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Sample records for interfacial polyelectrolyte complexation

  1. Soft microcapsules with highly plastic shells formed by interfacial polyelectrolyte-nanoparticle complexation.

    PubMed

    Kaufman, Gilad; Nejati, Siamak; Sarfati, Raphael; Boltyanskiy, Rostislav; Loewenberg, Michael; Dufresne, Eric R; Osuji, Chinedum O

    2015-10-14

    Composite microcapsules have been aggressively pursued as designed chemical entities for biomedical and other applications. Common preparations rely on multi-step, time consuming processes. Here, we present a single-step approach to fabricate such microcapsules with shells composed of nanoparticle-polyelectrolyte and protein-polyelectrolyte complexes, and demonstrate control of the mechanical and release properties of these constructs. Interfacial polyelectrolyte-nanoparticle and polyelectrolyte-protein complexation across a water-oil droplet interface results in the formation of capsules with shell thicknesses of a few μm. Silica shell microcapsules exhibited a significant plastic response at small deformations, whereas lysozyme incorporated shells displayed a more elastic response. We exploit the plasticity of nanoparticle incorporated shells to produce microcapsules with high aspect ratio protrusions by micropipette aspiration. PMID:26169689

  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. PMID:26172934

  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. 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. PMID:25771881

  5. Investigation of metal-polyelectrolyte complex toxicity.

    PubMed

    Karahan, Mesut; Mustafaeva, Zeynep; Koç, Rabia Çakır; Bağırova, Melahat; Allahverdiyev, Adil M

    2014-05-01

    Water-soluble binary and ternary copper complexes of polyelectrolytes were synthesized, and the toxicity of these complexes was tested in mouse fibroblast cell line (L929) in vitro. Both the binary and ternary complexes were prepared at the ratio of 0.4 mole copper(II) ions per monomer of acrylic acid and 0.5 mole copper(II) ions per monomer of methyl vinyl ether maleic anhydride, furthermore at the ratio of 1 and 2 mole bovine serum albumin per mole of polyacrylic acid and poly(methyl vinyl ether-co-maleic anhydride), respectively. Compared to binary copper(II)-polyelectrolyte complexes, these ternary complexes have been determined to be of least toxicity. PMID:22914259

  6. 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

  7. Saloplastic Macroporous Polyelectrolyte Complexes: Cartilage Mimics

    PubMed Central

    2011-01-01

    Complexes of sodium poly(4-styrenesulfonate) (NaPSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were formed on mixing equimolar solutions in high salt concentration. Under ultracentrifugal fields, the complex precipitates were transformed into compact polyelectrolyte complexes (CoPECs), which showed extensive porosity. The mechanical properties of CoPECS make them attractive for bioimplants and tissue engineering applications. Free NaPSS chains in the closed pores of CoPECs create excess osmotic pressure, which controls the pore size and contributes to the mechanical resistance of the material. The mechanical properties of CoPECs, modulated by the ionic strength of the doping medium, were studied by uniaxial tensile testing and the stress−strain data were fit to a three-element Maxwell model which revealed at least two regimes of stress relaxation. PMID:21132107

  8. 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.

  9. Polyelectrolyte complexes and salt: a computational study

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    Charged polymers, polyelectrolytes (PEs), are versatile materials with applications ranging from tissue engineering to sensing elements. In aqueous solutions, oppositely charged PEs form complexes which are known to be sensitive to added salt with responses including shrinking, flocculation or swelling, and at higher concentrations loosening and destabilization of the complex. However, the role of electrostatics, charge correlations, hydration, and ion specific interactions remain unclear. In this work, we use all-atom molecular dynamics with explicit water and ions to probe the effect of excess salt to DNA-polylysine complex formation and stability, and demonstrate the mechanism of PE and ion species specific salt-driven dissociation. The dissociation occurs accompanied by charge reversal in which charge correlations and ion binding chemistry play a role. Our results agree with experimental work on complex dissociation but in addition show the underlying microstructural correlations driving the behavior. We expand the full atomic level detail and dynamics results with theoretical and computational work describing the PE complex as oppositely charged rods to provide a more complete understanding of PE interactions in salt.

  10. 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. PMID:26775240

  11. 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.

  12. Nanocarrier for Oral Peptide Delivery Produced by Polyelectrolyte Complexation in Nanoconfinement.

    PubMed

    He, Wei; Parowatkin, Maria; Mailänder, Volker; Flechtner-Mors, Marion; Graf, Robert; Best, Andreas; Koynov, Kaloian; Mohr, Kristin; Ziener, Ulrich; Landfester, Katharina; Crespy, Daniel

    2015-08-10

    The hydrophilic peptide YY (PYY) is a promising hormone-based antiobesity drug. We present a new concept for the delivery of PYY from pH-responsive chitosan-based nanocarriers. To overcome the drawbacks while retaining the merits of the polyelectrolyte complex (PEC) method, we propose a one-pot approach for the encapsulation of a hydrophilic peptide drug in cross-linked PEC nanocarriers. First, the hydrophilic peptide is encapsulated via polyelectrolyte complexation within water-in-oil miniemulsion droplets. In a second step, the PEC surface is reinforced by controlled interfacial cross-linking. PYY is efficiently encapsulated and released upon pH change. Such nanocarriers are promising candidates for the fight against obesity and, in general, for the oral delivery of protein drugs. PMID:26161672

  13. Phase Transitions in Nanostructured Polyelectrolyte-Surfactant Complexes

    NASA Astrophysics Data System (ADS)

    Leonard, Michael; Strey, Helmut

    2001-03-01

    When a water-soluble polyelectrolyte is combined with an oppositely-charged surfactant solution at a stoichiometric charge ratio, self-assembly into highly-ordered, water-insoluble structures occurs. We have prepared such complexes with poly(sodium acrylate)-co-acrylamide, alginic acid, and chitosan, combined with cationic and anionic surfactants. The phases exhibited by these complexes in aqueous solution are highly sensitive to such factors as osmotic pressure, salt type, ionic strength, and polyelectrolyte charge density. In this study, we have used small angle X-ray scattering to examine osmotic stress-induced structural phase transitions in these complexes under these various environmental conditions. The morphological consequences of combining polyelectrolytes with swollen, emulsion-bound surfactant micelles were also investigated. Results of this work, as well as the potential to use these complexes as nanoporous, biocompatible materials, will be discussed.

  14. Simulation of complexes between linear polyelectrolyte and charged dendrimer

    NASA Astrophysics Data System (ADS)

    Pandav, Gunja; Ganesan, Venkat

    2014-03-01

    Complexes formed by electrostatic interactions between dendrimer having cationic terminal groups and anionic linear polyelectrolyte are studied using hybrid Monte Carlo simulations. The excluded volume interactions are modeled using a self-consistent field and the electrostatic interactions are computed by solving Poisson equation. Such framework facilitates simulating large scale three-dimensional systems. We primarily focus on the effect of dendrimer generation number, stiffness of polyelectrolyte chain and systematically study its effect on change in shape and size of complexes. Our results suggest that the dendrimer structure and charge distribution has a significant impact on the complex formation.

  15. 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

  16. 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. PMID:27336461

  17. 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.

  18. Water's Role in the Relaxation of Polyelectrolyte Complexes and Multilayers

    NASA Astrophysics Data System (ADS)

    Lutkenhaus, Jodie; Zhang, Yanpu; Reid, Dariya; Antila, Hanne; Yildirim, Erol; Zhang, Ran; Sammalkorpi, Maria

    In the last decade, evidence for an intriguing glass-transition-like phase transition has emerged in hydrated polyelectrolyte complex precipitates and polyelectrolyte multilayers. Although the transition is weak, it stimulates large-scale macroscopic phenomena such as multilayer shrinking, swelling, and rearrangement. To date, there is not a clear consensus on what causes this transition, although a growing body of evidence indicates that salt and water are key parameters. Recent simulations of hydrated polyelectrolyte complexes show that water molecules form a stabilizing hydrogen-bonded network and that this network is disrupted by dehydration of the polyanion at the thermal transition, leading to segmental relaxation of polymer chains. If true, this would explain the transition's dependence on water and extrinsic compensation as well as its glass transition-like character. This talk will focus upon water's role in the transition, in which a strong dependence on hydration is observed. Quartz crystal microbalance with dissipation (QCM-D) and modulated differential scanning calorimetry (MDSC) are used to track the transition in polyelectrolytes complexes as a function of hydration.

  19. Study of polyelectrolyte complexes of chitosan and sulfoethyl cellulose

    NASA Astrophysics Data System (ADS)

    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.

    2013-03-01

    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 μm) 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{3/+}) and negatively charged sulfoethyl cellulose groups (-SO{3/-}) during the growth of polyelectrolyte complexes results in a packing of chitosan chains in the multilayer film.

  20. 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.

  1. Polyelectrolyte-Surfactant Complexes: A New Class of Organogelators

    NASA Astrophysics Data System (ADS)

    Cavicchi, Kevin; Liu, Yuqing; Guzman, Gustavo

    2011-03-01

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

  2. Adsorption and viscoelastic analysis of polyelectrolyte-surfactant complexes on charged hydrophilic surfaces.

    PubMed

    Dhopatkar, Nishad; Park, Jung Hyun; Chari, Krishnan; Dhinojwala, Ali

    2015-01-27

    The aggregation of surfactants around oppositely charged polyelectrolytes brings about a peculiar bulk phase behavior of the complex, known as coacervation, and can control the extent of adsorption of the polyelectrolyte at an aqueous-solid interface. Adsorption kinetics from turbid premixed polyelectrolyte-surfactant mixtures have been difficult to measure using optical techniques such as ellipsometry and reflectometry, thus limiting the correlation between bulk phases and interfacial adsorption. Here, we investigated the adsorption from premixed solutions of a cationic polysaccharide (PQ10) and the anionic surfactant sodium dodecyl sulfate (SDS) on an amphoteric alumina surface using quartz crystal microbalance with dissipation (QCMD). The surface charge on the alumina was tuned by changing the pH of the premixed solutions, allowing us to assess the role of electrostatic interactions by studying the adsorption on both negatively and positively charged surfaces. We observed a maximum extent of adsorption on both negatively and positively charged surfaces from a solution corresponding to the maximum turbidity. Enhanced adsorption upon diluting the redissolved complexes at a high SDS concentration was seen only on the negatively charged surface, and not on the positively charged one, confirming the importance of electrostatic interactions in controlling the adsorption on a hydrophilic charged surface. Using the Voight based viscoelastic model, QCMD also provided information on the effective viscosity, effective shear modulus, and thickness of the adsorbed polymeric complex. The findings of viscoelastic analysis, corroborated by atomic force microscopy measurements, suggest that PQ10 by itself forms a flat, uniform layer, rigidly attached to the surface. The PQ10-SDS complex shows a heterogeneous surface structure, where the underlayer is relatively compact and tightly attached and the top is a loosely bound diffused overlayer, accounting for most of the adsorbate

  3. 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.

  4. 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.

  5. Interfacial tension of complex coacervated mussel adhesive protein according to the Hofmeister series.

    PubMed

    Lim, Seonghye; Moon, Dustin; Kim, Hyo Jeong; Seo, Jeong Hyun; Kang, In Seok; Cha, Hyung Joon

    2014-02-01

    Complex coacervation is a liquid-liquid phase separation in a colloidal system of two oppositely charged polyelectrolytes or colloids. The interfacial tension of the coacervate phase is the key parameter for micelle formation and interactions with the encapsulating material. However, the relationship between interfacial tensions and various salt solutions is poorly understood in complex coacervation. In the present work, the complex coacervate dynamics of recombinant mussel adhesive protein (MAP) with hyaluronic acid (HA) were determined in the presence of Hofmeister series salt ions. Using measurements of absorbance, hydrodynamic diameter, capillary force, and receding contact angle in the bulk phase, the interfacial tensions of complex coacervated MAP/HA were determined to be 0.236, 0.256, and 0.287 mN/m in 250 mM NaHCOO, NaCl, and NaNO3 solutions, respectively. The sequences of interfacial tensions and contact angles of the complex coacervates in the presence of three sodium salts with different anions were found to follow the Hofmeister ordering. The tendency of interfacial tension between the coacervate and dilute phases in the presence of different types of Hofmeister salt ions could provide a better understanding of Hofmeister effects on complex coacervated materials based on the protein-polysaccharide system. This information can also be utilized for microencapsulation and adsorption by controlling intramolecular interactions. In addition, the injection molding dynamics of mussel byssus formation was potentially explained based on the measured interfacial tension of coacervated MAP. PMID:24490867

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

    SciTech Connect

    Zhao, Mingtian; Li, Baohui E-mail: baohui@nankai.edu.cn; Zhou, Jihan; Su, Cuicui; Niu, Lin; Liang, Dehai E-mail: baohui@nankai.edu.cn

    2015-05-28

    Complexation behavior of oppositely charged polyelectrolytes in a solution is investigated using a combination of computer simulations and experiments, focusing on the influence of polyelectrolyte charge distributions along the chains on the structure of the polyelectrolyte complexes. The simulations are performed using Monte Carlo with the replica-exchange algorithm for three model systems where each system is composed of a mixture of two types of oppositely charged model polyelectrolyte chains (EGEG){sub 5}/(KGKG){sub 5}, (EEGG){sub 5}/(KKGG){sub 5}, and (EEGG){sub 5}/(KGKG){sub 5}, in a solution including explicit solvent molecules. Among the three model systems, only the charge distributions along the chains are not identical. Thermodynamic quantities are calculated as a function of temperature (or ionic strength), and the microscopic structures of complexes are examined. It is found that the three systems have different transition temperatures, and form complexes with different sizes, structures, and densities at a given temperature. Complex microscopic structures with an alternating arrangement of one monolayer of E/K monomers and one monolayer of G monomers, with one bilayer of E and K monomers and one bilayer of G monomers, and with a mixture of monolayer and bilayer of E/K monomers in a box shape and a trilayer of G monomers inside the box are obtained for the three mixture systems, respectively. The experiments are carried out for three systems where each is composed of a mixture of two types of oppositely charged peptide chains. Each peptide chain is composed of Lysine (K) and glycine (G) or glutamate (E) and G, in solution, and the chain length and amino acid sequences, and hence the charge distribution, are precisely controlled, and all of them are identical with those for the corresponding model chain. The complexation behavior and complex structures are characterized through laser light scattering and atomic force microscopy measurements. The order

  7. 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

  8. Poly-electrolyte complex: a novel system for biomedical applications and recent patents.

    PubMed

    Deeksha; Malviya, Rishabha; Sharma, Pramod Kr

    2014-01-01

    Polyelectrolyte complexes are getting more attention owing to their formation by the interaction of opposite charges with the help of electrostatic force. Polyelectrolyte complexation reduces the toxic effects of the cross-linking agents. Polyelectrolyte complexescan be classified on various bases. The current report highlights properties, factors affecting it and various technologies. In the present report we intend to discuss the applications of polyelectrolyte complexes such as biomedical, controlled delivery, medicine, and area which can cause controlled release in different aspects. Patents related to these inventions are added along with their pivotal roles. PMID:24962379

  9. 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.

  10. Effect of Polyelectrolyte Stiffness and Solution pH on the Nanostructure of Complexes Formed by Cationic Amphiphiles and Negatively Charged Polyelectrolytes.

    PubMed

    Ram-On, Maor; Cohen, Yachin; Talmon, Yeshayahu

    2016-07-01

    The interaction between amphiphiles and polyelectrolytes has been widely investigated in recent years due to their potential application in industry and medicine, with special focus on gene therapy. The cationic lipid dioleoyl trimethylammonium propane, DOTAP, and the oppositely charged polyelectrolytes, sodium poly(acrylic acid) and sodium poly(styrenesulfonate), form multilamellar complexes in water. Because of the different molecular stiffness of the two polyelectrolytes, they form different nanostructured complexes. Also, because of the different ionization behavior of the two polyelectrolytes, pH differently affects the complexation of the polyelectrolytes with didodecyldimethylammonium bromide (DDAB), another cationic surfactant. We used cryogenic temperature transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering (SAXS) to compare the nanostructures formed. Our results show that although the basic nanostructures of the complexes are always lamellar (multilamellar or unilamellar) the morphology of the complexes is affected by the polyelectrolyte rigidity and the solution pH. PMID:27049758

  11. 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.

  12. 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

  13. 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

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

    PubMed

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

    2016-04-19

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

  15. Preparation and adsorption of refined polyelectrolyte complex nanoparticles.

    PubMed

    Reihs, T; Müller, M; Lunkwitz, K

    2004-03-01

    We report on bulk and surface properties of centrifuged nonstoichiometric polyelectrolyte complex (PEC) dispersions. PECs were prepared by mixing poly(diallyldimethylammonium chloride) (PDADMAC) and sodium poly(maleic acid-co-alpha-methylstyrene) (PMA-MS) at the monomolar mixing ratio of 0.6 and polymer concentration >/=1 mmol/l. Centrifugation of initial PEC dispersions revealed three phases: supernatant (SUP), coacervate (COAC), and an insoluble precipitate. Mass, turbidity, particle hydrodynamic radii (R(h)), and the titratable charge amount were determined for those phases. The turbid COAC phase consisted of 200-nm nanoparticles and carried 60% of the polymer mass and 20% of the titratable charge amount of the initial PEC dispersion. The SUP phase showed no turbidity and no such nanoparticles, but carried 80% of the initial titratable charge amount, presumably caused by excess polycations. Furthermore, linear dependences of turbidity and R(h) on COAC concentration was observed. COAC adsorption was studied at polyelectrolyte multilayer (PEM) modified silicon surfaces in dependence on both adsorption time and concentration using attenuated total-reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The adsorption data were fitted by the simple Langmuir model. Comparison of COAC particles and polystyrene latices revealed similar adsorption features. SEM and AFM measurements resulted in hemispherically shaped adsorbed COAC particles with coverages >/=25%, whose calculated volumes correlated well with those in dispersion obtained by PCS. PMID:14757079

  16. Rheology and interfacial properties of aqueous solutions of the diblock polyelectrolyte poly(styrene-block-acrylic acid)

    NASA Astrophysics Data System (ADS)

    Kimerling, Abigail

    In aqueous solutions diblock polyelectrolytes with amphiphilic character form aggregate structures, which affect physical properties such as viscosity, elasticity, surface tension, and film hydrophilicity. Potential applications for diblock polyelectrolyte solutions include coatings, inks, oil recovery agents, personal care products, and biomaterials. By varying the diblock polyelectrolyte and solution properties, the solutions can be tuned to meet the needs of particular applications. The research objective was to identify the influences of block length, pH, and ionic strength on the rheological and interfacial properties of poly(styrene- b-acrylic acid) (PS-PAA) solutions. Six polymers with varied PS and PAA block lengths were examined, all at 1.0 wt% in aqueous solutions. The hydrophobicity of the PS block causes the formation of spherical micelles in aqueous solutions. Increasing the solution pH ionizes the PAA block, which leads to an increase in micelle corona thickness due to repulsions between chains. Major trends observed in the rheological and interfacial properties can be understood in terms of expected changes in the micelle size and interfacial self-assembly with pH, ionic strength, and block length. Addition of NaOH was found to increase the solution pH and initially led to increases in solution viscosity, elasticity, surface tension, and film hydrophilicity. This effect was attributed to creation of larger micelles and greater inter-micellar repulsions as the PAA chain became more fully charged. However, when the concentration of NaOH exceeded a critical value, the solution viscosity, elasticity, and film hydrophilicity decreased. It is believed this was due to charge shielding by excess sodium ions, leading to shrinkage of the micelle corona and smaller micelles. Increasing the PS-PAA solution ionic strength by adding NaCl also provided charge shielding, as observed by decreases in solution viscosity and elasticity. Increasing the length of either

  17. Molecular Dynamics Simulations of Polyelectrolyte-Polyampholyte Complexes. Effect of Solvent Quality and Salt Concentration.

    NASA Astrophysics Data System (ADS)

    Jeon, Junhwan; Dobrynin, Andrey

    2006-03-01

    Using molecular dynamics simulations we have studied complexation in polyelectrolyte-polyampholyte mixtures in poor solvent conditions for the polyelectrolyte backbone. In a poor solvent a polyelectrolyte form a necklace-like structure. Upon forming a complex with both random and diblock polyampholytes a polyelectrolyte chain changes its necklace conformation by forming one huge bead. The collapse of the polyelectrolyte chain occurs due to neutralization of the polyelectrolyte charge by polyampholytes. In the case of the random polyampholyte the more positively charged sections of the chain adsorb on the surface of the globular bead while more negatively charged chain sections form loops surrounding the collapsed core of the aggregate. In the case of diblock polyampholyte the positively charged block and a part of the negatively charged block wraps around the collapsed polyelectrolyte with a substantial section of the negatively charged block sticking out from the collapsed center of the aggregate. These structures appear as a result of optimization of the net electrostatic energy of the complex and short-range attractive interactions between monomers of the polyelectrolyte chain.

  18. 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. PMID:27152954

  19. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes.

    PubMed

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-28

    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. PMID:27131564

  20. 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.

  1. Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films.

    PubMed

    Patrício, Sónia; Cruz, Ana I; Biernacki, Krzysztof; Ventura, João; Eaton, Peter; Magalhães, Alexandre L; Moura, Cosme; Hillman, A Robert; Freire, Cristina

    2010-07-01

    A novel multilayer film containing a cationic phosphonium-derivatized Ni(salen)-type complex and poly(sodium-4-styrenesulfonate (NaPSS) was assembled onto quartz, mica, and metal surfaces using the layer-by-layer (LbL) technique. Spectroscopic (UV-vis) and gravimetric (QCM) responses for the multilayer films show regular stepwise growth and the signature of strong electrostatic interactions between the component layers. The gravimetric responses indicate the presence of substantial additional (net neutral) material in the PSS layers, which XPS shows is not polyelectrolyte or salt, so charge compensation is intrinsic; we deduce the presence of space-filling solvent. Direct electrostatic interaction of the two-component layers is enhanced by a secondary noncovalent interaction between the delocalized pi-systems of the two components. Permeability of the film to the redox probe [Fe(CN)(6)](3-/4-) was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Qualitatively similar results were obtained in the absence and presence of a precursor PSS/PAH multilayer, but with a general shift in kinetic and diffusional processes to longer time scales (lower frequencies) in the presence of the precursor layer and with increasing numbers of PSS/[Ni(salen)] bilayers. Quantitatively, the EIS data were interpreted using a capillary membrane model (CMM) to yield values of coverage, apparent charge transfer resistance, double-layer capacitance, pore size, and diffusion coefficient. The coverage values were consistent with a model in which there are no preferential growth sites and the surface charge density is independent of the number of bilayers. PMID:20476725

  2. 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

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

    NASA Astrophysics Data System (ADS)

    Shklovskii, Boris

    2009-03-01

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

  4. Thermal and pH Transitions in Polyelectrolyte Complexes and Multilayers

    NASA Astrophysics Data System (ADS)

    Lutkenhaus, Jodie

    2015-03-01

    When oppositely charged polymers are mixed in water, they form a polyelectrolyte complex. Analogously at a surface, oppositely charged polymers can be assembled to form a polyelectrolyte multilayer. Complexation is entropically driven, as it results in the release of small counter ions and water molecules into the surrounding media. First, the effect of time and temperature on the formation of polyelectrolyte complexes containing model polyelectrolytes poly(diallyldimethyl ammonium chloride) and poly(styrene sulfonate) is presented. We show that complexation is a time-dependent phenomena, which is consistent with complexes existing in a kinetically trapped state, rather than a thermodynamic equilibrium. Upon heating, a glassy-viscous transition that shows features of an LCST is demonstrated. Second, the effect of pH on polyelectrolyte multilayer microtubes is presented. The microtubes are made of poly(allylamine) and poly(acrylic acid), both of which are weak polyelectrolytes. Modulating the pH induces a nanoporous transition that results in nanoporous microtubes. These results, in summary, show that noncovalent interactions are very sensitive to external stimuli such as temperature and pH.

  5. 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. PMID:26630921

  6. Semi-permanent split end mending with a polyelectrolyte complex.

    PubMed

    Rigoletto, R; Zhou, Y; Foltis, L

    2007-01-01

    Split ends form through mechanical stresses during grooming procedures and are more likely to appear in hair damaged as a result of excessive combing forces. Although there are no conventional systems that will permanently mend split ends, a semi-permanent mending composition has been achieved through a polyelectrolyte complex. The complex is formed as a result of the ionic association of a cationic polymer, Polyquaternium-28, and an anionic polymer, PVM/MA Copolymer. Hair tresses containing tagged split ends are used in measuring mending efficacy. The tagging allows the fate of the split ends to be determined after different types of treatment regimens which test the durability of the mend. Monitoring of the repair and mending durability is carried out with the aid of a stereomicroscope. Results obtained with this method indicate that the complex both by itself and when formulated into a simple lotion provided a high level of split end mending not only after initial treatment but more importantly after combing showing the durability of the mend. Cumulative effects and durability to washing indicate that the polymer complex does not build up on the hair and rinses off with shampoo making possible its usage as a post shampoo treatment. The formulated lotion has higher durability performance as compared to a commercial product with a split end mending claim. The proposed mechanism of action entails a crosslinking microgel structure that infiltrates the damaged hair sites binding them together. This model is supported by the analysis of phase behavior, viscometry, Scanning Electron Microscopy, and absorption of ionic dyes. PMID:17728946

  7. 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.

  8. Polyelectrolyte complex nanoparticles from cationised gelatin and sodium alginate for curcumin delivery.

    PubMed

    Sarika, P R; James, Nirmala Rachel

    2016-09-01

    Self assembled hybrid polyelectrolyte complex (PEC) nanoparticles are prepared from cationically modified gelatin and sodium alginate (Alg) by electrostatic complexation between the polymers. Cationised gelatin (CG) is prepared by the reaction of gelatin with ethylenediamine. Structural changes in gelatin, after modification with ethylenediamine are investigated by XRD and (1)H NMR spectroscopy. Hybrid polyelectrolyte nanoparticles, labeled CG/Alg, are prepared by simple mixing of CG and Alg. CG/Alg complex shows spherical morphology as confirmed by scanning electron microscopy. These polyelectrolyte complex nanoparticles can be used for the encapsulation and delivery of natural antioxidant curcumin to carcinoma cells. CG/Alg nanoparticles show curcumin encapsulation efficiency of 69% and exhibit sustained release of curcumin in vitro. Anticancer activity of curcumin loaded CG/Alg nanoparticles towards MCF-7 cells is disclosed by MTT assay. Intracellular uptake of the drug encapsulated nanoparticles is confirmed by fluorescent imaging. PMID:27185149

  9. Effect of monovalent salt on the conformation of polyelectrolyte-surfactant complexes

    NASA Astrophysics Data System (ADS)

    Diehl, A.; Kuhn, P. S.

    2009-01-01

    We study the conformation of polyelectrolyte-surfactant complexes in the presence of monovalent salt. A simple model for the formation of these structures is presented in the framework of the Debye-Hückel-Bjerrum-Manning and Flory theories, with the hydrophobic interactions between the hydrocarbon tails of surfactant molecules treated in the spirit of van der Waals theory as an effective attraction. The extension of the polyelectrolyte-surfactant complexes is analyzed as a function of the salt concentration and a discrete conformational transition between a compact globule and an elongated coil is found, in agreement with experimental results for the unfolding transition of a DNA-cationic surfactant complex.

  10. 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

  11. Molecular dynamics simulations of polyelectrolyte-polyampholyte complexes. Effect of solvent quality and salt concentration.

    PubMed

    Jeon, Junhwan; Dobrynin, Andrey V

    2006-12-01

    Complexation between polyelectrolyte and polyampholyte chains in poor solvent conditions for the polyelectrolyte backbone has been studied by molecular dynamics simulations. In a poor solvent a polyelectrolyte forms a necklace-like structure consisting of polymeric globules (beads) connected by strings of monomers. The simulation results can be explained by assuming the existence of two different mechanisms leading to the necklace formation. In the case of weak electrostatic interactions, the necklace formation is driven by optimization of short-range monomer-monomer attraction and electrostatic repulsion between charged monomers on the polymer backbone. In the case of strong electrostatic interactions, the necklace structure appears as a result of counterion condensation. While the short-range attractions between monomers are still important, the correlation-induced attraction between condensed counterions and charged monomers and electrostatic repulsion between uncompensated charges provide significant contribution to optimization of the necklace structure. Upon forming a complex with both random and diblock polyampholytes, a polyelectrolyte chain changes its necklace conformation by forming one huge bead. The collapse of the polyelectrolyte chain occurs due to the neutralization of the polyelectrolyte charge by polyampholytes. In the case of the random polyampholyte, the more positively charged sections of the chain mix with negatively charged polyelectrolyte forming the globular bead while more negatively charged chain sections form loops surrounding the collapsed core of the aggregate. In the case of diblock polyampholyte, the positively charged block, a part of the negatively charged block, and a polyelectrolyte chain form a core of the aggregate with a substantial section of the negatively charged block sticking out from the collapsed core of the aggregate. In both cases the core of the aggregate has a layered structure that is characterized by the

  12. 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

  13. Complexes between high charge density cationic polyelectrolytes and anionic single- and double-tail surfactants.

    PubMed

    Mantzaridis, C; Mountrichas, G; Pispas, S

    2009-05-21

    Polyelectrolyte/surfactant complexes formed between well-defined linear flexible polyelectrolytes, namely, quaternized poly[3,5-bis(dimethylaminomethylene)hydroxystyrene] (Q-N-PHOS), bearing two cationic sites on each repeating unit, and two different anionic surfactants, namely, sodium dodecyl sulfate (SDS) with one hydrocarbon tail and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with two hydrocarbon chains, are studied by means of fluorescence spectroscopy, electrophoretic, dynamic and static light scattering, and atomic force microscopy. Depending on the surfactant state in initial solutions (i.e., below or above nominal critical micelle concentration, cmc) and final (-/+) charge ratio, self-assembly in nanoparticles of variable size, stability, and effective charge is possible. Spherical, rather polydispserse complexes are formed in all cases. Critical aggregation concentrations (cac) depend on the surfactant type, while hydrophobicity of the main polyelectrolyte chain plays a role in colloidal stability of the complex nanoparticles. PMID:19388679

  14. 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

    2016-10-01

    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. PMID:27312617

  15. 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. PMID:21318252

  16. Confined polyelectrolytes: The complexity of a simple system.

    PubMed

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

    2015-08-01

    The interaction between polyelectrolytes and counterions in confined situations and the mutual relationship between chain conformation and ion condensation is an important issue in several areas. In the biological field, it assumes particular relevance in the understanding of the packaging of nucleic acids, which is crucial in the design of gene delivery systems. In this work, a simple coarse-grained model is used to assess the cooperativity between conformational change and ion condensation in spherically confined backbones, with capsides permeable to the counterions. It is seen that the variation on the degree of condensation depends on counterion valence. For monovalent counterions, the degree of condensation passes through a minimum before increasing as the confining space diminishes. In contrast, for trivalent ions, the overall tendency is to decrease the degree of condensation as the confinement space also decreases. Most of the particles reside close to the spherical wall, even for systems in which the density is higher closer to the cavity center. This effect is more pronounced, when monovalent counterions are present. Additionally, there are clear variations in the charge along the concentric layers that cannot be totally ascribed to polyelectrolyte behavior, as shown by decoupling the chain into monomers. If both chain and counterions are confined, the formation of a counterion rich region immediately before the wall is observed. Spool and doughnut-like structures are formed for stiff chains, within a nontrivial evolution with increasing confinement. PMID:26096545

  17. Electrospinning polyelectrolyte complexes: pH-responsive fibers.

    PubMed

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

    2015-03-01

    Fibers were electrospun from a solution comprised of oppositely charged polyelectrolytes, in efforts to achieve highly confined macromolecular packaging. A stoichiometric ratio of poly(allylamine hydrochloride) and poly(acrylic acid) solution was mixed in an ethanol-water co-solvent. Differential scanning calorimetry (DSC) analysis of electrospun fibers demonstrated no indication of glass transition, Tg. Infrared spectroscopy (FTIR) analysis of the fibers as a function of temperature, demonstrated an amidation process at lower temperature compared to cast film. Polarized FTIR indicated a preference of the functional groups to be perpendicular to the fiber axis. These results imply formation of mixed phase fibers with enhanced conditions for intermolecular interactions, due to the highly aligned and confined assembly of the macromolecules. The tunable intermolecular interactions between the functional groups of the polyelectrolytes, impact pH-driven, reversible swelling-deswelling of the fibers. The degree of ionization of PAA at pH 5.5 and pH 1.8 varied from 85% to 18%, correspondingly, causing transformation of ionic interactions to hydrogen bonding between the functional groups. The chemical change led to a massive water diffusion of 500% by weight and to a marked increase of 400% in fiber diameter, at a rate of 0.50 μm s(-1). These results allow for manipulation and tailoring of key fiber properties for tissue engineering, membranes, and artificial muscle applications. PMID:25601204

  18. Tuning the structure of surfactant complexes with DNA and other polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Krishnaswamy, R.; Mitra, P.; Raghunathan, V. A.; Sood, A. K.

    2003-05-01

    We have carried out small-angle X-ray diffraction studies on complexes formed by the anionic polyelectrolytes, namely, sodium salts of double and single stranded (ds and ss) DNA, poly(glutamic acid) (PGA), poly(acrylic acid) (PAA), and poly(styrene sulfonate) (PSS) with a cationic surfactant system consisting of cetyltrimethylammonium bromide (CTAB) and sodium 3-hydroxy-2-naphthoate (SHN). All complexes have a two-dimensional (2D) hexagonal structure at low SHN concentrations. DNA-CTAB-SHN complexes exhibit a hexagonal to lamellar transition near the SHN concentration at which CTAB-SHN micelles show a cylinder to bilayer transformation. On the other hand, PGA and PAA complexes form a 2D centered rectangular phase at higher SHN concentrations, and PSS complexes show a primitive rectangular structure. These results provide a striking example of polyion specificity in polyelectrolyte-surfactant interactions.

  19. Complexation of cationic-neutral block polyelectrolyte with insulin and in vitro release studies.

    PubMed

    Pippa, Natassa; Karayianni, Maria; Pispas, Stergios; Demetzos, Costas

    2015-08-01

    Insulin (INS) was incorporated into complexes with the block polyelectrolyte quaternized poly[3,5-bis(dimethylaminomethylene)hydroxystyrene]-b-poly(ethylene oxide) (QNPHOSEO), which is a cationic-neutral block polyelectrolyte. Light scattering techniques are used in order to examine the size, the size distribution and the ζ-potential of the nanocarriers in aqueous and biological media, which are found to depend on the ratio of the components and the physicochemical parameters during and after complex preparation. Circular dichroism and infrared spectroscopy, employed to investigate the structure of the complexed INS, show no alteration of protein structure after complexation. In vitro release profiles of the entrapped protein are found to depend on the ratio of the components and the solution conditions used during preparation of the complexes. PMID:26101970

  20. Electrostatic complexation of polyelectrolyte and magnetic nanoparticles: from wild clustering to controllable magnetic wires

    NASA Astrophysics Data System (ADS)

    Yan, Minhao; Qu, Li; Fan, Jiangxia; Ren, Yong

    2014-05-01

    We present the electrostatic complexation between polyelectrolytes and charged nanoparticles. The nanoparticles in solution are γ-Fe2O3 (maghemite) spheres with 8.3 nm diameter and anionic surface charges. The complexation was monitored using three different formulation pathways such as direct mixing, dilution, and dialysis. In the first process, the hybrids were obtained by mixing stock solutions of polymers and nanoparticles. A `destabilization state' with sharp and intense maximum aggregation was found at charges stoichiometry (isoelectric point). While on the two sides of the isoelectric point, `long-lived stable clusters state' (arrested states) were observed. Dilution and dialysis processes were based on controlled desalting kinetics according to methods developed in molecular biology. Under an external magnetic field ( B = 0.3 T), from dialysis at isoelectric point and at arrested states, cationic polyelectrolytes can `paste' these magnetic nanoparticles (NPs) together to yield irregular aggregates (size of 100 μm) and regular rod-like aggregates, respectively. These straight magnetic wires were fabricated with diameters around 200 nm and lengths comprised between 1 μm and 0.5 mm. The wires can have either positive or negative charges on their surface. After analyzing their orientational behavior under an external rotating field, we also showed that the wires made from different polyelectrolytes have the same magnetic property. The recipe used a wide range of polyelectrolytes thereby enhancing the versatility and applied potentialities of the method. This simple and general approach presents significant perspective for the fabrication of hybrid functional materials.

  1. 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. PMID:26794762

  2. 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

  3. 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.

  4. 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. PMID:25454440

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

    PubMed

    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. PMID:26779881

  6. 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

  7. 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

  8. 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. PMID:25256478

  9. Effect of gold nanoparticles on the structure and electron-transfer characteristics of glucose oxidase redox polyelectrolyte-surfactant complexes.

    PubMed

    Cortez, M Lorena; Marmisollé, Waldemar; Pallarola, Diego; Pietrasanta, Lía I; Murgida, Daniel H; Ceolín, Marcelo; Azzaroni, Omar; Battaglini, Fernando

    2014-10-01

    Efficient electrical communication between redox proteins and electrodes is a critical issue in the operation and development of amperometric biosensors. The present study explores the advantages of a nanostructured redox-active polyelectrolyte-surfactant complex containing [Os(bpy)2Clpy](2+) (bpy=2,2'-bipyridine, py= pyridine) as the redox centers and gold nanoparticles (AuNPs) as nanodomains for boosting the electron-transfer propagation throughout the assembled film in the presence of glucose oxidase (GOx). Film structure was characterized by grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM), GOx incorporation was followed by surface plasmon resonance (SPR) and quartz-crystal microbalance with dissipation (QCM-D), whereas Raman spectroelectrochemistry and electrochemical studies confirmed the ability of the entrapped gold nanoparticles to enhance the electron-transfer processes between the enzyme and the electrode surface. Our results show that nanocomposite films exhibit five-fold increase in current response to glucose compared with analogous supramolecular AuNP-free films. The introduction of colloidal gold promotes drastic mesostructural changes in the film, which in turn leads to a rigid, amorphous interfacial architecture where nanoparticles, redox centers, and GOx remain in close proximity, thus improving the electron-transfer process. PMID:25171096

  10. 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

  11. 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. PMID:26955270

  12. 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. PMID:25458282

  13. 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.

  14. Electrostatically driven complexation of liposomes with a star-shaped polyelectrolyte to low-toxicity multi-liposomal assemblies.

    PubMed

    Yaroslavov, Alexander A; Sybachin, Andrey V; Zaborova, Olga V; Pergushov, Dmitry V; Zezin, Alexander B; Melik-Nubarov, Nikolay S; Plamper, Felix A; Müller, Axel H E; Menger, Frederic M

    2014-04-01

    Anionic liposomes are electrostatically complexed to a star-shaped cationic polyelectrolyte. Upon complexation, the liposomes retain their integrity and the resulting liposome-star complexes do not dissociate in a physiological solution with 0.15 M NaCl. This provides a multi-liposomal container for possible use as a high-capacity carrier. PMID:24243764

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

    PubMed

    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

  16. 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.

  17. 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

  18. CONTROLLED RELEASE OF REPIFERMIN® FROM POLYELECTROLYTE COMPLEXES STIMULATES ENDOTHELIAL CELL PROLIFERATION

    PubMed Central

    Huang, Min; Berkland, Cory

    2014-01-01

    The therapeutic value of many growth factors is often hindered by the narrow therapeutic index and sustained concentrations required for efficacy. Controlled release approaches provide a valuable tool to achieve these goals; however, growth factor stability must be maintained. Repifermin® is a truncated form of fibroblast growth factor-10, also known as keratinocyte growth factor-2, that exhibits promise in wound healing applications; however, controlled release formulation presents a challenge for this labile protein. Taking advantage of the heparin-binding motif of this class of biopharmaceuticals, Repifermin® was effectively stabilized and packaged in polyelectrolyte complexes. In the presence of dextran sulfate, the unfolding temperature of this growth factor was increased by ~10°C as confirmed by a variety of spectroscopic techniques. Dextran sulfate with bound Repifermin® was then complexed with several polycations (chitosan, poly-L-lysine, and polyethylenimine) resulting in the formation of ~250 nm polyelectrolyte complexes that entrapped the protein with ~70–80% efficiency. Release was controlled for more than 10 days and the mitogenic activity of Repifermin® on human umbilical cord vascular endothelial cells was significantly enhanced, whereas no effect was noted for free Repifermin®. PMID:18425807

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

    NASA Astrophysics Data System (ADS)

    Vögele, Martin; Holm, Christian; Smiatek, Jens

    2015-12-01

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

  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. Tuning nanoscale viscoelasticity of polyelectrolyte complexes with multiple types of cross-links

    NASA Astrophysics Data System (ADS)

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

    Mechanical properties of hydrogels are manifestation of cross-link type and density, fixed charges and water-polymer interactions. In this study, we revealed how different types of cross-links regulate the nanoscale viscoelasticity of polyelectrolyte networks. Ionically cross-linked PAH/PAA layer-by-layer complexes were modified to include covalent cross-links using EDC. AFM-nanoindentation and force relaxation were performed at various ionic strength (0.01-1M) and pH (1.5-5.5). As-assembled networks, held only by ionic cross-links, underwent >95% relaxation, dominated by cross-link breaking and re-formation. Addition of covalent cross-links increased the instantaneous modulus by 1.6-fold and attenuated relaxation to ~80% of net neutral states (pH >=3.5), as covalent cross-links provide additional elastic components. The network remained stabilized when all ionic cross-links were dissociated at pH <=1.5, whereby further attenuation to 31% in relaxation could be due to viscoelastic polymer conformational changes and fluid flow-induced poroelasticity. Taken together, this study demonstrates the potential of using multiple cross-linking types to tune the viscoelastic mechanisms in polyelectrolyte complexes.

  2. Conjugated polyelectrolyte-cisplatin complex nanoparticles for simultaneous in vivo imaging and drug tracking

    NASA Astrophysics Data System (ADS)

    Ding, Dan; Li, Kai; Zhu, Zhenshu; Pu, Kan-Yi; Hu, Yong; Jiang, Xiqun; Liu, Bin

    2011-05-01

    A molecular brush based on conjugated polyelectrolyte (CPE) grafted with dense poly(ethylene glycol) (PEG) chains was successfully complexed with an anticancer agent, cisplatin, to form cisplatin-loaded nanoparticles (CPE-PEG-Pt). The obtained nanoparticles have high far-red/near-infrared fluorescence and are able to release the drug in a continuous and slow manner. These nanoparticles have not only been used to visualize HepG2 cancer cells, but also served as an in vivo fluorescent imaging probe that simultaneously tracks the in vivo drug distribution in nude mice upon intravenous administration.A molecular brush based on conjugated polyelectrolyte (CPE) grafted with dense poly(ethylene glycol) (PEG) chains was successfully complexed with an anticancer agent, cisplatin, to form cisplatin-loaded nanoparticles (CPE-PEG-Pt). The obtained nanoparticles have high far-red/near-infrared fluorescence and are able to release the drug in a continuous and slow manner. These nanoparticles have not only been used to visualize HepG2 cancer cells, but also served as an in vivo fluorescent imaging probe that simultaneously tracks the in vivo drug distribution in nude mice upon intravenous administration. Electronic supplementary information (ESI) available: size distributions and 3D CLSM images. See DOI: 10.1039/c0nr00950d

  3. Microparticles based on chitosan/carboxymethylcellulose polyelectrolyte complexes for colon delivery of vancomycin.

    PubMed

    Cerchiara, T; Abruzzo, A; Parolin, C; Vitali, B; Bigucci, F; Gallucci, M C; Nicoletta, F P; Luppi, B

    2016-06-01

    The aim of this work was to prepare polyelectrolyte complexes based on chitosan (CH) and carboxymethylcellulose (CMC) for colon delivery of vancomycin (VM). Various batches of polyelectrolyte complexes, using three different CH/CMC weight ratios (3:1, 1:1 and 1:3), were prepared and collected as microparticles by spray-drying process. Microparticles were characterized in terms of yield, encapsulation efficiency, drug loading, morphology and mucoadhesion properties. Microparticles water-uptake and VM release as well as its protection against gastric pepsin degradation were also investigated. Finally, the antibacterial activity against Staphylococcus aureus, a Gram-positive model strain, was evaluated. The best formulation CH/CMC 1:3 was selected based on the encapsulation efficiency, water-uptake and drug release rate. Moreover, microparticles were able to prevent VM degradation and showed a good antibacterial activity against S. aureus. Finally, to improve the release of VM in the colon the selected formulation was coated with lauric acid. PMID:27083351

  4. Needlelike and spherical polyelectrolyte complex nanoparticles of poly(l-lysine) and copolymers of maleic acid.

    PubMed

    Müller, M; Reihs, T; Ouyang, W

    2005-01-01

    We report on the bulk and surface properties of dispersions consisting of nonstoichiometric polyelectrolyte complex (PEC) nanoparticles. PEC nanoparticles were prepared by mixing poly(l-lysine) (PLL) or poly(diallyldimethylammonium chloride) (PDADMAC) with poly(maleic acid-co-alpha-methylstyrene) (PMA-MS) or poly(maleic acid-co-propylene) (PMA-P). The monomolar mixing ratio was n-/n+ = 0.6, and the concentration ranged from 1 to 6 mmol/L. Subsequent centrifugation enabled the separation of the excess polycation, resulting in a stable coacervate phase further used in the experiments. The bulk phase parameters turbidity and hydrodynamic radius (R(h)) of the PEC nanoparticles showed a linear dependence on the total polymer content independently of the mixed polyelectrolytes. This can be interpreted by the increased collision probability of the polyelectrolyte chains when the overlap concentration is approached or exceeded. Different morphologies of the cationic PEC nanoparticles, which were solution-cast onto Si supports, were obtained by atomic force microscopy (AFM). The combinations of PLL/PMA-MS and PDADMAC/PMA-MS revealed more or less hemispherical particle shapes, whereas that of PLL/PMA-P revealed an elongated needlelike particle shape. Circular dichroism and attenuated total reflection Fourier transform infrared (ATR-FTIR) measurements proved the alpha-helical conformation for the PEC PLL/PMA-P and the random coil conformation for the PEC PLL/PMA-MS. We conclude that stiff alpha-helical PLL induces anisotropic elongated PEC nanoparticles, whereas randomly coiled PLL forms isotropic spherical PEC nanoparticles. PMID:15620340

  5. Mechanistic basis for unexpected bioavailability enhancement of polyelectrolyte complexes incorporating BCS class III drugs and carrageenans.

    PubMed

    Heinen, C; Reuss, S; Saaler-Reinhardt, S; Langguth, P

    2013-09-01

    The objective of this study was to investigate the potential of λ-carrageenan to work as an absorption modifying excipient in combination with formulations of BCS class 3 substances. Trospium chloride was used as a model BCS class 3 substance. Polyelectrolyte complexes of trospium and λ-carrageenan were produced by layer-by-layer complexation. A λ-carrageenan-containing formulation was administered either in capsules size 9 to rats by gavage or directly into ligated intestinal loops of rats. Exceptionally strong variations were observed in the plasma concentrations of the rats that received λ-carrageenan compared to the control group, but enhanced plasma concentrations were observed only in some of the rats. In vitro permeability studies were performed across Caco2-monolayers and across excised segments of rat jejunum in a modified Ussing chamber to learn more about the mechanism of absorption enhancement. The complex did not show any effect in Caco2-cells, but led to a major enhancement of permeability across excised segments in modified Ussing chambers. Carrageenan did not lead to alterations of tight junctions. The bioavailability enhancing effect thus was most likely due to an interaction of the polyelectrolyte-drug complex with the mucus, which provided an intimate contact between the drug and the absorbing surface. A similar effect was also achievable with other types of carrageenan and was also transferable to other compounds. In conclusion, λ-carrageenan-drug complexes show interesting excipient-drug-epithelium interactions - however, for full utilization of the permeation enhancing potential, an intimate and reproducible contact between absorbing epithelia and the complex is needed. PMID:23958316

  6. Polyelectrolyte complexes via desalting mixtures of hyaluronic acid and chitosan-Physicochemical study and structural analysis.

    PubMed

    Lalevée, G; Sudre, G; Montembault, A; Meadows, J; Malaise, S; Crépet, A; David, L; Delair, T

    2016-12-10

    Polyelectrolyte complexes (PECs) were prepared from Chitosan (CS) and Hyaluronic Acid (HYA) homogeneous mixtures of aqueous solutions. The method consisted of preparing a homogeneous mixture of the two polysaccharides via charge screening at high salt concentrations. Then, the mixture was dialyzed, leading to the controlled self-assembly of the two polyelectrolytes. Critical parameters like the chitosan degree of acetylation (DA) and molar mass (Mw), the residual salt concentration and the molar charge ratio r=nNH3(+) (CS)/nCOO(-) (HYA) accounted for the transition from homogeneous aqueous solutions to colloidal suspensions (r=0.1) or gel coacervates (r=0.5). The influence of the DA and Mw of CS was evaluated by visual observations, light scattering and rheological measurements. For low values of r, Small Angle X-ray Scattering (SAXS) experiments revealed that the HYA nanostructure was weakly affected by the presence of PECs. On the contrary, the structure was impacted when increasing r, revealing a heterogeneous aggregate morphology with ladder-like chain interactions. PMID:27577900

  7. Interfacial layers of complex-forming ionic surfactants with gelatin.

    PubMed

    Derkach, Svetlana R

    2015-08-01

    This review is devoted to discussing the results of studies of the influence of low-molecular weight surfactant additions on the composition and properties of gelatin adsorbed layers which are spontaneously created at water/air and water/non-polar-liquid interfaces. The interaction of surfactant with gelatin leads to the formation of complexes of variable content in the bulk of the aqueous phase. The composition content is determined by the component ratio and concentration of the added surfactant. The role of surfactants (anionic, cationic, non-ionic) capable of forming complexes with gelatin due to electrostatic and hydrophobic interactions is considered. Analysis of the interfacial layer properties is based on literature information, as well as the own author's data. These data include the results of measuring thermodynamic properties (interface tension), laws of formation (adsorption kinetics and thickness), and rheological properties of the layers, which are considered to be dependent on gelatin and surfactant concentration, pH, and temperature. The evolution of the interfacial layers' properties (with increasing surfactant concentration) is discussed in connection with the properties and content of gelatin-surfactant complexes appearing in the aqueous phase. Such an approach allows us to explain the main peculiarities of the layers' behavior including their stabilizing activity in relation to bilateral foam and emulsion films. PMID:24970019

  8. 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. PMID:26800902

  9. N,N-Dimethyl chitosan/heparin polyelectrolyte complex vehicle for efficient heparin delivery.

    PubMed

    Bueno, Pedro V A; Souza, Paulo R; Follmann, Heveline D M; Pereira, Antonio G B; Martins, Alessandro F; Rubira, Adley F; Muniz, Edvani C

    2015-04-01

    Polysaccharide-based device for oral delivery of heparin (HP) was successfully prepared. Previously synthesized N,N-dimethyl chitosan (DMC) (86% dimethylated by (1)H NMR spectroscopy) was complexed with HP by mixing HP and DMC aqueous solutions (both at pH 3.0). The polyelectrolyte complex (PEC) obtention was confirmed by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA/DTG) and wide-angle X-ray scattering (WAXS). In vitro controlled release assays of HP from PEC were investigated in the simulated intestinal fluid (SIF) and simulated gastric fluid (SGF). The PEC efficiently protected the HP in SGF condition in which HP is degraded. On the other hand, in SIF PEC promoted the releasing of 80 ± 1.5% of loaded HP. The promissory results indicated that the PEC based on DMC/HP presented potential as drug-carrier matrix, since biological activity of HP was improved at pH close to physiological condition. PMID:25625782

  10. Polyelectrolyte effects in polymers for lithography

    NASA Astrophysics Data System (ADS)

    Prabhu, Vivek

    2006-03-01

    The transformation of a solid-like film into a solution upon exposure to a miscible solvent is a complex process involving sluggish kinetic pathways associated with the slow transport of the liquid into the film and the evolution of the thermodynamic driving forces during the course of the dissolution process. In complex materials such as polymers, this process occurs in stages from the transformation of the glassy or crystalline film into a swollen state, followed at longer times by the final dissolution of the film. Dissolving polyelectrolyte films exhibit additional complexities in their dissolution dynamics over uncharged polymer films. Interfacial charge density, the dielectric constant of the medium, ionic strength and valence influence the phase behavior of charged polymers thus affecting their dissolution behavior. The dissolution mechanism can be tailored for different applications, for instance the microelectronics industry utilizes the selective dissolution of one component enabling lithographic pattern formation. We present neutron reflectivity and quartz crystal microbalance results to address polyelectrolyte effects in thin films such as the counterion distribution, quasi-equilibrium swelling and kinetics. V.M. Prabhu, R.L. Jones, E.K. Lin, W-L Wu. ``Polyelectrolyte effects in model photoresist developer solutions.'' J. Vac. Sci. and Tech.B, 21, 1403 (2003). V.M. Prabhu, B.D. Vogt, W-L. Wu, J. Douglas, E. Lin, S. Satija, D. Goldfarb, and H. Ito. ``Direct measurement of the counterion distribution within swollen polyelectrolyte films'' Langmuir Letter, 21, 6647 (2005).

  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. PMID:27367277

  12. Early Stage Kinetics in Polyelectrolyte Complexation Studied in a Stopped-Flow Configuration

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoqing; Haddou, Marie; Giermanska, Joanna; Schatz, Christophe; Chapel, Jean-Paul

    Polyelectrolyte complexes (PECs) are the association complexes formed between oppositely charged macromolecules. A large body of work has been devoted to the preparation and morphology characterizations of PECs. Much less attention was paid on formation kinetics of PECs, which often occurs under non-equilibrium conditions. Stopped-flow technique combined with light scattering was used to investigate the early stage complexation kinetics in the poly(acrylic acid) and poly(diallyldimethylammonium chloride) system. It was found that initial complexes form within a few ms. Depending on the PEs molar charge ratio z, initial complexes followed different evolution pathways. For z >0.7, a large complex aggregation ascribed to the onset of coacervation was identified by an increase of the scattered intensity while an unexpected decay was observed for z <0.7 where small PECs are formed. The appearance of characteristic bell-shaped curves in the presence of different ionic strengths (I) highlighted the strong influence of the interaction intensity on the complexation/reorganization kinetics. The results revealed distinct assembly and ageing mechanisms as a function of z, I and molecular weights.

  13. Water-soluble polyelectrolyte complexes of Astramol poly(propyleneimine) dendrimers with poly(methacrylate) anion.

    PubMed

    Zhiryakova, Marina V; Izumrudov, Vladimir A

    2014-11-26

    Water-soluble complexes formed by pyrenyl-tagged poly(methacrylate) anion with cationic DAB-dendr-(NH2)x of five generations, x = 4, 8, 16, 32, and 64 were prepared and studied. The ability of the dendrimers to quench the pyrenyl fluorescence was used to monitor formation/dissociation of the complexes by fluorescence quenching technique. In salt-free solutions, dissociation of the complexes occurred in highly acidic and highly alkaline media independently on the dendrimer generation, whereas stability of the complexes against destruction by added salt (NaCl) enhanced markedly with x increase. Phase separations were dependent on pH and charged ratio of the components, but independent of a dendrimer generation. By contrast, in water-salt solutions the generation had a profound impact on phase diagram manifested by a considerable extension of a heterogeneity region as x increased. These findings strongly suggest that the complexes obey the main regularities ascertained for polyelectrolyte complexes of oppositely charged polyions. The revealed possibility of preparing negatively charged and positively charged complexes with controllable stability and solubility demonstrates potentialities of Astramol dendrimers for design self-assembled and self-adjusted systems attractive for biotechnological and biomedical applications. PMID:25369241

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

    PubMed

    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 (Cu(2+)), 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

  15. Polyelectrolyte complex formation mediated immobilization of chitosan-invertase neoglycoconjugate on pectin-coated chitin.

    PubMed

    Gómez, Leissy; Ramírez, Hector L; Neira-Carrillo, Andrónico; Villalonga, Reynaldo

    2006-05-01

    Saccharomyces cerevisiae invertase, chemically modified with chitosan, was immobilized on pectin-coated chitin support via polyelectrolyte complex formation. The yield of immobilized enzyme protein was determined as 85% and the immobilized biocatalyst retained 97% of the initial chitosan-invertase activity. The optimum temperature for invertase was increased by 10 degrees C and its thermostability was enhanced by about 10 degrees C after immobilization. The immobilized enzyme was stable against incubation in high ionic strength solutions and was 4-fold more resistant to thermal treatment at 65 degrees C than the native counterpart. The biocatalyst prepared retained 96 and 95% of the original catalytic activity after ten cycles of reuse and 74 h of continuous operational regime in a packed bed reactor, respectively. PMID:16775742

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

    NASA Astrophysics Data System (ADS)

    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.

  17. 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.

  18. 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.

  19. NMR imaging of chitosan and carboxymethyl starch tablets: swelling and hydration of the polyelectrolyte complex.

    PubMed

    Wang, Y J; Assaad, E; Ispas-Szabo, P; Mateescu, M A; Zhu, X X

    2011-10-31

    The hydration and swelling properties of the tablets made of chitosan, carboxymethyl starch, and a polyelectrolyte complex of these two polysaccharides have been studied by NMR imaging. We studied the effect of pH and ionic strength on the swelling of the tablets and on the diffusion of fluid into the tablets in water and simulated physiological fluids. The pH value of the fluids exerts a more significant effect than their ionic strengths on the swelling of the tablets. The tablets are compared also with those made of cross-linked high amylose starch. The formation of complex helps to keep the integrity of the tablets in various media and render a slow and restricted swelling similar to that of the tablets of the cross-linked high amylase starch, which is significantly lower than the swelling of chitosan and of carboxymethyl starch. The capacities to modulate the release rate of drugs in different media are discussed by comparing the matrices and evaluating the preparation process of the complex. A sustained release of less soluble drugs such as aspirin in gastrointestinal fluids can be provided by the complex, due to the ionic interaction and hydrogen bonding between the drug and the biopolymer complex. PMID:21864660

  20. 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

  1. 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.

  2. 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. PMID:27448900

  3. 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

  4. 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

  5. Like-charged protein-polyelectrolyte complexation driven by charge patches

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  6. 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. PMID:26712704

  7. Exciton Transfer and Emergent Excitonic States in Oppositely-Charged Conjugated Polyelectrolyte Complexes.

    PubMed

    Hollingsworth, William R; Segura, Carmen; Balderrama, Jonathan; Lopez, Nathaniel; Schleissner, Pamela; Ayzner, Alexander L

    2016-08-11

    Photosynthetic organisms have mastered the use of "soft" macromolecular assemblies for light absorption and concentration of electronic excitation energy. Nature's design centers on an optically inactive protein-based backbone that acts as a host matrix for an array of light-harvesting pigment molecules. The pigments are organized in space such that excited states can migrate between molecules, ultimately delivering the energy to the reaction center. Here we report our investigation of an artificial light-harvesting energy transfer antenna based on complexes of oppositely charged conjugated polyelectrolytes (CPEs). The conjugated backbone and the charged side chains of the CPE lead to an architecture that simultaneously functions as a structural scaffold and an electronic energy "highway". We find that the process of ionic complex formation leads to a remarkable change in the excitonic wavefunction of the energy acceptor, which manifests in a dramatic increase in the fluorescence quantum yield. We argue that the extended backbone of the donor CPE effectively templates a planarized acceptor polymer, leading to excited states that are highly delocalized along the polymer backbone. PMID:27428604

  8. 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

  9. 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

    2016-09-01

    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. PMID:27185127

  10. 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

  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. 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

  13. Chitosan–pectin polyelectrolyte complex as a carrier for colon targeted drug delivery

    PubMed Central

    Pandey, Sonia; Mishra, Ashish; Raval, Pooja; Patel, Hetal; Gupta, Arti; Shah, Dinesh

    2013-01-01

    Objective The objective of present work was to prepare a polyelectrolyte complex (PEC) between chitosan (polycation) & pectin (polyanion) and to develop enteric coated tablets for colon delivery using the PEC. Methodology The PECs were prepared using different concentrations of chitosan and pectin. Drug loaded enteric coated tablets were prepared by wet granulation method using PEC to sustain the release at colon and coating was done with Eudragit S 100 to prevent the early release of the drug in stomach and intestine. Two independent variable, % PEC (chitosan/pectin) and % coating were optimized by 32 full factorial design. Statistical model were also used to supplement the optimization. DSC was performed to confirm the interaction between the polyions. Developed formulations were evaluated for physical appearance, weight variation, thickness, hardness, friability, % swelling, assay, in-vitro and ex-vivo drug release studies to investigate the PEC's ability to deliver the drug to colon. Ex-vivo release study using rat caecal content was also carried out on optimized formulation. Results and discussion DSC results confirmed chitosan/pectin interaction and subsequent formation of PEC. The optimized formulation containing 1.1% of PEC and 3% of coating showed highest swelling and release in alkaline pH mechanism of which was found to be microbial enzyme dependent degradation established by ex-vivo study using rat caecal content. PMID:24563596

  14. 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. PMID:26051341

  15. Formation of thermo-sensitive polyelectrolyte complex micelles from two biocompatible graft copolymers for drug delivery.

    PubMed

    Li, Guiying; Meng, Yanfeng; Guo, Lei; Zhang, Ting; Liu, Junshen

    2014-07-01

    Thermo-sensitive polyelectrolyte complex (PEC) micelles assembled from two biocompatible graft copolymers chitosan-g-poly(N-isopropylacrylamide) (CS-g-PNIPAM) and carboxymethyl cellulose-g-poly(N-isopropylacrylamide) (CMC-g-PNIPAM) were prepared for delivery of 5-fluorouracil (5-FU). The PEC micelles showed a narrow size distribution with core-shell structure, in which the core formed from positively charged CS and negatively charged CMC by electrostatic interactions and the shell formed from thermo-sensitive PNIPAM. The synthesized PEC micelles have lower critical solution temperatures (LCST) in the region of 37°C, which is favorable for smart drug delivery applications. The hydrogen bondings between PEC micelles and 5-FU increased the drug loading. Changing temperature, pH or ionic strength, a sustained and controlled release was observed due to the deformation of PEC micelles. Adding glutaraldehyde, a chemical crosslinking reagent, was an efficient way to reinforce the micelles structure and decrease the initial burst release. Cytotoxicity assays showed that drug-loaded PEC micelles retained higher cell inhibition efficiency in HeLa cells. PMID:23894021

  16. 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. PMID:27433574

  17. 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. PMID:23796577

  18. 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

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

    NASA Astrophysics Data System (ADS)

    Talukdar, Hrishikesh; Kundu, Sarathi; Basu, Saibal

    2016-09-01

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

  20. Polyelectrolyte complex of vancomycin as a nanoantibiotic: Preparation, in vitro and in silico studies.

    PubMed

    Sikwal, Dhiraj R; Kalhapure, Rahul S; Rambharose, Sanjeev; Vepuri, Suresh; Soliman, Mahmoud; Mocktar, Chunderika; Govender, Thirumala

    2016-06-01

    Delivery of antibiotics by various nanosized carriers is proving to be a promising strategy to combat limitations associated with conventional dosage forms and the ever-increasing drug resistance problem. This method entails improving the pharmacokinetic parameters for accumulation at the target infection site and reducing their adverse effects. It has been proposed that antibiotic nanoparticles themselves are more effective delivery system than encapsulating the antibiotic in a nanosystem. In this study, we report on nanoparticles of vancomycin (VCM) by self-assembled amphiphilic-polyelectrolyte complexation between VCM hydrochloride and polyacrylic acid sodium (PAA). The size, polydispersity index and zeta potential of the developed nanoplexes were 229.7±47.76nm, 0.442±0.075, -30.4±5.3mV respectively, whereas complexation efficiency, drug loading and percentage yield were 75.22±1.02%, 58.40±1.03% and 60.60±2.62% respectively. An in vitro cytotoxicity study on three mammalian cell lines using MTT assays confirmed the biosafety of the newly formulated nanoplexes. Morphological investigations using scanning electron microscope showed cube shaped hexagonal-like particles. In vitro drug release studies revealed that the drug was completely released from the nanoplexes within 12h. In silico studies revealed that the nano-aggregation was facilitated by means of self-association of VCM in the presence of the polymer. The supramolecular pattern of the drug self-association was found to be similar to that of the VCM dimer observed in the crystal structure of the VCM available in Protein Data Bank. In vitro antibacterial activity against susceptible and resistant Staphylococcus aureus proved that the potency of VCM was retained after being formulated as the nanoplex. In conclusion, VCM nanoplexes could be a promising nanodrug delivery system to treat infections of S. aureus origin. PMID:27040243

  1. In vitro interaction of polyelectrolyte nanocapsules with model cells.

    PubMed

    Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof

    2014-02-01

    The nanocapsules based on a liquid core with polyelectrolyte shells prepared by the technique of sequential adsorption of polyelectrolytes (LbL) were investigated to verify capsules bioacceptance. Using AOT (docusate sodium salt) as emulsifier, we obtained liquid cores, stabilized by the interfacial complex AOT/PLL (poly-l-lysine hydrobromide). These liquid cores were encapsulated by sequential adsorption of polyelectrolytes using biocompatible polyanion PGA (poly-l-glutamic acid sodium salt) and biocompatible polycation PLL. The average size of the formed capsules was 60-80 nm. The influence of a number of polyelectrolytes layer in the shell (thickness of polyelectrolytes shell), surface charge, and capsule doses on cell viability was studied in a cellular coculture assay. In order to improve nanocapsules biocompatibility, the PEG-ylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG poly(ethylene glycol)). For the most toxic nanocapsules (with only one polycation layer) about 90% of cells could survive when the concentration of nanocapsules was below 0.2 × 10(6) per one cell. That suggests that they use as a delivery vehicles is quite safe for living cells. Analysis of internalization of AOT(PLL/PGA)4-g-PEG in HEK 293 cells indicates that tested nanocapsules can easily penetrate cells membrane. PMID:24410319

  2. Cationic drug-based self-assembled polyelectrolyte complex micelles: Physicochemical, pharmacokinetic, and anticancer activity analysis.

    PubMed

    Ramasamy, Thiruganesh; Poudel, Bijay Kumar; Ruttala, Himabindu; Choi, Ju Yeon; Hieu, Truong Duy; Umadevi, Kandasamy; Youn, Yu Seok; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

    2016-10-01

    Nanofabrication of polymeric micelles through self-assembly of an ionic block copolymer and oppositely charged small molecules has recently emerged as a promising method of formulating delivery systems. The present study therefore aimed to investigate the interaction of cationic drugs doxorubicin (DOX) and mitoxantrone (MTX) with the anionic block polymer poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) and to study the influence of these interactions on the pharmacokinetic stability and antitumor potential of the formulated micelles in clinically relevant animal models. To this end, individual DOX and MTX-loaded polyelectrolyte complex micelles (PCM) were prepared, and their physicochemical properties and pH-responsive release profiles were studied. MTX-PCM and DOX-PCM exhibited a different release profile under all pH conditions tested. MTX-PCM exhibited a monophasic release profile with no initial burst, while DOX-PCM exhibited a biphasic release. DOX-PCM showed a higher cellular uptake than that shown by MTX-PCM in A-549 cancer cells. Furthermore, DOX-PCM induced higher apoptosis of cancer cells than that induced by MTX-PCM. Importantly, both MTX-PCM and DOX-PCM showed prolonged blood circulation. MTX-PCM improved the AUCall of MTX 4-fold compared to a 3-fold increase by DOX-PCM for DOX. While a definite difference in blood circulation was observed between MTX-PCM and DOX-PCM in the pharmacokinetic study, both MTX-PCM and DOX-PCM suppressed tumor growth to the same level as the respective free drugs, indicating the potential of PEGylated polymeric micelles as effective delivery systems. Taken together, our results show that the nature of interactions of cationic drugs with the polyionic copolymer can have a tremendous influence on the biological performance of a delivery system. PMID:27318960

  3. 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.

  4. Preparation of highly efficient MRI contrast agents through complexation of cationic Gd(III)-containing metallosurfactant with biocompatible polyelectrolytes.

    PubMed

    Chen, Yingying; Zhu, Qin; Cui, Xinghui; Tang, Weijun; Yang, Heng; Yuan, Yuan; Hu, Aiguo

    2014-09-22

    Novel contrast agents were developed through assembling of Gd(III) -containing metallosurfactant (MS) with biocompatible polyelectrolytes sodium hyaluronate (HA), heparinsodium (HS) and dextran sulfate sodium (DSS). The formed polyelectrolyte-surfactant complexes showed different structural patterns as the charge ratio increased, including spherical aggregates, rod-like aggregates and network patterns in monovalent HA system, while spherical structures emerged in multivalent HS and DSS systems. Energy dispersive spectroscopy analysis and scanning electron microscopy mapping showed the presence of Gd(III) in these complexes. Inductively coupled plasma atomic emission spectrometry was further used to quantify the contents of Gd(III) in the assemblies. T1 magnetic resonance imaging showed that these Gd(III) -loaded complexes exhibited relaxivity of up to 63.81 mM(-1)  s(-1) , much higher than that of Ominiscan (4.64 mM(-1)  s(-1) ). The cytotoxicity test in vitro demonstrated the excellent biocompatibility of these complexes, which is essential for clinical application. PMID:25116812

  5. The Interfacial Interaction Problem in Complex Multiple Porosity Fractured Reservoirs

    NASA Astrophysics Data System (ADS)

    Suarez-Arriaga, Mario-Cesar

    2003-04-01

    Many productive reservoirs (oil, gas, water, geothermal) are associated to natural fracturing. Fault zones and fractures act as open networks for fluid and energy flow from depth. Their petrophysical parameters are heterogeneous and randomly distributed, conforming extremely complex natural systems. Here, the simultaneous heat and mass flows are coupled to the deformation of thermoporoelastic rocks. The system's volume is divided into N interacting continua, each one occupying a region of space Vn wrapped by a surface Sn (n=1,N). The mass flow is represented by: ∂/∂t ∫ Vn ρf φdV + ∫ Sn F⃗M ṡ n⃗dS = ∫ Vn qMdV (3) Taking into account a non-isothermal process the coupled equation of energy is: ∂/∂t ∫ Vn [φρf hf + (1 - φ)ρrhr]dV + ∫ Sn F⃗E ṡ n⃗dS = ∫ Vn qEdV (4) Where t means time, φ is porosity, ρf, ρr are fluid and rock densities, F⃗M and F⃗E are total mass and energy flows, qM and qE are volumetric mass and energy extracted or injected into Vn, hf and hr are specific enthalpies for fluid and rock respectively. Rock deformation is coupled through the equation: ∇⃗ ṡ (ρf/μK ṡ ∇⃗pφ)Vn = φ (Dtρf + ρf/VφdVφ/dt)Vn (5) K is the absolute permeability tensor, μ means dynamic fluid viscosity, Dt is a total derivative, pφ is pore pressure and Vφ is the volume of pores in Vn. The N media interact with each other, every one has its own parameters and its own interporosity flow. Modelling these coupled phenomena requires to average highly contrasting physical properties, independently of the method used in the solution of equations. A lot of attention has been devoted to develop realistic numerical models to describe flows in reservoirs under exploitation. But to the best of our knowledge very little attention has been focused on the problem of interfacial interaction and averaging petrophysical parameters in multiple porosity reservoirs.

  6. 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. PMID:27474666

  7. Synthesis of nanosilver loaded chitosan/poly(acrylamide-co-itaconic acid) based inter-polyelectrolyte complex films for antimicrobial applications.

    PubMed

    Bajpai, S K; Jyotishi, Pooja; Bajpai, M

    2016-12-10

    In the present work, AgNPs loaded chitosan/poly(acrylamide-co-itaconic acid) inter-polyelectrolyte complex (IPC) films have been prepared for antimicrobial applications. The AgNPs-loaded IPC films have been characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Thermogravimetric analysis (TGA) and Surface plasmon resonance (SPR). Particle size of synthesized AgNPs was found to be in the range 10-30nm. These films exhibited a remarkable antibacterial property against strong pathogen E.Coli, thus offering their candidature for antimicrobial applications. PMID:27577913

  8. 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).

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

    PubMed Central

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

    2014-01-01

    Background Implant loosening or deficient osseointegration is a major problem in patients with systemic bone diseases (eg, osteoporosis). For this reason, the stimulation of the regional cell population by local and sustained drug delivery at the bone/implant interface to induce the formation of a mechanical stable bone is promising. The purpose of this study was to investigate the interaction of polymer-based nanoparticles with human bone marrow-derived cells, considering nanoparticles’ composition and surface net charge. Materials and methods Polyelectrolyte complex nanoparticles (PECNPs) composed of the polycations poly(ethyleneimine) (PEI), poly(L-lysine) (PLL), or (N,N-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). Results PECNPs ranging between ~50 nm and 150 nm were prepared. By varying the ratio of polycations and polyanions, PECNPs with a slightly positive (PEC+NP) or negative (PEC−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

  10. Complexation Between Weakly Basic Dendrimers and Linear Polyelectrolytes: Effects of Chain Stiffness, Grafts, and pOH

    NASA Astrophysics Data System (ADS)

    Lewis, Thomas; Pandav, Gunja; Omar, Ahmad; Ganesan, Venkat

    2013-03-01

    The unique architecture and high charge density of dendrimer molecules have attracted interest for their utilization in gene delivery applications. The strong binding affinity of cationic dendrimers to genetic materials make them effective gene delivery vectors not only by shielding the nucleic acid (NA) material from degradative enzymes in the blood stream, but also by reducing the overall negative charge of the dendrimer-NA material complex, which in turn creates more favorable interaction with the anionic cell membrane. However, the high cytotoxicities of cationic dendrimers have motivated the development of polyethylene glycol (PEG) conjugated dendrimer molecules, which have been shown to reduce dendrimer cytotoxicity while still retaining transfection ability. In order to gain insight into how the addition of neutral grafts affects the binding affinity and conformations of dendrimer-NA material complexes, we have developed and numerically solved a Self-Consistent Field Theory approach for both grafted and non-grafted annealed charged dendrimer molecules in the presence of linear polyelectrolyte molecules. Specifically, this work examines the effect of linear polyelectrolyte stiffness, grafting chain length, and solution pOH.

  11. Dermatan sulfate/chitosan polyelectrolyte complex with potential application in the treatment and diagnosis of vascular disease.

    PubMed

    Rasente, Rita Y; Imperiale, Julieta C; Lázaro-Martínez, Juan M; Gualco, Luciana; Oberkersch, Roxana; Sosnik, Alejandro; Calabrese, Graciela C

    2016-06-25

    Cardiovascular disease is the largest single cause of morbid-mortality in the world. However, there is still no pharmaceutical treatment that directly targets the blood vessel wall instead of just controlling the risk factors. Here, we produced polyelectrolyte complexes (PECs) by a simple and reproducible polyelectrolyte complexation method between low molecular mass dermatan sulfate (polyanionic polysaccharide) and chitosan (polycationic polysaccharide), and evaluated the cellular uptake by vascular endothelial cells. The composition and the composition homogeneity of PECs were confirmed by (13)C-CP-MAS spectroscopy and by polyacrylamide gel electrophoresis, respectively. The hydrodynamic radius, determined by dynamic light scattering, was 729±11nm. PECs were not cytotoxic for a murine heart endothelium-derived cell line. Fluorescent confocal microscopy showed the specific uptake of fluorescently-labeled PECs by endothelial cells when they were cultured alone or in the presence of macrophages. Overall, these findings confirmed the potential of these PECs for targeting different agents to the vessel wall in the prevention, diagnosis, and therapy of vascular disease. PMID:27083828

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

    PubMed

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

    2016-07-11

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

  13. Nasal inserts containing ondansetron hydrochloride based on Chitosan-gellan gum polyelectrolyte complex: In vitro-in vivo studies.

    PubMed

    Sonje, Ashish G; Mahajan, Hitendra S

    2016-07-01

    The aim of this study was the production of ondansetron hydrochloride loaded lyophilized insert for nasal delivery. The nasal insert was prepared by the lyophilisation technique using Chitosan-gellan gum polyelectrolyte complex as the polymer matrix. The ondansetron loaded inserts were evaluated with respect to water uptake, bioadhesion, drug release kinetic study, ex vivo permeation study, and in vivo study. Lyophilised nasal inserts were characterized by differential scanning calorimetry, scanning electron microscopy and X-ray diffraction study. Scanning electron microscopy confirmed the porous sponge like structure of inserts whereas release kinetic model revealed that drug release followed non-fickian case II diffusion. The nasal delivery showed improved bioavailability as compared to oral delivery. In conclusion, the ondansetron containing nasal inserts based on Chitosan-gellan gum complex with potential muco-adhesive potential is suitable for nasal delivery. PMID:27127060

  14. Diblock Polyelectrolytic Copolymers Containing Cationic Iron and Cobalt Sandwich Complexes: Living ROMP Synthesis and Redox Properties.

    PubMed

    Gu, Haibin; Ciganda, Roberto; Hernandez, Ricardo; Castel, Patricia; Zhao, Pengxiang; Ruiz, Jaime; Astruc, Didier

    2016-04-01

    Diblock metallopolymer polyelectrolytes containing the two redox-robust cationic sandwich units [CoCp'Cp](+) and [FeCp'(η(6)-C6 Me6)](+) (Cp = η(5)-C5 H5; Cp' = η(5)-C5H4-) as hexafluorophosphate ([PF6](-)) salts are synthesized by ring-opening metathesis polymerization using Grubbs' third generation catalyst. Their electrochemical properties show full chemical and electrochemical reversibilities allowing fine determination of the copolymer molecular weight using Bard-Anson's electrochemical method by cyclic voltammetry. PMID:26841204

  15. Molecular Dyhamics Simulation of the Interfacial Behavior of Aqueous Polyelectrolyte Solutions in Contact with Graphene surfaces in the Presence of Multivalent Cations

    SciTech Connect

    Chialvo, Ariel A; Simonson, J Michael {Mike}

    2008-01-01

    We present a detailed analysis of the behavior of aqueous electrolyte-polyelectrolyte systems in contact with neutral and charged graphene substrates, based on an extensive molecular dynamics simulation effort. Our study involves aqueous systems comprising short-chains of lithium-polystyrene sulfonate with explicit atomistic description of water, the chain backbones, and their interactions with all species in solution as well as with the graphene surface. We place special emphasis on the behavior of the axial profiles of species concentrations, local electrostatic charge density, electric field and corresponding surface-charge screening to provide a full characterization of the inhomogeneous environment at the solid-liquid interface, i.e., the electric double layer and the effect of the added salts (BaCl2 and LaCl3 ) on its structure. To complete the analysis, we assess the tendency toward ion pairing along planes parallel to the graphene surface and estimate, according to the axial distribution profiles, the strength of the adsorption of the polyelectrolyte, counterions, and other species in solution, in order to interpret the degree of surface-charge screening and the occurrence of surface-charge reversal. We present evidence of a recently reported new phenomenon of overcharging, and discuss the central role of the explicit description of the solvent on this occurrence. Moreover, to interpret the conformational behavior of the polyelectrolyte backbones we determine the axial profiles of the perpendicular and parallel components of the corresponding radius of gyration and end-to-end distance.

  16. Effect of temperature on the reentrant condensation in polyelectrolyte-liposome complexation.

    PubMed

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

    2008-11-01

    Interactions of oppositely charged macroions in aqueous solution give rise to intriguing aggregation phenomena, resulting in finite-size, long-lived clusters, characterized by a quite narrow size distribution. Particularly, the adsorption of highly charged linear polyelectrolytes on oppositely charged colloidal particles is strongly correlated and some short-range order arises from competing electrostatic interactions between like-charged polymer chains (repulsion) and between polymer chains and particle surface (attraction). In these systems, in an interval of concentrations around the isoelectric point, relatively large clusters of polyelectrolyte-decorated particles form. However, the mechanisms that drive the aggregation and stabilize, at the different polymer/particle ratios, a well-defined size of the aggregates are not completely understood. Nor is clear the role that the correlated polyion adsorption plays in the aggregation, although the importance of "patchy interactions" has been stressed as the possible source of attractive interaction term between colloidal particles. Different models have been proposed to explain the formation of the observed cluster phase. However, a central question still remains unanswered, i.e., whether the clusters are true equilibrium or metastable aggregates. To elucidate this point, in this work, we have investigated the effect of the temperature on the cluster formation. We employed liposomes built up by DOTAP lipids interacting with a simple anionic polyion, polyacrylate sodium salt, over an extended concentration range below and above the isoelectric condition. Our results show that the aggregation process can be described by a thermally activated mechanism. PMID:18831566

  17. 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.

  18. The influence of ionic strength and mixing ratio on the colloidal stability of PDAC/PSS polyelectrolyte complexes.

    PubMed

    Zhang, Yanpu; Yildirim, Erol; Antila, Hanne S; Valenzuela, Luis D; Sammalkorpi, Maria; Lutkenhaus, Jodie L

    2015-10-01

    Polyelectrolyte complexes (PECs) form by mixing polycation and polyanion solutions together, and have been explored for a variety of applications. One challenge for PEC processing and application is that under certain conditions the as-formed PECs aggregate and precipitate out of suspension over the course of minutes to days. This aggregation is governed by several factors such as electrostatic repulsion, van der Waals attractions, and hydrophobic interactions. In this work, we explore the boundary between colloidally stable and unstable complexes as it is influenced by polycation/polyanion mixing ratio and ionic strength. The polymers examined are poly(diallyldimethylammonium chloride) (PDAC) and poly(sodium 4-styrenesulfonate) (PSS). Physical properties such as turbidity, hydrodynamic size, and zeta potential are investigated upon complex formation. We also perform detailed molecular dynamics simulations to examine the structure and effective charge distribution of the PECs at varying mixing ratios and salt concentrations to support the experimental findings. The results suggest that the colloidally stable/unstable boundary possibly marks the screening effects from added salt, resulting in weakly charged complexes that aggregate. At higher salt concentrations, the complexes initially form and then gradually dissolve into solution. PMID:26268471

  19. 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. PMID:27467966

  20. 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

    2014-10-01

    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. PMID:25207753

  1. 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.

  2. A 'microfluidic pinball' for on-chip generation of Layer-by-Layer polyelectrolyte microcapsules.

    PubMed

    Kantak, Chaitanya; Beyer, Sebastian; Yobas, Levent; Bansal, Tushar; Trau, Dieter

    2011-03-21

    Inspired by the game of "pinball" where rolling metal balls are guided by obstacles, here we describe a novel microfluidic technique which utilizes micropillars in a flow channel to continuously generate, encapsulate and guide Layer-by-Layer (LbL) polyelectrolyte microcapsules. Droplet-based microfluidic techniques were exploited to generate oil droplets which were smoothly guided along a row of micropillars to repeatedly travel through three parallel laminar streams consisting of two polymers and a washing solution. Devices were prototyped in PDMS and generated highly monodisperse and stable 45±2 µm sized polyelectrolyte microcapsules. A total of six layers of hydrogen bonded polyelectrolytes (3 bi-layers) were adsorbed on each droplet within <3 minutes and a fluorescent intensity measurement confirmed polymer film deposition. AFM analysis revealed the thickness of each polymer layer to be approx. 2.8 nm. Our design approach not only provides a faster and more efficient alternative to conventional LbL deposition techniques, but also achieves the highest number of polyelectrolyte multilayers (PEMs) reported thus far using microfluidics. Additionally, with our design, a larger number of PEMs can be deposited without adding any extra operational or interfacial complexities (e.g. syringe pumps) which are a necessity in most other designs. Based on the aforementioned advantages of our device, it may be developed into a great tool for drug encapsulation, or to create capsules for biosensing where deposition of thin nanofilms with controlled interfacial properties is highly required. PMID:21218225

  3. 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. PMID:26478364

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

    SciTech Connect

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

    1987-04-21

    A metal lamina is described consisting of a steel and non ferrous metal base and a precoat polymer layer consisting of a zinc phosphating layer modified by a polymer coating of about 20A-40A thickness of a polyelectrolyte selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyitaconic acid, and poly-L-glutamic acid. The precoat polymer layer was applied from a zinc phosphate and polyelectrolyte composition wherein the polyelectrolyte is present in about 0.5-5% by weight and has a molecular weight of about 10,000-300,000.

  5. 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

  6. Monomodal polyelectrolyte complex nanoparticles of PDADMAC/Poly(styrenesulfonate): preparation and protein interaction.

    PubMed

    Ouyang, Wuye; Müller, Martin

    2006-11-01

    The binding of the model proteins HSA, LYZ and MYO to PEC nanoparticles is reported. PEC particles were prepared by mixing solutions of PDADMAC either with PSS or PMA-MS, followed by consecutive centrifugation. Monomodal anionic (PEC-1.50) and cationic (PEC-0.66) PEC particles were obtained using non-stoichiometric mixing ratios. PEC/protein conjugates were prepared by adding charged protein solutions to dispersions of respective like charged PEC particles, followed by one centrifugation step. Mixing proteins and PEC particles under attractive conditions led to flocculation of the dispersion. From CD, DLS and AFM the following trend for protein binding at PEC particles under repulsive conditions was obtained: HSA/PEC-1.50 > MYO/PEC-1.50 > LYZ/PEC-0.66. Protein uptakes up to 0.33 g x g(-1) (protein/PEC) (CD) and particle diameter enlargements up to 13 nm (AFM) were obtained at c(PROT) = 0.091 mg . mL(-1). Furthermore, novel spin coated films of PEC particles were interacted with proteins under both repulsive and attractive conditions. In-situ ATR FT-IR spectroscopy revealed that the adsorbed amount of HSA and LYZ under attractive conditions was significantly higher than under repulsive ones, which is analogous to protein adsorption at polyelectrolyte multilayers terminated either by polycation or polyanion. Similarly to the dispersed PEC/protein conjugates, under repulsive conditions the uptake of HSA was higher compared to LYZ. The shown protein uptake under repulsive conditions is related to concepts of mild enzyme or protein binding at nonbiogenic substrates. PMID:17099866

  7. Physical and bioengineering properties of polyvinyl alcohol lens-shaped particles versus spherical polyelectrolyte complex microcapsules as immobilisation matrices for a whole-cell Baeyer-Villiger monooxygenase.

    PubMed

    Schenkmayerová, Andrea; Bučko, Marek; Gemeiner, Peter; Treľová, Dušana; Lacík, Igor; Chorvát, Dušan; Ačai, Pavel; Polakovič, Milan; Lipták, Lukáš; Rebroš, Martin; Rosenberg, Michal; Stefuca, Vladimír; Neděla, Vilém; Tihlaříková, Eva

    2014-11-01

    Direct comparison of key physical and chemical-engineering properties of two representative matrices for multipurpose immobilisations was performed for the first time. Polyvinyl alcohol lens-shaped particles LentiKats® and polyelectrolyte complex microcapsules were characterised by advanced techniques with respect to the size distribution of the particles, their inner morphology as revealed by fluorescent probe staining, mechanical resistance, size-exclusion properties, determination of effective diffusion coefficient and environmental scanning electron microscope imaging. While spherical polyelectrolyte complex microcapsules composed of a rigid semipermeable membrane and a liquid core are almost uniform in shape and size (diameter of 0.82 mm; RSD = 5.6 %), lens-shaped LentiKats® are characterised by wider size distribution (diameter of 3.65 mm; RSD = 10.3 % and height of 0.341 mm; RSD = 32.3 %) and showed the same porous structure throughout their whole volume at the mesoscopic (micrometre) level. Despite differences in their inner structure and surface properties, the pore diameter of ∼ 2.75 nm for regular polyelectrolyte complex microcapsules and ∼ 1.89 nm for LentiKats® were similar. These results were used for mathematical modelling, which provided the estimates of the effective diffusion coefficient of sucrose. This value was 1.67 × 10(-10) m(2) s(-1) for polyelectrolyte complex microcapsules and 0.36 × 10(-10) m(2) s(-1) for LentiKats®. Recombinant cells Escherichia coli-overexpressing enzyme cyclopentanone monooxygenase were immobilised in polyelectrolyte complex microcapsules and LentiKats® for comparison of their operational stability using model Baeyer-Villiger oxidation of (±)-cis-bicyclo [3.2.0] hept-2-en-6-one to regioisomeric lactones as important chiral synthons for potential pharmaceuticals. Both immobilisation matrices rendered high operational stability for whole-cell biocatalyst with no reduction in the

  8. Design of a stable and methanol resistant membrane with cross-linked multilayered polyelectrolyte complexes for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Zhao, Chengji; Lin, Haidan; Zhang, Gang; Zhang, Yang; Ni, Jing; Ma, Wenjia; Na, Hui

    Sulfonated poly (arylene ether ketone) bearing carboxyl groups (SPAEK-C) membranes have been prepared as proton exchange membranes for applications in direct methanol fuel cells (DMFCs). Multilayered polyelectrolyte complexes (PECs) which applied as methanol barrier agents are prepared by alternate deposition of the oppositely charged amino-containing poly (ether ether ketone) (Am-PEEK) and the highly sulfonated SPAEK-C via a layer-by-layer method. The cross-linked PEC (c-PEC) is derived from a simple heat-induced cross-linking reaction between Am-PEEK and SPAEK-C. Fourier transform infrared spectroscopy confirms that Am-PEEK and SPAEK-C are assembled successfully in the multilayers. The morphology of the membranes is studied by scanning electron microscopy, which shows the presence of the thin layers coated on the SPAEK-C membrane. After PEC and c-PEC modification, the methanol permeability decreases obviously when compared to that of the pristine membrane. Notably, improved proton conductivities are obtained for the PEC modified membranes in comparison with the pristine membrane. Moreover, the selectivity of these modified membranes is one order of magnitude higher than that of Nafion 117. The thermal stability, oxidative stability, water uptake and swelling of PEC and c-PEC modified membranes are also investigated.

  9. 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.

  10. Insight into fractal self-assembly of poly(diallyldimethylammonium chloride)/sodium carboxymethyl cellulose polyelectrolyte complex nanoparticles.

    PubMed

    Zhao, Qiang; An, Quanfu; Qian, Jinwen; Wang, Xuesan; Zhou, Yang

    2011-12-22

    Poly(diallyldimethylammonium chloride)-sodium carboxymethyl cellulose polyelectrolyte complexes (PDDA-CMCNa PECs) solids were prepared and dispersed in NaOH aqueous solution. Self-assembly of PECs nanoparticles during the solvent evaporation was examined by field emission electron microscopy (FESEM), atomic force microscopy (AFM), and fractal dimension analysis. It was found that tree-shaped fractal patterns formed after the solvent (water) was dried at ambient temperatures, and the fractal pattern is composed of needle-shaped PEC aggregate (PECA) nanoparticles. Time-dependent FESEM observation revealed that the fractal pattern started with the formation of initial nucleon and it is growing, during which the diffusion limited aggregation (DLA) mechanism revealed and made the pattern branched. Physical insight into the DLA mechanism was discussed in detail. Effects of PEC concentrations, PEC compositions, solvent evaporation temperatures, pH of PEC dispersion, and chemical structures of PECs on the formation of self-assembled fractal pattern were studied. Generally, it was found that the morphologies, charge characters of PEC particles, and the solvent evaporation conditions play important roles during the fractal self-assembly process. PMID:22098094

  11. Chitosan-hyaluronic acid polyelectrolyte complex scaffold crosslinked with genipin for immobilization and controlled release of BMP-2.

    PubMed

    Nath, Subrata Deb; Abueva, Celine; Kim, Boram; Lee, Byong Taek

    2015-01-22

    Polyelectrolyte complex (PEC) is formed when polymers with opposite charges are combined in solution. PECs are recently gaining attention as carriers for controlled release of drugs and proteins. Herein, bone morphogenetic protein-2 (BMP-2) was immobilized in a PEC of natural polymers, chitosan and hyaluronic acid. Charge-to-charge stoichiometry of the formed PEC was estimated based on turbidity of combined chitosan and hyaluronic acid solutions. Free amino groups in chitosan were crosslinked with different amounts of genipin. The degree of crosslinking, consequently its effects in vitro in terms of swelling, degradation and cytocompatibility were analyzed. Immobilization of three different amount of BMP-2 in chitosan-hyaluronic acid PEC scaffold resulted sustained release of the growth factor for more than 30 days. Immobilization efficacies varied from 61% to 76% depending on the amount of BMP-2. Finally effects in osteogenic differentiation of the PEC with BMP-2 to MC3T3-E1 cells were determined by reverse transcriptase PCR. PMID:25439881

  12. 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. PMID:27406046

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

    DOE PAGESBeta

    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

  14. 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.

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

    PubMed

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

    2014-08-01

    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/cm(2) for 0.5 min; low light dose = 25 mW/cm(2) 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

  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. 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.

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

    PubMed

    Cametti, C; Truzzolillo, D

    2011-06-01

    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

  19. Conjugated Polyelectrolyte-Induced Self-Assembly of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2'-yl)pyridine Complexes.

    PubMed

    Chan, Kevin; Chung, Clive Yik-Sham; Yam, Vivian Wing-Wah

    2015-11-01

    Water-soluble cationic alkynylplatinum(II) 2,6-bis(benzimidazol-2'-yl)pyridine (bzimpy) complexes have been demonstrated to undergo supramolecular assembly with anionic polyelectrolytes in aqueous buffer solution. Metal-metal-to-ligand charge transfer (MMLCT) absorptions and triplet MMLCT ((3) MMLCT) emissions have been found in UV/Vis absorption and emission spectra of the electrostatic assembly of the complexes with non-conjugated polyelectrolytes, driven by Pt⋅⋅⋅Pt and π-π interactions among the complex molecules. Interestingly, the two-component ensemble formed by [Pt(bzimpy-Et){CCC6 H4 (CH2 NMe3 -4)}]Cl2 (1) with para-linked conjugated polyelectrolyte (CPE), PPE-SO3 (-) , shows significantly different photophysical properties from that of the ensemble formed by 1 with meta-linked CPE, mPPE-Ala. The helical conformation of mPPE-Ala allows the formation of strong mPPE-Ala-1 aggregates with Pt⋅⋅⋅Pt, electrostatic, and π-π interactions, as revealed by the large Stern-Volmer constant at low concentrations of 1. Together with the reasonably large Förster radius, large HOMO-LUMO gap and high triplet state energy of mPPE-Ala to minimize both photo-induced charge transfer (PCT) and Dexter triplet energy back-transfer (TEBT) quenching of the emission of 1, efficient Förster resonance energy transfer (FRET) from mPPE-Ala to aggregated 1 molecules and strong (3) MMLCT emission have been found, while the less strong PPE-SO3 (-) -1 aggregates and probably more efficient PCT and Dexter TEBT quenching would account for the lack of (3) MMLCT emission in the PPE-SO3 (-) -1 ensemble. PMID:26429604

  20. 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).

  1. 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. PMID:25567551

  2. 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. PMID:25886079

  3. 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

  4. 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.

  5. 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.

  6. Polyelectrolyte-surfactant complexes formed by poly[3,5-bis(trimethylammoniummethyl)4-hydroxystyrene iodide]-block-poly(ethylene oxide) and sodium dodecyl sulfate in aqueous solutions.

    PubMed

    Štěpánek, Miroslav; Matějíček, Pavel; Procházka, Karel; Filippov, Sergey K; Angelov, Borislav; Šlouf, Miroslav; Mountrichas, Grigoris; Pispas, Stergios

    2011-05-01

    Formation of polyelectrolyte-surfactant (PE-S) complexes of poly[3,5-bis(trimethylammoniummethyl)-4-hydroxystyrene iodide]-block-poly(ethylene oxide) (QNPHOS-PEO) and sodium dodecyl sulfate (SDS) in aqueous solution was studied by dynamic and electrophoretic light scattering, small-angle X-ray scattering (SAXS), atomic force microscopy, and fluorometry, using pyrene as a fluorescent probe. SAXS data from the QNPHOS-PEO/SDS solutions were fitted assuming contributions from free copolymer, PE-S aggregates described by a mass fractal model, and densely packed surfactant micelles inside the aggregates. It was found that, unlike other systems of a double hydrophilic block polyelectrolyte and an oppositely charged surfactant, PE-S aggregates of the QNPHOS-PEO/SDS system do not form core-shell particles and the PE-S complex precipitates before reaching the charge equivalence between dodecyl sulfate anions and QNPHOS polycationic blocks, most likely because of conformational rigidity of the QNPHOS blocks, which prevents the system from the corresponding rearrangement. PMID:21446735

  7. Polyelectrolyte Complexes of Low Molecular Weight PEI and Citric Acid as Efficient and Nontoxic Vectors for in Vitro and in Vivo Gene Delivery.

    PubMed

    Giron-Gonzalez, M Dolores; Salto-Gonzalez, Rafael; Lopez-Jaramillo, F Javier; Salinas-Castillo, Alfonso; Jodar-Reyes, Ana Belen; Ortega-Muñoz, Mariano; Hernandez-Mateo, Fernando; Santoyo-Gonzalez, Francisco

    2016-03-16

    Gene transfection mediated by the cationic polymer polyethylenimine (PEI) is considered a standard methodology. However, while highly branched PEIs form smaller polyplexes with DNA that exhibit high transfection efficiencies, they have significant cell toxicity. Conversely, low molecular weight PEIs (LMW-PEIs) with favorable cytotoxicity profiles display minimum transfection activities as a result of inadequate DNA complexation and protection. To solve this paradox, a novel polyelectrolyte complex was prepared by the ionic cross-linking of branched 1.8 kDa PEI with citric acid (CA). This system synergistically exploits the good cytotoxicity profile exhibited by LMW-PEI with the high transfection efficiencies shown by highly branched and high molecular weight PEIs. The polyectrolyte complex (1.8 kDa-PEI@CA) was obtained by a simple synthetic protocol based on the microwave irradiation of a solution of 1.8 kDa PEI and CA. Upon complexation with DNA, intrinsic properties of the resulting particles (size and surface charge) were measured and their ability to form stable polyplexes was determined. Compared with unmodified PEIs the new complexes behave as efficient gene vectors and showed enhanced DNA binding capability associated with facilitated intracellular DNA release and enhanced DNA protection from endonuclease degradation. In addition, while transfection values for LMW-PEIs are almost null, transfection efficiencies of the new reagent range from 2.5- to 3.8-fold to those of Lipofectamine 2000 and 25 kDa PEI in several cell lines in culture such as CHO-k1, FTO2B hepatomas, L6 myoblasts, or NRK cells, simultaneously showing a negligible toxicity. Furthermore, the 1.8 kDa-PEI@CA polyelectrolyte complexes retained the capability to transfect eukaryotic cells in the presence of serum and exhibited the capability to promote in vivo transfection in mouse (as an animal model) with an enhanced efficiency compared to 25 kDa PEI. Results support the polyelectrolyte complex

  8. Polyelectrolyte gels

    SciTech Connect

    Segalman, D.J.; Witkowski, W.R.

    1995-06-01

    Polyelectrolyte (PE) gels are swollen polymer/solvent networks that undergo a reversible volume collapse/expansion through various types of stimulation. Applications that could exploit this large deformation and solvent expulsion/absorption characteristics include robotic {open_quotes}fingers{close_quotes} and drug delivery systems. The goals of the research were to first explore the feasibility of using the PE gels as {open_quotes}smart materials{close_quotes} - materials whose response can be controlled by an external stimulus through a feedback mechanism. Then develop a predictive capability to simulate the dynamic behavior of these gels. This involved experimentally characterizing the response of well-characterized gels to an applied electric field and other stimuli to develop an understanding of the underlying mechanisms which cause the volume collapse. Lastly, the numerical analysis tool was used to simulate various potential engineering devices based on PE gels. This report discusses the pursuit of those goals through experimental and computational means.

  9. 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. PMID:25080085

  10. Single-molecule interfacial electron transfer in donor-bridge-nanoparticle acceptor complexes.

    PubMed

    Jin, Shengye; Snoeberger, Robert C; Issac, Abey; Stockwell, David; Batista, Victor S; Lian, Tianquan

    2010-11-18

    Photoinduced interfacial electron transfer (IET) in sulforhodamine B (SRhB)-aminosilane-Tin oxide (SnO(2)) nanoparticle donor-bridge-acceptor complexes has been studied on a single molecule and ensemble average level. On both SnO(2) and ZrO(2), the sum of single molecule fluorescence decays agree with the ensemble average results, suggesting complete sampling of molecules under single molecule conditions. Shorter fluorescence lifetime on SnO(2) than on ZrO(2) is observed and attributed to IET from SRhB to SnO(2). Single molecule lifetimes fluctuate with time and vary among different molecules, suggesting both static and dynamic IET heterogeneity in this system. Computational modeling of the complexes shows a distribution of molecular conformation, leading to a distribution of electronic coupling strengths and ET rates. It is likely that the conversion between these conformations led to the fluctuation of ET rate and fluorescence lifetime on the single molecule level. PMID:20225886

  11. Cationic conjugated polyelectrolyte/molecular beacon complex for sensitive, sequence-specific, real-time DNA detection.

    PubMed

    Feng, Xuli; Duan, Xinrui; Liu, Libin; An, Lingling; Feng, Fude; Wang, Shu

    2008-11-01

    A new fluorescence method has been developed for DNA detection at room temperature in a sensitive, selective, economical, and real-time manner that interfaces the superiority of a molecular beacon in mismatch discrimination with the light-harvesting property of water-soluble conjugated polyelectrolytes. The probe solution contains a cationic conjugated polyelectrolyte (PFP-NMe3+), a molecular beacon with a five base pairs double-stranded stem labeled at the 5'-terminus with fluorescein (DNA P-Fl), and ethidium bromide (EB, a specific intercalator of dsDNA). The electrostatic interactions between DNA P-Fl and PFP-NMe3+ keep them in close proximity, facilitating the fluorescence resonance energy transfer (FRET) from PFP-NMe3+ to fluorescein. Upon adding a complementary strand to the probe solution, the conformation of DNA P-Fl transits into dsDNA followed by the intercalation of EB into the grooves. Two-step FRET, from PFP-NMe3+ to DNA P-Fl (FRET-1), followed by FRET from DNA P-Fl to EB (FRET-2) takes place. In view of the observed fluorescein or EB emission changes, DNA can be detected in aqueous solution. Because the base mismatch in target DNA inhibits the transition of DNA P-Fl from the stem-loop to duplex structure, single nucleotide mismatch can be clearly detected. PMID:18834161

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Ishii, Ayumi; Hasegawa, Miki

    2015-06-01

    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.

  14. 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

  15. 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

    2016-07-01

    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. PMID:27299803

  16. Counter-ion distribution around flexible polyelectrolytes having different molecular architecture.

    PubMed

    Chremos, Alexandros; Douglas, Jack F

    2016-03-21

    We explore the monovalent counter-ion distribution around flexible highly-charged polyelectrolytes with different molecular architectures (linear chains, stars, and unknotted and trefoil rings) using molecular dynamics simulations that include an explicit solvent that interacts with the polyelectrolyte. In particular, we find that the molecular topology influences the fraction of counter-ions transiently associating with the polyelectrolyte on a scale of the order of the chain segments, forming a "condensed" counter-ion interfacial layer. As with the hydrogen bonding of water to proteins and other polymers, the persistence time of these interfacial "bound" counter-ions is relatively short, O(1 ps), and we characterize the fluctuations in the number of the counter-ions populating the interfacial layer. We also find that the counter-ions are distributed in a non-uniform fashion on the polyelectrolyte backbone, forming dynamical clusters whose form and average size is sensitive to molecular architecture. In addition, we find that the residual bound counter-ions, not located in either the interfacial layer or the bulk solution, form a diffuse ionic cloud around the polyelectrolyte due to the uncompensated polyelectrolyte charge along the backbone. Generally charge valence strongly influences the extent of the diffuse counter-ion cloud, but in the case of monovalent counter-ions, we find that the size of the diffuse counter-ion cloud nearly coincides with the polyelectrolyte radius of gyration, independent of molecular topology. PMID:26864861

  17. [Catalytic activity and the stability of horseradish peroxidase increase as a result of its incorporation into a polyelectrolyte complex with chitosan].

    PubMed

    Veselova, I A; Koreĭko, A V; Shekhovtsova, T N

    2009-01-01

    The incorporation of horseradish peroxidase into polyelectrolyte complexes with chitosans of different molecular weights (MW 5-150 kDa) yielded highly active and stable enzyme preparations. As a result of the selection of optimal conditions for the formation of peroxidase-chitosan complexes, it was found that 0.1% chitosan with a MW of 10 kDa had the strongest activatory effect on peroxidase (activation degree, > 70%) in the reaction of o-dianisidine oxidation by hydrogen peroxide. The complex formed by 0.001% chitosan with a molecular weight of 150 kDa was most stable: when immobilized on foamed polyurethane, it retained at least 50% of the initial activity for 550 days. The highest catalytic activity was exhibited in a 0.05 M phthalate buffer (pH 5.9-6.2) by the complex containing 0.006-0.009% chitosan in the indicator reaction. The activatory effect of the polysaccharide on the enzyme was determined by its influence on the binding and conversion of the reducting substrate peroxidase. PMID:19382699

  18. 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.)

  19. 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.)

  20. 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. PMID:25311176

  1. 3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate).

    PubMed

    Guzmán, Eduardo; Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel; Rubio, Ramón G

    2016-01-01

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

  2. 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

  3. Selective transport of ions and molecules across layer-by-layer assembled membranes of polyelectrolytes, p-sulfonato-calix[n]arenes and Prussian Blue-type complex salts.

    PubMed

    Tieke, Bernd; Toutianoush, Ali; Jin, Wanqin

    2005-11-30

    Our recent studies in the field of ultrathin membranes prepared upon layer-by-layer assembly of various polyionic compounds such as polyelectrolytes, calixarenes and polyelectrolytes, and metal hexacyanoferrate salts such as Prussian Blue are reviewed. It is demonstrated that polyelectrolyte multilayers can be used (a) as nanofiltration and reverse osmosis membranes suitable for water softening and seawater desalination and (b) as molecular sieves and ion sieves for size-selective separation of neutral and charged aromatic compounds. Furthermore, hybrid membranes of p-sulfonato-calixarenes and cationic polyelectrolytes showing specific host-guest interactions with permeating ions are described. The membranes exhibit high selectivities for distinct metal ions. Finally, it is demonstrated that purely inorganic membranes of Prussian Blue (PB) and analogues can be prepared upon multiple sequential adsorption of transition metal cations and hexacyanoferrate anions. Due to the porous lattice of PB, the membranes are useful as ion filters able to separate cesium from sodium ions, for example. PMID:16091277

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

    NASA Astrophysics Data System (ADS)

    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 1-2 mg 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.

  5. Effects of degree of quaternization on the preparation and characterization of insulin-loaded trimethyl chitosan polyelectrolyte complexes optimized by central composite design.

    PubMed

    Jin, Yun; Zhou, Dan; Yang, Hong-Yun; Zhu, Xi; Wang, Xiao-Ran; Zhang, Zhi-Rong; Huang, Yuan

    2012-01-01

    The aim of the present study was to investigate the effects of varying degrees of quaternization (DQ: 22, 35 and 41%) on the preparation and characterization of insulin (INS)-loaded polyelectrolyte complexes (PECs) prepared by N-trimethyl chitosan chloride (TMC). A two factor-five level central composite design was used for the optimization. The concentrations of INS and TMC were defined as independent variables, while the entrapment efficiency (EE%) and loading efficiency (LE%) as dependent variables. The three optimized INS-TMC PECs were characterized for their size, zeta potential, EE% and LE%. The morphology and electrostatic interaction of PECs were evaluated. Then, the stability in the enzyme solution and in vitro release as well as mucoadhesive properties of the three PECs were all investigated. The results showed that the size and EE% of the optimum formulations were significantly decreased using TMC of higher DQ, while the zeta potential and LE% were slightly influenced by DQ. The stability assay exhibited partial protection of TMC PECs, and the better protective effect was observed for PECs of higher DQ. The in vitro release study presented different initial and sustained release behaviors of INS-TMC PECs and the mucin adsorption study confirmed a positive correlation between the DQ and the mucoadhesive property of PECs. PMID:21563989

  6. Flexible polyelectrolyte conformation in the presence of oppositely charged surfactants.

    PubMed

    Kuhn, P S; Diehl, A

    2007-10-01

    Conformational behavior of flexible polyelectrolytes in the presence of monovalent cationic surfactants is examined. A simple model is presented for the formation of polyelectrolyte-surfactant complexes in salt-free solutions in the framework of the Debye-Hückel-Bjerrum-Manning and Flory theories, including explicitly the hydrophobic interactions between the associated surfactant molecules on the polyelectrolyte. The distribution of complexes is calculated as a function of the surfactant concentration and a discrete conformational transition between an elongated coil and a compact globule was found, in agreement with experimental observations. PMID:17995019

  7. 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. PMID:22298029

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

    NASA Astrophysics Data System (ADS)

    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.

  9. 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. PMID:23396269

  10. 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. PMID:25981870

  11. 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.

  12. Light-scattering study of polyelectrolyte complex formation between anionic and cationic nanogels in an aqueous salt-free system.

    PubMed

    Miyake, Masafumi; Ogawa, Kazuyoshi; Kokufuta, Etsuo

    2006-08-15

    We studied complex formation in an aqueous salt-free system (pH approximately 3 and at 25 degrees C) between nanogel particles having opposite charges. Anionic gel (AG) and cationic gel (CG) particles consist of lightly cross-linked N-isopropylacrylamide (NIPA) copolymers with 2-acrylamido-2-methylpropane sulfonic acid and with 1-vinylimidazole, respectively. The number of charges per particle was -4490 for AG and +20 300 for CG, as estimated from their molar masses (3.33 MD for AG and 11.7 MD for CG) by static light scattering (SLS) and their charge densities (1.35 mmol/g for AG and 1.74 mmol/g for CG) by potentiometric titration. The complexes were formed through the addition of AG to CG and vice versa using a turbidimetric titration technique. At the endpoint of the titration, the aggregate formed was a complex based upon stoichiometric charge neutralization: CG(n)()(+) + xAG(m)()(-) --> CG(n)()(+) (AG(m)()(-))(x)() where x = (n)()/(m)(). At different stages of the titration before the endpoint, the resulting complexes were examined in detail using dynamic light scattering, SLS, and electrophoretic light scattering (ELS). The main results are summarized as follows: (i) When AG with a hydrodynamic radius (R(h)) of 119 nm is added to CG (R(h) approximately 156 nm), the (R(h)) of the complex size decreases from 156 to 80 nm. (ii) In contrast to this (R(h)) change, the molar mass increases from 11.7 MD to 24 MD with increasing amounts of added AG. (iii) Upon addition of CG to AG, the complex formed has the same size ((R(h)) approximately 80 nm) and the same molar mass (55 +/- 2.5 MD) until 55 +/- 5% of AG has been consumed in the complexation. To understand these results, we used the following two models: the random model (RM), in which the added AG particles uniformly bind to all of the CG particles in the system via a strong electrostatic attraction, and the all-or-none model (AONM), in which part of the AG particles in the system preferably bind to the added CG

  13. 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. PMID:26486297

  14. pH-sensitive microparticles for oral drug delivery based on alginate/oligochitosan/Eudragit(®) L100-55 "sandwich" polyelectrolyte complex.

    PubMed

    Calija, Bojan; Cekić, Nebojša; Savić, Snežana; Daniels, Rolf; Marković, Bojan; Milić, Jela

    2013-10-01

    The primary objective of this study was to investigate the influence of the oligochitosan-Eudragit(®) L100-55 polyelectrolyte complex (OCH-EL PEC) on the pH-sensitivity of Eudragit(®) L100-55-treated alginate-oligochitosan microparticles. In order to achieve this, three types of naproxen-loaded microparticles were prepared under mild and environmentally friendly conditions using a custom made device with coaxial air flow: Ca-alginate (Ca-ALG), alginate-oligochitosan (ALG-OCH) and alginate-oligochitosan-Eudragit(®) L100-55 (ALG-OCH-EL) microparticles. After drying, the microparticles were subjected to microscopic analysis, and physicochemical and biopharmaceutical characterization. The non-covalent interaction between OCH and EL and the formation of OCH-EL PEC during the preparation procedure of the particles were verified by thermal and FT-IR analysis. The obtained particles exhibited acceptable sphericity and surface roughness due to the presence of the drug crystals (Ca-ALG particles) and OCH-EL PEC (ALG-OCH-EL particles). It was found that reinforcement of the ALG-OCH particles with OCH-EL PEC had no significant effect on the relatively high encapsulation efficiencies (>74.4%). The results of drug release studies confirmed the ability of ALG-OCH PEC to sustain drug release at pH 6.8 and 7.4. However, this PEC showed enhanced sensitivity to an acidic environment and to simulated intestinal fluid (pH 6.8) after prior exposure to an acidic medium. Additional treatment of ALG-OCH particles with EL and formation of "sandwich" ALG-OCH-EL PEC was essential not only to improve stability and decrease drug release in acidic medium, but also to achieve sustained release after the pH of dissolution medium was raised to 6.8. The obtained results suggested that ALG-OCH-EL microparticles have promising potential as pH-sensitive multiparticulate drug carriers for oral delivery of NSAIDs. PMID:23751419

  15. Computational study of interfacial charge transfer complexes of 2-anthroic acid adsorbed on a titania nanocluster for direct injection solar cells

    NASA Astrophysics Data System (ADS)

    Manzhos, Sergei; Kotsis, Konstantinos

    2016-09-01

    Adsorption and light absorption properties of interfacial charge transfer complexes of 2-anthroic acid and titania, promising for direct-injection solar cells, are studied ab initio. The formation of interfacial charge transfer bands is observed. The intensity of visible absorption is relatively low, highlighting a key challenge facing direct injection cells. We show that the popular strategy of using a lower level of theory for geometry optimization followed by single point calculations of adsorption or optical properties introduces significant errors which have been underappreciated: by up to 3 eV in adsorption energies, by up to 5 times in light absorption intensity.

  16. 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

  17. Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 4: growth of rat bone marrow stromal cells in three-dimensional hydrogels with positive and negative surface charges and in polyelectrolyte complexes.

    PubMed

    Lesný, P; Prádný, M; Jendelová, P; Michálek, J; Vacík, J; Syková, E

    2006-09-01

    The growth of bone marrow stromal cells was assessed in vitro in macroporous hydrogels based on 2-hydro- xyethyl methacrylate (HEMA) copolymers with different electric charges. Copolymers of HEMA with sodium methacrylate (MA(-)) carried a negative electric charge, copolymers of HEMA with [2-(methacryloyloxy)ethyl] trimethylammonium chloride (MOETA(-)) carried a positive electric charge and terpolymers of HEMA, MA(-) and MOETA(+) carried both, positive and negative electric charges. The charges in the polyelectrolyte complexes were shielded by counter-ions. The hydrogels had similar porosities, based on a comparison of their diffusion parameters for small cations as measured by the real-time tetramethylammonium iontophoretic method of diffusion analysis. The cell growth was studied in the peripheral and central regions of the hydrogels at 2 hours and 2, 7, 14 and 28 days after cell seeding. Image analysis revealed the highest cellular density in the HEMA-MOETA(+) copolymers; most of the cells were present in the peripheral region of the hydrogels. A lower density of cells but no difference between the peripheral and central regions was observed in the HEMA-MA(-) copolymers and in polyelectrolyte complexes. This study showed that positively charged functional groups promote the adhesion of cells. PMID:16932865

  18. A MOTIF-BASED METHOD FOR PREDICTING INTERFACIAL RESIDUES IN BOTH THE RNA AND PROTEIN COMPONENTS OF PROTEIN-RNA COMPLEXES

    PubMed Central

    MANN, CARLA M.; DOBBS, DRENA

    2015-01-01

    Efforts to predict interfacial residues in protein-RNA complexes have largely focused on predicting RNA-binding residues in proteins. Computational methods for predicting protein-binding residues in RNA sequences, however, are a problem that has received relatively little attention to date. Although the value of sequence motifs for classifying and annotating protein sequences is well established, sequence motifs have not been widely applied to predicting interfacial residues in macromolecular complexes. Here, we propose a novel sequence motif-based method for “partner-specific” interfacial residue prediction. Given a specific protein-RNA pair, the goal is to simultaneously predict RNA binding residues in the protein sequence and protein-binding residues in the RNA sequence. In 5-fold cross validation experiments, our method, PS-PRIP, achieved 92% Specificity and 61% Sensitivity, with a Matthews correlation coefficient (MCC) of 0.58 in predicting RNA-binding sites in proteins. The method achieved 69% Specificity and 75% Sensitivity, but with a low MCC of 0.13 in predicting protein binding sites in RNAs. Similar performance results were obtained when PS-PRIP was tested on two independent “blind” datasets of experimentally validated protein-RNA interactions, suggesting the method should be widely applicable and valuable for identifying potential interfacial residues in protein-RNA complexes for which structural information is not available. The PS-PRIP webserver and datasets are available at: http://pridb.gdcb.iastate.edu/PSPRIP/. PMID:26776208

  19. 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

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

    PubMed

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

    2016-05-18

    Nano-patterned materials are beneficial for applications such as solar cells, opto-electronics, and sensing owing to their periodic structure and high interfacial area. Here, we present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm(2)-scale areas. Chemically modified block copolymer thin films featuring alternating charged and neutral domains are used as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topography that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication. PMID:27104854

  1. 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.

  2. Polyelectrolyte complexes of hTERT siRNA and polyethyleneimine: Effect of degree of PEG grafting on biological and cellular activity.

    PubMed

    Safari, Fatemeh; Tamaddon, Ali M; Zarghami, Nosratollah; Abolmali, S; Akbarzadeh, Abolfazl

    2016-09-01

    Gene silencing by siRNA (short interfering RNA)-targeted human telomerase reverse transcriptase (hTERT) is considered a successful strategy for cancer gene therapy. Polyelectrolyte complexes (PEC) of siRNA and cationic polymers such as polyethyleneimine (PEI) have been widely used for cellular transfection; however, they demonstrate some disadvantages such as cytotoxicity and extracellular matrix restrictions. PEG grafting technology was used in an attempt to improve the biocompatibility of PECs. Considering that this technology may compromise the cellular uptake of PECs, we aimed to study the effect of degree of PEI PEGylation on the carrier cytotoxicity, cellular association, and transfection efficiency of hTERT siRNA in the lung cancer cell line A549. Activated NHS ester of methoxy PEG-COOH 5 KDa was grafted to hyperbranched PEI 25 KDa in the molar ratios of 0.2 and 1. The copolymers were characterized by (1)H-NMR spectroscopy. PECs of PEI or PEG-g-PEI with siRNA, alone or co-incubated with heparin sulfate, were studied by the ethidium bromide exclusion assay. Cytotoxicity of the polymers (PEG-g-PEI vs PEI), alone and upon formation of PEC nanoparticles with hTERT siRNA, was determined by a validated MTT assay, in comparison to a scrambled control sequence, in A549 human lung carcinoma cells. The cellular uptake of the PECs of FITC-labeled siRNA was investigated by flow cytometry at different N/P ratios, and the silencing effect of the transfected siRNA was compared to that of the control sequence for different PECs by real time RT-PCR. The cytotoxicity of PEI decreased significantly by PEG grafting, even at a low degree of PEGylation. Moreover, the nonspecific cytotoxicity of PECs decreased by PEG grafting. PECs of PEG-g-PEI showed more biologic stability on incubation with heparin sulfate. Average particle size and zeta potential of PEC nanoparticles were diminished for those of PEG-g-PEI. The cellular association was more pronounced at an N/P ratio of 2.5 for

  3. A self-healing hydrogel formation strategy via exploiting endothermic interactions between polyelectrolytes.

    PubMed

    Ren, Ying; Lou, Ruyun; Liu, Xiaocen; Gao, Meng; Zheng, Huizhen; Yang, Ting; Xie, Hongguo; Yu, Weiting; Ma, Xiaojun

    2016-05-01

    We report a strategy to synthesize self-healing hydrogels via exploiting endothermic interactions between polyelectrolytes. Natural polysaccharides and their derivatives were used to form reversible polyelectrolyte complexes by selecting appropriately charged chemical groups and counterions. This simple and effective method to fabricate self-healing hydrogels will find applications in diverse fields such as surface coating and 3D printing. PMID:27078585

  4. Lipoprotein insertion into membranes of various complexity: lipid sorting, interfacial adsorption and protein clustering.

    PubMed

    Erwin, Nelli; Sperlich, Benjamin; Garivet, Guillaume; Waldmann, Herbert; Weise, Katrin; Winter, Roland

    2016-04-01

    In a combined chemical-biological and biophysical approach we explored the membrane partitioning of the lipidated signaling proteins N-Ras and K-Ras4B into membrane systems of different complexity, ranging from one-component lipid bilayers and anionic binary and ternary heterogeneous membrane systems even up to partitioning studies on protein-free and protein-containing giant plasma membrane vesicles (GPMVs). To yield a pictorial view of the localization process, imaging using confocal laser scanning and atomic force microscopy was performed. The results reveal pronounced isoform-specific differences regarding the lateral distribution and formation of protein-rich membrane domains. Line tension is one of the key parameters controlling not only the size and dynamic properties of segregated lipid domains but also the partitioning process of N-Ras that acts as a lineactant. The formation of N-Ras protein clusters is even recorded for almost vanishing hydrophobic mismatch. Conversely, for K-Ras4B, selective localization and clustering are electrostatically mediated by its polybasic farnesylated C-terminus. The formation of K-Ras4B clusters is also observed for the multi-component GPMV membrane, i.e., it seems to be a general phenomenon, largely independent of the details of the membrane composition, including the anionic charge density of lipid headgroups. Our data indicate that unspecific and entropy-driven membrane-mediated interactions play a major role in the partitioning behavior, thus relaxing the need for a multitude of fine-tuned interactions. Such a scenario seems also to be reasonable recalling the high dynamic nature of cellular membranes. Finally, we note that even relatively simple models of heterogeneous membranes are able to reproduce many of the properties of much more complex biological membranes. PMID:26960984

  5. Structural features of interfacial tyrosine residue in ROBO1 fibronectin domain-antibody complex: Crystallographic, thermodynamic, and molecular dynamic analyses

    PubMed Central

    Nakayama, Taisuke; Mizohata, Eiichi; Yamashita, Takefumi; Nagatoishi, Satoru; Nakakido, Makoto; Iwanari, Hiroko; Mochizuki, Yasuhiro; Kado, Yuji; Yokota, Yuki; Satoh, Reiko; Tsumoto, Kouhei; Fujitani, Hideaki; Kodama, Tatsuhiko; Hamakubo, Takao; Inoue, Tsuyoshi

    2015-01-01

    ROBO1, fibronectin Type-III domain (Fn)-containing protein, is a novel immunotherapeutic target for hepatocellular carcinoma in humans. The crystal structure of the antigen-binding fragment (Fab) of B2212A, the monoclonal antibody against the third Fn domain (Fn3) of ROBO1, was determined in pursuit of antibody drug for hepatocellular carcinoma. This effort was conducted in the presence or absence of the antigen, with the chemical features being investigated by determining the affinity of the antibody using molecular dynamics (MD) and thermodynamics. The structural comparison of B2212A Fab between the complex and the free form revealed that the interfacial TyrL50 (superscripts L, H, and F stand for the residues in the light chain, heavy chain, and Fn3, respectively) played important roles in Fn3 recognition. That is, the aromatic ring of TyrL50 pivoted toward PheF68, forming a CH/π interaction and a new hydrogen bond with the carbonyl O atom of PheF68. MD simulations predicted that the TyrL50-PheF68 interaction almost entirely dominated Fab-Fn3 binding, and Ala-substitution of TyrL50 led to a reduced binding of the resultant complex. On the contrary, isothermal titration calorimetry experiments underscored that Ala-substitution of TyrL50 caused an increase of the binding enthalpy between B2212A and Fn3, but importantly, it induced an increase of the binding entropy, resulting in a suppression of loss in the Gibbs free energy in total. These results suggest that mutation analysis considering the binding entropy as well as the binding enthalpy will aid in the development of novel antibody drugs for hepatocellular carcinoma. PMID:25492858

  6. 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.

  7. Kinetics of thorium-polyelectrolyte interaction

    SciTech Connect

    Cacheris, W.P.

    1985-01-01

    The rate constants for thorium dissociation from humic acid, PMA (polymaleic acid) and PMVEMA (poly(-methylvinylether/maleic acid)) were measured in the pH range of 4.20 to 5.94. The rate of thorium dissociation from these polyelectrolytes was determined by measuring the rate at which thorium was complexed with an exchange ligand. Arsenazo III was employed as the exchange ligand and its complexation of thorium was monitored by visible spectroscopy. The dissociation of thorium from these polyelectrolytes occurred by several first order pathways. These pathways fit into two categories based on their dependence on pH, temperature and the amount of time thorium was in contact with the polyelectrolyte prior to dissociation. Less than 6 +/- 1 KJ/mole activation entropy was found for the first category of thorium dissociation. Between 20 +/- 2 and 30 +/- 2 KJ/mole activation energy and from -200 +/- 20 to -250 +/- 20 joule/mole-K/sup 0/ activation entropy was found for the second category of thorium dissociation.

  8. Novel routes for direct preparation of surface-modifying polyelectrolyte layers and patterned polymer surfaces

    NASA Astrophysics Data System (ADS)

    Sankhe, Amit Y.

    The focus of this research was on the use of surface-confined atom transfer radical polymerization (SC-ATRP) for growing surface-tethered brushes of electrolytic or charged monomers on solid substrates. The use of SC-ATRP to produce well-defined polymer brushes from monomers with non-ionic functionalities in aprotic solvents has been well documented. Although it is possible to produce PE brushes by postpolymerization chemical conversion of some neutral brushes, this approach limits the types of PE brushes that can be produced and uses organic solvents. Thus, to more widely open the design envelope in terms of types of PE brushes that can be made and to reduce the use of organic solvents, it would be beneficial to directly synthesize PE brushes using more environmentally friendly, "green" solvents, such as water, for the reaction media. But the direct ATRP of hydrophilic monomers with ionic groups presents new challenges due to the complex interactions of the charged monomers and water with the ATRP catalyst. In this dissertation, I report findings on SC-ATRP of charged monomers such as itaconic acid (IA), methacrylic acid (MAA) and sodium 4-styrenesulfonate (SS) in aqueous solutions. Surface-tethered polyelectrolyte brushes comprised of poly(itaconic acid) (PIA), poly(methacrylic acid) (PMAA) and poly(4-styrenesulfonate) (PSS) were grown using surface-confined atom transfer radical polymerization (ATRP). The surface-tethered initiator monolayer was formed by self-assembling 2-bromoisobutyryl bromide terminated thiol molecules on gold coated silicon substrates. This polymerization initiator molecule and a copper-based organometallic catalyst allowed tethered polyelectrolyte chains to be grown via radical polymerization at room temperature in aqueous solutions. To suppress consumption of the ATRP deactivator, a halide salt was added to the reaction mixture, which enabled controlled growth of the polyelectrolyte layers. Phase-modulated ellipsometry was used to follow

  9. 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.

  10. 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

  11. Ion transport through electrolyte/polyelectrolyte multi-layers.

    PubMed

    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

  12. 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

  13. 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.

  14. 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.

  15. Self-organization of multivalent counterions in polyelectrolyte brushes

    NASA Astrophysics Data System (ADS)

    Wu, Jianzhong

    2013-03-01

    The structure and interfacial properties of a polyelectrolyte brush (PEB) depend on a broad range of parameters such as the polymer charge and grafting density, counterion valence, salt concentration, and solvent conditions. These properties are of fundamental importance in technological applications of PEBs including colloid stabilization, surface modification and lubrication, and in functioning of biological systems such as genome packaging in single-strand DNA/RNA viruses. Despite intensive studies by experiments, molecular simulations, and myriad analytical methods including scaling analyses, self-consistent-field theory, and most recently density functional theory, the behavior of PEBs in the presence of multivalent counterions remains poorly understood. In this talk, I will present a density functional method for polyelectrolyte brushes and discuss self-organization of multivalent counterions within highly charged polyelectrolyte brushes. The counterion-mediated attraction between polyions leads to a first-order phase transition similar to that for a neutral brush in a poor solvent. The self-organization of multivalent counterions results in a wavelike electrostatic potential and charge density that oscillate between positive and negative values.

  16. Photothermally actuated interfacial hydration for fast friction switch on hydrophilic polymer brush modified PDMS sheet incorporated with Fe3O4 nanoparticles.

    PubMed

    Liu, Guoqiang; Cai, Meirong; Feng, Yange; Wang, Xiaolong; Zhou, Feng; Liu, Weimin

    2016-03-01

    A near-infrared light triggered fast interfacial friction switch was achieved with polyelectrolyte brush grafted PDMS embedded with Fe3O4 nanoparticles, where the in situ heating up of the photothermal Fe3O4 nanoparticles in the polymer matrix changes the interface humidity and thereafter alters the hydration level of the interfacial polymer brushes. PMID:26856309

  17. 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

  18. Charge on a weak polyelectrolyte

    NASA Astrophysics Data System (ADS)

    Wang, Shengqin; Granick, Steve; Zhao, Jiang

    2008-12-01

    Fluorescence measurements with single-molecule sensitivity are used to measure the hydrodynamic size and local pH of a weak polyelectrolyte, poly-2-vinyl pyridine end labeled with pH-sensitive dye, the polyelectrolyte having concentration so low (nanomolars) that molecular properties are resolvable only from fluorescence experiments and cannot be accessed by light scattering. We find that the local pH near the dye, inferred from its brightness, is consistently three orders of magnitude higher than the bulk pH. Upon varying the bulk pH, we measure the collapse point at which hydrophobic attraction overwhelms electrostatic repulsion between charged elements along the chain, and conclude that adding monovalent salt shifts this coil-to-globule collapse to higher pH than in the absence of salt. The influence of salt appears to shift the ionization equilibrium of this weak polyelectrolyte in the direction of the chain possessing enhanced electric charge at a given pH. Phenomenologically, this is opposite to the case for strong polyelectrolytes, although the mechanism differs.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. Compositional and pH effects on the interfacial tension between complex tar mixtures and aqueous solutions.

    PubMed

    Hauswirth, Scott C; Schultz, Pamela B; Miller, Cass T

    2012-09-18

    Tars at former manufactured gas plants (FMGPs) are a major environmental concern and present a number of challenges to remediators. This experimental study investigates the relationship between composition and tar-water interfacial tension (IFT), a property of primary importance in determining the transport of tar in porous media. Nine field-collected FMGP tars and a commercially available coal tar were characterized by means of fractionation, gas chromatography, Fourier transform infrared (FTIR) spectrometry, and vapor pressure osmometry. The tar-aqueous IFT of the tars, as well as resins and asphaltenes extracted therefrom, were measured over a range of pH. The IFTs were found to be strongly dependent on pH, with the lowest values obtained at high pH. The reduction of IFT at high pH was found to correlate well with the I(C═O) values from the FTIR analysis, which provide an indication of the relative amount of carbonyl groups present. Reductions of IFT at low pH were also observed and found to correlate well with the extractable base concentration. The aromaticity and asphaltene average molar mass are also correlated with IFT reductions at both low and high pH, suggestive of compositional patterns related to the tar source material. PMID:22901363

  4. Field-Theoretic Studies of Nanostructured Triblock Polyelectrolyte Gels

    NASA Astrophysics Data System (ADS)

    Audus, Debra; Fredrickson, Glenn

    2012-02-01

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

  5. 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. PMID:27456170

  6. 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. PMID:27221521

  7. Polyelectrolyte coatings for microchip capillary electrophoresis.

    PubMed

    Liu, Yan; Henry, Charles S

    2006-01-01

    In chip-based electrophoretic analysis of biomolecules, chemical modification of the microchannel is widely employed to reduce or eliminate the analyte-wall interactions and alter electroosmotic flow (EOF) in the microchannel. A stable polyelectrolyte multilayer coating is one common way to regulate or eliminate EOF and prevent analyte adsorption for the rapid, efficient separation of biomolecules within microchannels. A wide variety of polyelectrolytes have been used as coatings. This chapter deals with how to coat microchips with polyelectrolytes and the expected results using polybrene and dextran sulfate as models. The technique presented here is generally applicable to any polyelectrolyte. PMID:16790867

  8. Formation of redox-active self-assembled polyelectrolyte-surfactant complexes integrating glucose oxidase on electrodes: Influence of the self-assembly solvent on the signal generation.

    PubMed

    Cortez, M Lorena; Ceolín, Marcelo; Azzaroni, Omar; Battaglini, Fernando

    2015-10-01

    In this work the effects of the self-assembly solvent on the structure and electrochemical behavior of redox-active polyelectrolyte–surfactant complexes cast on electrode supports from aqueous and DMF solutions are presented. The complex studied is formed by complexation of osmium complex-modified polyallylamine (OsPA) with dodecyl sulfate (DS) surfactants. The structure of the films was characterized by GISAXS, showing that films present a lamellar mesostructure. However, when they are exposed to humid environments, films cast from aqueous solutions (OsPA–DSaq) undergo a structural transition that ultimately leads to the disappearance of the mesostructural order. On the other hand, OsPA–DS films cast from DMF solutions (OsPA–DSorg) revealed no significant changes upon exposure to humid environments. Both types of films were exposed to glucose oxidase (GOx), showing similar adsorption characteristics. Notwithstanding these similarities in GOx and content, OsPA–DSaq films revealed a more sensitive bioelectrocatalytical response to glucose as compared to OsPA–DSorg films. PMID:26094060

  9. 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.

  10. Conjugated polyelectrolytes: synthesis, photophysics, and applications.

    PubMed

    Jiang, Hui; Taranekar, Prasad; Reynolds, John R; Schanze, Kirk S

    2009-01-01

    Organic optoelectronic polymers have evolved to the point where fine structural control of the conjugated main chain, coupled with solubilizing and property-modifying pendant substituents, provides an entirely new class of materials. Conjugated polyelectrolytes (CPEs) provide a unique set of properties, including water solubility and processability, main-chain-controlled exciton and charge transport, variable band gap light absorption and fluorescence, ionic interactions, and aggregation phenomena. These characteristics allow these materials to be considered for use in applications ranging from light-emitting diodes and electrochromic color-changing displays, to photovoltaic devices and photodetectors, along with chemical and biological sensors. This Review describes the evolution of CPE structures from simple polymers to complex materials, describes numerous photophysical aspects, including amplified quenching in macromolecules and aggregates, and illustrates how the physical and electronic properties lead to useful applications in devices. PMID:19444838

  11. Microstructure of polyelectrolyte nanoaggregates studied by fluorescence probe method.

    PubMed

    Vasilescu, Marilena; Angelescu, Daniel G; Bandula, Rodica; Staikos, Georgios

    2011-11-01

    The microstructure of water soluble nanoaggregates based on polyelectrolyte complex formed by the cationic comb-type copolymer poly(acrylamide -co-[3- (methacryloyl-amino)propyl] trimethylammonium chloride)-graft- polyacrylamide [P(AM-co-MAPTAC)-g-PAM] and the anionic linear polyelectrolyte sodium polyacrylate (NaPA) was investigated using the fluorescence probe technique. The fluorescence probe were 1-anilinonaphthalene-8-sulfonic acid (ANS), pyrene (Py) and 1,10-bis(1-pyrene) decane (PD). The fluorescence properties in polyelectrolyte complex solutions, which are sensitive to either micropolarity (ANS, Py) or microviscosity (PD), were related to the quantities obtained in different pure or mixed solvents. Micropolarities were quantified utilizing the polarity common index (Reichardt) E(T)(30). ANS and Py showed a variation of the micropolarity with the charge ratio of the two polymers, with the lowest polarity reached at the complex neutralization. The PD probe, by its excimer-to-monomer fluorescence intensities ratio, enabled us to evidence the effect of the composition and the comb-type copolymer grafting density on the microviscosity of the interpolyelectrolytes aggregates. It has been found that the microviscosity increased with the density of the grafting PAM chains. PMID:21688051

  12. 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.

  13. Surfactant mediated polyelectrolyte self-assembly

    DOE PAGESBeta

    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 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

  14. Diffusion properties of inkjet printed ionic self-assembling polyelectrolyte hydrogels

    PubMed Central

    Limem, Skander; Calvert, Paul

    2015-01-01

    In the present work, Crank’s model was used to characterize solute transport in inkjet printed polyelectrolyte gels. The diffusion of a small charged molecule (fluorescein), various size linear uncharged molecules (dextrans), and a globular protein (albumin) in printed PSS-PDDA with near stoichiometric composition happened respectively at about 10−8, 10−9, and 10−10 cm2/sec. Polyelectrolyte complexes printed with non-stoichiometric ratios were found to be non-equilibrium structures consisting of three populations of polymer chains: fully complexed chains, chains in partial electrostatic interaction with the complex, and chains in excess having minimal interaction with the complex. This structure may be multiple phases. The applicability of hydrodynamic and free volume models to describe transport in printed polyelectrolyte gels was discussed. PMID:26417449

  15. Decreased Interfacial Tension of Demixed Aqueous Polymer Solutions due to Charge

    NASA Astrophysics Data System (ADS)

    Vis, Mark; Peters, Vincent F. D.; Blokhuis, Edgar M.; Lekkerkerker, Henk N. W.; Erné, Ben H.; Tromp, R. Hans

    2015-08-01

    Electric charge at the water-water interface of demixed solutions of neutral polymer and polyelectrolyte decreases the already ultralow interfacial tension. This is demonstrated in experiments on aqueous mixtures of dextran (neutral) and nongelling fish gelatin (charged). Upon phase separation, electric charge and a potential difference develop spontaneously at the interface, decreasing the interfacial tension purely electrostatically in a way that can be accounted for quantitatively by Poisson-Boltzmann theory. Interfacial tension is a key property when it comes to manipulating the water-water interface, for instance to create novel water-in-water emulsions.

  16. 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

  17. Changes in the Activity and Structure of Urease in the Interaction with Polyelectrolytes

    NASA Astrophysics Data System (ADS)

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

    2008-03-01

    The influence of polyelectrolytes on the structural and catalytic characteristics of urease ( Canavalia ensiformis) was studied by the methods of steady-state kinetics, fluorescence spectroscopy, and circular dichroism. It was shown that, of the four polyelectrolytes studied, two of which were negatively charged (polystyrene sulfonate and dextran sulfate) and two were positively charged (polyallylamine (PAA) and polydiallyl dimethylammonium chloride), only PAA was a potent urease inhibitor: 0.5 μg/ml of PAA provided a 50% degree of inhibition for enzyme at neutral pH. It was found that polyelectrolyte did not inhibit urease in the presence of micromolar concentrations of ammonium chloride. Based on the experimental data and the calculated structure of urease from Canavalia ensiformis and on the identity with the amino acid sequence of urease from Bacillus pasteurii, the mechanism of urease inactivation by the PAA polyelectrolyte is discussed. This mechanism does not resemble the inhibiting action of polyelectrolytes on the previously studied oligomeric proteins—lactate dehydrogenase, glutamate dehydrogenase, and hemoglobin. It is proposed that the specific cation-binding sites determining the structural dynamics of the enzyme-polyelectrolyte complex play the regulating role in the urease molecule.

  18. Bundle Binding in Polyelectrolyte Solutions

    SciTech Connect

    Stevens, M.J.

    1999-01-21

    Stiff polyelectrolytes are found to spontaneously form oriented bundles. Conditions under which bundling occurs are found. Molecular dynamics simulations show that divalent counterions are necessary, and the chains must be sufficiently long and stiff. No aggregation occurs for monovalent counterions. For flexible or short chains aggregation occurs, but bundle formation does not. Due to dynamical constraints the systems tend to order into a network of connected bundles, not a single bundle.

  19. 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

  20. Disentangling the Physical Processes Responsible for the Kinetic Complexity in Interfacial Electron Transfer of Excited Ru(II) Polypyridyl Dyes on TiO2.

    PubMed

    Zigler, David F; Morseth, Zachary A; Wang, Li; Ashford, Dennis L; Brennaman, M Kyle; Grumstrup, Erik M; Brigham, Erinn C; Gish, Melissa K; Dillon, Robert J; Alibabaei, Leila; Meyer, Gerald J; Meyer, Thomas J; Papanikolas, John M

    2016-04-01

    Interfacial electron transfer at titanium dioxide (TiO2) is investigated for a series of surface bound ruthenium-polypyridyl dyes whose metal-to-ligand charge-transfer state (MLCT) energetics are tuned through chemical modification. The 12 complexes are of the form Ru(II)(bpy-A)(L)2(2+), where bpy-A is a bipyridine ligand functionalized with phosphonate groups for surface attachment to TiO2. Functionalization of ancillary bipyridine ligands (L) enables the potential of the excited state Ru(III/)* couple, E(+/)*, in 0.1 M perchloric acid (HClO4(aq)) to be tuned from -0.69 to -1.03 V vs NHE. Each dye is excited by a 200 fs pulse of light in the visible region of the spectrum and probed with a time-delayed supercontiuum pulse (350-800 nm). Decay of the MLCT excited-state absorption at 376 nm is observed without loss of the ground-state bleach, which is a clear signature of electron injection and formation of the oxidized dye. The dye-dependent decays are biphasic with time constants in the 3-30 and 30-500 ps range. The slower injection rate constant for each dye is exponentially distributed relative to E(+/)*. The correlation between the exponentially diminishing density of TiO2 sub-band acceptor levels and injection rate is well described using Marcus-Gerischer theory, with the slower decay components being assigned to injection from the thermally equilibrated state and the faster components corresponding to injection from higher energy states within the (3)MLCT manifold. These results and detailed analyses incorporating molecular photophysics and semiconductor density of states measurements indicate that the multiexponential behavior that is often observed in interfacial injection studies is not due to sample heterogeneity. Rather, this work shows that the kinetic heterogeneity results from competition between excited-state relaxation and injection as the photoexcited dye relaxes through the (3)MLCT manifold to the thermally equilibrated state, underscoring the

  1. Polyelectrolyte Structure and Interactions in Model Cystic Fibrosis Sputum

    NASA Astrophysics Data System (ADS)

    Slimmer, Scott; Angelini, Thomas; Liang, Hongjun; Butler, John; Wong, Gerard C. L.

    2002-03-01

    Cystic fibrosis sputum is a complex fluid consisting of a number of components, including mucin (a glycoprotein), lysozyme (a cationic polypeptide), water, salt, as well as a high concentration of a number of anionic biological polyelectrolytes such as DNA and F-actin. The interactions governing these components are poorly understood, but may have important clinical consequences. For example, the formation of these biological polyelectrolytes into ordered gel phases may contribute significantly to the observed high viscosity of CF sputum. In this work, a number of model systems were created to simulate CF sputum in vitro, in order to elucidate the contributions of the different components. Preliminary results will be presented. This work was supported by NSF DMR-0071761, DOE DEFG02-91ER45439, the Beckman Young Investigator Program, and the Cystic Fibrosis Foundation.

  2. 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

  3. Flexible polyelectrolyte conformation in the presence of cationic and anionic surfactants

    NASA Astrophysics Data System (ADS)

    Passos, C. B.; Kuhn, P. S.; Diehl, A.

    2015-11-01

    In this work we have studied the conformation of flexible polyelectrolyte chains in the presence of cationic and anionic surfactant molecules. We developed a simple theoretical model for the formation of the polyelectrolyte-cationic surfactant complexes and mixed micelles formed by cationic and anionic surfactant molecules, in the framework of the Debye-Hückel-Bjerrum-Manning and Flory theories, with the hydrophobic interaction included explicitly as an effective short-ranged attraction between the surfactant hydrocarbon tails. This simple model allows us to calculate the extension of the polyelectrolyte-cationic surfactant complexes as a function of the anionic surfactant concentration, for different types of cationic and anionic surfactant molecules. A discrete conformational transition from a collapsed state to an elongated coil was found, for all surfactant chain lengths we have considered, in agreement with the experimental observations for the unfolding of ​DNA-cationic surfactant complexes.

  4. Compositions comprising coal, water and polyelectrolyte

    SciTech Connect

    Hansen, B.V.; Kalfue, S.S.; Mollberg, H.R.

    1985-08-20

    This invention relates to compositions substantially containing pulverized coal, water, polyelectrolyte and, optionally, a stabilizing agent. The polyelectrolyte is a water soluble polyethylene, optionally containing double bonds and/or branching points in the polymer chain, being directly substituted with (a) hydroxysulfonyloxy groups or (b) sulfo groups, (c) hydroxysulfonyloxy-lower alkyl groups which are partly or completely in salt form and optionally (d) substituents selected from hydroxy, lower alkyl, lower alkanoyloxy, carbamoyl, cyano, hydroxymethyl, chloro and phenyl, whereby the polyelectrolyte contains at most four different kinds of said optional substituents, and wherein the amount of sulfur of the polyelectrolyte is 2 to 25 percent by weight being calculated when the acid forming groups are present as free acids. Small amounts of these polyelectrolytes in water with a high percentage of pulverized coal form compositions, characterized by low viscosity, good flowability, pumpability and stability.

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

    PubMed

    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

  6. 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

  7. Interfacial Charge Transfer in Dye-Sensitized Solar Cells Using SCN-Free Terpyridine-Coordinated Ru Complex Dye and Co Complex Redox Couples.

    PubMed

    Kono, Takahiro; Masaki, Naruhiko; Nishikawa, Masahiro; Tamura, Rei; Matsuzaki, Hiroyuki; Kimura, Mutsumi; Mori, Shogo

    2016-07-01

    The efficiency of dye-sensitized solar cells (DSSCs) using Ru complex dyes and Co complex redox couples has been increased with a strategy to prevent charge recombination via the addition of bulky or lengthy peripheral units to the dyes. However, despite the efforts, most of the DSSCs are still suffering from nonunity quantum efficiency and fast recombination. We examine the effect of SCN ligand, which has been used for many Ru complex dyes and could attract positively charged Co complexes. We find that replacing the ligands with 2,6-bis(2'-(4'-trifluoromethyl)pyrazolyl)pyridine increases the quantum efficiency and electron lifetime. With the combination of the replacement of SCN ligands and the addition of bulky moiety, ∼80% external quantum efficiency is achieved. These suggest that not only the addition of a blocking effect but also the reduction of electrostatic and dispersion forces between dyes and Co complexes are essential to control the charge separation and recombination processes. PMID:27328462

  8. Cyto-mechanoresponsive polyelectrolyte multilayer films.

    PubMed

    Davila, Johanna; Chassepot, Armelle; Longo, Johan; Boulmedais, Fouzia; Reisch, Andreas; Frisch, Benoît; Meyer, Florent; Voegel, Jean-Claude; Mésini, Philippe J; Senger, Bernard; Metz-Boutigue, Marie-Hélène; Hemmerlé, Joseph; Lavalle, Philippe; Schaaf, Pierre; Jierry, Loïc

    2012-01-11

    Cell adhesion processes take place through mechanotransduction mechanisms where stretching of proteins results in biological responses. In this work, we present the first cyto-mechanoresponsive surface that mimics such behavior by becoming cell-adhesive through exhibition of arginine-glycine-aspartic acid (RGD) adhesion peptides under stretching. This mechanoresponsive surface is based on polyelectrolyte multilayer films built on a silicone sheet and where RGD-grafted polyelectrolytes are embedded under antifouling phosphorylcholine-grafted polyelectrolytes. The stretching of this film induces an increase in fibroblast cell viability and adhesion. PMID:22188330

  9. 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.

  10. Dynamics in Multicomponent Polyelectrolyte Solutions

    NASA Astrophysics Data System (ADS)

    Nagao, Michihiro

    2010-03-01

    Double-network hydrogels (DN-gel) prepared from the combination of a moderately cross-linked anionic polyelectrolyte (poly(2-acrylamido-2-methyl-1-propanesulfonic acid), PAMPS) and an un-cross-linked linear polymer (polyacrylamide, PAAm) solution show strong mechanical properties far superior to that of their individual constituents [1]. To determine the origin of the superior properties of DN-gels, we investigated the structure and the chain dynamics of model PAMPS/PAAm solution blends using small-angle neutron scattering and neutron spin-echo measurements [2]. Akcasu's dynamic scattering theory for a multicomponent system [3] is modified to include polyelectrolytes, and the resulting equation describes well the neutron spin-echo results over the entire wavevector range covered in our experiments. Parameters such as effective solvent viscosity were deduced from the measured data using the modified Akcasu equation. Both the relaxation time at large length scales (10-100 nm) and the segmental diffusion coefficient at short length scales (0.1-1 nm) or the effective solvent viscosity show good accordance with the macroscopic rheological behavior of the solution blends. [4pt] [1] J.P. Gong et al., Adv. Mater. 15, 1155 (2003). [0pt] [2] S. Lee et al., Macromolecules 42, 1293 (2009). [0pt] [2] A.Z. Akcasu, in Dynamic Liht Scattering, The Method and Some Applications; W. Brown Ed. (Oxford University Press, London 1992).

  11. Polyelectrolytes to produce nanosized polydopamine.

    PubMed

    Mateescu, Mihaela; Metz-Boutigue, Marie-Hélène; Bertani, Philippe; Ball, Vincent

    2016-05-01

    "Polydopamine" (PDA) is the oxidation product of dopamine and can be obtained as thin films covering the surface of all kinds of known materials and simultaneously as insoluble and useless precipitates from dopamine solutions in the presence of appropriate oxidants. The valorization of such precipitates to obtain stable suspensions of functional nanomaterials is highly desirable owing to the chemical and optical properties of PDA. We show that a vast repertoire of polyelectrolytes polycations as well as polyanions, allow to control the size of PDA particles in the 10-100 nm size range. Simultaneously to the production of smaller nanoparticles, a progressive inhibition of PDA deposition on the surface of quartz plates (as well as on the surface of the reaction vessel) is found as the concentration of the polyelectrolytes is increased in the dopamine solution. The mechanism of size control-inhibition of film deposition is investigated in the particular case of poly(allylamine) but remains not understood in the case of polyanions. PMID:26890383

  12. High-Permittivity Conjugated Polyelectrolyte Interlayers for High-Performance Bulk Heterojunction Organic Solar Cells.

    PubMed

    Kesters, Jurgen; Govaerts, Sanne; Pirotte, Geert; Drijkoningen, Jeroen; Chevrier, Michèle; Van den Brande, Niko; Liu, Xianjie; Fahlman, Mats; Van Mele, Bruno; Lutsen, Laurence; Vanderzande, Dirk; Manca, Jean; Clément, Sébastien; Von Hauff, Elizabeth; Maes, Wouter

    2016-03-01

    Conjugated polyelectrolyte (CPE) interfacial layers present a powerful way to boost the I-V characteristics of organic photovoltaics. Nevertheless, clear guidelines with respect to the structure of high-performance interlayers are still lacking. In this work, impedance spectroscopy is applied to probe the dielectric permittivity of a series of polythiophene-based CPEs. The presence of ionic pendant groups grants the formation of a capacitive double layer, boosting the charge extraction and device efficiency. A counteracting effect is the diminishing affinity with the underlying photoactive layer. To balance these two effects, we found copolymer structures containing nonionic side chains to be beneficial. PMID:26927416

  13. 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

    2014-05-01

    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. PMID:24811649

  14. 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.

  15. Pegylated polyelectrolyte nanoparticles containing paclitaxel as a promising candidate for drug carriers for passive targeting.

    PubMed

    Szczepanowicz, Krzysztof; Bzowska, Monika; Kruk, Tomasz; Karabasz, Alicja; Bereta, Joanna; Warszynski, Piotr

    2016-07-01

    Targeted drug delivery systems are of special importance in cancer therapies, since serious side effects resulting from unspecific accumulation of highly toxic chemotherapeutics in healthy tissues can restrict effectiveness of the therapy. In this work we present the method of preparing biocompatible, polyelectrolyte nanoparticles containing the anticancer drug that may serve as a vehicle for passive tumor targeting. The nanoparticles were prepared via direct encapsulation of emulsion droplets in a polyelectrolyte multilayer shell. The oil cores that contained paclitaxel were stabilized by docusate sodium salt/poly-l-lysine surface complex (AOT/PLL) and were encapsulated in shells formed by the LbL adsorption of biocompatible polyelectrolytes, poly-L-glutamic acid (PGA) and PLL up to 5 or 6 layers. The surface of the nanoparticles was pegylated through the adsorption of the pegylated polyelectrolyte (PGA-g-PEG) as the outer layer to prolong the persistence of the nanocarriers in the circulation. The synthesized nanoparticles were stable in cell culture medium containing serum and their average size was 100nm, which makes them promising candidates for passive targeted drug delivery. This notion was further confirmed by the results of studying the biological effects of nanoformulations on two tumor cell lines: mouse colon carcinoma cell line CT26-CEA and the mouse mammary carcinoma cell line 4T1. The empty polyelectrolyte nanoparticles did not affect the viability of the tested cells, whereas encapsulated paclitaxel retained its strong cytotoxic/cytostatic activity. PMID:27037784

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    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.

  17. Polyelectrolyte multilayered nanofilms as a novel approach for the protection of hydrogen storage materials.

    PubMed

    Borodina, T N; Grigoriev, D O; Andreeva, D V; Möhwald, H; Shchukin, D G

    2009-05-01

    This work describes the encapsulation of hydrogen storage materials from organic solvents. Due to complex formation the shell provides stability and selective permeability. Specifically, sodium borohydride particles were encapsulated within polymer films by the layer-by-layer self-assembly of oppositely charged polyelectrolytes (polyethyleneimine and poly(acrylonitrile-co-butadiene-co-acrylic acid)). The polymer nanofilm fabrication was performed using dichloromethane as a working media. IR spectroscopy was applied to investigate the chemical interaction between the polyelectrolytes. The multilayer film preparation was verified by Z-potential measurements, scanning electron microscopy, and confocal laser microscopy. The stability of sodium borohydride protected with a polyelectrolyte shell was increased compared to that of the pure material under ambient conditions. PMID:20355884

  18. Cell type dependent morphological adaptation in polyelectrolyte hydrogels governs chondrogenic fate.

    PubMed

    Raghothaman, Deepak; Leong, Meng Fatt; Lim, Tze Chiun; Wan, Andrew C A; Ser, Zheng; Lee, Eng Hin; Yang, Zheng

    2016-01-01

    Repair of critical-size articular cartilage defects typically involves delivery of cells in biodegradable, 3D matrices. Differences in the developmental status of mesenchymal stem cells (MSCs) and terminally differentiated mature chondrocytes might be a critical factor in engineering appropriate 3D matrices for articular cartilage tissue engineering. This study examined the relationship between material-driven early cell morphological adaptations and chondrogenic outcomes, by studying the influence of aligned collagen type I (Col I) presentation on chondrocytes and MSC in interfacial polyelectrolyte complexation (IPC)-based hydrogels. In the absence of Col I, both chondrocytes and MSCs adopted rounded cell morphology and formed clusters, with chondrocyte clusters favoring the maintenance of hyaline phenotype, while MSC clusters differentiated to fibro-superficial zone-like chondrocytes. Encapsulated chondrocytes in IPC-Col I hydrogel adopted a fibroblastic morphology forming fibro-superficial zone-like phenotype, which could be reversed by inhibiting actin polymerization using cytochalasin D (CytD). In contrast, adoption of fibroblastic morphology by encapsulated MSCs in IPC-Col I facilitated superior chondrogenesis, generating a mature, hyaline neocartilage tissue. CytD treatment abrogated the elongation of MSCs and brought about a single cell-like state, resulting in insignificant chondrogenic differentiation, underscoring the essential requirement of providing matrix environments that are amenable to cell-cell interactions for robust MSC chondrogenic differentiation. Our study demonstrates that MSCs and culture-expanded chondrocytes favour differential microenvironmental niches and emphasizes the importance of designing biomaterials that meet cell type-specific requirements, in adopting chondrocyte or MSC-based approaches for regenerating hyaline, articular cartilage. PMID:27041648

  19. 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.

  20. 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.

  1. Polyelectrolyte multilayered assemblies in biomedical technologies.

    PubMed

    Costa, Rui R; Mano, João F

    2014-05-21

    Layer-by-layer (LbL) was first introduced as a surface modification technique based on the sequential spontaneous adsorption of at least two distinct materials onto planar substrates. In the last two decades, this technique has been expanded to the coating of more convoluted geometries with high levels of tailored functionalization or with structural purposes. In this review, the potential uses of LbL films in biomedical engineering based mainly on the assembly of polyelectrolytes are reviewed. Examples of recent developments are provided, from the modification of substrates to improve their biointegration or to add specialized properties, to the three-dimensional extrapolation of this technique to more complex structures for cell seeding, drug delivery devices, biosensors and customizable microreactors. Future strategies and opportunities are compared with current medical and laboratorial methodologies. Through them, it is expected that LbL will contribute greatly to the development of new functional devices with high perspectives of return for the administration of active agents, supports for cells in regenerative medicine and tissue engineering, biosensing and construction of microtissues and disease models in the laboratory. PMID:24549278

  2. EFFECTS OF SYNTHETIC POLYELECTROLYTES ON SELECTED AQUATIC ORGANISMS

    EPA Science Inventory

    The acute toxicity of several polyelectrolytes to daphnids (Daphnia magna), fathead minnows (Pimephales promelas), gammarids (Gammarus pseudolimnaeus) and midges (Paratanytarsus parthenogeneticus) was tested. Most nonionic and anionic polyelectrolytes were not toxic at 100 mg/l w...

  3. 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. PMID:25453660

  4. Ion-specific effect on dynamics of polyelectrolyte chains.

    PubMed

    Luo, Zhenli; Wang, Xiaoyan; Zhang, Guangzhao

    2012-05-21

    The sedimentation of quaternized poly(4-vinyl pyridine) (QP4VP) or poly(N-methyl 4-vinyl pyridine iodide) in aqueous solution has been investigated by using an analytical ultracentrifuge (AUC) via sedimentation velocity (SV). When NaI is introduced, either the sedimentation coefficient (s) or apparent molar mass (Mw) of QP4VP increases with NaI concentration because the polyelectrolyte chains aggregate or even form precipitates due to hydrophobic interaction. Upon addition of NaCl, either s or Mw exhibits a maximum as NaCl concentration increases. The sedimentation in NaBr solution falls in between. Besides, the diffusion coefficient (D) shows a minimum as the added salt concentration increases when either of the salts is added. Isothermal titration calorimetry (ITC) measurements show that the enthalpy change increases from NaI over NaBr to NaCl when each of them is mixed with QP4VP, revealing that the order of the strength of the anion-pyridinium interaction is I(-) > Br(-) > Cl(-). When I(-) ions are added, they only screen the electrostatic interaction and no counterion competition happens. Upon addition of Cl(-) or Br(-) ions, the original counterions (I(-)) win the competition at low Cl(-) or Br(-) concentration, so that the added anions only screen the electrostatic interaction. When the concentration of Cl(-) or Br(-) ions is high enough, they replace I(-) ions to interact with the polyelectrolyte chains due to osmotic pressure. The present study demonstrates that the complex dynamics of the polyelectrolyte is greatly influenced by the ion-specific effect. PMID:22495384

  5. Temperature responsive behavior of polymer brush/polyelectrolyte multilayer composites.

    PubMed

    Micciulla, Samantha; Soltwedel, Olaf; Löhmann, Oliver; von Klitzing, Regine

    2016-01-28

    The complex interaction of polyelectrolyte multilayers (PEMs) physisorbed onto end-grafted polymer brushes with focus on the temperature-responsive behavior of the system is addressed in this work. The investigated brush/multilayer composite consists of a poly(styrene sulfonate)/poly(diallyldimethylammonium chloride) (PSS/PDADMAC) multilayer deposited onto the poly(N-isopropylacrylamide-b-dimethylaminoethyl methacrylate) P(NIPAM-b-DMAEMA) brush. Ellipsometry and neutron reflectometry were used to monitor the brush collapse with the thickness decrease as a function of temperature and the change in the monomer distribution perpendicular to the substrate at temperatures below, across and above the phase transition, respectively. It was found that the adsorption of PEMs onto polymer brushes had a hydrophobization effect on PDMAEMA, inducing the shift of its phase transition to lower temperatures, but without suppressing its temperature-responsiveness. Moreover, the diffusion of the free polyelectrolyte chains inside the charged brush was proved by comparing the neutron scattering length density profile of pure and the corresponding PEM-capped brushes, eased by the enhanced contrast between hydrogenated brushes and deuterated PSS chains. The results presented herein demonstrate the possibility of combining a temperature-responsive brush with polyelectrolyte multilayers without quenching the responsive behavior, even though significant interpolyelectrolyte interactions are present. This is of importance for the design of multicompartment coatings, where the brush can be used as a reservoir for the controlled release of substances and the multilayer on the top as a membrane to control the diffusion in/out by applying different stimuli. PMID:26612742

  6. 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

  7. Operational mechanism of conjugated polyelectrolytes.

    PubMed

    Tordera, Daniel; Kuik, Martijn; Rengert, Zachary D; Bandiello, Enrico; Bolink, Henk J; Bazan, Guillermo C; Nguyen, Thuc-Quyen

    2014-06-18

    Conjugated polyelectrolytes (CPEs) are versatile materials used in a range of organic optoelectronic applications. Because of their ionic/electronic nature, characterizing these materials is nontrivial, and their operational mechanism is not fully understood. In this work we use a methodology that combines constant-voltage-driven current-density transient measurements with fast current vs voltage scans to allow decoupling of ionic and electronic phenomena. This technique is applied to diodes prepared with cationic CPEs having different charge-compensating anions. Our results indicate that the operational mechanism of these devices is governed by electrochemical doping of the CPE. On the basis of the notion that the saturated depletion layer for the anions consists of the same π-conjugated backbone material, we discern how the extent and speed of formation of the doped region depend on the anion structure. Apart from addressing fundamental transport questions, this work provides a tool for future characterization of different CPEs and other similar systems. PMID:24855971

  8. 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).

  9. Weighing Polyelectrolytes Packaged in Viruslike Particles

    NASA Astrophysics Data System (ADS)

    Tresset, Guillaume; Tatou, Mouna; Le CÅ`ur, Clémence; Zeghal, Mehdi; Bailleux, Virginie; Lecchi, Amélie; Brach, Katarzyna; Klekotko, Magdalena; Porcar, Lionel

    2014-09-01

    This Letter reports on the remarkable selectivity of capsid proteins for packaging synthetic polyelectrolytes in viruslike particles. By applying the contrast variation method in small-angle neutron scattering, we accurately estimated the mean mass of packaged polyelectrolytes ⟨Mp⟩ and that of the surrounding capsid ⟨Mcap⟩. Remarkably, the mass ratio ⟨Mp⟩/⟨Mcap⟩ was invariant for polyelectrolyte molecular weights spanning more than 2 orders of magnitude. To do so, capsids either packaged several chains simultaneously or selectively retained the shortest chains that could fit the capsid interior. Our data are in qualitative agreement with theoretical predictions based on free energy minimization and emphasize the importance of protein self-energy. These findings may give new insights into the nonspecific origin of genome selectivity for a number of viral systems.

  10. Water distribution in multilayers of weak polyelectrolytes.

    PubMed

    Tanchak, Oleh M; Yager, Kevin G; Fritzsche, Helmut; Harroun, Thad; Katsaras, John; Barrett, Christopher J

    2006-05-23

    The water localization in thin polyelectrolyte multilayers assembled from poly(acrylic acid) and poly(allylamine hydrochloride) was investigated with neutron reflectivity in an atmosphere of controlled humidity and with bulk water. Water was found to be distributed asymmetrically within the multilayer and to localize preferentially at the polymer surface. The diffusion of water into the multilayer did not completely penetrate to the substrate, but instead there appeared to be an exclusion zone near the Si substrate. These results help to explain previous observations of anomalous water transport kinetics in weak polyelectrolyte systems. PMID:16700605

  11. Swelling of polyelectrolyte and polyzwitterion brushes by humid vapors

    NASA Astrophysics Data System (ADS)

    Genzer, Jan; Galvin, Casey; Dimitriou, Michael; Satija, Sushil

    2015-03-01

    Swelling behavior of polyelectrolyte and polyzwitterion brushes derived from poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) in water vapor is investigated using a combination of neutron and X-ray reflectivity and spectroscopic ellipsometry over a wide range of relative humidity (RH) levels. The extent of swelling depends strongly on the nature of the side-chain chemistry. For parent PDMAEMA, there is an apparent enrichment of vapor at the polymer/air interface. Despite extensive swelling at high humidity level, no evidence of charge repulsion is found in weak or strong polyelectrolyte brushes. Polyzwitterionic brushes swell to a greater extent than the quaternized brushes studied. However, for RH levels beyond 70%, the polyzwitterionic brushes start to exclude water molecules, leading to a decline in water volume fraction from the maximum of 0.30 down to 0.10. Using a gradient in polymer chain grafting density, we provide evidence that this behavior stems from the formation of inter- and intramolecular zwitterionic complexes.

  12. 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.

  13. 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.

  14. Biocidal activity of a light-absorbing fluorescent conjugated polyelectrolyte.

    PubMed

    Lu, Liangde; Rininsland, Frauke H; Wittenburg, Shannon K; Achyuthan, Komandoor E; McBranch, Duncan W; Whitten, David G

    2005-10-25

    Herein we describe studies that indicate a cationic conjugated polyelectrolyte shows biocidal activity against gram-negative bacteria (Escherichia coli, E. coli, BL21, with plasmids for Azurin and ampicillin resistance) and gram-positive bacterial spores (Bacillus anthracis, Sterne, B. anthracis, Sterne). These studies were carried out with aqueous suspensions of the conjugated polyelectrolyte, with the polyelectrolyte in supported formats and with samples in which the conjugated polyelectrolyte was coated on the bacteria. The results are interesting in that the biocidal activity is light-induced and appears effective due to the ability of the conjugated polyelectrolyte to form a surface coating on both types of bacteria. The effects observed here should be general and suggest that a range of conjugated polyelectrolytes in different formulations may provide a useful new class of biocides for both dark and light-activated applications. PMID:16229539

  15. 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 %. PMID:26346835

  16. 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. PMID:26726415

  17. 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

  18. Mesoscale modeling of polyelectrolyte brushes with salt.

    PubMed

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

    2010-06-01

    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. PMID:20455593

  19. Origin of translocation barriers for polyelectrolyte chains.

    PubMed

    Kumar, Rajeev; Muthukumar, M

    2009-11-21

    For single-file translocations of a charged macromolecule through a narrow pore, the crucial step of arrival of an end at the pore suffers from free energy barriers, arising from changes in intrachain electrostatic interaction, distribution of ionic clouds and solvent molecules, and conformational entropy of the chain. All contributing factors to the barrier in the initial stage of translocation are evaluated by using the self-consistent field theory for the polyelectrolyte and the coupled Poisson-Boltzmann description for ions without radial symmetry. The barrier is found to be essentially entropic due to conformational changes. For moderate and high salt concentrations, the barriers for the polyelectrolyte chain are quantitatively equivalent to that of uncharged self-avoiding walks. Electrostatic effects are shown to increase the free energy barriers, but only slightly. The degree of ionization, electrostatic interaction strength, decreasing salt concentration, and the solvent quality all result in increases in the barrier. PMID:19929072

  20. 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.

  1. Bioresorbable polyelectrolytes for smuggling drugs into cells.

    PubMed

    Jaganathan, Sripriya

    2016-06-01

    There is ample evidence that biodegradable polyelectrolyte nanocapsules are multifunctional vehicles which can smuggle drugs into cells, and release them upon endogenous activation. A large number of endogenous stimuli have already been tested in vitro, and in vivo research is escalating. Thus, the interest in the design of intelligent polyelectrolyte multilayer (PEM) drug delivery systems is clear. The need of the hour is a systematic translation of PEM-based drug delivery systems from the lab to clinical studies. Reviews on multifarious stimuli that can trigger the release of drugs from such systems already exist. This review summarizes the available literature, with emphasis on the recent progress in PEM-based drug delivery systems that are receptive in the presence of endogenous stimuli, including enzymes, glucose, glutathione, pH, and temperature, and addresses different active and passive drug targeting strategies. Insights into the current knowledge on the diversified endogenous approaches and methodological challenges may bring inspiration to resolve issues that currently bottleneck the successful implementation of polyelectrolytes into the catalog of third-generation drug delivery systems. PMID:25961363

  2. Algal Flocculation with Synthetic Organic Polyelectrolytes

    PubMed Central

    Tenney, Mark W.; Echelberger, Wayne F.; Schuessler, Ronald G.; Pavoni, Joseph L.

    1969-01-01

    The feasibility of removing algae from water and wastewater by chemical flocculation techniques was investigated. Mixed cultures of algae were obtained from both continuous- and batch-fed laboratory reactors. Representative cationic, anionic, and nonionic synthetic organic polyelectrolytes were used as flocculants. Under the experimental conditions, chemically induced algal flocculation occurred with the addition of cationic polyelectrolyte, but not with anionic or nonionic polymers, although attachment of all polyelectrolyte species to the algal surface is shown. The mechanism of chemically induced algal flocculation is interpreted in terms of bridging phenomena between the discrete algal cells and the linearly extended polymer chains, forming a three-dimensional matrix that is capable of subsiding under quiescent conditions. The degree of flocculation is shown to be a direct function of the extent of polymer coverage of the active sites on the algal surface, although to induce flocculation by this method requires that the algal surface charge must concurrently be reduced to a level at which the extended polymers can bridge the minimal distance of separation imposed by electrostatic repulsion. The influence of pH, algal concentration, and algal growth phase on the requisite cationic flocculant dose is also reported. PMID:5370666

  3. Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte.

    PubMed

    Grumelli, Doris E; Garay, Fernando; Barbero, Cesar A; Calvo, Ernesto J

    2006-08-10

    A probe beam deflection (PBD) study of ion exchange between an electroactive polymer poly(allylamine)-bipyridyl-pyridine osmium complex film and liquid electrolyte is reported. The PBD measurements were made simultaneously to chronoamperometric oxidation-reduction cycles, to be able to detect kinetic effects in the ion exchange. Layer-by-layer (LbL) self-assembled redox polyelectrolyte films with osmium bipyridyl complex covalently attached to poly(allylamine) (PAH-Os) and poly(styrene sulfonate) (PSS) have been built by alternate electrostatic adsorption from soluble polyelectrolytes. The ionic exchange during initial conditioning of the film ("break-in") undergoing oxidation-reduction cycles and recovery after equilibration in the reduced state have shown an exchange of anions and cations with time lag between them. The effect of the nature of cation on the ionic exchange has been investigated with dilute HCl, LiCl, NaCl, and CsCl electrolytes. The ratio of anion to cation exchanged at the film-electrolyte interface has a strong dependence on the nature of charge in the topmost layer, that is, when negatively charged PSS is the capping layer, a larger proportion of cation exchange is observed. This demonstrates that the electrical potential distribution at the redox polyelectrolyte multilayer (PEM)/electrolyte interface determines the ionic flux in response to charge injection in the film. PMID:16884254

  4. Cell Adhesion and Proliferation on the "Living" Surface of a Polyelectrolyte Multilayer.

    PubMed

    Arias, Carlos J; Surmaitis, Richard L; Schlenoff, Joseph B

    2016-05-31

    The adhesion of living eukaryotic cells to a substrate, one of the most complex problems in surface science, requires adsorption of extracellular proteins such as fibronectin. Thin films of polyelectrolyte complex made layer-by-layer (polyelectrolyte multilayers or PEMUs) offer a high degree of control of surface charge and composition-interconnected and essential variables for protein adhesion. Fibroblasts grown on multilayers of poly(styrenesulfonate), PSS, and poly(diallyldimethylammonium), PDADMA, with increasing thickness exhibit good adhesion until the 12th layer of polyelectrolyte has been added, whereupon there is a sudden transition to nonadhesive behavior. This sharp change is due to the migration of excess positive charge to the surface-a previously unrecognized property of PEMUs. Precise radiotracer assays of adsorbed (125)I-albumin show how protein adsorption is related to multilayer surface charge. With more negative surface charge density from the sulfonates of PSS, more albumin adsorbs to the surface. However, a loosely held or "soft corona" exchanges with serum protein under the Vroman effect, which is correlated with poor cell adhesion. A comprehensive view of cell adhesion highlights the central role of robust protein adhesion, which is required before any secondary effects of matrix stiffness on cell fate can come into play. PMID:27191244

  5. Polyelectrolyte multilayers impart healability to highly electrically conductive films.

    PubMed

    Li, Yang; Chen, Shanshan; Wu, Mengchun; Sun, Junqi

    2012-08-28

    Healable, electrically conductive films are fabricated by depositing Ag nanowires on water-enabled healable polyelectrolyte multilayers. The easily achieved healability of the polyelectrolyte multilayers is successfully imparted to the Ag nanowire layer. These films conveniently restore electrical conductivity lost as a result of damage by cuts several tens of micrometers wide when water is dropped on the cuts. PMID:22807199

  6. 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.

  7. 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.

  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. 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. PMID:27028166

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

    NASA Astrophysics Data System (ADS)

    Groehn, Franziska

    2015-03-01

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

  11. 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.

  12. 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.

  13. Interfacial behavior of asphaltenes.

    PubMed

    Langevin, Dominique; Argillier, Jean-François

    2016-07-01

    We review the existing literature on asphaltenes at various types of interfaces: oil-water, air-water, gas-oil and solid-liquid, with more emphasis on the oil-water interfaces. We address the role of asphaltene aggregation, recently clarified for asphaltenes in bulk by the Yen-Mullins model. We discuss the questions of adsorption reversibility and interfacial rheology, especially in connection with emulsion stability. PMID:26498501

  14. The interaction of humic substances with cationic polyelectrolytes.

    PubMed

    Kam, S K; Gregory, J

    2001-10-01

    The anionic charge carried by aquatic humic substances plays a major part in their interaction with metal ions and other cationic species. Removal of such substances by coagulation and flocculation can be, at least partly, determined by charge neutralisation. In this work, the charge densities of a commercial humic acid and an aquatic humic extract have been investigated by studying their interactions with a series of synthetic cationic polyelectrolytes. These covered a range of charge densities and molecular weights. The techniques used were colloid titration by spectrophotometry and streaming current detection, and flocculation determined by colour removal and by an optical monitoring method. For a given cationic polyelectrolyte, all four methods gave charge densities for humic substances which were in good agreement. However, systematic differences in the apparent humic charge density were found, depending on the charge density of the cationic polyelectrolyte used. With low charge density polyelectrolytes, the apparent anionic charge of the humic substances was found to be low. With higher polyelectrolyte charge densities, the apparent humic substance charge density increases and reaches a limiting value when the polyelectrolyte charge is greater than about 3 meq/g. This indicates a non-stoichiometric interaction between the anionic sites of the humic substances and the cationic charges of the low-charge polyelectrolytes. Optimum flocculation of humics occurred with less cationic charge in the case of low-charge polyelectrolytes than those with higher charge density. However, the degree of removal was considerably better in the latter case. In all cases, the molecular weight of the cationic polyelectrolytes (over a range from about 50,000 to 15 million) appeared to have no effect on the results. PMID:11561615

  15. 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

  16. 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.

  17. Intrinsic interfacial phenomena in manganite heterostructures

    NASA Astrophysics Data System (ADS)

    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.

  18. 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

  19. 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. PMID:27427617

  20. 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.

  1. Adsorption behavior of anionic polyelectrolyte for chemical mechanical polishing (CMP).

    PubMed

    Kim, Sarah; So, Jae-Hyun; Lee, Dong-Jun; Yang, Seung-Man

    2008-03-01

    In this work, we investigated the adsorption characteristics of anionic polyelectrolytes, which are used in shallow trench isolation chemical mechanical polishing with ceria abrasives. Specifically, the adsorption isotherms and chain conformation of anionic polyelectrolytes were studied in order to elucidate the difference in removal rates of silicon dioxide (SiO2) and silicon nitride (Si3N4) layers and the high selectivity characteristics of ceria slurry. Adsorption isotherms, FT-IR spectroscopy and contact angle measurements revealed that the anionic polyelectrolyte additives had much better adsorption affinities for the Si3N4 surface than for the SiO2 surface. Moreover, blanket wafer polishing results were successfully correlated with the adsorption isotherms of polyelectrolytes on the oxide particle suspensions. PMID:18078949

  2. Fluorescence array-based sensing of nitroaromatics using conjugated polyelectrolytes.

    PubMed

    Wu, Jiatao; Tan, Chunyan; Chen, Zhifang; Chen, Yu Zong; Tan, Ying; Jiang, Yuyang

    2016-05-23

    A sensor array consisting of six cationic fluorescent conjugated polyelectrolytes (CPEs) is reported, which could readily differentiate between nine closely related hydrophilic nitroaromatics (NACs) in separate aqueous solutions by fluorescence pattern recognition and linear discrimination analysis (LDA). PMID:27169808

  3. Interfacial solvation thermodynamics.

    PubMed

    Ben-Amotz, Dor

    2016-10-19

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. PMID:27545849

  4. 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.

  5. 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.

  6. Monte Carlo simulations of polyelectrolytes inside viral capsids

    NASA Astrophysics Data System (ADS)

    Angelescu, Daniel George; Bruinsma, Robijn; Linse, Per

    2006-04-01

    Structural features of polyelectrolytes as single-stranded RNA or double-stranded DNA confined inside viral capsids and the thermodynamics of the encapsidation of the polyelectrolyte into the viral capsid have been examined for various polyelectrolyte lengths by using a coarse-grained model solved by Monte Carlo simulations. The capsid was modeled as a spherical shell with embedded charges and the genome as a linear jointed chain of oppositely charged beads, and their sizes corresponded to those of a scaled-down T=3 virus. Counterions were explicitly included, but no salt was added. The encapisdated chain was found to be predominantly located at the inner capsid surface, in a disordered manner for flexible chains and in a spool-like structure for stiff chains. The distribution of the small ions was strongly dependent on the polyelectrolyte-capsid charge ratio. The encapsidation enthalpy was negative and its magnitude decreased with increasing polyelectrolyte length, whereas the encapsidation entropy displayed a maximum when the capsid and polyelectrolyte had equal absolute charge. The encapsidation process remained thermodynamically favorable for genome charges ca. 3.5 times the capsid charge. The chain stiffness had only a relatively weak effect on the thermodynamics of the encapsidation.

  7. Diffusiophoresis of a charged toroidal polyelectrolyte.

    PubMed

    Tseng, Shiojenn; Hsu, Yen-Rei; Hsu, Jyh-Ping

    2016-06-01

    Considering recent application of concentration driven motion of charged nanoparticles in sensing technology, we model the diffusiophoresis of an isolated toroidal polyelectrolyte (PE) for the first time. Choosing an aqueous KCl solution for illustration, its behavior under various conditions is simulated by varying the double layer thickness, the size of toroid, and its softness and fixed charge density. We show that the behavior of the present PE can be different both quantitatively and qualitatively from that of the corresponding spherical PE. This arises from the competition of the hydrodynamic force and the electric force acting on a PE. The geometry and the nature of a PE can also influence appreciably its behavior, yielding complicated and interesting results. PMID:26970033

  8. Conjugated Polyelectrolyte Nanoparticles for Apoptotic Cell Imaging.

    PubMed

    Liu, Yu; Wu, Pan; Jiang, Jianhua; Wu, Jiatao; Chen, Yan; Tan, Ying; Tan, Chunyan; Jiang, Yuyang

    2016-08-31

    Three anionic conjugated polyelectrolytes (CPEs) with poly(p-phenylene ethynylene thiophene) backbones were designed and synthesized, among which PPET3-CO2Na showed greater molar extinction coefficient with red-shifted bands in both absorption and emission spectra compared to the well-studied PPE-CO2Na polymer. PPET3-CO2Na was thus chosen to construct CPE-based nanoparticles (CPNs) with cationic octaarginine (R8) peptide through electrostatic-interaction-induced self-assembly. Due to plasma membrane permeabilization and mitochondrial outer membrane permeabilization (MOMP) in early apoptotic cells, PPET3/R8 CPNs demonstrated excellent colocalization with MitoTracker Red in apoptotic cells instead of normal cells, which had potential application in cell imaging for early apoptosis recognition. PMID:27525500

  9. The Adsorption of Polyelectrolytes on Hydroxyapatite Crystals.

    PubMed

    Tsortos; Nancollas

    1999-01-01

    The adsorption of two polyelectrolytes, poly-L-Glutamate and poly-L-Aspartate, on hydroxyapatite (HAP) crystals was studied both experimentally and theoretically. Langmuir adsorption isotherms were obtained for both these molecules, with binding constants K = 6 x 10(6) and 3 x 10(6) M-1, respectively, at 37.0 degreesC, pH 7.4, and 0.15 M ionic strength. A theoretical analysis of the data, based on a model proposed by Hesselink, suggested a "train-loop" type of adsorption with non-electrostatic energy terms 3.51 and 4.76 (kT) for poly-L-Glu and poly-L-Asp, respectively. Copyright 1999 Academic Press. PMID:9878142

  10. Adsorption of flexible polyelectrolytes on charged surfaces.

    PubMed

    Subbotin, A V; Semenov, A N

    2016-08-10

    Adsorption of weakly charged polyelectrolyte (PE) chains from dilute solution on an oppositely charged surface is studied using the self-consistent mean-field approach. The structure of the adsorbed polymer layer and its excess charge are analyzed in the most important asymptotic and intermediate regimes both analytically and numerically. Different regimes of surface charge compensation by PE chains including partial and full charge inversion are identified and discussed in terms of physical parameters like the magnitude of specific short-range interactions of PE segments with the surface, solvent quality and ionic strength. The effect of excluded-volume monomer interactions is considered quantitatively both in the marginally good and poor solvent regimes. PMID:27452184

  11. 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.

  12. Novel cationic polyelectrolyte coatings for capillary electrophoresis.

    PubMed

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

    2016-01-01

    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation. PMID:26464098

  13. Interfacial insert for electrical connectors

    NASA Technical Reports Server (NTRS)

    Macavay, D.

    1975-01-01

    The development of interfacial inserts for improved electric connectors is discussed. The inserts were manufactured from epoxy resins. The design features of the inserts and the manufacturing equipment are described. The reliability test program is reported. Drawings of the interfacial inserts are provided.

  14. 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.

  15. Polyelectrolyte/magnetite nanoparticle multilayers: preparation and structure characterization.

    PubMed

    Grigoriev, D; Gorin, D; Sukhorukov, G B; Yashchenok, A; Maltseva, E; Möhwald, H

    2007-11-20

    Polyelectrolyte composite planar films containing a different number of iron oxide (Fe3O4) nanoparticle layers have been prepared using the layer-by-layer adsorption technique. The nanocomposite assemblies were characterized by ellipsometry, UV-vis spectroscopy, and AFM. Linear growth of the multilayer thickness with the increase of the layer number, N, up to 12 reflects an extensive character of this parameter in this range. A more complicated behavior of the refractive index is caused by changes in the multilayer structure, especially for the thicker nanocomposites. A quantitative analysis of the nanocomposite structure is provided comparing a classical and a modified effective medium approach taking into account the influence of light absorption by the Fe3O4 nanoparticles on the complex refractive index of the nanocomposite and contributions of all components to film thickness. Dominant influence of co-adsorbed water on their properties was found to be another interesting peculiarity of the nanocomposite film. This effect, as well as possible film property modulation by light, is discussed. PMID:17958452

  16. More About Measuring Interfacial Tension Between Liquids

    NASA Technical Reports Server (NTRS)

    Rashidnia, Nasser; Balasubramaniam, R.; Del Signore, David M.

    1995-01-01

    Report presents additional discussion of technique for measuring interfacial tension between two immiscible liquids. Technique described in "Measuring Interfacial Tension Between Immiscible Liquids" (LEW-15855).

  17. Effects of Surfactants and Polyelectrolytes on the Interaction between a Negatively Charged Surface and a Hydrophobic Polymer Surface.

    PubMed

    Rapp, Michael V; Donaldson, Stephen H; Gebbie, Matthew A; Gizaw, Yonas; Koenig, Peter; Roiter, Yuri; Israelachvili, Jacob N

    2015-07-28

    We have measured and characterized how three classes of surface-active molecules self-assemble at, and modulate the interfacial forces between, a negatively charged mica surface and a hydrophobic end-grafted polydimethylsiloxane (PDMS) polymer surface in solution. We provide a broad overview of how chemical and structural properties of surfactant molecules result in different self-assembled structures at polymer and mineral surfaces, by studying three characteristic surfactants: (1) an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), (2) a cationic aliphatic surfactant, myristyltrimethylammonium bromide (MTAB), and (3) a silicone polyelectrolyte with a long-chain PDMS midblock and multiple cationic end groups. Through surface forces apparatus measurements, we show that the separate addition of three surfactants can result in interaction energies ranging from fully attractive to fully repulsive. Specifically, SDS adsorbs at the PDMS surface as a monolayer and modifies the monotonic electrostatic repulsion to a mica surface. MTAB adsorbs at both the PDMS (as a monolayer) and the mica surface (as a monolayer or bilayer), resulting in concentration-dependent interactions, including a long-range electrostatic repulsion, a short-range steric hydration repulsion, and a short-range hydrophobic attraction. The cationic polyelectrolyte adsorbs as a monolayer on the PDMS and causes a long-range electrostatic attraction to mica, which can be modulated to a monotonic repulsion upon further addition of SDS. Therefore, through judicious selection of surfactants, we show how to modify the magnitude and sign of the interaction energy at different separation distances between hydrophobic and hydrophilic surfaces, which govern the static and kinetic stability of colloidal dispersions. Additionally, we demonstrate how the charge density of silicone polyelectrolytes modifies both their self-assembly at polymer interfaces and the robust adhesion of thin PDMS films to target

  18. 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

  19. Aggrecan, an Unusual Polyelectrolyte: Review of Solution Behavior and Physiological Implications

    PubMed Central

    Chandran, Preethi L.; Horkay, Ferenc

    2011-01-01

    Aggrecan is a high molecular weight, bottlebrush-shaped, negative-charged biopolymer that forms supermolecular complexes with hyaluronic acid. In the extracellular matrix of cartilage, aggrecan-hyaluronic acid complexes are interspersed in the collagen matrix and provide the osmotic properties required to resist deswelling under compressive load. In this review we compile aggrecan solution behavior from different experimental techniques, and discuss them in the context of concentration regimes that were identified in osmotic pressure experiments. At low concentration, aggrecan exhibits microgel-like behavior. With increasing concentration, the bottlebrushes self assemble into large complexes. In the physiological concentration range (2 < caggrecan < 8 % w/w), the physical properties of the solution are dominated by repulsive electrostatic interactions between aggrecan complexes. We discuss the consequences of the bottlebrush architecture on the polyelectrolyte characteristics of the aggrecan molecule, and its implications for cartilage properties and function. PMID:21884828

  20. 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. PMID:27386567

  1. 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

  2. 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.

  3. 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.

  4. Influence of Corona Structure on Binding of an Ionic Surfactant in Oppositely Charged Amphiphilic Polyelectrolyte Micelles.

    PubMed

    Delisavva, Foteini; Uchman, Mariusz; Škvarla, Juraj; Woźniak, Edyta; Pavlova, Ewa; Šlouf, Miroslav; Garamus, Vasil M; Procházka, Karel; Štěpánek, Miroslav

    2016-04-26

    Interaction of polystyrene-block-poly(methacrylic acid) micelles (PS-PMAA) with cationic surfactant N-dodecylpyridinium chloride (DPCl) in alkaline aqueous solutions was studied by static and dynamic light scattering, SAXS, cryogenic transmission electron microscopy (cryo-TEM), isothermal titration calorimetry (ITC), and time-resolved fluorescence spectroscopy. ITC and fluorescence measurements show that there are two distinct regimes of surfactant binding in the micellar corona (depending on the DPCl content) caused by different interactions of DPCl with PMAA in the inner and outer parts of the corona. The compensation of the negative charge of the micellar corona by DPCl leads to the aggregation of PS-PMAA micelles, and the micelles form colloidal aggregates at a certain critical surfactant concentration. SAXS shows that the aggregates are formed by individual PS-PMAA micelles with intact cores and collapsed coronas interconnected with surfactant micelles by electrostatic interactions. Unlike polyelectrolyte-surfactant complexes formed by free polyelectrolyte chains, the PMAA/DPCl complex with collapsed corona does not contain surfactant micelles. PMID:27054848

  5. 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.

  6. 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.

  7. Electrokinetics in polyelectrolyte grafted nanofluidic channels modulated by the ion partitioning effect.

    PubMed

    Poddar, Antarip; Maity, Debonil; Bandopadhyay, Aditya; Chakraborty, Suman

    2016-07-01

    The effects of ion partitioning on the electrokinetics in a polyelectrolyte grafted nanochannel, which is the representative of a soft nanochannel, are analyzed. Earlier studies in this regard have considered low polyelectrolyte layer (PEL) grafting density at the rigid nanochannel wall and, hence, an equal permittivity inside and outside the grafted layer. In order to overcome this shortcoming, the concept of Born energy is revisited. The coupled system of the modified Poisson-Boltzmann and Navier-Stokes equation is solved numerically, going beyond the widely employed Debye-Hückel linearization and low PEL densities. The complex interplay between the hydrodynamics and charge distribution, modulated by the ion partitioning effect, along with their consequent effects on the streaming potential and electrokinetic energy conversion efficiency (EKEC) have been systemically investigated. It has been observed that the ion partitioning effect reduces the EKEC in comparison to the case with equal permittivity up to a certain electrical double layer thickness after which it increases the EKEC. For a high concentration of mobile charges within the PEL, the net gain in the maximum EKEC due to the ion partitioning effect is about 10 fold that of the case when the ion partitioning effect is not considered. We delve into the various scaling regimes in the streaming potential and intriguingly point out the exact location of peaks in efficiency. The present study also reveals the possibility of improvement in streaming potential mediated energy conversion by the use of polyelectrolyte materials, which possess substantially lower dielectric permittivity than the bulk electrolyte. PMID:27306568

  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. Preparation of polyelectrolytes for wastewater treatment.

    PubMed

    Radoiu, Marilena T; Martin, Diana I; Calinescu, Ioan; Iovu, Horia

    2004-01-01

    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%. PMID:14693435

  10. The viscosity of short polyelectrolyte solutions.

    PubMed

    Izzo, Dora; Cloitre, Michel; Leibler, Ludwik

    2014-03-21

    We consider the viscosity of solutions of highly charged short polyelectrolytes. Our system is a poly(styrene-maleic acid) copolymer solution (SMA) with various added salt concentrations in dilute and semidilute regimes. The SMA solutions show some particular features: (i) variations of the specific viscosity measured for different values of concentration and ionic strength can be rescaled on two universal curves when plotted as a function of the effective volume fraction; (ii) the reduced viscosity is proportional to the Debye length. In order to describe the viscosity of such a system we model the motion of the charged rods considering a simpler system: we replace each charged rod and its corresponding charge cloud by an effective neutral rod. This modified system is yet below the concentrated regime and, at most, steric interactions are left. In the semidilute regime, we model the rescaled rods moving under a mean field potential and obtain a dynamical equation for the orientational tensor, considered small, and the viscosity is derived from it. Within our mean field approach, the effects due to the rod Brownian motion and due to the potential cancel each other and the behavior of the viscosity is explained in terms of the effective volume fraction only. Our predictions are in good qualitative agreement with the experimental results over a wide range of parameters, and suggest a method for obtaining the rotational diffusion constant in the semidilute regime. PMID:24652236

  11. Force balances in systems of cylindrical polyelectrolytes.

    PubMed

    Brenner, S L; McQuarrie, D A

    1973-04-01

    A detailed analysis is made of the model system of two parallel cylindrical polyelectrolytes which contain ionizable groups on their surfaces and are immersed in an ionic bathing medium. The interaction between the cylinders is examined by considering the interplay between repulsive electrostatic forces and attractive forces of electrodynamic origin. The repulsive force arises from the screened coulomb interaction between the surface charge distributions on the cylinders and has been treated by developing a solution to the linearized Poisson-Boltzmann equation. The boundary condition at the cylinder surfaces is determined as a self-consistent functional of the potential, with the input consisting of the density of ionizable groups and their dissociation constants. It is suggested that a reasonably accurate representation for the form of the attractive force can be obtained by performing a pairwise summation of the individual interatomic forces. A quantitative estimate is obtained using a Hamaker constant chosen on the basis of rigorous calculations on simpler systems. It is found that a balance exists between these repulsive and attractive forces at separations in good agreement with those observed in arrays of tobacco mosaic virus and in the A band myosin lattice in striated muscle. The behavior of the balance point as a function of the pH and ionic strength of the bathing medium closely parallels that seen experimentally. PMID:4696760

  12. 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

    2012-05-01

    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. PMID:22506542

  13. Polyelectrolyte multilayer films: A sponge for insulin?

    PubMed

    Ladhari, Nadia; Hemmerlé, Joseph; Haikel, Youssef; Voegel, Jean-Claude; Ball, Vincent

    2010-01-01

    Considering restrictive diabetes treatments, new insulin administration strategies constitute a huge medical challenge. This study aimed at developing a new support for insulin reservoirs, using polyelectrolyte multilayer films (PEM films), and thus studying this hormone release in a progressive manner. At first, insulin was loaded in (PDADMAC-PAA)n films, by immerging them for various periods of time (2, 14 and 24 h) in a solution containing this protein. Confocal laser scanning microscopy (CLSM) revealed that insulin-FITC could diffuse inside the film with a bigger concentration in the upper part of the film (after 2 and 14 h in contact with the polypeptide solution), and then in the whole film (after 24 h) from a solution at pH=4.3 (below insulin's isolelectric point). Environmental scanning electron microscopy (ESEM) and CLSM showed that the film swells upon insulin loading. We finally investigated the insulin release by ATR-FTIR spectroscopy. It revealed that a loaded (PDADMAC-PAA)15 film, immerged in distilled water, showed no measurable insulin release. In contrast, a slow unloading was observed in the presence of a NaCl 0.15 M solution (salinity close to physiological serum). This study could open the route for a new way of insulin delivery. PMID:20930331

  14. 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.

  15. 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

  16. 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.

  17. Counterion-mediated protein adsorption into polyelectrolyte brushes.

    PubMed

    He, Su-Zhen; Merlitz, Holger; Sommer, Jens-Uwe; Wu, Chen-Xu

    2015-09-01

    We present molecular dynamics simulations of the interaction of fullerene-like, inhomogeneously charged proteins with polyelectrolyte brushes. A motivation of this work is the experimental observation that proteins, carrying an integral charge, may enter like-charged polymer brushes. Simulations of varying charge distributions on the protein surfaces are performed to unravel the physical mechanism of the adsorption. Our results prove that an overall neutral protein can be strongly driven into polyelectrolyte brush whenever the protein features patches of positive and negative charge. The findings reported here give further evidence that the strong adsorption of proteins is also driven by entropic forces due to counterion release, since charged patches on the surface of the proteins can act as multivalent counterions of the oppositely charged polyelectrolyte chains. A corresponding number of mobile co- and counterions is released from the brush and the vicinity of the proteins so that the entropy of the total system increases. PMID:26385737

  18. 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. PMID:27112858

  19. Polyelectrolyte Complex for Heparin Binding Domain Osteogenic Growth Factor Delivery.

    PubMed

    Wing Moon Lam, Raymond; Abbah, Sunny Akogwu; Ming, Wang; Naidu, Mathanapriya; Ng, Felly; Tao, Hu; Goh Cho Hong, James; Ting, Kang; Hee Kit, Wong

    2016-01-01

    During reconstructive bone surgeries, supraphysiological amounts of growth factors are empirically loaded onto scaffolds to promote successful bone fusion. Large doses of highly potent biological agents are required due to growth factor instability as a result of rapid enzymatic degradation as well as carrier inefficiencies in localizing sufficient amounts of growth factor at implant sites. Hence, strategies that prolong the stability of growth factors such as BMP-2/NELL-1, and control their release could actually lower their efficacious dose and thus reduce the need for larger doses during future bone regeneration surgeries. This in turn will reduce side effects and growth factor costs. Self-assembled PECs have been fabricated to provide better control of BMP-2/NELL-1 delivery via heparin binding and further potentiate growth factor bioactivity by enhancing in vivo stability. Here we illustrate the simplicity of PEC fabrication which aids in the delivery of a variety of growth factors during reconstructive bone surgeries. PMID:27585207

  20. 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.

  1. 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

  2. Nanometer-thick lateral polyelectrolyte micropatterns induce macrosopic electro-osmotic chaotic fluid instabilities.

    PubMed

    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. 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.

  4. Soft X-ray microscopy to characterize polyelectrolyte assemblies.

    PubMed

    Köhler, Karen; Déjugnat, Christophe; Dubois, Monique; Zemb, Thomas; Sukhorukov, Gleb B; Guttmann, Peter; Möhwald, Helmuth

    2007-07-26

    Transmission microscopy with soft X-rays (TXM) is applied to image in-situ polyelectrolyte assemblies in aqueous environment. The method is element specific and at this stage exhibits a lateral resolution of 20 nm. With the specific examples of hollow capsules and full spheres made of PAH/PSS polyelectrolyte multilayers, it is shown quantitatively that heat treatment irreversibly reduces the water content in the membrane. These experiments complement those reported recently on the polyion system PDADMAC/PSS, which shows a different glass-transition behavior. Finally, the potential and present limitations of TXM are discussed. PMID:17428089

  5. Adsorption of highly charged Gaussian polyelectrolytes onto oppositely charged surfaces

    NASA Astrophysics Data System (ADS)

    Dutta, Sandipan; Jho, Y. S.

    2016-03-01

    In many biological processes highly charged biopolymers are adsorbed onto oppositely charged surfaces of macroions and membranes. They form strongly correlated structures close to the surface which cannot be explained by the conventional Poisson-Boltzmann theory. In this work strong coupling theory is used to study the adsorption of highly charged Gaussian polyelectrolytes. Two cases of adsorptions are considered, when the Gaussian polyelectrolytes are confined (a) by one charged wall, and (b) between two charged walls. The effects of salt and the geometry of the polymers on their adsorption-depletion transitions in the strong coupling regime are discussed.

  6. Influence of network topology on the swelling of polyelectrolyte nanogels.

    PubMed

    Rizzi, L G; Levin, Y

    2016-03-21

    It is well-known that the swelling behavior of ionic nanogels depends on their cross-link density; however, it is unclear how different topologies should affect the response of the polyelectrolyte network. Here we perform Monte Carlo simulations to obtain the equilibrium properties of ionic nanogels as a function of salt concentration Cs and the fraction f of ionizable groups in a polyelectrolyte network formed by cross-links of functionality z. Our results indicate that the network with cross-links of low connectivity result in nanogel particles with higher swelling ratios. We also confirm a de-swelling effect of salt on nanogel particles. PMID:27004897

  7. Interaction of cellulose-based cationic polyelectrolytes with mucin.

    PubMed

    Mazoniene, Edita; Joceviciute, Simona; Kazlauske, Jurgita; Niemeyer, Bernd; Liesiene, Jolanta

    2011-03-01

    Mucoadhesivity of water-soluble polymers is an important factor, when testing their suitability for controlled drug delivery systems. For this purpose, the interaction of new cationic cellulose polyelectrolytes with lyophilized mucin was investigated by means of turbidimetric titration, microscopy and measurement of zeta potential and particle size changes in the system. Results show that the cellulose derivatives interact with mucin. This interaction became stronger if cellulose macromolecules contained positively charged groups and an electrostatic interaction with the negatively charged mucin particles occurred. Under certain conditions flocculation of mucin particles by the cellulose polyelectrolyte was observed. PMID:21134731

  8. Multilayered Polyelectrolyte Microcapsules: Interaction with the Enzyme Cytochrome C Oxidase

    PubMed Central

    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. PMID:25372607

  9. 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.

  10. 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.

  11. Chemical and structural changes in a pH-responsive mixed polyelectrolyte brush studied by infrared ellipsometry.

    PubMed

    Hinrichs, Karsten; Aulich, Dennis; Ionov, Leonid; Esser, Norbert; Eichhorn, Klaus-Jochen; Motornov, Mikhail; Stamm, Manfred; Minko, Sergiy

    2009-09-15

    This work provides direct chemical and structural insight into pH-dependent changes of an ultrathin (d=12 nm) mixed polyelectrolyte brush. In-situ infrared spectroscopic ellipsometry was used for the first time to study the gradual pH-responsive behavior of the brush, constituted of weak anionic and cationic polyelectrolytes, poly(acrylic acid) (PAA) and poly(2-vinylpyridine) (P2VP), respectively. The pH-dependent infrared fingerprints in the mid-infrared spectral range were analyzed as a function of chemical and structural changes in the mixed brush caused by pH changes. Thereby, the IR spectra were directly correlated to different chemical states of the brush, giving previously not accessible new information on the ionization of the thin film. In contrast to other techniques (e.g., classical attenuated total reflection IR spectroscopy) we used almost plane Si-substrates for the IR ellipsometric approach with application of a single reflection mode. The optical path through Si is of minimal length, which makes a large spectral range accessible. For the most pronounced bands of the carboxyl group at 1718 cm(-1) and the carboxylate ion at 1565 cm(-1), the band amplitudes were correlated with the degree of ionization of the carboxylic groups. Interpretation of the pH-dependent changes in the spectral signature reveals gradual changes of the chemical structures of the mixed brush between three distinct switchable states: strongly ionized PAA at pH 10, strongly ionized P2VP at pH 2, and mainly nonionized functional groups in a "dry" PAA-P2VP polyelectrolyte complex in the range from pH=4 to pH=7. At intermediate pH, the IR spectra confirm the previously made hypothesis of the formation of a polyelectrolyte complex between P2VP and PAA in the mixed brush. From IR spectra it is also concluded that the polyelectrolyte complex is formed as a result of a small fraction of ionized functional groups. PMID:19572506

  12. Layer-by-layer coating of textile with two oppositely charged cyclodextrin polyelectrolytes for extended drug delivery.

    PubMed

    Junthip, Jatupol; Tabary, Nicolas; Chai, Feng; Leclercq, Laurent; Maton, Mickael; Cazaux, Frederic; Neut, Christel; Paccou, Laurent; Guinet, Yannick; Staelens, Jean-Noel; Bria, Marc; Landy, David; Hédoux, Alain; Blanchemain, Nicolas; Martel, Bernard

    2016-06-01

    The coating of a nonwoven textile by polyelectrolyte multilayer film (PEM) issued from cationic and anionic β-cyclodextrin (βCD) polyelectrolytes according to the layer-by-layer (LbL) technique was successfully attempted. The tert-butyl benzoic acid (TBBA) was used as drug model to evaluate the loading capacity and sustained release properties of this PEM system. The build-up of the multilayer assembly was monitored in situ by optical waveguide lightmode spectroscopy (OWLS) on the one hand, and was assessed by gravimetry on the other hand when applied onto the textile substrate. In parallel, the complexation study of TBBA with both CD polyelectrolytes was also investigated by nuclear magnetic resonance (NMR) and isothermal titration calorimetry (ITC). The influence of thermal crosslinking of the multilayered coating on its stability and on TBBA release kinetics in phosphate buffered saline (PBS) at 37°C was studied. Finally, biological and microbiological tests were performed to investigate the cytocompatibility and the intrisic antibacterial activity of multilayer assemblies. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1408-1424, 2016. PMID:26833891

  13. Micropatterning neuronal cells on polyelectrolyte multilayers.

    PubMed

    Reyes, Darwin R; Perruccio, Elizabeth M; Becerra, S Patricia; Locascio, Laurie E; Gaitan, Michael

    2004-09-28

    This paper describes an approach to adhere retinal cells on micropatterned polyelectrolyte multilayer (PEM) lines adsorbed on poly(dimethylsiloxane) (PDMS) surfaces using microfluidic networks. PEMs were patterned on flat, oxidized PDMS surfaces by sequentially flowing polyions through a microchannel network that was placed in contact with the PDMS surface. Polyethyleneimine (PEI) and poly(allylamine hydrochloride) (PAH) were the polyions used as the top layer cellular adhesion material. The microfluidic network was lifted off after the patterning was completed and retinal cells were seeded on the PEM/PDMS surfaces. The traditional practice of using blocking agents to prevent the adhesion of cells on unpatterned areas was avoided by allowing the PDMS surface to return to its uncharged state after the patterning was completed. The adhesion of rat retinal cells on the patterned PEMs was observed 5 h after seeding. Cell viability and morphology on the patterned PEMs were assayed. These materials proved to be nontoxic to the cells used in this study regardless of the number of stacked PEM layers. Phalloidin staining of the cytoskeleton revealed no apparent morphological differences in retinal cells compared with those plated on polystyrene or the larger regions of PEI and PAH; however, cells were relatively more elongated when cultured on the PEM lines. Cell-to-cell communication between cells on adjacent PEM lines was observed as interconnecting tubes containing actin that were a few hundred nanometers in diameter and up to 55 microm in length. This approach provides a simple, fast, and inexpensive method of patterning cells onto micrometer-scale features. PMID:15379510

  14. Polyelectrolyte brushes: theory, modelling, synthesis and applications.

    PubMed

    Das, Siddhartha; Banik, Meneka; Chen, Guang; Sinha, Shayandev; Mukherjee, Rabibrata

    2015-11-28

    Polyelectrolyte (PE) brushes are a special class of polymer brushes (PBs) containing charges. Polymer chains attain "brush"-like configuration when they are grafted or get localized at an interface (solid-fluid or liquid-fluid) with sufficiently close proximity between two-adjacent grafted polymer chains - such a proximity triggers a particular nature of interaction between the adjacent polymer molecules forcing them to stretch orthogonally to the grafting interface, instead of random-coil arrangement. In this review, we discuss the theory, synthesis, and applications of PE brushes. The theoretical discussion starts with the standard scaling concepts for polymer and PE brushes; following that, we shed light on the state of the art in continuum modelling approaches for polymer and PE brushes directed towards analysis beyond the scaling calculations. A special emphasis is laid in pinpointing the cases for which the PE electrostatic effects can be de-coupled from the PE entropic and excluded volume effects; such de-coupling is necessary to appropriately probe the complicated electrostatic effects arising from pH-dependent charging of the PE brushes and the use of these effects for driving liquid and ion transport at the interfaces covered with PE brushes. We also discuss the atomistic simulation approaches for polymer and PE brushes. Next we provide a detailed review of the existing approaches for the synthesis of polymer and PE brushes on interfaces, nanoparticles, and nanochannels, including mixed brushes and patterned brushes. Finally, we discuss some of the possible applications and future developments of polymer and PE brushes grafted on a variety of interfaces. PMID:26399305

  15. 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. PMID:23320460

  16. [Investigation of the influence of temperature on polyelectrolyte microcapsules containing and not containing proteins].

    PubMed

    Guzhvina, D V; Dubrovskiĭ, A V; Shabarchina, L I; Sukhorukov, B I

    2010-01-01

    Using the methods of light scattering and optical microscopy, data on the thermosensitivity of hollow microcapsules generated by alternative layers of poly(allylamine) and poly(sterenesulfonate) polyelectrolyte and microcapsules with included polyelectrolyte complexes and proteins have been obtained. It has been shown that all three types of capsules shrink with increasing temperature and the time interval of thermal influence, and their diameter decreases. The thermosensitivity has been estimated by means of the temperature factor of shell shrinkage (Ec). For all three types of the microcapsules containing from 6 to 10 layers in the shell, the phenomenon of the thermosensitivity alternation depending on the number of shell layers was revealed. With an odd number of the shell layers, the shrinkage is stronger than with an even number. Using the transport proteins of blood hemoglobin and bovine serum albumin as an example, the dependence of the thermosensitivity of microcapsules on the quantity, the degree of ionization, and the conformational state of the incapsulating protein was investigated. PMID:20184141

  17. Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes.

    PubMed

    Alb, Alina M; Paril, Ahmet; Catalgil-Giz, Huceste; Giz, Ahmet; Reed, Wayne F

    2007-07-26

    Despite their importance in biological and technological contexts, copolymeric polyelectrolytes (or "copolyelectrolytes") continue to present challenges to theorists and experimentalists. The first results of a unified approach to the kinetics and mechanisms of copolyelectrolyte synthesis and the physical characteristics of the resulting polymers are presented. The free radical copolymerization of 4-vinylbenzenesulfonic acid sodium salt and acrylamide was monitored using automatic continuous online monitoring of polymerization reactions (ACOMP), from which the average bivariate composition and mass distributions were determined. Composition drift was related to the evolution of conductivity. In some cases bimodal populations of copolyelectrolyte and homopolymeric poly(acrylamide) resulted, i.e., blends of copolyelectrolyte and neutral homopolymer. The end-product scattering behavior depended on whether the end-product was bimodal or not, as demonstrated using automatic continuous mixing (ACM) in conjunction with light scattering and viscosity. Negative light-scattering third virial coefficients were found for bimodal end-products. This combined approach may allow connecting the synthesis kinetics to the resulting "trivariate" distribution of composition, molar mass, and linear charge density, which in turn controls the properties of end-product solutions, such as chain conformations, interparticle interactions, viscosity, interactions with colloids and other polymers, phase separation, etc. Unified results may allow testing and improvement of existing polyelectrolyte theories, development of new quantitative physicochemical models, provide advanced characterization methods, set the stage for studying more complex copolyelectrolytes, such as hydrophobically modified ones, and provide tools for ultimately controlling and tailoring the synthesis and properties of copolyelectrolytes. PMID:17441756

  18. 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).

  19. 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

  20. Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

    NASA Astrophysics Data System (ADS)

    Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

    2007-03-01

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

  1. Chlorine resistant glutaraldehyde crosslinked polyelectrolyte multilayer membranes for desalination.

    PubMed

    Cho, Kwun Lun; Hill, Anita J; Caruso, Frank; Kentish, Sandra E

    2015-05-01

    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. PMID:25776340

  2. 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).

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Time-Dependent Interfacial Properties and DNAPL Mobility

    SciTech Connect

    Tuck, D.M.

    1999-03-10

    Interfacial properties play a major role in governing where and how dense nonaqueous phase liquids (DNAPLs) move in the subsurface. Interfacial tension and contact angle measurements were obtained for a simple, single component DNAPL (tetrachloroethene, PCE), complex laboratory DNAPLs (PCE plus Sudan IV dye), and a field DNAPL from the Savannah River Site (SRS) M-Area DNAPL (PCE, trichloroethene [TCE], and maching oils). Interfacial properties for complex DNAPLs were time-dependent, a phenomenon not observed for PCE alone. Drainage capillary pressure-saturation curves are strongly influenced by interfacial properties. Therefore time-dependence will alter the nature of DNAPL migration and penetration. Results indicate that the time-dependence of PCE with relatively high Sudan IV dye concentrations is comparable to that of the field DNAPL. Previous DNAPL mobility experiments in which the DNAPL was dyed should be reviewed to determine whether time-dependent properties influenced the resutls. Dyes appear to make DNAPL more complex, and therefore a more realistic analog for field DNAPLs than single component DNAPLs.

  8. Self-assembled virus-membrane complexes

    SciTech Connect

    Yang, Lihua; Liang, Hongjun; Angelini, Thomas; Butler, John; Coridan, Robert; Tang, Jay; Wong, Gerard

    2010-11-16

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

  9. Probing aggregation and fibril formation of insulin in polyelectrolyte multilayers.

    PubMed

    Koo, Juny; Czeslik, Claus

    2012-06-01

    Ultrathin films are useful for coating materials and controlling drug delivery processes. Here, we explore the use of polyelectrolyte multilayers as templates for the formation of two-dimensional protein networks, which represent biocompatible and biodegradable ultrathin films. In a first step, we have studied the lateral aggregation and amyloid fibril formation of bovine insulin that is adsorbed at and confined within planar polyelectrolyte multilayers, assembled with poly(diallyldimethylammonium chloride) (PDDA), poly(styrenesulfonic acid) (PSS), and hyaluronic acid (HA). Si-PDDA-PSS-(insulin-PSS)(x) and Si-PDDA-PSS-(insulin-HA)(x) multilayers (x=1-4) have been prepared and characterized in the fully hydrated state by using X-ray reflectometry, attenuated total reflection-Fourier transform infrared spectroscopy and confocal fluorescence microscopy. The obtained data demonstrate a successful build-up of the insulin-polyelectrolyte multilayers on silicon wafers that grow strongly in thickness upon insulin adsorption on PSS and HA layers. The secondary structure analysis of insulin, based on the vibrational amide I'-band, indicates an enhanced intermolecular β-sheet formation within the multilayers at 70°C and pD=2, i.e. at conditions that promote insulin amyloid fibrils rich in β-sheet contents. However, insulin that is confined between two polyelectrolyte layers rather forms amorphous aggregates as can be inferred from confocal fluorescence images. Remarkably, when insulin is deposited as the top-layer, a partial conversion into a two-dimensional fibrillar network can be induced by adding amyloid seeds to the solution. Thus, the results of this study illustrate the capability of polyelectrolyte multilayers as templates for the growth of protein networks. PMID:22369752

  10. 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. PMID:25976124

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

    PubMed

    Burrows, Hugh D; Costa, Telma; Ramos, M Luisa; Valente, Artur J M; Stewart, Beverly; Justino, Licinia L G; Almeida, Aline I A; Catarina, Nathanny Lessa; Mallavia, Ricardo; Knaapila, Matti

    2016-06-22

    We have studied the interaction of 8-hydroxyquinoline-5-sulfonate (8-HQS) with the metal ions Al(iii) and Zn(ii) in aqueous solution in the presence of tetraalkylammonium surfactants using UV/vis absorption, fluorescence, NMR spectroscopy and electrical conductivity measurements, complemented by DFT calculations and molecular dynamics (MD) simulations. Under appropriate conditions, complexes between 8-HQS and metal ions form rapidly, and have similar electronic, spectroscopic and photophysical properties to the corresponding metal quinolates, such as Alq3. These interact with the cationic surfactants, leading to marked increases in fluorescence intensity. However, significant differences are seen in the behavior of the two metal ions. With aluminium, a stable [Al(8-QS)3](3-) anion is formed, and interacts, predominantly through electrostatic interactions, with the surfactant, without disrupting the metal ion coordination sphere. In contrast, with Zn(ii), there is a competition between the metal ion and surfactants in the interaction with 8-HQS, although the [Zn(8-QS)2(H2O)2](2-) species is stable at appropriate pH and surfactant concentration. The studies are extended to systems with the conjugated polyelectrolyte (CPE) poly-(9,9-bis(6-N,N,N-trimethylammonium)hexyl)-fluorene-phenylene bromide (HTMA-PFP), which has a similar alkylammonium chain to the surfactants. Mixing metal salt, 8-HQS and HTMA-PFP in the presence of a nonionic surfactant leads to the formation of a metal complex/CPE supramolecular assembly between the conjugated polyelectrolyte and the metal/8-HQS complex, as demonstrated by electronic energy transfer. The potential of these systems in sensing, light harvesting, and electron injection/transport layers in organic semiconductor devices is discussed. PMID:26817700

  12. Role of reactant transport in determining the properties of NIF shells made by interfacial polycondensation

    SciTech Connect

    Hamilton, K.E.; Letts, S.A.; Buckley, S.R.; Fearon, E.M.; Wilemski, G.; Cook, R.C.; Schroen-Carey, D.

    1997-03-01

    Polymer shells up to 2 mm in diameter were prepared using an interfacial polycondensation / cross-linking reaction occurring at the surface of an oil drop. The oil phase is comprised of a solution (20 wt% or less) of isophthaloyl dichloride (IPC) dissolved in an organic solvent. An interfacial reaction is initiated when the IPC-loaded oil drop is submerged in an aqueous solution of poly(p-vinylphenol) (PVP), a poly(electrolyte) at elevated pH. Composition, structure, and surface finish for fully-formed dry shells were assessed using a number of techniques including scanning electron microscopy (SEM), atomic force microscopy (AFM), fourier-transform infrared spectroscopy (FTIR), pyrolysis-gas chromatography (GC) mass spectroscopy (MS), microhardness measurements, gas permeability, and solvent permeability measurements. From deposition rate data, a reaction mechanism and key reaction parameters were identified. The deposition rate of shell membrane material was found to be a diffusion limited reaction of IPC through the forming membrane to the exterior shell interface (which is believed to be the reaction front). The final thickness of the film deposited at the interface and the rate of deposition were found to be strong functions of the IPC concentration and oil phase solvent. Films made with diethyl phthalate (DEP) were thinner and harder than films made using 1,6-dichlorohexane (DCH) as a solvent. Differences in solubility of the forming membrane in DCH and DEP appear to be able to account for the differences in deposition rate and the hardness (related to cross-linking density). The deposition can be thought of as a phase separation which is affected by both the poly(electrolyte) / ionomer transition and the amount of cross-linking. Finally, it was found that the choice of oil phase solvent profoundly affects the evolution of the outer surface roughness.

  13. 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. PMID:19217121

  14. Interfacial behavior of polymer electrolytes

    SciTech Connect

    Kerr, John; Kerr, John B.; Han, Yong Bong; Liu, Gao; Reeder, Craig; Xie, Jiangbing; Sun, Xiaoguang

    2003-06-03

    Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combined with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.

  15. The aqueous-polyelectrolyte dye solution as an active laser medium

    SciTech Connect

    Akimov, A I; Saletskii, A M

    2000-11-30

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

  16. 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

    2015-09-01

    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%. PMID:26280810

  17. Factors influencing polyelectrolyte-aptamer multilayered films with target-controlled permeability for sensing applications.

    PubMed

    Malile, Brian; Chen, Jennifer I L

    2016-06-01

    Portable, easy-to-use and cost-effective sensing devices are desirable in healthcare, environmental monitoring and food safety. Herein we employ polyelectrolyte-aptamer (PE-aptamer) multilayered films that exhibit target-responsive permeability for colorimetric and electrochemical sensing. We present the quantitative detection of an exemplary small molecule, quinine, and address the potential for detection in complex media by examining interference effects. We optimize the film composition and investigate the importance of the structural-switching ability of the aptamer. The results from both platforms are corroborated to provide an outlook on the applicability of the PE-aptamer film for sensing. The label-free detection combined with the readily adaptive assembly process could be invaluable for diverse analytical fields. PMID:26688863

  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. PMID:26913984

  19. On the scattering properties of polyelectrolyte gels

    NASA Astrophysics Data System (ADS)

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

    1992-08-01

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

  20. Study of the flow field in the magnetic rod interfacial stress rheometer.

    PubMed

    Verwijlen, Tom; Moldenaers, Paula; Stone, Howard A; Vermant, Jan

    2011-08-01

    Several technological applications, consumer products, and biological systems derive their functioning from the presence of a complex fluid interface with viscoelastic interfacial rheological properties. Measurements of the "excess" rheological properties of such an interface are complicated by the intimate coupling of the bulk and interfacial flows. In the present work, analytical, numerical, and experimental results of the interfacial flow fields in a magnetic rod interfacial stress rheometer (ISR) are presented. Mathematical solutions are required to correct the experimentally determined apparent interfacial shear moduli and phase angles for the drag exerted by the surrounding phases, especially at low Boussinesq numbers. Starting from the Navier-Stokes equations and using the generalized Boussinesq-Scriven equation as a suitable boundary condition, the problem is solved both analytically and numerically. In addition, experimental data of the interfacial flow field are reported, obtained by following the trajectories of tracer particles at the interface with time. Good agreement is found between the three methods, indicating that both the analytical solution and the numerical simulations give an adequate description of the flow field and the resulting local interfacial shear rate at the rod. Based on these results, an algorithm to correct the experimental data of the ISR is proposed and evaluated, which can be extended to different types of interfacial shear rheometers and geometries. An increased accuracy is obtained and the measurement range of the ISR is expanded toward viscosities and elastic moduli of smaller magnitude. PMID:21696160

  1. Chirality-selected phase behaviour in ionic polypeptide complexes

    SciTech Connect

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, III, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-14

    In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.

  2. Chirality-selected phase behaviour in ionic polypeptide complexes

    DOE PAGESBeta

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, III, Charles F.; Margossian, Khatcher O.; et al

    2015-01-14

    In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

  3. Chirality-selected phase behaviour in ionic polypeptide complexes

    PubMed Central

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-01

    Polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation. PMID:25586861

  4. Chirality-selected phase behaviour in ionic polypeptide complexes

    NASA Astrophysics Data System (ADS)

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-01

    Polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.

  5. Weak Polyelectrolyte-Clay Assemblies: Physical Mechanisms of Biological Response

    NASA Astrophysics Data System (ADS)

    Sukhishvili, Svetlana; Pavlukhina, Svetlana; Zhuk, Iryna

    2014-03-01

    We report on a highly efficient, non-leachable antibacterial coating, consisting of an ultrathin nanocomposite hydrogel capable of hosting, protecting and delivering antibiofilm agents in response to bacterial infection. Constructed using layer-by-layer (LbL) deposition of clay nanoplatelets and a weak polyelectrolyte and loaded with an antimicrobial agent (AmA), the coatings was highly resistant to colonization by Staphylococcus aureus. The high antibiofilm activity of the coating results from a combination of highly localized, bacteria-triggered AmA release and hydrogel swelling, as well as retention of AmA by clay nanoplatelets. We discuss the dependence of rheological and swelling properties of weak polyelectrolyte-clay assemblies on film thickness, clay platelet orientation and environmental pH.

  6. 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.}

  7. 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.

  8. The Hofmeister anion effect and the growth of polyelectrolyte multilayers.

    PubMed

    Salomäki, Mikko; Tervasmäki, Piia; Areva, Sami; Kankare, Jouko

    2004-04-27

    The influence of a variety of counteranions on the properties of polyelectrolyte multilayers deposited by layer-by-layer technique is studied by using ellipsometry and AFM. We found out that in thin dry multilayers (20-90 nm) ofpoly(4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium) (PDADMA), the thickness follows reasonably well the position of the counteranion in the Hofmeister series. The polyelectrolyte-counteranion interaction is studied by means of viscosity measurements of semidilute solutions of PDADMA in the presence of different anions. The dynamic viscosities follow the Hofmeister series of anions and correlate with the thickness of multilayers. Two parameters describing the interaction of ions with water, the Jones-Dole viscosity B coefficient and the hydration entropy, are used to explain the anion effect on the developing multilayer thickness. Reasonably smooth and monotonic functional dependence is observed between the layer thickness and these two parameters. PMID:15875399

  9. Nucleation and interfacial adsorption in ternary systems.

    PubMed

    Philippe, T

    2015-03-01

    Nucleation is studied in incompressible ternary fluids by examining the topology of the overall landscape of the energy surface. Minimum free energy paths for nucleation (MFEPs) of a single nucleus in an infinite matrix are computed with the string method in the framework of the continuum theory of nucleation for the regular solution. Properties of the critical nucleus are compared with the predictions of the classical nucleation theory. MFEPs are found to exhibit complex nucleation pathways with non-monotonic variations of compositions in the interfacial region, specifically adsorption of a component. In the symmetric regular solution, the minority component is found to segregate at the interface during nucleation with a concomitant depletion of the nucleus core, resulting in unpredicted partition of the non-selective component. Despite increasing the gradient energy, such inhomogeneity in composition is shown to lower the nucleation barrier. PMID:25747088

  10. 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.

  11. 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.

  12. Electric field-induced deformation of polyelectrolyte gels

    SciTech Connect

    Adolf, D.; Hance, B.G.

    1995-08-01

    Water-swollen polyelectrolyte gels deform in an electric field. We observed that the sign and magnitude of the deformation is dependent on the nature of the salt bath in which the gel is immersed and electrocuted. These results are compatible with a deformation mechanism based upon creation of ion density gradients by the field which, in turn, creates osmotic pressure gradients within the gel. A consistent interpretation results only if gel mobility is allowed as well as free ion diffusion and migration.

  13. Polyelectrolyte gels as bending actuators: modeling and numerical simulation

    NASA Astrophysics Data System (ADS)

    Wallmersperger, Thomas; Keller, Karsten; Attaran, Abdolhamid

    2013-04-01

    Polyelectrolyte gels are ionic electroactivematerials. They have the ability to react as both, sensors and actuators. As actuators they can be used e.g. as artificial muscles or drug delivery control; as sensors they may be used for measuring e.g. pressure, pH or other ion concentrations in the solution. In this research both, anionic and cationic polyelectrolyte gels placed in aqueous solution with mobile anions and cations are investigated. Due to external stimuli the polyelectrolyte gels can swell or shrink enormously by the uptake or delivery of solvent. In the present research a coupled multi-field problem within a continuum mechanics framework is proposed. The modeling approach introduces a set of equations governing multiple fields of the problem, including the chemical field of the ionic species, the electrical field and the mechanical field. The numerical simulation is performed by using the Finite Element Method. Within the study some test cases will be carried out to validate our model. In the works by Gülch et al., the application of combined anionic-cationic gels as grippers was shown. In the present research for an applied electric field, the change of the concentrations and the electric potential in the complete polymer is simulated by the given formulation. These changes lead to variations in the osmotic pressure resulting in a bending of different polyelectrolyte gels. In the present research it is shown that our model is capable of describing the bending behavior of anionic or cationic gels towards the different electrodes (cathode or anode).

  14. Azobenzene - functionalized polyelectrolyte nanolayers as ultrafast optoacoustic transducers.

    PubMed

    Pavlenko, E S; Sander, M; Mitzscherling, S; Pudell, J; Zamponi, F; Rössle, M; Bojahr, A; Bargheer, M

    2016-07-21

    We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε∼ 5 × 10(-4) is calibrated by ultrafast X-ray diffraction. PMID:27341685

  15. Azobenzene - functionalized polyelectrolyte nanolayers as ultrafast optoacoustic transducers

    NASA Astrophysics Data System (ADS)

    Pavlenko, E. S.; Sander, M.; Mitzscherling, S.; Pudell, J.; Zamponi, F.; Rössle, M.; Bojahr, A.; Bargheer, M.

    2016-07-01

    We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ~ 5 × 10-4 is calibrated by ultrafast X-ray diffraction.

  16. Polyelectrolyte adsorption layers studied by streaming potential and particle deposition.

    PubMed

    Adamczyk, Z; Zembala, M; Michna, A

    2006-11-15

    Adsorption of a cationic polyelectrolyte, polyallylamine hydrochloride (PAH), having a molecular weight of 70,000 on mica was characterized by the streaming potential method and by deposition of negative polystyrene latex particles. Formation of PAH layers was followed by determining the apparent zeta potential of surface zeta as function of bulk PAH concentration. The zeta potential was calculated from the streaming potential measured in the parallel-plate channel formed by two mica plates precovered by the polyelectrolyte. The experimental data were expressed as the dependence of the reduced zeta potential zeta/zeta0 on the PAH coverage Theta(PAH), calculated using the convective diffusion theory. It was found that for the ionic strength of 10(-2) M, the dependence of zeta/zeta0 on Theta(PAH) can be reflected by the theoretical model formulated previously for surfaces covered by colloid particles. The electrokinetic measurements were complemented by particle deposition experiments on PAH-covered mica surfaces. A direct correlation between the polymer coverage and the initial deposition rate of particles, as well as the jamming coverage, was found. For ThetaPAH > 0.3 the initial deposition rate attained the value predicted from the convective diffusion theory for homogeneous surfaces. The initial deposition rates for surfaces modified by PAH were compared with previous experimental and theoretical results obtained for heterogeneous surfaces formed by preadsorption of colloid particles. It was revealed that negative latex deposition occurred at surfaces exhibiting negative apparent zeta potential, which explained the anomalous deposition of particles observed in previous works. It was suggested that the combined electrokinetic and particle deposition methods can be used for detecting adsorbed polyelectrolytes at surfaces for coverage range of a percent. This enables one to measure bulk polyelectrolyte concentrations at the level of 0.05 ppm. PMID:16949085

  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. PMID:26671401

  18. Elastocapillary-mediated interfacial assembly

    NASA Astrophysics Data System (ADS)

    Evans, Arthur

    2015-11-01

    Particles confined to an interface are present in a large number of industrial applications and ubiquitous in cellular biophysics. Interactions mediated by the interface, such as capillary effects in the presence of surface tension, give rise to rafts and aggregates whose structure is ultimately determined by geometric characteristics of these adsorbed particles. A common strategy for assembling interfacial structures relies on exploiting these interactions by tuning particle anisotropy, either by constructing rigid particles with heterogeneous wetting properties or fabricating particles that have a naturally anisotropic shape. Less explored, however, is the scenario where the interface causes the particles to deform. In this talk I will discuss the implications for interfacial assembly using elastocapillary-mediated interactions. The competition between surface energy and elasticity can wrinkle and buckle adsorbed soft particles, leading to complicated (but programmable) aggregates.

  19. The evolution of cyclopropenium ions into functional polyelectrolytes

    DOE PAGESBeta

    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 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

  20. Nanostructured multilayer polyelectrolyte films with silver nanoparticles as antibacterial coatings.

    PubMed

    Kruk, Tomasz; Szczepanowicz, Krzysztof; Kręgiel, Dorota; Szyk-Warszyńska, L; Warszyński, Piotr

    2016-01-01

    Ultrathin polyelectrolyte films containing silver nanoparticles appear to be a promising material for antimicrobial coatings used in the medical area. The present work is focused on the formation of multilayer polyelectrolyte films using: polyethyleneimine (PEI) as polycation, Poly(sodium 4-styrenesulfonate) (PSS) as polyanions and negatively charged silver nanoparticles (AgNPs), which led to the polyelectrolyte-silver nanocomposite coatings. The film thickness and mass were measured by ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D) and the structure and morphology of films were visualized using scanning electron microscopy (SEM). Systematic increase of the UV-Vis absorption confirmed formation of the consecutive layers of the film. The analysis of bacteria cell adhesion to films surface was done by the luminometry measurement. Three gram-negative bacterial strains with strong adhesive properties were used in this study: Escherichia coli, Aeromonas hydrophila, and Asaia lannenesis. It was found that nanocomposite films have antimicrobial properties, which makes them very interesting for a number of practical applications, e.g. for the prevention of microbial colonization on treated surfaces. PMID:26193773

  1. 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.

  2. Highly active antibody-modified magnetic polyelectrolyte capsules.

    PubMed

    Valdepérez, Daniel; Del Pino, Pablo; Sánchez, Lourdes; Parak, Wolfgang J; Pelaz, Beatriz

    2016-07-15

    Polyelectrolyte hollow capsules are versatile platforms typically used for encapsulation of a wide variety of macromolecules in their cavity. The polymer shell of these capsules as composed by alternating layers of oppositely charged polyelectrolytes also allows for adding additional functionalities. The properties of the shell can be for example engineered by trapping different nanoparticles in-between the shell layers and/or by attaching bioactive molecules such as antibodies to the outermost layer. Herein, iron oxide NPs were inmobilized into the shell of polyelectrolyte capsules and the outermost layer of the shell was covalently modified with anti peroxidase antibodies. These capsules act as prototype model system, aiming to obtain a microstructure with the potential capability to specifically recognize and separate macromolecules. Due to the magnetic nanoparticles in the capsule shell, the capsules together with the attached target might be extracted by magnetic field gradients. Here we verified this approach by extracting horseradish peroxidase from a solution through magnetic separation with capsules bearing antibodies against horseradish peroxidase. The bioactivity of the capsules and the high degree of specific antibody functionalization were confirmed and quantified through an enzymatic reaction mediated by the extracted horseradish peroxidase. PMID:27089014

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

    PubMed

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

    2013-07-01

    A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer-by-layer technique on a silicon oxide surface modified with a 3-aminopropyltriethoxysilane (APTES) monolayer. The surface pK(a) value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer-by-layer assembly. Micropatterned polyelectrolyte films were obtained by deep-UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm(2) s(-1) in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field. PMID:23695862

  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. Fabrication of polyelectrolyte multilayered nano-capsules using a continuous layer-by-layer approach.

    PubMed

    Elizarova, Iuliia S; Luckham, Paul F

    2016-05-15

    The layer-by-layer approach is a highly versatile method for the fabrication of multilayered polymeric films and capsules. It has been widely investigated in research for various polyelectrolyte pairs and core template particles. However, the fabrication of nano-sized capsules at the larger scale is difficult and time consuming, due to the necessity of washing and centrifugation steps before the deposition of each polyelectrolyte layer. This results not only in a very long fabrication time, but also in the partial loss of particles during those intermediate steps. In this study, we introduced a continuous approach for the fabrication of multilayer polyelectrolyte based nano-capsules using calcium phosphate core nanoparticles and a tubular flow type reactor with the potential for synthesizing tens of milligrams of capsules per hour. Adsorption of the polyelectrolyte layer occurred in the tubing where particles and polyelectrolyte solution of choice were mixed, creating a layer of polyelectrolyte on the particles. After this, these newly surfaced-modified particles passed into the next segment of tubing, where they were mixed with a second polyelectrolyte of opposite charge. This process can be continuously repeated until the desired number of layers is achieved. One potential problem with this method concerned the presence of any excess polyelectrolyte in the tubing, so careful control of the amount of polymer added was crucial. It was found that slightly under dosing the amount of added polyelectrolyte ensured that negligible unadsorbed polyelectrolyte remained in solution. The particles created at each deposition step were stable, as they all had a zeta potential of greater than ±25mV. Furthermore the zeta potential measurements showed that charge reversal occurred at each stage. Having achieved the necessary number of polyelectrolyte layers, the calcium phosphate cores were easily removed via dissolution in either hydrochloric or acetic acid. PMID:26939072

  6. Introducing a high gravity field to enhance infiltration of small molecules into polyelectrolyte multilayers.

    PubMed

    Liu, Xiaolin; Zhao, Kun; Jiang, Chao; Wang, Yue; Shao, Lei; Zhang, Yajun; Shi, Feng

    2015-07-28

    Loading functional small molecules into nano-thin films is fundamental to various research fields such as membrane separation, molecular imprinting, interfacial reaction, drug delivery etc. Currently, a general demand for enhancing the loading rate without affecting the film structures exists in most infiltration phenomena. To handle this issue, we have introduced a process intensification method of a high gravity technique, which is a versatile energy form of mechanical field well-established in industry, into the investigations on diffusion/infiltration at the molecular level. By taking a polyelectrolyte multilayer as a model thin film and a photo-reactive molecule, 4,4'-diazostilbene-2,2'-disulfonic acid disodium salt (DAS), as a model small functional molecule, we have demonstrated remarkably accelerated adsorption/infiltration of DAS into a poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayer by as high as 20-fold; meanwhile, both the film property of the multilayer and photoresponsive-crosslinking function of DAS were not disturbed. Furthermore, the infiltration of DAS and the surface morphology of the multilayer could be tuned based on their high dependence on the intensity of the high gravity field regarding different rotating speeds. The mechanism of the accelerated adsorption/infiltration under the high gravity field was interpreted by the increased turbulence of the diffusing layer with the thinned laminar boundary layer and the stepwise delivery of the local concentration gradient from the solution to the interior of the multilayer. The introduction of mechanical field provides a simple and versatile strategy to address the paradox of the contradictory loading amount and loading rate, and thus to promote applications of various membrane processes. PMID:26086776

  7. Identifying Mechanisms of Interfacial Dynamics Using Single-Molecule Tracking

    PubMed Central

    Kastantin, Mark; Walder, Robert; Schwartz, Daniel K.

    2012-01-01

    The “soft” (i.e. non-covalent) interactions between molecules and surfaces are complex and highly-varied (e.g. hydrophobic, hydrogen bonding, ionic) often leading to heterogeneous interfacial behavior. Heterogeneity can arise either from spatial variation of the surface/interface itself or from molecular configurations (i.e. conformation, orientation, aggregation state, etc.). By observing adsorption, diffusion, and desorption of individual fluorescent molecules, single-molecule tracking can characterize these types of heterogeneous interfacial behavior in ways that are inaccessible to traditional ensemble-averaged methods. Moreover, the fluorescence intensity or emission wavelength (in resonance energy transfer experiments) can be used to simultaneously track molecular configuration and directly relate this to the resulting interfacial mobility or affinity. In this feature article, we review recent advances involving the use of single-molecule tracking to characterize heterogeneous molecule-surface interactions including: multiple modes of diffusion and desorption associated with both internal and external molecular configuration, Arrhenius activated interfacial transport, spatially dependent interactions, and many more. PMID:22716995

  8. Development of functionalised polyelectrolyte capsules using filamentous Escherichia coli cells

    PubMed Central

    2012-01-01

    Background Escherichia coli is one of the best studied microorganisms and finds multiple applications especially as tool in the heterologous production of interesting proteins of other organisms. The heterologous expression of special surface (S-) layer proteins caused the formation of extremely long E. coli cells which leave transparent tubes when they divide into single E. coli cells. Such natural structures are of high value as bio-templates for the development of bio-inorganic composites for many applications. In this study we used genetically modified filamentous Escherichia coli cells as template for the design of polyelectrolyte tubes that can be used as carrier for functional molecules or particles. Diversity of structures of biogenic materials has the potential to be used to construct inorganic or polymeric superior hybrid materials that reflect the form of the bio-template. Such bio-inspired materials are of great interest in diverse scientific fields like Biology, Chemistry and Material Science and can find application for the construction of functional materials or the bio-inspired synthesis of inorganic nanoparticles. Results Genetically modified filamentous E. coli cells were fixed in 2% glutaraldehyde and coated with alternating six layers of the polyanion polyelectrolyte poly(sodium-4styrenesulfonate) (PSS) and polycation polyelectrolyte poly(allylamine-hydrochloride) (PAH). Afterwards we dissolved the E. coli cells with 1.2% sodium hypochlorite, thus obtaining hollow polyelectrolyte tubes of 0.7 μm in diameter and 5–50 μm in length. For functionalisation the polyelectrolyte tubes were coated with S-layer protein polymers followed by metallisation with Pd(0) particles. These assemblies were analysed with light microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and transmission electron microscopy. Conclusion The thus constructed new material offers possibilities for diverse applications like novel catalysts or metal

  9. Equilibrium distribution of permeants in polyelectrolyte microcapsules filled with negatively charged polyelectrolyte: the influence of ionic strength and solvent polarity.

    PubMed

    Tong, Weijun; Song, Haiqing; Gao, Changyou; Möhwald, Helmuth

    2006-07-01

    The effects of ionic strength and solvent polarity on the equilibrium distribution of fluorescein (FL) and FITC-dextran between the interior of polyelectrolyte multilayer microcapsules filled with negatively charged strong polyelectrolyte and the bulk solution were systematically investigated. A negatively charged strong polyelectrolyte, poly(styrene sulfonate) (PSS), used for CaCO3 core fabrication, was entrapped inside the capsules. Due to the semipermeability of the capsule wall, a Donnan equilibrium between the inner solution within the capsules and the bulk solution was created. The equilibrium distribution of the negatively charged permeants was investigated by means of confocal laser scanning microscopy as a function of ionic strength and solvent polarity. The equilibrium distribution of the negatively charged permeants could be tuned by increasing the bulk ionic strength to decrease the Donnan potential. Decreasing the solvent polarity also could enhance the permeation of FL, which induces a sudden increase of permeation when the ethanol volume fraction was higher than 0.7. This is mainly attributed to the precipitation of PSS. A theoretical model combining the Donnan equilibrium and Manning counterion condensation was employed to discuss the results. PMID:16805590

  10. Preparation and Evaluation of Diclofenac Sodium Tablet Coated with Polyelectrolyte Multilayer Film Using Hypromellose Acetate Succinate and Polymethacrylates for pH-Dependent, Modified Release Drug Delivery.

    PubMed

    Jeganathan, Balamurugan; Prakya, Vijayalakshmi; Deshmukh, Abhijit

    2016-06-01

    Polyelectrolyte multilayer (PEM) film formed due to the electrostatic interaction between oppositely charged polyelectrolytes is of considerable interest because of their potential applications as both drug carriers and surface-modifying agents. In this study, in vitro studies were carried out on polyelectrolyte complexes formulated with Eudragit E (EE) and hypromellose acetate succinate (HPMCAS). The complexes of EE and HPMCAS were formulated by non-stoichiometric method. The prepared IPCs were investigated using Fourier transform infrared spectroscopy. Diclofenac sodium (DS) tablets were prepared and were coated with polymer solution of HPMCAS and EE to achieve pH-dependent and sustained-release tablets. Tablets were evaluated for their physical characteristics and in vitro drug release. The results of pharmacokinetic studies in rabbits showed that the selected formulation (F6) exhibited a delayed peak plasma concentration and marked sustained-release effect of drug in the in vivo drug release in comparison with marketed tablet. The suitable combination of PEM film based on EE and HPMCAS demonstrated potential candidate for targeted release of DS in the lower part of the gastrointestinal (GI) tract. PMID:26283195

  11. Structure Formation in Salt-Free Solutions of Amphiphilic Sulfonated Polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Bockstaller, Michael; Koehler, Werner

    2000-03-01

    Self-assembled systems have long attracted attention due to their practical importance in many technical and biological fields. Dodecyl-substituted poly(para-phenylen)sulfonates (abbreviated PPPS) are highly charged polyelectrolytes which in the uncharged state have been investigated extensively and an intrinsic persistence length of 15 nm has been reported. Due to their hydrophobic side chains, PPPS are compatible with water only as micellar aggregates and tend to form supramolecular structures even at concentrations as low as 10-5mol_mon.units/l. Because of the rodlike conformation of PPPS, this self-assembly leads to aggregates of anisotropic shape. Therefore, depolarized light scattering was employed to yield complementary information about structure and dynamics of these complex fluids. Aqueous solutions of PPPS at room temperature undergo a structural transition at a critical concentration of c_crit.=0.016 g/l. This transition is characterized by a strong increase of scattered intensity in forward direction and dynamic depolarized scattering. Above c_crit. the cylindrical micelles (L=310 nm, d=3.1 nm, N_radial=12) self assembly into large ellipsoidal clusters of size in the μ m range. Due to the strong increase of depolarized scattered intensity there has to be a preferential orientation of the micelles inside those clusters, which thus represent a lyotropic mesophase. By combining static and dynamic light scattering for the low q-range as well as small angle x-ray scattering for the higher q-range it is possible to determine size and shape of each aggregation step. Decreasing the molecular weight of the PPPS has profound influence on the micellar length and hence on c_crit. which is close to the overlap concentration (c ~ 1/L^3) allowing for the observation of the polyelectrolyte effect.

  12. Gradients of physical and biochemical cues on polyelectrolyte multilayer films generated via microfluidics.

    PubMed

    Almodóvar, Jorge; Crouzier, Thomas; Selimović, Šeila; Boudou, Thomas; Khademhosseini, Ali; Picart, Catherine

    2013-04-21

    The cell microenvironment is a complex and anisotropic matrix composed of a number of physical and biochemical cues that control cellular processes. A current challenge in biomaterials is the engineering of biomimetic materials which present spatially controlled physical and biochemical cues. The layer-by-layer assembly of polyelectrolyte multilayers (PEM) has been demonstrated to be a promising candidate for a biomaterial mimicking the native extracellular matrix. In this work, gradients of biochemical and physical cues were generated on PEM films composed of hyaluronan (HA) and poly(l-lysine) (PLL) using a microfluidic device. As a proof of concept, four different types of surface concentration gradients adsorbed onto the films were generated. These included surface concentration gradients of fluorescent PLL, fluorescent microbeads, a cross-linker, and one consisting of a polyelectrolyte grafted with a cell adhesive peptide. In all cases, reproducible centimeter-long linear gradients were obtained. Fluorescence microscopy, Fourier transform infrared spectroscopy and atomic force microscopy were used to characterize these gradients. Cell responses to the stiffness gradient and to the peptide gradient were studied. Pre-osteoblastic cells were found to adhere and spread more along the stiffness gradient, which varied linearly from 200 kPa-600 kPa. Myoblast cell spreading also increased throughout the length of the increasing RGD-peptide gradient. This work demonstrates a simple method to modify PEM films with concentration gradients of non-covalently bound biomolecules and with gradients in stiffness. These results highlight the potential of this technique to efficiently and quickly determine the optimal biochemical and mechanical cues necessary for specific cellular processes. PMID:23440074

  13. Fine Adjustment of Interfacial Potential between pH-Responsive Hydrogels and Cell-Sized Particles.

    PubMed

    Monzel, Cornelia; Veschgini, Mariam; Madsen, Jeppe; Lewis, Andrew L; Armes, Steven P; Tanaka, Motomu

    2015-08-11

    We quantitatively determined interfacial potentials between cell-sized particles and stimulus-responsive hydrogels using a microinterferometer. The hydrogel is based on physically interconnected ABA triblock copolymer micelles comprising an inner biocompatible PMPC block and two outer pH-responsive PDPA blocks. The out-of-plane temporal fluctuation in the position of the cell-sized particles was calculated from changes in the interference pattern measured by Reflection Interference Contrast Microscopy (RICM), thus yielding the particle-substrate interaction potential V (Δh). Measurements in pH buffers ranging from 7.0 to 7.8 resulted in a systematic reduction in height of the potential minima ⟨Δh⟩ and a concomitant increase in the potential curvature V″ (Δh). The experimental data were analyzed by applying the modified Ross and Pincus model for polyelectrolytes, while accounting for gravitation, lubrication and van der Waals interactions. Elastic moduli calculated from V″ (Δh) were in good agreement with those measured by Atomic Force Microscopy. The ability to fine-tune both the gel elasticity and the interfacial potential at around physiological pH makes such triblock copolymer hydrogels a promising biocompatible substrate for dynamic switching of cell-material interactions. PMID:26190346

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

    DOEpatents

    Chen, Liaohai

    2004-05-18

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

  15. Interfacial functionalization and engineering of nanoparticles

    NASA Astrophysics Data System (ADS)

    Song, Yang

    The intense research interest in nanoscience and nanotechnology is largely fueled by the unique properties of nanoscale materials. In this dissertation, the research efforts are focused on surface functionalization and interfacial engineering of functional nanoparticles in the preparation of patchy nanoparticles (e.g., Janus nanoparticles and Neapolitan nanoparticles) such that the nanoparticle structures and properties may be manipulated to an unprecedented level of sophistication. Experimentally, Janus nanoparticles were prepared by an interfacial engineering method where one hemisphere of the originally hydrophobic nanoparticles was replaced with hydrophilic ligands at the air|liquid or solid|liquid interface. The amphiphilic surface characters of the Janus nanoparticles were verified by contact angle measurements, as compared to those of the bulk-exchange counterparts where the two types of ligands were distributed rather homogeneously on the nanoparticle surface. In a further study, a mercapto derivative of diacetylene was used as the hydrophilic ligands to prepare Janus nanoparticles by using hydrophobic hexanethiolate-protected gold nanoparticles as the starting materials. Exposure to UV irradiation led to effective covalent cross-linking between the diacetylene moieties of neighboring ligands and hence marked enhancement of the structural integrity of the Janus nanoparticles, which was attributable to the impeded surface diffusion of the thiol ligands on the nanoparticle surface, as manifested in fluorescence measurements of aged nanoparticles. More complicated bimetallic AgAu Janus nanoparticles were prepared by interfacial galvanic exchange reactions of a Langmuir-Blodgett monolayer of 1-hexanethiolate-passivated silver nanoparticles on a glass slide with gold(I)-mercaptopropanediol complex in a water/ethanol solution. The resulting nanoparticles exhibited an asymmetrical distribution not only of the organic capping ligands on the nanoparticle surface but

  16. One-step spray-dried polyelectrolyte microparticles enhance the antigen cross-presentation capacity of porcine dendritic cells.

    PubMed

    Devriendt, Bert; Baert, Kim; Dierendonck, Marijke; Favoreel, Herman; De Koker, Stefaan; Remon, Jean Paul; De Geest, Bruno G; Cox, Eric

    2013-06-01

    Vaccination is regarded as the most efficient and cost-effective way to prevent infectious diseases. Vaccine design nowadays focuses on the implementation of safer recombinant subunit vaccines. However, these recombinant subunit antigens are often poor immunogens and several strategies are currently under investigation to enhance their immunogenicity. The encapsulation of antigens in biodegradable microparticulate delivery systems seems a promising strategy to boost their immunogenicity. Here, we evaluate the capacity of polyelectrolyte complex microparticles (PECMs), fabricated by single step spray-drying, to deliver antigens to porcine dendritic cells and how these particles affect the functional maturation of dendritic cells (DCs). As clinically relevant model antigen F4 fimbriae, a bacterial adhesin purified from a porcine-specific enterotoxigenic Escherichia coli strain was chosen. The resulting antigen-loaded PECMs are efficiently internalised by porcine monocyte-derived DCs. F4 fimbriae-loaded PECMs (F4-PECMs) enhanced CD40 and CD25 surface expression by DCs and this phenotypical maturation correlated with an increased secretion of IL-6 and IL-1β. More importantly, F4-PECMs enhance both the T cell stimulatory and antigen presentation capacity of DCs. Moreover, PECMs efficiently promoted the CD8(+) T cell stimulatory capacity of dendritic cells, indicating an enhanced ability to cross-present the encapsulated antigens. These results could accelerate the development of veterinary and human subunit vaccines based on polyelectrolyte complex microparticles to induce protective immunity against a variety of extra- and intracellular pathogens. PMID:23207327

  17. Measuring Interfacial Tension Between Immiscible Liquids

    NASA Technical Reports Server (NTRS)

    Rashidnia, Nasser; Balasubramaniam, R.; Delsignore, David M.

    1995-01-01

    Glass capillary tube technique measures interfacial tension between two immiscible liquids. Yields useful data over fairly wide range of interfacial tensions, both for pairs of liquids having equal densities and pairs of liquids having unequal densities. Data on interfacial tensions important in diverse industrial chemical applications, including enhanced extraction of oil; printing; processing foods; and manufacture of paper, emulsions, foams, aerosols, detergents, gel encapsulants, coating materials, fertilizers, pesticides, and cosmetics.

  18. Interfacial reactions between titanium and borate glass

    SciTech Connect

    Brow, R.K.; Saha, S.K.; Goldstein, J.I.

    1992-12-31

    Interfacial reactions between melts of several borate glasses and titanium have been investigated by analytical scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). A thin titanium boride interfacial layer is detected by XPS after short (30 minutes) thermal treatments. ASEM analyses after longer thermal treatments (8--120 hours) reveal boron-rich interfacial layers and boride precipitates in the Ti side of the interface.

  19. Exploring interfacial ferromagnetism in manganite-based superlattices

    NASA Astrophysics Data System (ADS)

    Yi, Di; Flint, Charles; Suzuki, Yuri

    Heterointerface of complex oxides provides a rich playground to explore the emergent phenomena that are not found in bulk. In particular, emergent interfacial ferromagnetism has been successfully demonstrated in heterostructures composed of materials which are paramagnetic and antiferromagnetic in bulk. In our previous work, leakage of itinerant electrons from a paramagnetic metal to an antiferromagnetic insulator has been shown to give rise to interfacial ferromagnetism in CaMnO3 based superlattices. However interfacial ferromagnetism in insulating superlattices suggests a more complicated scenario. Therefore a thorough investigation of coupling between charge, lattice and spin degrees of freedom is necessary. In this talk, we focus on the NdNiO3 /CaMnO3 system. By choosing a paramagnetic layer that undergoes a metal-insulator transition, we can explore the role of electron itinerancy in interfacial ferromagnetism in the same sample to eliminate the inconsistencies that may originate from the deposition of multiple samples. We demonstrate that NdNiO3 exhibits a metal-insulator transition as a function of temperature, which can be tuned as a function of film thickness. We have also grown NdNiO3 /CaMnO3 heterostructures with excellent crystallinity. Preliminary transport measurements indicate that the presence of an adjacent CaMnO3 layer also affects the transport in NdNiO3 so that charge transfer from the itinerant layer into the adjacent antiferromagnetic insulating CaMnO3 is likely not the only contribution to interfacial ferromagnetism.

  20. Interfacial nanorheology: Probing molecular mobility in mesoscopic polymeric systems

    NASA Astrophysics Data System (ADS)

    Sills, Scott E.

    Investigating the finite size limited structural relaxations in mesoscopic polymer systems is central to nanotechnological applications involving thin films, complex structures, and nanoscale phase-separated systems; for example, polymer electrolyte membranes, optoelectronic devices, and ultrahigh-density thermomechanical data storage (terabit recording). In such systems, bulk statistical averaging and continuum models are jeopardized. Interfacial constraints lead to bulk-deviating molecular dynamics and dictate material and transport properties. The objective of this dissertation is to provide insight to the exotic mesoscopic behaviors in thin films by developing novel rheological and tribological analytical methods based on scanning probe microscopy (SPM). Activation energies are deduced for the molecular motions associated with internal friction dissipation, and the temperature resolved length scale for cooperative motion during the glass transition is directly obtained for polystyrene. These results confirm the dynamical heterogeneity of the glass transition and reveal a crossover from intra- to inter-molecular relaxation in the transition regime. The impact of dimensional constraints on molecular mobility in ultrathin polymer films is explored through interfacial glass-transition profiles. With these profiles, a structural model of the rheological changes near interfacial boundaries is constructed as function of molecular weight and crosslinking density. The manifestation of interfacial constraints in nanotechnological applications is illustrated for thermomechanical recording, where rheological gradients near the substrate dictate the contact pressure and strain shielding at the substrate compromises film stability. A foundation for the critical aspects of interfacial stability is developed, and mechanically graded interfaces and modulus-matching techniques are explored as a means of improving the stability, durability, and stress transmission characteristics

  1. Mass transfer and interfacial properties in two-phase microchannel flows

    NASA Astrophysics Data System (ADS)

    Martin, Jeffrey D.; Hudson, Steven D.

    2009-11-01

    Drop-based microfluidic devices are becoming more common, and molecular mass transfer and drop circulation are issues that often affect the performance of such devices. Moreover, interfacial properties and surfactant mass transfer rates govern emulsion behavior. Since these phenomena depend strongly on drop size, measurement methods using small drops and flow typical of applications are desired. Using mineral oil as a continuous phase, water droplets and an alcohol surfactant, we demonstrate here a microfluidic approach to measure the interrelated phenomena of dynamic interfacial tension, surfactant mass transfer and interfacial retardation that employs droplet flows in a microchannel with constrictions/expansions. Interfacial flow is influenced markedly by adsorption of surfactant: severe interfacial retardation (by a factor of 30) is observed at low surfactant concentrations and interface remobilization is observed at higher surfactant concentrations. The interfacial tension is described by Langmuir kinetics and the parameters for interfaces with mineral oil (studied here) compare closely with those previously found at air interfaces. For the conditions explored, the surfactant mass transfer is described well by a mixed kinetic-diffusion limited model, and the desorption rate coefficients are measured to be both approximately 70 s-1. The transition from a diffusion-controlled to mixed diffusion-kinetic mass transfer mechanism predicted with reducing drop size is verified. This experimental approach (i.e. adjustable geometry and drop size and height) can therefore probe interfacial dynamics in simple and complex flow.

  2. Impact of interfacial tension on residual CO2 clusters in porous sandstone

    NASA Astrophysics Data System (ADS)

    Jiang, Fei; Tsuji, Takeshi

    2015-03-01

    We develop a numerical simulation that uses the lattice Boltzmann method to directly calculate the characteristics of residual nonwetting-phase clusters to quantify capillary trapping mechanisms in real sandstone. For this purpose, a digital-rock-pore model reconstructed from micro-CT-scanned images of Berea sandstone is filtered and segmented into a binary file. The residual-cluster distribution is generated following simulation of the drainage and imbibition processes. The characteristics of the residual cluster in terms of size distribution, major length, interfacial area, and sphericity are investigated under conditions of different interfacial tension (IFT). Our results indicate that high interfacial tension increases the residual saturation and leads to a large size distribution of residual clusters. However, low interfacial tension results in a larger interfacial area, which is beneficial for dissolution and reaction processes during geological carbon storage. Analysis of the force balance acting on the residual clusters demonstrates that trapping stability is higher in high interfacial tension case, and the interfacial tension should be a controlling factor for the trapping stability in addition to the pore geometry and connectivity. The proposed numerical method can handle the complex displacement of multicomponent systems in porous media. By using this method, we can obtain residual-cluster distributions under different conditions for optimizing the storage capacity of carbon-storage projects.

  3. Investigation of metal nanoparticles encapsulated in polyelectrolyte multilayers for catalytic and antibacterial applications

    NASA Astrophysics Data System (ADS)

    Kidambi, Srividhya

    Metal nanoparticles are an interesting class of materials because they often exhibit properties different from those of the corresponding bulk metals. For example, bulk Au is not catalytically active, but recent studies show that Au nanoparticles can serve as catalysts for oxidation and hydrogenation reactions. Without a suitable support, however, metal particles aggregate, reducing surface area and eventually affecting the particle properties. To overcome this problem, this research employs the layer-by-layer (LbL) assembly technique, which was introduced by Decher in 1991, as a convenient method to prevent the aggregation of nanoparticles and immobilize them on solid supports. While the multilayers help in stabilizing the nanoparticles, they also aid in retaining important properties of Pd (catalytic) and silver (antibacterial) nanoparticles. Catalytic Pd nanoparticles in multilayer polyelectrolyte films can be easily prepared by alternating depositions of poly(acrylic acid) (PAA) and a polyethylenimine (PEI)-Pd(II) complex on alumina, and subsequent reduction of the Pd(II) by NaBH4. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of alpha-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-l-penten-3-ol. In a related system, alternating adsorption of PdCl42- and polyethylenimine (PEI), followed by reduction of Pd(II), yields catalysts with a higher activity than found in [PAA/PEI-Pd(0)]nPAA films due to greater accessibility of the Pd nanocatalysts. In the [PAA/PEI-Pd(0)] nPAA system, turnover frequency decreases with the number of layers deposited, suggesting that the outer layer of the film is primarily responsible for catalysis. In contrast, turnover frequency increases with the number of deposited layers for reduced [PdCl42-/PEI] n films. We

  4. Interfacial effect on physical properties of composite media: Interfacial volume fraction with non-spherical hard-core-soft-shell-structured particles

    PubMed Central

    Xu, Wenxiang; Duan, Qinglin; Ma, Huaifa; Chen, Wen; Chen, Huisu

    2015-01-01

    Interfaces are known to be crucial in a variety of fields and the interfacial volume fraction dramatically affects physical properties of composite media. However, it is an open problem with great significance how to determine the interfacial property in composite media with inclusions of complex geometry. By the stereological theory and the nearest-surface distribution functions, we first propose a theoretical framework to symmetrically present the interfacial volume fraction. In order to verify the interesting generalization, we simulate three-phase composite media by employing hard-core-soft-shell structures composed of hard mono-/polydisperse non-spherical particles, soft interfaces, and matrix. We numerically derive the interfacial volume fraction by a Monte Carlo integration scheme. With the theoretical and numerical results, we find that the interfacial volume fraction is strongly dependent on the so-called geometric size factor and sphericity characterizing the geometric shape in spite of anisotropic particle types. As a significant interfacial property, the present theoretical contribution can be further drawn into predicting the effective transport properties of composite materials. PMID:26522701

  5. Interfacial effect on physical properties of composite media: Interfacial volume fraction with non-spherical hard-core-soft-shell-structured particles.

    PubMed

    Xu, Wenxiang; Duan, Qinglin; Ma, Huaifa; Chen, Wen; Chen, Huisu

    2015-01-01

    Interfaces are known to be crucial in a variety of fields and the interfacial volume fraction dramatically affects physical properties of composite media. However, it is an open problem with great significance how to determine the interfacial property in composite media with inclusions of complex geometry. By the stereological theory and the nearest-surface distribution functions, we first propose a theoretical framework to symmetrically present the interfacial volume fraction. In order to verify the interesting generalization, we simulate three-phase composite media by employing hard-core-soft-shell structures composed of hard mono-/polydisperse non-spherical particles, soft interfaces, and matrix. We numerically derive the interfacial volume fraction by a Monte Carlo integration scheme. With the theoretical and numerical results, we find that the interfacial volume fraction is strongly dependent on the so-called geometric size factor and sphericity characterizing the geometric shape in spite of anisotropic particle types. As a significant interfacial property, the present theoretical contribution can be further drawn into predicting the effective transport properties of composite materials. PMID:26522701

  6. Interfacial effect on physical properties of composite media: Interfacial volume fraction with non-spherical hard-core-soft-shell-structured particles

    NASA Astrophysics Data System (ADS)

    Xu, Wenxiang; Duan, Qinglin; Ma, Huaifa; Chen, Wen; Chen, Huisu

    2015-11-01

    Interfaces are known to be crucial in a variety of fields and the interfacial volume fraction dramatically affects physical properties of composite media. However, it is an open problem with great significance how to determine the interfacial property in composite media with inclusions of complex geometry. By the stereological theory and the nearest-surface distribution functions, we first propose a theoretical framework to symmetrically present the interfacial volume fraction. In order to verify the interesting generalization, we simulate three-phase composite media by employing hard-core-soft-shell structures composed of hard mono-/polydisperse non-spherical particles, soft interfaces, and matrix. We numerically derive the interfacial volume fraction by a Monte Carlo integration scheme. With the theoretical and numerical results, we find that the interfacial volume fraction is strongly dependent on the so-called geometric size factor and sphericity characterizing the geometric shape in spite of anisotropic particle types. As a significant interfacial property, the present theoretical contribution can be further drawn into predicting the effective transport properties of composite materials.

  7. Nanocapsules templated on liquid cores stabilized by graft amphiphilic polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Szafraniec, Joanna; Janik, Małgorzata; Odrobińska, Joanna; Zapotoczny, Szczepan

    2015-03-01

    A surfactant-free method of preparation of nanocapsules templated on liquid cores using amphiphilic graft polyelectrolytes was developed. A model photoactive copolymer, poly(sodium 2-acrylamido-2-methyl-1-propanesulfonate) with grafted poly(vinylnaphthalene) chains (PAMPS-graft-PVN) was used to stabilize toluene droplets in an aqueous emulsion. The macromolecules, due to their amphiphilic character and the presence of strong ionic groups, tend to undergo intramolecular aggregation in water but at the water-oil interface less compact conformation is preferred with PVN grafts anchoring in the oil phase and the charged PAMPS main chains residing in the aqueous phase, thus stabilizing the nanoemulsion droplets. Formation of such nanocapsules was confirmed by dynamic light scattering measurements as well as SEM and cryo-TEM imaging. Grafting density and content of the chromophores in the graft copolymers were varied in order to achieve high stability of the coated nanodroplets. It was shown that the capsules are better stabilized by the copolymers with many short hydrophobic grafts than with fewer but longer ones. Use of photoactive polyelectrolytes enabled spectroscopic investigation of the relationship between conformation of the macromolecules and stabilization of the oil-core nanocapsules. Long-term stability of the nanocapsules was achieved and further increased by multilayer shell formation using polyelectrolytes deposited via the layer-by-layer approach. The obtained capsules served as efficient nanocontainers for a hydrophobic fluorescent probe. The proposed strategy of nanocapsule preparation may be easily extended to biologically relevant polymers and applied to fabricate liquid core nanodelivery systems without the need of using low molecular weight additives which may have adverse effects in numerous biomedical applications.A surfactant-free method of preparation of nanocapsules templated on liquid cores using amphiphilic graft polyelectrolytes was developed

  8. Building a road map for tailoring multilayer polyelectrolyte films

    SciTech Connect

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

    2012-01-01

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

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

    PubMed

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

    2014-01-14

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

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

    SciTech Connect

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

    2014-01-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  12. Contraction of weak polyelectrolyte multilayers in response to organic solvents.

    PubMed

    Gu, Yuanqing; Ma, Yubing; Vogt, Bryan D; Zacharia, Nicole S

    2016-02-14

    Weak polyelectrolyte multilayers (PEMs) prepared by the layer-by-layer assembly technique have recently been found to demonstrate a unique contraction upon exposure to organic solvents. This response is dependent upon which organic solvent is employed, and fundamental questions have not been clarified regarding the correlation of the magnitude of the film contraction with solvent type. In this work, we used solubility parameters to analyze the response of branched poly(ethylene imine)/poly(acrylic acid) (BPEI/PAA) multilayers when exposed to a variety of solvents. BPEI/PAA multilayers were immersed in a series of 16 different organic solvents and solvent mixtures. Immersion in organic solvent caused film dehydration and therefore contraction and also induced changes in the mechanical properties of PEMs. The film thickness was the best predictor of how a film swelled in water or contracted in organic solvent when using different batches of commercially available polyelectrolytes, rather than polyelectrolyte assembly pH conditions. The degree of film contraction was correlated with Hansen and Kamlet-Taft solubility parameters as well as solvent dielectric constant. In most cases, the hydrogen bonding ability of solvents is the primary factor to determine the magnitude of film contraction. For these solvents, increasing the temperature which corresponds to decreasing the strength of hydrogen bonding, also decreases the ability to dehydrate the films. For solvents that do not follow these trends with the strength of hydrogen bonding, a stronger correlation was found between contraction and dielectric constant, indicating that both traditional solvent quality arguments and electrostatics are important to understanding the contraction of PEMs in organic solvents. PMID:26699080

  13. Granulating titania powder by colloidal route using polyelectrolytes.

    PubMed

    Pringuet, Antoine; Pagnoux, Cécile; Videcoq, Arnaud; Baumard, Jean-François

    2008-10-01

    A new, convenient, and inexpensive approach to process and granulate titania powders by a chemical route is proposed. It is based on the use of a formulation that includes a polyanion such as poly(sodium 4-styrenesulfonate) (PSS). Such a polyelectrolyte is most often considered to achieve dispersion of oxide powders in water. Basically, it adsorbs onto the surface of particles and induces electrical and/or steric interactions between particles in the suspension, which prevents agglomeration and rapid sedimentation. The advantages of polyelectrolytes in ceramic processing is well documented in the literature to produce low viscosity suspensions that are further used to form ceramic parts. In the case of TiO2 powders, such aqueous dispersions were obtained by adding small quantities of PSS. However, when exploring the behavior of mixtures containing lower contents of dispersant, we have discovered that, well below the optimum concentration required to get stable dispersions, the polyelectrolyte can act as a binder for titania particles. This can confer cohesion to the agglomerates, which can be processed to form large size (e.g., millimeter size) spheres. This phenomenon takes place when the oxide surface carries both positive and negative electrical charges and can be explained on a simple basis involving surface chemistry. For the optimum concentration of PSS that disperses titania, a polycation such as chitosan should be added to get spheres. This simple technique is expected to receive increasing attention due its potentialities and strong advantages with respect to other granulation techniques, such as spray-drying, which are energy consuming. PMID:18774832

  14. Wavebreaking of Interfacial Stokes Flows

    NASA Astrophysics Data System (ADS)

    Maiden, Michelle; Lowman, Nicholas; Anderson, Dalton; Hoefer, Mark

    2015-11-01

    Viscous fluid conduits provide a versatile system for the study of dissipationless, dispersive hydrodynamics. A dense, viscous fluid serves as the background media through which a less dense, less viscous fluid buoyantly rises. If fluid is continuously injected into the exterior fluid, an interface forms that behaves like a deformable pipe. Conservation of mass implies that the interfacial dynamics are conservative, i.e., they behave like a superfluid. Through buoyancy, high viscosity contrast, and a long wave assumption, conduit interfacial dynamics can be modeled by a scalar, nonlinear, dispersive wave equation with no assumption on amplitude. Experiments involving solitons, wavebreaking leading to dispersive shock waves (DSWs), and their interactions will be presented. The results include the refraction and absorption of a soliton by a DSW and the refraction of a DSW by a second DSW, resulting in two-phase behavior. Excellent agreement between nonlinear wave (Whitham) averaging, numerics, and laboratory experiments will be presented. The nonlinear wave dynamics observed in this model system have implications for a broad range of other conservative dispersive hydrodynamic systems. Support provided by NSF CAREER DMS-1255422, NSF GRFP.

  15. Protein interfacial structure and nanotoxicology

    NASA Astrophysics Data System (ADS)

    White, John W.; Perriman, Adam W.; McGillivray, Duncan J.; Lin, Jhih-Min

    2009-02-01

    Here we briefly recapitulate the use of X-ray and neutron reflectometry at the air-water interface to find protein structures and thermodynamics at interfaces and test a possibility for understanding those interactions between nanoparticles and proteins which lead to nanoparticle toxicology through entry into living cells. Stable monomolecular protein films have been made at the air-water interface and, with a specially designed vessel, the substrate changed from that which the air-water interfacial film was deposited. This procedure allows interactions, both chemical and physical, between introduced species and the monomolecular film to be studied by reflectometry. The method is briefly illustrated here with some new results on protein-protein interaction between β-casein and κ-casein at the air-water interface using X-rays. These two proteins are an essential component of the structure of milk. In the experiments reported, specific and directional interactions appear to cause different interfacial structures if first, a β-casein monolayer is attacked by a κ-casein solution compared to the reverse. The additional contrast associated with neutrons will be an advantage here. We then show the first results of experiments on the interaction of a β-casein monolayer with a nanoparticle titanium oxide sol, foreshadowing the study of the nanoparticle "corona" thought to be important for nanoparticle-cell wall penetration.

  16. Interfacial engineering of microstructured materials

    NASA Astrophysics Data System (ADS)

    Poda, Aimee

    The tribological behavior of octadecyltrichlorosilane self assembled monolayers (OTS-SAMs) has been successfully exploited to reduce energy losses and to produce adequate adhesion barrier properties on many MEMS surfaces. Unfortunately, performance discrepancies are reported in the literature between films produced on smooth surfaces as compared to typical MEMS surfaces maintaining topographical roughness. Rational explanations in terms of reproducibility issues, production considerations, and the scale of measurement technique have been introduced to account for some of the variation. The tribological phenomena at the micro-scale are complicated by the fact that rather than inertial effects, the forces associated with the surface become dominant factors influencing the mechanical behavior of contacting components. In MEMS, real mechanical contacts typically consist of a few nanometer scale asperities. Furthermore, various surface topographies exist for MEMS device fabrication and their corresponding asperity profiles can vary drastically based on the production process. This dissertation presents research focusing on the influence of topographical asperities on OTS film properties of relevance for efficient tribological improvement. A fundamental approach has been taken to carefully examine the factors that contribute to high quality film formation, specifically formation temperature and the role of interfacial water layer associated with the sample surface. As evidenced on smooth surfaces, the characteristics for successful tribological performance of OTS films are strongly dependent on the lateral packing density and molecular orientation of the monolayer. Limited information is available on how monolayers associate on topographical asperities and whether these topographical asperities influence the interfacial reactivity of MEMS surfaces. A silica film produced from a low temperature, vapor-phase hydrolysis of tetrachlorosilane with a tunable topography is

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

    SciTech Connect

    Khashirov, Azamat A.; Zhansitov, Azamat A.; Khashirova, Svetlana Yu.; Zaikov, Genadiy E.

    2014-05-15

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

  18. Freestanding polyelectrolyte films as sensors for osmotic pressure.

    PubMed

    Nolte, Marc; Dönch, Ingo; Fery, Andreas

    2006-09-11

    Freestanding ultrathin polyelectrolyte-multilayer membranes, transferred to topographically structured polydimethylsiloxane (PDMS), are used as mechanical sensors. Due to the membranes' semipermeability, high-molecular-weight molecules can be either entrapped inside them or excluded, thus generating an osmotic pressure. This leads to a deformation. We investigate the deformation as a function of the osmotic pressure and present an analytical theory that fully describes the data. Thus, osmotic pressures can be determined quantitatively. The individual osmotic-sensitive elements have only microscopic dimensions, and arrays can be easily produced. PMID:16929555

  19. Grafted polyelectrolyte membranes for lithium batteries and fuel cells

    SciTech Connect

    Kerr, John B.

    2003-06-24

    Polyelectrolyte materials have been developed for lithium battery systems in response to the severe problems due to salt concentration gradients that occur in composite electrodes (aka membrane-electrode assemblies). Comb branch polymer architectures are described which allow for grafting of appropriate anions on to the polymer and also for cross-linking to provide for appropriate mechanical properties. The interactions of the polymers with the electrode surfaces are critical for the performance of the system and some of the structural features that influence this will be described. Parallels with the fuel cell MEA structures exist and will also be discussed.

  20. Enhanced radiation therapy with internalized polyelectrolyte modified nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhang, Peipei; Qiao, Yong; Wang, Chaoming; Ma, Liyuan; Su, Ming

    2014-08-01

    A challenge of X-ray radiation therapy is that high dose X-ray under therapeutic conditions damages normal cells. This paper describes a nanoparticle-based method to enhance X-ray radiation therapy by delivering radio-sensitizing gold nanoparticles into cancer cells. The nanoparticles have been modified with cationic polyelectrolytes to allow internalization. Upon X-ray irradiation of nanoparticles, more photoelectrons and Auger electrons are generated to cause water ionization, leading to formation of free radicals that damage DNA of cancer cells. The X-ray dose required for DNA damage and cell killing is reduced by delivering gold nanoparticles inside cancer cells.

  1. Cornea, and the swelling of polyelectrolyte gels of biological interest

    NASA Astrophysics Data System (ADS)

    Elliott, Gerald F.; Hodson, Stuart A.

    1998-10-01

    Biological polyelectrolyte gels consist of insoluble aggregates of molecules which collectively form structural fibrils and these fibrils, or their chemically bound side chains, have a net electrical charge. These gels may be visualized as negatively charged fibrils immersed in aqueous solutions which include free diffusible ions (mainly sodium, potassium and chloride). All living cells and most of the extracellular spaces of the body are polyelectrolyte gels and they strive to swell by the absorption of additional fluid because of the Donnan potentials generated by their fixed charge. We review Donnan swelling using the cornea of the eye as prime material. Donnan swelling requires knowledge of only one parameter such as: (a) the electrical potential within the gel or (b) the distribution of any mobile ion inside and outside the gel or (c) measurement of the gel pressure or (d) the fixed charge density on the fibrils, in order to calculate all the other relevant factors. We describe the conditions (which usually exist in biological tissue) when the microscopic distribution of the fixed charge density within the gel is not important to the Donnan phenomena. Fixed charge density is generated by two sources: permanent negative charges in the structural fibrils and transient mobile ion binding to the fibrils. Ion binding to large molecules is reviewed. In the case of the cornea, transient mobile ion binding is the predominant factor in generating fixed charge density under physiological conditions. An irreversible thermodynamic treatment of gel swelling shows the intrinsic instability of polyelectrolyte gels and suggests new ways of approaching a microscopic model for osmosis. In order to stabilize the two forces (osmotic potential and chemical potential) which generate the polyelectrolyte gel instability we review the types of third forces which must be present in order to stabilize biological gels. These third forces include van der Waal's force, metabolically driven

  2. Interactional behavior of the polyelectrolyte poly sodium 4-styrene sulphonate (NaPSS) with imidazolium based surface active ionic liquids in an aqueous medium.

    PubMed

    Sharma, Renu; Kamal, Ajar; Kang, Tejwant Singh; Mahajan, Rakesh Kumar

    2015-09-28

    The present study aims to develop an understanding of the interactions between an anionic polyelectrolyte, poly sodium 4-styrene sulphonate (NaPSS), and cationic surface active imidazolium based ionic liquids (SAILs), [Cnmim][Cl] (n = 10, 12, 14) using a multi-technique approach. Various physicochemical and electrochemical techniques such as surface tension, conductivity, fluorescence, isothermal titration calorimetry (ITC), dynamic light scattering (DLS), turbidity, potentiometry, cyclic voltammetry (CV), and differential pulse voltammetry (DPV) are employed to obtain comprehensive information about NaPSS-SAIL interactions. Different stages of interaction, corresponding to the critical aggregation concentration (cac), critical saturation concentration (Cs) and critical micelle concentration (cmc) have been observed owing to the strong electrostatic and hydrophobic interactions, and the results obtained from different techniques complement each other very well. The results extracted from DLS and turbidity measurements clearly indicated that the size of the micelle like aggregates first decreases and then increases in the presence of polyelectrolyte. The binding isotherms obtained using potentiometry show a concentration dependence and the highly co-operative nature of the interactions which is attributed to aggregation of the polyelectrolyte-SAIL complexes. The diffusion coefficients (Dm) of the electroactive probe in the pure and NaPSS-SAIL mixed systems were obtained, which were further used to obtain the values of the micellar self-diffusion coefficients (D) and inter-micellar interaction parameters (kd). PMID:26300416

  3. Topology-generating interfacial pattern formation during liquid metal dealloying

    PubMed Central

    Geslin, Pierre-Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

    2015-01-01

    Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Moreover, we deduce scaling laws governing microstructural length scales and dealloying kinetics. PMID:26582248

  4. Topology-generating interfacial pattern formation during liquid metal dealloying.

    PubMed

    Geslin, Pierre-Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

    2015-01-01

    Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Moreover, we deduce scaling laws governing microstructural length scales and dealloying kinetics. PMID:26582248

  5. Topology-generating interfacial pattern formation during liquid metal dealloying

    NASA Astrophysics Data System (ADS)

    Geslin, Pierre-Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

    2015-11-01

    Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Moreover, we deduce scaling laws governing microstructural length scales and dealloying kinetics.

  6. Interfacial Reactivity of Radionuclides: Emerging Paradigms from Molecular Level Observations

    SciTech Connect

    Felmy, Andrew R.; Ilton, Eugene S.; Rosso, Kevin M.; Zachara, John M.

    2011-08-15

    Over the past few decades use of an increasing array of molecular-level analytical probes has provided new detailed insight into mineral and radionuclide interfacial reactivity in subsurface environments. This capability has not only helped change the way mineral surface reactivity is studied but also how field-scale contaminant migration problems are addressed and ultimately resolved. Here we overview examples of relatively new interfacial reactivity paradigms with implications for future research directions. Specific examples include understanding: the role of site-to-site electron conduction at mineral surfaces and through bulk mineral phases, effects of local chemical environment on the stability of intermediate species in oxidation/reduction reactions, and the importance of mechanistic reaction pathway for defining possible reaction products and thermodynamic driving force. The discussion also includes examples of how detailed molecular/microscopic characterization of field samples has changed the way complex contaminant migration problems were conceptualized and modeled.

  7. Interfacial exciplex formation in bilayers of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Nobuyasu, R. S.; Araujo, K. A. S.; Cury, L. A.; Jarrosson, T.; Serein-Spirau, F.; Lère-Porte, J.-P.; Dias, F. B.; Monkman, A. P.

    2013-10-01

    The donor-acceptor interactions in sequential bilayer and blend films are investigated. Steady-state and time-resolved photoluminescence (PL) were measured to characterize the samples at different geometries of photoluminescence collection. At standard excitation, with the laser incidence at 45° of the normal direction of the sample surface, a band related to the aggregate states of donor molecules appears for both blend and bilayer at around 540 nm. For the PL spectra acquired from the edge of the bilayer, with the laser incidence made at normal direction of the sample surface (90° geometry), a new featureless band emission, red-shifted from donor and acceptor emission regions was observed and assigned as the emission from interfacial exciplex states. The conformational complexity coming from donor/acceptor interactions at the heterojunction interface of the bilayer is at the origin of this interfacial exciplex emission.

  8. Topology-generating interfacial pattern formation during liquid metal dealloying

    DOE PAGESBeta

    Geslin, Pierre -Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

    2015-11-19

    Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growthmore » of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Furthermore, we deduce scaling laws governing microstructural length scales and dealloying kinetics.« less

  9. Topology-generating interfacial pattern formation during liquid metal dealloying

    SciTech Connect

    Geslin, Pierre -Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

    2015-11-19

    Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Furthermore, we deduce scaling laws governing microstructural length scales and dealloying kinetics.

  10. Sound-induced Interfacial Dynamics in a Microfluidic Two-phase Flow

    NASA Astrophysics Data System (ADS)

    Mak, Sze Yi; Shum, Ho Cheung

    2014-11-01

    Retrieving sound wave by a fluidic means is challenging due to the difficulty in visualizing the very minute sound-induced fluid motion. This work studies the interfacial response of multiphase systems towards fluctuation in the flow. We demonstrate a direct visualization of music in the form of ripples at a microfluidic aqueous-aqueous interface with an ultra-low interfacial tension. The interface shows a passive response to sound of different frequencies with sufficiently precise time resolution, enabling the recording of musical notes and even subsequent reconstruction with high fidelity. This suggests that sensing and transmitting vibrations as tiny as those induced by sound could be realized in low interfacial tension systems. The robust control of the interfacial dynamics could be adopted for droplet and complex-fiber generation.

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

    NASA Astrophysics Data System (ADS)

    Chremos, Alexandros; Douglas, Jack F.

    2016-04-01

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

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

    PubMed

    Chremos, Alexandros; Douglas, Jack F

    2016-04-28

    We investigate the influence of counter-ion valency on the flexibility of highly charged flexible polymer chains using molecular dynamics simulations that include both salt and an explicit solvent. As observed experimentally, we find that divalent counter-ions greatly reduce the chain persistence length, lp, in comparison with monovalent counter-ions. On the other hand, polyelectrolyte chains having trivalent counter-ions adopt a much more compact conformation than polyelectrolytes having monovalent and divalent counter-ions. We demonstrate that the tendency of polyelectrolyte chains to become deformed by proximal high valence counter-ions is due to chain "coiling" around the counter-ions. In particular, we find that the number of contacts that the proximal counter-ions have with the polyelectrolyte dictates the extent of chain coiling. This ion-binding induced coiling mechanism influences not only the conformational properties of the polyelectrolyte, but also the counter-ion distribution around the chain. Specifically, we find that higher valent counter-ions lead both to a counter-ion enrichment in close proximity to the polyelectrolyte and to a significant reduction in the spatial extent of the diffuse counter-ion cloud around the polyelectrolyte. PMID:27131566

  13. Interfacial material for solid oxide fuel cell

    DOEpatents

    Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

    1999-01-01

    Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

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

    PubMed

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

    2015-11-28

    The layer-by-layer construction of interfacial architectures displaying stimuli-responsive control of mass transport is attracting increasing interest in materials science. In this work, we describe the creation of interfacial architectures displaying pH-dependent ionic transport properties which until now have not been observed in polyelectrolyte multilayers. We describe a novel approach to create pH-controlled ion-rectifying systems employing polyelectrolyte multilayers assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA), alternately deposited with poly(diallyldimethylammonium chloride) (PDADMAC). The conceptual framework is based on the very contrasting and differential interactions of PSS and MA units with PDADMAC. In our setting, sulfonate groups play a structural role by conferring stability to the multilayer due to the strong electrostatic interactions with the polycations, while the weakly interacting MA groups remain "silent" within the film and then act as on-demand pH-responsive units. When these multilayers are combined with a strong cationic capping layer that repels the passage of cationic probes, a pH-gateable rectified transport of anions is observed. Concomitantly, we also observed that these functional properties are significantly affected when multilayers are subjected to extensive pH cycling as a consequence of irreversible morphological changes taking place in the film. We envision that the synergy derived from combining weak and strong interactions within the same multilayer will play a key role in the construction of new interfacial architectures displaying tailorable ion transport properties. PMID:26489595

  15. Removal and recovery of furfural, 5-hydroxymethylfurfural, and acetic acid from aqueous solutions using a soluble polyelectrolyte.

    PubMed

    Carter, Brian; Gilcrease, Patrick C; Menkhaus, Todd J

    2011-09-01

    In the cellulosic ethanol process, furfural, 5-hydroxymethylfurfural (HMF), and acetic acid are formed during the high temperature acidic pretreatment step needed to convert biomass into fermentable sugars. These compounds can inhibit cellulase enzymes and fermentation organisms at relatively low concentrations (≥ 1 g/L). Effective removal of these inhibitory compounds would allow the use of more severe pretreatment conditions to improve sugar yields and lead to more efficient fermentations; if recovered and purified, they could also be sold as valuable by-products. This study investigated the separation of aldhehydes (furfural and HMF) and organic acid (acetic acid) inhibitory compounds from simple aqueous solutions by using polyethyleneimene (PEI), a soluble cationic polyelectrolyte. PEI added to simple solutions of each inhibitor at a ratio of 1 mol of functional group to 1 mol inhibitor removed up to 89.1, 58.6, and 81.5 wt% of acetic acid, HMF, and furfural, respectively. Furfural and HMF were recovered after removal by washing the polyelectrolyte/inhibitor complex with dilute sulfuric acid solution. Recoveries up to 81.0 and 97.0 wt% were achieved for furfural and HMF, respectively. The interaction between PEI and acetic acid was easily disrupted by the addition of chloride ions, sulfate ions, or hydroxide ions. The use of soluble polymers for the removal and recovery of inhibitory compounds from biomass slurries is a promising approach to enhance the efficiency and economics of an envisioned biorefinery. PMID:21455937

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

    PubMed Central

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

    2013-01-01

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

  17. Self-assembled hyaluronate/protamine polyelectrolyte nanoplexes: synthesis, stability, biocompatibility and potential use as peptide carriers.

    PubMed

    Umerska, Anita; Paluch, Krzysztof J; Martinez, Maria-Jose Santos; Corrigan, Owen I; Medina, Carlos; Tajber, Lidia

    2014-12-01

    This work investigates a new type of polyelectrolyte complex nanocarrier composed of hyaluronic acid (HA) and protamine (PROT). Small (approximately 60 nm) and negatively charged nanoparticles (NPs) with a polydispersity index of less than 0.2 were obtained with properties that were dependent on the mixing ratio, concentration of polyelectrolytes and molecular weight of HA. Salmon calcitonin (sCT) was efficiently (up to 100%) associated with the NPs, and the drug loading (9.6-39% w/w) was notably high, possibly due to an interaction between HA and sCT. The NPs released -70-80% of the sCT after 24 hours, with the estimated total amount of released sCT depending on the amount of HA and PROT present in the NPs. The isoelectric point of the NPs was close to pH 2, and the negative surface charge was maintained above this pH. The HA/PROT nanoplexes protected the sCT from enzymatic degradation and showed low toxicity to intestinal epithelial cells, and thus may be a promising oral delivery system for peptides. PMID:26000379

  18. Impact of thermal annealing on wettability and antifouling characteristics of alginate poly-l-lysine polyelectrolyte multilayer films.

    PubMed

    Diamanti, Eleftheria; Muzzio, Nicolas; Gregurec, Danijela; Irigoyen, Joseba; Pasquale, Miguel; Azzaroni, Omar; Brinkmann, Martin; Moya, Sergio Enrique

    2016-09-01

    Polyelectrolyte multilayers (PEMs) of poly-l-lysine (PLL) and alginic acid sodium salt (Alg) are fabricated applying the layer by layer technique and annealed at a constant temperature; 37, 50 and 80°C, for 72h. Atomic force microscopy reveals changes in the topography of the PEM, which is changing from a fibrillar to a smooth surface. Advancing contact angle in water varies from 36° before annealing to 93°, 77° and 95° after annealing at 37, 50 and 80°C, respectively. Surface energy changes after annealing were calculated from contact angle measurements performed with organic solvents. Quartz crystal microbalance with dissipation, contact angle and fluorescence spectroscopy measurements show a significant decrease in the adsorption of the bovine serum albumin protein to the PEMs after annealing. Changes in the physical properties of the PEMs are interpreted as a result of the reorganization of the polyelectrolytes in the PEMs from a layered structure into complexes where the interaction of polycations and polyanions is enhanced. This work proposes a simple method to endow bio-PEMs with antifouling characteristics and tune their wettability. PMID:27209385

  19. Interfacial behaviours of smart composites

    NASA Astrophysics Data System (ADS)

    Poon, Chi-Kin

    The success of conventional fiber reinforced composites (FRC) relies on the quality of bonding between fibers and matrix. A review of literatures shows that there is a lack of theoretical models and experimental findings on the interfacial behaviours of the SMA-composites. In the past, the operation limit as well as the ideal actuation condition of SMA inclusions could not be predicted accurately during the design stage and the SMA-composite structures may therefore suffer a potential risk of sudden failure due to overloading or over-actuation. The theoretical models developed in this research provide a study basis for the prediction of internal stresses and interfacial strength of the SMA-composites. Martensite volume fraction is considered as a critical parameter which determines the material properties and shape memory effect (SME) of the SMA inclusions. The proposed model reproduce the SMA behaviour inside a substrate, evolutions of martensite volume fraction and elastic modulus of SMA, and the internal stresses along the embedded length in different loading and actuation scenarios. The concepts of 'constant martensite volume fraction region (CMR)' and 'constant axial stress region (CASR)' are proposed to justify the desired SMA actuation. In addition, substantial improvement of the initial debond stress is predicted with the increase of the actuation temperature. The 'Optimum Actuation Condition (OAC)' that ensures the reinforcement of SMA composite but avoids the failure of composite interface due to over-actuation is also defined to optimize the application of SME in the composite structure within a safety actuation limit. A simplified OAC (SOAC) is also developed to provide an analytical solution of OAC and thus the ideal actuation temperature for achieving such specific actuation condition can be estimated more easily. Single fiber pullout test and finite element analysis (FEA) are employed to evaluate the interfacial behaviours and analyze the stress

  20. Submicron Patterning of Polymer Brushes: An Unexpected Discovery from Inkjet Printing of Polyelectrolyte Macroinitiators.

    PubMed

    Parry, Adam V S; Straub, Alexander J; Villar-Alvarez, Eva M; Phuengphol, Takdanai; Nicoll, Jonathan E R; W K, Xavier Lim; Jordan, Lianne M; Moore, Katie L; Taboada, Pablo; Yeates, Stephen G; Edmondson, Steve

    2016-07-27

    Using an electrostatic-based super inkjet printer we report the high-resolution deposition of polyelectrolyte macroinitiators and subsequent polymer brush growth using SI-ARGET-ATRP. We go on to demonstrate for the first time a submicron patterning phenomenon through the addition of either a like charged polyelectrolyte homopolymer or through careful control of ionic strength. As a result patterning of polymer brushes down to ca. 300 nm is reported. We present a possible mechanistic model and consider how this may be applied to other polyelectrolyte-based systems as a general method for submicron patterning. PMID:27400396

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

    PubMed

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

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins. PMID:25393374

  2. Encapsidation of Linear Polyelectrolyte in a Viral Nanocontainer

    NASA Astrophysics Data System (ADS)

    Hu, Yufang

    2005-03-01

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

  3. Theory of volume transition in polyelectrolyte gels with charge regularization.

    PubMed

    Hua, Jing; Mitra, Mithun K; Muthukumar, M

    2012-04-01

    We present a theory for polyelectrolyte gels that allow the effective charge of the polymer backbone to self-regulate. Using a variational approach, we obtain an expression for the free energy of gels that accounts for the gel elasticity, free energy of mixing, counterion adsorption, local dielectric constant, electrostatic interaction among polymer segments, electrolyte ion correlations, and self-consistent charge regularization on the polymer strands. This free energy is then minimized to predict the behavior of the system as characterized by the gel volume fraction as a function of external variables such as temperature and salt concentration. We present results for the volume transition of polyelectrolyte gels in salt-free solvents, solvents with monovalent salts, and solvents with divalent salts. The results of our theoretical analysis capture the essential features of existing experimental results and also provide predictions for further experimentation. Our analysis highlights the importance of the self-regularization of the effective charge for the volume transition of gels in particular, and for charged polymer systems in general. Our analysis also enables us to identify the dominant free energy contributions for charged polymer networks and provides a framework for further investigation of specific experimental systems. PMID:22482584

  4. Unifying Self-Consistent Field Theory for Weak Polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Witte, Kevin; Won, You-Yeon

    2008-03-01

    A self-consistent field (SCF) theory for weak polyelectrolytes has been derived from a grand canonical partition function. The formalism accounts for the location and mixing of the charged and uncharged polymer species, treating the local (spatially dependent) charge fraction as a field variable with which to minimize the total free energy. This method of the derivation gives the resulting equations, especially those governing the local charge fraction, that are identical to the results obtained by Szleifer and coworkers (J. Polym. Sci. B Polym. Phys., 2006) who built upon the mean-field ``annealed'' free energy expression proposed by Raphael and Joanny (Europhys. Lett., 1990). However, we show that these results are further identical to the ``two-state'' model of Borukhov, Andelman and Orland (Eur. Phys. J. B, 1998), namely, the potential field due to the polymer charges with which the chains interact and the local charge fraction are shown to be exactly equal. This annealed model is derived by averaging the partition function with regard to the monomer charges. The charged and uncharged states are weighted by their probabilities which is, in our notation, the bulk charge fraction and one minus the bulk charge fraction, respectively. The utility of this theory is demonstrated by comparing its predictions against various experimental results from bulk potentiometric measurements and also from polyelectrolyte brush compression studies.

  5. Hybrid particle-field molecular dynamics simulation for polyelectrolyte systems.

    PubMed

    Zhu, You-Liang; Lu, Zhong-Yuan; Milano, Giuseppe; Shi, An-Chang; Sun, Zhao-Yan

    2016-04-14

    To achieve simulations on large spatial and temporal scales with high molecular chemical specificity, a hybrid particle-field method was proposed recently. This method is developed by combining molecular dynamics and self-consistent field theory (MD-SCF). The MD-SCF method has been validated by successfully predicting the experimentally observable properties of several systems. Here we propose an efficient scheme for the inclusion of electrostatic interactions in the MD-SCF framework. In this scheme, charged molecules are interacting with the external fields that are self-consistently determined from the charge densities. This method is validated by comparing the structural properties of polyelectrolytes in solution obtained from the MD-SCF and particle-based simulations. Moreover, taking PMMA-b-PEO and LiCF3SO3 as examples, the enhancement of immiscibility between the ion-dissolving block and the inert block by doping lithium salts into the copolymer is examined by using the MD-SCF method. By employing GPU-acceleration, the high performance of the MD-SCF method with explicit treatment of electrostatics facilitates the simulation study of many problems involving polyelectrolytes. PMID:27001709

  6. A facile route to synthesize silver nanoparticles in polyelectrolyte capsules.

    PubMed

    Anandhakumar, S; Raichur, Ashok M

    2011-06-01

    We are reporting a novel green approach to incorporate silver nanoparticles (NPs) selectively in the polyelectrolyte capsule shell for remote opening of polyelectrolyte capsules. This approach involves in situ reduction of silver nitrate to silver NPs using PEG as a reducing agent (polyol reduction method). These nanostructured capsules were prepared via layer by layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on silica template followed by the synthesis of silver NPs and subsequently the dissolution of the silica core. The size of silver nanoparticles synthesized was 60±20 nm which increased to 100±20 nm when the concentration of AgNO(3) increased from 25 mM to 50 mM. The incorporated silver NPs induced rupture and deformation of the capsules under laser irradiation. This method has advantages over other conventional methods involving chemical agents that are associated with cytotoxicity in biological applications such as drug delivery and catalysis. PMID:21333503

  7. Surface friction of hydrogels with well-defined polyelectrolyte brushes.

    PubMed

    Ohsedo, Yutaka; Takashina, Rikiya; Gong, Jian Ping; Osada, Yoshihito

    2004-08-01

    Hydrogels of poly(2-hydroxyethyl methacrylate) (PHEMA) with well-defined polyelectrolyte brushes of poly(sodium 4-styrenesulfonate) (PNaSS) of various molecular weights were synthesized, keeping the distance between the polymer brushes constant at ca. 20 nm. The effect of polyelectrolyte brush length on the sliding friction against a glass plate, an electrorepulsive solid substrate, was investigated in water in a velocity range of 7.5 x 10(-5) to 7.5 x 10(-2) m/s. It is found that the presence of polymer brush can dramatically reduce the friction when the polymer brushes are short. With an increase in the length of the polymer brush, this drag reduction effect only works at a low sliding velocity, and the gel with long polymer brushes even shows a higher friction than that of a normal network gel at a high sliding velocity. The strong polymer length and sliding velocity dependence indicate a dynamic mechanism of the polymer brush effect. PMID:15274553

  8. Dynamics of a polyelectrolyte under a constant electric field

    NASA Astrophysics Data System (ADS)

    Park, Pyeong Jun

    2015-11-01

    We perform a molecular dynamics simulation of a polyelectrolyte in a viscous fluid under an external electric field to study the dynamics of gel-free electrophoresis. To incorporate the hydrodynamic effects, we employ a coarse-grained description of water by using multiparticle collision dynamics. We use a screened Coulomb interaction among the monomers and explicit monovalent counterions to model the electrostatic interactions in an ionic solution. The mobility of the polyelectrolyte µ is obtained as a function of the molecular weight N, the electric field strength E,and the Debye screening length of the solvent λ. The mobility is found to be independent of N for large N and to exhibit a maximum at a certain N for a large λ, which are in agreement with experimental results. The dependence of µ on E is also examined and discussed by considering the effects of an electric field on counterion condensation. The dependence of µ on λ shows a discrepancy between our simulation and experiments, which implies that the added salts not only screen out the Coulomb interaction but also participate in the counterion condensation significantly.

  9. Theory of volume transition in polyelectrolyte gels with charge regularization

    NASA Astrophysics Data System (ADS)

    Hua, Jing; Mitra, Mithun K.; Muthukumar, M.

    2012-04-01

    We present a theory for polyelectrolyte gels that allow the effective charge of the polymer backbone to self-regulate. Using a variational approach, we obtain an expression for the free energy of gels that accounts for the gel elasticity, free energy of mixing, counterion adsorption, local dielectric constant, electrostatic interaction among polymer segments, electrolyte ion correlations, and self-consistent charge regularization on the polymer strands. This free energy is then minimized to predict the behavior of the system as characterized by the gel volume fraction as a function of external variables such as temperature and salt concentration. We present results for the volume transition of polyelectrolyte gels in salt-free solvents, solvents with monovalent salts, and solvents with divalent salts. The results of our theoretical analysis capture the essential features of existing experimental results and also provide predictions for further experimentation. Our analysis highlights the importance of the self-regularization of the effective charge for the volume transition of gels in particular, and for charged polymer systems in general. Our analysis also enables us to identify the dominant free energy contributions for charged polymer networks and provides a framework for further investigation of specific experimental systems.

  10. Interfacial instabilities and Kapitsa pendula

    NASA Astrophysics Data System (ADS)

    Krieger, Madison

    2015-11-01

    Determining the critera for onset and amplitude growth of instabilities is one of the central problems of fluid mechanics. We develop a parallel between the Kapitsa effect, in which a pendulum subject to high-frequency low-amplitude vibrations becomes stable in the inverted position, and interfaces separating fluids of different density. It has long been known that such interfaces can be stabilized by vibrations, even when the denser fluid is on top. We demonstrate that the stability diagram for these fluid interfaces is identical to the stability diagram for an appopriate Kapitsa pendulum. We expand the robust, ``dictionary''-type relationship between Kapitsa pendula and interfacial instabilities by considering the classical Rayleigh-Taylor, Kelvin-Helmholtz and Plateau instabilities, as well as less-canonical examples ranging in scale from the micron to the width of a galaxy.

  11. Interfacial adhesion - Theory and experiment

    NASA Technical Reports Server (NTRS)

    Ferrante, John; Banerjea, Amitava; Bozzolo, Guillermo H.; Finley, Clarence W.

    1988-01-01

    Adhesion, the binding of different materials at an interface, is of general interest to many branches of technology, e.g., microelectronics, tribology, manufacturing, construction, etc. However, there is a lack of fundamental understanding of such diverse interfaces. In addition, experimental techniques generally have practical objectives, such as the achievement of sufficient strength to sustain mechanical or thermal effects and/or have the proper electronic properties. In addition, the theoretical description of binding at interfaces is quite limited, and a proper data base for such theoretical analysis does not exist. This presentation will review both experimental and theoretical aspects of adhesion in nonpolymer materials. The objective will be to delineate the critical parameters needed, governing adhesion testing along with an outline of testing objectives. A distinction will be made between practical and fundamental objectives. Examples are given where interfacial bonding may govern experimental consideration. The present status of theory is presented along with recommendations for future progress and needs.

  12. Interfacial adhesion: Theory and experiment

    NASA Technical Reports Server (NTRS)

    Ferrante, John; Bozzolo, Guillermo H.; Finley, Clarence W.; Banerjea, Amitava

    1988-01-01

    Adhesion, the binding of different materials at an interface, is of general interest to many branches of technology, e.g., microelectronics, tribology, manufacturing, construction, etc. However, there is a lack of fundamental understanding of such diverse interfaces. In addition, experimental techniques generally have practical objectives, such as the achievement of sufficient strength to sustain mechanical or thermal effects and/or have the proper electronic properties. In addition, the theoretical description of binding at interfaces is quite limited, and a proper data base for such theoretical analysis does not exist. This presentation will review both experimental and theoretical aspects of adhesion in nonpolymer materials. The objective will be to delineate the critical parameters needed, governing adhesion testing along with an outline of testing objectives. A distinction will be made between practical and fundamental objectives. Examples are given where interfacial bonding may govern experimental consideration. The present status of theory is presented along wiith recommendations for future progress and needs.

  13. Highly sensitive self-complementary DNA nanoswitches triggered by polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Wu, Jincai; Yu, Feng; Zhang, Zheng; Chen, Yong; Du, Jie; Maruyama, Atsushi

    2015-12-01

    Dimerization of two homologous strands of genomic DNA/RNA is an essential feature of retroviral replication. Herein we show that a cationic comb-type copolymer (CCC), poly(l-lysine)-graft-dextran, accelerates the dimerization of self-complementary stem-loop DNA, frequently found in functional DNA/RNA molecules, such as aptamers. Furthermore, an anionic polymer poly(sodium vinylsulfonate) (PVS) dissociates CCC from the duplex shortly within a few seconds. Then single stem-loop DNA spontaneously transforms from its dimer. Thus we can easily control the dimer and stem-loop DNA by switching on/off CCC activity. Both polyelectrolytes and DNA concentrations are in the nanomole per liter range. The polyelectrolyte-assisted transconformation and sequences design strategy ensures the reversible state control with rapid response and effective switching under physiologically relevant conditions. A further application of this sensitive assembly is to construct an aptamer-type drug delivery system, bind or release functional molecules responding to its transconformation.Dimerization of two homologous strands of genomic DNA/RNA is an essential feature of retroviral replication. Herein we show that a cationic comb-type copolymer (CCC), poly(l-lysine)-graft-dextran, accelerates the dimerization of self-complementary stem-loop DNA, frequently found in functional DNA/RNA molecules, such as aptamers. Furthermore, an anionic polymer poly(sodium vinylsulfonate) (PVS) dissociates CCC from the duplex shortly within a few seconds. Then single stem-loop DNA spontaneously transforms from its dimer. Thus we can easily control the dimer and stem-loop DNA by switching on/off CCC activity. Both polyelectrolytes and DNA concentrations are in the nanomole per liter range. The polyelectrolyte-assisted transconformation and sequences design strategy ensures the reversible state control with rapid response and effective switching under physiologically relevant conditions. A further application of

  14. Ecotoxicities of polyquaterniums and their associated polyelectrolyte-surfactant aggregates (PSA) to Gambusia holbrooki.

    PubMed

    Cumming, Janet L; Hawker, Darryl W; Nugent, Kerry W; Chapman, Heather F

    2008-02-01

    The toxicity of 11 polyquaterniums used in cosmetic applications, and polydimethyldiallylammonium chloride (poly(DADMAC)) were studied for toxicity of the polyquaternium alone, and of a polyquaternium/anionic surfactant complex as occurs in some cosmetic formulations. The surfactant used in the study was sodium dodecyl sulfate (SDS), which is used in cosmetic formulations under its International Nomenclature of Cosmetic Ingredients (INCI) name Sodium Laurel Sulfate. In fish immobilization studies with Gambusia holbrooki, the EC(50) of the polyquaternium/surfactant complex was found to be the same as or similar to the EC(50) for the polyquaternium alone. The toxicity of the polyquaterniums investigated was similar to the published values for other cationic polyelectrolytes and cationic surfactants, in the range from < 1.0 to 10 mg/L, with the exception of low charge density cellulosic polyquaterniums. The anionic surfactant alone was not toxic to fish in the concentration range tested. Results thus showed the toxicity of the polyquaternium was not mitigated by the presence of the anionic surfactant. PMID:18172802

  15. Tunable Interfacial Thermal Conductance by Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Shen, Meng

    We study the mechanism of tunable heat transfer through interfaces between solids using a combination of non-equilibrium molecular dynamics simulation (NEMD), vibrational mode analysis and wave packet simulation. We investigate how heat transfer through interfaces is affected by factors including pressure, interfacial modulus, contact area and interfacial layer thickness, with an overreaching goal of developing fundamental knowledge that will allow one to tailor thermal properties of interfacial materials. The role of pressure and interfacial stiffness is unraveled by our studies on an epitaxial interface between two Lennard-Jones (LJ) crystals. The interfacial stiffness is varied by two different methods: (i) indirectly by applying pressure which due to anharmonic nature of bonding, increases interfacial stiffness, and (ii) directly by changing the interfacial bonding strength by varying the depth of the potential well of the LJ potential. When the interfacial bonding strength is low, quantitatively similar behavior to pressure tuning is observed when the interfacial thermal conductance is increased by directly varying the potential-well depth parameter of the LJ potential. By contrast, when the interfacial bonding strength is high, thermal conductance is almost pressure independent, and even slightly decreases with increasing pressure. This decrease can be explained by the change in overlap between the vibrational densities of states of the two crystalline materials. The role of contact area is studied by modeling structures comprised of Van der Waals junctions between single-walled nanotubes (SWCNT). Interfacial thermal conductance between SWCNTs is obtained from NEMD simulation as a function of crossing angle. In this case the junction conductance per unit area is essentially a constant. By contrast, interfacial thermal conductance between multiwalled carbon nanotubes (MWCNTs) is shown to increase with diameter of the nanotubes by recent experimental studies [1

  16. Tunable Interfacial Thermal Conductance by Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Shen, Meng

    We study the mechanism of tunable heat transfer through interfaces between solids using a combination of non-equilibrium molecular dynamics simulation (NEMD), vibrational mode analysis and wave packet simulation. We investigate how heat transfer through interfaces is affected by factors including pressure, interfacial modulus, contact area and interfacial layer thickness, with an overreaching goal of developing fundamental knowledge that will allow one to tailor thermal properties of interfacial materials. The role of pressure and interfacial stiffness is unraveled by our studies on an epitaxial interface between two Lennard-Jones (LJ) crystals. The interfacial stiffness is varied by two different methods: (i) indirectly by applying pressure which due to anharmonic nature of bonding, increases interfacial stiffness, and (ii) directly by changing the interfacial bonding strength by varying the depth of the potential well of the LJ potential. When the interfacial bonding strength is low, quantitatively similar behavior to pressure tuning is observed when the interfacial thermal conductance is increased by directly varying the potential-well depth parameter of the LJ potential. By contrast, when the interfacial bonding strength is high, thermal conductance is almost pressure independent, and even slightly decreases with increasing pressure. This decrease can be explained by the change in overlap between the vibrational densities of states of the two crystalline materials. The role of contact area is studied by modeling structures comprised of Van der Waals junctions between single-walled nanotubes (SWCNT). Interfacial thermal conductance between SWCNTs is obtained from NEMD simulation as a function of crossing angle. In this case the junction conductance per unit area is essentially a constant. By contrast, interfacial thermal conductance between multiwalled carbon nanotubes (MWCNTs) is shown to increase with diameter of the nanotubes by recent experimental studies [1

  17. Nanotube attachment for prevention of interfacial delamination

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, Sharmila M.; Karumuri, Anil K.

    2010-09-01

    A new approach to suppressing interfacial delamination in composites has been investigated. It involves growing strongly attached nanotubes on the surface of the core phase prior to matrix infiltration. Unusually durable interfaces between epoxy and graphite have been demonstrated using this technique. Two types of graphitic core materials have been studied: complex cellular foams having open-interconnected porosity and highly oriented pyrolitic graphite (HOPG) providing a model flat interface. When untreated foam is infiltrated with epoxy, the resulting composite is brittle, and shatters before 10% compression. However, when carbon nanotubes (CNTs) are grown on the foam prior to epoxy infiltration, the specimen becomes pliable, and visibly flattens out rather than fracturing. Model studies on a flat graphite-epoxy interface were performed by joining two HOPG specimens with a thin layer of epoxy, and testing the flexural response of the 'seam' using the three-point bend test. The untreated HOPG sandwich fails easily, whereas nanotube-attached HOPG sandwich shows an over three times increase in flexural load-carrying capacity, close to that of seamless monolithic graphite having identical dimensions. Microscopic evaluations of fractured interfaces indicate that, in all geometries, CNT grafting prevents delamination at the graphite-epoxy interface, and forces any crack(s) to propagate through the graphitic phase. This added inter-laminar strength and toughness can be related to the hierarchical morphology of the interface created by CNT attachment, and unprecedented composite structures can be envisioned.

  18. Interfacial dilatational deformation accelerates particle formation in monoclonal antibody solutions.

    PubMed

    Lin, Gigi L; Pathak, Jai A; Kim, Dong Hyun; Carlson, Marcia; Riguero, Valeria; Kim, Yoen Joo; Buff, Jean S; Fuller, Gerald G

    2016-04-14

    Protein molecules are amphiphilic moieties that spontaneously adsorb at the air/solution (A/S) interface to lower the surface energy. Previous studies have shown that hydrodynamic disruptions to these A/S interfaces can result in the formation of protein aggregates that are of concern to the pharmaceutical industry. Interfacial hydrodynamic stresses encountered by protein therapeutic solutions under typical manufacturing, filling, and shipping conditions will impact protein stability, prompting a need to characterize the contribution of basic fluid kinematics to monoclonal antibody (mAb) destabilization. We demonstrate that dilatational surface deformations are more important to antibody stability when compared to constant-area shear of the A/S interface. We have constructed a dilatational interfacial rheometer that utilizes simultaneous pressure and bubble shape measurements to study the mechanical stability of mAbs under interfacial aging. It has a distinct advantage over methods utilizing the Young-Laplace equation, which incorrectly describes viscoelastic interfaces. We provide visual evidence of particle ejection from dilatated A/S interfaces and spectroscopic data of ejected mAb particles. These rheological studies frame a molecular understanding of the protein-protein interactions at the complex-fluid interface. PMID:26891116

  19. Incorporating interfacial phenomena in solidification models

    NASA Technical Reports Server (NTRS)

    Beckermann, Christoph; Wang, Chao Yang

    1994-01-01

    A general methodology is available for the incorporation of microscopic interfacial phenomena in macroscopic solidification models that include diffusion and convection. The method is derived from a formal averaging procedure and a multiphase approach, and relies on the presence of interfacial integrals in the macroscopic transport equations. In a wider engineering context, these techniques are not new, but their application in the analysis and modeling of solidification processes has largely been overlooked. This article describes the techniques and demonstrates their utility in two examples in which microscopic interfacial phenomena are of great importance.

  20. Drug delivery and cell interaction of adhesive poly(ethyleneimine)/sulfated polysaccharide complex particle films.

    PubMed

    Müller, Martin; Torger, Bernhard; Wehrum, Diana; Vehlow, David; Urban, Birgit; Woltmann, Beatrice; Hempel, Ute

    2015-01-01

    Herein, the authors report and review polyelectrolyte complex (PEC) nanoparticles (NPs) loaded with zoledronate (ZOL) and simvastatin and their effects on bone cells. PEC NPs are intended for modification of bone substitute materials. For characterization, they can be solution casted on germanium (Ge) substrates serving as analytically accessible model substrate. PEC NPs were generated by mixing poly(ethyleneimine) (PEI) either with linear cellulose sulfate (CS) or with branched dextransulfate (DS). Four important requirements for drug loaded PEC NPs and their films are addressed herein, which are the colloidal stability of PEC dispersions (1), interfacial stability (2), cytocompatibility (3), and retarded drug release (4). Dynamic light scattering measurements (DLS) showed that both PEI/CS and PEI/DS PEC NP were obtained with hydrodynamic radii in the range of 35-170 nm and were colloidally stable up to several months. Transmission FTIR spectroscopy evidenced that films of both systems were stable in contact to the release medium up to several days. ZOL-loaded PEI/CS nanoparticles, which were immobilized on an osteoblast-derived extracellular matrix, reduced significantly the resorption and the metabolic activity of human monocyte-derived osteoclasts. FTIR spectroscopy at cast PEC/drug films at Ge substrates revealed retarded drug releases in comparison to the pure drug films. PMID:25708630

  1. How Multivalent Must An Ion Be Before It Can Generate Like-Charge Polyelectrolyte Attraction?

    NASA Astrophysics Data System (ADS)

    Butler, John C.; Angelini, Thomas; Liang, Hongjun; Wong, Gerard C. L.

    2003-03-01

    Empirically, it is known that multivalent ions generate attractions between like-charged polyelectrolytes in a wide range of systems, while monovalent ions do not. It is also known that different ion valences are required to condense different polyelectrolytes. How multivalent does an ion have to be before it can condense a given polyelectrolyte? Using the charge-tunable M13 filamentous virus system and a family of artificial homologous divalent ions of different effective sizes, we have constructed a multivalent ion-polyelectrolyte phase diagram, and find an experimentally motivated general criterion for like-charged attraction based on the ion size and the Gouy-Chapman length. This work was supported by NSF DMR-0071761, DOE DEFG02-91ER45439, the Beckman Young Investigator Program, and the Cystic Fibrosis Foundation.

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

    PubMed

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

    2011-11-24

    Interactions of nerve G-agents (sarin and soman) and their simulants DMMP (dimethyl methylphosphonate) and DIFP (diisopropyl fluorophosphate) with water and components of polyelectrolyte membranes are studied using ab initio calculations in conjunction with thermodynamic modeling using the conductor-like screening model for real solvents (COSMO-RS). To test reliability of COSMO-RS calculations, we measured the vapor-liquid equilibrium in DMMP-water mixtures and found quantitative agreement between computed and experimental results. Using COSMO-RS, we studied the interactions of phosphororganic agents with the characteristic fragments of perfluorinated and sulfonated polystyrene (sPS) polyelectrolytes, which are explored for protective clothing membranes. We found that both simulants, DIFP and DMMP, mimic the thermodynamic properties of G-agents reasonably well; however, there are certain specific differences that are discussed. We also suggested that sPS-based polyelectrolytes have less affinity for phosphorganic agents compared to prefluorinated polyelectrolytes similar to Nafion. PMID:21988501

  3. Advancements to the theory of free solution electrophoresis of polyelectrolytes

    NASA Astrophysics Data System (ADS)

    McCormick, Laurette

    Capillary electrophoresis (CE) is the workhorse of countless analytical laboratories and is used routinely in various industries including pharmaceutical, forensic and clinical applications. Basically, CE is a method for separating charged molecular species in a buffer-filled capillary by the application of an electric field; the analytes move from one end of the capillary to the detector at the other end at speeds determined by their charge, size and shape. Generally, in free solution CE uniformly charged polyelectrolytes (such as DNA) are free-draining, meaning that their speed is independent of their size. Hence, until recently, a gel or other sieving medium has been necessary for the separation of polyelectrolytes; however, modifying uniformly charged polymers on the molecular level, via conjugation to uncharged polymers, allows for separation in free solution CE. In this thesis, advancements to the theory of free solution electrophoresis of polyelectrolytes, in particular, to the theories for two new free solution electrophoresis methods relying on conjugation, are presented. The first method, called End Labelled Free Solution Electrophoresis (ELFSE), can be used to sequence DNA, a negatively charged polymer in solution. Two different means of improving the resolution of ELFSE are predicted, one based on the molecular end effect, the other based on using a controlled electro-osmotic flow. In addition, a theory for the segregation of the DNA and label coils in ELFSE is presented. The second method is called Free Solution Conjugate Electrophoresis (FSCE); it allows for characterization of a sample of neutral polymers differing in length. The relevant theory, developed herein, elucidates how to accurately determine the molar mass distribution of the sample through FSCE measurements. In addition, supporting theories are developed that clarify the correct equation for the diffusion coefficient of molecules undergoing free solution electrophoresis, as well as

  4. Physicochemically functional ultrathin films by interfacial polymerization

    DOEpatents

    Lonsdale, H.K.; Babcock, W.C.; Friensen, D.T.; Smith, K.L.; Johnson, B.M.; Wamser, C.C.

    1990-08-14

    Interfacially-polymerized ultrathin films containing physicochemically functional groups are disclosed, both with and without supports. Various applications are disclosed, including membrane electrodes, selective membranes and sorbents, biocompatible materials, targeted drug delivery, and narrow band optical absorbers. 3 figs.

  5. Physicochemically functional ultrathin films by interfacial polymerization

    DOEpatents

    Lonsdale, Harold K.; Babcock, Walter C.; Friensen, Dwayne T.; Smith, Kelly L.; Johnson, Bruce M.; Wamser, Carl C.

    1990-01-01

    Interfacially-polymerized ultrathin films containing physicochemically functional groups are disclosed, both with and without supports. Various applications are disclsoed, including membrane electrodes, selective membranes and sorbents, biocompatible materials, targeted drug delivery, and narrow band optical absorbers.

  6. Cantilever based optical interfacial force microscope

    NASA Astrophysics Data System (ADS)

    Bonander, Jeremy R.; Kim, Byung I.

    2008-03-01

    We developed a cantilever based optical interfacial force microscopy (COIFM) that employs a microactuated silicon cantilever and optical detection method to establish the measurement of the single molecular interactions using the force feedback technique. Through the direct measurement of the COIFM force-distance curves, we have demonstrated that the COIFM is capable of unveiling structural and mechanical information on interfacial water at the single molecular level over all distances between two hydrophilic surfaces.

  7. Manipulating Assembly, Disassembly and Exchange in Responsive Polyelectrolyte Multilayers

    NASA Astrophysics Data System (ADS)

    Hammond, Paula

    2008-03-01

    Polyelectrolyte multilayer assembly is based on the alternating adsorption of multilvalent positively and negatively charged species to create ionically crosslinked thin films with nanoscale control of film composition and function. We have utilized this method of assembly to manipulate ion transport, molecular transport, and electrochemical transport in these films, enabling the generation of a range of organic and organic-inorganic devices. Biological materials applications are also derived from such films, enabling their use as drug delivery devices. In each of these applications, it is desired to control interdiffusion and exchange within the multilayer systems to maintain desired function and generate isolated regions of composition and function within the z-direction of the film. Here we address these applications and means of controlling this phenomenon. Furthermore, it is desirable to induce controlled means of disassembly of these multilayer thin films. We will address a number of approaches for achieving this, including hydrolytic degradation, hydrogen bond dissociation, and controlled deconstruction on electrochemical impulse.

  8. "Like-charge attraction" between anionic polyelectrolytes: molecular dynamics simulations.

    PubMed

    Molnar, Ferenc; Rieger, Jens

    2005-01-18

    "Like-charge attraction" is a phenomenon found in many biological systems containing DNA or proteins, as well as in polyelectrolyte systems of industrial importance. "Like-charge attraction" between polyanions is observed in the presence of mobile multivalent cations. At a certain limiting concentration of cations, the negatively charged macroions cease to repel each other and even an attractive force between the anions is found. With classical molecular dynamics simulations it is possible to elucidate the processes that govern the attractive behavior with atomistic resolution. As an industrially relevant example we study the interaction of negatively charged carboxylate groups of sodium polyacrylate molecules with divalent cationic Ca2+ counterions. Here we show that Ca2+ ions initially associate with single chains of polyacrylates and strongly influence sodium ion distribution; shielded polyanions approach each other and eventually "stick" together (precipitate), contrary to the assumption that precipitation is initially induced by intermolecular Ca2+ bridging. PMID:15641856

  9. Origin of Lateral Nanoscale Heterogeneities in Weak Polyelectrolyte Brushes

    NASA Astrophysics Data System (ADS)

    Won, You-Yeon; Witte, Kevin; Hur, Jaehyun

    2009-03-01

    In this talk, we will first discuss experimental evidence of lateral nanoscale heterogeneities in a single-component weak polyelectrolyte brush system under zero to low salt conditions. Using an amphiphilic diblock copolymer, poly(2-(dimethylamino)ethyl methacrylate-b-n-butyl acrylate) (PDMAEMA-PnBA), for Langmuir film compression and Langmuir-Blodgett deposition on a hydrophobic substrate followed by fluid AFM imaging, we show the existence of regions of different brush heights, indicative of the thermodynamic instability (and resultant local clustering) of the PDMAEMA chains in the low-salt limit. Using SCF and scaling theories, we will also show that the lateral heterogeneities occur due to the combined effects of (i) the osmotic instability regulated by charge equilibrium and (ii) the hydrophobicity of the chains.

  10. Evaluation of the counterion condensation theory of polyelectrolytes.

    PubMed Central

    Stigter, D

    1995-01-01

    We compare free energies of counterion distributions in polyelectrolyte solutions predicted from the cylindrical Poisson-Boltzmann (PB) model and from the counterion condensation theories of Manning: CC1 (Manning, 1969a, b), which assumes an infinitely thin region of condensed counterions, and CC2 (Manning, 1977), which assumes a region of finite thickness. We consider rods of finite radius with the linear charge density of B-DNA in 1-1 valent and 2-2 valent salt solutions. We find that under all conditions considered here the free energy of the CC1 and the CC2 models is higher than that of the PB model. We argue that counterion condensation theory imposes nonphysical constraints and is, therefore, a poorer approximation to the underlying physics based on continuum dielectrics, point-charge small ions, Poisson electrostatics, and Boltzmann distributions. The errors in counterion condensation theory diminish with increasing distance from, or radius of, the polyion. PMID:8527651

  11. Polyelectrolyte coating of ferumoxytol nanoparticles for labeling of dendritic cells

    NASA Astrophysics Data System (ADS)

    Celikkin, Nehar; Jakubcová, Lucie; Zenke, Martin; Hoss, Mareike; Wong, John Erik; Hieronymus, Thomas

    2015-04-01

    Engineered magnetic nanoparticles (MNPs) are emerging to be used as cell tracers, drug delivery vehicles, and contrast agents for magnetic resonance imaging (MRI) for enhanced theragnostic applications in biomedicine. In vitro labeling of target cell populations with MNPs and their implantation into animal models and patients shows promising outcomes in monitoring successful cell engraftment, differentiation and migration by using MRI. Dendritic cells (DCs) are professional antigen-presenting cells that initiate adaptive immune responses. Thus, DCs have been the focus of cellular immunotherapy and are increasingly applied in clinical trials. Here, we addressed the coating of different polyelectrolytes (PE) around ferumoxytol particles using the layer-by-layer technique. The impact of PE-coated ferumoxytol particles for labeling of DCs and Flt3+ DC progenitors was then investigated. The results from our studies revealed that PE-coated ferumoxytol particles can be readily employed for labeling of DC and DC progenitors and thus are potentially suitable as contrast agents for MRI tracking.

  12. Cellular response to titanium discs coated with polyelectrolyte multilayer films

    NASA Astrophysics Data System (ADS)

    Zhan, Jing; Luo, Qiao-jie; Huang, Ying; Li, Xiao-dong

    2014-09-01

    The purpose of this study was to investigate the effects of polyelectrolyte multilayer (PEM) coatings on the biological behavior of titanium (Ti) substrates. Collagen type Ι/hyaluronic acid (Col/HA) and chitosan/hyaluronic acid (Chi/HA) multilayer PEM coatings were introduced onto Ti substrates using layer-by-layer assembly. Contact angle instruments and quartz crystal microbalance were used for film characterization. The results obtained showed that both Col/HA and Chi/HA surfaces had high hydrophilicity and promoted cell adhesion in MC3T3-E1 pre-osteoblast and human gingival fibroblast cells. In addition, the synthesis of function-related proteins and gene expression levels in both MC3T3-E1 and fibroblast cells was higher for the Col/HA coating compared with the Chi/HA coating, indicating better cellular response to the Col/HA coating.

  13. Dispersion of single-walled carbon nanotubes using polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Aldea, G.; Nunzi, J. M.

    2009-02-01

    In order to produce high performance SWNT-based products, it is necessary to make them soluble, reaching a certain degree of dispersion and stability in solution. Since SWNTs are mostly inert, being neither hydrophilic nor lipophilic, their use suffers from poor dispersion capability and weak interaction with other partners. Therefore, activating and modifying their surface is an essential prerequisite to processing. We report on a versatile nondestructive strategy for the non-covalent functionalization of SWNT by polyelectrolytes based on maleic anhydride copolymers. To evaluate competing stabilization characteristics, we explored the dispersing power of a range of maleic anhydride copolymers functionalized with several chromophore units: pyrene, cholesterol and Disperse Red 1. The surface modification of SWNT is straightforward and efficient for making them dispersible in water and in other organic solvents and for producing nanometer-scale materials suitable for nanotechnology, medicinal chemistry and environment friendly solar cell applications.

  14. Simulations of stretching a flexible polyelectrolyte with varying charge separation

    NASA Astrophysics Data System (ADS)

    Stevens, M. J.; Saleh, O. A.

    2016-07-01

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

  15. Magnetic Compression of Polyelectrolyte Microcapsules for Controlled Release.

    PubMed

    Hu, Yanan; Liu, Chuanyong; Li, Dongzhi; Long, Yue; Song, Kai; Tung, Chen-Ho

    2015-10-20

    In this study, microcapsules with a magnetic particle as the core and polyelectrolyte multilayers as the shell were fabricated. The cavity of the microcapsules was created by etching the SiO2 layer, which was first coated on the magnetic core particle, and the size of the cavity can be adjusted by the thickness of the SiO2 layer. This magnetically responsive microcapsule deforms upon application of a constant magnetic field and results in the release of the core content, and the release velocity could be controlled by the strength of the magnetic field. This release mechanism is proactive and repeatable, combined with its localized and remote controllability; it can be a powerful tool for delivering medical agents on site. PMID:26402037

  16. Modeling interfacial fracture in Sierra.

    SciTech Connect

    Brown, Arthur A.; Ohashi, Yuki; Lu, Wei-Yang; Nelson, Stacy A. C.; Foulk, James W.,; Reedy, Earl David,; Austin, Kevin N.; Margolis, Stephen B.

    2013-09-01

    This report summarizes computational efforts to model interfacial fracture using cohesive zone models in the SIERRA/SolidMechanics (SIERRA/SM) finite element code. Cohesive surface elements were used to model crack initiation and propagation along predefined paths. Mesh convergence was observed with SIERRA/SM for numerous geometries. As the funding for this project came from the Advanced Simulation and Computing Verification and Validation (ASC V&V) focus area, considerable effort was spent performing verification and validation. Code verification was performed to compare code predictions to analytical solutions for simple three-element simulations as well as a higher-fidelity simulation of a double-cantilever beam. Parameter identification was conducted with Dakota using experimental results on asymmetric double-cantilever beam (ADCB) and end-notched-flexure (ENF) experiments conducted under Campaign-6 funding. Discretization convergence studies were also performed with respect to mesh size and time step and an optimization study was completed for mode II delamination using the ENF geometry. Throughout this verification process, numerous SIERRA/SM bugs were found and reported, all of which have been fixed, leading to over a 10-fold increase in convergence rates. Finally, mixed-mode flexure experiments were performed for validation. One of the unexplained issues encountered was material property variability for ostensibly the same composite material. Since the variability is not fully understood, it is difficult to accurately assess uncertainty when performing predictions.

  17. Electric Field Induced Interfacial Instabilities

    NASA Technical Reports Server (NTRS)

    Kusner, Robert E.; Min, Kyung Yang; Wu, Xiao-Lun; Onuki, Akira

    1996-01-01

    The study of the interface in a charge-free, nonpolar, critical and near-critical binary fluid in the presence of an externally applied electric field is presented. At sufficiently large fields, the interface between the two phases of the binary fluid should become unstable and exhibit an undulation with a predefined wavelength on the order of the capillary length. As the critical point is approached, this wavelength is reduced, potentially approaching length-scales such as the correlation length or critical nucleation radius. At this point the critical properties of the system may be affected. In zero gravity, the interface is unstable at all long wavelengths in the presence of a field applied across it. It is conjectured that this will cause the binary fluid to break up into domains small enough to be outside the instability condition. The resulting pattern formation, and the effects on the critical properties as the domains approach the correlation length are of acute interest. With direct observation, laser light scattering, and interferometry, the phenomena can be probed to gain further understanding of interfacial instabilities and the pattern formation which results, and dimensional crossover in critical systems as the critical fluctuations in a particular direction are suppressed by external forces.

  18. Interfacial Design for Joining Technologies: An Historical Perspective

    NASA Astrophysics Data System (ADS)

    Janczak-Rusch, J.; Kaptay, G.; Jeurgens, L. P. H.

    2014-05-01

    This paper gives an historic perspective of the concept of "Interfacial Design" in joined (e.g. soldered, brazed, diffusion bonded) assemblies. During the course of history, the awareness grew that the interface in a material joint can be perceived at different length scales. With the continuing development of joining materials and technologies, it became evident that the performance of assemblies is critically dependent on the structure and composition of the multiple internal interfaces in the material joints. Resulting trends in the microstructural design of soldering, brazing, and other bonding materials by smart engineering of internal interfaces, as driven by increasingly complex technological requirements, are briefly addressed.

  19. Delayed response of interfacial tension in propagating chemical waves of the Belousov-Zhabotinsky reaction without stirring.

    PubMed

    Tanaka, Ryo; Nomoto, Tomonori; Toyota, Taro; Kitahata, Hiroyuki; Fujinami, Masanori

    2013-11-01

    Time-resolved measurements of the interfacial tension of propagating chemical waves of the Belousov-Zhabotinsky reaction based on the iron complex catalysts were carried out without stirring by monitoring the frequency of capillary waves with the quasi-elastic laser scattering method. A delayed response of the interfacial tension with respect to absorption was found with the delay being ligand-dependent when the reaction was conducted at a liquid/liquid interface. This behavior is attributed to differences in adsorption activity of the hydrophobic metal catalyst. The delay time and the increase in interfacial tension were also reproduced by a model considering the rate constants of equilibrium adsorption. PMID:24107133

  20. Interfacial area transport in bubbly flow

    SciTech Connect

    Ishii, M.; Wu, Q.; Revankar, S.T.

    1997-12-31

    In order to close the two-fluid model for two-phase flow analyses, the interfacial area concentration needs to be modeled as a constitutive relation. In this study, the focus was on the investigation of the interfacial area concentration transport phenomena, both theoretically and experimentally. The interfacial area concentration transport equation for air-water bubbly up-flow in a vertical pipe was developed, and the models for the source and sink terms were provided. The necessary parameters for the experimental studies were identified, including the local time-averaged void fraction, interfacial area concentration, bubble interfacial velocity, liquid velocity and turbulent intensity. Experiments were performed with air-water mixture at atmospheric pressure. Double-sensor conductivity probe and hot-film probe were employed to measure the identified parameters. With these experimental data, the preliminary model evaluation was carried out for the simplest form of the developed interfacial area transport equation, i.e., the one-dimensional transport equation.