivery vehicles for the oral administration of protein-based therapeutics. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Highly Versatile Polyelectrolyte Complexes for Improving the Enzyme Replacement Therapy of Lysosomal Storage Disorders.

    PubMed

    Giannotti, Marina I; Abasolo, Ibane; Oliva, Mireia; Andrade, Fernanda; García-Aranda, Natalia; Melgarejo, Marta; Pulido, Daniel; Corchero, José L; Fernández, Yolanda; Villaverde, Antonio; Royo, Miriam; García-Parajo, María F; Sanz, Fausto; Schwartz, Simó

    2016-10-05

    Lysosomal storage disorders are currently treated by enzyme replacement therapy (ERT) through the direct administration of the unprotected recombinant protein to the patients. Herein we present an ionically cross-linked polyelectrolyte complex (PEC) composed of trimethyl chitosan (TMC) and α-galactosidase A (GLA), the defective enzyme in Fabry disease, with the capability of directly targeting endothelial cells by incorporating peptide ligands containing the RGD sequence. We assessed the physicochemical properties, cytotoxicity, and hemocompatibility of RGD-targeted and untargeted PECs, the uptake by endothelial cells and the intracellular activity of PECs in cell culture models of Fabry disease. Moreover, we also explored the effect of different freeze-drying procedures in the overall activity of the PECs. Our results indicate that the use of integrin-binding RGD moiety within the PEC increases their uptake and the efficacy of the GLA enzyme, while the freeze-drying allows the activity of the therapeutic protein to remain intact. Overall, these results highlight the potential of TMC-based PECs as a highly versatile and feasible drug delivery system for improving the ERT of lysosomal storage disorders.

  15. Polyelectrolyte complex of carboxymethyl starch and chitosan as protein carrier: oral administration of ovalbumin.

    PubMed

    Assaad, Elias; Blemur, Lindsay; Lessard, Martin; Mateescu, Mircea Alexandru

    2012-01-01

    A novel carboxymethyl starch (CMS)/chitosan polyelectrolyte complex (PEC) was proposed as an excipient for oral administration of ovalbumin. The dissolution of ovalbumin from monolithic tablets (200 mg, 2.1 × 9.6 mm, 50% loading) obtained by direct compression was studied. When CMS was used as an excipient, more than 70% of the loaded ovalbumin remained undigested after 1 h of incubation in simulated gastric fluid (SGF) with pepsin. The complete dissolution, after transfer of tablets into simulated intestinal fluid (SIF) with pancreatin, occurred within a total time of about 6 h. Higher protection (more than 90% stability in SGF) and longer dissolution (more than 13 h) were obtained with 50% CMS/50% chitosan physical mixture or with PEC excipients. A lower proportion of chitosan was needed for PEC than for the CMS/chitosan mixture to obtain a similar dissolution profile. The high protection against digestion by pepsin, the various release times and the mucoadhesion properties of these excipients based on CMS favor the development of suitable carriers for oral vaccinations.

  16. Recent development of chitosan-based polyelectrolyte complexes with natural polysaccharides for drug delivery.

    PubMed

    Luo, Yangchao; Wang, Qin

    2014-03-01

    Chitosan, as a unique positively charged polysaccharide, has been one of the most popular biopolymers for development of drug delivery systems for various applications, due to its promising properties, including high biocompatibility, excellent biodegradability, low toxicity, as well as abundant availability and low production cost. Since last decade, increasing attention has been attracted by delivery systems fabricated from natural biopolymer-based polyelectrolyte complexes (PEC), formed by electrostatic interactions between two oppositely charged biopolymers. In order to tailor specific applications of chitosan-based PEC drug delivery systems, various forms have been developed in recent years, including nanoparticles, microparticles, beads, tablets, gels, as well as films and membranes. The present review focuses on the recent advances in drug delivery applications of chitosan-based PEC with other natural polysaccharides, including alginate, hyaluronic acid, pectin, carrageenan, xanthan gum, gellan gum, gum arabic, and carboxymethyl cellulose, etc. The fabrication techniques, characterizations, as well as in vitro and in vivo evaluations of each PEC delivery system are discussed in detail. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Amoxicillin Loaded Chitosan–Alginate Polyelectrolyte Complex Nanoparticles as Mucopenetrating Delivery System for H. Pylori

    PubMed Central

    Arora, Saahil; Gupta, Sankalp; Narang, Raj K.; Budhiraja, Ramji D.

    2011-01-01

    The present study has been undertaken to apply the concept of nanoparticulate mucopenetrating drug delivery system for complete eradication of Helicobacter pylori (H. pylori), colonised deep into the gastric mucosal lining. Most of the existing drug delivery systems have failed on account of either improper mucoadhesion or mucopenetration and no dosage form with dual activity of adhesion and penetration has been designed till date for treating H. pylori induced disorders. In the present study, novel chitosan-alginate polyelectrolyte complex (CS-ALG PEC) nanoparticles of amoxicillin have been designed and optimized for various variables such as pH and mixing ratio of polymers, concentrations of polymers, drug and surfactant, using 33 Box-Behnken design. Various studies like particle size, surface charge, percent drug entrapment, in-vitro mucoadhesion and in-vivo mucopenetration of nanoparticles on rat models were conducted. The optimised FITC labelled CS-ALG PEC nanoparticles have shown comparative low in-vitro mucoadhesion with respect to plain chitosan nanoparticles, but excellent mucopenetration and localization as observed with increased fluorescence in gastric mucosa continuously over 6 hours, which clinically can help in eradication of H. pylori. PMID:21886911

  18. Polyelectrolyte complex containing silver nanoparticles with antitumor property on Caco-2 colon cancer cells.

    PubMed

    Martins, Alessandro F; Follmann, Heveline D M; Monteiro, Johny P; Bonafé, Elton G; Nocchi, Samara; Silva, Cleiser T P; Nakamura, Celso V; Girotto, Emerson M; Rubira, Adley F; Muniz, Edvani C

    2015-08-01

    Polyelectrolyte complex (beads) based on N,N,N-trimethyl chitosan/alginate was successful obtained and silver nanoparticles (AgNPs) were loaded within beads. In vitro cytotoxicity assays using beads/silver nanoparticles (beads/AgNPs) provided results, indicating that this material significantly inhibited the growth of colon cancer cells (Caco-2). In vitro release studies showed that the beads stabilized AgNPs and repressed Ag(0) oxidation under gastric conditions (pH 2.0). On the other hand, at physiological condition (pH 7.4) the beads/AgNPs released 3.3 μg of Ag(+) per each beads milligram. These studies showed that the concentration of Ag(+) released (3.3 μg) was cytotoxic for the Caco-2 cells and was not cytotoxic on healthy VERO cells. This result opens new perspectives for the manufacture of biomaterials based on beads/AgNPs with anti-tumor properties. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Synergistic strengthening of polyelectrolyte complex membranes by functionalized carbon nanotubes and metal ions

    PubMed Central

    Liu, Tao; An, Quan-Fu; Zhao, Qiang; Wu, Jia-Kai; Song, Yi-Hu; Zhu, Bao-Ku; Gao, Cong-Jie

    2015-01-01

    Hydrophilic polymers have garnered much attention due to their critical roles in various applications such as molecular separation membranes, bio-interfaces, and surface engineering. However, a long-standing problem is that their mechanical properties usually deteriorate at high relative humidity (RH). Through the simultaneous incorporation of functionalized carbon nanotubes and copper ions (Cu2+), this study introduces a facile method to fabricate high strength polyelectrolyte complex nanohybrid membranes resistant to high RH (90%). For example, the tensile strength of the nanohybrid membranes is 55 MPa at 90% RH (80% of the original value at 30% RH). These results are explained by copper ions depressing the swelling degree of the membrane, and functionalized carbon nanotubes promoting stress transfer between the polymer matrix and them. The nanohybrid membranes are efficient in separating water/alcohol mixtures containing relatively high water content (up to 30 wt%), whereas common hydrophilic polymer membranes usually suffer from excessive swelling under this condition. PMID:25586650

  20. Complexation of a polyelectrolyte with oppositely charged spherical macroions: Giant inversion of charge.[1

    NASA Astrophysics Data System (ADS)

    Nguyen, Toan T.; Shklovskii, Boris I.

    2001-03-01

    Complexation of a long flexible polyelectrolyte (PE) molecule with oppositely charged spherical particles such as colloids, micelles, or globular proteins in a salty water solution is studied. PE binds spheres winding around them, while spheres repel each other and form almost periodic necklace. If the total charge of PE is larger than total charge of spheres, repulsive correlations of PE turns on a sphere lead to inversion of the net charge of each sphere. In the opposite case, we predict another correlation effect: under-screened by PE spheres bind to PE in such a great number that they invert the charge of PE. The inverted charge by absolute value can be larger than the bare charge of PE even when screening by monovalent salt is weak. At larger concentrations of monovalent salt, the inverted charge can reach giant proportions. Our theory is in qualitative agreement with recent experiments on micelles-PE systems[2]. A stiff PE is also considered and compared to a flexible one of the same linear charge density. Charge inversion for a stiff PE is found to be stronger than for a flexible PE at large monovalent salt concentration and weaker at small salt concentration. [1]Toan The Nguyen and Boris I. Shklovskii, cond-mat/0011096 (2000), submitted to J. Chem. Phys. [2]Y. Wang, K. Kimura, Q. Huang, P. L. Dubin, W. Jaeger, Macromolecules, 32 (1999) 7128.

  1. Chitosan/pectin/gum Arabic polyelectrolyte complex: process-dependent appearance, microstructure analysis and its application.

    PubMed

    Tsai, Ruei-Yi; Chen, Pin-Wen; Kuo, Ting-Yun; Lin, Che-Min; Wang, Da-Ming; Hsien, Tzu-Yang; Hsieh, Hsyue-Jen

    2014-01-30

    Novel chitosan/pectin/gum Arabic polyelectrolyte complex (PEC) solutions and membranes with various compositions were prepared for biomedical applications. The appearance of the PEC solutions, either clear or turbid, was process-dependent and depended on how the three components were dissolved and mixed. The addition of gum Arabic to the chitosan and pectin significantly decreased the viscosities of the resultant PEC solutions due to the formation of globe-like microstructures that was accompanied by network-like microstructures and other molecular entanglements. The mechanical strength and hydrophilicity of the PEC membranes manufactured from the PEC solutions, especially for a weight ratio of 84/8/8 (chitosan/pectin/gum Arabic), were enhanced compared to pure chitosan membranes. Moreover, the use of the 84/8/8 PEC membranes as a drug carrier exhibited steady and fairly complete release of a drug (insulin) for 6h. Based on these promising results, the chitosan/pectin/gum Arabic PEC membranes have great potential in controlled drug release applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Self-assembled polyelectrolyte complexes films as efficient compression coating layers for controlled-releasing tablets.

    PubMed

    Li, Wenyan; Huo, Mengmeng; Sen Chaudhuri, Arka; Yang, Chen; Cao, Dazhong; Wu, Zhenghong; Qi, Xiaole

    2017-05-01

    Currently, polysaccharide-based hydrogels are widely studied macromolecular networks to modify drug dissolution from controlled-releasing matrix tablets. Among them, polyelectrolyte complexes (PEC) films consisted of chitosan (CS) and sodium alginate (SA) could be obtained via spontaneously assembling under physiological gastrointestinal environment. Here, we utilized these self-assembled PEC films as an efficient coating materials to develop controlled-released matrix tablets through compression coating process, with paracetamol (APAP) as model drug. The constitutive and morphology characteristic studies on these PEC films illustrated that the mixture of CS and SA with the weight ratio of 1:1 would be an promising outer layer for compression-coating tablets. In addition, the in vitro drug releasing behavior experiments demonstrated that the optimized compression coating tablets displayed satisfied zero-order drug releasing profits. Furthermore, the in vivo pharmacokinetic studies of these APAP loaded compression-coated tablets in New Zealand rabbits gave that the Tmax (12.32 ± 1.05 h) was significantly prolonged (p < 0.01), compared to that (0.89 ± 0.26 h) of common APAP tablets (Jinfuning(®)) after oral administration. These studies suggest that the compression-coated tablets with self-assembled PEC film as coating outer layer may be a promising strategy for peroral controlled release delivery system of water soluble drugs.

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

    NASA Astrophysics Data System (ADS)

    Nejati Moshtaghin, Mahboubeh

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

  4. Follicular dermal papilla structures by organization of epithelial and mesenchymal cells in interfacial polyelectrolyte complex fibers.

    PubMed

    Lim, Tze Chiun; Leong, Meng Fatt; Lu, Hongfang; Du, Chan; Gao, Shujun; Wan, Andrew C A; Ying, Jackie Y

    2013-09-01

    The hair follicle is a regenerating organ that produces a new hair shaft during each growth cycle. Development and cycling of the hair follicle is governed by interactions between the epithelial and mesenchymal components. Therefore, development of an engineered 3D hair follicle would be useful for studying these interactions to identify strategies for treatment of hair loss. We have developed a technique suitable for assembly of different cell types in close proximity in fibrous hydrogel scaffolds with resolutions of ∼50 μm. By assembly of dermal papilla (DP) and keratinocytes, structures similar to the native hair bulb arrangement are formed. Gene expression of these constructs showed up-regulation of molecules involved in epithelial-mesenchymal interactions of the hair follicle. Implantation of the follicular structures in SCID mice led to the formation of hair follicle-like structures, thus demonstrating their hair inductive ability. The transparency of the fiber matrix and the small dimensions of the follicular structures allowed the direct quantitation of DP cell proliferation by confocal microscopy, clearly illustrating the promoting or inhibitory effects of hair growth regulating agents. Collectively, our results suggested a promising application of these 3D engineered follicular structures for in vitro screening and testing of drugs for hair growth therapy.

  5. Dynamically reconfigurable complex emulsions via tunable interfacial tensions

    NASA Astrophysics Data System (ADS)

    Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

    2015-02-01

    Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with

  6. Dynamically reconfigurable complex emulsions via tunable interfacial tensions

    PubMed Central

    Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

    2015-01-01

    Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including multiple emulsions and Janus droplets which contain hemispheres of differing material, are of increasing importance1 in pharmaceuticals and medical diagnostics2, in the fabrication of microparticles and capsules3–5 for food6, in chemical separations7, in cosmetics8, and in dynamic optics9. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets’ physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes10, to small-volume but more precise microfluidic methods11,12. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have greatly increased utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of

  7. Biological and polymeric self-assembled hybrid systems: structure and properties of thylakoid/polyelectrolyte complexes.

    PubMed

    Dementiev, A A; Baikov, A A; Ptushenko, V V; Khomutov, G B; Tikhonov, A N

    2005-06-15

    A novel hybrid system composed of biological components and synthetic polymer, thylakoid/polycation complex, has been formed and studied. Effects of complex formation on the structure, electrostatics and functioning of thylakoid membranes have been examined. Thylakoids from bean leaves were used to form complexes with polycation polyallylamine hydrochloride (PAAH) in two systems: (i) thylakoid/polycation complexes formed in an aqueous bulk phase, and (ii) immobilized thylakoid/polycation planar complexes. Immobilized on a solid substrate surface, thylakoid/polycation complexes were prepared using layer-by-layer stepwise alternate adsorption technique, i.e., via the sequential alternate adsorption of thylakoids and polycation molecules. The morphology of built up structures was investigated by scanning electron microscopy. Light-induced electron transport in chloroplasts was studied by the electron paramagnetic resonance (EPR) method. Spin probe technique was employed to study the structural and electrostatic characteristics of thylakoid membranes. We have found that efficiency of light-induced electron transport in thylakoid membranes and membrane structure were not changed noticeably by PAAH binding to thylakoids in a wide range of PAAH concentrations. The data obtained indicate the physiologically-soft character of polycation interactions with thylakoid membranes and demonstrate effectiveness of interfacial self-assembly approach to fabrication of complex planar functional nanostructures from biological components and synthetic polymers.

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

    PubMed

    Kulig, Dominika; Zimoch-Korzycka, Anna; Król, Żaneta; Oziembłowski, Maciej; Jarmoluk, Andrzej

    2017-01-06

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

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

    NASA Astrophysics Data System (ADS)

    Hastuti, Budi; Mudasir, Siswanta, Dwi; Triyono

    2016-02-01

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

  10. Sulfadiazine—Chitosan Conjugates and Their Polyelectrolyte Complexes with Hyaluronate Destined to the Management of Burn Wounds

    PubMed Central

    Dumitriu, Raluca Petronela; Profire, Lenuta; Nita, Loredana Elena; Dragostin, Oana Maria; Ghetu, Nicolae; Pieptu, Dragoș; Vasile, Cornelia

    2015-01-01

    In the present study polyelectrolyte complexes (PECs) based on new sulfadiazine-chitosan conjugates with sodium hyaluronate have been developed with potential use in treatment of burn wounds. The PECs were chemically characterized using Fourier Transform—Infrared Spectroscopy, Scanning Electon Microscopy and Near Infrared Chemical Imaging Technique. The swelling behavior and in vitro sulfadiazine release were also investigated. The antimicrobial activity was evaluated towards three bacterial strains: Escherichia coli, Listeria monocytogenes and Salmonella thyphymurium. The developed PECs demonstrated their antimicrobial efficiency against tested bacterial strains, the PECs containing sulfadiazine-modified chitosan being more active than PECs containing unmodified chitosan. PMID:28787940

  11. Polyelectrolyte Solutions

    NASA Astrophysics Data System (ADS)

    Colby, Ralph H.

    2008-03-01

    Pierre-Gilles de Gennes once described polyelectrolytes as the ``least understood form of condensed matter''. In this talk, I will describe the state of the polyelectrolyte field before and after de Gennes' seminal contributions published 1976-1980. De Gennes clearly explained why electrostatic interactions only stretch the polyelectrolyte chains on intermediate scales in semidilute solution (between the electrostatic blob size and the correlation length) and why the scattering function has a peak corresponding to the correlation length (the distance to the next chain). Despite many other ideas being suggested since then, the simple de Gennes scaling picture of polyelectrolyte conformation in solution has stood the test of time. How that model is used today, including consequences for dynamics in polyelectrolyte solutions, and what questions remain, will clarify the importance of de Gennes' ideas.

  12. Absorption spectra and spectral-kinetic characteristics of the fluorescence of Sanguinarine in complexes with polyelectrolytes and DNA

    NASA Astrophysics Data System (ADS)

    Motevich, I. G.; Strekal, N. D.; Nowicky, J. W.; Maskevich, S. A.

    2010-07-01

    The absorption spectra and stationary and time resolved fluorescence spectra of the isoquinoline alkaloid sanguinarine are studied in aqueous media and during interactions with synthetic polyelectrolytes (polystyrene sulfonate and polyallylamine) and a natural polyelectrolyte (DNA).

  13. Formation of κ-carrageenan-gelatin polyelectrolyte complexes studied by (1)H NMR, UV spectroscopy and kinematic viscosity measurements.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Vovk, Mikhail A; Tolstoy, Peter M

    2016-10-20

    The intermolecular interactions between an anionic polysaccharide from the red algae κ-carrageenan and a gelatin polypeptide, forming stoichiometric polysaccharide-polypeptide (bio)polyelectrolyte complexes in the aqueous phase, were examined. The major method of investigation was high-resolution (1)H NMR spectroscopy. Additional data were obtained by UV absorption spectroscopy, light scattering dispersion and capillary viscometry. Experimental data were interpreted in terms of the changing roles of electrostatic interactions, hydrophobic interactions and hydrogen bonds when κ-carrageenan-gelatin complexes are formed. At high temperatures, when biopolymer macromolecules in solution are in the state of random coil, hydrophobic interactions make a major contribution to complex stabilization. At the temperature of gelatin's coil→helix conformational transition and at lower temperatures, electrostatic interactions and hydrogen bonds play a defining role in complex formation. A proposed model of the κ-carrageenan-gelatin complex is discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed

    Woltmann, Beatrice; Torger, Bernhard; Müller, Martin; Hempel, Ute

    2014-01-01

    Implant loosening or deficient osseointegration is a major problem in patients with systemic bone diseases (eg, osteoporosis). For this reason, the stimulation of the regional cell population by local and sustained drug delivery at the bone/implant interface to induce the formation of a mechanical stable bone is promising. The purpose of this study was to investigate the interaction of polymer-based nanoparticles with human bone marrow-derived cells, considering nanoparticles' composition and surface net charge. Polyelectrolyte complex nanoparticles (PECNPs) composed of the polycations poly(ethyleneimine) (PEI), poly(L-lysine) (PLL), or (N,N-diethylamino)ethyldextran (DEAE) in combination with the polyanions dextran sulfate (DS) or cellulose sulfate (CS) were prepared. PECNPs' physicochemical properties (size, net charge) were characterized by dynamic light scattering and particle charge detector measurements. Biocompatibility was investigated using human mesenchymal stromal cells (hMSCs) cultured on immobilized PECNP films (5-50 nmol·cm(-2)) by analysis for metabolic activity of hMSCs in dependence of PECNP surface concentration by MTS (3-[4,5-dimethylthiazol-2-yl]-5-[3-carboxymethoxyphenyl]-2-[4-sulfophenyl]-2H-tetrazolium, inner salt) assay, as well as cell morphology (phase contrast microscopy). PECNPs ranging between ~50 nm and 150 nm were prepared. By varying the ratio of polycations and polyanions, PECNPs with a slightly positive (PEC(+)NP) or negative (PEC(-)NP) net charge were obtained. The PECNP composition significantly affected cell morphology and metabolic activity, whereas the net charge had a negligible influence. Therefore, we classified PECNPs into "variant systems" featuring a significant dose dependency of metabolic activity (DEAE/CS, PEI/DS) and "invariant systems" lacking such a dependency (DEAE/DS, PEI/CS). Immunofluorescence imaging of fluorescein isothiocyanate isomer I (FITC)-labeled PECNPs suggested internalization into hMSCs remaining

  15. Local and systemic delivery of VEGF siRNA using polyelectrolyte complex micelles for effective treatment of cancer.

    PubMed

    Kim, Sun Hwa; Jeong, Ji Hoon; Lee, Soo Hyeon; Kim, Sung Wan; Park, Tae Gwan

    2008-07-14

    For efficient cancer therapy, small interfering RNA (siRNA) should be stably and efficiently delivered into the target tissue and readily taken up by cancer cells. To address these needs, a polyelectrolyte complex (PEC) micelle-based siRNA delivery system was developed for anti-angiogenic gene therapy. The interaction between poly(ethylene glycol) (PEG)-conjugated vascular endothelial growth factor siRNA (VEGF siRNA-PEG) and polyethylenimine (PEI) led to the spontaneous formation of nanoscale polyelectrolyte complex micelles (VEGF siRNA-PEG/PEI PEC micelles), having a characteristic siRNA/PEI PEC inner core with a surrounding PEG shell layer. Intravenous as well as intratumoral administration of the PEC micelles significantly inhibited VEGF expression at the tumor tissue and suppressed tumor growth in an animal tumor model without showing any detectable inflammatory responses in mice. Upon examination of the PEC micelle distribution and in vivo optical imaging following intravenously injection, enhanced accumulation of the PEC micelles was also observed in the tumor region. This study demonstrates the feasibility of using PEC micelles as a potential carrier for therapeutic siRNAs in local and systemic treatment of cancer.

  16. Novel polyelectrolytes

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  17. Cytotoxic activity of paclitaxel incorporated into polyelectrolyte nanocapsules

    NASA Astrophysics Data System (ADS)

    Karabasz, Alicja; Bzowska, Monika; Łukasiewicz, Sylwia; Bereta, Joanna; Szczepanowicz, Krzysztof

    2014-04-01

    Nanoencapsulation is a promising solution for the delivery of chemotherapeutics to tumors. A method of preparation of drug-loaded nanocapsules based on the liquid core encapsulation by a sequential adsorption of a polyelectrolyte is described. An easily evaporative solvent, chloroform, was used as an oil phase. An interfacial complex formed with an oil-soluble, Food and Drug Administration-approved surfactant, and polycation poly- l-lysine (PLL) was used as a microemulsion stabilizer. A polyelectrolyte multilayer shell was constructed by a sequential adsorption of polyelectrolytes using biocompatible polyelectrolytes (PLL as a polycation and poly- l-glutamic acid as a polyanion). A hydrophobic anticancer agent, paclitaxel, was successfully encapsulated in the nanocarriers with the average size of 100 nm. In vitro analysis of the effects of nanoformulations was performed using a mouse colon carcinoma cell line CT26-CEA. Biocompatibility of the nanocapsules was evaluated using various biochemical assays. The results indicate that the cell viability was diminished by positively but not by negatively charged nanocarriers. Analysis of the cellular uptake of nanocapsules determined by flow cytometry and confocal microscopy confirmed their accumulation inside the cells. Encapsulated paclitaxel retains its cytotoxic/cytostatic activity; although its effects were weaker than those of the corresponding concentrations of the free drug. The generated nanocapsules seem to be a valuable vehicle for tumor drug delivery; although further work is needed to increase their overall activity.

  18. In vitro-in vivo evaluation of xanthan gum and eudragit inter polyelectrolyte complex based sustained release tablets

    PubMed Central

    Deb, Tamal Krishna; Ramireddy, B.; Moin, Afrasim; Shivakumar, H.G.

    2015-01-01

    Introduction: Polyelectrolyte complexes (PECs) are the association complexes formed between oppositely charged particles (e.g., polymer-polymer, polymer-drug and polymer-drug-polymer). These are formed due to electrostatic interaction between oppositely charged polyions. Diclofenac is a nonsteroidal anti-inflammatory drug (NSAID) advocated in use of painful and inflammatory rheumatic and certain non-rheumatic conditions. The drug has a relatively short elimination half-life, which limits the potential for drug accumulation. As an analgesic, it has a fast onset and long duration of action. Aim: invitro-invivo evaluation of Xanthan gum and Eudragit E100 inter polyelectrolyte complex based sustained release tablet. Materials and Method: Xanthan gum and Eudragit E100 were used as PEC and were prepared using different proportions i.e. in 1:1 to 1:6 ratio. The optimum ratio of E100 and XG was 1:6 used to characterize the IPC and the formulation of tablet. The tablets were prepared by wet granulation using PVP K30 as binder. Results and Discussion: FT-IR and DSC studies confirmed the formation of IPC. Scanning Electron Microscopy (SEM) studies showed highly porous tablet surface. The tablets were evaluated for hardness, weight variation, and drug content, found to be within limits. In vitro and in vivo studies concluded that tablets showed sustained release profile. The short term stability study of the optimized formulation indicated that the formulation was stable. Conclusion: Since the Poly Electrolyte Complex delay the release of the drug, it can be employed in formulating sustained release matrix tablets. PMID:25599035

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

    PubMed

    Cheow, Wean Sin; Hadinoto, Kunn

    2012-04-01

    Nanoscale antibiotic delivery has emerged as a promising therapeutic means to treat lung biofilm infection owed to its sputum penetrating ability. Due to the high antibiotic dosage requirement in anti-biofilm therapy, the most suitable formulation for this purpose is the antibiotic nanoparticles themselves, instead of the more extensively studied antibiotic-loaded nano-carriers, which often exhibit low drug loading. The present work details the preparation and characterization of antibiotic nanoparticle complex (or nanoplex) by self-assembly amphiphile-polyelectrolyte complexation process. Ofloxacin (OFX) and levofloxacin (LEV) are used as the antibiotics with dextran sulfate (DXT) as the polyelectrolyte. The nanoplex possesses high drug loading (up to 80%) and size<400nm ideal for sputum penetration. Unlike existing methods to prepare drug nanoparticles, the present method is fast, energy-minimal, solvent-free, and highly efficient as manifested in nearly 100% of drug is transformed into nanoplex. The effects of drug-to-polyelectrolyte charge ratio, pH, drug, and salt concentrations on the nanoplex characteristics (i.e. size, stability, drug loading) are investigated from which the optimal preparation conditions have been identified. Higher complexation efficiency and stronger agglomeration tendency are observed for LEV nanoplex owed to its higher hydrophobicity. The antibiotics are completely released from the nanoplex in aqueous salt solution within 3h and their antimicrobial activity is preserved upon complexation. The nanoplex is readily transformed into amorphous dry powders that remain stable after one-month storage owed to the high glass transition temperature. The antibiotic nanoplexes are highly charged enabling their subsequent functionalization for targeted delivery and controlled drug release purposes.

  20. Effect of polyelectrolytes on (de)stability of liquid foam films.

    PubMed

    Fauser, Heiko; von Klitzing, Regine

    2014-09-28

    The review addresses the influence of polyelectrolytes on the stabilisation of free-standing liquid foam films, which affects the stability of a whole macroscopic foam. Both the composition of the film surface and the stratification of the film bulk drives the drainage and the interfacial forces within a foam film. Beside synthetic polyelectrolytes also natural polyelectrolytes like cellulose, proteins and DNA are considered.

  1. Molecular Dynamics Studies of Interfacial Properties of Complex Liquid Systems

    NASA Astrophysics Data System (ADS)

    Ouyang, Jian

    1995-01-01

    Molecular dynamics simulations have been used to investigate the interfacial properties of linear and branched chain alkane molecule condensed systems. The only notable effect of branching in our studies is the reduction of system ordering and layering since the degree of branching in the systems is very small. It is found that thin alkane films, adsorbed on a solid substrate at a temperature well above its bulk melting temperature, have about up to four well defined layers near the substrate. Within these layers, molecules are parallel to the substrate and exhibit domains of short range ordering. At the liquid-vapor interface, the molecular segment density tail is well fit by an error function indicating that the molecular height distribution obeys the Gaussian law predicted from the capillary wave model. At a temperature around the liquid bulk solidification temperature, a first order phase transition occurs at the liquid-vapor interfacial region of the alkane thin films. Molecules in this region pack hexagonally and align themselves parallel to the interface normal with a small cant angle. Below this crystalline monolayer, there are four sharp layers where molecules lie parallel to the substrate surface with enhanced domains of transverse ordering. It is observed that the contact angle of an alkane nanodroplet on top of a solid surface increases when the solid-liquid interaction strength decreases, or the molecule length increases. Due to the fact that almost all the molecules are in the liquid-vapor interfacial region, a nanodroplet with molecules of a length comparable to the droplet dimension has clear layers from the solid-liquid interface to the top of the droplet. This layering reduces when the size of the droplet increases or the molecule length decreases. Substrates do not create, but enhance the layering. It is also noticed that in the confined thin fluid films, liquid molecules exhibit partially solid-like characteristics behavior with the ability to

  2. Versatile electron-collecting interfacial layer by in situ growth of silver nanoparticles in nonconjugated polyelectrolyte aqueous solution for polymer solar cells.

    PubMed

    Yuan, Kai; Chen, Lie; Chen, Yiwang

    2014-10-02

    Novel PEIE-Ag composites by in situ growth of silver nanoparticles in poly(ethylenimine)-ethoxylated (PEIE) aqueous solution are explored as an efficient interfacial layer for improving inverted polymer solar cells (PSCs) performance. The hybrid PEIE-Ag interfacial material is simple to fabricate only via ultraviolet irradiation with good water-solubility and unique film formation. The generated Ag nanoparticles can anchor in the PEIE polymer chains to form a conductive continuous interpenetrating network structure. Combining of the advantages of PEIE and Ag nanoparticles, the PEIE-Ag shows enhanced charge transport, electron selective and collection, and improved light-harvesting, mainly due to the surface plasmon resonance effect, better energy alignment induced by the formation of ideal dipole layer, as well as the improved conductivity. These distinguished interfacial properties result in the power conversion efficiency of inverted PSCs based on poly[4,8-bis(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b]dithiophene-2,6-diyl]-alt-[2-(2-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl] (PBDTTT-C-T) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) photoactive layer substantially improved up to 7.66% from 6.11%. Moreover, the device performance is insensitively dependent on the thickness of the PEIE-Ag interfacial layer, broadening the thicknesses selection window for interfacial materials. These results demonstrate that PEIE-Ag is a potential interfacial material compatible with roll-to-roll techniques and suitable for printed electronic devices.

  3. Interfacial self-assembly of metal-mediated viologen-like coordination polyelectrolyte hybrids of the bisterpyridine ligand and their optical, electrochemical, and electrochromic properties.

    PubMed

    Zhang, Chao-Feng; Liu, An; Chen, Meng; Nakamura, Chikashi; Miyake, Jun; Qian, Dong-Jin

    2009-06-01

    Metal-mediated coordination polyelectrolyte multilayers with a bisterpyridine ligand (Bisterpy) have been self-assembled at air-water interfaces via coordination reactions of the bidentate ligand Bisterpy with inorganic salts in the subphases. To avoid dissolution of the viologen-like coordination polyelectrolyte monolayers, anionic poly(styrenesulfonic acid-o-maleic) (PSS) acid was added in the subphases as a supporting layer. The average molecular area of the ligand Bisterpy could reach 1.2-1.5 nm(2) on the surfaces of the subphases containing mixtures of inorganic salts (M) and PSS, although the ligand was unable to form a stable monolayer on the pure water surface. The Langmuir-Blodgett (LB) method was used to deposit the Bisterpy/PSS and M-Bisterpy/PSS hybrid multilayers on the substrate surfaces, which were characterized by using absorption and fluorescence spectroscopy as well as electrochemical analysis. Quasi-reversible redox waves were recorded and centered at about -0.68 and -0.92 V (vs Ag/AgCl), respectively, corresponding to the two-electron process of the ligand, Bisterpy2+ <--> Bisterpy(*+) <--> Bisterpy(0), which were slightly shifted to lower potentials in the LB films of metal-mediated coordination polymers. The film compositions were determined by using X-ray photoelectron spectroscopy. The as-prepared LB films showed strong stability and good electrochromic response upon the applied potential of -1.1 V vs Ag/AgCl and thus could act as potential materials in the development of redox-based molecular switches and display devices.

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  5. Preparation of polyelectrolyte complex nanoparticles of chitosan and poly(2-acry1amido-2-methylpropanesulfonic acid) for doxorubicin release.

    PubMed

    Zhang, Liping; Wang, Jie; Ni, Caihua; Zhang, Yanan; Shi, Gang

    2016-01-01

    A new kind of polyelectrolyte complex (PEC) based on cationic chitosan (CS) and anionic poly(2-acry1amido-2-methylpropanesulfonic acid) (PAMPS) was prepared using a polymer-monomer pair reaction system. Chitosan was mixed with 2-acry1amido-2-methylpropanesulfonic acid) (AMPS) in an aqueous solution, followed by polymerization of AMPS. The complex was formed by electrostatic interaction of NH3(+) groups of CS and SO3(-) groups of AMPS, leading to a formation of complex nanoparticles of CS-PAMPS. A series of nanoparticles were obtained by changing the weight ratio of CS to AMPS, the structure and properties of nanoparticles were investigated. It was observed that the nanoparticles possessed spherical morphologies with average diameters from 255 nm to 390 nm varied with compositions of the nanoparticles. The nanoparticles were used as drug vehicles for doxorubicin, displaying relative high drug loading rate and encapsulation rate. The vitro release profiles revealed that the drug release could be controlled by adjusting pH of the release media. The nanoparticles demonstrated apparent advantages such as simple preparation process, free of organic solvents, size controllable, good biodegradability and biocompatibility, and they could be potentially used in drug controlled release field.

  6. A mycelium with polyelectrolyte complex-bunched hyphae: several important factors affecting on the fermentation performance at a very high cell density.

    PubMed

    Mizunuma, Takato; Kokufuta, Etsuo; Sato, Seigo

    2007-05-15

    We have reported in the previous paper (Colloids Surf. B (2006) in press) a marked increase in the rate of gluconic acid production at a very high cell concentration (40 g/l) of filamentous fungus (Aspergillus niger IFO 31012) which was immobilized with polyelectrolyte complex consisting of potassium poly(vinyl alcohol) sulfate and trimethylammonium glycol chitosan iodide [6-O-(2-hydroxyethyl)-2-(trimethylammonio)-chitosan iodide]. The present study was carried out to look at what factors play a crucial role in this enhancement. We measured viscosity of broth, mass-transfer coefficient (k(L)a) for oxygen and diffusion coefficient of glucose (substrate). It has become apparent that there is only a difference in the diffusion coefficient of glucose between the free and immobilized cells. Therefore, we believe that the diffusion limitation by substrates as a problem in submerged mycelial processes is improved by immobilization based on polyelectrolyte complexes.

  7. Elaboration of stable and antibody functionalized positively charged colloids by polyelectrolyte complexation between chitosan and hyaluronic acid.

    PubMed

    Polexe, Ramona C; Delair, Thierry

    2013-07-19

    In this study, we describe the elaboration of multifunctional positively charged polyelectrolyte complex (PEC) nanoparticles, designed to be stable at physiological salt concentration and pH, for effective targeted delivery. These nanoparticles were obtained by charge neutralization between chitosan (CS) as polycation and hyaluronic acid (HA) as polyanion. We showed that the course of the complexation process and the physico-chemical properties of the resulting colloids were impacted by (i) internal parameters such as the Degree of Acetylation (DA, i.e., the molar ration of acetyl glucosamine residues) and molar mass of CS, the HA molar mass and (ii) external parameters like the charge mixing ratio and the polymer concentrations. As a result, nonstoichiometric colloidal PECs were obtained in water or PBS (pH 7.4) and remained stable over one month. The polymer interactions were characterized by thermal analysis (DSC and TGA) and the morphology was studied by scanning electron microscopy. A model antibody, anti-ovalbumine (OVA) immunoglobulin A (IgA) was sorbed on the particle surface in water and PBS quantitatively in 4 h. The CS-HA/IgA nanoparticles average size was between 425-665 nm with a positive zeta potential. These results pointed out that CS-HA can be effective carriers for use in targeted drug delivery.

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

    PubMed

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

    2016-01-28

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

  9. Subcritical Water Induced Complexation of Soy Protein and Rutin: Improved Interfacial Properties and Emulsion Stability.

    PubMed

    Chen, Xiao-Wei; Wang, Jin-Mei; Yang, Xiao-Quan; Qi, Jun-Ru; Hou, Jun-Jie

    2016-09-01

    Rutin is a common dietary flavonoid with important antioxidant and pharmacological activities. However, its application in the food industry is limited mainly because of its poor water solubility. The subcritical water (SW) treatment provides an efficient technique to solubilize and achieve the enrichment of rutin in soy protein isolate (SPI) by inducing their complexation. The physicochemical, interfacial, and emulsifying properties of the complex were investigated and compared to the mixtures. SW treatment had much enhanced rutin-combined capacity of SPI than that of conventional method, ascribing to the well-contacted for higher water solubility of rutin with stronger collision-induced hydrophobic interactions. Compared to the mixtures of rutin with proteins, the complex exhibited an excellent surface activity and improved the physical and oxidative stability of its stabilized emulsions. This improving effect could be attributed to the targeted accumulation of rutin at the oil-water interface accompanied by the adsorption of SPI resulting in the thicker interfacial layer, as evidenced by higher interfacial protein and rutin concentrations. This study provides a novel strategy for the design and enrichment of nanovehicle providing water-insoluble hydrophobic polyphenols for interfacial delivery in food emulsified systems. © 2016 Institute of Food Technologists®

  10. Characterization of interfacial solvent in protein complexes and contribution of wet spots to the interface description.

    PubMed

    Teyra, Joan; Pisabarro, M T

    2007-06-01

    Water networks in protein interfaces can complement direct interactions contributing significantly to molecular recognition, function, and stability of protein association. Thus, water can be seen as an extension or addition of protein structural features, which may add plenty of information to protein interfacial definition. However, solvent is frequently neglected in protein interaction studies. Analysis of the interfacial information contained in the PDB is essential to achieve more accurate descriptions of protein interfaces. With this aim, we have used the SCOWLP database (http://www.scowlp.org) and applied computational geometry methods to extract and analyze interfacial information of a high-resolution nonredundant dataset of 176 protein complexes containing obligate and transient interfaces. We have identified all interfacial residues and characterized them in terms of temperature factors, secondary structure, residue composition, and pairing preferences to understand their contribution to the interface description. We have paid special attention to water-bridged residues; focusing on those that interact only mediated by a water molecule called wet spots. Our results show that 40.1% of the interfacial residues are interacting through water and that wet spots represent a 14.5% of the total, emphasizing the importance of the inclusion of solvent in protein interaction studies, and the contribution of wet spots to interfacial description. Wet spots present similar characteristics to residues binding buried water molecules in the core or cavities of proteins; being preferably located in nonregular secondary structures and establishing hydrogen bonds by their main-chains. We observe that obligate and transient interfaces present a comparable amount of solvent. Moreover, the role of solvent in both complex types differs according to the different nature of their interfaces. The information obtained in our studies will assist in the process of accomplishing more

  11. Design of chitospheres loaded with pristine polymer particles for extended drug delivery via polyelectrolyte complexation and particulate leaching.

    PubMed

    Ramburrun, Poornima; Choonara, Yahya E; Kumar, Pradeep; du Toit, Lisa C; Pillay, Viness

    2015-02-01

    The aim of this study was to investigate the drug release from swellable chitospheres laden with pristine polymethylmethacrylate (PMMA) nanoparticles. Chitosan matrices were prepared by sodium tripolyphosphate crosslinking from a chitosan suspension containing the model BCS class II drug, indomethacin. PMMA particles were added to the chitospheres as the modulator for drug release. Swelling and erosion studies in conjunction with textural profiling provided an understanding of the dominant and underlying drug release mechanisms of the ionically crosslinked chitospheres loaded with the pristine PMMA particles. A series of drug release studies performed in PBS pH 7.4 showed that the pristine particle-loaded chitospheres released indomethacin over 144 h in a first-order manner with 50% drug release occurring over 48 h. The study also revealed that in situ porogen leaching for pore creation and polyelectrolyte complex formation were the main mechanisms of release from the chitospheres. The results of this study may be utilized for the development of neuro-implants for controlled delivery of bioactives to the brain where scaffolds of superior mechanical strength and reduced swelling properties are required. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Preparation and characterization of polyelectrolyte complex nanoparticles based on poly (malic acid), chitosan. A pH-dependent delivery system.

    PubMed

    Arif, Muhammad; Raja, Mazhar Ali; Zeenat, Shah; Chi, Zhe; Liu, Chenguang

    2017-01-01

    The main objective of this work was to develop polyelectrolyte complex (PEC) nanoparticles based on poly (malic acid), chitosan (PMLA/CS) as pH-dependent delivery systems. The results indicated that the PMLA/CS Nps were successfully prepared. The prepared PMLA/CS Nps showed spherical morphology with a mean diameter of 212.81 nm and negative surface charge of -24.60 mV, and revealing significant pH-sensitive properties as the mass ratio of PMLA to CS was 5:5. The prepared PMLA/CS Nps were characterized by FT-IR, TEM and DLS. The prepared PMLA/CS Nps remained stable over a temperature range of 4-53 °C. Doxorubicin (Dox) as a model drug was loaded on the nanoparticles through the physical adsorption method. The high drug loading efficiency (16.9%) and the sustained release patterns in acidic media were observed, and the release accelerated in alkaline solutions. MTT based cytotoxic analysis also depicted the non-toxic nature of PMLA/CS Nps, while Dox-PMLA/CS Nps showed dose-dependent cytotoxicity towards MDA-MB-231 cells. Hence, the nanoparticles could be potentially applied as pH sensitive drug vehicles for controlled release.

  13. Continuous testing system for Baeyer-Villiger biooxidation using recombinant Escherichia coli expressing cyclohexanone monooxygenase encapsulated in polyelectrolyte complex capsules.

    PubMed

    Bučko, Marek; Schenkmayerová, Andrea; Gemeiner, Peter; Vikartovská, Alica; Mihovilovič, Marko D; Lacík, Igor

    2011-08-10

    An original strategy for universal laboratory testing of Baeyer-Villiger monooxygenases based on continuous packed-bed minireactor connected with flow calorimeter and integrated with bubble-free oxygenation is reported. Model enantioselective Baeyer-Villiger biooxidations of rac-bicyclo[3.2.0]hept-2-en-6-one to corresponding lactones (1R,5S)-3-oxabicyclo-[3.3.0]oct-6-en-3-one and (1S,5R)-2-oxabicyclo-[3.3.0]oct-6-en-3-one as important chiral synthons for the synthesis of bioactive compounds were performed in the minireactor equipped with a column packed with encapsulated recombinant cells Escherichia coli overexpressing cyclohexanone monooxygenase. The cells were encapsulated in polyelectrolyte complex capsules formed by reaction of oppositely charged polymers utilizing highly reproducible and controlled encapsulation process. Encapsulated cells tested in minireactor exhibited high operational stability with 4 complete substrate conversions to products and 6 conversions above 80% within 14 repeated consecutive biooxidation tests. Moreover, encapsulated cells showed high enzyme stability during 91 days of storage with substrate conversions above 80% up to 60 days of storage. Furthermore, usable thermometric signal of Baeyer-Villiger biooxidation obtained by flow calorimetry using encapsulated cells was utilized for preparatory kinetic study in order to guarantee sub-inhibitory initial substrate concentration for biooxidation tests.

  14. Distinctive viscoelastic and viscoplastic nanomechanics of ionically cross-linked polyelectrolyte complexes under intermittent relaxation and creep

    NASA Astrophysics Data System (ADS)

    Han, Biao; Ma, Tianzhu; Lee, Daeyeon; Shenoy, Vivek; Han, Lin

    This study aims to reveal unique nanoscale viscoelastic and viscoplastic properties of ionically linked polyelectrolyte networks. Layer-by-layer PAH/PAA complexes were tested by four continuous loading cycles in aqueous solutions. In each cycle, AFM-nanoindentation via a microspherical tip (R =5 μm) was applied up to 1 μN force, followed by a 30-60 sec hold at either a constant indentation depth to measure relaxation, or a constant force to measure creep. At a highly cross-linked, net neutral state (0.01M, pH 5.5), instantaneous modulus increased by 2.7-fold from first to last cycle, while the degree of relaxation (>95%) remain consistent. These results indicate repeated loading increases local cross-link density, while relaxation is consistently dominated by cross-link breaking and re-formation. In contrast, under creep, modulus increased by a similar 3.5-fold, and degree of creep is significantly attenuated from ~50% to 45% from first to last cycle. Results from creep suggest constant viscous flow of polymer chains in the absence of permanent anchorage. As a result, an irreversible deformation (~370nm) was observed after multiple creep cycles, suggesting the presence of viscoplasticity.

  15. Dual-Charged Hollow Fiber Membranes for Low-Pressure Nanofiltration Based on Polyelectrolyte Complexes: One-Step Fabrication with Tailored Functionalities.

    PubMed

    Gherasim, Cristina Veronica; Luelf, Tobias; Roth, Hannah; Wessling, Matthias

    2016-07-27

    A new nanofiltration (NF) hollow fiber membrane is developed by using two oppositely charged polyelectrolytes coagulating into a polyelectrolyte complex (PEC) onto polyether sulfone base polymer. The particular membrane architecture emerges during a single-step procedure, allowing setting both the porous negatively charged support of the hollow fiber and the separation layer containing also the positive polyelectrolyte (PEI/PDADMAC) through a single layer dry-jet wet spinning process. The novelty is two-pronged: the composition of the hollow fiber membrane itself and its fabrication procedure (one-step fabrication of membranes employing polyelectrolytes). These result in highly permeable hollow fiber membranes with a stable separation layer and performance at par with the membranes reported in literature obtained by multistep processes. More importantly, the membranes are obtained through a simple, very fast (one-step), and less expensive procedure. The best performance among these newly obtained hollow-fiber membranes is achieved by PD5% hollow fiber (MWCO of 300 Da), which showed 7.6 L/m(2)·h·bar permeability and ∼90% rejection of MgCl2, MgSO4, and Na2SO4 at 2 bar pressure. Thus, the resulting membranes not only have the advantages of the hollow-fiber configuration, but perform very well at extremely low pressures (the lowest reported in the literature). The broad impact of the results presented in this Article lies in the potential to dramatically reduce both the fabrication (duration and complexity) and the price and desalination costs of highly performing NF hollow fiber membranes. These might result in interesting potential applications and open new directions toward designing efficient functional NF hollow fibers for water desalination.

  16. Stability enhanced polyelectrolyte-coated gold nanorod-photosensitizer complexes for high/low power density photodynamic therapy

    PubMed Central

    Shi, Zhenzhi; Ren, Wenzhi; Gong, An; Zhao, Xinmei; Zou, Yuehong; Brown, Eric Michael Bratsolias; Chen, Xiaoyuan; Wu, Aiguo

    2015-01-01

    Photodynamic therapy (PDT) is a promising treatment modality for cancer and other malignant diseases, however safety and efficacy improvements are required before it reaches its full potential and wider clinical use. Herein, we investigated a highly efficient and safe photodynamic therapy procedure by developing a high/low power density photodynamic therapy mode (high/low PDT mode) using methoxypoly(ethylene glycol) thiol (mPEG-SH) modified gold nanorod (GNR)-AlPcS4 photosensitizer complexes. mPEG-SH conjugated to the surface of simple polyelectrolyte-coated GNRs was verified using Fourier transform infrared spectroscopy; this improved stability, reduced cytotoxicity, and increased the encapsulation and loading efficiency of the nanoparticle dispersions. The GNR-photosensitizer complexes were exposed to the high/low PDT mode (high light dose = 80 mW/cm2 for 0.5 min; low light dose = 25 mW/cm2 for 1.5 min), and a high PDT efficacy leads to approximately 90% tumor cell killing. Due to synergistic plasmonic photothermal properties of the complexes, the high/low PDT mode demonstrated improved efficacy over using single wavelength continuous laser irradiation. Additionally, no significant loss in viability was observed in cells exposed to free AlPcS4 photosensitizer under the same irradiation conditions. Consequently, free AlPcS4 released from GNRs prior to cellular entry did not contribute to cytotoxicity of normal cells or impose limitations on the use of the high power density laser. This high/low PDT mode may effectively lead to a safer and more efficient photodynamic therapy for superficial tumors. PMID:24855961

  17. Synthesis of conducting polyelectrolyte complexes of polyaniline and poly(2-acrylamido-3-methyl-1-propanesulfonic acid) catalyzed by pH-stable palm tree peroxidase.

    PubMed

    Caramyshev, Alexei V; Evtushenko, Evgeny G; Ivanov, Viktor F; Barceló, Alfonso Ros; Roig, Manuel G; Shnyrov, Valery L; van Huystee, Robert B; Kurochkin, Iliya N; Vorobiev, Andrey Kh; Sakharov, Ivan Yu

    2005-01-01

    Comparison of the stability of five plant peroxidases (horseradish, royal palm tree leaf, soybean, and cationic and anionic peanut peroxidases) was carried out under acidic conditions favorable for synthesis of polyelectrolyte complexes of polyaniline (PANI). It demonstrates that palm tree peroxidase has the highest stability. Using this peroxidase as a catalyst, the enzymatic synthesis of polyelectrolyte complexes of PANI and poly(2-acrylamido-3-methyl-1-propanesulfonic acid) (PAMPS) was developed. The template polymerization of aniline was carried out in aqueous buffer at pH 2.8. Varying the concentrations of aniline, PAMPS, and hydrogen peroxide as reagents, favorable conditions for production of PANI were determined. UV-vis-NIR absorption and EPR demonstrated that PAMPS and PANI formed the electroactive complex similar to PANI doped traditionally using low molecular weight sulfonic acids. The effect of pH on conformational variability of the complex was evaluated by UV-vis spectroscopy. Atomic force microscopy showed that a size of the particles of the PANI-PAMPS complexes varied between 10 and 25 nm, depending on a concentration of PAMPS in the complex. The dc conductivity of the complexes depends also on the content of PAMPS, the higher conductivity being for the complexes containing the lower content of the polymeric template.

  18. On the phase diagram of reentrant condensation in polyelectrolyte-liposome complexation

    NASA Astrophysics Data System (ADS)

    Sennato, S.; Bordi, F.; Cametti, C.

    2004-09-01

    Complexation of polyions with oppositely charged spherical liposomes has been investigated by means of dynamic light scattering measurements and a well-defined reentrant condensation has been observed. The phase diagram of charge inversion, recently derived [T. T. Nguyen and B. I. Shklovskii, J. Chem. Phys. 115, 7298 (2001)] for the complexation of DNA with charged spherical macroions, has been employed in order to define the boundaries of the region where polyion-liposome complexes begin to condense, forming larger aggregates, and where aggregates dissolve again, towards isolated polyion-coated-liposome complexes. A reasonable good agreement is observed in the case of complexes formed by negatively charged polyacrylate sodium salt polyions and liposomes built up by cationic lipids (dioleoyltrimethylammoniumpropane), in an extended liposome concentration range.

  19. Many facets of the polyelectrolyte and oppositely charged colloidal particle complexation: counterion release and electrical conductivity behavior.

    PubMed

    Cametti, C; Truzzolillo, D

    2011-06-09

    The lateral correlated adsorption of polyions onto oppositely charged vesicles, leading to the formation of stable equilibrium clusters of mesoscopic size, is associated to the release of a fraction of counterions, initially condensed on the polyion chains. This ulterior release of counterions provokes an increase of the number of free ions, besides the ones due to the partial ionization of both charged particles and polyions, that can be appropriately monitored by means of electrical conductivity measurements of the whole system. We have investigated this behavior in a suspension of cationic vesicles made up by dioleoyl trimethyl ammonium propane (DOTAP) liposomial vesicles interacting with an anionic polyelectrolyte composed by polyacrylate sodium salt. This system has been in the past extensively studied by us by means of different experimental techniques, and its behavior has been sufficiently characterized, as far as hydrodynamic and electrical properties are concerned. In this note, we report on the dc electrical conductivity behavior during the whole aggregation process, from the single polyion-coated liposomal particles, to polyion-induced liposome clusters, to finally polyion-fully covered liposomes, in polyion excess conditions. We have evaluated the excess of released counterions on the basis of the standard theory of the electrical properties of aqueous charged solutions and compared this quantity with the one predicted by the lateral correlation adsorption model. The agreement is quite good, offering strong experimental evidence of the role played by the release of counterions in the aggregation process. Finally, we have considered a similar liposomial system, where the lateral correlation adsorption was inhibited by structural reasons, having replaced the polyion by a simple electrolyte, whose dissociated ions will adsorb randomly at the particle surface, rather than in a correlated manner. In this case, no counterion release upon complexation occurs

  20. Interfacial Magnetism in Complex Oxide Heterostructures Probed by Neutrons and X-rays

    DOE PAGES

    Liu, Yaohua; Ke, Xianglin

    2015-09-02

    Magnetic complex-oxide heterostructures are of keen interest because a wealth of phenomena at the interface of dissimilar materials can give rise to fundamentally new physics and potentially valuable functionalities. Altered magnetization, novel magnetic coupling and emergent interfacial magnetism at the epitaxial layered-oxide interfaces have all been intensively investigated, which shapes our understanding on how to utilize those materials, particularly for spintronics. Neutron and x-ray based techniques have played a decisive role in characterizing interfacial magnetic structures and clarifying the underlying physics in this rapidly developing field. Here we review some recent experimental results, with an emphasis on those studied viamore » polarized neutron reflectometery and polarized x-ray absorption spectroscopy. We conclude with some perspectives.« less

  1. Interfacial Magnetism in Complex Oxide Heterostructures Probed by Neutrons and X-rays

    SciTech Connect

    Liu, Yaohua; Ke, Xianglin

    2015-09-02

    Magnetic complex-oxide heterostructures are of keen interest because a wealth of phenomena at the interface of dissimilar materials can give rise to fundamentally new physics and potentially valuable functionalities. Altered magnetization, novel magnetic coupling and emergent interfacial magnetism at the epitaxial layered-oxide interfaces have all been intensively investigated, which shapes our understanding on how to utilize those materials, particularly for spintronics. Neutron and x-ray based techniques have played a decisive role in characterizing interfacial magnetic structures and clarifying the underlying physics in this rapidly developing field. Here we review some recent experimental results, with an emphasis on those studied via polarized neutron reflectometery and polarized x-ray absorption spectroscopy. We conclude with some perspectives.

  2. Examination of biogenic selenium-containing nanosystems based on polyelectrolyte complexes by atomic force, Kelvin probe force and electron microscopy methods

    SciTech Connect

    Sukhanova, T. E. Vylegzhanina, M. E.; Valueva, S. V.; Volkov, A. Ya.; Kutin, A. A.; Temiryazeva, M. P.; Temiryazev, A. G.

    2016-06-17

    The morphology and electrical properties of biogenic selenium-containing nanosystems based on polyelectrolyte complexes (PECs) were examined using AFM, Kelvin Probe Force and electron microscopy methods. It has been found, that prepared nanostructures significantly differed in their morphological types and parameters. In particular, multilayers capsules can be produced via varying synthesis conditions, especially, the selenium–PEC mass ratio ν. At the “special point” (ν = 0.1), filled and hollow nano- and microcapsules are formed in the system. The multilayer character of the capsules walls is visible in the phase images. Kelvin Probe Force images showed the inhomogeneity of potential distribution in capsules and outside them.

  3. The effect of ionic correlations on ion distribution across polyelectrolyte blend interfaces

    NASA Astrophysics Data System (ADS)

    Kwon, Ha-Kyung; Olvera de La Cruz, Monica

    Recent developments in high-density energy storage and generation devices have identified as polyelectrolyte blends and copolymers as suitable candidate materials for use in these applications, as they combine the low volatility and high flexibility of polymers with ion-selective conductivity of the charge-carrying backbone. It has been shown that in polyelectrolyte melts, where the dielectric constant is relatively low, ionic correlations can significantly reduce miscibility, inducing phase separation even at negative values of χN. At selected values of ionic coupling strengths, the polyelectrolyte blend exhibits a triple point, where coexistence is observed between phases with different concentrations and ordering of ions. When salt is added, the system undergoes re-entrant behavior as electrostatic effects are screened out. Using a hybrid of self-consistent field and liquid state theories (SCFT-LS), we investigate the distribution of ions across the interface in polyelectrolyte blends. We demonstrate that the inclusion of ionic correlations induces complex charge-dependent adsorption behavior at the interface, leading to changes in the interfacial width and miscibility of the blend. This work was performed under the following financial assistance Award 70NANB14H012 from U.S. Department of Commerce, National Insti- tute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

  4. Electrospun chitosan-alginate nanofibers with in situ polyelectrolyte complexation for use as tissue engineering scaffolds.

    PubMed

    Jeong, Sung In; Krebs, Melissa D; Bonino, Christopher A; Samorezov, Julia E; Khan, Saad A; Alsberg, Eben

    2011-01-01

    Electrospun natural biopolymers are of great interest in the field of regenerative medicine due to their unique structure, biocompatibility, and potential to support controlled release of bioactive agents and/or the growth of cells near a site of interest. The ability to electrospin chitosan and alginate to form polyionic complexed nanofibrous scaffolds was investigated. These nanofibers crosslink in situ during the electrospinning process, and thus do not require an additional chemical crosslinking step. Although poly(ethylene oxide) (PEO) is required for the electrospinning, it can be subsequently removed from the nanofibers simply by incubating in water for a few days, as confirmed by attenuated total reflectance Fourier transform infrared. Solutions that allowed uniform nanofiber formation were found to have viscosities in the range of 0.15-0.7 Pa·s and conductivities below 4 mS/cm for chitosan-PEO and below 2.2 mS/cm for alginate-PEO. The resultant nanofibers both before and after PEO extraction were found to be uniform and on the order of 100 nm as determined by scanning electron microscopy. The dynamic rheological properties of the polymer mixtures during gelation indicated that the hydrogel mixtures with low storage moduli provided uniform nanofiber formation without beaded structures. Increased amounts of chitosan in the PEO-extracted chitosan-alginate nanofibers resulted in a lower swelling ratio. Additionally, these nanofibrous scaffolds exhibit increased cell adhesion and proliferation compared to those made of alginate alone, due to the presence of the chitosan, which promotes the adsorption of serum proteins. Thus, these nanofibrous scaffolds formed purely via ionic complexation without toxic crosslinking agents have great potential for guiding cell behavior in tissue regeneration applications.

  5. Chitosan-gum arabic polyelectrolyte complex films: physicochemical, mechanical and mucoadhesive properties.

    PubMed

    Sakloetsakun, Duangkamon; Preechagoon, Detpon; Bernkop-Schnürch, Andreas; Pongjanyakul, Thaned

    2016-08-01

    By blending chitosan (CS) and gum arabic (GA), a powerful biomaterial complex might be obtained due to the unique properties of CS and the low viscosity and good emulsifying properties of GA. The objectives of this study were to prepare and examine the properties of dispersions and films of CS and GA as a function of the mixing weight ratio, pH value and molecular weight of CS. The dispersions were characterized by turbidity, zeta potential and cytotoxicity and then the dispersions were cast into films. Physicochemical properties of the film were performed. CS-GA dispersions exhibited higher turbidity and a lower zeta potential with an increase in the GA ratio. Continuous films of the CS-GA could be formed at all ratios. CS and GA could molecularly interact via electrostatic forces and intermolecular hydrogen bonding. The CS-GA (1:0.5) films exhibited relatively low water uptake, erosion, water vapor permeability and puncture strength compared to the CS films. Furthermore, the CS-GA films demonstrated good mucoadhesive properties, allowing for adhesion to the mucosal membrane. Based on these results, it could be advantageous to use CS-GA films as film formers for the formulation of coatings and drug delivery systems.

  6. Phase behavior of electrostatically complexed polyelectrolyte gels using an embedded fluctuation model.

    PubMed

    Audus, Debra J; Gopez, Jeffrey D; Krogstad, Daniel V; Lynd, Nathaniel A; Kramer, Edward J; Hawker, Craig J; Fredrickson, Glenn H

    2015-02-14

    Nanostructured, responsive hydrogels formed due to electrostatic interactions have promise for applications such as drug delivery and tissue mimics. These physically cross-linked hydrogels are composed of an aqueous solution of oppositely charged triblocks with charged end-blocks and neutral, hydrophilic mid-blocks. Due to their electrostatic interactions, the end-blocks microphase separate and form physical cross-links that are bridged by the mid-blocks. The structure of this system was determined using a new, efficient embedded fluctuation (EF) model in conjunction with self-consistent field theory. The calculations using the EF model were validated against unapproximated field-theoretic simulations with complex Langevin sampling and were found consistent with small angle X-ray scattering (SAXS) measurements on an experimental system. Using both the EF model and SAXS, phase diagrams were generated as a function of end-block fraction and polymer concentration. Several structures were observed including a body-centered cubic sphere phase, a hexagonally packed cylinder phase, and a lamellar phase. Finally, the EF model was used to explore how parameters that directly relate to polymer chemistry can be tuned to modify the resulting phase diagram, which is of practical interest for the development of new hydrogels.

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

    DOEpatents

    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.

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

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Carciello, N.R.

    1987-04-21

    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 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 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. 5 figs.

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

    PubMed

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

    2017-07-11

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

  10. Ionizing radiation in the polyelectrolytes technology

    NASA Astrophysics Data System (ADS)

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

    1999-01-01

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

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

    PubMed

    Etrych, Tomás; Leclercq, Laurent; Boustta, Mahfoud; Vert, Michel

    2005-06-01

    Controlled drug delivery and gene transfection involve contact of artificial polyelectrolytic systems that can interact dramatically with biopolymers and cells when they are introduced in blood. Given the complexity of body aqueous media in terms of physical chemistry, a model approach was selected in attempt to understand the behavior of artificial polyelectrolytes introduced in body fluids. Selection in terms of molecular weight was highlighted in a previous paper. In the present study the formation and the stability of fractions obtained when a polycation is added to a polyanion according to a titrating process mimicking injection into blood was considered for different polycation/polyanion couples. Poly(amino serinate) and poly(L-lysine) were used as polybases, and poly(acrylic acid), poly(L-lysine citramide) and poly(L-lysine citramide imide) as polyacids. Four fractions corresponding to different positive/negative charge ratios were formed for each couple. At low polyion concentration (13 mg/L) and given salt concentration, the stability of the complex fractions depended on molecular weight and charge density of the polyions. The NaCl concentration required to destabilize the different interpolyelectrolyte complexes was found to decrease from the first fraction to the fourth one. Upon decreasing the salt concentration, macroscopic flocculation occurred in the case of PLL/PAA complex fractions only. For the other couples, dynamic light scattering showed that several hundreds nanometer sized particles were formed that were stable in a broad range of NaCl concentration, including the physiological 0.15 ionic strength. At higher polyion concentrations, stable solid precipitate was formed regardless of the system. The absence of flocculation in the case of highly diluted poly(L-lysine citramide) and poly(L-lysine citramide imide) polyanions in salted media is assigned to the presence of non-ionic hydroxyl and amide polar groups along the complexed chains. Data

  12. Thin films of protein (BSA, lysozyme) - Polyelectrolyte (PSS) complexes show larger red-shift in optical emissions irrespective of protein conformation

    NASA Astrophysics Data System (ADS)

    Talukdar, Hrishikesh; Kundu, Sarathi

    2017-09-01

    Protein-polyelectrolyte complexes (PPC) are prepared using globular proteins (BSA, lysozyme) and optically active polyelectrolyte poly (sodium 4-styrenesulfonate) (PSS) in aqueous solutions and as thin films on solid substrates to explore their structures and optical behaviors. Out-of-plane structures of PPC films having ≈15-60 nm thicknesses are investigated from X-ray reflectivity and their relatively smooth surface morphologies are obtained from atomic force microscopy. ATR-FTIR spectroscopy confirms that the conformation of BSA proteins inside the films of PSSB (PSS+BSA) is nearly same with pure BSA but for lysozyme inside PSSL (PSS+lysozyme) conformation modifies which is evidenced from the shifting of the amide-I band of each protein. However, irrespective of the conformation variation of proteins larger red-shifts of ≈30 nm in optical emissions are obtained from the thin films of PPC. Relatively enhance dissipation of energy thorough non-radiative transition of the fluorophore residues in the dry state is the most probable reason for such larger optical red-shifts.

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

    PubMed

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

    2016-11-29

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

  14. Effect of poly(vinyl alcohol-co-vinyl acetate) copolymer blockiness on the dynamic interfacial tension and dilational viscoelasticity of polymer-anionic surfactant complex at the water-1-chlorobutane interface.

    PubMed

    Atanase, Leonard Ionut; Bistac, Sophie; Riess, Gérard

    2015-04-07

    Poly(vinyl alcohol-co-vinyl acetate) (PVA) copolymers obtained by partial hydrolysis of poly(vinyl acetate) (PVAc) are of practical importance for many applications, including emulsion and suspension polymerization processes. Their molecular characteristics have a major influence on the colloidal and interfacial properties. The most significant characteristics are represented by the average degree of hydrolysis D̅H̅, average degree of polymerization D̅P̅w̅ but also by the average acetate sequence length n(VAc)(0) which designates the so-called blockiness. Colloidal aggregates were observed in the aqueous PVA solutions having a D̅H̅ value of 73 mol%. The volume fraction of these aggregates at a given D̅H̅ value is directly correlated to the blockiness. Three PVA samples with identical D̅H̅ and D̅P̅w̅ but different blockiness were examined. By pendant drop and oscillating pendant drop techniques it was shown that the PVA sample having the lowest blockiness and thus the lowest volume fraction of colloidal aggregates has lower interfacial tension and elastic modulus E' values. On the contrary, the corresponding values are highest for PVA sample of higher blockiness. In the presence of sodium dodecyl sulfate (SDS), the colloidal aggregates are disaggregated by complex formation due to the hydrophobic-hydrophobic interactions. The PVA-SDS complex acts as a partial polyelectrolyte that induces the stretching of the chains and thus a reduction of the interface thickness. In this case, the interfacial tension and the elastic modulus both increase with increasing SDS concentration for all three PVA samples and the most significant effect was noticed for the most "blocky" copolymer sample.

  15. Application of Polyelectrolyte Complex Nanoparticles in Increasing the Lifetime of Poly(Vinyl Sulfonate) Scale Inhibitor in Berea Sandstone Rock

    NASA Astrophysics Data System (ADS)

    Veisi, Masoumeh

    Water flooding is used extensively in oil fields to maintain reservoir pressure and displace oil. However, seawater containing high concentrations of sulfate ion may form scale precipitate when mixed with incompatible formation water containing barium and strontium ions. Formation of scales such as barium sulfate can pose costly operational problems by plugging the injection and production wells. Polymers such as poly(vinyl sulfonate) (PVS) are well-known scale inhibitors which can effectively prevent the formation of barium sulfate. Squeeze treatment is a common method which can be used to inject the PVS in the reservoir. In this process, PVS solution is injected into production wells and the inhibitor is adsorbed on reservoir rocks and released during subsequent production of reservoir fluids. Once inhibitor concentration decreases to its minimum effective concentration (MEC), the process needs to be repeated. However, the low adsorption of PVS onto the rock results in a very short squeeze lifetime rendering the treatment uneconomical. In this research, the application of polyelectrolyte complexes (PECs) to increase the squeeze treatment lifetime of PVS was examined. The objective of the project was to develop PEC nanoparticles (NPs) which would improve the PVS adsorption on the rock through charge alteration. The PECs entrapped the PVS in their structure and released the polymer gradually when pH or ionic strength of the surrounding brine increased. PVS adsorption followed by a slow release of the polymer can maintain the scale inhibitor concentration above MEC for longer, and therefore extend the squeeze treatment lifetime. Positively charged nanoparticles consisting of poly(ethyleneimine) and poly(vinyl sulfonate) (PEI-PVS) were prepared and optimized to maximize PVS entrapment in the PEC structure. The stability of the nanoparticles at different temperatures and over time was confirmed. Their stability in the presence of mono and divalent cations was also

  16. Interfacial phenomena at a surface of individual and complex fumed nanooxides.

    PubMed

    Gun'ko, V M; Turov, V V; Zarko, V I; Goncharuk, O V; Pakhlov, E M; Skubiszewska-Zięba, J; Blitz, J P

    2016-09-01

    Investigations of interfacial and temperature behaviors of nonpolar and polar adsorbates interacting with individual and complex fumed metal or metalloid oxides (FMO), initial and subjected to various treatments or chemical functionalization and compared to such porous adsorbents as silica gels, precipitated silica, mesoporous ordered silicas, filled polymeric composites, were analyzed. Complex nanooxides include core-shell nanoparticles, CSNP (50-200nm in size) with titania or alumina cores and silica or alumina shells in contrast to simple and smaller nanoparticles of individual FMO. CSNP could be destroyed under high-pressure cryogelation (HPCG) or mechanochemical activation (MCA). These treatments affect the structure of aggregates of nanoparticles and agglomerates of aggregates, resulting in their becoming more compacted. The analysis shows that complex FMO could be more sensitive to external actions than simple nanooxides such as fumed silica. Any treatment of 'soft' FMO affects the interfacial and temperature behaviors of polar and nonpolar adsorbates. Rearrangement of secondary particles and surface functionalization affects the freezing-melting point depression of adsorbates. For some adsorbates, open hysteresis loops became readily apparent in adsorption-desorption isotherms. Clustering of adsorbates bound in textural pores in aggregates of nanoparticles (i.e., voids between nanoparticles in secondary structures) causes reduced changes in enthalpy during phase transitions (freezing, fusion, evaporation). Freezing point depression and melting point elevation cause significant hysteresis freezing-melting effects for adsorbates bound to FMO in the textural pores. Relaxation phenomena for both low- and high-molecular weight adsorbates or filled polymeric composites are affected by the morphology of primary particles, structural organization of secondary particles of differently treated or functionalized FMO, content of adsorbates, co-adsorption order, and

  17. Local Water Dynamics in Coacervated Polyelectrolytes Monitored Through Dynamic Nuclear Polarization-Enhanced 1H NMR

    PubMed Central

    Kausik, Ravinath; Srivastava, Aasheesh; Korevaar, Peter A.; Stucky, Galen; Waite, J. Herbert

    2009-01-01

    We present the first study of quantifying the diffusion coefficient of interfacial water on polyelectrolyte surfaces of systems fully dispersed in bulk water under ambient conditions. Such measurements were made possible through the implementation of a recently introduced Dynamic Nuclear Polarization (DNP) technique to selectively amplify the nuclear magnetic resonance (NMR) signal of hydration water that is interacting with specifically located spin labels on polyelectrolyte surfaces. The merit of this novel capability is demonstrated in this report through the measurement of solvent microvisosity on the surface of two types of oppositely charged polyelectrolytes, when freely dissolved versus when complexed to form a liquid-liquid colloidal phase called complex coacervates. These complex coacervates were formed through electrostatic complexation between the imidazole-based cationic homopolymer poly(N-vinylimidazole) (PVIm), and anionic polypeptide polyaspartate (PAsp) in the pH range of 4.5 – 6.0, under which conditions the coacervate droplets are highly fluidic yet densely packed with polyelectrolytes. We also investigated the rotational diffusion coefficients of the spin labels covalently bound to the polyelectrolyte chains for both PVIm and PAsp, showing a 5 fold change in the rotational correlation time as well as anisotropy parameter upon coacervation, which represents a surprisingly small decrease given the high polymer concentration inside the dense microdroplets. For both DNP and ESR experiments, the polymers were covalently tagged with stable nitroxide radical spin labels (∼1 wt %) to probe the local solvent and polymer segment dynamics. We found that the surface water diffusion coefficients near uncomplexed PVIm and PAsp at pH 8 differ, and are around D∼1.3×10−9 m2 / s. In contrast, inside the complex coacervate phase, the water diffusion coefficient in the immediate vicinity of either polyelectrolyte was D∼ 0.25×10−9 m2 / s, which is about

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

    DOEpatents

    Sugama, Toshifumi; Kukacka, L.E.; Carciello, N.R.

    1985-11-05

    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/sup 0/C. The polyelectrolyte or the precoat is present in about 0.5 to 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/sup 0/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 x 10/sup 5/ gave improved ductility modulus effect.

  19. Modified interfacial statistical associating fluid theory: a perturbation density functional theory for inhomogeneous complex fluids.

    PubMed

    Jain, Shekhar; Dominik, Aleksandra; Chapman, Walter G

    2007-12-28

    A density functional theory based on Wertheim's first order perturbation theory is developed for inhomogeneous complex fluids. The theory is derived along similar lines as interfacial statistical associating fluid theory [S. Tripathi and W. G. Chapman, J. Chem. Phys. 122, 094506 (2005)]. However, the derivation is more general and applies broadly to a range of systems, retaining the simplicity of a segment density based theory. Furthermore, the theory gives the exact density profile for ideal chains in an external field. The general avail of the theory has been demonstrated by applying the theory to lipids near surfaces, lipid bilayers, and copolymer thin films. The theoretical results show excellent agreement with the results from molecular simulations.

  20. Modified interfacial statistical associating fluid theory: A perturbation density functional theory for inhomogeneous complex fluids

    NASA Astrophysics Data System (ADS)

    Jain, Shekhar; Dominik, Aleksandra; Chapman, Walter G.

    2007-12-01

    A density functional theory based on Wertheim's first order perturbation theory is developed for inhomogeneous complex fluids. The theory is derived along similar lines as interfacial statistical associating fluid theory [S. Tripathi and W. G. Chapman, J. Chem. Phys. 122, 094506 (2005)]. However, the derivation is more general and applies broadly to a range of systems, retaining the simplicity of a segment density based theory. Furthermore, the theory gives the exact density profile for ideal chains in an external field. The general avail of the theory has been demonstrated by applying the theory to lipids near surfaces, lipid bilayers, and copolymer thin films. The theoretical results show excellent agreement with the results from molecular simulations.

  1. Growth Kinetics of Polyelectrolyte Complexes Formed from Oppositely-Charged Homopolymers Studied by Time-Resolved Ultra-Small-Angle X-ray Scattering.

    PubMed

    Takahashi, Rintaro; Narayanan, Theyencheri; Sato, Takahiro

    2017-02-16

    We have monitored the kinetic process of polyelectrolyte complex formation between sodium polyacrylate (SPA) and polyallylamine hydrochrolide (PAH) in aqueous NaCl solution by time-resolved ultra-small-angle X-ray scattering (TR-USAXS) combined with rapid mixing. SPA and PAH with different NaCl concentrations from 0 to 1 M were rapidly mixed in equimolar concentration of the monomer units using a stopped-flow apparatus with a dead time of about 2.5 ms. Within the dead time, percolated aggregate-like structures were observed suggesting that the initially formed small charge neutral aggregates further assembled to form higher order agglomerates. The early stage time evolution of the molar mass of the global structure in the presence of NaCl was found to be comparable to the Brownian-coagulation rate.

  2. Preparation and biocompatibility of nanohybrid scaffolds by in situ homogeneous formation of nano hydroxyapatite from biopolymer polyelectrolyte complex for bone repair applications.

    PubMed

    Chen, Jingdi; Yu, Qifeng; Zhang, Guodong; Yang, Shen; Wu, Jiulin; Zhang, Qiqing

    2012-05-01

    The achievement of nano distribution for inorganic reinforced filler is a big challenge to three-dimensional porous composite scaffolds. In this paper, a homogeneous nano hydroxyapatite/polyelectrolyte complex (HAP/PEC) hybrid scaffold was developed and investigated. Based on the enhancing properties of the formation of PEC between chitosan and hyaluronic acid, the introduction of nano HAP via in situ crystallization from the PEC achieved nano distribution in the PEC matrix and supplied nano topographies of extracellular environments for the nanohybrid scaffold. The biocompatibility and bioactivity were evaluated by Human bone mesenchymal stem cells (hBMSCs) proliferation (MTT assay), maturation (alkaline phosphatase (ALP) activity) and histological analysis. The in vitro tests show the scaffold is excellent for cell penetration, growth, and proliferation and it is promising for bone repair application.

  3. Cast adhesive polyelectrolyte complex particle films of unmodified or maltose-modified poly(ethyleneimine) and cellulose sulphate: fabrication, film stability and retarded release of zoledronate.

    PubMed

    Torger, Bernhard; Vehlow, David; Urban, Birgit; Salem, Samaa; Appelhans, Dietmar; Müller, Martin

    2013-12-01

    The bone therapeutic drug zoledronate (ZOL) was loaded at and released by polyelectrolyte complex (PEC) particle films composed of either pure poly(ethyleneimine) (PEI) or maltose-modified poly(ethyleneimine) (PEI-M) and oppositely charged cellulose sulfate attached to model germanium (Ge) substrates by solution casting. Dispersions of colloidally stable polyelectrolyte complex (PEC) particles in the size range 11-141 nm were obtained by mixing PEI or PEI-M, CS and ZOL in defined stoichiometric ratios. TRANS-FTIR spectroscopy was used to determine the stability of the PEC films against detachment, in-situ-ATR-FTIR spectroscopy for the ZOL loss in the PEC film and UV-VIS spectroscopy for the ZOL enrichment of the release medium. Films of casted ZOL/CS/PEI-M or ZOL/CS/PEI particles were stable in contact to water, while films of the pure drug (ZOL) and of the binary systems ZOL/PEI-M or ZOL/PEI were not stable against detachment. Retarded releases of ZOL from various PEC films compared to the pure drug film were observed. The molecular weight of PEI showed a considerable effect on the initial burst (IB) of ZOL. No significant effect of the maltose modification of PEI-25 K on IB could be found. Generally, after one day the ZOL release process was finished for all measured ZOL/PEC samples and residual amounts of 0-30% were obtained. Surface adhesive drug loaded PEC particles are promising drug delivery systems to supply and release a defined amount of bone therapeutics and to functionalize bone substitution materials.

  4. Comparing interfacial dynamics in protein-protein complexes: an elastic network approach.

    PubMed

    Zen, Andrea; Micheletti, Cristian; Keskin, Ozlem; Nussinov, Ruth

    2010-08-08

    The transient, or permanent, association of proteins to form organized complexes is one of the most common mechanisms of regulation of biological processes. Systematic physico-chemical studies of the binding interfaces have previously shown that a key mechanism for the formation/stabilization of dimers is the steric and chemical complementarity of the two semi-interfaces. The role of the fluctuation dynamics at the interface of the interacting subunits, although expectedly important, proved more elusive to characterize. The aim of the present computational study is to gain insight into salient dynamics-based aspects of protein-protein interfaces. The interface dynamics was characterized by means of an elastic network model for 22 representative dimers covering three main interface types. The three groups gather dimers sharing the same interface but with good (type I) or poor (type II) similarity of the overall fold, or dimers sharing only one of the semi-interfaces (type III). The set comprises obligate dimers, which are complexes for which no structural representative of the free form(s) is available. Considerations were accordingly limited to bound and unbound forms of the monomeric subunits of the dimers. We proceeded by first computing the mobility of amino acids at the interface of the bound forms and compare it with the mobility of (i) other surface amino acids (ii) interface amino acids in the unbound forms. In both cases different dynamic patterns were observed across interface types and depending on whether the interface belongs to an obligate or non-obligate complex. The comparative investigation indicated that the mobility of amino acids at the dimeric interface is generally lower than for other amino acids at the protein surface. The change in interfacial mobility upon removing "in silico" the partner monomer (unbound form) was next found to be correlated with the interface type, size and obligate nature of the complex. In particular, going from the

  5. Interfacial Electron Transfer in TiO2 Surfaces Sensitized with Ru(II)-Polypyridine Complexes

    NASA Astrophysics Data System (ADS)

    Jakubikova, Elena; Snoeberger, Robert C., III; Batista, Victor S.; Martin, Richard L.; Batista, Enrique R.

    2009-07-01

    Studies of interfacial electron transfer (IET) in TiO2 surfaces functionalized with (1) pyridine-4-phosphonic acid, (2) [Ru(tpy)(tpy(PO3H2))]2+, and (3) [Ru(tpy)(bpy)(H2O)-Ru(tpy)(tpy(PO3H2))]4+ (tpy = 2,2':6,2''-terpyridine; bpy = 2,2'-bipyridine) are reported. We characterize the electronic excitations, electron injection time scales, and interfacial electron transfer (IET) mechanisms through phosphonate anchoring groups. These are promising alternatives to the classic carboxylates of conventional dye-sensitized solar cells since they bind more strongly to TiO2 surfaces and form stable covalent bonds that are unaffected by humidity. Density functional theory calculations and quantum dynamics simulations of IET indicate that electron injection in 1-TiO2 can be up to 1 order of magnitude faster when 1 is attached to TiO2 in a bidentate mode (τ ˜ 60 fs) than when attached in a monodentate motif (τ ˜ 460 fs). The IET time scale also depends strongly on the properties of the sensitizer as well as on the nature of the electronic excitation initially localized in the adsorbate molecule. We show that IET triggered by the visible light excitation of 2-TiO2 takes 1-10 ps when 2 is attached in a bidentate mode, a time comparable to the lifetime of the excited electronic state. IET due to visible-light photoexcitation of 3-TiO2 is slower, since the resulting electronic excitation remains localized in the tpy-tpy bridge that is weakly coupled to the electronic states of the conduction band of TiO2. These results are particularly valuable to elucidate the possible origin of IET efficiency drops during photoconversion in solar cells based on Ru(II)-polypyridine complexes covalently attached to TiO2 thin films with phosphonate linkers.

  6. Interfacial electron transfer in TiO(2) surfaces sensitized with Ru(II)-polypyridine complexes.

    PubMed

    Jakubikova, Elena; Snoeberger, Robert C; Batista, Victor S; Martin, Richard L; Batista, Enrique R

    2009-11-12

    Studies of interfacial electron transfer (IET) in TiO(2) surfaces functionalized with (1) pyridine-4-phosphonic acid, (2) [Ru(tpy)(tpy(PO(3)H(2)))](2+), and (3) [Ru(tpy)(bpy)(H(2)O)-Ru(tpy)(tpy(PO(3)H(2)))](4+) (tpy = 2,2':6,2''-terpyridine; bpy = 2,2'-bipyridine) are reported. We characterize the electronic excitations, electron injection time scales, and interfacial electron transfer (IET) mechanisms through phosphonate anchoring groups. These are promising alternatives to the classic carboxylates of conventional dye-sensitized solar cells since they bind more strongly to TiO(2) surfaces and form stable covalent bonds that are unaffected by humidity. Density functional theory calculations and quantum dynamics simulations of IET indicate that electron injection in 1-TiO(2) can be up to 1 order of magnitude faster when 1 is attached to TiO(2) in a bidentate mode (tau approximately 60 fs) than when attached in a monodentate motif (tau approximately 460 fs). The IET time scale also depends strongly on the properties of the sensitizer as well as on the nature of the electronic excitation initially localized in the adsorbate molecule. We show that IET triggered by the visible light excitation of 2-TiO(2) takes 1-10 ps when 2 is attached in a bidentate mode, a time comparable to the lifetime of the excited electronic state. IET due to visible-light photoexcitation of 3-TiO(2) is slower, since the resulting electronic excitation remains localized in the tpy-tpy bridge that is weakly coupled to the electronic states of the conduction band of TiO(2). These results are particularly valuable to elucidate the possible origin of IET efficiency drops during photoconversion in solar cells based on Ru(II)-polypyridine complexes covalently attached to TiO(2) thin films with phosphonate linkers.

  7. Investigation of using Polyelectrolytes as an Interlayer on Polymer Solar Cells

    NASA Astrophysics Data System (ADS)

    Chen, Wei-Chih; Hsiao, Yung-Cheng; Huang, Yi-Chiang; Lee, Hsu-Feng; Huang, Wen-Yao

    2017-04-01

    A new approach to improve hole extraction anode interfacial layer by introducing polyelectrolytes in polymer solar cells (PSCs). The polyelectrolytes interfacial layer is prepared simply spin-coating on the ITO substrate. Remarkable improvement in the open-circuit voltage(Voc) and short-circuit current density (Jsc) of the PSCs could be achieved upon the introduction of polyelectrolytes anode interfacial layer. To study the effect of polyelectrolytes anode interfacial layer on the device efficiency. The polyelectrolytes are analyzed, exhibited good thermal stability and high transmittance over 85% in visible light region. According to our experiments and measurements, insertion of polyelectrolytes anode interfacial layer can decrease spatial barriers at the active layer/ITO interfaces, planarize the ITO substrate and modify surface of ITO.The PSCs under the optimized structure of ITO/SA8/P3HT:PCBM/LiF/Al exhibited open-circuit voltage of 0.62 V, short-circuit current density of 7.15 mA/cm2, fill factor of 54.84%, and power conversion efficiency of 2.43% at AM 1.5G of 100 mW/cm2

  8. Electro-responsive polyelectrolyte-coated surfaces.

    PubMed

    Sénéchal, V; Saadaoui, H; Rodriguez-Hernandez, J; Drummond, C

    2017-07-01

    The anchoring of polymer chains at solid surfaces is an efficient way to modify interfacial properties like the stability and rheology of colloidal dispersions, lubrication and biocompatibility. Polyelectrolytes are good candidates for the building of smart materials, as the polyion chain conformation can often be tuned by manipulation of different physico-chemical variables. However, achieving efficient and reversible control of this process represents an important technological challenge. In this regard, the application of an external electrical stimulus on polyelectrolytes seems to be a convenient control strategy, for several reasons. First, it is relatively easy to apply an electric field to the material with adequate spatiotemporal control. In addition, in contrast to chemically induced changes, the molecular response to a changing electric field occurs relatively quickly. If the system is properly designed, this response can then be used to control the magnitude of surface properties. In this work we discuss the effect of an external electric field on the adhesion and lubrication properties of several polyelectrolyte-coated surfaces. The influence of the applied field is investigated at different pH and salt conditions, as the polyelectrolyte conformation is sensitive to these variables. We show that it is possible to fine tune friction and adhesion using relatively low applied fields.

  9. Polyelectrolytes: Wastewater and sewage treatment. (Latest citations from the Selected Water Resources Abstracts database). Published Search

    SciTech Connect

    Not Available

    1993-02-01

    The bibliography contains citations concerning polyelectrolytes in wastewater and water treatment. Topics include flocculation, coagulation, separation techniques, pollutant identification, water pollution sources, and sludge dehydration. Hospital wastewater processing, methods of synthesizing polyelectrolyte complexes, and performance evaluations of polyelectrolytes are also discussed. (Contains 250 citations and includes a subject term index and title list.)

  10. Polyelectrolytes: Wastewater and sewage treatment. (Latest citations from the Selected Water Resources Abstracts database). Published Search

    SciTech Connect

    Not Available

    1994-04-01

    The bibliography contains citations concerning polyelectrolytes in wastewater and water treatment. Topics include flocculation, coagulation, separation techniques, pollutant identification, water pollution sources, and sludge dehydration. Hospital wastewater processing, methods of synthesizing polyelectrolyte complexes, and performance evaluations of polyelectrolytes are also discussed. (Contains 250 citations and includes a subject term index and title list.)

  11. Dual ionic interaction system based on polyelectrolyte complex and ionic, injectable, and thermosensitive hydrogel for sustained release of human growth hormone.

    PubMed

    Park, Mi-Ran; Seo, Bo-Bae; Song, Soo-Chang

    2013-01-01

    A dual ionic interaction system composed of a positively charged polyelectrolyte complex (PEC) containing human growth hormone (hGH) and anionic thermosensitive hydrogel has been suggested for sustained delivery of bioactive hGH. The PEC was prepared by ionic interaction between negatively charged hGH and positively charged protamine sulfate (PS) to suppress diffusion of hGH. Moreover, we loaded the positively charged PEC into an anionic, injectable, and thermosensitive poly(organophosphazene) hydrogel to enhance sustained release of hGH by dual ionic interactions. PS formed a spherical complex with hGH, and their ionic interaction grew stronger with increasing amounts of PS. From a weight ratio of 0.5, the PS/hGH complex had a size and zeta-potential that were constantly maintained around 500 nm and +8 mV, respectively, in 0.9% NaCl. The PEC-loaded hydrogels suppressed the initial burst release of hGH and extended the release period in vitro and in vivo. In a pharmacokinetic study in rats, the PEC-loaded anionic hydrogel extended half-life 13-fold with similar area under the curve (AUC) compared to hGH solution. Furthermore, single injection of PEC-loaded anionic hydrogel showed a more increased growth rate than daily injection of hGH solution for 7 days in hypophysectomized rats, demonstrating its potential as an injectable, sustained delivery system that can release bioactive hGH.

  12. Preparation and pH controlled release of polyelectrolyte complex of poly(L-malic acid-co-D,L-lactic acid) and chitosan.

    PubMed

    Wang, Jie; Ni, Caihua; Zhang, Yanan; Zhang, Meng; Li, Wang; Yao, Bolong; Zhang, Liping

    2014-03-01

    The copolymer of poly(L-malic acid-co-D,L-lactic acid) (PML) was synthesized through a direct polycondensation of L-malic acid (MA) and D,L-lactic acid (LA). Then, a new polyelectrolyte complex (PEC) based on the complexation between the copolymer (PML) and chitosan (CS) was prepared. The PEC formed stable nano particles in aqueous solutions with pH 3-5, and the nano particles had the diameters in a range of 316-590 nm (varied with the components of PML and CS). Doxorubicin (DOX) as a model drug was loaded on the nano particles through the physical adsorption and complexation, and part of DOX formed the secondary particles by self-aggregation. The high drug loading efficiency (16.5%) and the sustained release patterns in acidic media were observed, and the release accelerated in alkaline solutions. The nano particles could be potentially applied as pH sensitive drug vehicles for controlled release.

  13. Polyelectrolyte complexes of poly[(2-dimethylamino) ethyl methacrylate]/chondroitin sulfate obtained at different pHs: I. Preparation, characterization, cytotoxicity and controlled release of chondroitin sulfate.

    PubMed

    Bonkovoski, Letícia C; Martins, Alessandro F; Bellettini, Ismael C; Garcia, Francielle P; Nakamura, Celso V; Rubira, Adley F; Muniz, Edvani C

    2014-12-30

    For the first time, polyelectrolyte complex based on poly[(2-dimethylamino) ethyl methacrylate] (PDMAEMA) and chondroitin sulfate (CS) was prepared. The properties of novel material and precursors were investigated by WAXS, FTIR, TGA, SEM and DLS analysis. The PDMAEMA/CS PECs presented hydrophilic-hydrophobic transition at pHs 6.0, 7.0 and 8.0 whereas the non-complexed PDMAEMA showed such a transition at pH 8.0 and not at pHs 6.0 and 7.0. Studies of CS release from PECs at pHs 6 and 8 confirmed that the samples possess the potential to release the CS in alkaline and not in acidic conditions. Since PECs are thermo-responsive due to the reduction of LCST caused by the increase in pH, the release of CS was dependent on temperature and pH factors. Cytotoxicity assays using healthy VERO cells showed that the complexation between CS and PDMAEMA increased the PECs' biocompatibility related to PDMAEMA. However, the biocompatibility depends on the amount of CS present in the PECs.

  14. Reaction of discoidal complexes of apolipoprotein A-I and various phosphatidylcholines with lecithin cholesterol acyltransferase. Interfacial effects.

    PubMed

    Jonas, A; Zorich, N L; Kézdy, K E; Trick, W E

    1987-03-25

    Complexes of phospholipids-apolipoprotein A-I-cholesterol, containing various bulk phosphatidylcholines or a matrix of the ether analog of 1-palmitoyl 2-oleoyl phosphatidylcholine including test phosphatidylcholines were used as substrates for human lecithin-cholesterol acyltransferase. The enzymatic reaction rates for both series of complexes were determined as a function of temperature, particle concentration, neutral salt concentration, and the type of anion present in solution. The kinetic results support the hypothesis that phospholipids, in discoidal complexes, modulate the reaction rates by molecular effects at the active site, but also by interfacial effects on the interaction of the enzyme with the particles. The relevant interfacial parameters are the lipid packing at the interface and the structure of apolipoprotein A-I.

  15. Interfacial complex formation in uranyl extraction by tributyl phosphate in dodecane diluent: a molecular dynamics study.

    PubMed

    Ye, Xianggui; Cui, Shengting; de Almeida, Valmor; Khomami, Bamin

    2009-07-23

    Atomistic simulations have been carried out in a multicomponent two-phase system (aqueous and organic phases in direct contact) to investigate the interfacial molecular mechanisms leading to uranyl extraction from the aqueous to organic phase. The aqueous phase consists of the dissolved ions UO2(2+) and nitrate NO3-, with or without H3O+, in water to describe acidic or neutral condition; the organic phase consists of tributyl phosphate, the extractant, in dodecane as the diluent. We find that the interface facilitates the formation of various uranyl complexes, with a general formula UO2(2+)(NO3-)n *mTBP*kH2O, with n+m+k=5, suggesting a 5-fold coordination. The coordination for all three molecular entities has the common feature that they all bind to the uranyl at the uranium atom with an oxygen atom in the equatorial plane perpendicular to the molecular axis of the uranyl, forming a 5-fold symmetry plane. Nitric acid has a strong effect in enhancing the formation of extractable species, which is consistent with experimental findings.

  16. Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

    PubMed

    Hernandez-Pascacio, Jorge; Piñeiro, Ángel; Ruso, Juan M; Hassan, Natalia; Campbell, Richard A; Campos-Terán, José; Costas, Miguel

    2016-07-05

    The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface. The interfacial layer formed is not in fast dynamic equilibrium with the subphase as the resulting morphology is locked in a kinetically trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in the bulk and at the interface of what might have seemed initially like a simple system.

  17. An Interfacial Europium Complex on SiO2 Nanoparticles: Reduction-Induced Blue Emission System

    PubMed Central

    Ishii, Ayumi; Hasegawa, Miki

    2015-01-01

    In this study, Eu-coated SiO2 nanoparticles have been prepared, consisting of an interfacial complex of Eu and 1,10-phenanthroline (phen) at the solid surfaces of the SiO2/Eu nanostructures. The as-prepared SiO2/Eu/phen nanoparticles exhibits sharp red emission via energy transfer from the phen to the EuIII. After sintering at 200 °C in air, the emission is tuned from red to blue. The blue emission is originated from EuII. This reduction-induced emissive phenomenon resulted from the electron-donating environment created by the surrounding phen and SiO2, which is the first reported fabrication of a stable EuII-based emissive material using mild conditions (reaction in air and at low temperature) and an organic-inorganic hybrid nanostructure. The existence of two different stable oxidation states with characteristic emissions, blue emissive EuII and red emissive EuIII, suggests significant potential applications as novel luminescent materials with inorganic-organic hybrid structures. PMID:26122318

  18. Intracellular siRNA delivery system using polyelectrolyte complex micelles prepared from VEGF siRNA-PEG conjugate and cationic fusogenic peptide.

    PubMed

    Lee, Soo Hyeon; Kim, Sun Hwa; Park, Tae Gwan

    2007-06-01

    To develop a small interfering RNA (siRNA) delivery system with low cytotoxicity and high transfection efficiency, siRNA was conjugated to poly(ethylene glycol) via a disulfide linkage (siRNA-PEG) to prepare polyelectrolyte complex micelles (PECMs) by condensing with a cationic fusogenic peptide (KALA). The siRNA-PEG conjugate exhibited enhanced resistance to degradation from nucleases. Anionic siRNA-PEG conjugate and cationic KALA, when mixed in an aqueous phase, spontaneously formed nano-sized PECMs (<200nm) that have an inner core of charge neutralized siRNA/KALA complex surrounded by a PEG corona. Vascular endothelial growth factor (VEGF) siRNA was used to demonstrate VEGF sequence-specific gene inhibition in prostate carcinoma cells (PC-3 cells). The extent of gene silencing was gradually increased with increasing nitrogen to phosphate (N/P) ratio and the concentration of siRNA-PEG/KALA PECMs. These results suggest that the formulation of siRNA-PEG/KALA PECMs could be widely applied for intracellular delivery of various therapeutic siRNAs.

  19. Spin-Coated Polyelectrolyte Coacervate Films.

    PubMed

    Kelly, Kristopher D; Schlenoff, Joseph B

    2015-07-01

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

  20. 3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate)

    PubMed Central

    Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel

    2016-01-01

    Summary This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers. PMID:26977377

  1. In situ-ATR-FTIR analysis on the uptake and release of streptomycin from polyelectrolyte complex layers.

    PubMed

    Torger, B; Müller, M

    2013-03-01

    In-situ ATR-FTIR spectroscopy and line shape analysis of the diagnostic spectral region was used to quantify the bound amount and release of the antibiotic streptomycin (STRP) at polyelectrolyte (PEL) multilayers (PEM) of poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAA) or PEI and sodium alginate (ALG). Unlike common concepts based on the drug enrichment of the release medium, this analytical concept allowed to measure quantitatively the drug depletion in the delivery matrix. The measured kinetic in situ ATR-FTIR data were analysed by a modified Korsmeyer-Peppas equation based on two characteristic release parameters k and n. As main experimental parameters the number of PEL layers (adsorption steps) z and the STRP/PEL ratio were varied. For z=8 the STRP/PEL ratio showed the most significant influence on release kinetics, whereby for STRP/PEL=1:25 slowest (n=0.77) and lowest (k=21.4%) and for STRP/PEL=1:5 most rapid (n=0.30) and highest (k=58.6%) drug releases were found. PEM-PEI/ALG-8 (STRP/PEL=1:5) revealed slower release rates (n=0.58) and lower released STRP amounts (k=17.1%) compared to PEI/PAA. UV-VIS data on time dependent STRP enrichment of the release medium showed a similar trend compared to respective ATR-FTIR data on STRP depletion in PEM. Released amounts of around 1-2mg from the herein introduced PEM films could be determined. The introduced analytical concept will be used as screening tool for other drugs, drug eluting films and bone substituting materials. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed

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

    1997-07-20

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

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

    PubMed

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

    2015-06-17

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

  4. Multipoint covalent immobilization of lipase on chitosan hybrid hydrogels: influence of the polyelectrolyte complex type and chemical modification on the catalytic properties of the biocatalysts.

    PubMed

    Mendes, Adriano A; de Castro, Heizir F; Rodrigues, Dasciana de S; Adriano, Wellington S; Tardioli, Paulo W; Mammarella, Enrique J; Giordano, Roberto de C; Giordano, Raquel de L C

    2011-08-01

    This work aimed at the production of stabilized derivatives of Thermomyces lanuginosus lipase (TLL) by multipoint covalent immobilization of the enzyme on chitosan-based matrices. The resulting biocatalysts were tested for synthesis of biodiesel by ethanolysis of palm oil. Different hydrogels were prepared: chitosan alone and in polyelectrolyte complexes (PEC) with κ-carrageenan, gelatin, alginate, and polyvinyl alcohol (PVA). The obtained supports were chemically modified with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to increase support hydrophobicity, followed by activation with different agents such as glycidol (GLY), epichlorohydrin (EPI), and glutaraldehyde (GLU). The chitosan-alginate hydrogel, chemically modified with TNBS, provided derivatives with higher apparent hydrolytic activity (HA(app)) and thermal stability, being up to 45-fold more stable than soluble lipase. The maximum load of immobilized enzyme was 17.5 mg g(-1) of gel for GLU, 7.76 mg g(-1) of gel for GLY, and 7.65 mg g(-1) of gel for EPI derivatives, the latter presenting the maximum apparent hydrolytic activity (364.8 IU g(-1) of gel). The three derivatives catalyzed conversion of palm oil to biodiesel, but chitosan-alginate-TNBS activated via GLY and EPI led to higher recovered activities of the enzyme. Thus, this is a more attractive option for both hydrolysis and transesterification of vegetable oils using immobilized TLL, although industrial application of this biocatalyst still demands further improvements in its half-life to make the enzymatic process economically attractive.

  5. Confined Flocculation of Ionic Pollutants by Poly(L-dopa)-Based Polyelectrolyte Complexes in Hydrogel Beads for Three-Dimensional, Quantitative, Efficient Water Decontamination.

    PubMed

    Yu, Li; Liu, Xiaokong; Yuan, Weichang; Brown, Lauren Joan; Wang, Dayang

    2015-06-16

    The development of simple and recyclable adsorbents with high adsorption capacity is a technical imperative for water treatment. In this work, we have successfully developed new adsorbents for the removal of ionic pollutants from water via encapsulation of polyelectrolyte complexes (PECs) made from positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(l-3,4-dihydroxyphenylalanine) (PDopa), obtained via the self-polymerization of l-3,4-dihydroxyphenylalanine (l-Dopa). Given the outstanding mass transport through the hydrogel host matrixes, the PDopa-PAH PEC guests loaded inside can effectively and efficiently remove various ionic pollutants, including heavy metal ions and ionic organic dyes, from water. The adsorption efficiency of the PDopa-PAH PECs can be quantitatively correlated to and tailored by the PDopa-to-PAH molar ratio. Because PDopa embodies one catechol group, one carboxyl group, and one amino group in each repeating unit, the resulting PDopa-PAH PECs exhibit the largest capacity of adsorption of heavy metal ions compared to available adsorbents. Because both PDopa and PAH are pH-sensitive, the PDopa-PAH PEC-loaded agarose hydrogel beads can be easily and completely recovered after the adsorption of ionic pollutants by adjusting the pH of the surrounding media. The present strategy is similar to the conventional process of using PECs to flocculate ionic pollutants from water, while in our system flocculation is confined to the agarose hydrogel beads, thus allowing easy separation of the resulting adsorbents from water.

  6. Trapping, pattern formation, and ordering of polyelectrolyte/single-wall carbon nanotube complexes at the air/water and air/solid interfaces.

    PubMed

    Hernandez-López, José Luis; Alvizo-Paez, Edgar Rogelio; Moya, Sergio Enrique; Ruiz-García, Jaime

    2006-11-23

    The Langmuir and Langmuir-Blodgett (LB) techniques have been applied in a novel approach to build structurally well-ordered, oriented, and organized assemblies of water-soluble single-wall carbon nanotubes (ws-SWCNTs) at the air/water and air/solid interfaces. The SWCNTs were rendered hydrophilic by complexing them with a quenched polyelectrolyte. We observed that the ws-SWCNT concentration at the air/water interface increases with time condensing into different patterns, among which are isolated soap-froths, rings, and the aggregation of cumuli-like 2D-structures. These patterns were recorded at different compression-expansion stages by Brewster angle microscopy (BAM). From the isotherm measurements, we are able to determine the diffusion process by which ws-SWCNT concentration builds up at the water surface. The corresponding LB films were very stable and could be transferred onto mica substrates easily. Atomic force microscopy (AFM) images revealed that the morphology of these films is surface-pressure dependent, and aligned structures with a nematic-like order formed closely packed mono- or multilayer films. The assembly of 2D-nanostructures by means of this approach offers a great potential for emergent technological applications using modified water-soluble SWCNTs.

  7. On the ability of molecular dynamics simulation and continuum electrostatics to treat interfacial water molecules in protein-protein complexes

    PubMed Central

    Copie, Guillaume; Cleri, Fabrizio; Blossey, Ralf; Lensink, Marc F.

    2016-01-01

    Interfacial waters are increasingly appreciated as playing a key role in protein-protein interactions. We report on a study of the prediction of interfacial water positions by both Molecular Dynamics and explicit solvent-continuum electrostatics based on the Dipolar Poisson-Boltzmann Langevin (DPBL) model, for three test cases: (i) the barnase/barstar complex (ii) the complex between the DNase domain of colicin E2 and its cognate Im2 immunity protein and (iii) the highly unusual anti-freeze protein Maxi which contains a large number of waters in its interior. We characterize the waters at the interface and in the core of the Maxi protein by the statistics of correctly predicted positions with respect to crystallographic water positions in the PDB files as well as the dynamic measures of diffusion constants and position lifetimes. Our approach provides a methodology for the evaluation of predicted interfacial water positions through an investigation of water-mediated inter-chain contacts. While our results show satisfactory behaviour for molecular dynamics simulation, they also highlight the need for improvement of continuum methods. PMID:27905545

  8. Diffusion of polyelectrolytes in polyelectrolyte gels

    NASA Astrophysics Data System (ADS)

    Rahalkar, Anand; Muthukumar, Murugappan

    2015-03-01

    Using dynamic light scattering, we have investigated the diffusion coefficient of sodium poly(styrene sulfonate) in a matrix of poly(acrylamide-co-acrylate) gels. The diffusion coefficient of the probe polyelectrolyte exhibits a crossover behavior from a particle-diffusion to entropic-barrier dominated diffusion, as the molecular weight is increased. The effect of electrostatics, by varying the charge density of the matrix, on probe diffusion constant will be presented.

  9. In vivo bioactivity of rhBMP-2 delivered with novel polyelectrolyte complexation shells assembled on an alginate microbead core template.

    PubMed

    Abbah, Sunny-Akogwu; Liu, Jing; Lam, Raymond W M; Goh, James C H; Wong, Hee-Kit

    2012-09-10

    Electrostatic interactions between polycations and polyanions are being explored to fabricate polyelectrolyte complexes (PEC) that could entrap and regulate the release of a wide range of biomolecules. Here, we report the in vivo application of PEC shells fabricated from three different polycations: poly-l-ornithine (PLO), poly-l-arginine (PLA) and DEAE-dextran (DEAE-D) to condense heparin on the surface of alginate microbeads and further control the delivery of recombinant human bone morphogenetic protein 2 (rhBMP-2) in spinal fusion application. We observed large differences in the behavior of PEC shells fabricated from the cationic polyamino acids (PLO and PLA) when compared to the cationic polysaccharide, DEAE-D. Whereas DEAE-D-based PEC shells eroded and released rhBMP-2 over 2 days in vitro, PLO- and PLA-based shells retained at least 60% of loaded rhBMP-2 after 3 weeks of incubation in phosphate-buffered saline. In vivo implantation in a rat model of posterolateral spinal fusion revealed robust bone formation in the PLO- and PLA-based PEC shell groups. This resulted in a significantly enhanced mechanical stability of the fused segments. However, bone induction and biomechanical stability of spine segments implanted with DEAE-D-based carriers were significantly inferior to both PLO- and PLA-based PEC shell groups (p<0.01). From these results, we conclude that PEC shells incorporating native heparin could be used for growth factor delivery in functional bone tissue engineering application and that PLA- and PLO-based complexes could represent superior options to DEAE-D for loading and in vivo delivery of bioactive BMP-2 in this approach.

  10. Scaling properties of the shear modulus of polyelectrolyte complex coacervates: a time-pH superposition principle.

    PubMed

    Tekaat, M; Bütergerds, D; Schönhoff, M; Fery, A; Cramer, C

    2015-09-21

    We analyze the scaling properties of pH-dependent shear modulus spectra of complex coacervates made of weak polyanions and strong polycations. For the first time, we report on a "time-pH superposition principle". This principle implies that the charge density in complex coacervates made of not fully charged polyions only influences the time scale of the relaxation dynamics, but not the mechanisms of the underlying dynamics.

  11. In-vitro evaluation of the effect of polymer structure on uptake of novel polymer-insulin polyelectrolyte complexes by human epithelial cells.

    PubMed

    Ibie, C; Knott, R; Thompson, C J

    2015-02-01

    The biocompatibility and cellular uptake of polymer, insulin polyelectrolyte complexes (PECs) prepared using polyallylamine-based polymers was evaluated in-vitro using Caco-2 cell monolayers as a predictive model for human small intestinal epithelial cells. Poly(allyl amine) (PAA) and Quaternised PAA (QPAA) were thiolated using either carbodiimide mediated conjugation to N-acetylcysteine (NAC) or reaction with 2-iminothiolane hydrochloride yielding their NAC and 4-thiobutylamidine (TBA) conjugates, respectively. The effect of polymer quaternisation and/or thiolation on the IC50 of PAA was determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay carried out on Caco-2 cells (with and without a 24 h recovery period after samples were removed). Uptake of PECs by Caco-2 cells was monitored by microscopy using fluorescein isothiocyanate (FITC) labelled insulin and rhodamine-labelled polymers at polymer:insulin ratios (4:5) after 0.5, 1, 2 and 4 h incubation in growth media (±calcium) and following pre-incubation with insulin. MTT results indicated that quaternisation of PAA was associated with an improvement in IC50 values; cells treated with QPAA (0.001-4 mg mL(-1)) showed no signs of toxicity following a 24 h cell recovery period, while thiolation of QPAA resulted in a decrease in the IC50. Cellular uptake studies showed that within 2-4 h, QPAA and QPAA-TBA insulin PECs were taken up intracellularly, with PECs being localised within the perinuclear area of cells. Further investigation showed that uptake of PECs was unaffected when calcium-free media was used, while presaturating insulin receptors affected the uptake of QPAA, insulin PECs, but not QPAA-TBA PECs. The biocompatibility of PAA and uptake of insulin was improved by both thiol and quaternary substitution.

  12. Luminescence Titrations of Polyelectrolytes.

    DTIC Science & Technology

    1984-05-01

    aluentered JA Week N it ditiu’I ken A60010 IL. SUPPLEMENTARY NOTES IS. Kay WORDS (CaaIAhu. an revrn ide "I .. eesese md =0uI1Y 6F we"A amA .) Polyele...Polyelectrolytes are also seeing increasing use as agents for the preparation of chemically modified electrodes (3,4). The equivalent weight (EW) of the...sufficiently large, Imax will be reached after a small excess of polyelectrolyte solution has been added. Standard (28) extrapolation procedures may then be used

  13. Effect of polyelectrolyte adsorption on lateral distribution and dynamics of anionic lipids: a Monte Carlo study of a coarse-grain model.

    PubMed

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

    2014-09-01

    We employ Monte Carlo simulations to investigate the interaction between an adsorbing linear flexible cationic polyelectrolyte and a ternary mixed fluid membrane containing neutral (phosphatidylcholine, PC), monovalent (phosphatidylserine, PS), and multivalent (phosphatidylinositol, PIP2) anionic lipids. We systematically explore the influences of polyelectrolyte chain length, polyelectrolyte charge density, polyelectrolyte total charge amount, and salt solution ionic strength on the static and dynamic properties of different anionic lipid species. Our results show that the multivalent PIP2 lipids dominate the polyelectrolyte-membrane interaction and competitively inhibit polyelectrolyte-PS binding. When the total charge amount of the polyelectrolyte is less than that of the local oppositely charged PIP2 lipids, the polyelectrolyte can drag the bound multivalent lipids to diffuse on the membrane, but cannot interact with the PS lipids. Under this condition, the diffusion behaviors of the polyelectrolyte closely follow the prediction of the Rouse model, and the polyelectrolyte chain properties determine the adsorption amount, concentration gradients, and hierarchical mobility of the bound PIP2 lipids. However, when the total charge amount of the polyelectrolyte is larger than that of the local PIP2 lipids, the polyelectrolyte further binds the PS lipids around the polyelectrolyte-PIP2 complex to achieve local electrical neutrality. In this condition, parts of the polyelectrolyte desorb from the membrane and show faster mobility, and the bound PS presents much faster mobility than the segregated PIP2. This work provides an explanation for heterogeneity formation in different anionic lipids induced by polyelectrolyte adsorption.

  14. Structural transitions of encapsidated polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Angelescu, D. G.; Linse, P.; Nguyen, T. T.; Bruinsma, R. F.

    2008-03-01

    Conformations and structural transitions of polyelectrolytes strictly confined onto a spherical 2D surface have been investigated by scaling descriptions based on physical arguments concerning polyelectrolyte adsorption onto planar surface and liquid crystals as well as by Monte Carlo simulations using a bead-spring model with short-range and electrostatic repulsions. In case of the electrostatic screened regime, a disordered-ordered (spiral) transition at increasing persistence length of the chain was found. It was predicted that the transition occurred when the persistence length is comparable with the mean spacing between adjacent strands of the ordered chain. The presence of a non-screened electrostatic repulsion led to a more complex behavior with i) a re-entrant order-disorder transition and ii) a tennis ball texture as an additional smectic/nematic structure. The various competing structures given by the theory were recovered by the Monte Carlo simulations, which also indicated that the tennis ball texture was favored over the spiral structure by the long-range interactions for semi-flexible chains.

  15. DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

    PubMed

    Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

    2017-09-24

    We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H2O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

  16. Triggered Release of Encapsulated Cargo from Photoresponsive Polyelectrolyte Nanocomplexes

    PubMed Central

    2016-01-01

    Combining the numerous advantages of using light as a stimulus, simple free radical random copolymerization, and the easy, all-aqueous preparation of polyelectrolyte complexes (PECs), we prepared photolabile PEC nanoparticles and demonstrated their rapid degradation under UV light. As a proof of concept demonstration, the dye Nile Red was encapsulated in the PECs and successfully released into the surrounding solution as the polyelectrolyte nanocomplex carriers dissolved upon light irradiation. PMID:27526052

  17. Engineering interfacial properties by anionic surfactant-chitosan complexes to improve stability of oil-in-water emulsions.

    PubMed

    Zinoviadou, Kyriaki G; Scholten, Elke; Moschakis, Thomas; Biliaderis, Costas G

    2012-03-01

    Oil-in-water emulsions (10% w/w n-tetradecane) were prepared at pH = 5.7 by using, as surface active agents, electrostatically formed complexes of sodium stearoyl lactylate (SSL) at a concentration of 0.4% (w/w) and chitosan (CH) in a concentration range between 0 and 0.48% w/w. The use of complexes in emulsions with a low concentration of CH (<0.24% w/w) resulted in highly flocculated systems; instead, with increased level of CH, the emulsions had a smaller average droplet size and exhibited greater stability during storage. Emulsions stabilised by SSL/CH complexes showed non-Newtonian flow behavior with pronounced shear thinning. Among all formulations studied none showed a gel-like behavior since in all cases the G' (storage modulus) was lower that G'' (loss modulus). Adsorption kinetics of pure SSL and SSL/CH complexes to the oil/water interfaces were evaluated using an automated drop tensiometer (ADT). Even though complexation of SSL with CH resulted in a delay of the adsorption of the surface active species at the oil/water interface, the inclusion of the polysaccharide resulted in substantially improved interfacial properties as indicated by a significant increase of the dilatational modulus. Furthermore, the enhanced interfacial properties of the emulsion droplets resulted in improved stability against freeze-thaw cycling. The results of this study may facilitate the development of frozen food products such as desserts with an ameliorated stability and favorable sensorial characteristics.

  18. Surface tension of polyelectrolyte coacervates

    NASA Astrophysics Data System (ADS)

    Qin, Jian; Priftis, Dimitrios; Farina, Robert; Perry, Sarah; Leon, Lorraine; Whitmer, Jonathan; Hoffman, Kyle; Tirrell, Matthew; de Pablo, Juan J.

    2014-03-01

    Stoichiometric solutions of polycations and polyanions can phase separate, resulting in the coexistence of a supernatant phase and a polymer-rich complex phase. The complex phase may be liquid-like or solid-like, depending on the ionic strength and the temperature. Liquid-like complexes, known as ``coacervates'', retain a large amount of water, up to 70-80% by weight, and exhibit an ultra-low interfacial tension with the coexisting supernatant phase (smaller than the water surface tension by three orders of magnitude). Previous experiments have observed that this interfacial tension decreases with the amount of salt, and vanishes near a critical salt concentration according to a 3 / 2 power of the salt undersaturation. In this work we derive analytical expressions for the interfacial tension in both the low and high charge density limits. For solutions with added salts, we provide explicit expressions for the interfacial tension near the critical salt concentration and explain the 3 / 2 power dependence. Our results are shown to be in good agreement with experiment.

  19. A quantitative framework for understanding complex interactions between competing interfacial processes and in situ biodegradation.

    PubMed

    Johnson, Mark A; Song, Xin; Seagren, Eric A

    2013-03-01

    In situ bioremediation of contaminated groundwater is made technologically challenging by the physically, chemically, and biologically heterogeneous subsurface environment. Subsurface heterogeneities are important because of influences on interfacial mass transfer processes that impact the availability of substrates to microorganisms. The goal of this study was to perform a "proof-of-concept" evaluation of the utility of a quantitative framework based on a set of dimensionless coefficients for evaluating the effects of competing physicochemical interfacial and biokinetic processes at the field scale. First, three numerical modeling experiments were completed, demonstrating how the framework can be used to identify the rate-limiting process for the overall bioremediation rate, and to predict what engineered enhancements will alleviate the rate-limiting process. Baseline conditions for each scenario were established to examine intrinsic biodegradation with a given rate-limiting process (either dispersion, biokinetics, or sorption). Then different engineering treatments were examined. In each case, the treatment predicted to be appropriate for addressing the overall rate-limiting process based on the quantitative framework alleviated the limitation more successfully, and enhanced the in situ biodegradation rate more than the alternative enhancements. Second, the quantitative framework was applied to a series of large-scale laboratory and field-scale experiments, using reported parameter estimates to calculate the relevant dimensionless coefficients and predict the rate-limiting process(es). Observations from the studies were then used to evaluate those predictions.

  20. Scaling Theory of Polyelectrolyte Nanogels

    NASA Astrophysics Data System (ADS)

    Qu, Li-Jian

    2017-08-01

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

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

    DOE PAGES

    Oded, Meirav; Kelly, Stephen T.; Gilles, Mary K.; ...

    2016-04-07

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

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

    SciTech Connect

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

    2016-04-07

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

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

    USGS Publications Warehouse

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

    1991-01-01

    Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

  4. Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

    PubMed

    Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

    2015-11-28

    Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

  5. Electrowetting of Weak Polyelectrolyte-Coated Surfaces.

    PubMed

    Sénéchal, Vincent; Saadaoui, Hassan; Rodriguez-Hernandez, Juan; Drummond, Carlos

    2017-05-23

    Polymer coatings are commonly used to modify interfacial properties like wettability, lubrication, or biocompatibility. These properties are determined by the conformation of polymer molecules at the interface. Polyelectrolytes are convenient elementary bricks to build smart materials, given that polyion chain conformation is very sensitive to different environmental variables. Here we discuss the effect of an applied electric field on the properties of surfaces coated with poly(acrylic acid) brushes. By combining atomic force microscopy, quartz crystal microbalance, and contact angle experiments, we show that it is possible to precisely tune polyion chain conformation, surface adhesion, and surface wettability using very low applied voltages if the polymer grafting density and environmental conditions (pH and ionic strength) are properly formulated. Our results indicate that the effective ionization degree of the grafted weak polyacid can be finely controlled with the externally applied field, with important consequences for the macroscopic surface properties.

  6. Polyelectrolytes: wastewater and sewage treatment. January 1977-June 1988 (Citations from the Selected Water Resources Abstracts data base). Report for January 1977-June 1988

    SciTech Connect

    Not Available

    1988-07-01

    This bibliography contains citations concerning polyelectrolytes in waste water and water treatment. Topics include flocculation, coagulation, separation techniques, pollutant identification, water pollution sources, sludge dehydration, and descriptions of specific studies. Hospital waste water processing, methods of synthesizing polyelectrolyte complexes, and performance evaluations of polyelectrolytes are discussed. (This updated bibliography contains 257 citations, 22 of which are new entries to the previous edition.)

  7. Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

    SciTech Connect

    Sibener, Steven J.

    2014-03-11

    This research program explored the efficacy of using molecular-level manipulation, imaging and scanning tunneling spectroscopy in conjunction with supersonic molecular beam gas-surface scattering to significantly enhance our understanding of chemical processes occurring on well-characterized interfaces. One program focus was on the spatially-resolved emergent behavior of complex reaction systems as a function of the local geometry and density of adsorbate-substrate systems under reaction conditions. Another focus was on elucidating the emergent electronic and related reactivity characteristics of intentionally constructed single and multicomponent atom- and nanoparticle-based materials. We also examined emergent chirality and self-organization in adsorbed molecular systems where collective interactions between adsorbates and the supporting interface lead to spatial symmetry breaking. In many of these studies we combined the advantages of scanning tunneling (STM) and atomic force (AFM) imaging, scanning tunneling local electronic spectroscopy (STS), and reactive supersonic molecular beams to elucidate precise details of interfacial reactivity that had not been observed by more traditional surface science methods. Using these methods, it was possible to examine, for example, the differential reactivity of molecules adsorbed at different bonding sites in conjunction with how reactivity is modified by the local configuration of nearby adsorbates. At the core of this effort was the goal of significantly extending our understanding of interfacial atomic-scale interactions to create, with intent, molecular assemblies and materials with advanced chemical and physical properties. This ambitious program addressed several key topics in DOE Grand Challenge Science, including emergent chemical and physical properties in condensed phase systems, novel uses of chemical imaging, and the development of advanced reactivity concepts in combustion and catalysis including carbon

  8. Reaction-complexation coupling between an enzyme and its polyelectrolytic substrate: determination of the dissociation constant of the hyaluronidase-hyaluronan complex from the hyaluronidase substrate-dependence.

    PubMed

    Lenormand, Hélène; Amar-Bacoup, Fériel; Vincent, Jean-Claude

    2013-01-01

    Hyaluronan (HA) is catalytically hydrolyzed by hyaluronidase (HAase). Depending on pH, HA is able to form a non-productive electrostatic complex with HAase in addition to the classical enzyme-substrate complex. Experiments have shown the strong inhibition of the HA hydrolysis catalyzed by HAase when performed at high HA over HAase concentration ratio and low ionic strength. The substrate-dependence thus shows a non-classic inhibition of HAase at high substrate concentrations due to the sequestration of HAase by HA in the electrostatic complex. The modeling of the HA/HAase system is characteristic of a reaction-complexation coupling and it is very difficult to study reaction or binding, separately. Here, we have established the equation controlling the global system and shown that the substrate-dependence of such a system is a direct combination of a pure Michaelis-Menten equation associated with the reaction and a hyperbolic curve associated with the binding. At low substrate concentrations, the hyperbola, representing the relative part of HAase not sequestered by HA, can be assimilated to a straight line. We have established the relationship between the slope of that straight line and the dissociation constant of the electrostatic HA-HAase complex. Fitting the theoretical equation to the experimental data allowed us to determine, for the first time, the Kd value of the non-productive HA-HAase complex at low ionic strength. Copyright © 2013. Published by Elsevier B.V.

  9. Indium tin oxide with zwitterionic interfacial design for biosensing applications in complex matrices

    NASA Astrophysics Data System (ADS)

    Darwish, Nadia T.; Alias, Yatimah; Khor, Sook Mei

    2015-01-01

    Biosensing interfaces consisting of linker molecules (COOH or NH2) and charged, antifouling moieties ((sbnd SO3- and N+(Me)3) for biosensing applications were prepared for the first time by the in situ deposition of mixtures of aryl diazonium cations on indium tin oxide (ITO) electrodes. A linker molecule is required for the attachment of biorecognition molecules (e.g., antibodies, enzymes, DNA chains, and aptamers) close to the transducer surface. The attached molecules improve the biosensing sensitivity and also provide a short response time for analyte detection. Thus, the incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. The reductive adsorption behavior and electrochemical measurement were studied for (1) an individual compound and (2) a mixture of antifouling zwitterionic molecules together with linker molecules [combination 1: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 1,4-phenylenediamine (PPD); combination 2: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 4-aminobenzoic acid (PABA)] of aryl diazonium cations grafted onto an ITO electrode. The mixture ratios of SP:TMAP:PPD and SP:TMAP:PABA that provided the greatest resistance to non-specific protein adsorptions of bovine serum albumin labeled with fluorescein isothiocyanate (BSA-FITC) and cytochrome c labeled with rhodamine B isothiocyanate (RBITC-Cyt c) were determined by confocal laser scanning microscopy (CLSM). For the surface antifouling study, we used 2-[2-(2-methoxyethoxy) ethoxy]acetic acid (OEG) as a standard control because of its prominent antifouling properties. Surface compositions of combinations 1 and 2 were characterized using X-ray photoelectron spectroscopy (XPS). Field-emission scanning electron microscopy (FE-SEM) was used to characterize the morphology of the grafted films to confirm the even distribution between linker and antifouling molecules grafted onto the ITO surfaces

  10. Metal speciation in a complexing soft film layer: a theoretical dielectric relaxation study of coupled chemodynamic and electrodynamic interfacial processes.

    PubMed

    Merlin, Jenny; Duval, Jérôme F L

    2012-04-07

    We report a comprehensive formalism for the dynamics of metal speciation across an interphase formed between a complexing soft film layer and an electrolyte solution containing indifferent ions and metal ions that form complexes with charged molecular ligands distributed throughout the film. The analysis integrates the intricate interplay between metal complexation kinetics and diffusive metal transfer from/toward the ligand film, together with the kinetics of metal electrostatic partitioning across the film/solution interphase. This partitioning is determined by the settling dynamics of the interfacial electric double layer (EDL), as governed by time-dependent conduction-diffusion transports of both indifferent and reactive metal ions. The coupling between such chemodynamic and electrodynamic processes is evaluated via derivation of the dielectric permittivity increment for the ligand film/electrolyte interphase that is perturbed upon application of an ac electric field (pulsation ω) between electrodes supporting the films. The dielectric response is obtained from the ω-dependent distributions of all ions across the ligand film, as ruled by coupled Poisson-Nernst-Planck equations amended for a chemical source term involving the intra-film complex formation and dissociation pulsations (ω(a) and ω(d) respectively). Dielectric spectra are discussed for bare and film coated-electrodes over a wide range of field pulsations and Deborah numbers De = ω(a,d)/ω(diff), where ω(diff) is the electric double layer relaxation pulsation. The frequency-dependent dynamic or inert character of the formed metal complexes is then addressed over a time window that ranges from transient to fully relaxed EDL. The shape and magnitude of the dielectric spectra are further shown to reflect the lability of dynamic complexes, i.e. whether the overall speciation process at a given pulsation ω is primarily rate-limited either by complexation kinetics or by ion-transport dynamics. The

  11. Study of polyelectrolytes for Los Alamos National Laboratory. Final report

    SciTech Connect

    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.

  12. A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.; Bennett, William R.

    2007-01-01

    The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

  13. Interfacial Complex Formation in Uranyl Extraction by Tributyl-Phosphate in Dodecane Diluent: A Molecular Dynamics Study

    SciTech Connect

    de Almeida, Valmor F; Cui, Shengting; Ye, Xianggui; Khomami, Bamin

    2009-01-01

    Atomistic simulations have been carried out in a multicomponent two-phase system (aqueous and organic phases in direct contact) to investigate the interfacial molecular mechanisms leading to uranyl extractionfrom the aqueous to organic phase. The aqueous phase consists of the dissolved ions UO2^2+ and nitrate NO3-,with or without H3O+, in water to describe acidic or neutral condition; the organic phase consists of tributyl phosphate, the extractant, in dodecane as the diluent. We find that the interface facilitates the formation of various uranyl complexes, with a general formula UO2^2+(NO3-)n mTBP kH2O, with n + m + k ) 5, suggesting a 5-fold coordination. The coordination for all three molecular entities has the common feature that they all bind to the uranyl at the uranium atom with an oxygen atom in the equatorial plane perpendicular to the molecular axis of the uranyl, forming a 5-fold symmetry plane. Nitric acid has a strong effect in enhancing the formation of extractable species, which is consistent with experimental findings.

  14. Polyelectrolytes and Their Biological Interactions

    PubMed Central

    Katchalsky, A.

    1964-01-01

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

  15. Aggregation dynamics of rigid polyelectrolytes

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    Similarly charged polyelectrolytes are known to attract each other and aggregate into bundles when the charge density of the polymers exceeds a critical value that depends on the valency of the counterions. The dynamics of aggregation of such rigid polyelectrolytes are studied using large scale molecular dynamics simulations. We find that the morphology of the aggregates depends on the value of the charge density of the polymers. For values close to the critical value, the shape of the aggregates is cylindrical with height equal to the length of a single polyelectrolyte chain. However, for larger values of charge, the linear extent of the aggregates increases as more and more polymers aggregate. In both the cases, we show that the number of aggregates decrease with time as power laws with exponents that are not numerically distinguishable from each other and are independent of charge density of the polymers, valency of the counterions, density, and length of the polyelectrolyte chain. We model the aggregation dynamics using the Smoluchowski coagulation equation with kernels determined from the molecular dynamics simulations and justify the numerically obtained value of the exponent. Our results suggest that once counterions condense, effective interactions between polyelectrolyte chains short-ranged and the aggregation of polyelectrolytes are diffusion-limited.

  16. Optically active polyelectrolyte multilayers as membranes for chiral separations.

    PubMed

    Rmaile, Hassan H; Schlenoff, Joseph B

    2003-06-04

    Ultrathin films of chiral polyelectrolyte complex, prepared by the multilayering process, exhibit selectivity in the membrane separations of optically active compounds, such as l- and d-ascorbic acid. The flux through these polyelectrolyte multilayers, PEMUs, is exceptionally high and may be controlled by the concentration of salt present in the permeating solutions. Both in-situ ATR-FTIR and chiral capillary electrochromatography indicate that flux selectivity is mainly kinetically controlled, stemming from a difference in diffusion rates of various enantiomers through PEMUs, rather than a difference in partitioning.

  17. Ion transport through electrolyte/polyelectrolyte multi-layers

    NASA Astrophysics Data System (ADS)

    Femmer, Robert; Mani, Ali; Wessling, Matthias

    2015-06-01

    Ion transport of multi-ionic solutions through layered electrolyte and polyelectrolyte structures are relevant in a large variety of technical systems such as micro and nanofluidic devices, sensors, batteries and large desalination process systems. We report a new direct numerical simulation model coined EnPEn: it allows to solve a set of first principle equations to predict for multiple ions their concentration and electrical potential profiles in electro-chemically complex architectures of n layered electrolytes E and n polyelectrolytes PE. EnPEn can robustly capture ion transport in sub-millimeter architectures with submicron polyelectrolyte layers. We proof the strength of EnPEn for three yet unsolved architectures: (a) selective Na over Ca transport in surface modified ion selective membranes, (b) ion transport and water splitting in bipolar membranes and (c) transport of weak electrolytes.

  18. Ion transport through electrolyte/polyelectrolyte multi-layers

    PubMed Central

    Femmer, Robert; Mani, Ali; Wessling, Matthias

    2015-01-01

    Ion transport of multi-ionic solutions through layered electrolyte and polyelectrolyte structures are relevant in a large variety of technical systems such as micro and nanofluidic devices, sensors, batteries and large desalination process systems. We report a new direct numerical simulation model coined EnPEn: it allows to solve a set of first principle equations to predict for multiple ions their concentration and electrical potential profiles in electro-chemically complex architectures of n layered electrolytes E and n polyelectrolytes PE. EnPEn can robustly capture ion transport in sub-millimeter architectures with submicron polyelectrolyte layers. We proof the strength of EnPEn for three yet unsolved architectures: (a) selective Na over Ca transport in surface modified ion selective membranes, (b) ion transport and water splitting in bipolar membranes and (c) transport of weak electrolytes. PMID:26111456

  19. Strong and weak adsorptions of polyelectrolyte chains onto oppositely charged spheres

    NASA Astrophysics Data System (ADS)

    Cherstvy, Andrey; Winkler, Roland

    2007-03-01

    We investigate the complexation of long thin polyelectrolyte chains with the oppositely charged sphere. In the limit of strong adsorption, when strongly charged polyelectrolyte chains adapt definite wrapped conformations on the sphere surface (solenoidal, tennis-ball-like, etc.), we analytically solve the linear Poisson-Boltzmann equation and calculate the electrostatic potential and energy of the complex. We discuss some biological applications of the obtained results, including those for DNA wrapping in the nucleosome core particles and for aggregate formation of DNA with oppositely charged nano-spheres studied in vitro. For weak adsorption, when a flexible weakly charged polyelectrolyte chain is localized next to the sphere in solution, we solve the Edwards equation for the chain conformations in the Hulth'en potential. The latter is used as an approximation for the screened Debye-H"uckel potential of the sphere. For arbitrary sphere radius, we predict the critical conditions for polyelectrolyte adsorption as a coupling between critical sphere and polyelectrolyte charge densities, sphere radius, temperature, and ionic strength in solution. We find that the critical charge density of the sphere exhibits a distinctively different dependence on the Debye screening length than for polyelectrolyte adsorption onto a flat surface. We compare our findings with experimental measurements on complex formation of various polyelectrolytes (DNA, PSS, AMPS, etc.) with oppositely charged colloidal particles and cationic micelles, where similar universal scaling relations for the sphere charge density have been revealed.

  20. Dynamic Multiscale Simulation of Polyelectrolyte Nanoassemblies

    DTIC Science & Technology

    2008-08-21

    REPORT Dynamic Multiscale Simulation of Polyelectrolyte Nanoassemblies 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: The goal of this project is to...Std. Z39.18 - 31-May-2008 Dynamic Multiscale Simulation of Polyelectrolyte Nanoassemblies Report Title ABSTRACT The goal of this project is to...Total Number: Sub Contractors (DD882) Inventions (DD882) Final Progress Report Dynamic Multiscale Simulation of Polyelectrolyte Nanoassemblies

  1. Bundle Formation in Polyelectrolyte Brushes

    NASA Astrophysics Data System (ADS)

    Günther, J. U.; Ahrens, H.; Förster, S.; Helm, C. A.

    2008-12-01

    Bundle formation of the vertically oriented polyelectrolytes within polyelectrolyte brushes is studied with x-ray reflectivity and grazing-incidence diffraction as a function of grafting density and ion concentration. At 0.8 Molar monomer concentration and without added salt, a bundle consists of two chains and is 50 Å long. On the addition of up to 1M CsCl, the aggregation number increases up to 15 whereas the bundle length approaches a limiting value, 20 Å. We suggest that the bundle formation is determined by a balance between long-ranged electrostatic repulsion, whose range and amplitude is decreased on salt addition, and short-ranged attraction.

  2. Structure of a Premicellar Complex of Alkyl Sulfates with the Interfacial Binding Surfaces of 4 Subunits of Phospholipase A2✰

    PubMed Central

    Pan, Ying H.; Bahnson, Brian J.

    2010-01-01

    The properties of three discrete premicellar complexes (E1#, E2#, E3#) of pig pancreatic group-IB secreted phospholipase A2 (sPLA2) with monodisperse alkyl sulfates has been characterized [Berg, O. G., et al., Biochemistry 43, 7999–8013, 2004]. Here we have solved the 2.7 Å crystal structure of group-IB sPLA2 complexed with 12 molecules of octyl sulfate (C8S) in a form consistent with a tetrameric oligomeric that exists during the E1# phase of premicellar complexes. The alkyl tails of the C8S molecules are centered in the middle of the tetrameric cluster of sPLA2 subunits. Three of the four sPLA2 subunits also contain a C8S molecule in the active site pocket. The sulfate oxygen of a C8S ligand is complexed to the active site calcium in 3 of the 4 protein active sites. The interactions of the alkyl sulfate head group with Arg-6 and Lys-10, as well as the backbone amide of Met-20, are analogous to those observed in the previously solved sPLA2 crystal structures with bound phosphate and sulfate anions. The cluster of three anions found in the present structure is postulated to be the site for nucleating the binding of anionic amphiphiles to the interfacial surface of the protein, and therefore this binding interaction has implications for interfacial activation of the enzyme. PMID:20302975

  3. Interfacial Instabilities in Evaporating Drops

    NASA Astrophysics Data System (ADS)

    Moffat, Ross; Sefiane, Khellil; Matar, Omar

    2007-11-01

    We study the effect of substrate thermal properties on the evaporation of sessile drops of various liquids. An infra-red imaging technique was used to record the interfacial temperature. This technique illustrates the non-uniformity in interfacial temperature distribution that characterises the evaporation process. Our results also demonstrate that the evaporation of methanol droplets is accompanied by the formation of wave-trains in the interfacial temperature field; similar patterns, however, were not observed in the case of water droplets. More complex patterns are observed for FC-72 refrigerant drops. The effect of substrate thermal conductivity on the structure of the complex pattern formation is also elucidated.

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

    NASA Astrophysics Data System (ADS)

    Riffard, Lucie

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

  5. Macrojunctions ordering in polyelectrolyte hydrogels

    NASA Astrophysics Data System (ADS)

    Török, Gy; Lebedev, V. T.; Cser, L.; Buyanov, A. L.; Revelskaya, L. G.

    2000-03-01

    We studied the structure of polyelectrolyte hydrogels of sodium polyacrylate cross-linked by macromolecular allyldextran (supergels). Using high-resolution SANS we have found the specific ordering of macrojunctions (structure's period ∼130 nm) that may be reliable for the network's anomaly swelling.

  6. Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

    NASA Astrophysics Data System (ADS)

    Plucktaveesak, Nopparat

    The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly

  7. Polyelectrolyte multilayer capsules with quantum dots for biomedical applications.

    PubMed

    Adamczak, M; Hoel, H J; Gaudernack, G; Barbasz, J; Szczepanowicz, K; Warszyński, P

    2012-02-01

    The aim of this work was to encapsulate the CdTe quantum dots within the nanocapsules that were prepared by the layer-by-layer adsorption of polyelectrolytes. Two different polyelectrolyte pairs were used as components of the shell: synthetic polycation poly(allyamine hydrochloride) (PAH), together with anionic poly(sodium styrene sulfonate) (PSS), and biocompatible cationic poly-L-lysine hydrobromide in a pair with biocompatible anionic poly-D-glutamic acid sodium salt (PGA). The saturation method was used for formation of consecutive layers on the initial CdTe-polyelectrolyte complex. A growth of the polyelectrolyte shell was followed with the electrophoretic mobility and light scattering measurements, in order to determine the zeta potential and the size of capsules, respectively. The fluorescent spectra of the quantum dots, which are embedded within the capsules, were characterized with spectrofluorimeter. Later on, they were deposited on a negatively charged mica surface and studied by the means of atomic force microscopy (AFM). In order to estimate the cytotoxicity of capsules, their influence on the B-lymphoblastoid cell line proliferation and on unspecific binding to the P-blood mononuclear cells was examined using the flow cytometry.

  8. Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films

    PubMed Central

    Ball, Vincent

    2012-01-01

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

  9. Advanced Polyelectrolyte-Modified Zinc Phosphate Coatings

    DTIC Science & Technology

    1995-09-01

    September 1995 4 . TITLE AND SUBTITLE Advanced Polyelectrolyte-Modified Zinc Phosphate Coatings 6. AUTHOR(S) T. Sugama, N. Carciello and C.I...ADVANCED POLYELECTROLYTE-MODIFIED ZINC PHOSPHATE COATINGS ft PAL - ?y- 3 $> Phase I. Annual Report (October 1994 - September 1995) ^ by T. Sugama, N...and Cr-nitrates, 3 ) the substitution of environmentally safe polyelectrolyte for the conventional chrome-based compounds in the rinsing process, 4

  10. Layer-by-layer polyelectrolyte deposition: a mechanism for forming biocomposite materials

    PubMed Central

    Tan, YerPeng; Yildiz, Umit Hakan; Wei, Wei; Waite, J. Herbert; Miserez, Ali

    2014-01-01

    Complex coacervates prepared from poly-Aspartic acid (polyAsp) and poly-L-Histidine (polyHis) were investigated as models of the metastable protein phases used in the formation of biological structures such as squid beak. When mixed, polyHis and polyAsp form coacervates whereas poly-L-Glutamic acid (polyGlu) forms precipitates with polyHis. Layer-by-layer (LbL) structures of polyHis-polyAsp on gold substrates were compared with those of precipitate-forming polyHis-polyGlu by monitoring with iSPR and QCM-D. PolyHis-polyAsp LbL was found to be stiffer than polyHis-polyGlu LbL with most water evicted from the structure but with sufficient interfacial water remaining for molecular rearrangement to occur. This thin layer is believed to be fluid and like preformed coacervate films, capable of spreading over both hydrophilic ethylene glycol as well as hydrophobic monolayers. These results suggest that coacervate-forming polyelectrolytes deserve consideration for potential LbL applications and point to LbL as an important process by which biological materials form. PMID:23600626

  11. A united physicochemical description of the protonation and metal ion complexation equilibria of natural organic acids (humic and fulvic acids). 2. Influence of polyelectrolyte properties and functional group heterogeneity on the protonation equilibria of fulvic acid

    USGS Publications Warehouse

    Ephraim, J.; Alegret, S.; Mathuthu, A.; Bicking, M.; Malcolm, R.L.; Marinsky, J.A.

    1986-01-01

    Potentiometric studies of the neutralization of several fulvic acid sources with standard base in aqueous and nonaqueous media have been conducted. Analysis of the results with a recently developed unified physicochemical model has shown that the protonation behavior of these fulvic acid sources is a reflection of (1) their polyelectrolyte nature and (2) their heterogeneity. It has been possible to ascribe the polyelectrolyte properties observed to a rather inflexible fulvic acid molecule whose variably charged surface is impermeable to simple electrolyte. ?? 1986 American Chemical Society.

  12. Polyelectrolyte/surfactant films spread from neutral aggregates.

    PubMed

    Campbell, Richard A; Tummino, Andrea; Noskov, Boris A; Varga, Imre

    2016-06-28

    We describe a new methodology to prepare loaded polyelectrolyte/surfactant films at the air/water interface by exploiting Marangoni spreading resulting from the dynamic dissociation of hydrophobic neutral aggregates dispensed from an aqueous dispersion. The system studied is mixtures of poly(sodium styrene sulfonate) with dodecyl trimethylammonium bromide. Our approach results in the interfacial confinement of more than one third of the macromolecules in the system even though they are not even surface-active without the surfactant. The interfacial stoichiometry of the films was resolved during measurements of surface pressure isotherms in situ for the first time using a new implementation of neutron reflectometry. The interfacial coverage is determined by the minimum surface area reached when the films are compressed beyond a single complete surface layer. The films exhibit linear ripples on a length scale of hundreds of micrometers during the squeezing out of material, after which they behave as perfectly insoluble membranes with consistent stoichiometric charge binding. We discuss our findings in terms of scope for the preparation of loaded membranes for encapsulation applications and in deposition-based technologies.

  13. Macroion Interaction at Polyelectrolyte Brush Interfaces

    NASA Astrophysics Data System (ADS)

    Qu, Chen

    2015-03-01

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

  14. Remarks on Polyelectrolyte Conformation

    NASA Astrophysics Data System (ADS)

    de Gennes, P. G.; Pincus, P.; Velasco, R. M.; Brochard, F.

    chaque cha.ne a le comportement d.une succession des petites pelotes (blobs) de taille 03BE. Les effets électrostatiques sont importants à l.intérieur d'un blobs et analogues au cas (1). Mais ces interactions sont écrantées entre les blobs ; chaque cha.ne a un comportement idéal à grande échelle et son rayon est R(c) ~ c-¼ N½. Si on suppose que les effets dynamiques des enchevêtrements sont faibles on trouve une valeur pour la viscosité ηsp/c ~ Nc-½ We discuss the conformations of linear polyions assuming that a) the corresponding uncharged chain is flexible ; b) electrostatic forces dominate the monomer-monomer interactions; c) no salt is added. 1) For the dilute case (non overlapping chains) correcting a recent self-consistent calculation by Richmond [1a], we find an overall polyion size R = Nd which is a linear function of the polymerization index N in agreement with the early work of Hermans and Overbeek, [1b], Kuhn, Kunzle, and Katchalsky [1c]. 2) There is a range of very low concentration c (c** < c < c*) where the chains do not overlap (c < c*) but where the electrostatic interactions between polyions are much larger than thermal energies (c > c**) : here we expect that the polyions build up a 3-dimensional periodic lattice ; however, the detection of such an extremely dilute lattice appears difficult. 3) Practically all experiments on salt-free polyelectrolytes have been performed at concentrations c > c* where different chains overlap each other. To discuss this regime we restrict our attention to cases where the charge per unit length is near (or above) the condensation threshold : then a single length ξ(c) characterizes the correlation; in 3 dimensions ξ scales like the Debye radius associated with the counter ions. We consider several possible conformations : a) hexagonal lattice of rigid rods ; b) cubic lattice of rigid rods; c) isotropic phase of partially flexible chains. The various rigid rod structures appear to have very similar

  15. Surfactant mediated polyelectrolyte self-assembly

    SciTech Connect

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

    2015-11-25

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

  16. Surfactant mediated polyelectrolyte self-assembly

    DOE PAGES

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

    2015-11-25

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

  17. Surface sliding friction of negatively charged polyelectrolyte gels.

    PubMed

    Kagata, Go; Gong, Jian Ping

    2007-04-15

    The friction between two polyelectrolyte gels carrying the same or opposite sign of charges has been investigated using a rheometer. It is found that the friction was strongly dependent on the interfacial interaction between two gel surfaces. In the repulsive interaction case, especially, the friction was extremely low. The friction behavior is attempted to be described in terms of the hydrodynamic lubrication of the solvent layer between two like-charged gel surfaces, which is formed due to the electrostatic repulsion of the two gel surfaces. From the theoretical analysis (hydrodynamic mechanism), the friction behaviors were explained qualitatively, all of the experimental results, nevertheless, could not be understood well. The viscoelastic feature of the gel and the non-Newtonian behavior of water at the friction interface are considered to be important to elucidate the gel friction.

  18. Nanohybrid conjugated polyelectrolytes: highly photostable and ultrabright nanoparticles

    NASA Astrophysics Data System (ADS)

    Darwish, Ghinwa H.; Karam, Pierre

    2015-09-01

    We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (~109, on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques.We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (~109, on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the

  19. The effect of nature of polyions and treatment after deposition on wetting characteristics of polyelectrolyte multilayers

    NASA Astrophysics Data System (ADS)

    Kolasińska, Marta; Warszyński, Piotr

    2005-10-01

    The sequential adsorption of oppositely charged polyelectrolytes (PE) occurs to be a powerful tool for obtaining various materials of precisely defined properties. The interfacial features of PE multilayer films are governed by the choice of polycation/polyanion pairs and the conditions of film formation. Additionally, the long time exposure to the conditions different than that encountered during formation usually affects polyelectrolyte multilayer structure. The wettability of heterogeneous surfaces produced by 'layer-by-layer' (LbL) adsorption of polyelectrolytes was investigated in this work. We focused on the influence of film treatment after deposition on wetting properties of obtained multilayers. The effect of the nature of the first layer was also studied. Apart from simple arrangements: (polyallylamine hydrochloride)/(polysodium 4-styrenesulfonate) (PAH/PSS) and (poly- L-lysine hydrobromide)/(poly- L-glutamic acid sodium salt) (PLL/PGA) more complicated structures were considered having as a first layer two types of polyethylene imines (PEI) of different molecular weight. Wetting properties of such polyelectrolyte films were determined experimentally by contact angle measurements using technique of direct image analysis of the shape of sessile drop.

  20. Polyelectrolyte multilayers: An odyssey through interdisciplinary science

    NASA Astrophysics Data System (ADS)

    Jaber, Jad A.

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

  1. Effect of time on the interfacial and foaming properties of beta-lactoglobulin/acacia gum electrostatic complexes and coacervates at pH 4.2.

    PubMed

    Schmitt, Christophe; da Silva, Tânia Palma; Bovay, Claudine; Rami-Shojaei, Sabrina; Frossard, Philippe; Kolodziejczyk, Eric; Leser, Martin E

    2005-08-16

    The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on

  2. Charge regularization in phase separating polyelectrolyte solutions.

    PubMed

    Muthukumar, M; Hua, Jing; Kundagrami, Arindam

    2010-02-28

    Theoretical investigations of phase separation in polyelectrolyte solutions have so far assumed that the effective charge of the polyelectrolyte chains is fixed. The ability of the polyelectrolyte chains to self-regulate their effective charge due to the self-consistent coupling between ionization equilibrium and polymer conformations, depending on the dielectric constant, temperature, and polymer concentration, affects the critical phenomena and phase transitions drastically. By considering salt-free polyelectrolyte solutions, we show that the daughter phases have different polymer charges from that of the mother phase. The critical point is also altered significantly by the charge self-regularization of the polymer chains. This work extends the progress made so far in the theory of phase separation of strong polyelectrolyte solutions to a higher level of understanding by considering chains which can self-regulate their charge.

  3. Charge regularization in phase separating polyelectrolyte solutions

    PubMed Central

    Muthukumar, M.; Hua, Jing; Kundagrami, Arindam

    2010-01-01

    Theoretical investigations of phase separation in polyelectrolyte solutions have so far assumed that the effective charge of the polyelectrolyte chains is fixed. The ability of the polyelectrolyte chains to self-regulate their effective charge due to the self-consistent coupling between ionization equilibrium and polymer conformations, depending on the dielectric constant, temperature, and polymer concentration, affects the critical phenomena and phase transitions drastically. By considering salt-free polyelectrolyte solutions, we show that the daughter phases have different polymer charges from that of the mother phase. The critical point is also altered significantly by the charge self-regularization of the polymer chains. This work extends the progress made so far in the theory of phase separation of strong polyelectrolyte solutions to a higher level of understanding by considering chains which can self-regulate their charge. PMID:20192314

  4. Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine

    PubMed Central

    Skounas, Spyridon; Methenitis, Constantinos; Pneumatikakis, George; Morcellet, Michel

    2010-01-01

    The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H2O2] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293–308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands. PMID:20721280

  5. Kinetic Studies and Mechanism of Hydrogen Peroxide Catalytic Decomposition by Cu(II) Complexes with Polyelectrolytes Derived from L-Alanine and Glycylglycine.

    PubMed

    Skounas, Spyridon; Methenitis, Constantinos; Pneumatikakis, George; Morcellet, Michel

    2010-01-01

    The catalytic decomposition of hydrogen peroxide by Cu(II) complexes with polymers bearing L-alanine (PAla) and glycylglycine (PGlygly) in their side chain was studied in alkaline aqueous media. The reactions were of pseudo-first order with respect to [H(2)O(2)] and [L-Cu(II)] (L stands for PAla or PGlygly) and the reaction rate was increased with pH increase. The energies of activation for the reactions were determined at pH 8.8, in a temperature range of 293-308 K. A suitable mechanism is proposed to account for the kinetic data, which involves the Cu(II)/Cu(I) redox pair, as has been demonstrated by ESR spectroscopy. The trend in catalytic efficiency is in the order PGlygly>PAla, due to differences in modes of complexation and in the conformation of the macromolecular ligands.

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

    PubMed

    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.

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

    PubMed

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

    2017-01-01

    Multilayer coatings consisting of oppositely charged polyelectrolytes have proven to be extraordinarily effective oxygen barriers but require many processing steps to fabricate. In an effort to prepare high oxygen barrier thin films more quickly, a polyelectrolyte complex coacervate composed of polyethylenimine and polyacrylic acid is prepared. The coacervate fluid is applied as a thin film using a rod coating process. With humidity and thermal post-treatment, a 2 µm thin film reduces the oxygen transmission rate of 0.127 mm poly(ethylene terephthalate) by two orders of magnitude, rivalling conventional oxygen barrier technologies. These films are fabricated in ambient conditions using low-cost, water-based solutions, providing a tremendous opportunity for single-step deposition of polymeric high barrier thin films. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Hydrophobically modified polyelectrolytes: Characterization, aggregation and adsorption

    NASA Astrophysics Data System (ADS)

    Islam, Mohammad Ferdous

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

  9. Phase diagrams of polyelectrolyte solutions

    NASA Astrophysics Data System (ADS)

    Mahdi, Khaled A.

    We study the phase diagram of polyelectrolyte solutions in salt and salt-free environments. We examine the phase behavior of polyelectrolyte solutions, in the semidilute regime, using different physical models, namely the Random Phase Approximation (RPA) and the cross-linked model. In the RPA, we calculate the electrostatic free energy by summing all the fluctuations of the chains and all present ionic species. Within this approximation, the phase diagrams of salt-free polyelectrolyte solutions show phase separation even without including short-range attractions or ion condensation. We find that the phase behavior of large chains resembles the phase diagram of polymer network solutions. That is, the equilibrium is established between a network phase and a chain-free phase. Upon the addition of salt, the dissociated ions increase the entropy of the system and overcome the energy from the electrostatic fluctuations. When the short-range attraction between monomers is included in the model, the free energy predicts phase segregation for all salt valences at high salt concentrations (1 mol/l and higher). The phenomenon is called salting-out and occurs simply because the addition of salt reduces the quality of the solvent and induces precipitation. However, phase segregation in the presence of multivalent ions in polyelectrolyte solutions occurs at low salt concentrations (less than 1 mol/l). We propose that this phase separation is due to polyions cross-linked by multivalent ions. We constructed a phenomenological two-state model to examine this phenomenon. The two phases coexisting in the solution are a network-like phase and a polymer-free phase. The polymer-free phase is modeled using Debye-Huckel theory. In the cross-linked phase, each condensed multivalent ion attracts an equal number of monomers creating a neutral cluster. The energy of the cluster is evaluated by a simple Coulombic energy. The bare monomer charges between the linkages are treated as line of

  10. Nanohybrid conjugated polyelectrolytes: highly photostable and ultrabright nanoparticles.

    PubMed

    Darwish, Ghinwa H; Karam, Pierre

    2015-10-07

    We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (∼10(9), on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques.

  11. Interfacial charge-transfer transitions and reorganization energies in sulfur-bridged TiO2-x-benzenedithiol complexes (x: o, m, p).

    PubMed

    Fujisawa, Jun-Ichi; Muroga, Ryuki; Hanaya, Minoru

    2016-08-10

    Surface complexes formed between TiO2 nanoparticles and enediol compounds such as 1,2-benzenediol (o-BDO) via Ti-O-C linkages show absorption of visible light due to interfacial charge-transfer (ICT) transitions. The ICT transitions take place from the π-conjugated systems to TiO2. Recently, we reported a surface complex formed between TiO2 and 1,2-benzenedithiol (o-BDT) via Ti-S-C linkages. This sulfur-bridged complex shows ICT transitions from the sulfur bridging atoms to TiO2. Interestingly, it was demonstrated that the ICT transitions in the sulfur-bridged TiO2-o-BDT complex induce photoelectric conversion more efficiently than those in the oxygen-bridged TiO2-o-BDO complex. This result suggests that carrier recombination is suppressed with the sulfur bridging atoms. In this paper, we examine ICT transitions and reorganization energies in the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) and compare them with those in the oxygen-bridged TiO2-x-BDO complexes. The estimated reorganization energies for the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) are much smaller than those for the oxygen-bridged TiO2-x-BDO ones. Based on the Marcus theory, the small reorganization energy calculated for the TiO2-o-BDT complex, which is less than half of that for the TiO2-o-BDO complex, increases the activation energy of carrier recombination. The small reorganization energy is attributed to the characteristic distribution of the highest occupied molecular orbital (HOMO) on the sulfur-bridging atoms in the TiO2-o-BDT complex, which inhibits structural changes in the benzene ring in the ICT excited state. Our work reveals the important role of the sulfur bridging atoms in the suppression of carrier recombination.

  12. Ultrathin self-assembled polyelectrolyte multilayer membranes

    NASA Astrophysics Data System (ADS)

    Tieke, B.; van Ackern, F.; Krasemann, L.; Toutianoush, A.

    The paper is concerned with ultrathin membranes prepared upon alternating layer-by-layer adsorption of cationic and anionic polyelectrolytes on a porous substructure. The formation of the polyelectrolyte multilayer membranes is characterised and the transport of gases, liquid mixtures and ions across the membranes is studied. In particular, the use of the membranes for alcohol/water separation under pervaporation conditions, and for the separation of mono- and divalent ions is described. It is demonstrated that upon a suitable choice of polyelectrolytes and substructures, and a careful optimisation of preparation and operation conditions, membranes can be tailored exhibiting an excellent separation capability.

  13. Polyelectrolyte-graphene Nanocomposites for Biosensing Applications

    PubMed Central

    Priftis, Dimitrios

    2015-01-01

    Due to their unique structure, the optical and mechanical properties graphene and its derivatives (e.g. graphene oxide, reduced graphene oxide) have captured the attention of a constantly increasing number of scientists with regards to biomolecule sensing. This mini review focuses on one specific type of sensor, that consisting of graphene and polyelectrolytes. Polyelectrolyte-graphene nanocomposites exhibit outstanding detection capabilities by synergistically combining the characteristics of both components, outperforming traditional sensors in many cases. Characteristics and mechanistic details of the most important polyelectrolyte-graphene based sensors will be discussed in detail in addition to some current challenges and future perspectives. PMID:27713667

  14. Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  15. Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

    PubMed Central

    Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

    2016-01-01

    We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

  16. Spatial distribution of protein molecules adsorbed at a polyelectrolyte multilayer

    NASA Astrophysics Data System (ADS)

    Jackler, Guido; Czeslik, Claus; Steitz, Roland; Royer, Catherine A.

    2005-04-01

    The spatial distribution of protein molecules interacting with a planar polyelectrolyte multilayer was determined using neutron reflectometry. Staphylococcal nuclease (SNase) was used as model protein that was adsorbed to the multilayer at 22°C and 42°C . At each temperature, the protein solution was adjusted to pD -values of 4.9 and 7.5 to vary the net charge of the protein molecules. The multilayer was built up on a silicon wafer by the deposition of poly(ethylene imine) (PEI), poly(styrene sulfonate) (PSS), and poly(allylamine hydrochloride) (PAH) in the order Si-PEI-PSS- (PAH-PSS)5 . Applying the contrast variation technique, two different neutron reflectivity curves were measured at each condition of temperature and pD -value. From the analysis of the curves, protein density profiles normal to the interface were recovered. Remarkably, it has been found that SNase is partially penetrating into the polyelectrolyte multilayer after adsorption at all conditions studied. The measured neutron reflectivities are consistent with a penetration depth of 50Å at pD=4.9 and 25Å at pD=7.5 . Since SNase has an isoelectric point of pH=9.5 , it carries a net positive charge at both pD -values and interacts with the PSS final layer under electrostatic attraction conditions. However, when increasing the temperature, the amount of adsorbed protein is increasing at both pD -values indicating the dominance of entropic driving forces for the protein adsorption. Interestingly, at pD=4.9 where the protein charge is relatively high, this temperature-induced mass increase of immobilized protein is more pronounced within the polyelectrolyte multilayer, whereas at pD=7.5 , closer to the isoelectric point of SNase, raising the temperature has mainly the effect to accumulate protein molecules outside the polyelectrolyte multilayer at the water interface. It is suggested that the penetration of SNase into the polyelectrolyte multilayer is related to a complexation mechanism. The

  17. Interfacial Hydration, Dynamics and Electron Transfer: Multi-Scale ET Modeling of the Transient [Myoglobin, Cytochrome b5] Complex

    PubMed Central

    Keinan, Shahar; Nocek, Judith M.; Beratan, David N.; Hoffman, Brian M.

    2012-01-01

    Formation of a transient [myoglobin (Mb), cytochrome b5 (cyt b5)] complex is required for the reductive repair of inactive ferri-Mb to its functional ferro-Mb state. The [Mb, cyt b5] complex exhibits dynamic docking (DD), with its cyt b5 partner in rapid exchange at multiple sites on the Mb surface. A triple mutant (Mb(3M)) was designed as part of efforts to shift the electron-transfer process to the simple docking (SD) regime, in which reactive binding occurs at a restricted, reactive region on the Mb surface that dominates the docked ensemble.1 An electrostatically-guided Brownian dynamics (BD) docking protocol was used to generate an initial ensemble of reactive configurations of the complex between unrelaxed partners. This ensemble samples a broad and diverse array of heme-heme distances and orientations. These configurations seeded all-atom constrained molecular dynamics simulations (MD) to generate relaxed complexes for the calculation of electron tunneling matrix elements (TDA) through tunneling-pathway analysis. This procedure for generating an ensemble of relaxed complexes combines the ability of BD calculations to sample the large variety of available conformations and interprotein distances, with the ability of MD to generate the atomic level information, especially regarding the structure of water molecules at the protein-protein interface, that defines electron-tunneling pathways. We used the calculated TDA values to compute ET rates for the [Mb(wt), cyt b5] complex and for the complex with a mutant that has a binding free energy strengthened by three D/E → K charge-reversal mutations, [Mb(3M), cyt b5]. The calculated rate constants are in agreement with the measured values, and the mutant complex ensemble has many more geometries with higher TDA values than does the wild-type Mb complex. Interestingly, water plays a double role in this electron-transfer system, lowering the tunneling barrier as well as inducing protein interface remodeling that

  18. Luminescence quenching of a phosphorescent conjugated polyelectrolyte.

    PubMed

    Haskins-Glusac, Ksenija; Pinto, Mauricio R; Tan, Chunyan; Schanze, Kirk S

    2004-11-17

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

  19. Polyelectrolyte adsorption, interparticle forces, and colloidal aggregation.

    PubMed

    Szilagyi, Istvan; Trefalt, Gregor; Tiraferri, Alberto; Maroni, Plinio; Borkovec, Michal

    2014-04-21

    This review summarizes the current understanding of adsorption of polyelectrolytes to oppositely charged solid substrates, the resulting interaction forces between such substrates, and consequences for colloidal particle aggregation. The following conclusions can be reached based on experimental findings. Polyelectrolytes adsorb to oppositely charged solid substrates irreversibly up to saturation, whereby loose and thin monolayers are formed. The adsorbed polyelectrolytes normally carry a substantial amount of charge, which leads to a charge reversal. Frequently, the adsorbed films are laterally heterogeneous. With increasing salt levels, the adsorbed mass increases leading to thicker and more homogeneous films. Interaction forces between surfaces coated with saturated polyelectrolyte layers are governed at low salt levels by repulsive electric double layer interactions, and particle suspensions are stable under these conditions. At appropriately high salt levels, the forces become attractive, principally due to van der Waals interactions, but eventually also through other forces, and suspensions become unstable. This situation can be rationalized with the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). Due to the irreversible nature of the adsorption process, stable unsaturated layers form in colloidal particle suspensions at lower polyelectrolyte doses. An unsaturated polyelectrolyte layer can neutralize the overall particle surface charge. Away from the charge reversal point, electric double layer forces are dominant and particle suspensions are stable. As the charge reversal point is approached, attractive van der Waals forces become important, and particle suspensions become unstable. This behaviour is again in line with the DLVO theory, which may even apply quantitatively, provided the polyelectrolyte films are sufficiently laterally homogeneous. For heterogeneous films, additional attractive patch-charge interactions may become important

  20. Energy Conversion in Polyelectrolyte Hydrogels

    SciTech Connect

    Erbas, Aykut; Olvera de la Cruz, Monica

    2015-08-18

    Using extensive molecular dynamics simulations of polyelectrolyte hydrogels we demonstrate that, on deformation, these hydrogels adjust their deformed state predominantly by altering electrostatic interactions between their charged groups rather than excluded-volume and bond energies. On deformation, due to the hydrogel’s inherent tendency to preserve electroneutrality in its interior, the translational entropy of counterions decreases and the total electrostatic energy becomes more attractive. This result is valid for a wide range of compression ratios and Bjerrum lengths. The change in the electrostatic energy is more marked in highly swollen gels at low ionic strengths. At high Bjerrum lengths, where most of the counterions are condensed on hydrogel chains and the gel resembles a neutral system, the electrostatic-energy change with deformation is weaker.

  1. Interaction between two polyelectrolyte brushes.

    PubMed

    Kumar, N Arun; Seidel, Christian

    2007-08-01

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

  2. Kinetics of the iodine- and bromine-mediated transport of halide ions: demonstration of an interfacial complexation mechanism.

    PubMed Central

    Klotz, K H; Benz, R

    1993-01-01

    Stationary and kinetic experiments were performed on lipid bilayer membranes to study the mechanism of iodine- and bromine-mediated halide transport in detail. The stationary conductance data suggested that four different 1:1 complexes between I2 and Br2 and the halides I- and Br- were responsible for the observed conductance increase by iodine and bromine (I3-, I2Br-, Br2I-, and Br3-). Charge pulse experiments allowed the further elucidation of the transport mechanism. Only two of three exponential voltage relaxations predicted by the Läuger model could be resolved under all experimental conditions. This means that either the heterogeneous complexation reactions kR (association) and kD (dissociation) were too fast to be resolved or that the neutral carriers were always in equilibrium within the membrane. Experiments at different carrier and halide concentrations suggested that the translocation of the neutral carrier is much faster than the other processes involved in carrier-mediated ion transport. The model was modified accordingly. From the charge pulse data at different halide concentrations, the translocation rate constant of the complexed carriers, kAS, the dissociation constant, kD, and the total surface concentration of charged carriers, NAS, could be evaluated from one single charge pulse experiment. The association rate of the complex, kR, could be obtained in some cases from the plot of the stationary conductance data as a function of the halide concentration in the aqueous phase. The translocation rate constant, kAS, of the different complexes is a function of the image force and of the Born charging energy. It increases 5000-fold from Br3- to I3- because of an enlarged ion radius. PMID:8312500

  3. Polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent counterions: a Monte Carlo simulation study.

    PubMed

    Luque-Caballero, Germán; Martín-Molina, Alberto; Quesada-Pérez, Manuel

    2014-05-07

    Both experiments and theory have evidenced that multivalent cations can mediate the interaction between negatively charged polyelectrolytes and like-charged objects, such as anionic lipoplexes (DNA-cation-anionic liposome complexes). In this paper, we use Monte Carlo simulations to study the electrostatic interaction responsible for the trivalent-counterion-mediated adsorption of polyelectrolytes onto a like-charged planar surface. The evaluation of the Helmholtz free energy allows us to characterize both the magnitude and the range of the interaction as a function of the polyelectrolyte charge, surface charge density, [3:1] electrolyte concentration, and cation size. Both polyelectrolyte and surface charge favor the adsorption. It should be stressed, however, that the adsorption will be negligible if the surface charge density does not exceed a threshold value. The effect of the [3:1] electrolyte concentration has also been analyzed. In certain range of concentrations, the counterion-mediated attraction seems to be independent of this parameter, whereas very high concentrations of salt weaken the adsorption. If the trivalent cation diameter is doubled the adsorption moderates due to the excluded volume effects. The analysis of the integrated charge density and ionic distributions suggests that a delicate balance between charge inversion and screening effects governs the polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent cations.

  4. Influence of Higher Valence Ions on Flexible Polyelectrolytes Stiffness and Counter-ion Distribution

    NASA Astrophysics Data System (ADS)

    Chremos, Alexandros; Douglas, Jack F.

    We investigate the influence of counter-ion valency on the flexibility of highly charged flexible polymer chains by molecular dynamics simulations that include both salt and an explicit solvent. A theoretical understanding of solutions of these molecules (e.g., DNA, RNA, and sulfonate polyestyrene) has been slow to develop due to the complex coupling between the polyelectrolyte conformation and the ionic species in solution due to their long range Coulomb interactions. As observed experimentally, we find that divalent counter-ions greatly reduce the chain persistence length, in comparison to monovalent counter-ions, an effect correlated with the tendency of the polyelectrolyte chain to become distorted by divalent counter-ions. We rationalize these results by with the substantial increase of counter-ion population at the interface with the polyelectrolyte, which not only leads to a more effective screening of the bare charge, but also leads to charge inversion in the trivalent counter-ion case. These conformational changes with counter-ion valency are also associated with a drastic increase of the number of contacts the counter-ions have at the interface with polyelectrolyte, an effect associated with polyelectrolyte chain ``coiling'' around the counter-ions. NIST Postdoctoral Fellowship.

  5. Study of interfacial charge-transfer complex on TiO{sub 2} particles in aqueous suspension by second-harmonic generation

    SciTech Connect

    Liu, Y.; Dadap, J.I.; Zimdars, D.; Eisenthal, K.B.

    1999-04-01

    Titanium dioxide (TiO{sub 2}) is a wide band-gap semiconductor having two common crystal forms: rutile and anatase. Due to its high physical and chemical stability, it is extensively studied as a photocatalyst for photolysis of water, and for oxidative photomineralization of organic pollutants in wastewater, aimed at harvesting solar energy. The authors report the first direct observation of an interfacial charge-transfer complex using second-harmonic spectroscopy. The second-harmonic spectrum of catechol adsorbed on 0.4 micron-sized TiO{sub 2} (anatase) colloidal particles in aqueous suspension reveals a charge-transfer band centered at 2.72 eV (456 nm). In addition, the adsorption isotherm of catechol on the colloidal TiO{sub 2} suspension was obtained and gave an excellent fit to the Langmuir adsorption model. From this, the authors infer the free energy of the adsorption to be {Delta}G{degree} = {minus}6.8 kcal/mol.

  6. Treatment of effluents of poultry slaughterhouse with aluminum salts and natural polyelectrolytes.

    PubMed

    Ikeda, E; Rodrigues, D G; Nozaki, J

    2002-08-01

    A mixture of aluminum salts and natural polyelectrolytes, extracted from the cactus Opuntia ficus indica, has been used for cleaning of wastewater from poultry slaughterhouse. The aggregation and settling properties of colloids and complex organics such as oil, grease, fats, proteins, and suspended solids, was increased if compared with conventional methods of wastewater treatment using only aluminum or iron sulfate. A mixture of aluminum salt in a concentration range of 300 to 600 mg l(-1) and natural polyelectrolytes of 0.6 to 0.8 mg l(-1) was used for flocculation and coagulation. The combination of coagulant and natural polyelectrolytes was able to remove chemical oxygen demand (86%), oil and grease (93%), turbidity (89%), and suspended solids (93%). Methanization activity was also investigated for the effluents in natura.

  7. Interfacial Widths of Conjugated Polymer Bilayers

    SciTech Connect

    NCSU; UC Berkeley; UCSB; Advanced Light Source; Garcia, Andres; Yan, Hongping; Sohn, Karen E.; Hexemer, Alexander; Nguyen, Thuc-Quyen; Bazan, Guillermo C.; Kramer, Edward J.; Ade, Harald

    2009-08-13

    The interfaces of conjugated polyelectrolyte (CPE)/poly[2-methoxy-5-(2{prime}-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) bilayers cast from differential solvents are shown by resonant soft X-ray reflectivity (RSoXR) to be very smooth and sharp. The chemical interdiffusion due to casting is limited to less than 0.6 nm, and the interface created is thus nearly 'molecularly' sharp. These results demonstrate for the first time and with high precision that the nonpolar MEH-PPV layer is not much disturbed by casting the CPE layer from a polar solvent. A baseline is established for understanding the role of interfacial structure in determining the performance of CPE-based polymer light-emitting diodes. More broadly, we anticipate further applications of RSoXR as an important tool in achieving a deeper understanding of other multilayer organic optoelectronic devices, including multilayer photovoltaic devices.

  8. Effect of Protein Supercharging on Interaction with Polyelectrolytes

    NASA Astrophysics Data System (ADS)

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

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

  9. Electrochemically addressed crosslinks in polyelectrolyte multilayers: Cyclic duravoltammetry

    PubMed Central

    Reisch, Andreas; Moussallem, Maroun D.

    2011-01-01

    In situ nanoindentation was performed on a multilayer of poly(acrylic acid) and a high molecular weight, pendant chain polyviologen under controlled electrochemical potential. The modulus of the thin film of polyelectrolyte complex was reversibly modulated, by about an order of magnitude, upon changing the state of charge within the material using the electrochemically active and addressable viologen repeat units. The applied potential, under aqueous conditions, is believed to control the extent of crosslink formation. Simultaneous quartz crystal microbalance measurements revealed the flux of ions into or out of the multilayer during redox cycling. Apparent film modulus also depends on the identity of the last layer. PMID:21718024

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

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

    PubMed

    Carnal, Fabrice; Stoll, Serge

    2011-10-27

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

  12. Biocompatible long-sustained release oil-core polyelectrolyte nanocarriers: From controlling physical state and stability to biological impact.

    PubMed

    Szczepanowicz, Krzysztof; Bazylińska, Urszula; Pietkiewicz, Jadwiga; Szyk-Warszyńska, Lilianna; Wilk, Kazimiera A; Warszyński, Piotr

    2015-08-01

    It has been generally expected that the most applicable drug delivery system (DDS) should be biodegradable, biocompatible and with incidental adverse effects. Among many micellar aggregates and their mediated polymeric systems, polyelectrolyte oil-core nanocarriers have been found to successfully encapsulate hydrophobic drugs in order to target cells and avoid drug degradation and toxicity as well as to improve drug efficacy, its stability, and better intracellular penetration. This paper reviews recent developments in the formation of polyelectrolyte oil-core nanocarriers by subsequent multilayer adsorption at micellar structures, their imaging, physical state and stability, drug encapsulation and applications, in vitro release profiles and in vitro biological evaluation (cellular uptake and internalization, biocompatibility). We summarize the recent results concerning polyelectrolyte/surfactant interactions at interfaces, fundamental to understand the mechanisms of formation of stable polyelectrolyte layered structures on liquid cores. The fabrication of emulsion droplets stabilized by synergetic surfactant/polyelectrolyte complexes, properties, and potential applications of each type of polyelectrolyte oil-core nanocarriers, including stealth nanocapsules with pegylated shell, are discussed and evaluated. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Electrostatic Properties of an Entirely Hydrophilic Polyelectrolyte.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Popov, Alexei

    2007-03-01

    A new of class of polyelectrolyte ionenes is described, one with an entirely hydrophilic backbone of quaternized nitrogens connected by polyoxyethylene spacers of controlled length. The chemistry of these pegylated ionenes yields solubility at constant charge density in solvents of varying dielectric constant; it also allows for controlled variation of polyelectrolyte charge density through choice of monomers. Such features make the new ionenes ideal model polyelectrolytes on which to test theories for electrostatic properties of polyelectrolytes. In particular, we report on the use of electrophoresis to measure effective charge density for different charge spacings and dielectric constants. In conformance with previous results for aliphatic ionenes, we find counterion condensation for pegylated ionenes at conditions different than classical predictions. Counterion condensation -- a constant effective charge density - is encountered in univalent electrolyte by the lowering of dielectric constant even when the dimensionless charge density is less than unity; conditions for the condensation depend on counterion identity (size). Additional studies on various anionic polyelectrolytes dissolved in nonaqueous solvents reproduce the same trends, suggesting their universality.

  14. Synthesis of pH-responsive polysilane with polyelectrolyte side chains through γ-ray-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Tanaka, Hidenori; Kawade, Yasushi; Sato, Nobuhiro; Matsuyama, Tomochika

    2012-02-01

    Polysilanes with polyelectrolyte side chains are synthesized by two methods utilizing γ-ray-induced grafting and the pH responsiveness for one of those polymers is revealed mainly by investigating interfacial behavior of its monolayer at the air/water interface. In the first synthetic method, poly(methyl acrylate) is grafted onto poly(methyl- n-propylsilane) (PMPrS) through γ-ray-induced grafting, and then the PMA chains are hydrolyzed to poly(acrylic acid) resulting in the yield of ca. 97%. Thus PMPrS with polyelectrolyte side chains is successfully synthesized by the graft chain hydrolysis. The other method is the direct grafting of electrolyte monomers. Poly(methacrylic acid)-grafted PMPrS (PMPrS- g-PMAA) can be obtained through γ-ray-induced grafting of methacrylic acid monomers onto PMPrS chains, which shows the effectiveness of radiation grafting for the synthesis of polyelectrolyte graft copolymers. PMPrS- g-PMAA exhibits pH responsive behavior. In addition to the pH-dependence of water solubility, interfacial behavior also depends on the pH. Langmuir monolayers of PMPrS- g-PMAA exhibit different surface pressure-area isotherms according to the grafting yield and the pH of the subphase water. This result suggests that radiation modification is useful for fabricating polysilane-based ordered materials responsive to outer stimuli.

  15. Energy conversion in polyelectrolyte hydrogels

    NASA Astrophysics Data System (ADS)

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

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

  16. Magnaporthe oryzae Glycine-Rich Secretion Protein, Rbf1 Critically Participates in Pathogenicity through the Focal Formation of the Biotrophic Interfacial Complex

    PubMed Central

    Ishii-Minami, Naoko; Kawahara, Yoshihiro; Yoshida, Yuri; Okada, Kazunori; Ando, Sugihiro; Matsumura, Hideo; Terauchi, Ryohei; Minami, Eiichi; Nishizawa, Yoko

    2016-01-01

    Magnaporthe oryzae, the fungus causing rice blast disease, should contend with host innate immunity to develop invasive hyphae (IH) within living host cells. However, molecular strategies to establish the biotrophic interactions are largely unknown. Here, we report the biological function of a M. oryzae-specific gene, Required-for-Focal-BIC-Formation 1 (RBF1). RBF1 expression was induced in appressoria and IH only when the fungus was inoculated to living plant tissues. Long-term successive imaging of live cell fluorescence revealed that the expression of RBF1 was upregulated each time the fungus crossed a host cell wall. Like other symplastic effector proteins of the rice blast fungus, Rbf1 accumulated in the biotrophic interfacial complex (BIC) and was translocated into the rice cytoplasm. RBF1-knockout mutants (Δrbf1) were severely deficient in their virulence to rice leaves, but were capable of proliferating in abscisic acid-treated or salicylic acid-deficient rice plants. In rice leaves, Δrbf1 inoculation caused necrosis and induced defense-related gene expression, which led to a higher level of diterpenoid phytoalexin accumulation than the wild-type fungus did. Δrbf1 showed unusual differentiation of IH and dispersal of the normally BIC-focused effectors around the short primary hypha and the first bulbous cell. In the Δrbf1-invaded cells, symplastic effectors were still translocated into rice cells but with a lower efficiency. These data indicate that RBF1 is a virulence gene essential for the focal BIC formation, which is critical for the rice blast fungus to suppress host immune responses. PMID:27711180

  17. Polyionic vaccine adjuvants: another look at aluminum salts and polyelectrolytes

    PubMed Central

    2015-01-01

    Adjuvants improve the adaptive immune response to a vaccine antigen by modulating innate immunity or facilitating transport and presentation. The selection of an appropriate adjuvant has become vital as new vaccines trend toward narrower composition, expanded application, and improved safety. Functionally, adjuvants act directly or indirectly on antigen presenting cells (APCs) including dendritic cells (DCs) and are perceived as having molecular patterns associated either with pathogen invasion or endogenous cell damage (known as pathogen associated molecular patterns [PAMPs] and damage associated molecular patterns [DAMPs]), thereby initiating sensing and response pathways. PAMP-type adjuvants are ligands for toll-like receptors (TLRs) and can directly affect DCs to alter the strength, potency, speed, duration, bias, breadth, and scope of adaptive immunity. DAMP-type adjuvants signal via proinflammatory pathways and promote immune cell infiltration, antigen presentation, and effector cell maturation. This class of adjuvants includes mineral salts, oil emulsions, nanoparticles, and polyelectrolytes and comprises colloids and molecular assemblies exhibiting complex, heterogeneous structures. Today innovation in adjuvant technology is driven by rapidly expanding knowledge in immunology, cross-fertilization from other areas including systems biology and materials sciences, and regulatory requirements for quality, safety, efficacy and understanding as part of the vaccine product. Standardizations will aid efforts to better define and compare the structure, function and safety of adjuvants. This article briefly surveys the genesis of adjuvant technology and then re-examines polyionic macromolecules and polyelectrolyte materials, adjuvants currently not known to employ TLR. Specific updates are provided for aluminum-based formulations and polyelectrolytes as examples of improvements to the oldest and emerging classes of vaccine adjuvants in use. PMID:25648619

  18. Directed motion of proteins along tethered polyelectrolytes.

    PubMed

    Henzler, Katja; Rosenfeldt, Sabine; Wittemann, Alexander; Harnau, Ludger; Finet, Stephanie; Narayanan, Theyencheri; Ballauff, Matthias

    2008-04-18

    We present the first time-resolved investigation of motions of proteins in densely grafted layers of spherical polyelectrolyte brushes. Using small-angle x-ray scattering combined with rapid stopped-flow mixing, we followed the uptake of bovine serum albumin by poly(acrylic acid) layer with high spatial and temporal resolution. We find that the total amount of adsorbed protein scales with time as t(1/4). This subdiffusive behavior is explained on the basis of directed motion of the protein along the polyelectrolyte chains.

  19. Polymer-surfactant complexes for microencapsulation of vitamin E and its release.

    PubMed

    Sharipova, A A; Aidarova, S B; Grigoriev, D; Mutalieva, B; Madibekova, G; Tleuova, A; Miller, R

    2016-01-01

    Microencapsulation of vitamin E directly from oil-in-water (o/w) emulsions was carried out by means of a novel practically relevant approach. For the first time, a preformed polyelectrolyte-surfactant complex (sodium polystyrene sulfonate/dodecyl trimethyl ammonium bromide) was simultaneously used as an electrosteric emulsion stabilizer and as a charged precursor for the following build up of microcapsules. Subsequently, a layer-by-layer technique was applied to emulsions leading to the formation of core-shell microcapsules with oily cores and polyelectrolyte shells. The effect of the complexes on the process of emulsion formation and on the stability and characteristics of the resulting emulsions was investigated by measurements of dynamic and equilibrium interfacial tension, size distribution (DLS) and interfacial charge (zeta-potential). The resulting microcapsules were characterized by confocal laser scanning microscopy (CLSM), Cryo-SEM, size distribution and zeta-potential measurements on each stage of the shell assembly. The release kinetics of vitamin E was monitored during the consecutive steps of the encapsulation procedure using UV-vis spectroscopy and showed the progressive enhancement of sustainability. The developed approach may be promising for the practical use in the cosmetic and food industry. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Interfacial effects in multilayers

    SciTech Connect

    Barbee, T.W., Jr.

    1998-04-01

    Interfacial structure and the atomic interactions between atoms at interfaces in multilayers or nano-laminates have significant impact on the physical properties of these materials. A technique for the experimental evaluation of interfacial structure and interfacial structure effects is presented and compared to experiment. In this paper the impact of interfacial structure on the performance of x-ray, soft x-ray and extreme ultra-violet multilayer optic structures is emphasized. The paper is concluded with summary of these results and an assessment of their implications relative to multilayer development and the study of buried interfaces in solids in general.

  1. Electrochromism and electrocatalysis in viologen polyelectrolyte multilayers

    SciTech Connect

    Stepp, J.; Schlenoff, J.B.

    1997-06-01

    Polyelectrolyte multilayers were constructed from a polyviologen and poly(styrene sulfonate) using an alternating polyion solution deposition technique. In situ absorption spectroscopy showed multilayers to be strongly electrochromic. Oxygen reduction at multilayer-coated conducting glass electrodes was also shown to be facilitated.

  2. Actuation and ion transportation of polyelectrolyte gels

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Wang, Xiao

    2010-04-01

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

  3. Polyelectrolyte solutions: Excluded-volume considerations

    NASA Astrophysics Data System (ADS)

    Mattoussi, Hedi; Karasz, Frank E.

    1993-12-01

    We provide experimental evidence for the electrostatically related excluded-volume effects on the colligative properties and the single chain behavior of polyelectrolyte solutions in the dilute regime. The data are compared to the theory developed by Fixman, Skolnick, Odijk, and Houwaart. Good agreement between these theoretical considerations and the experimental data is observed.

  4. Tailored polyelectrolyte thin film multilayers to modulate cell adhesion.

    PubMed

    Muzzio, Nicolás E; Pasquale, Miguel A; Moya, Sergio E; Azzaroni, Omar

    2017-08-29

    The layer-by-layer assembly of polyelectrolyte multilayers (PEMs) from natural or synthetic polyelectrolytes constitutes a very versatile and simple strategy to modify surfaces and modulate cell behavior. PEMs assembled from natural polyelectrolytes are very appealing for biological and medical applications due to their high biocompatibility. However, PEMs from natural polyelectrolytes display poor cell adhesion as they are soft materials with an elasticity modulus of a few kilopascal. In this report, the authors present results on the modulation of cell adhesion of different immortalized cell lines by PEMs. Two strategies are employed to vary cell adhesion: (1) a heterogeneous polyelectrolyte multilayer is assembled employing a rigid bottom block including a synthetic polyelectrolyte with a soft upper block of natural polyelectrolytes and (2) polyelectrolyte multilayers from natural polyelectrolytes are thermally annealed after assembly. The physicochemical characteristics of the PEMs change upon thermal treatment. Depending on the composition of the polyelectrolyte multilayer, cell adhesion may be enhanced or reduced. Based on the impact on PEM properties and cell adhesion caused by thermal annealing, a temperature gradient is applied to a PEM of poly-l-lysine/alginate to induce a spatial variation of PEM properties, resulting in a gradient in cell adhesion. The strategies shown here can be employed as simple alternatives to tailor PEM properties by means of fully biocompatible procedures.

  5. Energetic and entropic forces governing the attraction between polyelectrolyte-grafted colloids.

    PubMed

    Arya, Gaurav

    2009-12-03

    The energetic and entropic interactions governing the attraction between like-charged colloidal particles grafted with oppositely charged polyelectrolyte chains in a monovalent electrolyte are investigated computationally. We employ coarse-grained models of the colloids with varying surface and polyelectrolyte charges and Monte Carlo simulations to compute the potential of mean force between two colloidal particles as a function of their separation distance. By categorizing the potentials as attractive or purely repulsive, we obtain the extent and location of the attractive-force regime within the two-dimensional parameter space comprised of the colloid surface and polyelectrolyte charge. The attractive regime is found to occupy the inside of a hyperbola in this charge space, whose shape and size is determined by a complex interplay between energetic and entropic interactions. In particular, we find that the strength of attraction at short distances is governed by a balance between favorable energetic and entropic terms arising from polymer-bridging interactions, unfavorable energies arising from the mutual repulsion of the colloid surfaces and polyelectrolyte chains, and unfavorable entropies arising from the overlap and crowding effects of chains confined between the colloid surfaces. A phenomenological model is proposed to explain the hyperbolic shape of the attractive regime and make useful predictions about changes in its shape and location for conditions not investigated in this study.

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

    PubMed

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

    2017-07-23

    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.

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

    PubMed

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

    2011-12-15

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

  8. Interfacial inhibitors of protein-nucleic acid interactions.

    PubMed

    Pommier, Yves; Marchand, Christophe

    2005-07-01

    This essay develops the paradigm of "Interfacial Inhibitors" (Pommier and Cherfils, TiPS, 2005, 28: 136) for inhibitory drugs beside orthosteric (competitive or non-competitive) and allosteric inhibitors. Interfacial inhibitors bind with high selectivity to a binding site involving two or more macromolecules within macromolecular complexes undergoing conformational changes. Interfacial binding traps (generally reversibly) a transition state of the complex, resulting in kinetic inactivation. The exemplary case of interfacial inhibitor of protein-DNA interface is camptothecin and its clinical derivatives. We will also provide examples generalizing the interfacial inhibitor concept to inhibitors of topoisomerase II (anthracyclines, ellipticines, epipodophyllotoxins), gyrase (quinolones, ciprofloxacin, norfloxacin), RNA polymerases (alpha-amanitin and actinomycin D), and ribosomes (antibiotics such as streptomycin, hygromycin B, tetracycline, kirromycin, fusidic acid, thiostrepton, and possibly cycloheximide). We discuss the implications of the interfacial inhibitor concept for drug discovery.

  9. Solution dynamics of synthetic and natural polyelectrolytes

    NASA Astrophysics Data System (ADS)

    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

  10. Polyelectrolyte/Graphene Oxide Barrier Film for Flexible OLED.

    PubMed

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

    2015-10-01

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

  11. Spontaneous surface flattening via layer-by-layer assembly of interdiffusing polyelectrolyte multilayers.

    PubMed

    Kim, Young Hun; Lee, Yong Man; Park, Juhyun; Ko, Min Jae; Park, Jong Hyeok; Jung, Woncheol; Yoo, Pil J

    2010-11-16

    We report a facile means to achieve planarization of nonflat or patterned surfaces by utilizing the layer-by-layer (LbL) assembly of highly diffusive polyelectrolytes. The polyelectrolyte pair of linear polyethylenimine (LPEI) and poly(acrylic acid) (PAA) is known to maintain intrinsic diffusive mobility atop or even inside ionically complexed films prepared by LbL deposition. Under highly hydrated and swollen conditions during the sequential film buildup process, the LbL-assembled film of LPEI/PAA undergoes a topological self-deformation for minimizing surface area to satisfy the minimum-energy state of the surface, which eventually induces surface planarization along with spontaneous filling of surface textures or nonflat structures. This result is clearly different from other cases of applying nondiffusive polyelectrolytes onto patterned surfaces or confined structures, wherein surface roughening or incomplete filling is developed with the LbL assembly. Therefore, the approach proposed in this study can readily allow for surface planarization with the deposition of a relatively thin layer of polyelectrolyte multilayers. In addition, this strategy of planarization was extended to the surface modification of an indium tin oxide (ITO) substrate, where surface smoothing and enhanced optical transmittance were obtained without sacrificing the electronic conductivity. Furthermore, we investigated the potential applicability of surface-treated ITO substrates as photoelectrodes of dye-sensitized solar cells prepared at room temperature. As a result, an enhanced photoconversion efficiency and improved device characteristics were obtained because of the synergistic role of polyelectrolyte deposition in improving the optical properties and acting as a blocking layer to prevent electron recombination with the electrolytes.

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

    PubMed

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

    2015-09-21

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

  13. Mesoscale modeling of polyelectrolyte brushes with salt.

    PubMed

    Ibergay, Cyrille; Malfreyt, Patrice; Tildesley, Dominic J

    2010-06-03

    We report dissipative particle dynamics (DPD) simulations of a polyelectrolyte brush under athermal solvent conditions. The electrostatic interactions are calculated using the particle-particle particle-mesh (PPPM) method with charges distributed over the particles. The polymer beads, counterions, co-ions, and solvent particles are modeled explicitly. The DPD simulations show a dependence of the brush height on the grafting density and the charge fraction that is typical of the nonlinear osmotic brush regime. We report the effect of the addition of salt on the structural properties of the brush. In the case of a polyelectrolyte brush with a high surface coverage, the simulations reproduce the transition between the nonlinear osmotic brush regime where the thickness of the brush is independent of the salt concentration and the salted regime where the brush height decreases weakly with the salt concentration.

  14. Salt-induced aggregation of stiff polyelectrolytes.

    PubMed

    Fazli, Hossein; Mohammadinejad, Sarah; Golestanian, Ramin

    2009-10-21

    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.

  15. Ion diffusion coefficients through polyelectrolyte multilayers: temperature and charge dependence.

    PubMed

    Ghostine, Ramy A; Schlenoff, Joseph B

    2011-07-05

    The diffusion coefficient is a fundamental parameter for devices exploiting the ion transport properties of polyelectrolyte multilayers (PEMUs) and complexes. Here, the transport of ferricyanide through a multilayer made from poly(diallyldimethylammonium chloride) (PDADMA) and polystyrene sulfonate (PSS) was studied as a function of temperature or salt concentration. Accurate and precise measurements of ion diffusion coefficients were obtained using steady-state electrochemistry to determine the flux and Fourier transform infrared (FTIR) spectroscopy to measure the PEMU concentration. It was found that the concentration of ferricyanide inside the film decreased with temperature. Membrane transport is strongly thermally activated with activation energy 98 kJ mol(-1). A potential shift with decreasing salt concentration in cyclic voltammograms was translated into a differential flux caused by significantly higher diffusion coefficients for ferricyanide as compared to ferrocyanide. © 2011 American Chemical Society

  16. Responsive interfaces grafted with polyelectrolyte or polyampholyte

    NASA Astrophysics Data System (ADS)

    Tran, Yvette; Sanjuan, Sarah; Pantoustier, Nadège; Perrin, Patrick

    2007-01-01

    We synthesize and investigate the swelling behavior of polyelectrolyte and polyampholyte grafted layers on planar substrates. The polymer brushes are prepared using the "grafting from" method with surface-initiated atom transfer radical polymerization (ATRP), which allows a good control of the chain length and a weak polydispersity of chains. Ellipsometry and neutron reflectivity are used to determine the swollen thickness and the monomer volume fraction profile. The scaling behavior of the neutral polymer brush and the strong polyelectrolyte brush is in good agreement with scaling laws predicted by mean-field theories. The swelling behavior of the pH-responsive polybase brush is between the situation of the neutral polymer brush in good solvent and the quenched polyelectrolyte. Polyampholyte brushes are contracted in the pH range of zero net charge. A barrier zone likely due to the attraction between positively and negatively charged monomer units is observed in the density profile. This barrier could prevent from a collective ionization of the chains and reduce the expected collapse of the brush.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Self-assembly of interfacial and photoactive layers via one-step solution processing for efficient inverted organic solar cells.

    PubMed

    Kang, Hongkyu; Lee, Jinho; Jung, Suhyun; Yu, Kilho; Kwon, Sooncheol; Hong, Soonil; Kee, Seyoung; Lee, Seongyu; Kim, Dongwon; Lee, Kwanghee

    2013-12-07

    Vertically self-assembled bilayers with an interfacial bottom layer and a photoactive top layer are demonstrated via a single coating step of a blend composed of an amine-containing nonconjugated polyelectrolyte (NPE) and an organic electron donor-acceptor bulk heterojunction composite. The self-assembled NPE layer reduces the work function of an indium tin oxide (ITO) cathode, which leads to efficient inverted organic solar cells without any additional interface engineering of the ITO.

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

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoxia; Zhao, Kongshuang

    2017-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Sing, Charles; Olvera de La Cruz, Monica

    2015-03-01

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

  2. Electronic structures of TiO2-TCNE, -TCNQ, and -2,6-TCNAQ surface complexes studied by ionization potential measurements and DFT calculations: Mechanism of the shift of interfacial charge-transfer bands

    NASA Astrophysics Data System (ADS)

    Fujisawa, Jun-ichi; Hanaya, Minoru

    2016-06-01

    Interfacial charge-transfer (ICT) transitions between inorganic semiconductors and π-conjugated molecules allow direct charge separation without loss of energy. This feature is potentially useful for efficient photovoltaic conversions. Charge-transferred complexes of TiO2 nanoparticles with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its analogues (TCNX) show strong ICT absorption in the visible region. The ICT band was reported to be significantly red-shifted with extension of the π-conjugated system of TCNX. In order to clarify the mechanism of the red-shift, in this work, we systematically study electronic structures of the TiO2-TCNX surface complexes (TCNX; TCNE, TCNQ, 2,6-TCNAQ) by ionization potential measurements and density functional theory (DFT) calculations.

  3. Viscosity of Aqueous Polyelectrolyte Solutions with Oppositely Charged Surfactant

    NASA Astrophysics Data System (ADS)

    Eggert, Matthew; Colby, Ralph

    2006-03-01

    The viscosity of polyelectrolyte solutions with oppositely charged surfactants is measured for a series of anionic polyelectrolytes of variable hydrophobicity (alternating copolymers of sodium maleate with hydrocarbon comonomers) in the presence of cationic trimethyl ammonium bromides with various alkyl tail lengths. These results are compared with a simple model that modifies the scaling theory for unentangled semidilute polyelectrolyte solutions to account for the addition of oppositely charged surfactant. The surfactant lowers the viscosity of these solutions through two means. The polyelectrolyte binds to the surface of the surfactant micelle, reducing the effective chain length of the polymer. The binding also causes counterions of the polyelectrolyte and the surfactant to be released into solution, acting as a salt that screens the repulsion between charges of the polyelectrolyte, causing the chains to have smaller size. The fraction of effectively charged monomers (i.e., free counterions) on the polyelectrolyte is measured via an ion-selective electrode, meaning the simple model has no adjustable parameters. Additional electrodes are used to measure the amount of free surfactant in solution in order to estimate the amount of surfactant associated with each polyelectrolyte chain.

  4. Polyelectrolyte adsorption kinetics under an applied electric potential: Strongly versus weakly charged polymers.

    PubMed

    Olsen, Christel; Van Tassel, Paul R

    2009-01-15

    Previous work has demonstrated adsorption of weakly basic polycations to a conducting substrate to be continuous, i.e. asymptotically linear in time over hours, under an applied anodic potential [A.P. Ngankam, P.R. Van Tassel, Proc. Natl. Acad. Sci. USA 104 (2007) 1140]. Adsorption without apparent saturation requires an interfacial charge regulation, which is possible for weakly charged polymers via segment deprotonation. We investigate here whether deprotonation is a necessary condition for continuous adsorption by comparing the behavior of a weakly and a strongly charged polyelectrolyte, the latter containing permanently charged segments incapable of deprotonation. We employ optical waveguide lightmode spectroscopy (OWLS) to measure adsorption of poly(N-vinyl imidazole) (PVI), a weakly basic polycation, and quaternized poly(N-vinyl imidazole) (QPVI), a structurally similar polymer with ca. 20% of its monomers containing a permanent positive charge, onto indium tin oxide (ITO). Under open circuit conditions, we observe both PVI and QPVI adsorption to reach a rapid saturation and be essentially irreversible. In contrast, at an ITO potential of 1.5 V (versus hydrogen) in a 0.1 M NaCl solution, we observe adsorption of both PVI and QPVI to be continuous and reversible. In salt free solution, we observe PVI but not QPVI to exhibit continuous adsorption at 1.5 V, and for both polymers to be essentially irreversibly attached. We propose interfacial charge regulation to occur via a deprotonation mechanism for PVI, and via a counterion condensation mechanism for QPVI. Continuous adsorption is therefore possible for a strongly charged polyelectrolyte, via a counterion condensation mechanism; this finding opens the door to nanofilms of controlled polymer content containing permanent charges.

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

    PubMed

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

    2017-05-04

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

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

    PubMed

    Kurth, Dirk G

    2002-04-01

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

  7. The effects of salts on polyelectrolyte systems

    NASA Astrophysics Data System (ADS)

    Zissu, Jonathan Adam

    The effects of salts on the behavior of polyelectrolyte systems were investigated. The phase behavior of polyelectrolyte solutions in the presence of added salt was calculated by combining the free energies due to Flory-Huggins mixing and Debye-Huckel electrostatics, with both terms modified for our polyelectrolyte solutions. Using the calculated phase diagrams, we found that most results give a typical polymer-solvent-nonsolvent phase diagram, with the solvent acting as a "nonsolvent" (since we assume that the polymer-solvent interaction parameter, chi, is positive) and the dissociated salt acting as a "solvent". However, for high charges of the salt ions, we found a completely different phase diagram, one which can be explained by a "salting out effect" where the addition of salt over a certain concentration threshold causes complete phase separation over all concentrations of polymer and solvent. Also, the density and repulsive force profiles for a system comprised of two parallel, planar, uncharged surfaces uniformly covered with poly electrolyte brushes in an electrolyte solution was calculated using a computational enumeration of a one-dimensional random walk model. For large surface separations, we found three different density profiles: a Gaussian regime when kappa is large, a stretched regime when kappa is intermediate in value, and a "pancake" regime, with chains collapsed onto their grafted surface, when kappa is small. For small surface separations, the first two regimes are replaced with an interpenetrating regime, where the density is essentially uniform across the entire region between the surfaces. For intermediate surface separations, the repulsive force scales as exp (- Ak12 D), unlike what is expected using Gouy-Chapman theory.

  8. Self-assembly in block polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Vishnyakov, Aleksey; Neimark, Alexander V.

    2011-02-01

    The self-consistent field theory (SCFT) complemented with the Poisson-Boltzmann equation is employed to explore self-assembly of polyelectrolyte copolymers composed of charged blocks A and neutral blocks B. We have extended SCFT to dissociating triblock copolymers and demonstrated our approach on three characteristic examples: (1) diblock copolymer (AB) melt, (2) symmetric triblock copolymer (ABA) melt, (3) triblock copolymer (ABA) solution with added electrolyte. For copolymer melts, we varied the composition (that is, the total fraction of A-segments in the system) and the charge density on A blocks and calculated the phase diagram that contains ordered mesophases of lamellar, gyroid, hexagonal, and bcc symmetries, as well as the uniform disordered phase. The phase diagram of charged block copolymer melts in the charge density - system composition coordinates is similar to the classical phase diagram of neutral block copolymer melts, where the composition and the Flory mismatch interaction parameter χ _{AB} are used as variables. We found that the transitions between the polyelectrolyte mesophases with the increase of charge density occur in the same sequence, from lamellar to gyroid to hexagonal to bcc to disordered morphologies, as the mesophase transitions for neutral diblocks with the decrease of χ _{AB}. In a certain range of compositions, the phase diagram for charged triblock copolymers exhibits unexpected features, allowing for transitions from hexagonal to gyroid to lamellar mesophases as the charge density increases. Triblock polyelectrolyte solutions were studied by varying the charge density and solvent concentration at a fixed copolymer composition. Transitions from lamellar to gyroid and gyroid to hexagonal morphologies were observed at lower polymer concentrations than the respective transitions in the similar neutral copolymer, indicating a substantial influence of the charge density on phase behavior.

  9. Counterion-Induced Attraction between Rigid Polyelectrolytes

    SciTech Connect

    Gro Bruinsma, R.F.; Gro Mashl, R.J.; Gelbart, W.M.

    1997-03-01

    We report on results of long-time Brownian-dynamics simulations of electrostatic interactions between two rigid polyelectrolyte rods. We find that the interaction can be both repulsive, as obtained from mean-field theory, and attractive. The onset of attraction depends not only on the fixed charge density of the rod, but also on its radius. The attractive force is found to be due to the development of positional correlations between the counterions condensed on the two rods, for which we propose a simple analytical model. {copyright} {ital 1997} {ital The American Physical Society}

  10. Evolution of growth modes for polyelectrolyte bundles.

    PubMed

    Lai, Ghee Hwee; Coridan, Rob; Zribi, Olena V; Golestanian, Ramin; Wong, Gerard C L

    2007-05-04

    Multivalent ions induce attractions between polyelectrolytes, but lead to finite-sized bundles rather than macroscopic phase separation. The kinetics of aggregation and bundle formation of actin is tracked using two different fluorescently labeled populations of F-actin. It is found that the growth mode of these bundles evolves with time and salt concentration, varying from an initial lateral growth to a longitudinal one at later stages. The results suggest that kinetics play a role in bundle growth, but not in the lateral size of bundles, which is constant for linear and branched topologies.

  11. A Molecular Imprinting Strategy Employing Polyelectrolyte Multilayers

    NASA Astrophysics Data System (ADS)

    Olugebefola, Solar C.

    2005-03-01

    Polyelectrolyte multilayers were assembled from poly(allylamine hydrochloride) (PAH), poly(acrylic acid) (PAA) and poly(acrylic acid-r-vinyl benzyl acetate) (xPAA), derivatized from PAA. The pHs of polymer assembly solutions were controlled to yield high surface area film morphologies for adsorption. Assembled films were photo crosslinked in the presence of adsorbed template molecules and the template removed to yield selective binding sites. Quartz crystal microbalance measurements of adsorption onto films templated with bovine serum albumin show higher affinity for BSA compared to films crosslinked with no templating.

  12. Luminescence Probe Studies of Nafion Polyelectrolytes.

    DTIC Science & Technology

    1983-10-07

    I iD-Ri33 519 LUMINESCENCE PROBE STUDIES OF NRFION FOLYELECTROLYTES i/i (U) TEXAS A AND M UNIV COLLEGE STATION DEPT OF CHEMIISTRY N E PRIETO ET AL...Task No. NR 627-838 TECHNICAL REPORT NO. 2 *Luminescence Probe Studi s of Nafion Polyelectrolytes Pby Nelson E. Prieto and Charles R. Martin 41...E. Prieto and Charles R. Martin N00014-82K-0612 9. PERFORMING ORGANIZATION NAME AND ADDRESS _%. -PROGRAM ELEMENT. PROJECT. TASK AREA & WORKC UNIT

  13. Emulsions for interfacial filtration.

    SciTech Connect

    Grillet, Anne Mary; Bourdon, Christopher Jay; Souza, Caroline Ann; Welk, Margaret Ellen; Hartenberger, Joel David; Brooks, Carlton, F.

    2006-11-01

    We have investigated a novel emulsion interfacial filter that is applicable for a wide range of materials, from nano-particles to cells and bacteria. This technology uses the interface between the two immiscible phases as the active surface area for adsorption of targeted materials. We showed that emulsion interfaces can effectively collect and trap materials from aqueous solution. We tested two aqueous systems, a bovine serum albumin (BSA) solution and coal bed methane produced water (CBMPW). Using a pendant drop technique to monitor the interfacial tension, we demonstrated that materials in both samples were adsorbed to the liquid-liquid interface, and did not readily desorb. A prototype system was built to test the emulsion interfacial filter concept. For the BSA system, a protein assay showed a progressive decrease in the residual BSA concentration as the sample was processed. Based on the initial prototype operation, we propose an improved system design.

  14. Enhanced efficiency of single and tandem organic solar cells incorporating a diketopyrrolopyrrole-based low-bandgap polymer by utilizing combined ZnO/polyelectrolyte electron-transport layers.

    PubMed

    Jo, Jang; Pouliot, Jean-Rémi; Wynands, David; Collins, Samuel D; Kim, Jin Young; Nguyen, Thanh Luan; Woo, Han Young; Sun, Yanming; Leclerc, Mario; Heeger, Alan J

    2013-09-14

    Power conversion efficiency up to 8.6% is achieved for a solution-processed tandem solar cell based on a diketopyrrolopyrrole-containing polymer as the low-bandgap material after using a thin polyelectrolyte layer to modify the electron-transport ZnO layers, indicating that interfacial engineering is a useful approach to further enhancing the efficiency of tandem organic solar cells.

  15. Polyelectrolyte multilayer-cushioned fluid lipid bilayers: a parachute model.

    PubMed

    Shao, Jingxin; Wen, Caixia; Xuan, Mingjun; Zhang, Hongyue; Frueh, Johannes; Wan, Mingwei; Gao, Lianghui; He, Qiang

    2017-01-18

    Lipid bilayer membranes supported on polyelectrolyte multilayers are widely used as a new biomembrane model that connects biological and artificial materials since these ultrathin polyelectrolyte supports may mimic the role of the extracellular matrix and cell skeleton in living systems. Polyelectrolyte multilayers were fabricated by a layer-by-layer self-assembly technique. A quartz crystal microbalance with dissipation was used in real time to monitor the interaction between phospholipids and polyelectrolytes in situ on a planar substrate. The surface properties of polyelectrolyte films were investigated by the measurement of contact angles and zeta potential. Phospholipid charge, buffer pH and substrate hydrophilicity were proved to be essential for vesicle adsorption, rupture, fusion and formation of continuous lipid bilayers on the polyelectrolyte multilayers. The results clearly demonstrated that only the mixture of phosphatidylcholine and phosphatidic acid (4 : 1) resulted in fluid bilayers on chitosan and alginate multilayers with chitosan as a top layer at pH 6.5. A coarse-grained molecular simulation study elucidated that the exact mechanism of the formation of fluid lipid bilayers resembles a "parachute" model. As the closest model to the real membrane, polyelectrolyte multilayer-cushioned fluid lipid bilayers can be appropriate candidates for application in biomedical fields.

  16. Molecular Origins of Thermal Transitions in Polyelectrolyte Assemblies

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  17. Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  18. The effects of acrylamide polyelectrolytes on aquatic organisms: relating toxicity to chain architecture.

    PubMed

    Costa, R; Pereira, J L; Gomes, J; Gonçalves, F; Hunkeler, D; Rasteiro, M G

    2014-10-01

    Understanding the inherent toxicity of water-soluble synthetic polyelectrolytes is critical for adequate risk management as well as enhancing product design when biological activity is a key performance index (e.g. for application in biofouling bivalves' control). The toxicity of two cationic acrylamide copolymers with different chain branching degree was evaluated. Standard ecotoxicity tests were conducted with microalgae and daphnids. The susceptibility of Corbicula fluminea, as a biofouling bivalve, was also evaluated. The effect of polyelectrolyte on the test media viscosity and the polymer chain size distributions under the experimental conditions were also examined. The susceptibility of the microalgae to both polymers was similar. As the complexity and size of the test organisms increased, differences in toxicity due to different chain architecture were noticeable. The more branched polymer was significantly less toxic to both daphnids and the bivalves, which could be linked to the distinctive features of its bimodal size chain distribution. This architecture resulted in both more compact globular molecules and the formation of aggregates, which reduce the polymer interaction with the biological surfaces. The results of this study promote the incorporation of environmental considerations in polyelectrolyte development and contribute to the design of improved solutions for controlling biofouling bivalves. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Electrostatic correlations and the polyelectrolyte self energy.

    PubMed

    Shen, Kevin; Wang, Zhen-Gang

    2017-02-28

    We address the effects of chain connectivity on electrostaticfluctuations in polyelectrolyte solutions using a field-theoretic, renormalizedGaussian fluctuation (RGF) theory. As in simple electrolyte solutions [Z.-G. Wang,Phys. Rev. E 81, 021501 (2010)], the RGF provides a unified theory forelectrostatic fluctuations, accounting for both dielectric and charge correlationeffects in terms of the self-energy. Unlike simple ions, the polyelectrolyte self energydepends intimately on the chain conformation, and our theory naturally provides aself-consistent determination of the response of intramolecular chain structure topolyelectrolyte and salt concentrations. The effects of the chain-conformation on theself-energy and thermodynamics are especially pronounced for flexiblepolyelectrolytes at low polymer and salt concentrations, where application of thewrong chain structure can lead to a drastic misestimation of the electrostaticcorrelations. By capturing the expected scaling behavior of chain size from dilute tosemi-dilute regimes, our theory provides improved estimates of the self energy at lowpolymer concentrations and correctly predicts the eventual N-independenceof the critical temperature and concentration of salt-free solutions of flexiblepolyelectrolytes. We show that the self energy can be interpreted in terms of aninfinite-dilution energy μm,0(el) and a finite concentrationcorrelation correction μ(corr) which tends to cancel out the formerwith increasing concentration.

  20. Electrostatic correlations and the polyelectrolyte self energy

    NASA Astrophysics Data System (ADS)

    Shen, Kevin; Wang, Zhen-Gang

    2017-02-01

    We address the effects of chain connectivity on electrostaticfluctuations in polyelectrolyte solutions using a field-theoretic, renormalizedGaussian fluctuation (RGF) theory. As in simple electrolyte solutions [Z.-G. Wang,Phys. Rev. E 81, 021501 (2010)], the RGF provides a unified theory forelectrostatic fluctuations, accounting for both dielectric and charge correlationeffects in terms of the self-energy. Unlike simple ions, the polyelectrolyte self energydepends intimately on the chain conformation, and our theory naturally provides aself-consistent determination of the response of intramolecular chain structure topolyelectrolyte and salt concentrations. The effects of the chain-conformation on theself-energy and thermodynamics are especially pronounced for flexiblepolyelectrolytes at low polymer and salt concentrations, where application of thewrong chain structure can lead to a drastic misestimation of the electrostaticcorrelations. By capturing the expected scaling behavior of chain size from dilute tosemi-dilute regimes, our theory provides improved estimates of the self energy at lowpolymer concentrations and correctly predicts the eventual N-independenceof the critical temperature and concentration of salt-free solutions of flexiblepolyelectrolytes. We show that the self energy can be interpreted in terms of aninfinite-dilution energy μm,0 el and a finite concentrationcorrelation correction μcorr which tends to cancel out the formerwith increasing concentration.

  1. Configurational properties of a single semiflexible polyelectrolyte

    NASA Astrophysics Data System (ADS)

    Ghosh, K.; Carri, Gustavo A.; Muthukumar, M.

    2001-09-01

    Using a variational calculation, we have considered the effect of chain length, intrinsic backbone stiffness, solvent quality, and salt concentration on the behavior of a single semiflexible polyelectrolyte in dilute solution. Explicitly, we have calculated the radius of gyration (Rg) and effective persistence length for different solvent qualities and salt concentrations. For an isolated semiflexible polyelectrolyte with increasing molecular weight, there can be five regimes with effective exponent ν (defining the molecular weight dependence of Rg) being 1, 1/2, 1, 2/5, and 1/2 in the absence of nonelectrostatic excluded volume interaction. This suggests a double crossover behavior from rodlike to Gaussian and then to Gaussian again as the chain length is increased. During the second crossover, ν can be as high as 1, although the actual value of Rg is order of magnitude smaller than the rodlike value. There can be another regime in this second crossover where the apparent exponent is 2/5 due to additional self-screening arising from counterions of the polymer. This self-screening can significantly reduce Rg, although the asymptotic exponent 2/5 may not be observable due to physical constraints. A thorough analysis of the crossover behavior is presented.

  2. Electrophoresis of a polyelectrolyte through a nanopore

    NASA Astrophysics Data System (ADS)

    Ghosal, Sandip

    2006-11-01

    Translocation of polyelectrolytes (such as DNA) through natural and artificial nanopores can be detected with single molecule resolution by monitoring the resistivity of the pore (Nature Biotechnology (2001) 19, pp. 248). The technique could evolve into a technology for sequencing DNA at speeds that are orders of magnitude faster than what is currently possible. Here a hydrodynamic model to determine the electrophoretic speed of a polyelectrolyte through a nanopore is presented. It is assumed that the speed is determined by a balance of electrical and viscous forces arising from within the pore and that classical continuum electrostatics and hydrodynamics may be considered applicable. An explicit formula for the translocation speed as a function of the pore geometry and other physical parameters is obtained and is shown to be consistent with experimental measurements on DNA translocation through nanopores in silicon membranes. Secondary effects such as the hydrodynamic friction on the part of the polymer outside the nanopore must also be considered to explain the weak dependence of the translocation speed on the polymer length.

  3. Clusters in strong polyelectrolyte solutions in the condensation theory approach.

    PubMed

    Perico, Angelo; Rapallo, Arnaldo

    2011-02-07

    The interaction free energy of parallel clusters of like-charged rod polyelectrolytes in solution is calculated in the framework of the extended condensation theory. For sufficiently high linear charge density of the polyelectrolyte, clustering takes place. The greater is the number of polyelectrolytes participating to the cluster, the smaller is the equilibrium interpolyelectrolyte distance, and the deeper is the corresponding free energy minimum. It is a counterintuitive organization due to the increasing of the counterion condensed charge and condensation volume, taking place as the polyelectyrolytes approach each other.

  4. Quantum field theory of polyelectrolyte-counterion condensation

    NASA Astrophysics Data System (ADS)

    Dewey, T. G.

    1988-10-01

    A simple quantum theory of polyelectrolyte-counterion interactions is presented. A model Hamiltonian is employed which describes both the polyelectrolyte and the counterion as free, spinless fermions. This Hamiltonian is transformed into a form which is isomorphous with traditional Hamiltonians used to describe phase transitions. The difference between this theory and early theories of superconductivity is that the counterion-counterion interaction energies will be quite large and will persist at high temperatures. The counterion condensate is a collective mode resulting from polyelectrolyte-mediated polarizations. Colligative properties for this model are compared with the Poisson-Boltzmann theory and to Manning's condensation theory.

  5. Interfacial bonding stability

    NASA Technical Reports Server (NTRS)

    Boerio, J.

    1984-01-01

    Interfacial bonding stability by in situ ellipsometry was investigated. It is found that: (1) gamma MPS is an effective primer for bonding ethylene vinyl acetate (EVA) to aluminum; (2) ellipsometry is an effective in situ technique for monitoring the stability of polymer/metal interfaces; (3) the aluminized back surface of silicon wafers contain significant amounts of silicon and may have glass like properties.

  6. Self-organization, interfacial interaction and photophysical properties of gold nanoparticle complexes derived from resilin-mimetic fluorescent protein rec1-resilin.

    PubMed

    Mayavan, Sundar; Dutta, Naba K; Choudhury, Namita R; Kim, Misook; Elvin, Christopher M; Hill, Anita J

    2011-04-01

    In this investigation we report the synthesis of optically coupled hybrid architectures based on a new biomimetic fluorescent protein rec1-resilin and nanometer-scale gold nanoparticles (AuNPs) in a one-step method using a non-covalent mode of binding protocol. The presence of uniformly distributed fluorophore sequences, -Ser(Thr)-Tyr-Gly- along the molecular structure of rec1-resilin provides significant opportunity to synthesize fluorophore-modified AuNPs bioconjugates with unique photophysical properties. The detailed analyses of the AuNP-bioconjugates, synthesized under different experimental conditions using spectroscopic, microscopic and scattering techniques demonstrate the organizational pathways and the electronic and photophysical properties of the developed AuNP-rec1-resilin bioconjugates. The calculation of the bimolecular quenching constant using the Stern-Volmer equation confirms that the dominant mechanism involved in quenching of fluorescence of rec1-resilin in the presence of AuNP is static. Photoacoustic infrared spectroscopy was employed to understand the nature of the interfacial interaction between the AuNP and rec1-resilin and its evolution with pH. In such bioconjugates the quenched emission of fluorescence by AuNP on the fluorophore moiety of rec1-resilin in the immediate vicinity of the AuNP has significant potential for fluorescence-based detection schemes, sensors and also can be incorporated into nanoparticle-based devices. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Modulation of organic interfacial spin polarization by interfacial angle

    NASA Astrophysics Data System (ADS)

    Zhang, Zhao; Li, Ying; Zhang, Guang-ping; Ren, Jun-feng; Wang, Chuan-kui; Hu, Gui-chao

    2017-01-01

    Based on ab initio theory, we theoretically investigated the interfacial spin polarization by adsorbing a benzene-dithiolate molecule onto a nickel surface with different interfacial angles. A variable magnitude and even an inversion of the interfacial spin polarization are observed with the increase of the interfacial angle. The orbital analysis shows that the interfacial spin polarization is codetermined by two kinds of orbital hybridization between the molecule and the ferromagnet, the pz-d hybridization and the sp3-d hybridization, which show different dependence on the angle. These results indicate a new way to manipulate the spin polarization at organic spinterface.

  8. Three-Dimensional Visualization of Interfacial Phenomena Using Confocal Microscopy

    NASA Astrophysics Data System (ADS)

    Shieh, Ian C.

    Surfactants play an integral role in numerous functions ranging from stabilizing the emulsion in a favorite salad dressing to organizing the cellular components that make life possible. We are interested in lung surfactant, which is a mixture of lipids and proteins essential for normal respiration because it modulates the surface tension of the air-liquid interface of the thin fluid lining in the lungs. Through this surface tension modulation, lung surfactant ensures effortless lung expansion and prevents lung collapse during exhalation, thereby effecting proper oxygenation of the bloodstream. The function of lung surfactant, as well as numerous interfacial lipid systems, is not solely dictated by the behavior of materials confined to the two-dimensional interface. Rather, the distributions of materials in the liquid subphase also greatly influence the performance of interfacial films of lung surfactant. Therefore, to better understand the behavior of lung surfactant and other interfacial lipid systems, we require a three-dimensional characterization technique. In this dissertation, we have developed a novel confocal microscopy methodology for investigating the interfacial phenomena of surfactants at the air-liquid interface of a Langmuir trough. Confocal microscopy provides the excellent combination of in situ, fast, three-dimensional visualization of multiple components of the lung surfactant system that other characterization techniques lack. We detail the solutions to the numerous challenges encountered when imaging a dynamic air-liquid interface with a high-resolution technique like confocal microscopy. We then use confocal microscopy to elucidate the distinct mechanisms by which a polyelectrolyte (chitosan) and nonadsorbing polymer (polyethylene glycol) restore the function of lung surfactant under inhibitory conditions mimicking the effects of lung trauma. Beyond this physiological model, we also investigate several one- and two-component interfacial films

  9. Sinusoidal Forcing of Interfacial Films

    NASA Astrophysics Data System (ADS)

    Rasheed, Fayaz; Raghunandan, Aditya; Hirsa, Amir; Lopez, Juan

    2015-11-01

    Fluid transport, in vivo, is accomplished via pumping mechanisms of the heart and lungs, which results in biological fluids being subjected to oscillatory shear. Flow is known to influence biological macromolecules, but predicting the effect of shear is incomplete without also accounting for the influence of complex interfaces ubiquitous throughout the body. Here, we investigated the oscillatory response of the structure of aqueous interfacial films using a cylindrical knife edge viscometer. Vitamin K1 was used as a model monolayer because its behaviour has been thoroughly quantified and it doesn't show any measurable hysteresis. The monolayer was subjected to sinusoidal forcing under varied conditions of surface concentrations, periodic frequencies, and knife edge amplitudes. Particle Image Velocimetry(PIV) data was collected using Brewster Angle Microscopy(BAM), revealing the influence of oscillatory interfacial shear stress on the monolayer. Insights were gained as to how the velocity profile dampens at specific distances from the knife edge contact depending on the amplitude, frequency, and concentration of Vitamin K1. Supported by NNX13AQ22G, National Aeronautics and Space Administration.

  10. Investigation of multilayered polyelectrolyte thin films by means of refractive index measurements, FT-IR spectroscopy and SEM

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    Multilayered polyelectrolyte films are promising structures in the biomedical field. In order to meet the demands for biomedical applications, the structures have to be built from biocompatible and/or biodegradable, nontoxic starting materials, possessing some specific functional properties, depending on the particular application. In the present study, the multilayered polyelectrolyte films with potential use as buccal bioadhesive drug delivery systems were investigated. They were prepared via layer-by-layer deposition of successive nanolayers onto substrate. Three different biopolymers were used. The substrate, from poly(lactic acid), was solvent casted. After that, it was subjected to corona treatment, which ensures surface charge excess for the multilayer deposition. The nanolayers were prepared either from 0.01 g/L solutions of chitosan or 0.05 g/L xanthan. Acetate buffer (pH 4.5 and ionic strength 1 M) was used as a solvent. The substrate was dipped successively into one of the solutions, allowing formation of polyelectrolyte complexes of chitosan (polycation) and xanthan (polyanion). The substrates was treated in negative corona. The multilayered structures consisted of 8, 9, 14, 15 or 20 nanolayers. Number of techniques, such refractive index measurements, FT- IR spectroscopy and SEM morphology were employed in order to monitor the properties of the so prepared multilayered polyelectrolyte films.

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

    PubMed

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

    2016-06-01

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

  12. Protein-Polyelectrolyte Coacervates: A Novel State of Biomacromolecular Fluids

    NASA Astrophysics Data System (ADS)

    Dubin, P.; Bohidar, H.; Hashizdume, A.; Ké, P.; Bloomfield, V.; Lal, J.; Morishima, Y.; Naumann, C.; Russo, P.; Skobeleva, V.

    2002-03-01

    A challenging problem in complex fluids is the organization and dynamics of charged biopolymers in the highly concentrated intracellular milieu. Proteins with a patchwork of positive and negative charges interact with nucleic acids and membranes that are predominantly negatively charged. The resulting coulombic interactions can lead to both stabilizing repulsions and association or aggregation, depending on a delicate balance of charge density and concentration. We studied the microstructure of a model biocomplex polyelectrolyte formed by pH-induced complexation of serum albumin with the strong polycation PDMDAAC Structure and dynamics are probed using SANS, static and dynamic light scattering, rheology, FRAP, rheology, and TIRF. Optically clear phases ("coacervates") are formed with protein in excess of 200 g/L, concentrations normally not homogeneously sustainable in aqueous solutions but characteristic of those in cells. The solutions display very large shear viscosities, but exhibit protein diffusivities only an order of magnitude below those in dilute protein solution, which explains in part the retention of activity when such coacervates are prepared with enzymes. The results from SANS, LS, FRAP, TIRF and rheology reveal a solution-like state in which homogeneous fluid-like domains coexist with denser and more nearly charge-neutralized domains which inhibit local protein diffusion and confer transient network viscoelasticity.

  13. A multiphasic model for the volume change of polyelectrolyte hydrogels

    NASA Astrophysics Data System (ADS)

    Feng, Ligang; Jia, Yuxi; Chen, Xiliang; Li, Xue; An, Lijia

    2010-09-01

    A multiphasic model for the volume change of polyelectrolyte hydrogels that takes into account conservation of mass and momentum is derived. The gradient of chemical/electrochemical potentials of water and mobile ions is taken as the driving force for the volume change of the polyelectrolyte hydrogel, which is damped by the frictional forces between different phases and balanced by the elastic restoring force of the polymer network. Employing the model constructed here, the free swelling of a spherical polyelectrolyte hydrogel immersed in salt solution is simulated by the finite element method. The simulation shows that the polyelectrolyte hydrogel swells from the surface to the interior when the concentration of the external salt solution decreases. The swelling kinetics for ordinary hydrogels with high frictional coefficient between the polymer network and water is controlled by the collective diffusion of the polymer network, while for fast-response hydrogels it is controlled by the ionic diffusion in the hydrogel.

  14. Nematic ordering in dilute solutions of rodlike polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Potemkin, Igor I.; Khokhlov, Alexei R.

    2004-06-01

    Quantitative theory of orientational behavior of rodlike polyelectrolytes in dilute solution is developed. We find that in salt-free solutions many-body Coulomb interactions between macro- and counterions favor nematic ordering. It is shown that the orientationally isotropic phase of the solution becomes unstable toward nematic ordering at polymer concentration smaller than the overlap concentration. Our predictions are consistent with experimental observations for synthetic polyelectrolytes poly(p-phenylene)sulfonates in aqueous solutions.

  15. Promotion of osteoblast proliferation on complex coacervation-based hyaluronic acid – recombinant mussel adhesive protein coatings on titanium

    PubMed Central

    Hwang, Dong Soo; Waite, J. Herbert; Tirrell, Matthew

    2010-01-01

    Many biological polyelectrolytes are capable of undergoing a fluid–fluid phase separation known as complex coacervation. Coacervates were prepared using hyaluronic acid (HA) and a recombinant fusion protein consisting of mussel adhesive motifs and the RGD peptide (fp-151-RGD). The low interfacial energy of the coacervate was exploited to coat titanium (Ti), a metal widely used in implant materials. The coacervate effectively distributed both HA and fp-151-RGD over the Ti surfaces and enhanced osteoblast proliferation. Approximately half of total fp-151-RGD and HA in the solution transferred to the titanium surface within 2 h. Titanium coated with coacervates having high residual negative surface charge showed the highest cell proliferation of preosteoblast cells (MC-3T3) compared to the treatments tested. Indeed, MC-3T3 cells on complex coacervate coated titanium foils exhibited over 5 times greater cell proliferation than bare, HA coated or fp-151-RGD coated titanium. PMID:19892396

  16. Polyfluorene Electrolytes Interfacial Layer for Efficient Polymer Solar Cells: Controllably Interfacial Dipoles by Regulation of Polar Groups.

    PubMed

    Liu, Huimin; Hu, Lin; Wu, Feiyan; Chen, Lie; Chen, Yiwang

    2016-04-20

    The polar groups in the conjugated polyelectrolytes (CPEs) can create the favorable dipoles at the electrode/active layer interface, which is critical for the CPEs to minimize the interfacial energy barrier in polymer solar cells (PSCs). Herein, a series of CPEs based on poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-co-2,7-(9,9-dioctylfluorene)] derivates (PFNs) (PFN30, PFN50, PFN70, and PFN100) with different mole ratio of polar groups (-N(C2H5)2) were designed and synthesized to investigate the effect of the numbers of polar groups on the interfacial dipoles. Controllably interfacial dipoles could be readily achieved by only tuning the numbers of -N(C2H5)2 in PFNs, as revealed by the work function of the PFNs modified ITO gradually reduced as the loadings of the -N(C2H5)2 increased. In addition, increasing the numbers of -N(C2H5)2 in PFNs were also favorable for developing the smooth and homogeneous morphology of the active layer. As a result, the content of the polar amine in the PFNs exerted great influence on the performance of polymer solar cells. Increasing the numbers of the pendent -N(C2H5)2 could effectively improve the power conversion efficiency (PCE) of the devices. Among these PFNs, PFN100 with the highest content of -N(C2H5)2 polar groups delivered the device with the best PCE of 3.27%. It indicates tailoring the content of the polar groups in the CPEs interlayer is a facial and promising approach for interfacial engineering to developing high performance PSCs.

  17. Solvation and dissociation in weakly ionized polyelectrolytes.

    PubMed

    Onuki, Akira; Okamoto, Ryuichi

    2009-03-26

    We present a Ginzburg-Landau theory of inhomogeneous polyelectrolytes with a polar solvent. First, we take into account the molecular (solvation) interaction among the ions, the charged monomers, the uncharged monomers, and the solvent molecules, together with the electrostatic interaction with a composition-dependent dielectric constant. Second, we treat the degree of ionization as a fluctuating variable dependent on the local electric potential. With these two ingredients included, our results are as follows. (i) We derive a mass reaction law and a general expression for the surface tension. (ii) We calculate the structure factor of the composition fluctuations as a function of various parameters of the molecular interactions, which provides a general criterion of the formation of mesophases. (iii) We numerically examine some typical examples of interfaces and mesophase structures, which strongly depend on the molecular interaction parameters.

  18. Highly Swollen Porous Microstructures in Polyelectrolyte Multilayers

    NASA Astrophysics Data System (ADS)

    Cho, Chungyeon; Kaiser, Jeremy; Zacharia, Nicole

    2011-03-01

    We investigated the creation of porous morphologies from polyelectrolyte multilayers (PEMs) consisting of linear poly(ethylenimine) and poly(acrylic acid), and poly (allylamine hydrochloride) and poly (acrylic acid) as a function of pH and immersion time under post-base assembly treatment. The porous transition is linked to the neutralization of the polycations electrolytes as well as ionization of PAA by the exposing LbL films to high pH. This causes PEMs to undergo spinodal decomposition, creating pores and an increase in film thickness. By using reactive wet stamping technique, we were able to locally cause porosity changes under high pH conditions in the LbL films. Further investigation of the mechanical properties of patterned LbL films was done by performing nano-indentation analysis. The results showed clear difference of physical properties such as hardness and modulus between stamped and unstamped regions based on porous transition.

  19. Effects of carboxylic polyelectrolytes on the growth of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Euvrard, M.; Martinod, A.; Neville, A.

    2011-02-01

    In this paper experimental results are reported on the effects of anionic polyelectrolytes (polyaspartate and polymaleic acid) on the formation of calcium carbonate on a metallic substrate. An experimental procedure which permits the in situ and real-time growth of particles in the micrometric range to be followed was used. By using image analysis, the determination of the morphometric parameters of crystals was done. Jointly, an adsorption study of the polyelectrolytes on calcite was conducted to complement the study of the interactions between polyelectrolytes and crystals. It has been shown that polyaspartate (PASP) and polymaleic acid (PMA) may influence the nucleation/growth process of calcium carbonate. At low concentrations (of about 1×10 -5 mol dm -3), PMA and PASP reduce the surface coverage of deposits on the substrate by decreasing the number of micron size particles and/or the sizes of mineral. When the polyelectrolytes were added after 10 min of the experiment, they significantly decreased the growth rate of the crystals. Following the adsorption of the polyelectrolytes on the submicron size crystals of calcite complements this research. Langmuir isotherms show that PASP and PMA adsorb on calcite suggesting that the polyelectrolytes may block the active sites of growth of crystals.

  20. Adsorption of hydrophobically modified polyelectrolytes at the n-octane/water interface.

    PubMed

    Barraza, R G; Olea, A F; Martinez, F; Ruiz-Tagle, I

    2003-05-15

    The interfacial activity of polyelectrolytes carrying alkyl side chains of different length has been studied. Potassium salts of poly(maleic acid-co-1-olefins), PA-n K2 with n=12 , 14, 16, 18, were synthesized, and the interfacial tension at the aqueous solution/n -octane interface was measured as a function of the length of the alkyl side chain. The results show that the interfacial tension lowering, the limiting excess concentration Gamma (m), and the efficiency of adsorption pC (20) depend on the number of methylene groups in the alkyl side chain. According to Rosen the last two parameters define two different contributions to the standard free energy of adsorption: one arises from the distribution of the polymer between the bulk of the solution and the interface Delta G (dist )(0), and another comes from the configuration adopted at the interface Delta G (int )(0). These free energies were plotted as a function of the number of carbon atoms in the alkyl side chain and a linear relation was found for both of them. From these plots contributions of 0.83 and -0.58 per methylene group were determined for Delta G (0)(dist ) and Delta G (0)(int ), respectively. The positive value for the incremental free energy of distribution is attributed to the formation of a polymer micelle which is stabilized by longer alkyl side chains. On the other hand, the negative value for Delta G (0)(int ) indicates that at the interface the polymer adopts a configuration where the hydrocarbon tail is interacting with the octane molecules.

  1. Iridium Interfacial Stack (IRIS)

    NASA Technical Reports Server (NTRS)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  2. Preferential enhancement of reverse dermal Arthus reaction by polyelectrolytes: in vivo and in vitro evidence for mediation by oxygen-derived radicals and their metabolites

    SciTech Connect

    Ginsberg, I.; Warren, J.S.; Johnson, K.J.; Ward, P.A.

    1986-03-05

    The ability of cationic and anionic polyelectrolytes (polyhistidine, histone, poly-arginine and polyanetholsulfonate) to modulate an acute immune complex (IgG-BSA) mediated inflammatory response was studied. Tissue injury elicited in rats by the reverse dermal Arthus reaction was increased 20-60% by complexing the antibody and polyelectrolye prior to intradermal injection. Intravenous administration of polyethylene glycol-coupled (PEG) superoxide dismutase (4125 U) produced a 30-70% suppression of this tissue injury. PEG-catalase (2000 U) had no suppressive effect. Concomitant in vitro functional studies (enzyme release, O/sub 2//sup -/ and H/sub 2/O/sub 2/ generation and chemiluminescence) of rat neutrophils stimulated with preformed immune complexes modified with polyelectrolytes demonstrated 2-fold increase in O/sub 2//sup -/ generation, modest increases in H/sub 2/O/sub 2/ generation and large increases in chemiluminescence. There was no change in enzyme (..beta..-glucuronidase) secretion. The polyelectrolytes employed in this study did not alter the capacity of preformed IgG-BSA complexes to fix complement. These studies suggest that immune complexes modified with either cationic or anionic polyelectrolytes have increased phlogistic potential that is at least in part mediated by enhanced generation of oxygen-derived metabolites and not by increased enzyme secretion or by increased fixation of complement.

  3. Design and engineering of disulfide crosslinked nanocomplexes of polyamide polyelectrolytes: stability under biorelevant conditions and potent cellular internalization of entrapped model peptide.

    PubMed

    Sharma, Aashish; Kundu, Somanath; Reddy M, Amarendar; Bajaj, Avinash; Srivastava, Aasheesh

    2013-07-01

    Counter polyelectrolytes (PEs) having a degradable polyamide backbone and controlled thiolation are prepared. Their nanosized polyelectrolyte complexes (PECs) spontaneously crosslink under ambient conditions via bioreducible disulfide bonds. These PECs are regenerable after centrifugation, and resist degradation by proteases. They are stable to variations of pH and electrolyte concentration, similar to those encountered in biological milieu. However, they are unraveled in reductive conditions. These PECs act as efficient vectors for delivering entrapped cargo. They entrap with high efficiency, and controllably release, fluorescein isothiocyanate (FITC)-insulin (a model peptide) in vitro. Potent cellular internalization of FITC-insulin within human lung cancer cells with high cell viability is demonstrated.

  4. Osteoconductive Protamine-based Polyelectrolyte Multilayer Functionalized Surfaces

    PubMed Central

    Samuel, Raymond E.; Shukla, Anita; Paik, Daniel H.; Wang, Mary X.; Fang, Jean C.; Schmidt, Daniel J.

    2011-01-01

    The integration of orthopedic implants with host bone presents a major challenge in joint arthroplasty, spinal fusion and tumor reconstruction. The cellular microenvironment can be programmed via implant surface functionalization allowing direct modulation of osteoblast adhesion, proliferation, and differentiation at the implant-bone interface. The development of layer-by-layer assembled polyelectrolyte multilayer (PEM) architectures has greatly expanded our ability to fabricate intricate nanometer to micron scale thin film coatings that conform to complex implant geometries. The in vivo therapeutic efficacy of thin PEM implant coatings for numerous biomedical applications has previously been reported. We have fabricated protamine-based PEM thin films that support the long-term proliferation and differentiation of pre-osteoblast cells on non-cross-linked film coated surfaces. These hydrophilic PEM functionalized surfaces with nanometer-scale roughness facilitated increased deposition of calcified matrix by osteoblasts in vitro, and thus offer the potential to enhance implant integration with host bone. The coatings can make an immediate impact in the osteogenic culture of stem cells and assessment of the osteogenic potential of new therapeutic factors. PMID:21764442

  5. Viscoelastic Nanomechanics of Ionically Cross-linked Polyelectrolyte Networks

    NASA Astrophysics Data System (ADS)

    Han, Biao; Lee, Daeyeon; Han, Lin

    2015-03-01

    Understanding the mechanics of ionic polyelectrolyte networks is critical for applications where nm-to-um mechanics is the key to success. This study aims to reveal the roles of ionic cross-links and fixed charges in the viscoelasticity of layer-by-layer poly(allylamine hydrochloride)/poly(acrylic acid) microfilms, PAH/PAA, a complex held by pH-sensitive amine-carboxyl links. AFM-nanoindentation and force relaxation (tip R =12.5um) was performed at ionic strength(IS) =0.01-1.0M, pH =5.5-2.0 (pKa of PAA =2.3). When pH changes from 5.5 to 2.0, the films swell for 4x from densely linked, net neutral state to loosely linked, positively charged one. A >100x reduction in indentation modulus was observed at all IS, suggesting the dominance of decrease in cross-link density. In most states, more than 90% force relaxation was observed, where cross-link breaking/reformation likely dominates viscoelasticity. However, at pH =2.5 and IS =0.01M, when electrical double layer repulsion is important (Debye length =3nm), relaxation was about 60%, highlighting the contribution of fixed charges. In summary, this study revealed unique viscoelastic behaviors of PAH/PAA due to the pH- and IS-dependent cross-link and charge densities.

  6. Self-Assembly of Polyoxometalate and Polyelectrolyte Macroions into Mechanically Strong Supramolecular Hydrogels

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Zhu, Y. Elaine

    Polyoxometalate (POM) macroions are the nanoclusters of transition metal oxide with size 1-10 nm and well-defined structure at the atom level. Because of their stoichiometric surface groups and high solubility in polar solvents to form thermodynamically stable solution, POMs are studied as excellent model macroions at nanoscale. In this work, we explore the electrostatic controlled self-assembly of anionic POMs and cationic or zwitterionic polyelectrolytes (PEs) in aqueous solution. Specifically we examine the complex formation of zwitterionic poly (3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide) (PSBMA) and cationic poly(diallyldimethylammonium chloride) (PDADMAC) with tungstate based POMs of varied valence. The phase diagram of POM/polyelectrolyte complexes is determined with varied POM/PE charge ratios. It is interesting to observe the coacervation of POMs with PSBMA. With cationic PDADMAC, hybrid POM-PDADMAC hydrogels can be formed. Nevertheless, POM-PDADMAC complexes exhibit much enhanced mechanical properties in comparison to polymer hydrogel. The viscoelastic properties of hybrid macroion complexes strongly depend on PDADMAC concentration, POM-to-PDADMAC molar ratio, the size and valence of POMs. At the intermediate range of POM-to-PDADMAC concentration ratio, shear thickening and strain hardening are observed with soft supramolecular hydrogels, which is resulted from the non-Gaussian stretching of polymer chains.

  7. Aqueous phase behavior of polyelectrolytes with amphiphilic counterions modulated by cyclodextrin: the role of polyion flexibility.

    PubMed

    Carlstedt, Jonas; Bilalov, Azat; Olsson, Ulf

    2012-07-21

    Polyelectrolytes with amphiphilic counterions, PEACs, are water insoluble because the amphiphiles self-assemble into highly charged micelles that strongly associate with the equally highly charged polyions. However, in the presence of water soluble cyclodextrins (CDs) that form inclusion complexes with the amphiphiles and prevent micellization, PEACs become soluble as the dispersed amphiphiles behave essentially as simple monovalent counterions. In this paper, we illustrate, by example, how strongly the ternary phase behavior of PEAC:CD:water depends on the polyion flexibility; for a highly flexible polyion (polyacrylate) the amphiphilic aggregates dictate the phase behavior, whereas a much stiffer polyion (DNA) itself dictates liquid crystalline ordering.

  8. New Ru(II)/Os(II)-polypyridyl complexes for coupling to TiO2 surfaces through acetylacetone functionality and studies on interfacial electron-transfer dynamics.

    PubMed

    Banerjee, Tanmay; Biswas, Abul Kalam; Sahu, Tuhin Subhra; Ganguly, Bishwajit; Das, Amitava; Ghosh, Hirendra Nath

    2014-09-28

    New Ru(ii)- and Os(ii)-polypyridyl complexes have been synthesized with pendant acetylacetone (acac) functionality for anchoring on nanoparticulate TiO2 surfaces with a goal of developing an alternate sensitizer that could be utilized for designing an efficient dye-sensitized solar cell (DSSC). Time-resolved transient absorption spectroscopic studies in the femtosecond time domain have been carried out. The charge recombination rates are observed to be very slow, compared with those for strongly coupled dye molecules having catechol as the anchoring functionality. The results of such studies reveal that electron-injection rates from the metal complex-based LUMO to the conduction band of TiO2 are faster than one would expect for an analogous complex in which the chromophoric core and the anchoring moiety are separated with multiple saturated C-C linkages. Such an observation is rationalized based on computational studies, and a relatively smaller spatial distance between the dye LUMO and the TiO2 surface accounted for this. Results of this study are compared with those for analogous complexes having a gem-dicarboxy group as the anchoring functionality for covalent binding to the TiO2 surface to compare the role of binding functionalities on electron-transfer dynamics.

  9. Intrinsic interfacial phenomena in manganite heterostructures.

    PubMed

    Vaz, C A F; Walker, F J; Ahn, C H; Ismail-Beigi, S

    2015-04-01

    We review recent advances in our understanding of interfacial phenomena that emerge when dissimilar materials are brought together at atomically sharp and coherent interfaces. In particular, we focus on phenomena that are intrinsic to the interface and review recent work carried out on perovskite manganites interfaces, a class of complex oxides whose rich electronic properties have proven to be a useful playground for the discovery and prediction of novel phenomena.

  10. Interfacial chemistry in solvent extraction systems

    SciTech Connect

    Neuman, R.D.

    1993-01-01

    Research this past year continued to emphasize characterization of the physicochemical nature of the microscopic interfaces, i.e., reversed micelles and other association microstructures, which form in both practical and simplified acidic organophosphorus extraction systems associated with Ni, Co, and Na in order to improve on the model for aggregation of metal-extractant complexes. Also, the macroscopic interfacial behavior of model extractant (surfactant) molecules was further investigated. 1 fig.

  11. Interfacial chemistry in solvent extraction systems

    SciTech Connect

    Neuman, R.D.

    1992-01-01

    Research last year emphasized the nature of microscopic interfaces, i. e., reversed micelles and other association microstructures, which form in both practical and simplified acidic organophosphorus extraction systems associated with Ni, Co and Na in order to improve on a recently proposed model for aggregation of metal-extractant complexes. Also, the macroscopic interfacial behavior of extractant molecules and their interactions with metal ions which occur in hydrometallurgical solvent extraction systems were further investigated.

  12. Interfacial instabilities in vibrated fluids

    NASA Astrophysics Data System (ADS)

    Porter, Jeff; Laverón-Simavilla, Ana; Tinao Perez-Miravete, Ignacio; Fernandez Fraile, Jose Javier

    2016-07-01

    Vibrations induce a range of different interfacial phenomena in fluid systems depending on the frequency and orientation of the forcing. With gravity, (large) interfaces are approximately flat and there is a qualitative difference between vertical and horizontal forcing. Sufficient vertical forcing produces subharmonic standing waves (Faraday waves) that extend over the whole interface. Horizontal forcing can excite both localized and extended interfacial phenomena. The vibrating solid boundaries act as wavemakers to excite traveling waves (or sloshing modes at low frequencies) but they also drive evanescent bulk modes whose oscillatory pressure gradient can parametrically excite subharmonic surface waves like cross-waves. Depending on the magnitude of the damping and the aspect ratio of the container, these locally generated surfaces waves may interact in the interior resulting in temporal modulation and other complex dynamics. In the case where the interface separates two fluids of different density in, for example, a rectangular container, the mass transfer due to vertical motion near the endwalls requires a counterflow in the interior region that can lead to a Kelvin-Helmholtz type instability and a ``frozen wave" pattern. In microgravity, the dominance of surface forces favors non-flat equilibrium configurations and the distinction between vertical and horizontal applied forcing can be lost. Hysteresis and multiplicity of solutions are more common, especially in non-wetting systems where disconnected (partial) volumes of fluid can be established. Furthermore, the vibrational field contributes a dynamic pressure term that competes with surface tension to select the (time averaged) shape of the surface. These new (quasi-static) surface configurations, known as vibroequilibria, can differ substantially from the hydrostatic state. There is a tendency for the interface to orient perpendicular to the vibrational axis and, in some cases, a bulge or cavity is induced

  13. Effect of nanoscale patterned interfacial roughness on interfacial toughness.

    SciTech Connect

    Zimmerman, Jonathan A.; Moody, Neville Reid; Mook, William M.; Kennedy, Marian S.; Bahr, David F.; Zhou, Xiao Wang; Reedy, Earl David, Jr.

    2007-09-01

    The performance and the reliability of many devices are controlled by interfaces between thin films. In this study we investigated the use of patterned, nanoscale interfacial roughness as a way to increase the apparent interfacial toughness of brittle, thin-film material systems. The experimental portion of the study measured the interfacial toughness of a number of interfaces with nanoscale roughness. This included a silicon interface with a rectangular-toothed pattern of 60-nm wide by 90-nm deep channels fabricated using nanoimprint lithography techniques. Detailed finite element simulations were used to investigate the nature of interfacial crack growth when the interface is patterned. These simulations examined how geometric and material parameter choices affect the apparent toughness. Atomistic simulations were also performed with the aim of identifying possible modifications to the interfacial separation models currently used in nanoscale, finite element fracture analyses. The fundamental nature of atomistic traction separation for mixed mode loadings was investigated.

  14. Amplified fluorescence sensing of protease activity with conjugated polyelectrolytes

    PubMed Central

    Pinto, Mauricio R.; Schanze, Kirk S.

    2004-01-01

    Fluorescent conjugated polyelectrolytes with pendant ionic sulfonate and carboxylate groups are used to sense protease activity. Inclusion of the fluorescent conjugated polyelectrolyte into the assay scheme leads to amplification of the sensory response. The sensing mechanism relies on an electrostatic interaction between the conjugated polyelectrolyte and a peptide substrate that is labeled with a fluorescence quencher. Enzyme activity and hydrolysis kinetics are measured in real time by using fluorescence spectroscopy. Two approaches are presented. In the first approach, a fluorescence turn-on sensor was developed that is based on the use of p-nitroanilide-labeled peptide substrates. In this system enzyme-catalyzed peptide hydrolysis is signaled by an increase in the fluorescence from the conjugated polyelectrolyte. The turn-on system was used to sense peptidase and thrombin activity when the concentrations of the enzyme and substrate are in the nanomolar regime. Kinetic parameters were recovered from real-time assays. In the second approach, a fluorescence turn-off sensor was developed that relies on a peptide-derivatized rhodamine substrate. In the turn-off system enzyme-catalyzed peptide hydrolysis is signaled by a decrease in the fluorescence intensity of the conjugated polyelectrolyte. PMID:15136727

  15. Amplified fluorescence sensing of protease activity with conjugated polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Pinto, Mauricio R.; Schanze, Kirk S.

    2004-05-01

    Fluorescent conjugated polyelectrolytes with pendant ionic sulfonate and carboxylate groups are used to sense protease activity. Inclusion of the fluorescent conjugated polyelectrolyte into the assay scheme leads to amplification of the sensory response. The sensing mechanism relies on an electrostatic interaction between the conjugated polyelectrolyte and a peptide substrate that is labeled with a fluorescence quencher. Enzyme activity and hydrolysis kinetics are measured in real time by using fluorescence spectroscopy. Two approaches are presented. In the first approach, a fluorescence turn-on sensor was developed that is based on the use of p-nitroanilide-labeled peptide substrates. In this system enzyme-catalyzed peptide hydrolysis is signaled by an increase in the fluorescence from the conjugated polyelectrolyte. The turn-on system was used to sense peptidase and thrombin activity when the concentrations of the enzyme and substrate are in the nanomolar regime. Kinetic parameters were recovered from real-time assays. In the second approach, a fluorescence turn-off sensor was developed that relies on a peptide-derivatized rhodamine substrate. In the turn-off system enzyme-catalyzed peptide hydrolysis is signaled by a decrease in the fluorescence intensity of the conjugated polyelectrolyte.

  16. Ion transferring in polyelectrolyte networks in electric fields

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

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

    2016-11-04

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

  18. Calorimetric determination of surfactant/polyelectrolyte binding isotherms.

    PubMed

    Lapitsky, Yakov; Parikh, Maider; Kaler, Eric W

    2007-07-26

    Mixing of oppositely charged surfactants and polyelectrolytes in aqueous solutions leads to cooperative surfactant adsorption onto the polyelectrolyte chains. Experimental determination of surfactant/polyelectrolyte binding isotherms is usually done using custom-built surfactant-ion-specific electrodes. As an alternative, we present an indirect isotherm approximation method that uses conventional isothermal titration calorimetry (ITC). The calorimetric data is fitted to the two-binding-state Satake-Yang adsorption model, which quantifies the extent of binding in terms of the binding constant (Ku) and the cooperativity parameter (u). This approach is investigated using two surfactant/polyelectrolyte mixtures: sodium perfluorooctanoate (FC7) and N,N,N-trimethylammonium derivatized hydroxyethyl cellulose (UCARE Polymer JR-400), whose binding behavior follows the Satake-Yang model, and dodecyltrimethylammonium bromide (DTAB) and poly(styrenesulfonate) (NaPSS), whose behavior deviates dramatically from the Satake-Yang model. These studies demonstrate that, in order to apply the indirect ITC method of binding isotherm determination, the surfactant/polyelectrolyte adsorption process must have no more than two dominant binding states. Thus, the technique works well for the FC7/JR-400 mixture. It fails in the case of the DTAB/NaPSS adsorption, but its mode of failure offers insight into the multiple-binding-state adsorption mechanism.

  19. Preparation of polyelectrolytes for wastewater treatment.

    PubMed

    Radoiu, Marilena T; Martin, Diana I; Calinescu, Ioan; Iovu, Horia

    2004-01-02

    Liquid-phase polymerisation of acrylamide-acrylic acid to form polyelectrolytes used in wastewater cleaning was examined using accelerated electron beam and microwave irradiation methods. Polymerisation was carried out in aqueous solutions at temperatures approximately 60 degrees C. Monomers total concentration was established at 40% (36% acrylamide and 4% acrylic acid). Only using the features of simultaneous radiation-induction and microwave heating can result in the formation of linear polymer chains with good water solubility and low residual monomer concentration. The flocculation capacity of the obtained polymers was tested using two wastewaters, one sampled from a slaughterhouse and the other from a vegetable oil plant. Quality indicators such as total suspended matters (TSM), chemical oxygen demand (COD), biological oxygen demand (BOD) and fat, oils and grease (FOG) were measured before and after the treatment with polymeric flocculants and compared with the results obtained in classical treatment with Al(2)(SO(4))(3). It was found that the combined treatment with polymers and Al(2)(SO(4))(3) increases the degree of purification of both wastewaters up to 99%.

  20. Macroion induced dehydration of weak polyelectrolyte brushes

    NASA Astrophysics Data System (ADS)

    Zheng, Zhongli; Zhu, Y. Elaine

    2014-03-01

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

  1. Immobilization of enzyme on chiral polyelectrolyte surface.

    PubMed

    Ding, Chao; Sun, Hanjun; Ren, Jinsong; Qu, Xiaogang

    2017-02-01

    Chiral D- and L-N-acryloyl aspartic acid (NAsp) polyelectrolyte (PE) surfaces with similar chemical compositions and physical properties but opposite chirality are designed for enzyme immobilization. Enzymes immobilized onto the chiral PE surfaces present high chiral preference, namely L-NAsp PE surface can keep most of the catalytic activity of the immobilized enzymes, however, for enzymes immobilized on D-NAsp PE surface a large decrease in catalytic activity occurred which was 11 times lower compared with L-NAsp PE surface. This phenomenon of chiral effect on enzymes immobilization can be explained by attenuated total reflectance (ATR) and circular dichroism (CD) results. The results exhibited that L-NAsp PE surface could preserve most of the secondary structures of immobilized enzymes while on D-NAsp PE surface with a large conformation alteration. These chiral surface induced differences after enzyme immobilization can be further used for logic operation. These results imply a novel strategy for the design of new enzymes immobilization materials based on the chiral effect and expand the applications of enzymes in biochips, chemical transformations and chiral biodevices.

  2. Antibacterial polyelectrolyte micelles for coating stainless steel.

    PubMed

    Falentin-Daudré, Céline; Faure, Emilie; Svaldo-Lanero, Tiziana; Farina, Fabrice; Jérôme, Christine; Van De Weerdt, Cécile; Martial, Joseph; Duwez, Anne-Sophie; Detrembleur, Christophe

    2012-05-08

    In this study, we report on the original synthesis and characterization of novel antimicrobial coatings for stainless steel by alternating the deposition of aqueous solutions of positively charged polyelectrolyte micelles doped with silver-based nanoparticles with a polyanion. The micelles are formed by electrostatic interaction between two oppositely charged polymers: a polycation bearing 3,4-dihydroxyphenylalanine units (DOPA, a major component of natural adhesives) and a polyanion (poly(styrene sulfonate), PSS) without using any block copolymer. DOPA units are exploited for their well-known ability to anchor to stainless steel and to form and stabilize biocidal silver nanoparticles (Ag(0)). The chlorine counteranion of the polycation forms and stabilizes biocidal silver chloride nanoparticles (AgCl). We demonstrate that two layers of micelles (alternated by PSS) doped with silver particles are enough to impart to the surface strong antibacterial activity against gram-negative E. coli. Moreover, micelles that are reservoirs of biocidal Ag(+) can be easily reactivated after depletion. This novel water-based approach is convenient, simple, and attractive for industrial applications.

  3. Modeling of Polyelectrolyte Adsorption from Micellar Solutions onto Biomimetic Substrates.

    PubMed

    Banerjee, Soumi; Cazeneuve, Colette; Baghdadli, Nawel; Ringeissen, Stéphanie; Léonforte, Fabien; Leermakers, Frans A M; Luengo, Gustavo S

    2017-09-21

    Depositing cationic polyelectrolytes (PEs) from micellar solutions that include surfactants (SU) onto surfaces is a rich, complex, highly relevant, and challenging topic that covers a broad field of practical applications (e.g., from industrial to personal care). The role of the molecular architecture of the constituents of the PEs are often overruled, or at least and either, underestimated in regard to the surface properties. In this work, we aim to evaluate the effect of a model biomimetic surface that shares the key characteristics of the extreme surface of hair and its concomitant chemo- and physisorbed properties onto the deposition of a complex PEs:SU system. To tackle out the effect of the molecular architecture of the PEs, we consider (i) a purely linear and hydrophilic PE (P100) and (ii) a PE with lateral amphiphilic chains (PegPE). Using numerical self-consistent field calculations, we show that the architecture of the constituents interfere with the surface properties in a nonintuitive way such that, depending on the amphiphilicity and hydrophilicity of the PEs and the hydrophobicity of the surface, a re-entrant adsorbing transition can be observed, the lipid coverage of the model hair surface being the unique control parameter. Such a behavior is rationalized by the anticooperative associative properties of the coacervate micelles in solution, which is also controlled by the architecture of the PEs and SU. We now expect that PEs adsorption, as a rule, is governed by the molecular details of the species in solution as well as the surface specificities. We emphasize that molecular realistic modeling is essential to rationalize and optimize the adsorption process of, for example, polymer conditioning agents in water-rinsed cosmetic or textile applications.

  4. The evolution of cyclopropenium ions into functional polyelectrolytes

    PubMed Central

    Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; Brucks, Spencer D.; Killops, Kato L.; Bandar, Jeffrey S.; Torsitano, Christopher; Balsara, Nitash P.; Lambert, Tristan H.; Campos, Luis M.

    2015-01-01

    Versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion. We demonstrate the facile synthesis of a series of polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. The materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes. PMID:25575214

  5. The evolution of cyclopropenium ions into functional polyelectrolytes

    SciTech Connect

    Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; Brucks, Spencer D.; Killops, Kato L.; Bandar, Jeffrey S.; Torsitano, Christopher; Balsara, Nitash P.; Lambert, Tristan H.; Campos, Luis M.

    2015-01-09

    We report that versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion.We demonstrate the facile synthesis of a series of polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. In conclusion, the materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes.

  6. Electrochemical mechanism of ion current rectification of polyelectrolyte gel diodes.

    PubMed

    Yamamoto, Tetsuya; Doi, Masao

    2014-06-17

    Polyelectrolyte gel diodes that are double layers of two oppositely charged polyelectrolyte gels, sandwiched by two symmetric electrodes, are emergent ionic devices. These diodes are designed to rectify ion currents with a physical mechanism that is analogous to conventional semiconductor diodes-the asymmetry in the permeability of ions across the interfaces between the two oppositely charged gels. Here we show that polyelectrolyte gel diodes indeed rectify steady currents with a physical mechanism that is very different from conventional diodes by using a simple electrochemical model; electric currents are limited by electrochemical reactions that are driven by potential drops at electrodes and these potential drops markedly change with changing the direction of applied voltages due to the redistribution of non-reactive counterions, leading to rectified ion currents. This concept is relatively generic and thus may provide insight in the physics of analogous ionic and biomimetic systems that show electrochemical reactions.

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

    PubMed

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

    2010-06-01

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

  8. An Invisible Bend Sensor Based on Porous Crosslinked Polyelectrolyte Film

    SciTech Connect

    Zhang, Q.; Saraf, Laxmikant V.; Smith, James R.; Jha, P.; Hua, Feng

    2009-04-29

    This paper describes the fabrication of a porous cross-linked polyelectrolyte membrane and the characterization of its humidity sensitivity performance. Electrostatic self-assembly, combined with acid treatment, and post-deposition annealing produced the membrane. The fabrication process offers the ability to control the thickness of the membrane, as well as enabling the engineering of the humidity sensitivity properties. A transparent humidity sensor was fabricated by integrating the membrane into a capacitive structure. In order to improve the moisture absorption and diffusion, both the polyelectrolyte layer and the electrode were made porous. The membrane was cross-linked to enhance the durability in high humid environments. Such a polyelectrolyte membrane showed high sensitivity to relative humidity variation over a range of 25-99%. The see-through property of the structure adds extra features and benefits to the sensor.

  9. Transparent Humidity Sensor Using Cross-Linked Polyelectrolyte Membrane

    SciTech Connect

    Zhang, Q.; Smith, James R.; Saraf, Laxmikant V.; Hua, Feng

    2009-07-02

    This paper describes the fabrication of a porous cross-linked polyelectrolyte membrane and the characterization of its humidity sensitivity performance. Electrostatic self-assembly, combined with acid treatment, and post-deposition annealing produced the membrane. The fabrication process offers the ability to control the thickness of the membrane, as well as enabling the engineering of the humidity sensitivity properties. A transparent humidity sensor was fabricated by integrating the membrane between two parallel electrodes. In order to improve the moisture absorption and diffusion, both the polyelectrolyte layer and the electrode were made porous. The membrane was cross-linked to enhance the durability in high humid environments. Such a polyelectrolyte membrane showed high sensitivity to relative humidity variation over a range of 25%–99%. The see-through property of the structure adds extra features and benefits to the sensor.

  10. Correlating the compliance and permeability of photocrosslinked polyelectrolyte multilayers

    PubMed Central

    Lehaf, Ali M.; Moussallem, Maroun D.; Schlenoff, Joseph B.

    2011-01-01

    Photocrosslinkable polyelectrolyte multilayers were made from poly(allylamine), PAH and poly(acrylic acid), PAA, modified with a photosensitive benzophenone. Nanoindentation, using atomic force microscopy, AFM, of these and unmodified PAH/PAA multilayers was used to assess their mechanical properties in situ under aqueous buffer. Under the conditions employed (and a 20 nm AFM radius tip) reliable nanoindentations that appeared to be decoupled from the properties of the silicon substrate were obtained for films greater than 150 nm in thickness. A strong difference in apparent modulus was observed for films terminated with positive as compared to negative polyelectrolyte. Films terminated with PAA were more glassy, suggesting better charge matching of polyelectrolytes. Multilayers irradiated up to 100 minutes showed a smooth and controlled increase in modulus, with little change in water contact angle. The permeability to iodide ion, measured electrochemically, also decreased in a controlled fashion PMID:21443175

  11. The evolution of cyclopropenium ions into functional polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; Brucks, Spencer D.; Killops, Kato L.; Bandar, Jeffrey S.; Torsitano, Christopher; Balsara, Nitash P.; Lambert, Tristan H.; Campos, Luis M.

    2015-01-01

    Versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion. We demonstrate the facile synthesis of a series of polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. The materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes.

  12. Microcapsule Buckling Triggered by Compression-Induced Interfacial Phase Change.

    PubMed

    Salmon, Andrew Roy; Parker, Richard M; Groombridge, Alexander S; Maestro, Armando; Coulston, Roger J; Hegemann, Jonas; Kierfeld, Jan; Scherman, Oren A; Abell, Chris

    2016-10-04

    There is an emerging trend towards the fabrication of microcapsules at liquid interfaces. In order to control the parameters of such capsules, the interfacial processes governing their formation must be understood. Here, poly(vinyl alcohol) films are assembled at the interface of water-in-oil microfluidic droplets. The polymer is cross-linked using cucurbit[8]uril ternary supramolecular complexes. It is shown that compression-induced phase change causes the onset of buckling in the interfacial film. On evaporative compression, the interfacial film both increases in density and thickens, until it reaches a critical density and a phase change occurs. We show that this increase in density can be simply related to the film Poisson ratio and area compression. This description captures fundamentals of many compressive interfacial phase changes and can also explain the observation of a fixed thickness-to-radius ratio at buckling, (T/R)buck.

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

    SciTech Connect

    Hoffmann, Ingo; Farago, Bela; Schweins, Ralf; Falus, Peter; Sharp, Melissa; Prévost, Sylvain; Gradzielski, Michael

    2015-08-21

    the dynamics especially of the polyelectrolyte within the complexes.

  14. Towards a Modeling Framework for Thermodynamics and Transport Coefficients in Polyelectrolyte Assemblies

    NASA Astrophysics Data System (ADS)

    Larson, Ronald; Salehi, Ali

    A continuum description of polyelectrolyte (PE) equilibrium gelation, and the kinetics of assembly is developed, accounting for PE chain diffusion, complexation, network relaxation is reported here. Using a combination of Flory-Huggins and Flory-Rehner free energy model, an upper-convected Maxwell model to describe polyelectrolyte gel stress and relaxation, and a Poisson equation for the electrostatic potential profiles, we develop a model that can account for both equilibrium properties of PE gels and for transport of PE's and ions during layer-by-layer assembly. As PE chains diffuse, counterions readjust themselves to minimize the net local charge, but fail to do so completely as they would have to pay a significant entropic penalty. Diffusion of PE chains predominantly driven by the electrostatic field induced by the entropy of counterions is characterized by pulse-like PE composition profiles. Even without considering chain complexation, we demonstrate that it is possible to at least qualitatively explain the non-monotonic variation of PEM growth kinetics versus salt concentration, observed experimentally.

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

    PubMed

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

    2011-02-14

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

  16. Radius of gyration and intrinsic viscosity of polyelectrolyte solutions

    SciTech Connect

    Milas, M.; Borsali, R.; Rinaudo, M.

    1993-12-31

    Relatively low molecular weights polyelectrolytes (10{sup 4}-10{sup 6}) behave as worm-like chain when electrostatic repulsions are assumed to govern the excluded volume parameter. Under such conditions, predictions of chain expansion and effect of polyelectrolyte concentrations are made assuming that unperturbed dimensions could be obtained at infinite salt content. Experimental studies of an ionic polysaccharide, namely the Na-hyaluronate, were done and the values obtained for the radius of gyration as well as the intrinsic viscosity at different charge densities are in good agreement with the predictions.

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

    SciTech Connect

    Schanze, Kirk S

    2014-08-05

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

  18. Effect of dielectric discontinuity on a spherical polyelectrolyte brush.

    PubMed

    Tergolina, Vinicius B; Dos Santos, Alexandre P

    2017-09-21

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

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

    PubMed

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

    2014-01-01

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

  20. Mechanobiology of interfacial growth

    NASA Astrophysics Data System (ADS)

    Ciarletta, P.; Preziosi, L.; Maugin, G. A.

    2013-03-01

    A multiscale analysis integrating biomechanics and mechanobiology is today required for deciphering the crosstalk between biochemistry, geometry and elasticity in living materials. In this paper we derive a unified thermomechanical theory coupling growth processes with mass transport phenomena across boundaries and/or material interfaces. Inside a living system made by two contiguous bodies with varying volumes, an interfacial growth mechanism is considered to force fast but continuous variations of the physical fields inside a narrow volume across the material interface. Such a phenomenon is modelled deriving homogenized surface fields on a growing non-material discontinuity, possibly including a singular edge line. A number of balance laws is derived for imposing the conservation of the thermomechanical properties of the biological system. From thermodynamical arguments we find that the normal displacement of the non-material interface is governed by the jump of a new form of material mechanical-energy flux, also involving the kinetic energies and the mass fluxes. Furthermore, the configurational balance indicates that the surface Eshelby tensor is the tangential stress measure driving the material inhomogeneities on the non-material interface. Accordingly, stress-dependent evolution laws for bulk and interfacial growth processes are derived for both volume and surface fields. The proposed thermomechanical theory is finally applied to three biological system models. The first two examples are focused on stress-free growth problems, concerning the morphogenesis of animal horns and of seashells. The third application finally deals with the stress-driven surface evolution of avascular tumours with heterogeneous structures. The results demonstrate that the proposed theory can successfully model those biological systems where growth and mass transport phenomena interact at different length-scales. Coupling biological, mechanical and geometrical factors, the proposed

  1. Nanometer-thick lateral polyelectrolyte micropatterns induce macrosopic electro-osmotic chaotic fluid instabilities

    NASA Astrophysics Data System (ADS)

    Wessling, M.; Morcillo, L. Garrigós; Abdu, S.

    2014-03-01

    Electro-convective vortices in ion concentration polarization under shear flow have been of practical relevance for desalination processes using electrodialysis. The phenomenon has been scientifically disregarded for decades, but is recently embraced by a growing fluid dynamics community due its complex superposition of multi-scale gradients in electrochemical potential and space charge interacting with emerging complex fluid momentum gradients. While the visualization, quantification and fundamental understanding of the often-chaotic fluid dynamics is evolving rapidly due to sophisticated simulations and experimentation, little is known whether these instabilities can be induced and affected by chemical topological heterogeneity in surface properties. In this letter, we report that polyelectrolyte layers applied as micropatterns on ion exchange membranes induce and facilitate the electro-osmotic fluid instabilities. The findings stimulate a variety of fundamental questions comparable to the complexity of today's turbulence research.

  2. Nanometer-thick lateral polyelectrolyte micropatterns induce macrosopic electro-osmotic chaotic fluid instabilities

    PubMed Central

    Wessling, M.; Morcillo, L. Garrigós; Abdu, S.

    2014-01-01

    Electro-convective vortices in ion concentration polarization under shear flow have been of practical relevance for desalination processes using electrodialysis. The phenomenon has been scientifically disregarded for decades, but is recently embraced by a growing fluid dynamics community due its complex superposition of multi-scale gradients in electrochemical potential and space charge interacting with emerging complex fluid momentum gradients. While the visualization, quantification and fundamental understanding of the often-chaotic fluid dynamics is evolving rapidly due to sophisticated simulations and experimentation, little is known whether these instabilities can be induced and affected by chemical topological heterogeneity in surface properties. In this letter, we report that polyelectrolyte layers applied as micropatterns on ion exchange membranes induce and facilitate the electro-osmotic fluid instabilities. The findings stimulate a variety of fundamental questions comparable to the complexity of today's turbulence research. PMID:24598972

  3. Ultrafast active mixer using polyelectrolytic ion extractor.

    PubMed

    Chun, Honggu; Kim, Hee Chan; Chung, Taek Dong

    2008-05-01

    We report on a low voltage, straight/smooth surface, and efficient active micromixer. The mixing principle is based on alternative ion depletion-enrichment using a pair of positively charged polyelectrolytic gel electrodes (pPGEs), which face each other joined by a microchannel. This system has an external AC signal source electrically connected to the pPGEs via the respective 1 M KCl solutions and Ag/AgCl electrodes. When an electric bias is applied between the two pPGEs, anions are extracted through one of the pPGEs to create a local ion-deficient region. Simultaneously, an ion-rich area appears near the other pPGE due to an inward anionic flux. As the direction of the charge flow is periodically reversed by the AC signal source, the ion depletion-enrichment regions are alternately swapped with each other on the 'push-pull' basis. The turmoil between the pPGEs quickly mixes the solutions in the microchannel without any mechanical moving part or specially machined structures. In the proposed system, both AC frequency and current density can be easily and finely controlled so that one can quickly find the optimal conditions for a given sample. The micromixer as made showed a mixing efficiency higher than 90% for sample solutions of 1 mM Rhodamine 6G and PBS at pH 7.4 when the flow rate was under 6 mm s(-1). In addition to the solution-solution mixing, the micromixer can effectively mix suspended microparticles with solution. As a representative example, rapid and efficient lysis of human red blood cells was demonstrated allowing minimal damage of the white blood cells.

  4. Amplified quenching of a conjugated polyelectrolyte by cyanine dyes.

    PubMed

    Tan, Chunyan; Atas, Evrim; Müller, Jürgen G; Pinto, Mauricio R; Kleiman, Valeria D; Schanze, Kirk S

    2004-10-27

    The conjugated polyelectrolyte PPESO3 features a poly(phenylene ethynylene) backbone substituted with anionic 3-sulfonatopropyloxy groups. PPESO3 is quenched very efficiently (KSV > 10(6) M(-1)) by cationic energy transfer quenchers in an amplified quenching process. In the present investigation, steady-state and picosecond time-resolved fluorescence spectroscopy are used to examine amplified quenching of PPESO3 by a series of cyanine dyes via singlet-singlet energy transfer. The goal of this work is to understand the mechanism of amplified quenching and to characterize important parameters that govern the amplification process. Steady-state fluorescence quenching of PPESO3 by three cationic oxacarbocyanine dyes in methanol solution shows that the quenching efficiency does not correlate with the Forster radius computed from spectral overlap of the PPESO3 fluorescence with the cyanines' absorption. The quenching efficiency is controlled by the stability of the polymer-dye association complex. When quenching studies are carried out in water where PPESO3 is aggregated, changes observed in the absorption and fluorescence spectra of 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HMIDC) indicate that the polymer templates the formation of a J-aggregate of the dye. The fluorescence dynamics in the PPESO3/HMIDC system were probed by time-resolved upconversion and the results show that PPESO3 to HMIDC energy transfer occurs on two distinctive time scales. At low HMIDC concentration, the dynamics are dominated by an energy transfer pathway with a time scale faster than 4 ps. With increasing HMIDC concentration, an energy pathway with a time scale of 0.1-1 ns is active. The prompt pathway (tau < 4 ps) is attributed to quenching of delocalized PPESO3 excitons created near the HMIDC association site, whereas the slow phase is attributed to intra- and interchain exciton diffusion to the HMIDC. Copyright 2004 American Chemical Society

  5. New polyelectrolyte complex from pectin/chitosan and montmorillonite clay.

    PubMed

    da Costa, Marcia Parente Melo; de Mello Ferreira, Ivana Lourenço; de Macedo Cruz, Mauricio Tavares

    2016-08-01

    A new nanocomposite hydrogel was prepared by forming a crosslinked hybrid polymer network based on chitosan and pectin in the presence of montmorillonite clay. The influence of clay concentration (0.5 and 2% wt) as well as polymer ratios (1:1, 1:2 and 2:1) was investigated carefully. The samples were characterized by different techniques: transmission and scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, swelling degree and compression test. Most samples presented swelling degree above 1000%, which permits characterizing them as superabsorbent material. Images obtained by transmission electron microscopy showed the presence of clay nanoparticles into hydrogel. The hydrogels' morphological properties were evaluated by scanning electron microscope in high and low-vacuum. The micrographs showed that the samples presented porous. The incorporation of clay produced hydrogels with differentiated morphology. Thermogravimetric analysis results revealed that the incorporation of clay in the samples provided greater thermal stability to the hydrogels. The compression resistance also increased with addition of clay.

  6. Interfacial gauge methods for incompressible fluid dynamics

    PubMed Central

    Saye, Robert

    2016-01-01

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of “gauge freedom” to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work, high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena. PMID:27386567

  7. Interfacial gauge methods for incompressible fluid dynamics.

    PubMed

    Saye, Robert

    2016-06-01

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of "gauge freedom" to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work, high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena.

  8. Interfacial gauge methods for incompressible fluid dynamics

    DOE PAGES

    Saye, R.

    2016-06-10

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of "gauge freedom" to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work,more » high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena.« less

  9. Interfacial gauge methods for incompressible fluid dynamics

    SciTech Connect

    Saye, R.

    2016-06-10

    Designing numerical methods for incompressible fluid flow involving moving interfaces, for example, in the computational modeling of bubble dynamics, swimming organisms, or surface waves, presents challenges due to the coupling of interfacial forces with incompressibility constraints. A class of methods, denoted interfacial gauge methods, is introduced for computing solutions to the corresponding incompressible Navier-Stokes equations. These methods use a type of "gauge freedom" to reduce the numerical coupling between fluid velocity, pressure, and interface position, allowing high-order accurate numerical methods to be developed more easily. Making use of an implicit mesh discontinuous Galerkin framework, developed in tandem with this work, high-order results are demonstrated, including surface tension dynamics in which fluid velocity, pressure, and interface geometry are computed with fourth-order spatial accuracy in the maximum norm. Applications are demonstrated with two-phase fluid flow displaying fine-scaled capillary wave dynamics, rigid body fluid-structure interaction, and a fluid-jet free surface flow problem exhibiting vortex shedding induced by a type of Plateau-Rayleigh instability. The developed methods can be generalized to other types of interfacial flow and facilitate precise computation of complex fluid interface phenomena.

  10. Electrophoresis of DNA and other polyelectrolytes: Physical mechanisms

    NASA Astrophysics Data System (ADS)

    Viovy, Jean-Louis

    2000-07-01

    The dramatic recent advances in molecular biology, which have opened a new era in medicine and biotechnology, rely on improved techniques to study large molecules. Electrophoresis is one of the most important of these. Separation of DNA by size, in particular, is at the heart of genome mapping and sequencing and is likely to play an increasing role in diagnosis. This article reviews, from the point of view of a physicist, the mechanisms responsible for electrophoretic separation of polyelectrolytes. This separation is mainly performed in gels, and a wide variety of migration mechanisms can come into play, depending on the polyelectrolyte's architecture, on the electric fields applied, and on the properties of the gel. After a brief review of the thermodynamic and electrohydrodynamic principles relating to polyelectrolyte solutions, the author treats the phenomenology of electrophoresis and describes the conceptual and theoretical tools in the field. The reptation mechanisms, by which large flexible polyelectrolytes thread their way through the pores of the gel matrix, play a prominent role. Biased reptation, the extension of this model to electrophoresis, provides a very intuitive framework within which numerous physical ideas can be introduced and discussed. It has been the most popular theory in this domain, and it remains an inspiring concept for current development. There have also been important advances in experimental techniques such as single-molecule viodeomicroscopy and the development of nongel separation media and mechanisms. These, in turn, form the basis for fast-developing and innovative technologies like capillary electrophoresis, electrophoresis on microchips, and molecular ratchets.

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

    NASA Astrophysics Data System (ADS)

    Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

    2011-03-01

    The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

  12. Super-stoichiometric charge neutralization in particle-polyelectrolyte systems.

    PubMed

    Kleimann, Jörg; Gehin-Delval, Cécile; Auweter, Helmut; Borkovec, Michal

    2005-04-12

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

  13. Splaying hyperthin polyelectrolyte multilayers to increase their gas permeability.

    PubMed

    Yi, Song; Lin, Cen; Regen, Steven L

    2015-01-28

    The concept of splayed, hyperthin polyelectrolyte multilayers (PEMs) is introduced in which a bulky, hydrophilic and charged pendant group is used to increase the gas permeability of a PEM without reducing its permeation selectivity. Proof of principle studies are reported using nm-thick PEMs made from poly(sodium 4-styrene sulfonate) () and poly(allylamine hydrochloride) () bearing bulky cobaltocenium ions.

  14. Theory of competitive counterion adsorption on flexible polyelectrolytes: divalent salts.

    PubMed

    Kundagrami, Arindam; Muthukumar, M

    2008-06-28

    The counterion distribution around an isolated flexible polyelectrolyte in the presence of a divalent salt is evaluated using the adsorption model [M. Muthukumar, J. Chem. Phys. 120, 9343 (2004)] that considers the Bjerrum length, salt concentration, and local dielectric heterogeneity as physical variables in the system. Self-consistent calculations of effective charge and size of the polymer show that divalent counterions replace condensed monovalent counterions in competitive adsorption. The theory further predicts that at modest physical conditions for a flexible polyelectrolytes such as sodium polystyrene sulfonate in aqueous solutions polymer charge is compensated and reversed with increasing divalent salt. Consequently, the polyelectrolyte shrinks and reswells. Lower temperatures and higher degrees of dielectric heterogeneity between chain backbone and solvent enhance condensation of all species of ions. Complete diagrams of states for the effective charge calculated as functions of the Coulomb strength and salt concentration suggest that (a) overcharging requires a minimum Coulomb strength and (b) progressively higher presence of salt recharges the polymer due to either electrostatic screening (for low Coulomb strengths) or coion condensation (for high Coulomb strengths). Consideration of ion-bridging by divalent counterions leads to a first-order collapse of polyelectrolytes in modest presence of divalent salts and at higher Coulomb strengths. The authors' theoretical predictions are in agreement with the generic results from experiments and simulations.

  15. Observation of Molecular Diffusion in Polyelectrolyte-Wrapped SERS Nanoprobes

    PubMed Central

    2015-01-01

    The popularity of nanotechnology-based sensing technologies has rapidly expanded within the past decade. Surface-enhanced Raman spectroscopy (SERS) is one such technique capable of chemically specific and highly sensitive measurements. The careful preparation of SERS-active nanoprobes is immensely vital for biological applications where nanoprobes are exposed to harsh ionic and protein rich microenvironments. Encapsulation of optical reporter molecules via layer-by-layer (LbL) polyelectrolyte wrapping is an emerging technique that also permits facile modification of surface chemistry and charge. LbL wrapping can be performed within a few hours and does not require the use of organic solvents or hazardous silanes. Nonetheless, the stability of its products requires further characterization and analysis. In this study, Raman-active methylene blue molecules were electrostatically encapsulated within alternating layers of cationic and anionic polyelectrolytes surrounding gold nanospheres. We observed molecular diffusion of methylene blue through polyelectrolyte layers by monitoring the change in SERS intensity over a period of more than 5 weeks. To minimize diffusion and improve the long-term storage stability of our nanoprobes, two additional nanoprobe preparation techniques were performed: thiol coating and cross-linking of the outer polyelectrolyte layer. In both cases, molecular diffusion is significantly diminished. PMID:24998291

  16. Titration of hydrophobic polyelectrolytes using Monte Carlo simulations.

    PubMed

    Ulrich, Serge; Laguecir, Abohachem; Stoll, Serge

    2005-03-01

    The conformation and titration curves of weak (or annealed) hydrophobic polyelectrolytes have been examined using Monte Carlo simulations with screened Coulomb potentials in the grand canonical ensemble. The influence of the ionic concentration pH and presence of hydrophobic interactions has been systematically investigated. A large number of conformations such as extended, pearl-necklace, cigar-shape, and collapsed structures resulting from the subtle balance of short-range hydrophobic attractive interactions and long-range electrostatic repulsive interactions between the monomers have been observed. Titration curves were calculated by adjusting the pH-pK(0) values (pK(0) represents the intrinsic dissociation constant of an isolated monomer) and then calculating the ionization degree alpha of the polyelectrolyte. Important transitions related to cascades of conformational changes were observed in the titration curves, mainly at low ionic concentration and with the presence of strong hydrophobic interactions. We demonstrated that the presence of hydrophobic interactions plays an important role in the acid-base properties of a polyelectrolyte in promoting the formation of compact conformations and hence decreasing the polyelectrolyte degree of ionization for a given pH-pK(0) value.

  17. [The electrostatic contribution to interactions of some enzymes with polyelectrolytes].

    PubMed

    Saburova, E A; Dybovskaia, Iu N; Sivezhelezov, V S; Elfamova, L I

    2005-01-01

    To explain the inhibitory action of polyelectrolytes on enzymes and, in particular, to define potentially reactive zones for the binding of polyelectrolyte, the electric potential of enzymes lactate dehydrogenase and glutamate dehydrogenase was calculated using the solution of the Poisson-Boltzmann equation by a numerical method with the use of the Gauss-Seidel relaxation method at three pH values: 6.5, 7.0, and 8.0 and three values of ionic strength: 50, 100, and 150 mm. On the basis of these calculations and their visualization, representative sites for favorable binding of polyanions were determined as extended areas on the surface of proteins with the positive potential in the neutral pH region. It was shown that there is a correlation between the area of positive potential and the efficiency of enzyme inactivation for a number of pH values and concentrations of salt for two enzymes. The calculations performed allowed one to explain the inhibitory action of polyelectrolytes on the specified enzymes to understand the difference between the values of polyelectrolyte inactivation constants for the two enzymes and estimate the minimal areas of the positive potential on the protein surface that provide their effective inhibition.

  18. Electrostatics and charge regulation in polyelectrolyte multilayered assembly.

    PubMed

    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.

  19. Structure and dynamics of polyelectrolyte surfactant mixtures under conditions of surfactant excess

    NASA Astrophysics Data System (ADS)

    Hoffmann, Ingo; Simon, Miriam; Farago, Bela; Schweins, Ralf; Falus, Peter; Holderer, Olaf; Gradzielski, Michael

    2016-09-01

    Oppositely charged polyelectrolyte (PE) surfactant mixtures can self-assemble into a large variety of mesoscopic structures, so-called polyelectrolyte surfactant complexes (PESCs). These structures directly affect the macroscopic behavior of such solutions. In this study, we investigated mixtures of the cationically charged PE JR 400 and the anionic surfactant SDS with the help of different neutron scattering and fluorescence methods. While an excess of PE charges in semi-dilute solutions causes an increase of viscosity, it has been observed that an excess of surfactant charges reduces the viscosity while precipitation is observed at charge equilibrium. The increase in viscosity had been investigated before and was attributed to the formation of cross links between PE chains. In this publication we focus our attention on the reduction of viscosity which is observed with an excess of surfactant charges. It is found that the PE chains form relatively large and densely packed clusters near the phase boundary on the surfactant rich side, thereby occupying less space and reducing the viscosity. For even higher surfactant concentrations, individual surfactant decorated PE chains are observed and their viscosity is found to be similar to that of the pure PE.

  20. Correlated adsorption of polyelectrolytes in the "charge inversion" of colloidal particles

    NASA Astrophysics Data System (ADS)

    Sennato, S.; Bordi, F.; Cametti, C.

    2004-10-01

    In this letter, we study the complexation of spherical colloidal particles induced by oppositely charged polyelectrolytes by means of dynamic light scattering technique. We employed cationic liposomes, 100 nm in diameter, and compared their aggregation behavior in the presence of differently organized counterions, i.e. simple uni-valent ions, deriving from the dissociation of NaCl salt, and multi-ions bounded to a polymer chain (large-valence polyions deriving from the ionization of two polyelectrolyte chains, polyacrylate and DNA). We show that the system behaves differently and, in the presence of oppositely charged polyions, undergoes a well-defined re-entrant condensation, following a charge inversion effect, as a function of the counterion concentration in the aqueous phase. Our results present a clear evidence of the role played by the lateral correlation of polyion chains onto the charged-particle surface, in terms of a simple Wigner crystal theory, according to the idea developed by Nguyen et al. (Rev. Mod. Phys. 74 (2002) 329).

  1. Design of an Inflammation-Sensitive Polyelectrolyte-Based Topical Drug Delivery System for Arthritis.

    PubMed

    Bijukumar, Divya; Choonara, Yahya E; Murugan, Karmani; Choonara, Bibi Fatima; Kumar, Pradeep; du Toit, Lisa C; Pillay, Viness

    2016-10-01

    The most successful treatment strategy for arthritis is intra-articular injections that are costly and have reduced patient compliance. The purpose of the current study was to develop an inflammation-sensitive system for topical drug administration. Multi-macromolecular alginate-hyaluronic acid-chitosan (A-H-C) polyelectrolyte complex nanoparticles, loaded with indomethacin were developed employing pre-gel and post-gel techniques in the presence of dodecyl-L-pyroglutamate (DLP). In addition to in vitro studies, in silico simulations were performed to affirm and associate the molecular interactions inherent to the formulation of core all-natural multi-component biopolymeric architectures composed of an anionic (alginate), a cationic (chitosan), and an amphi-ionic polyelectrolytic (hyaluronic acid) macromolecule. The results demonstrated that DLP significantly influenced the size of the synthesized nanoparticles. Drug-content analysis revealed higher encapsulation efficiency (77.3%) in the presence of DLP, irrespective of the techniques used. Moreover, in vitro drug release studies showed that indomethacin release from the nanosystem was significantly improved (98%) in Fenton's reagent. Drug permeation across a cellulose membrane using a Franz diffusion cell system showed an initial surge flux (0.125 mg/cm(-2)/h), followed by sustained release of indomethacin for the post-gel nanoparticles revealing its effective skin permeation efficiency. In conclusion, the study presents novel nanoparticles which could effectively encapsulate and deliver hydrophobic drugs to the target site, particularly for arthritis.

  2. Multiscale modeling of dendrimers and their interactions with bilayers and polyelectrolytes.

    PubMed

    Lee, Hwankyu; Larson, Ronald G

    2009-01-19

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

  3. Encapsulation of poly(D,L-lactide) microparticles with polyelectrolyte multilayers for antigen delivery.

    PubMed

    Hsu, Paul Yueh-Jen; Yang, Ya-Wun

    2014-01-01

    Poly(D,L-lactide) (PLA) microparticles containing the ovalbumin (OVA) model antigen were prepared by the double-emulsion and solvent evaporation method, followed by encapsulation with alternating layers of the polyelectrolytes, consisting of protamine sulfate and dextran sulfate of various molecular weights. The physicochemical properties, including particle size and zeta potentials, were characterised. Treatment of mouse macrophages with surface-modified PLA microparticles stimulated the generation of reactive oxygen species (ROS), such as hydrogen peroxide and superoxide, which was detected by the fluorescent probes, 2',7'-dichlorofluorescein diacetate (DCFH-DA) and hydroethidine (HE). Incubation of murine bone marrow-derived dendritic cells (BMDCs) with the encapsulated PLA microparticles enhanced the presentation of OVA soluble antigens in B3Z cells, an OVA-specific CD8(+) T cell hybridoma. Results obtained in this study demonstrated the potential use of polyelectrolyte-encapsulated biodegradable microparticles for delivery of soluble antigens to the antigen-presenting cells and stimulation of effective antigen presentation in the context of class I major histocompatibility complex.

  4. Shaping calcite crystals by means of comb polyelectrolytes having neutral hydrophilic teeth.

    PubMed

    Malferrari, Danilo; Fermani, Simona; Galletti, Paola; Goisis, Marco; Tagliavini, Emilio; Falini, Giuseppe

    2013-02-12

    Comb polyelectrolytes (CPs) having neutral hydrophilic teeth, similar to double hydrophilic block copolymers, are a powerful tool to modify the chemical-physical properties of inorganic crystalline materials. One of their main applications is in concrete technology, where they work as superplasticizers, particle-dispersing agents. Here, CPs, having the same poly(acrylic acid) (PAA) backbone chain and differing in the grafting with methoxy poly(ethylene glycol) chains (MPEG) of two molecular weights, were used to investigate the influence of tooth chains in polymer aggregation and in control on morphology and aggregation of calcite particles. These polymers aggregate, forming interpolymer hydrogen bonds between carboxylic groups and ether oxygen functionalities. The presence of calcium ions in solution further enhances aggregation. Crystallization experiments of calcite in the presence of CPs show that the specificity of interactions between polymers and crystal planes and control on aggregation and size of particles is a function of the content and chain length of the MPEG in the PAA backbone. These parameters limit and can make specific the electrostatic interactions with ionic crystalline planes. Moreover, the mechanism of crystallization, classical or nonclassical, is addressed by the CP structure and concentration. These findings have implications in the understanding of the complex chemical processes associated to concrete superplasticizers action and in the study of the biomineralization processes, where biological comb polyelectrolytes, the acidic glycoproteins, govern formation of calcitic structures.

  5. Influence of synthetic polyelectrolytes on the growth and properties of hyaluronan-chitosan multilayers.

    PubMed

    Salomäki, Mikko; Kankare, Jouko

    2009-02-09

    Both hyaluronan (HA) and chitosan (CHI) are biocompatible polysaccharide electrolytes. The multilayers formed by these polyelectrolytes alone are known to be rather soft and strongly viscoelastic. In this work we study multilayers formed by incorporating synthetic nonsaccharide polyelectrolytes such as polyallylamine (PAH) and poly(acrylic acid) (PAA) in various proportions into the HA/CHI layers. The buildup was followed on a quartz crystal resonator. Surface acoustic impedance recorded in these measurements, in suitable conditions, gives a spiral when plotted in the complex plane. The shape of this spiral depends on the viscoelasticity of the layer material and regularity of the growth process. We found that poly(acrylic acid) destroys the soft diffuse matrix formed by hyaluronan. It forms diffusion barriers when deposited sparsely between the layers. If its proportion is higher, the film growth adopts a linear buildup in the layer-by-layer process. The linear buildup of CHI/PAA reveals that the buildup regime of a multilayer film does not determine the viscoelastic properties of the film. Linearly and exponentially growing films may have very similar mechanical properties. Polyacrylic acid forms a kind of scaffold inside the film giving the natively soft hyaluronan/chitosan film more mechanical strength. The optimal combination gave more than 100-fold increase in the shear modulus.

  6. Conformal nano-thin modified polyelectrolyte coatings for encapsulation of cells.

    PubMed

    Granicka, L H; Antosiak-Iwańska, M; Godlewska, E; Strawski, M; Szklarczyk, M; Maranowski, B; Kowalewski, C; Wiśniewsk, J

    2011-10-01

    Encapsulation of cells in polymeric shells allows for separation of biological material from produced factors, which may find biotechnological and biomedical applications. Human T-lymphocyte cell line Jurkat as well as rat pancreatic islets were encapsulated using LbL technique within shells of polyelectrolyte modified by incorporation of biotin complexed with avidin to improve cell coating and to create the potential ability to elicit specific biochemical responses. The coating with nano-thin modified shells allowed for maintenance of the evaluated cells' integrity and viability during the 8-day culture. The different PE impact may be observed on different biological materials. The islets exhibited lower mitochondrial activity than the Jurkat cells. Nevertheless, coating of cells with polyelectrolyte modified membrane allowed for functioning of both model cell types: 10 μm leukemia cells or 150 μm islets during the culture. Applied membranes maintained the molecular structure during the culture period. The conclusion is that applied modified membrane conformation may be recommended for coating shells for biomedical purposes.

  7. Dynamics of interfacial pattern formation

    NASA Technical Reports Server (NTRS)

    Ben-Jacob, E.; Goldenfeld, N.; Langer, J. S.; Schon, G.

    1983-01-01

    A phenomenological model of dendritic solidification incorporating interfacial kinetics, crystalline anisotropy, and a local approximation for the dynamics of the thermal diffusion field is proposed. The preliminary results are in qualitative agreement with natural dendrite-like pattern formation.

  8. High temperature interfacial superconductivity

    SciTech Connect

    Bozovic, Ivan; Logvenov, Gennady; Gozar, Adrian Mihai

    2012-06-19

    High-temperature superconductivity confined to nanometer-scale interfaces has been a long standing goal because of potential applications in electronic devices. The spontaneous formation of a superconducting interface in bilayers consisting of an insulator (La.sub.2CuO.sub.4) and a metal (La.sub.1-xSr.sub.xCuO.sub.4), neither of which is superconducting per se, is described. Depending upon the layering sequence of the bilayers, T.sub.c may be either .about.15 K or .about.30 K. This highly robust phenomenon is confined to within 2-3 nm around the interface. After exposing the bilayer to ozone, T.sub.c exceeds 50 K and this enhanced superconductivity is also shown to originate from a 1 to 2 unit cell thick interfacial layer. The results demonstrate that engineering artificial heterostructures provides a novel, unconventional way to fabricate stable, quasi two-dimensional high T.sub.c phases and to significantly enhance superconducting properties in other superconductors. The superconducting interface may be implemented, for example, in SIS tunnel junctions or a SuFET.

  9. N-type Self-Doping of Fluorinate Conjugated Polyelectrolytes for Polymer Solar Cells: Modulation of Dipole, Morphology, and Conductivity.

    PubMed

    Liu, Huimin; Huang, Liqiang; Cheng, Xiaofang; Hu, Aifeng; Xu, Haitao; Chen, Lie; Chen, Yiwang

    2017-01-11

    For the conjugated polyelectrolytes (CPEs) interlayers, many studies focus on the modulation of interfacial dipoles in the polymer solar cells (PSCs) by altering the side polar groups but usually ignore the functions of conjugated backbone engineering (CBE) through the delicate design to improve their functions. Herein, novel alcohol-soluble CPEs by incorporation of fluorinate benzene onto the backbone, namely PFf1B and PFf4B, have been synthesized to modulate the interfacial dipoles and charge mobility. A favorable bidipole composed of ion-induced dipole and F hydrogen bond-induced dipole was discovered to be responsible for the tunable work function of indium tin oxide (ITO) electrode. Moreover, a desirable nanowires morphology of the upper active layer has also been obtained with the help of the self-assembly of fluorinated CPEs. More intriguingly, an unusual n-type doping favored by fluorine-induced electron transfer (FIET) was observed in these CPEs, leading to the improvement in the electron mobility. As a consequence, these fluorinated CPEs were demonstrated with a general application in the PSCs based on various active layers. Note that PFf4B with the highest loading of F atoms can work efficiently in a thickness of up to 31.8 nm, which broke the thickness limitation of most reported CPEs interlayer.

  10. Monte Carlo simulations of flexible polyelectrolytes inside viral capsids with dodecahedral charge distribution

    NASA Astrophysics Data System (ADS)

    Angelescu, Daniel George; Linse, Per

    2007-05-01

    Structural properties of encapsidated flexible polyelectrolytes in viral capsids with dodecahedral charge distribution have been investigated by Monte Carlo simulations using a coarse-grained model. Several capsid charge distributions ranging from a homogeneous surface charge distribution (λ=0) to a complete dodecahedral distribution (λ=1) at constant total capsid charge and fixed radial location of the capsid charges have been considered. The radial and lateral organizations of the polyelectrolyte have been examined as a function of the polyelectrolyte length and capsid charge distribution. With short polyelectrolytes a single polyelectrolyte layer was formed at the inner capsid surface, whereas at increasing polyelectrolyte length also a uniform polyelectrolyte density inside the surface layer was established. At low λ , the polyelectrolyte layer was laterally isotropic, but at λ≥0.05 a dodecahedral structure started to appear. At λ=1 , the polyelectrolyte followed essentially a path along the edges of a dodecahedron. With sufficiently long chains, all edges were decorated with polyelectrolyte, facilitated by loop formation. For an undercharged capsid, the capsid counterions inside the capsid also adopted a dodecahedral distribution.

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

    PubMed

    Biesheuvel, P Maarten; van der Veen, Marijn; Norde, Willem

    2005-03-10

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

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

    PubMed

    Bekri, Samya; Leclercq, Laurent; Cottet, Hervé

    2015-06-19

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

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

    USGS Publications Warehouse

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

    1984-01-01

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

  14. Smart interfacial bonding alloys

    SciTech Connect

    R. Q. Hwang; J. C. Hamilton; J. E. Houston

    1999-04-01

    The goal of this LDRD was to explore the use of the newly discovered strain-stabilized 2-D interfacial alloys as smart interface bonding alloys (SIBA). These materials will be used as templates for the heteroepitaxial growth of metallic thin films. SIBA are formed by two metallic components which mix at an interface to relieve strain and prevent dislocations from forming in subsequent thin film growth. The composition of the SIBA is determined locally by the amount of strain, and therefore can react smartly to areas of the highest strain to relieve dislocations. In this way, SIBA can be used to tailor the dislocation structure of thin films. This project included growth, characterization and modeling of films grown using SIBA templates. Characterization will include atomic imaging of the dislocations structure, measurement of the mechanical properties of the film using interface force microscopy (IFM) and the nanoindenter, and measurement of the electronic structure of the SIBA with synchrotron photoemission. Resistance of films to sulfidation and oxidation will also be examined. The Paragon parallel processing computer will be used to calculate the structure of the SIBA and thin films in order to develop ability to predict and tailor SIBA and thin film behavior. This work will lead to the possible development of a new class of thin film materials with properties tailored by varying the composition of the SIBA, serving as a buffer layer to relieve the strain between the substrate and the thin film. Such films will have improved mechanical and corrosion resistance allowing application as protective barriers for weapons applications. They will also exhibit enhanced electrical conductivity and reduced electromigration making them particularly suitable for application as interconnects and other electronic needs.

  15. Polyelectrolytes Multilayers to Modulate Cell Adhesion: A Study of the Influence of Film Composition and Polyelectrolyte Interdigitation on the Adhesion of the A549 Cell Line.

    PubMed

    Muzzio, Nicolás E; Pasquale, Miguel A; Gregurec, Danijela; Diamanti, Eleftheria; Kosutic, Marija; Azzaroni, Omar; Moya, Sergio E

    2016-04-01

    Polyelectrolyte multilayers (PEMs) with different polycation/polyanion pairs are fabricated by the layer-by-layer technique employing synthetic, natural, and both types of polyelectrolytes. The impact of the chemical composition of PEMs on cell adhesion is assessed by studying cell shape, spreading area, focal contacts, and cell proliferation for the A549 cell line. Cells exhibit good adhesion on PEMs containing natural polycations and poly(sodium 4-styrenesulfonate) (PSS) as polyanion, but limited adhesion is observed on PEMs fabricated from both natural polyelectrolytes. PEMs are then assembled, depositing a block of natural polyelectrolytes on top of a stiffer block with PSS as polyanion. Cell adhesion is enhanced on top of the diblock PEMs compared to purely natural PEMs. This fact could be explained by the interdigitation between polyelectrolytes from the two blocks. Diblock PEM assembly provides a simple means to tune cell adhesion on biocompatible PEMs.

  16. Interfacial rheology of surface-active biopolymers: Acacia senegal gum versus hydrophobically modified starch.

    PubMed

    Erni, Philipp; Windhab, Erich J; Gunde, Rok; Graber, Muriel; Pfister, Bruno; Parker, Alan; Fischer, Peter

    2007-11-01

    Acacia gum is a hybrid polyelectrolyte containing both protein and polysaccharide subunits. We study the interfacial rheology of its adsorption layers at the oil/water interface and compare it with adsorbed layers of hydrophobically modified starch, which for economic and political reasons is often used as a substitute for Acacia gum in technological applications. Both the shear and the dilatational rheological responses of the interfaces are considered. In dilatational experiments, the viscoelastic response of the starch derivative is just slightly weaker than that for Acacia gum, whereas we found pronounced differences in shear flow: The interfaces covered with the plant gum flow like a rigid, solidlike material with large storage moduli and a linear viscoelastic regime limited to small shear deformations, above which we observe apparent yielding behavior. In contrast, the films formed by hydrophobically modified starch are predominantly viscous, and the shear moduli are only weakly dependent on the deformation. Concerning their most important technological use as emulsion stabilizers, the dynamic interfacial responses imply not only distinct interfacial dynamics but also different stabilizing mechanisms for these two biopolymers.

  17. Experimentally Determined Interfacial Area Between Immiscible Fluids in Porous Media

    SciTech Connect

    Crandall, Dustin; Niessner, J; Hassanizadeh, S.M; Smith, Duane

    2008-01-01

    When multiple fluids flow through a porous medium, the interaction between the fluid interfaces can be of great importance. While this is widely recognized in practical applications, numerical models often disregard interactios between discrete fluid phases due to the computational complexity. And rightly so, for this level of detail is well beyond most extended Darcy Law relationships. A new model of two-phase flow including the interfacial area has been proposed by Hassarizadeh and Gray based upon thermodynamic principles. A version of this general equation set has been implemented by Nessner and Hassarizadeh. Many of the interfacial parameters required by this equation set have never been determined from experiments. The work presented here is a description of how the interfacial area, capillary pressure, interfacial velocity and interfacial permeability from two-phase flow experiments in porous media experiments can be used to determine the required parameters. This work, while on-going, has shown the possibility of digitizing images within translucent porous media and identifying the location and behavior of interfaces under dynamic conditions. Using the described methods experimentally derived interfacial functions to be used in larger scale simulations are currently being developed. In summary, the following conclusions can be drawn: (1) by mapping a pore-throat geometry onto an image of immiscible fluid flow, the saturation of fluids and the individual interfaces between the fluids can be identified; (2) the resulting saturation profiles of the low velocity drainage flows used in this study are well described by an invasion percolation fractal scaling; (3) the interfacial area between fluids has been observed to increase in a linear fashion during the initial invasion of the non-wetting fluid; and (4) the average capillary pressure within the entire cell and representative elemental volumes were observed to plateau after a small portion of the volume was

  18. From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

    DOE PAGES

    Oded, Meirav; Kelly, Stephen T.; Gilles, Mary K.; ...

    2016-07-05

    The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segmentsmore » into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. In conclusion, these insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.« less

  19. From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

    SciTech Connect

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

    2016-07-05

    The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segments into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. In conclusion, these insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.

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

    PubMed

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

    2017-02-15

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

  1. Plastic behaviour of polyelectrolyte microcapsules derived from colloid templates.

    PubMed

    Bäumler, H; Artmann, G; Voigt, A; Mitlöhner, R; Neu, B; Kiesewetter, H

    2000-01-01

    The deformability and osmotic properties of hollow microcapsules were studied by means of the micropipette video microscopic technique. The microcapsules were prepared by consecutive multiple adsorption of the polyanion, poly(styrene sulphonate), and the polycation, poly(allylamine hydrochloride), onto melamine formaldehyde resin latex of 5 microm diameter, which was decomposed after completing the coating by transferring to hydrochloric acid of pH 1.1. The polyelectrolyte microcapsules reacted to micropipette suction with plastic deformation. If lipids are added to the polyelectrolyte layers, the capsules cannot be visibly deformed by micropipette suction up to 10(4) N/m2. However, plastic shrinking was observed if the stress was generated by the osmotic pressure of a sucrose solution of 10(6) N/m2.

  2. Osmotic and Salted Brush Phase of Polyelectrolyte Brushes

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

  3. A molecular-thermodynamic model for polyelectrolyte solutions

    NASA Astrophysics Data System (ADS)

    Jiang, Jianwen; Liu, Honglai; Hu, Ying; Prausnitz, J. M.

    1998-01-01

    Polyelectrolyte solutions are modeled as freely tangent-jointed, charged hard-sphere chains and corresponding counterions in a continuum medium with permitivity ɛ. 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 Γ 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.

  4. A molecular-thermodynamic model for polyelectrolyte solutions

    SciTech Connect

    Jiang, J.; Liu, H.; Hu, Y.; Prausnitz, J.M.

    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.}

  5. Electro-osmotic flow of semidilute polyelectrolyte solutions

    NASA Astrophysics Data System (ADS)

    Uematsu, Yuki; Araki, Takeaki

    2013-09-01

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

  6. The influence of microwave heating on the characteristics of polyelectrolytes.

    PubMed

    Martin, D; Mateescu, E; Ighigeanu, D; Jianu, A

    2000-01-01

    Results obtained by microwave (MW) and simultaneous microwave and electron beam (MW + EB) application in the chemistry of acrylamide and acrylic acid co-polymers (PA type polyelectrolytes) are presented. Comparative results concerning the molecular weight (Mw) and Huggins' constant for the acrylamide copolymers obtained by classical heating, MW heating, EB irradiation and simultaneous MW + EB treatment are reported. MW heating produces high PA water solubility but median Mw values; EB irradiation gives high Mw values but associated with a cross-linked structure (poor water solubility) while MW energy addition to EB energy gives simultaneously high Mw values and high PA water solubility. A MW installation of 2.45 GHz and 2.5 kW, designed to provide small-scale commercial production of PA polyelectrolytes, is described.

  7. Integral equation theory for counterion distribution in polyelectrolyte solutions

    NASA Astrophysics Data System (ADS)

    Shew, Chwen-Yang; Yethiraj, Arun

    1998-03-01

    An integral equation theory is developed to explore the behavior of rigid and flexible polyelectolyte solutions with explicit counter ions. The theory makes predictions for the distribution of counterions around the polyion in addition to polyion-polyion correlation and polymer conformations. For rigid polyelectrolytes, the theory is to fit the scattering spectra of tobacco mosaic virus solutions. In dilute solutions, the effective charge decreases as concentration is increased. The results are consistent with the nature of TMV molecules as weak polyacids. For flexible polyelectrolytes, we have extended the previous work of one component thread model and Koyama chain model to this system. The counterion distribution is very sensitive to polyion concentration. Theoretical calculations are consistent with simulation results.

  8. Photocontrolled adsorption of polyelectrolyte molecules on a silicon substrate.

    PubMed

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

    2013-12-31

    We report on a change in the properties of monomolecular films of polyelectrolyte molecules, induced by illuminating the silicon substrate on which they adsorb. It was found that under illumination the thickness of the adsorbed layer decreases by at least 27% and at the same time the roughness is significantly reduced in comparison to a layer adsorbed without irradiation. Furthermore, the homogeneity of the film topography and the surface potential is shown to be improved by illumination. The effect is explained by a change in surface charge density under irradiation of n- and p-type silicon wafers. The altered charge density in turn induces conformational changes of the adsorbing polyelectrolyte molecules. Their photocontrolled adsorption opens new possibilities for selective manipulation of adsorbed films. This possibility is of potential importance for many applications such as the production of well-defined coatings in biosensors or microelectronics.

  9. Study of the interaction between a diblock polyelectrolyte PDMA-b-PAA and a gemini surfactant 12-6-12 in basic media.

    PubMed

    Kang, Hongmei; Peng, Baoliang; Liang, Yanyan; Han, Xia; Liu, Honglai

    2009-05-01

    The interactions between negatively charged diblock polyelectrolyte PDMA(71)-b-PAA(59) and oppositely charged gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) in basic media were studied using dynamic light scattering, fluorescence spectroscopy, surface tension, and (1)H NMR. With increased addition of surfactant, the conformation of polyelectrolyte experienced changes from the initial unimer with open-extended PAA block, to the nano-scaled aggregates/complexes with a maximum hydrodynamic diameter (D(h)), and finally to the stable complexes with a smaller D(h). Accordingly, the value of D(h) during the whole process of increasing the surfactant concentration changed from 14-17 nm, to 184 nm, and to the final 70 nm, respectively. This transformation was driven by the electrostatic attractive/repulsive interactions, the hydrophobic interaction between hydrophobic surfactant tails, and the hydrophilicity of PDMA block.

  10. Enhanced Power-Conversion Efficiency in Inverted Bulk Heterojunction Solar Cells using Liquid-Crystal-Conjugated Polyelectrolyte Interlayer.

    PubMed

    Liu, Chao; Tan, Yun; Li, Chunquan; Wu, Feiyan; Chen, Lie; Chen, Yiwang

    2015-09-02

    Two novel liquid-crystal-conjugated polyelectrolytes (LCCPEs) poly[9,9-bis[6-(4-cyanobiphenyloxy)-hexyl]-fluorene-alt-9,9-bis(6-(N,N-diethylamino)-hexyl)-fluorene] (PF6Ncbp) and poly[9,9-bis[6-(4-cyanobiphenyloxy)-hexyl]-fluorene-alt-9,9-bis(6-(N-methylimidazole)-hexyl]-fluorene] (PF6lmicbp) are obtained by covalent linkage of the cyanobiphenyl mesogen polar groups onto conjugated polyelectrolytes. After deposition a layer of LCCPEs on ZnO interlayer, the spontaneous orientation of liquid-crystal groups can induce a rearrangement of dipole moments at the interface, subsequently leading to the better energy-level alignment. Moreover, LCCPEs favors intimate interfacial contact between ZnO and the photon harvesting layer and induce active layer to form the nanofibers morphology for the enhancement of charge extraction, transportation and collection. The water/alcohol solubility of the LCCPEs also enables them to be environment-accepted solvent processability. On the basis of these advantages, the poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C60-butyric acid methyl ester (PC60BM)-based inverted polymer solar cells (PSCs) combined with ZnO/PF6Ncbp and ZnO/PF6lmicbp bilayers boost the power conversion efficiency (PCE) to 3.9% and 4.2%, respectively. Incorporation of the ZnO/PF6lmicbp into the devices based on a blend of a narrow band gap polymer thieno[3,4-b]thiophene/benzodithiophene (PTB7) with [6,6]-phenyl C70-butyric acid methyl ester (PC71BM) affords a notable efficiency of 7.6%.

  11. Chlorine resistant glutaraldehyde crosslinked polyelectrolyte multilayer membranes for desalination.

    PubMed

    Cho, Kwun Lun; Hill, Anita J; Caruso, Frank; Kentish, Sandra E

    2015-05-06

    Crosslinked polyelectrolyte multilayer membranes are synthesized with salt rejection values approaching those of commercial desalination membranes, but with increased chlorine resistance. The membranes are fabricated directly onto porous commercial substrates. Subsequent crosslinking of the polycation layers with glutaraldehyde leads to NaCl rejections of up to 97%, while the incorporation of a highly sulfonated polysulfone polyanion leads to high chlorine resistance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Ecologically benign polymers: the case of maleic polyelectrolytes.

    PubMed

    Chitanu, Gabrielle Charlotte; Carpov, Adrian

    2002-04-15

    The paper discusses a series of results that evidence the favorable effect of maleic polyelectrolytes in different fields in which a protective action of the environment is attained: (i) the exploitation of geothermal water, which is a cleaner source of energy; (ii) the improvement or preservation of the structure of agricultural soils; (iii) the substitution of phosphates in detergents; and (iv) the reduction of chromium load of effluents from tanning plants.

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

    NASA Astrophysics Data System (ADS)

    Sen, Swati; Kundagrami, Arindam

    2015-12-01

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

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

    SciTech Connect

    Sen, Swati; Kundagrami, Arindam

    2015-12-14

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

  15. Adipogenic differentiation of mesenchymal stem cells on micropatterned polyelectrolyte surfaces.

    PubMed

    Kawazoe, Naoki; Guo, Likun; Wozniak, Michal J; Imaizumi, Yumie; Tateishi, Tetsuya; Zhang, Xingdong; Chen, Guoping

    2009-01-01

    Three kinds of photoreactive polyelectrolytes of polyallylamine (PAAm), poly(acrylic acid) (PAAc), and poly(vinyl alcohol) (PVA) were synthesized by the introduction of azidophenyl groups in the respective polymers. The photoreactive PAAm, PAAc, and PVA were micropatterned on polystyrene surfaces by photolithography. Observation with optical microscopy and scanning probe microscopy demonstrated the formation of a striped pattern of polyelectrolytes with a width of 200 microm. The micropatterned polyelectrolytes swelled in water. The micropatterned surfaces were used for cell culture of mesenchymal stem cells (MSCs) and their effects on adipogenic differentiation were investigated. The MSCs adhered to and proliferated evenly on the PAAm- and PAAc-patterned surfaces while they formed a cell pattern on the PVA-patterned surface. The PAAm-, PAAc-grafted, and polystyrene surfaces supported cell adhesion while the PVA-grafted surface did not. When cultured in adipogenic differentiation medium, the adipogenic differentiation of MSCs on the polyelectrolyte-patterned surfaces was demonstrated by the formation of lipid vacuoles and gene expression analysis. Oil Red-O-positive cells showed an even distribution on the PAAm- and PAAc-patterned surfaces, while they showed a pattern on the PVA-patterned surface. The fraction of Oil RedO-positive cells increased with culture time. The MSCs cultured on the PAAm-, PAAc-grafted, and polystyrene surfaces in adipogenic differentiation medium expressed the adipogenesis marker genes of peroxisome proliferator-activated receptor gamma2 (PPARgamma2), lipoprotein lipase (LPL), and fatty acid binding protein 4 (FABP4). These results indicate that the PAAm-, and PAAc-grafted, and polystyrene surfaces supported the adipogenesis of MSCs while a PVA-grafted surface did not.

  16. A rotating disk electrokinetic method for characterizing polyelectrolyte pharmaceutical gels.

    PubMed

    Qu, Beibei; Lee, Ping I

    2012-05-01

    Charge groups in polyelectrolyte gels can affect the entrapment and release of ionic drugs as well as influencing the stability of colloidal and nanoparticulate drug delivery systems. An accurate knowledge of gel charge properties is therefore important to the understanding and design of such drug delivery systems. Existing rotating disk method for quantifying the surface potential of flat surfaces is based on the classical electrokinetic model that neglects the effect of surface conductivity and is therefore only applicable to ion-impenetrable hard surfaces. This classical electrokinetic model would be inaccurate for polyelectrolyte gel systems involving ion-penetrable charged layers or "soft" surfaces. In this study, we developed a new rotating disk model for characterizing charge properties of ion penetrable soft surfaces and tested it on polyvinyl alcohol (PVA)/polyacrylic acid (PAA), gelatin, and gelatin/PAA polyelectrolyte gels. In addition to classical electrokinetic parameters, the contribution of surface conductivity known to be very significant for soft and ion-penetrable gel surfaces has been taken into account in this new rotating disk model. Based on this new approach, two rotating gel disks of different radius but with identical gel composition and preparation procedures were employed for determining the gel surface potential and density of fixed charge groups. A comparison of the resulting data with that obtained from existing rotating disk model ignoring the surface conductivity reveals a significant underestimation of the gel surface potential and the density of fixed charge groups by the ion-impenetrable hard surface approach. Our results thus confirm that the contribution of surface conductivity is significant in the electrokinetic characterization of polyelectrolyte gels that can be evaluated with our new rotating disk model. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed

    Sen, Swati; Kundagrami, Arindam

    2015-12-14

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

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

    PubMed

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

    2016-08-01

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

  19. Conformations of polyelectrolyte macromolecules with different charge density in solutions of different ionic strengths

    NASA Astrophysics Data System (ADS)

    Dommes, O. A.; Okatova, O. V.; Pavlov, G. M.

    2016-11-01

    Studies of charged polymer chains are interesting in both fundamental and applied aspects. Especially, polyelectrolytes attract huge attention of researchers due to their ability to form interpolymer complexes with synthetic and biopolymers. The study was carried out on the fractions of hydrophilic copolymers of N-methyl-N-vinyl acetamide and N-methyl-N-vinyl amine hydrochloride of different degrees of polymerization and of different charge density using methods of molecular hydrodynamics. Hydrodynamic and conformational characteristics as well as molar masses of isolated molecules were estimated. In addition, the intrinsic viscosity of fractions was studied at the extreme ionic strengths - in distilled water (∼10-6M) and in 6M NaCl. Scaling relations for intrinsic viscosity, sedimentation and translational diffusion coefficients with molar mass were obtained. Conformational behavior of macromolecules with different linear charge density was compared.

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

    NASA Astrophysics Data System (ADS)

    Lal, Jyotsana; Hakem, Ilhem-Faiza

    2004-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  2. Protein adsorption and interfacial rheology interfering in dilatational experiment

    NASA Astrophysics Data System (ADS)

    Rühs, P. A.; Scheuble, N.; Windhab, E. J.; Fischer, P.

    2013-05-01

    The static and dilatational response of β-lactoglobulin fibrils and native β-lactoglobulin (monomers) at water-air and water-oil interfaces (pH 2) was measured using the pendant drop method. The resulting adsorption behavior and viscoelasticity is dependent of concentration and adsorption time. The interfacial pressure of the β-lactoglobulin fibrils obtained in static measurements was 16-18 mN/m (against air) and 7 mN/m (against oil) for all concentrations. With higher concentrations, faster adsorption kinetics and slightly higher interfacial and surface pressure is achieved but did not lead to higher viscoelastic moduli. The transient saturation of the interface is similar for both the fibril solution and the monomers, however the fibril solution forms a strong viscoelastic network. To evaluate the superimposed adsorption behavior and rheological properties, the formed interfacial layer was subjected to dilatational experiments, which were performed by oscillating the surface area of the drop in sinusoidal and sawtooth (diagonal) deformation manner. The sinusoidal oscillations (time depended area deformation rate) result in a complex interfacial tension behavior against air and oil interfaces and show remarkable differences during compression and expansion as emphasized by Lissajous figures. For diagonal (constant area deformation rate) experiments, a slight bending of the interfacial tension response was observed at low frequencies emphasizing the influence of protein adsorption during rheological measurements.

  3. Dynamic surface tension of polyelectrolyte/surfactant systems with opposite charges: two states for the surfactant at the interface.

    PubMed

    Ritacco, Hernán A; Busch, Jorge

    2004-04-27

    The molecular reorientation model of Fainerman et al. is conceptually adapted to explain the dynamic surface tension behavior in polyelectrolyte/surfactant systems with opposite charges. The equilibrium surface tension curves and the adsorption dynamics may be explained by assuming that there are two different states for surfactant molecules at the interface. One of these states corresponds to the adsorption of the surfactant as monomers, and the other to the formation of a mixed complex at the surface. The model also explains the plateaus that appear in the dynamic surface tension curves and gives a picture of the adsorption process.

  4. Charged colloids and polyelectrolytes: from statics to electrokinetics

    NASA Astrophysics Data System (ADS)

    Löwen, H.; Esztermann, A.; Wysocki, A.; Allahyarov, E.; Messina, R.; Jusufi, A.; Hoffmann, N.; Gottwald, D.; Kahl, G.; Konieczny, M.; Likos, C. N.

    2005-01-01

    A review is given on recent studies of charged colloidal suspensions and polyelectrolytes both in static and non-equilibrium situations. As far as static equilibrium situations are concerned, we discuss three different problems: 1) Sedimentation density profiles in charged suspensions are shown to exhibit a stretched non-bariometric wing at large heights and binary suspensions under gravity can exhibit an analog of the brazil-nut effect known from granular matter, i.e. the heavier particles settle on top of the lighter ones. 2) Soft polyelectrolyte systems like polyelectrolyte stars and microgels show an ultra-soft effective interaction and this results into an unusual equilibrium phase diagram including reentrant melting transitions and stable open crystalline lattices. 3) The freezing transition in bilayers of confined charged suspensions is discussed and a reentrant behaviour is obtained. As far as nonequilibrium problems are concerned, we discuss an interface instability in oppositely driven colloidal mixtures and discuss possible approaches to simulate electrokinetic effects in charged suspensions.

  5. The evolution of cyclopropenium ions into functional polyelectrolytes

    DOE PAGES

    Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; ...

    2015-01-09

    We report that versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion.We demonstrate the facile synthesis of a series ofmore » polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. In conclusion, the materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes.« less

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

    PubMed

    Ge, Qingchun; Su, Jincai; Amy, Gary L; Chung, Tai-Shung

    2012-03-15

    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 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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Antibacterial polyelectrolyte-coated Mg alloys for biomedical applications

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  8. Polyelectrolyte effects on the crystallization phenomena of the lithium carbonate

    NASA Astrophysics Data System (ADS)

    Watamura, Hiroto; Marukawa, Hironobu; Hirasawa, Izumi

    2013-06-01

    Anionic polyelectrolyte effects on the lithium carbonate crystallization phenomena were investigated. Li2CO3 crystals were obtained by reactive crystallization with seed crystals. Polyelectrolytes were dissolved into the reactive field before the reaction. Obtained crystals were observed with scanning electron microscopy (SEM) and crystal size and agglomeration degree were measured by the SEM images. The results show that Li2CO3 crystallized different shape and size from absence of polyelectrolyte in those reactive fields. Especially polyacrylic acid (PAA) improved on the agglomeration of the crystals and shaped them high aspect needles. Thus other experimental conditions including PAA molecular weight and concentration, reaction time, supersaturation by Li concentration were investigated in addition. As a result, obtained crystals were not different in each PAA molecular weight reactive fields. Meanwhile PAA concentration has optimum range. Li2CO3 formed less agglomeration and higher aspect around 1 g/l. In the concentration, Li2CO3 did not agglomerate regardless of aging time and Li concentration. Moreover crystals became rectangle shape in higher Li concentration.(020) face intensity of the rectangle shape