Sample records for based polyelectrolyte complexes

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

    Directory of Open Access Journals (Sweden)


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

  2. Triclosan loaded electrospun nanofibers based on a cyclodextrin polymer and chitosan polyelectrolyte complex. (United States)

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


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

  3. Ultrasonic compatibilization of polyelectrolyte complex based on polysaccharides for biomedical applications


    Belluzo, M. Soledad; Medina, Lara F.; Cortizo, Ana María; Cortizo, María Susana


    In recent years, there has been an increasing interest in the design of biomaterials for cartilage tissue engineering. This type of materials must meet several requirements. In this study, we apply ultrasound to prepare a compatibilized blend of polyelectrolyte complexes (PEC) based on carboxymethyl cellulose (CMC) and chitosan (CHI), in order to improve stability and mechanical properties through the interpolymer macroradicals coupling produced by sonochemical reaction. We study the kinetic ...

  4. Characterization for Soil Fixation by Polyelectrolyte Complex

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


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

  5. Synthesis and characterization of chitosan-based polyelectrolyte complexes, doped by quantum dots (United States)

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


    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.


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    Ashwini Rajendra


    Full Text Available Recent years there has been greater utilization of natural polymers in the development of delivery systems. The present work is an effort towards development of matrix tablets using polyelectrolyte complex formed between the oppositely charged natural polymers like okra mucilage obtained from pods of Abelmoschus esculentus and chitosan. The effect of pH and polymer volume ratio on yield of polyelectrolyte complex was studied. It was observed that the yield was maximum (96.45% at pH 5 and at polymer volume ratio of 9:1 between okra mucilage and chitosan. The prepared polyelectrolyte complex was also characterised by conductimetry, FTIR, DSC. The results confirmed the formation of polyelectrolyte complex between the natural polymers. The matrix tablets were formulated for model drug diclofenac sodium using the best polyelectrolyte complex at different drug to polymer ratios and compared with formulations containing individual polymers as well as marketed formulation. The prepared formulations showed satisfactory physical parameters. Formulations F2 and F3 extended the drug release for more than 8 h with (83.87± 0.8321% and (77.125± 0.125% drug release respectively in 8 h. The formulations F2 and F3 followed zero order kinetics with anomalous diffusion mechanism. The mean dissolution times were 3.6042 and 3.5935 hrs and the % dissolution efficiency were 54.9467 and 55.7203 % for formulations F2 and F3 respectively. The similarity factor f2 for formulation F2 was 61.6751 and for formulation F3, it was found to be 60.5025.The formulations were found to be stable.

  7. Saloplastics: processing compact polyelectrolyte complexes. (United States)

    Schaaf, Pierre; Schlenoff, Joseph B


    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.

  8. Stereoregularity Drives Precipitation in Polyelectrolyte Complex Formation (United States)

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


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

  9. Microencapsulation of Ginger Volatile Oil Based on Gelatin/Sodium Alginate Polyelectrolyte Complex. (United States)

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


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

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

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    Sonje, Ashish G.; Mahajan, Hitendra S., E-mail:


    The aim of this study was the production of ondansetron hydrochloride loaded lyophilized insert for nasal delivery. The nasal insert was prepared by the lyophilisation technique using Chitosan–gellan gum polyelectrolyte complex as the polymer matrix. The ondansetron loaded inserts were evaluated with respect to water uptake, bioadhesion, drug release kinetic study, ex vivo permeation study, and in vivo study. Lyophilised nasal inserts were characterized by differential scanning calorimetry, scanning electron microscopy and X-ray diffraction study. Scanning electron microscopy confirmed the porous sponge like structure of inserts whereas release kinetic model revealed that drug release followed non-fickian case II diffusion. The nasal delivery showed improved bioavailability as compared to oral delivery. In conclusion, the ondansetron containing nasal inserts based on Chitosan–gellan gum complex with potential muco-adhesive potential is suitable for nasal delivery. - Highlights: • Chitosan–gellan gum polyelectrolyte complex based inserts have been prepared. • The synthesized polymer complex demonstrated important insert properties. • No toxicity was observed toward nasal mucosa. • In vivo study demonstrates the enhancement of bioavailability.

  11. Structures of some surfactant–polyelectrolyte complexes

    Indian Academy of Sciences (India)

    Rema Krishnaswamy; V A Raghunathan; A K Sood


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

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

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    David Vehlow


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

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

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    Gudrun Petzold


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

  14. Modeling competitive substitution in a polyelectrolyte complex

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


    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.

  15. Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations. (United States)

    Ou, Zhaoyang; Muthukumar, M


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

  16. Complex Formation Between Polyelectrolytes and Ionic Surfactants



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

  17. Structural study of coacervation in protein-polyelectrolyte complexes (United States)

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


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

  18. Complex coacervation of supercharged proteins with polyelectrolytes. (United States)

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


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

  19. Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions (United States)

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


    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.

  20. Novel porous scaffolds of pH responsive chitosan/carrageenan-based polyelectrolyte complexes for tissue engineering. (United States)

    Araujo, J V; Davidenko, N; Danner, M; Cameron, R E; Best, S M


    Polyelectrolyte complexes (PECs) represent promising materials for drug delivery and tissue engineering applications. These substances are obtained in aqueous medium without the need for crosslinking agents. PECs can be produced through the combination of oppositely charged medical grade polymers, which include the stimuli responsive ones. In this work, three-dimensional porous scaffolds were produced through the lyophilization of pH sensitive PECs made of chitosan (CS) and carrageenan (CRG). CS:CRG molar ratios of 1:1 (CSCRG1), 2:1 (CSCRG2), and 3:1 (CSCRG3) were used. The chemical compositions of the PECs, as well as their influence in the final structure of the scaffolds were meticulously studied. In addition, the pH responsiveness of the PECs in a range including the physiological pH values of 7.4 (simulating normal physiological conditions) and 4.5 (simulating inflammatory response) was assessed. Results showed that the PECs produced were stable at pH values of 7.4 and under but dissolved as the pH increased to nonphysiological values of 9 and 11. However, after dissolution, the PEC could be reprecipitated by decreasing the pH to values close to 4.5. The scaffolds obtained presented large and interconnected pores, being equally sensitive to changes in the pH. CSCRG1 scaffolds appeared to have higher hydrophilicity and therefore higher water absorption capacity. The increase in the CS:CRG molar ratios improved the scaffold mechanical properties, with CSCRG3 presenting the higher compressive modulus under wet conditions. Overall, the PEC scaffolds appear promising for tissue engineering related applications that require the use of pH responsive materials stable at physiological conditions.

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

    NARCIS (Netherlands)

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


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

  2. Complex Coacervation composed of Polyelectrolytes Alginate and Chitosan

    Institute of Scientific and Technical Information of China (English)



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

  3. Solubilization of trichloroethylene by polyelectrolyte/surfactant complexes

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


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

  4. Linear Viscoelasticity and Swelling of Polyelectrolyte Complex Coacervates (United States)

    Hamad, Fawzi; Colby, Ralph


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

  5. Mesenchymal stem cell recruitment by stromal derived factor-1-delivery systems based on chitosan/poly(γ-glutamic acid polyelectrolyte complexes

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    RM Gonçalves


    Full Text Available Human mesenchymal stem cells (hMSCs have an enormous potential for tissue engineering and cell-based therapies. With a potential of differentiation into multiple lineages and immune-suppression, these cells play a key role in tissue remodelling and regeneration.Here a method of hMSC recruitment is described, based on the incorporation of a chemokine in Chitosan (Ch/Poly(γ-glutamic acid (γ-PGA complexes. Ch is a non-toxic, cationic polysaccharide widely investigated. γ-PGA is a hydrophilic, non-toxic, biodegradable and negatively charged poly-amino acid. Ch and γ-PGA, being oppositely charged, can be combined through electrostatic interactions. These biocompatible structures can be used as carriers for active substances and can be easily modulated in order to control the delivery of drugs, proteins, DNA, etc.Using the layer-by-layer method, Ch and γ-PGA were assembled into polyelectrolyte multilayers films (PEMs with thickness of 120 nm. The chemokine stromal-derived factor-1 (SDF-1 was incorporated in these complexes and was continuously released during 120 h. The method of SDF-1 incorporation is of crucial importance for polymers assembly into PEMs and for the release kinetics of this chemokine. The Ch/γ-PGA PEMs with SDF-1 were able to recruit hMSCs, increasing the cell migration up to 6 fold to a maximum of 16.2 ± 4.9 cells/mm2. The controlled release of SDF-1 would be of great therapeutic value in the process of hMSC homing to injured tissues. This is the first study suggesting Ch/γ-PGA PEMs as SDF-1 reservoirs to recruit hMSCs, describing an efficient method of chemokine incorporation that allows a sustained released up to 5 days and that can be easily scaled-up.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

    Directory of Open Access Journals (Sweden)

    Rondon Céline


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

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


    Ankerfors, Caroline


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

  9. Polyelectrolyte Complexation: A Field-Theoretic Description of Phase Behavior (United States)

    Audus, Debra; Fredrickson, Glenn


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

  10. Dual ionic interaction system based on polyelectrolyte complex and ionic, injectable, and thermosensitive hydrogel for sustained release of human growth hormone. (United States)

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


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

  11. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes (United States)

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike


    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.

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

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


    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.

  13. Complexation of oppositely charged polyelectrolytes in gene delivery and biology (United States)

    Shklovskii, Boris


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

  14. Fibers by interfacial polyelectrolyte complexation – processes, materials and applications

    Directory of Open Access Journals (Sweden)

    Andrew C.A. Wan


    Full Text Available Interfacial polyelectrolyte (polyion complexation (IPC is a process whereby fibers and capsules are formed through interactions at the interface of oppositely charged polymers. Since its discovery in the late 1990s, the IPC fiber process, in particular, has been investigated for various applications such as tissue engineering, drug delivery, flexible electronics and biosensing. The advent of the IPC fiber and process has been supported by its unique mechanism of formation that makes it amenable to encapsulation and functionalization. In this first review on IPC fibers, we consolidate the current knowledge of the IPC process, mechanism of fiber formation and fiber physical properties, while documenting the various polycation–polyanion pairs and encapsulants that have been used to date. We review the rapidly accumulating literature on IPC fibers for tissue engineering, describing how they have been used to release protein factors in a sustained manner, made into random or spatially well-defined scaffolds and decorated with appropriate functionalities and extracellular matrices in order to tailor the microenvironment for cell growth and function.

  15. Characterization of Responsive Hydrogel Nanoparticles upon Polyelectrolyte Complexation

    Directory of Open Access Journals (Sweden)

    Su-Kyoung Lee


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

  16. Complexation and coacervation of like-charged polyelectrolytes inspired by mussels. (United States)

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


    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.

  17. Complex coacervation: A field theoretic simulation study of polyelectrolyte complexation (United States)

    Lee, Jonghoon; Popov, Yuri O.; Fredrickson, Glenn H.


    Using the complex Langevin sampling strategy, field theoretic simulations are performed to study the equilibrium phase behavior and structure of symmetric polycation-polyanion mixtures without salt in good solvents. Static structure factors for the segment density and charge density are calculated and used to study the role of fluctuations in the electrostatic and chemical potential fields beyond the random phase approximation. We specifically focus on the role of charge density and molecular weight on the structure and complexation behavior of polycation-polyanion solutions. A demixing phase transition to form a ``complex coacervate'' is observed in strongly charged systems, and the corresponding spinodal and binodal boundaries of the phase diagram are investigated.

  18. Polyelectrolyte complex/PVA membranes for diffusion dialysis. (United States)

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


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

  19. Polymer Physics Prize Lecture: Polyelectrolyte complexes: New routes to useful soft materials (United States)

    Tirrell, Matthew


    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.

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

    Directory of Open Access Journals (Sweden)

    Sarah L. Perry


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

  1. Tailor-made release triggering from hot-melt extruded complexes of basic polyelectrolyte and poorly water-soluble drugs. (United States)

    Kindermann, Christoph; Matthée, Karin; Strohmeyer, Jutta; Sievert, Frank; Breitkreutz, Jörg


    The aim of the study was the formulation of polyelectrolyte complexes composed of poorly water-soluble acid drugs and basic polymethacrylates by hot-melt extrusion enabling a tailor-made release pattern by the addition of inorganic salts. The influence of different electrolytes was analyzed at varying conditions in order to control drug delivery from the complexes. Poorly water-soluble model drugs naproxen and furosemide were applied in their non-ionic form. After hot-melt extrusion of the naproxen-polymethacrylate powder blend, XRPD and DSC measurements indicated the formation of a single-phase amorphous system. Milled extrudates were stable under storage at long-term and intermediate conditions. Polyelectrolyte complex formation by an acid-base reaction during hot-melt extrusion could be proven by the lack of vibrations of dimethylamino and carboxylic groups by FT-IR and Raman spectroscopy. The complexes did not dissolve in demineralized water. Drug release could be immediately induced by addition of neutral electrolytes. Tailor-made dissolution profiles were realized by controlled electrolyte triggering. Maximal effects were achieved by concentrations of 0.05-0.15 M NaCl. Different anions of alkali halogenides revealed variant magnitudes of the effect depending on the anion radius. Polyelectrolyte complex formation and dissolution principles were also confirmed for furosemide.

  2. Metallosupramolecular coordination polyelectrolytes: potential building blocks for molecular-based devices. (United States)

    Kurth, Dirk G


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

  3. Polyelectrolyte Properties in Mono and Multi-Valent Ionic Media: Brushes and Complex Coacervates (United States)

    Farina, Robert M.

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

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

    Directory of Open Access Journals (Sweden)

    Woltmann B


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  6. Counterions release from electrostatic complexes of polyelectrolytes and proteins of opposite charge : a direct measurement

    CERN Document Server

    Gummel, Jérémie; Boué, François


    Though often considered as one of the main driving process of the complexation of species of opposite charges, the release of counterions has never been experimentally directly measured on polyelectrolyte/proteins complexes. We present here the first structural determination of such a release by Small Angle Neutron Scattering in complexes made of lysozyme, a positively charged protein and of PSS, a negatively charged polyelectrolyte. Both components have the same neutron density length, so their scattering can be switched off simultaneously in an appropriate "matching" solvent; this enables determination of the spatial distribution of the single counterions within the complexes. The counterions (including the one subjected to Manning condensation) are expelled from the cores where the species are at electrostatic stoichiometry.

  7. Alcohol--Induced Polyelectrolyte-Surfactant Complex Coacervate Systems: Characterization and Applications in Enzyme and Protein Extraction (United States)

    Nejati Moshtaghin, Mahboubeh

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

  8. Fracturing fluid cleanup by controlled release of enzymes from polyelectrolyte complex nanoparticles (United States)

    Barati Ghahfarokhi, Reza

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


    Institute of Scientific and Technical Information of China (English)

    Hui-dan Liu; Takahiro Sato


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

  10. Rapid polyelectrolyte-based membrane immunoassay for the herbicide butachlor. (United States)

    Dzantiev, B B; Byzova, N A; Zherdev, A V; Hennion, M C


    Oppositely charged water-soluble polyelectrolytes were used in the developed membrane immunoenzyme assay for the herbicide butachlor. High-affinity and rapid binding between polyanion polymethacrylate and polycation poly(N-ethyl-4-vinylpyridinium) was applied to separate reacted and free immunoreactants. Competitive immunoassay format with peroxidase-labeled antigen was realized. The insoluble colored product of the peroxidase reaction was formed by bound labeled immune complexes and was reflectometrically detected. The assay combines short duration (15 min), high sensitivity (0.03 g/mL) and availability for out-of-laboratory testing. Different image processing algorithms were used to determine the herbicide content. Low variation coefficients of the measurements in the proposed quantitative assay, namely 4.8-9.0% for the range of antigen concentrations from 0.1 to 3.0 ng/mL, are evidence of the assay effectiveness. Possibility to control the butachlor content in mineral, artesian, and drinking water was demonstrated.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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. Polyelectrolyte membranes based on hydrocarbon polymer containing fullerene (United States)

    Saga, Shota; Matsumoto, Hidetoshi; Saito, Keiichiro; Minagawa, Mie; Tanioka, Akihiko

    In the present study, composite polyelectrolyte membranes were prepared from sulfonated polystyrene and fullerene. The additive effect of the fullerene on the membrane properties - electric resistance, mechanical strength, oxidation resistance, and methanol permeability - were measured. The addition of fullerene improved the oxidation resistance, and reduced the methanol crossover. The mechanical strength of the fullerene-composite membrane, on the other hand, was not improved. The direct methanol fuel cell (DMFC) based on a 1.4 wt% fullerene-composite membrane showed the highest power density of 47 mW cm -2 at the current density of 200 mA cm -2 (this value is 60% of the Nafion-based DMFC). The transmission electron microscopy (TEM) observations suggest that the improved dispersity of the fullerene and the reduced number of micropores in the membranes would improve its performance in the fuel cell.

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

    Directory of Open Access Journals (Sweden)

    Zakieh I. Al-Kurdi


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

  14. Hydrophilic drug encapsulation in shell-core microcarriers by two stage polyelectrolyte complexation method. (United States)

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


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

  15. Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes. (United States)

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


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

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

    Directory of Open Access Journals (Sweden)

    Lim CM


    Full Text Available Chaemin Lim,1,* Yu Seok Youn,2,* Kyung Soo Lee,1 Ngoc Ha Hoang,1 Taehoon Sim,1 Eun Seong Lee,3 Kyung Taek Oh1 1Department of Pharmaceutical Sciences, College of Pharmacy, Chung-Ang University, Seoul, 2Department of Pharmaceutical Sciences, School of Pharmacy, Sungkyunkwan University, Suwon, 3Division of Biotechnology, The Catholic University of Korea, Gyeonggi-do, South Korea *These authors contributed equally to this work Abstract: A polyelectrolyte ionomer complex (PIC composed of cationic and anionic polymers was developed for nanomedical applications. Here, a poly(ethylene glycol–poly(lactic acid–poly(ethylene imine triblock copolymer (PEG–PLA–PEI and a poly(aspartic acid (P[Asp] homopolymer were synthesized. These polyelectrolytes formed stable aggregates through electrostatic interactions between the cationic PEI and the anionic P(Asp blocks. In particular, the addition of a hydrophobic PLA and a hydrophilic PEG to triblock copolyelectrolytes provided colloidal aggregation stability by forming a tight hydrophobic core and steric hindrance on the surface of PIC, respectively. The PIC showed different particle sizes and zeta potentials depending on the ratio of cationic PEI and anionic P(Asp blocks (C/A ratio. The doxorubicin (dox-loaded PIC, prepared with a C/A ratio of 8, demonstrated pH-dependent behavior by the deprotonation/protonation of polyelectrolyte blocks. The drug release and the cytotoxicity of the dox-loaded PIC (C/A ratio: 8 increased under acidic conditions compared with physiological pH, due to the destabilization of the formation of the electrostatic core. In vivo animal imaging revealed that the prepared PIC accumulated at the targeted tumor site for 24 hours. Therefore, the prepared pH-sensitive PIC could have considerable potential as a nanomedicinal platform for anticancer therapy. Keywords: polyelectrolyte ionomer complex, PEG–PLA–PEI, nanomedicine, pH-sensitive, animal imaging

  17. Formation of redispersible polyelectrolyte complex nanoparticles from gallic acid-chitosan conjugate and gum arabic. (United States)

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


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

  18. Polyelectrolyte complex of carboxymethyl starch and chitosan as protein carrier: oral administration of ovalbumin. (United States)

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


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

  19. Effects of conformational ordering on protein/polyelectrolyte electrostatic complexation: ionic binding and chain stiffening. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Khairul Anuar Mat Amin


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

  1. Molecular Weight and Charge Density Asymmetry in Polyelectrolyte Complexation (United States)

    Audus, Debra; Fredrickson, Glenn; Duechs, Dominik


    We investigate the phase diagram of oppositely charged polymers in a good solvent using a field-theoretic model. Mean-field solutions fail to predict the experimentally observed macroscopic phase separation into a solvent-rich phase and a dense liquid aggregate of polymers - a ``complex coacervate.'' We therefore study the model within a one-loop approximation, which accounts for Gaussian fluctuations in electrostatic and chemical potentials. Our particular focus is the effect of molecular weight, ionic strength, and charge asymmetry on the phase envelope. A set of dimensionless parameters is identified that dictate the size and shape of the two-phase region. Our results should be helpful in guiding experimental studies of coacervation.

  2. New polyelectrolyte complex from pectin/chitosan and montmorillonite clay. (United States)

    da Costa, Marcia Parente Melo; de Mello Ferreira, Ivana Lourenço; de Macedo Cruz, Mauricio Tavares


    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.

  3. Synthesis, self-assembly and photoinduced surface-relief gratings of a polyacrylate-based Azo polyelectrolyte (United States)

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


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

  4. Ionizing radiation in the polyelectrolytes technology (United States)

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


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

  5. Swellable drug-polyelectrolyte matrices of drug-carboxymethylcellulose complexes. Characterization and delivery properties. (United States)

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


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

  6. Chemosensors and biosensors based on polyelectrolyte microcapsules containing fluorescent dyes and enzymes. (United States)

    Kazakova, Lyubov I; Shabarchina, Lyudmila I; Anastasova, Salzitsa; Pavlov, Anton M; Vadgama, Pankaj; Skirtach, Andre G; Sukhorukov, Gleb B


    The concept of enzyme-assisted substrate sensing based on use of fluorescent markers to detect the products of enzymatic reaction has been investigated by fabrication of micron-scale polyelectrolyte capsules containing enzymes and dyes in one entity. Microcapsules approximately 5 μm in size entrap glucose oxidase or lactate oxidase, with peroxidase, together with the corresponding markers Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (Ru(dpp)) complex and dihydrorhodamine 123 (DHR123), which are sensitive to oxygen and hydrogen peroxide, respectively. These capsules are produced by co-precipitation of calcium carbonate particles with the enzyme followed by layer-by-layer assembly of polyelectrolytes over the surface of the particles and incorporation of the dye in the capsule interior or in the multilayer shell. After dissolution of the calcium carbonate the enzymes and dyes remain in the multilayer capsules. In this study we produced enzyme-containing microcapsules sensitive to glucose and lactate. Calibration curves based on fluorescence intensity of Ru(dpp) and DHR123 were linearly dependent on substrate concentration, enabling reliable sensing in the millimolar range. The main advantages of using these capsules with optical recording is the possibility of building single capsule-based sensors. The response from individual capsules was observed by confocal microscopy as increasing fluorescence intensity of the capsule on addition of lactate at millimolar concentrations. Because internalization of the micron-sized multi-component capsules was feasible, they could be further optimized for in-situ intracellular sensing and metabolite monitoring on the basis of fluorescence reporting.

  7. Electrostatics of Rigid Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Wong, G.C.L.


    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.

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

    Institute of Scientific and Technical Information of China (English)

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


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

  9. Generation of mechanical force by grafted polyelectrolytes in an electric field: application to polyelectrolyte-based nano-devices (United States)

    Brilliantov, N. V.; Budkov, Yu. A.; Seidel, C.


    We analyse theoretically and by means of molecular dynamics (MD) simulations the generation of mechanical force by a polyelectrolyte (PE) chain grafted to a plane. The PE is exposed to an external electric field that favours its adsorption on the plane. The free end of the chain is linked to a deformable target body. By varying the field, one can alter the length of the non-adsorbed part of the chain. This entails variation of the deformation of the target body and hence variation of the force arising in the body. Our theoretical predictions for the generated force are in very good agreement with the MD data. Using the theory developed for the generated force, we study the effectiveness of possible PE-based nano-vices, composed of two clenching planes connected by PEs and exposed to an external electric field. We exploit the Cundall-Strack solid friction model to describe the friction between a particle and the clenching planes. We compute the diffusion coefficient of a clenched particle and show that it drastically decreases even in weak applied fields. This demonstrates the efficacy of the PE-based nano-vices, which may be a possible alternative to the existing nanotube nano-tweezers and optical tweezers. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  10. Auricularia auricular polysaccharide-low molecular weight chitosan polyelectrolyte complex nanoparticles: Preparation and characterization

    Directory of Open Access Journals (Sweden)

    Wei Xiong


    Full Text Available Novel polyelectrolyte complex nanoparticles (AAP/LCS NPs were prepared in this study and these were produced by mixing negatively charged auricularia auricular polysaccharide (AAP with positively charged low molecular weight chitosan (LCS in an aqueous medium. The AAP was extracted and purified from auricularia auricular, and then characterized by micrOTOF-Q mass spectrometry, UV/Vis spectrophotometry, moisture analyzer and SEM. The yield, moisture, and total sugar content of the AAP were 4.5%, 6.2% and 90.12% (w/w, respectively. The AAP sample was water-soluble and exhibited white flocculence. The characteristics of AAP/LCS NPs, such as the particle size, zeta potential, morphology, FT-IR spectra, DSC were investigated. The results obtained revealed that the AAP/LCS NPs had a spherical shape with a diameter of 223 nm and a smooth surface, and the results of the FT-IR spectra and DSC investigations indicated that there was an electrostatic interaction between the two polyelectrolyte polymers. Bovine serum albumin (BSA, pI = 4.8 and bovine hemoglobin (BHb, pI = 6.8 were used as model drugs to investigate the loading and release features of the AAP/LCS NPs. The results obtained showed that the AAP/LCS NPs had a higher entrapment efficiency (92.6% for BHb than for BSA (81.5%. The cumulative release of BSA and BHb from AAP/LCS NPs after 24 h in vitro was 95.4% and 91.9%, respectively. The in vitro release demonstrated that AAP/LCS NPs provided a sustained release matrix suitable for the delivery of protein drugs. These studies demonstrate that AAP/LCS NPs have a very promising potential as a delivery system for protein drugs.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


    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.

  13. Preparation and chemical and biological characterization of a pectin/chitosan polyelectrolyte complex scaffold for possible bone tissue engineering applications. (United States)

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


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

  14. Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides (United States)

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


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

  15. A two-step process for controlling the surface smoothness of polyelectrolyte-based microcapsules. (United States)

    Lacík, I; Anilkumar, A V; Wang, T G


    Biocompatibility is one of the crucial requirements to be fulfilled when designing devices for immunoisolation of transplanted cells. The quality of the capsule surface (smoothness/roughness) influences the nature of cell overgrowth on it by immunocytes, which eventually may lead to the transplant failure. A microcapsule has been developed based on the polyelectrolyte complexation of the polyanions sodium alginate and cellulose sulphate with the polycation poly(methylene-co-guanidine), which was successfully tested in rodent animal models. Recently, the principles for controlling the surface smoothness of these capsules has been identified. This paper reports on a two-step process used for production of stable capsules with improved surface properties. The methodology involves separating the process of drop shape recovery and precursor capsule formation from the process of membrane formation by applying a two-reactor design. The multi-loop reactors are connected in series, and the process separation is given by the different composition of cation solutions flowing in each reactor. This process enables one to prepare the microcapsule immunoisolation device, which can differ in the extent of surface roughness and, thus, is suitable for studying the effect of surface morphology of the immunoisolation device on cell overgrowth. The effect of this process on the capsule permeability has also been evaluated.

  16. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Cha, E.H. [The Faculty of Liberal Arts (Chemistry), Hoseo University, Asan Choongnam 336-795 (Korea); Lim, S.A. [Functional Proteomics Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Park, J.H. [Department of Herbal Medicine, Hoseo University, Asan Choongnam 336-795 (Korea); Kim, D.W. [Department of Chemical Technology, Han Bat National University, Daejon 305-719 (Korea); Macfarlane, D.R. [School of Chemistry, Monash University, Clayton, Vic. 3800 (Australia)


    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N,N-dimethyl-N-propyl-N-butyl ammonium tricyanomethanide (N{sub 1134}TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 x 10{sup -3} S cm{sup -1} at 25 C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 x 10{sup -3} S cm{sup -1} at 25 C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N{sub 1134}TCM (2.48 x 10{sup -3} S cm{sup -1}). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N{sub 1134}TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species. (author)

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

    Talukdar, Hrishikesh; Kundu, Sarathi; Basu, Saibal


    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.

  18. Continuous testing system for Baeyer-Villiger biooxidation using recombinant Escherichia coli expressing cyclohexanone monooxygenase encapsulated in polyelectrolyte complex capsules. (United States)

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


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

  19. One-Step Generation of Cell-Encapsulating Compartments via Polyelectrolyte Complexation in an Aqueous Two Phase System. (United States)

    Hann, Sarah D; Niepa, Tagbo H R; Stebe, Kathleen J; Lee, Daeyeon


    Diverse fields including drug and gene delivery and live cell encapsulation require biologically compatible encapsulation systems. One widely adopted means of forming capsules exploits cargo-filled microdroplets in an external, immiscible liquid phase that are encapsulated by a membrane that forms by trapping of molecules or particles at the drop surface, facilitated by the interfacial tension. To eliminate the potentially deleterious oil phase often present in such processes, we exploit the aqueous two phase system of poly(ethylene glycol) (PEG) and dextran. We form capsules by placing dextran-rich microdroplets in an external PEG-rich phase. Strong polyelectrolytes present in either phase form complexes at the drop interface, thereby forming a membrane encapsulating the fluid interior. This process requires considerable finesse as both polyelectrolytes are soluble in either the drop or external phase, and the extremely low interfacial tension is too weak to provide a strong adsorption site for these molecules. The key to obtaining microcapsules is to tune the relative fluxes of the two polyelectrolytes so that they meet and complex at the interface. We identify conditions for which complexation can occur inside or outside of the drop phase, resulting in microparticles or poor encapsulation, respectively, or when properly balanced, at the interface, resulting in microcapsules. The resulting microcapsules respond to the stimuli of added salts or changes in osmotic pressure, allowing perturbation of capsule permeability or triggered release of capsule contents. We demonstrate that living cells can be sequestered and interrogated by encapsulating Pseudomonas aeruginosa PAO1 and using a Live/Dead assay to assess their viability. This method paves the way to the formation of a broad variety of versatile functional membranes around all aqueous capsules; by tuning the fluxes of complexing species to interact at the interface, membranes comprising other complexing

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

    Directory of Open Access Journals (Sweden)

    Dominika Kulig


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

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Marie Francene Arnobit Cutiongco


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

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

    Hastuti, Budi; Mudasir, Siswanta, Dwi; Triyono


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

    Energy Technology Data Exchange (ETDEWEB)

    Sikwal, Dhiraj R.; Kalhapure, Rahul S.; Rambharose, Sanjeev; Vepuri, Suresh; Soliman, Mahmoud; Mocktar, Chunderika; Govender, Thirumala, E-mail:


    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 ± 47.76 nm, 0.442 ± 0.075, − 30.4 ± 5.3 mV 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 12 h. 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. - Highlights: • Self-assembly of vancomycin to form cube

  5. Green preparation of antibiotic nanoparticle complex as potential anti-biofilm therapeutics via self-assembly amphiphile-polyelectrolyte complexation with dextran sulfate. (United States)

    Cheow, Wean Sin; Hadinoto, Kunn


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

  6. Polysaccharides-based polyelectrolyte nanoparticles as protein drugs delivery system

    Energy Technology Data Exchange (ETDEWEB)

    Shu Shujun; Sun Lei; Zhang Xinge, E-mail: [Nankai University, Key Laboratory of Functional Polymer Materials Ministry of Education, Institute of Polymer Chemistry (China); Wu Zhongming [Tianjin Medical University, Metabolic Diseases Hospital (China); Wang Zhen; Li Chaoxing, E-mail: [Nankai University, Key Laboratory of Functional Polymer Materials Ministry of Education, Institute of Polymer Chemistry (China)


    Polysaccharides-based nanoparticles were prepared by synthesized quaternized chitosan and dextran sulfate through simple ionic-gelation self-assembled method. Introduction of quaternized groups was intended to increase water solubility of chitosan and make the nanoparticles have broader pH sensitive range which can remain more stable in physiological pH and decrease the loss of protein drugs caused by the gastric cavity. The load of BSA was affected by molecular parameter, i.e., degree of substitution, and average molecular weight of quaternized chitosan, as well as concentration of BSA. Fast release occurred in phosphate buffer solution (pH 7.4) while the release was slow in hydrochloric acid (pH 1.4). The drug release mechanism is Fickian diffusion through release kinetics analysis. Cell uptake demonstrated nanoparicles can internalize into Caco-2 cells, which suggested that nanoparticles had good biocompatibility. No significant conformation change was noted for the released BSA in comparison with native BSA using circular dichroism spectroscopy. This kind of novel composite nanoparticles may be a promising delivery system for oral protein and peptide drugs.

  7. Poly(3-hydroxybutyrate)/caffeic acid electrospun fibrous materials coated with polyelectrolyte complex and their antibacterial activity and in vitro antitumor effect against HeLa cells

    Energy Technology Data Exchange (ETDEWEB)

    Ignatova, Milena G. [Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev St, Bl. 103A, BG-1113 Sofia (Bulgaria); Manolova, Nevena E., E-mail: [Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev St, Bl. 103A, BG-1113 Sofia (Bulgaria); Rashkov, Iliya B. [Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev St, Bl. 103A, BG-1113 Sofia (Bulgaria); Markova, Nadya D. [Institute of Microbiology, Bulgarian Academy of Sciences, Acad. G. Bonchev Bl. 26, BG-1113 Sofia (Bulgaria); Toshkova, Reneta A.; Georgieva, Ani K.; Nikolova, Elena B. [Institute of Experimental Morphology, Pathology and Anthropology with Museum, Bulgarian Academy of Sciences, Acad. G. Bonchev St, bl. 25, BG-1113 Sofia (Bulgaria)


    The purpose of this work was to investigate the possibility for the preparation of new poly(3-hydroxybutyrate) (PHB)/poly(ethylene glycol) (PEG)-based fibrous materials containing natural phenolic compound caffeic acid (CA) of diverse architectures, as well as to study the impact of the fiber composition on the in vitro CA release profile and on the biological properties of the fibrous materials. The application of the one-pot electrospinning enabled the fabrication of nanofibrous materials from PHB and PEG loaded with the CA. Materials with targeted design were obtained by coating with polyelectrolyte complex of alginate (Alg) and N,N,N-trimethylchitosan (TMCh). Three different processing paths were used to obtain coated mats: (i) with CA incorporated in the PHB/PEG core; (ii) with CA embedded in the Alg layer; and (iii) with CA included in the TMCh layer. The in vitro release of CA was modulated by controlling the composition and the architecture of the nanofibrous mats. The performed microbiological screening and MTT cell viability studies revealed that in contrast to the bare mats, the CA-containing nanofibrous materials were effective in suppressing the growth of the Gram-positive bacteria Staphylococcus aureus and the Gram-negative bacteria Escherichia coli and displayed good cytotoxicity against human cervical HeLa tumor cells. In addition, the proliferation of murine spleen lymphocytes and peritoneal macrophages was increased by the prepared CA-containing nanofibrous materials. The obtained materials are promising for antibacterial wound dressing applications as well as for application in local treatment of cervical tumors. - Highlights: • New caffeic acid-loaded materials from PHB and PEG were prepared by electrospinning. • Different design is achieved by coating and formation of polyelectrolyte complexes. • The control on the architecture of the mats enables modulating caffeic acid release. • The caffeic acid-loaded mats suppress the growth of

  8. Fiber Optic Humidity Sensor Based on Self-Assembled Polyelectrolyte Multilayers

    Institute of Scientific and Technical Information of China (English)


    Polyelectrolyte multilayers were self-assembled onto planar glass substrates and multimode optic fibers. The multilayer thin films deposited on glass substrates were characterized by using UV-vis spectroscopy and X-ray photoelectron spectroscopy. The multilayer thin films containing hydrophilic side-groups possessed are affinity for water molecules. The adsorption and desorption of free water vapor gave rise to the changes in the refractive index and in the reflectance of the thin films. A multilayer thin film based fiber optic humidity sensor with an LED light source of 0.85 μm was designed. Under certain conditions, the reflected light intensity of the thin film sensor was a function of the humidity of air. About 30 bilayers was optimal for the multilayer thin film sensor working at wavelength of 0.85 μm. This sensor can work over almost the whole relative humidity range with very good sensitivity.

  9. Approach Based on Polyelectrolyte-Induced Nanoassemblies for Enhancing Sensitivity of Pyrenyl Probes. (United States)

    Yao, Zhiyi; Qiao, Yadong; Liang, Haiqin; Ge, Wenqi; Zhang, Li; Cao, Zhong; Wu, Hai-Chen


    We have developed a unique approach for enhancing the sensitivity of pyrenyl probes based on polyelectrolyte-induced nanoassemblies and explored its sensing application toward 2,4,6-trinitrophenol (TNP). The key issue of the method is the formation of the nanoassemblies which possess high-density charges, specific surface area, and inner hydrophobic regions. These properties would help increase the loading of analytes and promote probe-analyte interactions, thereby leading to the prominent enhancement of the sensitivity. In the course of TNP detection, pyrene nanoassemblies can bind TNP efficiently through cooperative noncovalent interactions including electrostatic, π-π stacking, and charge-transfer interactions, resulting in the distinct fluorescent responses of pyrene moieties. This system has excellent selectivity and sensitivity for TNP detection. The detection limit is as low as 5 nM. It may be used for monitoring the TNP concentrations in real-world samples.

  10. The influence of ionic strength and mixing ratio on the colloidal stability of PDAC/PSS polyelectrolyte complexes. (United States)

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


    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.


    Directory of Open Access Journals (Sweden)

    Marcin Głodniok


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

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

    Institute of Scientific and Technical Information of China (English)

    CHEN You-fang; LIN Xian-fu


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

  13. Polyelectrolyte complexes of N,N,N-trimethyl chitosan/heparin obtained at different p H: I. Preparation, characterization and controlled release of heparin

    Energy Technology Data Exchange (ETDEWEB)



    N,N,N-trimethyl chitosan (TMC) was synthesized through the N-methylation of chitosan (CHT) and characterized by FTIR spectroscopy. Polyelectrolytes complexes (PECs) based on TMC and Heparin (HP) were prepared at different pHs (5, 8, 10 and 12) and characterized through FTIR spectroscopy, DSC and TGA curves and WAXS profiles. It was verified that the thermal stability of PECs is higher as higher is the pH of feed solution used for PEC formation. At basic conditions the complexation between TMC and HP is more effective and alterations on WAXS profiles of PECs in relation to the precursor (TMC) were clearly observed. Also, WAXS profiles show that the PEC crystallinity depends on the pH used for the complexation. These results match to the FTIR, DSC and TGA data. Due to the more intense electrostatic interactions, at higher pHs the unlike polymers chains (TMC and HP) are closer enough to produce more stable PECs. Through of the delivery curves was showed that PEC8 is a promising material for uses in oral site-specific HP release systems. This fact is directly related to the thermal properties of PEC8. (author)

  14. Some variables affecting the characteristics of Eudragit E-sodium alginate polyelectrolyte complex as a tablet matrix for diltiazem hydrochloride. (United States)

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


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

  15. Sustained, Controlled and Stimuli-Responsive Drug Release Systems Based on Nanoporous Anodic Alumina with Layer-by-Layer Polyelectrolyte (United States)

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


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

  16. Functional finishing of aminated polyester using biopolymer-based polyelectrolyte microgels. (United States)

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


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

  17. Design of a stable and methanol resistant membrane with cross-linked multilayered polyelectrolyte complexes for direct methanol fuel cells (United States)

    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.

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

    Directory of Open Access Journals (Sweden)



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

  19. Healable, Transparent, Room-Temperature Electronic Sensors Based on Carbon Nanotube Network-Coated Polyelectrolyte Multilayers. (United States)

    Bai, Shouli; Sun, Chaozheng; Yan, Hong; Sun, Xiaoming; Zhang, Han; Luo, Liang; Lei, Xiaodong; Wan, Pengbo; Chen, Xiaodong


    Transparent and conductive film based electronics have attracted substantial research interest in various wearable and integrated display devices in recent years. The breakdown of transparent electronics prompts the development of transparent electronics integrated with healability. A healable transparent chemical gas sensor device is assembled from layer-by-layer-assembled transparent healable polyelectrolyte multilayer films by developing effective methods to cast transparent carbon nanotube (CNT) networks on healable substrates. The healable CNT network-containing film with transparency and superior network structures on self-healing substrate is obtained by the lateral movement of the underlying self-healing layer to bring the separated areas of the CNT layer back into contact. The as-prepared healable transparent film is assembled into healable transparent chemical gas sensor device for flexible, healable gas sensing at room temperature, due to the 1D confined network structure, relatively high carrier mobility, and large surface-to-volume ratio. The healable transparent chemical gas sensor demonstrates excellent sensing performance, robust healability, reliable flexibility, and good transparency, providing promising opportunities for developing flexible, healable transparent optoelectronic devices with the reduced raw material consumption, decreased maintenance costs, improved lifetime, and robust functional reliability.

  20. Composition and structural transitions of polyelectrolyte-surfactant complexes in the presence of fatty acid studied by NMR and cryo-SEM. (United States)

    Totland, Christian; Martinez-Santiago, Jose; Ananthapadmanabhan, Kavssery P; Somasundaran, Ponisseril


    Insoluble complexes formed when a cationic polyelectrolyte is neutralized by the oppositely charged surfactant sodium dodecylethersulfate (SDES) in the presence and absence of lauric acid (LA) have been examined directly using NMR spectroscopy and cryo-SEM. Below the SDES critical micelle concentration (CMC') the insoluble complex contains about 10 times more water than just above CMC'. This is related to a structural transition of the complex, where water is contained mainly in larger compartments below CMC' and then mainly in narrower compartments above CMC'. The structure of the complex's solid matrix was monitored by recording two-dimensional T2-diffusion correlation spectra of the water proton resonance, which reveal the presence of several different water environments which correspond to different complex structures. Structural features in the micrometer range were confirmed using cryo-SEM. When LA is present, the larger water compartments seen below CMC' are to some extent present in the entire SDES concentration range, which is not the case in the absence of LA. Furthermore, the inclusion of LA into the SDES aggregates above CMC' leads to a lamellar sheetlike organization of the polyelectrolyte-stabilized surfactant phase. In the absence of LA, a stringy network of fibers is seen in cryo-SEM images, indicating a spherical or rodlike SDES phase. Consequently, the complex without LA holds about 1.7-1.9 times more water than the complex with LA above the SDES CMC'. T1 relaxation, (13)C chemical shifts, and (1)H resonance line widths of SDES in the system support the above observations. The combination of MAS NMR, T2-diffusion correlation, and cryo-SEM proved to be an effective method for studying structural transitions in the surfactant-polyelectrolyte(-LA) insoluble complexes.

  1. Sequestration of rhBMP-2 into self-assembled polyelectrolyte complexes promotes anatomic localization of new bone in a porcine model of spinal reconstructive surgery. (United States)

    Abbah, Sunny-Akogwu; Lam, Wing Moon Raymond; Hu, Tao; Goh, James; Wong, Hee-Kit


    Efficient and therapeutically safe delivery of recombinant human bone morphogenetic protein 2 (rhBMP-2) continues to be a central issue in bone tissue engineering. Recent evidence indicates that layer-by-layer self-assembly of polyelectrolyte complexes (PECs) can be used to recreate synthetic matrix environments that would act as tuneable reservoirs for delicate biomolecules and cells. Although preliminary in vitro as well as small-animal in vivo studies support this premise, translation into clinically relevant bone defect volumes in larger animal models remains unreported. Here we explored the use of native heparin-based PEC, deposited on a hydrated alginate gel template, to load bioactive rhBMP-2 and to facilitate lumbar interbody spinal fusion in pigs. We observed that triple PEC deposits with the highest protein sequestration efficiency and immobilization capacity promoted higher volume of new bone formation when compared with single PEC with low sequestration efficiency and immobilization capacity. This also resulted in a significantly enhanced biomechanical stability of the fused spinal segment when compared with PEC carriers with relatively low protein sequestration and immobilization capacities (pcollagen sponge carriers. We conclude that this growth factor sequestration platform is effective in the healing of clinically relevant bone defect volume and could overcome some of the safety concerns and limitations currently associated with rhBMP-2 therapy such as excessive heterotopic ossification.

  2. Effects of Polyelectrolyte Complex Micelles and Their Components on the Enzymatic Activity of Lipase

    NARCIS (Netherlands)

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


    The enzymatic activity of Hi-lipase embedded in complexes of poly-2-methylvinylpyridinium-co-poly(ethylene oxide) (P2MVP(41)-PEG(205)) and poly(acrylic acid)(PAA(139)) is studied as a function of the PAA(139) + P2MVP(41) - PEO(205) complex composition. The measurements revealed that there are severa

  3. Impact of polyelectrolytes and their corresponding multilayers to human primary endothelial cells. (United States)

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


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

  4. Rodlike Complexes of a Polyelectrolyte (Hyaluronan) and a Protein (Lysozyme) observed by SANS

    CERN Document Server

    Boué, François; Cousin, Fabrice; Grillo, Isabelle; Morfin, Isabelle; 10.1021/bm100861g


    We study by Small Angle Neutron Scattering (SANS) the structure of Hyaluronan -Lysozyme complexes. Hyaluronan (HA) is a polysaccharide of 9 nm intrinsic persistence length that bears one negative charge per disaccharide monomer (Mmol = 401.3 g/mol); two molecular weights, Mw = 6000 and 500 000 Da were used. The pH was adjusted at 4.7 and 7.4 so that lysozyme has a global charge of +10 and + 8 respectively. The lysozyme concentration was varied from 3 to 40 g/L, at constant HA concentration (10 g/L). At low protein concentration, samples are monophasic and SANS experiments reveal only fluctuations of concentration although, at high protein concentration, clusters are observed by SANS in the dense phase of the diphasic samples. In between, close to the onset of the phase separation, a distinct original scattering is observed. It is characteristic of a rod-like shape, which could characterize "single" complexes involving one or a few polymer chains. For the large molecular weight (500 000) the rodlike rigid doma...

  5. Phase behavior of electrostatically complexed polyelectrolyte gels using an embedded fluctuation model. (United States)

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


    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.

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


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


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

  7. Polyelectrolyte Complexes of a Cationic All Conjugated Fluorene Thiophene Diblock Copolymer with Aqueous DNA

    DEFF Research Database (Denmark)

    Knaapila, Matti; Costa, Telma; Garamus, Vasil M.;


    We report on the structural and colorimetric effects of interaction of aqueous ∼0.06–1% poly[9,9-bis(2-ethylhexyl)fluorene]-b-poly[3-6-trimethylammoniumhexyl)thiophene] bromide (PF2/6-P3TMAHT) with double-stranded DNA to form PF2/6-P3TMAHT(DNA)x where x is the molar ratio of DNA base pairs to P3T...... photoluminescence (PL) is significantly quenched by DNA with increasing x, and the changing P3TMAHT/PF2/6 band ratio allows quantitative DNA detection. Sixteen-fold dilution does not change aggregate structure, but PL is blue-shifted, indicating weakened intermolecular interactions....

  8. In-vitro evaluation of the effect of polymer structure on uptake of novel polymer-insulin polyelectrolyte complexes by human epithelial cells. (United States)

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


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

  9. Changes in the Activity and Structure of Urease in the Interaction with Polyelectrolytes (United States)

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


    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.

  10. Adsorption of weak polyelectrolytes on charged nanoparticles. Impact of salt valency, pH, and nanoparticle charge density. Monte Carlo simulations. (United States)

    Carnal, Fabrice; Stoll, Serge


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  12. Efficient inverted polymer solar cells based on conjugated polyelectrolyte and zinc oxide modified ITO electrode

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Tao; Zhu, Xiaoguang; Tu, Guoli, E-mail: [Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhou, Lingyu [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory of Clean Energy, Dalian 116023 (China); Zhang, Jian, E-mail: [Department of Material Science and Engineering, Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004 (China)


    Efficient inverted polymer solar cells (PSCs) were constructed by utilizing a conjugated polyelectrolyte PF{sub EO}SO{sub 3}Na and zinc oxide to modify the indium tin oxide (ITO) electrode. The ITO electrode modified by PF{sub EO}SO{sub 3}Na and zinc oxide possesses high transparency, increased electron mobility, smoothened surface, and lower work function. PTB7:PC{sub 71}BM inverted PSCs containing the modified ITO electrode achieved a high power conversion efficiency (PCE) of 8.49%, exceeding that of the control device containing a ZnO modified ITO electrode (7.48%). Especially, PCE-10:PC{sub 71}BM inverted polymer solar cells achieved a high PCE up to 9.4%. These results demonstrate a useful approach to improve the performance of inverted polymer solar cells.

  13. Polysaccharide-based polyelectrolytes hollow microcapsules constructed by layer-by-layer technique. (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  15. Coencapsulation of oxygen carriers and glucose oxidase in polyelectrolyte complex capsules for the enhancement of D-gluconic acid and delta-gluconolactone production. (United States)

    Bucko, Marek; Gemeiner, Peter; Vikartovská, Alica; Mislovicová, Danica; Lacík, Igor; Tkác, Ján


    A novel encapsulated oxidative biocatalyst comprising glucose oxidase (GOD) coencapsulated with oxygen carriers within polyelectrolyte complex capsules was developed for the production of D-gluconic acid and delta-gluconolactone. The capsules containing immobilized GOD were produced by polyelectrolyte complexation with sodium alginate (SA) and cellulose sulfate (CS) as polyanions, poly(methylene-co-guanidine) (PMCG) as the polycation, CaCl(2) as the gelling agent and NaCl as the antigelling agent (GOD-SA-CS/PMCG capsules). Poly(dimethylsiloxane) (PDMS) and an emulsion of n-dodecane (DOD) or perfluorodecaline (PFD) with PDMS were used as the oxygen carriers and MnO(2) was used as a hydrogen peroxide decomposition catalyst. Water-soluble PDMS was found to act as both an oxygen carrier and an emulsifier of water-insoluble DOD and PFD. Stable microcapsules could be produced with concentrations of up to 4% (w/w) of PDMS, 10% (w/w) of DOD and PFD, and 25% (w/w) of MnO(2) in the polyanion solution of SA and CS. Roughly a two-fold increase in the GOD activity from 21.0+/-1.1 to 38.4+/-2.0 U*g(-1) and product space-time yields (STY) from 44.3+/-2.0 to 83.4+/-3.4 g*H*day(-1) could be achieved utilizing coencapsulated oxygen carriers compared to GOD encapsulated in the absence of oxygen carriers. This enhanced production does not significantly depend on the selected oxygen carrier under the conditions used in this study.

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

    CERN Document Server

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


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

  17. Polyelectrolyte Coacervates Deposited as High Gas Barrier Thin Films. (United States)

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


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

  18. Spin-Coated Polyelectrolyte Coacervate Films. (United States)

    Kelly, Kristopher D; Schlenoff, Joseph B


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

  19. A ratiometric nanosensor based on conjugated polyelectrolyte-stabilized AgNPs for ultrasensitive fluorescent and colorimetric sensing of melamine. (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

    徐毅; 冯剑; 尚亚卓; 刘洪来


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

  1. Counterion effects on fluorescence energy transfer in conjugated polyelectrolyte-based DNA detection. (United States)

    Nag, Okhil Kumar; Kang, Mijeong; Hwang, Sungu; Suh, Hongsuk; Woo, Han Young


    Cationic poly[9,9'-bis[6''-(N,N,N-trimethylammonium)hexyl]fluorene-co-alt-phenylene]s with five different counterions (CIs) were synthesized and studied as fluorescence resonance energy transfer (FRET) donors (D) to dye-labeled DNA (FRET acceptor, A). The polymers with different CIs show the same pi-conjugated electronic structure with similar absorption (lambda(abs) = approximately 380 nm) and photoluminescence (lambda(PL) = approximately 420 nm) emission spectra in water. The CIs accompanying the polymer chain are expected to affect the D/A complexation and modify the D-A intermolecular separation by acting as a spacer. Polymers with different CIs function differently as FRET excitation donors to fluorescein (Fl)-labeled single-stranded DNA (ssDNA-Fl). The FRET-induced Fl emission was enhanced significantly by the larger CI-exchanged polymers. The polymers with the CIs of tetrakis(1-imidazolyl)borate (FPQ-IB) and tetraphenylborate (FPQ-PB) showed a 2-4-fold enhancement in the FRET-induced signal compared with the polymer with bromide (FPQ-BR). The delayed FRET signal saturation and low association constants (K(a)) with ssDNA-Fl (3.53 x 10(6) M(-1) for FPQ-BR and 1.80 x 10(6) M(-1) for FPQ-PB) were measured for the polymers with larger CIs. The delayed acceptor saturation strengthens the antenna effect and reduces self-quenching of Fl by increasing the polymer concentration near Fl. The weak polymer/ssDNA-Fl association reduces the amount of energy-wasting charge transfer by increasing D-A intermolecular separation. The combined effects lead to increase the overall FRET-induced signal.

  2. Preparation and static contact angle measurement of NaCS/PDMDAAC polyelectrolyte complex membranes%NaCS/PDMDAAC聚电解质复合膜的制备及静态接触角测定

    Institute of Scientific and Technical Information of China (English)

    李鸣明; 姚善泾


    @@ 引言 膜技术是21世纪工业技术改造中的一项极为重要的高新技术,新型膜材料的开发将极大地推动膜技术的改造和膜工业的发展[1-2].近年来,聚电解质复合物(polyelectrolyte complex)成为一种新型高分子复合膜材料.

  3. Polyelectrolyte films based on chitosan/olive oil and reinforced with cellulose nanocrystals. (United States)

    Pereda, Mariana; Dufresne, Alain; Aranguren, Mirta I; Marcovich, Norma E


    Composite films designed as potentially edible food packaging were prepared by casting film-forming emulsions based on chitosan/glycerol/olive oil containing dispersed cellulose nanocrystals (CNs). The combined use of cellulose nanoparticles and olive oil proved to be an efficient method to reduce the inherently high water vapor permeability of plasticized chitosan films, improving at the same time their tensile behavior. At the same time, it was found that the water solubility slightly decreased as the cellulose content increased, and further decreased with oil addition. Unexpectedly, opacity decreased as cellulose content increased, which balanced the reduced transparency due to lipid addition. Contact angle decreased with CN addition, but increased when olive oil was incorporated. Results from dynamic mechanical tests revealed that all films present two main relaxations that could be ascribed to the glycerol- and chitosan-rich phases, respectively. The response of plasticized chitosan-nanocellulose films (without lipid addition) was also investigated, in order to facilitate the understanding of the effect of both additives.


    Directory of Open Access Journals (Sweden)

    Elina Orblin


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

  5. Conjugated polyelectrolytes fundamentals and applications

    CERN Document Server

    Liu, Bin


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

  6. Static and ultrafast optical properties of nanolayered composites. Gold nanoparticles embedded in polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Kiel, Mareike


    In the course of this thesis gold nanoparticle/polyelectrolyte multilayer structures were prepared, characterized, and investigated according to their static and ultrafast optical properties. Using the dip-coating or spin-coating layer-by-layer deposition method, gold-nanoparticle layers were embedded in a polyelectrolyte environment with high structural perfection. Typical structures exhibit four repetition units, each consisting of one gold-particle layer and ten double layers of polyelectrolyte (cationic+anionic polyelectrolyte). The structures were characterized by X-ray reflectivity measurements, which reveal Bragg peaks up to the seventh order, evidencing the high stratification of the particle layers. In the same measurements pronounced Kiessig fringes were observed, which indicate a low global roughness of the samples. Atomic force microscopy (AFM) images verified this low roughness, which results from the high smoothing capabilities of polyelectrolyte layers. This smoothing effect facilitates the fabrication of stratified nanoparticle/polyelectrolyte multilayer structures, which were nicely illustrated in a transmission electron microscopy image. The samples' optical properties were investigated by static spectroscopic measurements in the visible and UV range. The measurements revealed a frequency shift of the reflectance and of the plasmon absorption band, depending on the thickness of the polyelectrolyte layers that cover a nanoparticle layer. When the covering layer becomes thicker than the particle interaction range, the absorption spectrum becomes independent of the polymer thickness. However, the reflectance spectrum continues shifting to lower frequencies (even for large thicknesses). The range of plasmon interaction was determined to be in the order of the particle diameter for 10 nm, 20 nm, and 150 nm particles. The transient broadband complex dielectric function of a multilayer structure was determined experimentally by ultrafast pump

  7. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    Energy Technology Data Exchange (ETDEWEB)

    Demirsoy, Fatma Funda Kaya [Ankara University, The Central Laboratory of The Institute of Biotechnology (Turkey); Eruygur, Nuraniye [Gazi University, Department of Pharmacognosy, Faculty of Pharmacy (Turkey); Süleymanoğlu, Erhan, E-mail: [Gazi University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)


    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg{sup 2+}-ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized.

  8. Polyelectrolyte-based electrochemiluminescence enhancement for Ru(bpy){sub 3}{sup 2+} loaded by SiO{sub 2} nanoparticle carrier and its high sensitive immunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Zhi-Li; Song, Tian-Mei; Chen, Zhe [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); Guo, Wu-Run [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002 (China); Xie, Hong-Ping, E-mail: [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); Xie, Lian, E-mail: [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China)


    Highlights: • Preparation of strong ECL nanoparticles PAA–Ru@SiO{sub 2}/[PAA⋯Ru&Nafion⋯Ru]. • Ion-pair macromolecule PAA–Ru formed to greatly increase the doping amount. • PAA&Nafion membrane increased the amount of ion-exchanged Ru(bpy){sub 3}{sup 2+}. • PAA&Nafion membrane enhanced the ability of electron transfer. • Realized antibody labeling and established a high-sensitive immunoassay. - Abstract: In this paper the strong electrochemiluminescence (ECL) nanoparticles have been prepared based on the anionic polyelectrolyte sodium polyacrylate (PAA)-ECL enhancement for Ru(bpy){sub 3}{sup 2+}, which were loaded by the carrier of SiO{sub 2} nanoparticle. There were two kinds of Ru(bpy){sub 3}{sup 2+} for the as-prepared nanoparticles, the doped one and the exchanged one. The former was loaded inside the ECL nanoparticles by doping, in a form of ion-pair macromolecules PAA–Ru(bpy){sub 3}{sup 2+}. The corresponding ECL was enhanced about 2 times owing to the doping increase of Ru(bpy){sub 3}{sup 2+}. The latter was loaded on the PAA-doped Nafion membrane by ion exchange. The corresponding ECL was enhanced about 3 times owing to the ion-exchanging increase of Ru(bpy){sub 3}{sup 2+}. At the same time, ECL intensity of the doped-inside Ru(bpy){sub 3}{sup 2+} was further enhanced 13 times because polyelectrolyte PAA in the doped membrane could obviously enhance electron transfer between the doped Ru(bpy){sub 3}{sup 2+} and the working electrode. Furthermore, based on hydrophobic regions of the doped membrane antibody labeling could be easily realized by the as-prepared nanoparticles and then a high sensitive ECL immunoassay for HBsAg was developed. The linear range was between 1.0 and 100 pg mL{sup −1} (R{sup 2} = 0.9912). The detection limit could be as low as 0.11 pg mL{sup −1} (signal-to-noise ratio = 3)

  9. Improving Photocatalytic Activity through Electrostatic Self-Assembly: Polyelectrolytes as Tool for Solar Energy Conversion? (United States)

    Groehn, Franziska


    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.

  10. Polyelectrolyte (PE) induced interactions between Charged and zwitterionic Colloids (United States)

    Pryamitsyn, Victor; Ganesan, Venkat


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

  11. Protein adsorption in polyelectrolyte brush type cation-exchangers. (United States)

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


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

  12. Biological and Biomimetic Comb Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Aristeidis Papagiannopoulos


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

  13. Synthesis of Sensitive Polyelectrolyte Complex Nanoparticles and the Controlled Release of 5-FU%敏感性聚电解质纳米粒子的制备及对5-FU的控制释放

    Institute of Scientific and Technical Information of China (English)

    戚旻熠; 于娜娜; 李桂英


    以壳聚糖( CS)和海藻酸钠( SA)为原料,通过接枝共聚制备了壳聚糖接枝聚N-乙烯基吡烙烷酮( CS-g-PVP)和海藻酸钠接枝聚N-乙烯基吡烙烷酮(SA-g-PVP),然后利用静电自组装得到了pH敏感性聚电解质纳米粒子,研究了纳米粒子对5-氟尿嘧啶的负载及释放性能的影响。傅立叶红外光谱验证了聚合物的结构。当CS-g-PVP与SA-g-PVP体积比为3∶7时,形成的纳米粒子结构最稳定。透射电镜表明纳米粒子具有较规则的球形结构,尺寸在30~50 nm左右。聚电解质纳米粒子对5-FU表现出较高的负载能力,环境pH值和离子强度等因素对5-FU的释放有影响。%pH-sensitive polyelectrolyte complex nanoparticles assembled from chitosan-graft-poly ( 1-vinyl-2-pyrrolidone) (CS-g-PVP) and sodium alginate-graft-poly(1-vinyl-2-pyrrolidone) (SA-g-PVP) were prepared for entrapment and release of 5-fluorouracil ( 5-FU ) . The structure of polymers was determined by fourier-transformed infrared spectroscopy ( FTIR) . The highly aggregated nanoparticle was formed at the weight ratio of CS-g-PVP and SA-g-PVP is 3∶7 with a core formed from positively charged CS and negatively charged SA and a shell formed from hydrophilic PVP. The size and morphology of the nanoparticles was observed by transmis-sion electron microscopy ( TEM) . The dried particles gave the normally spheres with an average diameter of 30~50 nm. The CS-g-PVP/SA-g-PVP polyelectrolyte complex nanoparticles exhibited high drug loading content and encapsulation efficiency for 5-FU. Decreasing pH to weak acid or increasing ionic strength of nanoparticles solution,a sustained and controlled drug release was observed due to the deformation of nanoparticles.

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

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


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

  15. Study on Alginate–Chitosan Complex Formed with Different Polymers Ratio

    Directory of Open Access Journals (Sweden)

    Dominika Kulig


    Full Text Available Biomaterials based on polyelectrolyte complexation are an innovative concept of coatings and packaging production to be applied in a wide range of food products. The aim of this study was to obtain and characterize a sodium alginate–chitosan complex material with variable degree of polyion interactions by complexation of oppositely charged polysaccharides. In order to characterize polyelectrolyte complexes, theromogravimetric analysis (TGA, dynamic mechanical thermal analysis (DMTA, nuclear magnetic resonance (NMR, Fourier transform infrared spectroscopy (FT-IR, matrix-assisted laser desorption/ionization technique with time of flight analyzer (MALDI-TOF, and scanning electron microscopy (SEM were performed. TGA analysis showed that thermal decomposition temperature depends on the polymer ratio (R and thermal resistance of samples was improved by increasing chitosan dosage. Accordingly to DMTA results, polyelectrolyte complexation led to obtain more flexible and resistant to mechanical deformation materials. Comparative analysis of the FTIR spectra of single polyelectrolytes, chitosan and alginate, and their mixtures indicated the formation of the polyelectrolyte complex without addition of reinforcing substances. MALDI-TOF analysis confirms the creation of polyelectrolyte aggregates (~197 Da in samples with R ≥ 0.8; and their chemical stability and safety were proven by NMR analysis. The higher R the greater the number of polyanion–polycation aggregates seen in SEM as film morphology roughness.


    Energy Technology Data Exchange (ETDEWEB)

    Schanze, Kirk S [University of Florida


    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.

  17. Multilayered polyelectrolyte microcapsules: interaction with the enzyme cytochrome C oxidase. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Laura Pastorino

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

  19. Building Highly Flexible Polyelectrolyte Nanotubes

    Institute of Scientific and Technical Information of China (English)


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

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

    NARCIS (Netherlands)

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


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

  1. Accumulation of small protein molecules in a macroscopic complex coacervate

    NARCIS (Netherlands)

    Lindhoud, S.; Claessens, M.M.A.E.


    To obtain insight into the accumulation of proteins into macroscopic complex coacervate phases, the lysozyme concentration in complex coacervates containing the cationic polyelectrolyte poly-(N,N dimethylaminoethyl methacrylate) and the anionic polyelectrolyte polyacrylic acid was investigated as a

  2. Field-Theoretic Studies of Nanostructured Triblock Polyelectrolyte Gels (United States)

    Audus, Debra; Fredrickson, Glenn


    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.


    Institute of Scientific and Technical Information of China (English)

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


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

  4. Electrostatics and charge regulation in polyelectrolyte multilayered assembly. (United States)

    Cherstvy, Andrey G


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

  5. Polyelectrolyte properties of proteoglycan monomers (United States)

    Li, Xiao; Reed, Wayne F.


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

  6. Aptasensor for electrochemical sensing of angiogenin based on electrode modified by cationic polyelectrolyte-functionalized graphene/gold nanoparticles composites. (United States)

    Chen, Zhengbo; Zhang, Chenmeng; Li, Xiaoxiao; Ma, He; Wan, Chongqing; Li, Kai; Lin, Yuqing


    Herein, a label-free and highly sensitive electrochemical aptasensor for the detection of angiogenin was proposed based on a conformational change of aptamer and amplification by poly(diallyldimethyl ammonium chloride) (PDDA)-functionalized graphene/gold nanoparticles (AuNPs) composites-modified electrode. PDDA-functionalized graphene (P-GR) nanosheets as the building block in the self-assembly of GR nanosheets/AuNPs heterostructure enhanced the electrochemical detection performance. The electrochemical aptasensor has an extraordinarily sensitive response to angiogenin in a linear range from 0.1pM to 5nM with a detection limit of 0.064pM. The developed sensor provides a promising strategy for the cancer diagnosis in medical application in the future.

  7. Enhanced optical and nonlinear optical responses in a polyelectrolyte templated Langmuir-Blodgett film. (United States)

    Rajesh, K; Balaswamy, B; Yamamoto, K; Yamaki, H; Kawamata, J; Radhakrishnan, T P


    Optical and nonlinear optical properties like fluorescence and second harmonic generation (SHG) of molecular materials can be strongly influenced by the mode of assembly of the molecules. The Langmuir-Blodgett (LB) technique is an elegant route to the controlled assembly of molecules in ultrathin films, and complexation of ionic amphiphiles in the Langmuir film by polyions introduced in the aqueous subphase provides a simple and efficient access to further control, stabilization, and optimization. The monolayer LB film of the hemicyanine-based amphiphile, N-n-octadecyl-4-[2-(4-(N,N-ethyloctadecylamino)phenyl)ethenyl]pyridinium possessing a "tail-head-tail" structure, shows fluorescence as well as SHG response. The concomitant enhancement of both of these linear and nonlinear optical attributes is achieved through templating with the polyanion of carboxymethylcellulose. Brewster angle and atomic force microscopy reveal the influence of polyelectrolyte templating on the morphology of the Langmuir and LB films. Polarized absorption and fluorescence spectroscopy provide insight into the impact of complexation with the polyelectrolyte on the orientation and deaggregation of the hemicyanine headgroup leading to fluorescence and SHG enhancement in the LB film.

  8. Conductivity study of solid polyelectrolytes based on hydroiodide salt of poly(4-vinyl pyridine-co-butylmethacrylate), poly(4-vinyl pyridine-co-butylacrylate)

    Indian Academy of Sciences (India)

    Samadrita Goswami; Aradhana Dutta


    The chain flexibility of poly(4-vinylpyridine) was tried to increase by lowering its glass transition temperature (g) and by increasing its amorphous region by copolymerizing with butyl methacrylate and butylacrylate which act as internal plasticizer. The copolymers were prepared in five different feed molar ratios to optimize the required properties such as higher room temperature conductivity and better film-forming capacity. The conductivity and conduction behaviour of the copolymers, as well as their hydroiodide salts have been reported. There was about 103–104-fold increase in room temperature conductivity of these plasticized polyelectrolytes.

  9. Interactions of phosphororganic agents with water and components of polyelectrolyte membranes. (United States)

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


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

  10. Fibrillar films obtained from sodium soap fibers and polyelectrolyte multilayers. (United States)

    Zawko, Scott A; Schmidt, Christine E


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

  11. Flexible polyelectrolyte conformation in the presence of cationic and anionic surfactants (United States)

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


    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.

  12. Microgel-based engineered nanostructures and their applicability with template-directed layer-by-layer polyelectrolyte assembly in protein encapsulation. (United States)

    Shenoy, Dinesh B; Sukhorukov, Gleb B


    A novel strategy for the fabrication of microcapsules is elaborated by employing biomacromolecules and a dissolvable template. Calcium carbonate (CaCO(3)) microparticles were used as sacrificial templates for the two-step deposition of polyelectrolyte coatings by surface controlled precipitation (SCP) followed by the layer-by-layer (LbL) adsorption technique to form capsule shells. When sodium alginate was used for inner shell assembly, template decomposition with an acid resulted in simultaneous formation of microgel-like structures due to calcium ion-induced gelation. An extraction of the calcium after further LbL treatment resulted in microcapsules filled with the biopolymer. The hollow as well as the polymer-filled polyelectrolyte capsules were characterized using confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and scanning force microscopy (SFM). The results demonstrated multiple functionalities of the CaCO(3) core - as supporting template, porous core for increased polymer accommodation/immobilization, and as a source of shell-hardening material. The LbL treatment of the core-inner shell assembly resulted in further surface stabilization of the capsule wall and supplementation of a nanostructured diffusion barrier for encapsulated material. The polymer forming the inner shell governs the chemistry of the capsule interior and could be engineered to obtain a matrix for protein/drug encapsulation or immobilization. The outer shell could be used to precisely tune the properties of the capsule wall and exterior. [Diagram: see text] Confocal laser scanning microscopy (CLSM) image of microcapsules (insert is after treating with rhodamine 6G to stain the capsule wall).

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

    Energy Technology Data Exchange (ETDEWEB)

    Balastre, M.


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

  14. Responsive polyelectrolyte hydrogels and soft matter micromanipulation

    NARCIS (Netherlands)

    Glazer, P.J.


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

  15. Complex amine-based reagents (United States)

    Suslov, S. Yu.; Kirilina, A. V.; Sergeev, I. A.; Zezyulya, T. V.; Sokolova, E. A.; Eremina, E. V.; Timofeev, N. V.


    Amines for a long time have been applied to maintaining water chemistry conditions (WCC) at power plants. However, making use of complex reagents that are the mixture of neutralizing and the filmforming amines, which may also contain other organic components, causes many disputes. This is mainly due to lack of reliable information about these components. The protective properties of any amine with regard to metal surfaces depend on several factors, which are considered in this article. The results of applying complex reagents to the protection of heating surfaces in industrial conditions and estimated behavior forecasts for various reagents under maintaining WCC on heat-recovery boilers with different thermal circuits are presented. The case of a two-drum heat-recovery boiler with in-line drums was used as an example, for which we present the calculated pH values for various brands of reagents under the same conditions. Work with different reagent brands and its analysis enabled us to derive a composition best suitable for the conditions of their practical applications in heat-recovery boilers at different pressures. Testing the new amine reagent performed at a CCPP power unit shows that this reagent is an adequate base for further development of reagents based on amine compounds. An example of testing a complex reagent is shown created with the participation of the authors within the framework the program of import substitution and its possible use is demonstrated for maintaining WCC of power-generating units of combined-cycle power plants (CCPP) and TPP. The compliance of the employed reagents with the standards of water chemistry conditions and protection of heating surfaces were assessed. The application of amine-containing reagents at power-generating units of TPP makes it possible to solve complex problems aimed at ensuring the sparing cleaning of heating surfaces from deposits and the implementation of conservation and management of water chemistry condition

  16. Charge-regularization effects on polyelectrolytes (United States)

    Muthukumar, Murugappan


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

  17. Antibacterial polyelectrolyte-coated Mg alloys for biomedical applications (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Markus Heikki Juhani Korhonen


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

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

    Institute of Scientific and Technical Information of China (English)

    ZHU Xin-Sheng; Kwang-Ho CHOO


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

  20. Tunable protein-resistance of polycation-terminated polyelectrolyte multilayers. (United States)

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


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

  1. Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zielińska, Katarzyna, E-mail:; Leeuwen, Herman P. van


    Highlights: • For the first time SPME fiber is coated with polyelectrolyte layer. • Sorption of nanoparticles on the solid phase surface is prevented. • Polyelectrolyte-modified fiber enables extraction of free analyte in presence of sorbing nanoparticles. - Abstract: In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimethylammonium chloride), and poly(sodium 4-styrenesulfonate). The modified fiber provides reproducible, convenient and fast extraction capabilities toward the model analyte, triclosan (TCS). A negatively charged polyelectrolyte coating prevents sorbing oxidic nanoparticles from both partitioning into the PDMS phase and aggregation at its surface. The results for the TCS/nanoparticle sample show that the polyelectrolyte layer-modified solid phase extracts just the free form of the organic compound and enables dynamic speciation analysis of the nanoparticulate target analyte complex.

  2. Effect of Moisture on the Electrorheological Properties of Chitosan and Chitosan-Cu2+ Complex Polyelectrolyte Particles%水分对甲壳胺类高分子聚电解质的 电流变剪切性能的影响

    Institute of Scientific and Technical Information of China (English)

    张建华; 陶德华; 张直明


    The effect of moisture on the electrorheological (ER) propertiesof polyelectrolyte suspensions of chitosan and chitosan-Cu2+ complex particles dispersed in castor oil was investigated. It has been found that the polyelectrolyte suspensions did not show ER effect in the absence of moisture. The value of shear stress (τ) or apparent shear stress (Δτ) increased with the increase of moisture content and no saturated phenomenon was observed. When the moisture content came to about 12.5% of the dispersed particle content, a sharp increase in the leaking current density (J) appeared. Furthermore, the action mechanism of moisture in the polyelectrolyte suspensions of chitosan and chitosan-Cu2+ complex particles dispersed in castor oil is governed by its content therein and the compositions of the suspensions. Under the action of electric field or moisture, the -NH2 of chitoson or chitoson-Cu2+ complex particles are easy to dissociate from the polyelectrolytes bond to form the movable ions (-NH3+). When the moisture content is lower, the number of -NH3+ increases with the increase of its content. The ER effect is enhanced because -NH3+ can enlarge the induced-dipoile of the solid particles. On the other hand, for the suspension compositional molecules having hydrogen bond (—OH), when the moisture content is higher, the hydrogen bond action is stronger and thus it is easy to form “hydrogen bond bridge” with the co-action of the electric field. So the higher of the moisture, the larger the number of -NH3+ or hydrogen bond bridges in the suspension compositional molecules, the stronger the ER properties. The effect of moisture on the J is also elucidated by the same action mechanism. When moisture content is lower, the main action of -NH3+ is to enhance the induced dipolar interaction of the polyelectrolyte particles and there are ont any transit particles, so the value of J is lower. Which moisture content is higher, the “free water” in the suspensions will

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

    Directory of Open Access Journals (Sweden)

    Sergio P. Campana-Filho


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

  4. Treatment of effluents of poultry slaughterhouse with aluminum salts and natural polyelectrolytes. (United States)

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


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

  5. Effect of Protein Supercharging on Interaction with Polyelectrolytes (United States)

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

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

  6. Molecular Dynamics Simulations of Polyelectrolyte Solutions (United States)

    Dobrynin, Andrey


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

  7. Investigation on the interaction of Safranin T with anionic polyelectrolytes by spectrophotometric method. (United States)

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


    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.

  8. Energy conversion in polyelectrolyte hydrogels (United States)

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

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

  9. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets. (United States)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M; Ye, Mingxin


    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.

  10. Systematic modification of the rheological properties of colloidal suspensions with polyelectrolyte multilayers. (United States)

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


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

  11. Polyelectrolyte multilayers prepared from water-soluble poly(alkoxythiophene) derivatives. (United States)

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


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

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

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


    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.


    Directory of Open Access Journals (Sweden)

    I. M. Neelov


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

  14. Complexity measurement based on information theory and kolmogorov complexity. (United States)

    Lui, Leong Ting; Terrazas, Germán; Zenil, Hector; Alexander, Cameron; Krasnogor, Natalio


    In the past decades many definitions of complexity have been proposed. Most of these definitions are based either on Shannon's information theory or on Kolmogorov complexity; these two are often compared, but very few studies integrate the two ideas. In this article we introduce a new measure of complexity that builds on both of these theories. As a demonstration of the concept, the technique is applied to elementary cellular automata and simulations of the self-organization of porphyrin molecules.

  15. Molecular Thermodynamic Model for Polyelectrolyte Solutions with Added Salts

    Institute of Scientific and Technical Information of China (English)

    ZHANGBo; CAIJun; 等


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

  16. Structure-property relationships in the design, assembly and applications of polyelectrolyte multilayer thin films (United States)

    Rmaile, Hassan H.

    Ultrathin films consisting of an alternating sequence of positively and negatively charged polyelectrolytes have been prepared by means of the electrostatic layer-by-layer sequential assembly technique. To augment their typical applications in the water treatment, personal care as well as the pulp and paper industry, the structure and the design of these polyelectrolytes were tailored synthetically to satisfy the requirements of different types of applications. Some were used for surface modifications, hydrophobic and hydrophilic coatings, corrosion protection, conducting and biocompatible surfaces. Others were found to be very efficient for membrane and chromatographic applications. The ease with which these multilayer coatings can be constructed, their robustness and stability make them very good candidates for industrial applications. The dissertation focuses mainly on the structure-property relationships of these polyelectrolytes and their corresponding thin films. Various polyelectrolytes were synthesized or modified in a strategic approach and gave novel and promising properties. Some of them exhibited permeabilities that were higher than any membranes reported in the literature. Also, some are potentially very useful for designing drug delivery systems such as tablets or encapsulations since they were shown to control the permeability of sample drugs and vitamins very efficiently based on their sensitivity to pH changes. Other synthesized polyelectrolytes proved to be very effective in preventing protein adsorption or promoting cell growth and differentiation. Some systems were very useful as robust stationary phases for simple chiral separations in capillary electrochromatography. Along with modifications and improvements, the approach might one day be applied commercially for chiral separations using high performance liquid chromatography and replace currently used stationary phases. Last but not least, the potential for these polyelectrolytes and their

  17. Actuation and ion transportation of polyelectrolyte gels (United States)

    Hong, Wei; Wang, Xiao


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

  18. Complex Wavelet Based Modulation Analysis

    DEFF Research Database (Denmark)

    Luneau, Jean-Marc; Lebrun, Jérôme; Jensen, Søren Holdt


     because only the magnitudes are taken into account and the phase data is often neglected. We remedy this problem with the use of a complex wavelet transform as a more appropriate envelope and phase processing tool. Complex wavelets carry both magnitude and phase explicitly with great sparsity and preserve well...... polynomial trends. Moreover an analytic Hilbert-like transform is possible with complex wavelets implemented as an orthogonal filter bank. By working in an alternative transform domain coined as “Modulation Subbands”, this transform shows very promising denoising capabilities and suggests new approaches for joint...

  19. Durer-pentagon-based complex network

    Directory of Open Access Journals (Sweden)

    Rui Hou


    Full Text Available A novel Durer-pentagon-based complex network was constructed by adding a centre node. The properties of the complex network including the average degree, clustering coefficient, average path length, and fractal dimension were determined. The proposed complex network is small-world and fractal.

  20. Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

    CERN Document Server

    Voisin, D


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  2. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation. (United States)

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


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

  3. Polyelectrolytes from NS-novolak production waste

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Vaginal inserts based on chitosan and carboxymethylcellulose complexes for local delivery of chlorhexidine: preparation, characterization and antimicrobial activity. (United States)

    Bigucci, Federica; Abruzzo, Angela; Vitali, Beatrice; Saladini, Bruno; Cerchiara, Teresa; Gallucci, Maria Caterina; Luppi, Barbara


    The aim of this work was to prepare vaginal inserts based on chitosan/carboxymethylcellulose polyelectrolyte complexes for local delivery of chlorhexidine digluconate. Complexes were prepared with different chitosan/carboxymethylcellulose molar ratios at a pH value close to pKa interval of the polymers and were characterized in terms of physico-chemical properties, complexation yield and drug loading. Then complexes were used to prepare inserts as vaginal dosage forms and their physical handling, morphology, water-uptake ability and drug release properties as well as antimicrobial activity toward Candida albicans and Escherichia coli were evaluated. Results confirmed the ionic interaction between chitosan and carboxymethylcellulose and the influence of the charge amount on the complexation yield. Complexes were characterized by high values of drug loading and showed increasing water-uptake ability with the increase of carboxymethylcellulose amount. The selection of appropriate chitosan/carboxymethylcellulose molar ratios allowed to obtain cone-like shaped solid inserts, easy to handle and able to hydrate releasing the drug over time. Finally, the formulated inserts showed antimicrobial activity against common pathogens responsible for vaginal infections.

  5. Cationic β-cyclodextrin polymer applied to a dual cyclodextrin polyelectrolyte multilayer system. (United States)

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


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


    Institute of Scientific and Technical Information of China (English)

    Zhan-wen Xing; Heng-te Ke; Shao-qin Liu; Zhi-fei Dai; Jin-rui Wang; Ji-bin Liu


    Objective To prepare and characterize polyelectrolyte multilayer film coated microbubbles for use as ultrasound contrast agent (UCA) and evaluate its effects in ultrasonic imaging on normal rabbit's fiver parenchyma.Methoda Pcrfluorocarbon (PFC)-containing microbubbles (ST68-PFC) were prepared by sonication based on surfactant ( Span 60 and Tween 80). Subsequently, the resulting ST68-PFC microbnbbles were coated using oppositely charged polyclectrolytes by microbubble-templated layer-by-layer self-assembly technique via electrostatic interaction.The enhancement effects in ultrasonic imaging on normal rabbit's liver parenchyma were assessed.Results The obtained microbubbles exhibited a narrow size distribution. The polyelectrolytes were successfully assembled onto the surface of ST68-PFC microbubbles. In vivo experiment showed that polyelectrolyte multilayer film coated UCA effectively enhanced the imaging of rabbit's liver parenchyma.Conclnsions The novel microbubbles UCA coated with polyelectrolyte multilayer, when enabled more function,has no obvious difference in enhancement effects compared with the pre-modified microbnbbles. The polymers with chemically active groups ( such as amino group and carboxyl group) can be used as the outermost layer for attachment of targeting ligands onto microbubbles, allowing selective targeting of the microbubbles to combine with desired sites.

  7. Physico-mechanical analysis data in support of compatibility of chitosan/κ-carrageenan polyelectrolyte films achieved by ascorbic acid, and the thermal degradation theory of κ-carrageenan influencing the properties of its blends

    Directory of Open Access Journals (Sweden)

    Mahdiyar Shahbazi


    Full Text Available This article presents the complementary data regarding compatibilization of chitosan/κ-carrageenan polyelectrolyte complex for synthesizing of a soft film using ascorbic acid. It includes the thermal-theory for estimating the degradation of κ-carrageenan, as reflected in alteration of the structural properties of the blend. The data has been provided to demonstrate that the blend solution based on chitosan, a polycation, and κ-carrageenan, a polyanion polymer, produces an incompatible polyelectrolyte composite, susceptible to coaservative phase separation. We present further data on water resistance, water barrier property, mechanical parameters, scanning electron micrograph, as well as contact angle image dataset of the chitosan/κ-carrageenan film. The physical data were collected by water solubility and water permeability assays, with a view to elucidate the role of ascorbic acid in the compatibility of polyelectrolyte blends. The mechanical data is obtained from a stress–strain curve for evaluation of tensile strength and elongation at break point of the chitosan/κ-carrageenan film. The microstructure observations were performed using scanning electron micrograph. These dataset confirm fabrication of a soft film in the presence of ascorbic acid, with reduced heterogeneities in the polyelectrolyte film structure. The κ-carrageenan was also treated by a thermal process, prior to inclusion into the chitosan solution, to investigate the impact of this on the mechanical and structural features of the resulting blend. We present the required data and the theoretical analysis supporting the thermal chain degradation of a polymer and its effects on behavior of the film. Additional information, characterizing the hydrophobicity of the surface of the blend layers is obtained by measuring water contact angles using a contact anglemeter.

  8. Physico-mechanical analysis data in support of compatibility of chitosan/κ-carrageenan polyelectrolyte films achieved by ascorbic acid, and the thermal degradation theory of κ-carrageenan influencing the properties of its blends. (United States)

    Shahbazi, Mahdiyar; Ettelaie, Rammile; Rajabzadeh, Ghadir


    This article presents the complementary data regarding compatibilization of chitosan/κ-carrageenan polyelectrolyte complex for synthesizing of a soft film using ascorbic acid. It includes the thermal-theory for estimating the degradation of κ-carrageenan, as reflected in alteration of the structural properties of the blend. The data has been provided to demonstrate that the blend solution based on chitosan, a polycation, and κ-carrageenan, a polyanion polymer, produces an incompatible polyelectrolyte composite, susceptible to coaservative phase separation. We present further data on water resistance, water barrier property, mechanical parameters, scanning electron micrograph, as well as contact angle image dataset of the chitosan/κ-carrageenan film. The physical data were collected by water solubility and water permeability assays, with a view to elucidate the role of ascorbic acid in the compatibility of polyelectrolyte blends. The mechanical data is obtained from a stress-strain curve for evaluation of tensile strength and elongation at break point of the chitosan/κ-carrageenan film. The microstructure observations were performed using scanning electron micrograph. These dataset confirm fabrication of a soft film in the presence of ascorbic acid, with reduced heterogeneities in the polyelectrolyte film structure. The κ-carrageenan was also treated by a thermal process, prior to inclusion into the chitosan solution, to investigate the impact of this on the mechanical and structural features of the resulting blend. We present the required data and the theoretical analysis supporting the thermal chain degradation of a polymer and its effects on behavior of the film. Additional information, characterizing the hydrophobicity of the surface of the blend layers is obtained by measuring water contact angles using a contact anglemeter.

  9. A SVD Based Image Complexity Measure

    DEFF Research Database (Denmark)

    Gustafsson, David Karl John; Pedersen, Kim Steenstrup; Nielsen, Mads


    Images are composed of geometric structures and texture, and different image processing tools - such as denoising, segmentation and registration - are suitable for different types of image contents. Characterization of the image content in terms of geometric structure and texture is an important...... problem that one is often faced with. We propose a patch based complexity measure, based on how well the patch can be approximated using singular value decomposition. As such the image complexity is determined by the complexity of the patches. The concept is demonstrated on sequences from the newly...... collected DIKU Multi-Scale image database....

  10. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin


    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

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

    NARCIS (Netherlands)

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


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

  12. Voltage-controlled metal binding on polyelectrolyte-functionalized nanopores. (United States)

    Actis, Paolo; Vilozny, Boaz; Seger, R Adam; Li, Xiang; Jejelowo, Olufisayo; Rinaudo, Marguerite; Pourmand, Nader


    Most of the research in the field of nanopore-based platforms is focused on monitoring ion currents and forces as individual molecules translocate through the nanopore. Molecular gating, however, can occur when target analytes interact with receptors appended to the nanopore surface. Here we show that a solid state nanopore functionalized with polyelectrolytes can reversibly bind metal ions, resulting in a reversible, real-time signal that is concentration dependent. Functionalization of the sensor is based on electrostatic interactions, requires no covalent bond formation, and can be monitored in real time. Furthermore, we demonstrate how the applied voltage can be employed to tune the binding properties of the sensor. The sensor has wide-ranging applications and, its simplest incarnation can be used to study binding thermodynamics using purely electrical measurements with no need for labeling.

  13. Fine tuning of the pH-sensitivity of laponite-doxorubicin nanohybrids by polyelectrolyte multilayer coating. (United States)

    Xiao, Shili; Castro, Rita; Maciel, Dina; Gonçalves, Mara; Shi, Xiangyang; Rodrigues, João; Tomás, Helena


    Despite the wide research done in the field, the development of advanced drug delivery systems with improved drug delivery properties and effective anticancer capability still remains a great challenge. Based on previous work that showed the potentialities of the nanoclay Laponite as a pH-sensitive doxorubicin (Dox) delivery vehicle, herein we report a simple method to modulate its extent of drug release at different pH values. This was achieved by alternate deposition of cationic poly(allylamine) hydrochloride and anionic poly(sodium styrene sulfonate) (PAH/PSS) polyelectrolytes over the surface of Dox-loaded Laponite nanoparticles using the electrostatic layer-by-layer (LbL) self-assembly approach. The successful formation of polyelectrolyte multilayer-coated Dox/Laponite systems was confirmed by Dynamic Light Scattering and zeta potential measurements. Systematic studies were performed to evaluate their drug release profiles and anticancer efficiency. Our results showed that the presence of the polyelectrolyte multilayers improved the sustained release properties of Laponite and allowed a fine tuning of the extension of drug release at neutral and acidic pH values. The cytotoxicity presented by polyelectrolyte multilayer-coated Dox/Laponite systems towards MCF-7 cells was in accordance with the drug delivery profiles. Furthermore, cellular uptake studies revealed that polyelectrolyte multilayer-coated Dox/Laponite nanoparticles can be effectively internalized by cells conducting to Dox accumulation in cell nucleus.

  14. Bicontinuous Fluid Structure with Low Cohesive Energy: Molecular Basis for Exceptionally Low Interfacial Tension of Complex Coacervate Fluids. (United States)

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


    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.

  15. Self-organized nanoparticles based on drug-interpolyelectrolyte complexes as drug carriers

    Energy Technology Data Exchange (ETDEWEB)

    Palena, M. C.; Manzo, R. H.; Jimenez-Kairuz, A. F., E-mail: [Universidad Nacional de Cordoba, UNITEFA-CONICET, Departamento de Farmacia, Facultad de Ciencias Quimicas (Argentina)


    Potential applications in drug delivery from nanostructures composed of two oppositely charged polymethacrylates, eudragit{sup Registered-Sign} L100 (EL) and eudragit{sup Registered-Sign} EPO (EE), loaded with three model basic drugs (D), atenolol, propranolol, and metroclopramide were evaluated. The self-organized nanoparticles based on drug-interpolyelectrolyte complexes (DIPEC), (EL-D{sub 50})-EE{sub X}, were obtained by mixing the aqueous dispersions of both polyelectrolytes at room temperature in an ultrasound bath. Dispersions of (EL-D{sub 50}) neutralized with increasing proportions of EE exhibited a rise of turbidity, particle sizes in the range of 150-400 nm, and high negative zeta potential. The sign of zeta potential was shifted from negative to positive by changes in composition of DIPEC. Freeze dried DIPEC were easily redispersed in water yielding nearly the same parameters of fresh dispersions. In vitro release experiments using Franz cells showed that DIPEC systems behave as a drug reservoir that slowly releases the drug as water is placed in the receptor compartment. The release rate was raised by ionic exchange with counterions present in simulated physiological fluids placed in the receptor media. Delivery of D from DIPEC exhibited a remarkable robustness toward simulated physiological media of different pH. The DIPEC systems exhibit interesting properties to design nanoparticulate drug delivery systems for oral and/or topical routes.

  16. Nanoparticle-based membrane assembly and silicification in coacervate microdroplets as a route to complex colloidosomes. (United States)

    Fothergill, James; Li, Mei; Davis, Sean A; Cunningham, John A; Mann, Stephen


    The chemical construction of complex colloidosomes consisting of a molecularly crowded polyelectrolyte-enriched interior surrounded by a continuous shell of closely packed silica nanoparticles is studied using optical and fluorescence microscopy, high-resolution X-ray microcomputed tomography, and synchrotron radiation X-ray tomographic microscopy. The colloidosomes are prepared by addition of partially hydrophobic silica nanoparticles to dodecane dispersions of positively or negatively charged coacervate microdroplets consisting of aqueous mixtures of poly(diallyldimethylammonium chloride) (PDDA) and adenosine 5'-triphosphate (ATP) or PDDA and poly(acrylic acid) (PAA), respectively. Interfacial assembly of the nanoparticles produces a polydisperse population of well-defined PDDA/PAA droplets with diameters ranging from 50 to 950 μm. In contrast, reconstruction of the PDDA/ATP coacervate interior occurs on addition of the silica nanoparticles to produce a nanoparticle-stabilized oil-in-coacervate-in-oil multiphase emulsion. Transfer of the coacervate-containing colloidosomes into water and replication of their internal structure are achieved by addition of tetramethoxysilane, which serves as both a cross-linking and silicification agent to produce mineralized PDDA/PAA or PDDA/ATP microstructures with a uniform solidified texture or multichambered interior, respectively. The integration of colloidosome and coacervate technologies offers a route to a new type of multifunctional microcompartmentalized system based on the membrane-mediated incarceration of molecularly crowded chemical environments.

  17. Complex Wavelet Transform-Based Face Recognition

    Directory of Open Access Journals (Sweden)


    Full Text Available Complex approximately analytic wavelets provide a local multiscale description of images with good directional selectivity and invariance to shifts and in-plane rotations. Similar to Gabor wavelets, they are insensitive to illumination variations and facial expression changes. The complex wavelet transform is, however, less redundant and computationally efficient. In this paper, we first construct complex approximately analytic wavelets in the single-tree context, which possess Gabor-like characteristics. We, then, investigate the recently developed dual-tree complex wavelet transform (DT-CWT and the single-tree complex wavelet transform (ST-CWT for the face recognition problem. Extensive experiments are carried out on standard databases. The resulting complex wavelet-based feature vectors are as discriminating as the Gabor wavelet-derived features and at the same time are of lower dimension when compared with that of Gabor wavelets. In all experiments, on two well-known databases, namely, FERET and ORL databases, complex wavelets equaled or surpassed the performance of Gabor wavelets in recognition rate when equal number of orientations and scales is used. These findings indicate that complex wavelets can provide a successful alternative to Gabor wavelets for face recognition.

  18. Polyelectrolyte decomplexation via addition of salt: charge correlation driven zipper. (United States)

    Antila, Hanne S; Sammalkorpi, Maria


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

  19. Polyelectrolytes-promoted Forward Osmosis Processes

    KAUST Repository

    Ge, Q.C.


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

  20. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets (United States)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M.; Ye, Mingxin


    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. Electronic supplementary information (ESI) available: SEM, AFM and TEM characterization of PAA-MoS2 and PAM-MoS2 nanocomposites. More characterization and electrochemical properties of LBL films

  1. Rheological Behavior of the Guanidio Polyelectrolytes

    Institute of Scientific and Technical Information of China (English)

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


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

  2. Characterization of polyelectrolyte behavior of the polysaccharides chitosan, heparin, and hyaluronan, by light scattering and viscometry. (United States)

    Boddohi, Soheil; Yonemura, Susan; Kipper, Matt


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

  3. Interpretation with a Donnan-based concept of the influence of simple salt concentration on the apparent binding of divalent ions to the polyelectrolytes polystyrenesulfonate and dextran sulfate (United States)

    Marinsky, J.A.; Baldwin, Robert F.; Reddy, M.M.


    It has been shown that the apparent enhancement of divalent metal ion binding to polyions such as polystyrenesulfonate (PSS) and dextran sulfate (DS) by decreasing the ionic strength of these mixed counterion systems (M2+, M+, X-, polyion) can be anticipated with the Donnan-based model developed by one of us (J.A.M.). Ion-exchange distribution methods have been employed to measure the removal by the polyion of trace divalent metal ion from simple salt (NaClO4)-polyion (NaPSS) mixtures. These data and polyion interaction data published earlier by Mattai and Kwak for the mixed counterion systems MgCl2-LiCl-DS and MgCl2-CsCl-DS have been shown to be amenable to rather precise analysis by this model. ?? 1985 American Chemical Society.

  4. Fluorescent Polystyrene Sulfonate for Polyelectrolyte Studies (United States)

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


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

  5. Phenalenyl-based mononuclear dysprosium complexes

    Directory of Open Access Journals (Sweden)

    Yanhua Lan


    Full Text Available The phenalenyl-based dysprosium complexes [Dy(PLN2(HPLNCl(EtOH] (1, [Dy(PLN3(HPLN]·[Dy(PLN3(EtOH]·2EtOH (2 and [Dy(PLN3(H2O2]·H2O (3, HPLN being 9-hydroxy-1H-phenalen-1-one, have been synthesized. All compounds were fully characterized by means of single crystal X-ray analysis, paramagnetic 1H NMR, MALDI-TOF mass spectrometry, UV–vis spectrophotometry and magnetic measurements. Both static (dc and dynamic (ac magnetic properties of these complexes have been investigated, showing slow relaxation of magnetization, indicative of single molecule magnet (SMM behavior. Attempts to synthesize sublimable phenalenyl-based dysprosium complexes have been made by implementing a synthetic strategy under anhydrous conditions. The sublimed species were characterized and their thermal stability was confirmed. This opens up the possibility to deposit phenalenyl-based lanthanides complexes by sublimation onto surfaces, an important prerequisite for ongoing studies in molecular spintronics.

  6. Interest of Polyelectrolyte Multilayer thin Films in Tissue Engineering:Application to Vascular Allograft

    Institute of Scientific and Technical Information of China (English)

    Halima KERDJOUDJ; Cedric BOURA; Vanessa MOBY; Dominique DUMAS; Luc MARCHAL; Jean-Claude VOEGEL; Jean-Fran(c)ois STOLTZ; Patrick MENU


    @@ 1 Introduction Obstructive atherosclerosis vascular disease remains one of the greatest public health threats in the world. Surgical treatment to replace diseased blood vessels is usually done using major human allografts (veins or arteries) or synthetic prosthesis ( PTFE, Dacron). However, these substitutes have not a good pateney, because of the lack of endothelial cells (ECs) layer, which prevents thrombus formation. The challenge of tissue engineering vessels is to build-up blood/substitute interface near native vessels.In order to improve ECs adhesion, it is necessary to precoat the intra-luminal vessel. Recently, a new surface modification technique arose, based on the alternate adsorption of oppositely charged polyelectrolytes. Our objective was to favour the endothelialization of the cryo-preserved allografts, treated with a thin polyelectrolyte multilayered film, made of PSS (poly (sodium-4-styrenesulfonate) ) or PAH (poly (allylamine hydrochloride) ).

  7. Cell adhesive behavior on thin polyelectrolyte multilayers: cells attempt to achieve homeostasis of its adhesion energy. (United States)

    Mehrotra, Sumit; Hunley, S Christopher; Pawelec, Kendell M; Zhang, Linxia; Lee, Ilsoon; Baek, Seungik; Chan, Christina


    Linearly growing ultrathin polyelectrolyte multilayer (PEM) films of strong polyelectrolytes, poly(diallyldimethylammonium chloride) (PDAC), and sulfonated polystyrene, sodium salt (SPS) exhibit a gradual shift from cytophilic to cytophobic behavior, with increasing thickness for films of less than 100 nm. Previous explanations based on film hydration, swelling, and changes in the elastic modulus cannot account for the cytophobicity observed with these thin films as the number of bilayers increases. We implemented a finite element analysis to help elucidate the observed trends in cell spreading. The simulation results suggest that cells maintain a constant level of energy consumption (energy homeostasis) during active probing and thus respond to changes in the film stiffness as the film thickness increases by adjusting their morphology and the number of focal adhesions recruited and thereby their attachment to a substrate.


    Institute of Scientific and Technical Information of China (English)

    Hai-hu Yu; De-sheng Jiang


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Polyelectrolyte Multilayers: Towards Single Cell Studies

    Directory of Open Access Journals (Sweden)

    Dmitry Volodkin


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

  11. Novel cationic polyelectrolyte coatings for capillary electrophoresis. (United States)

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


    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.

  12. A complexity theory based on Boolean algebra

    DEFF Research Database (Denmark)

    Skyum, Sven; Valiant, Leslie


    relevance in Turing-machine-based complexity theory can be replicated easily and naturally in this elementary framework. Finer distinctions about the computational relationships among natural problems can be made than in previous formulations and some negative results are proved.......A projection of a Boolean function is a function obtained by substituting for each of its variables a variable, the negation of a variable, or a constant. Reducibilities among computational problems under this relation of projection are considered. It is shown that much of what is of everyday...

  13. Electrokinetics of pH-regulated zwitterionic polyelectrolyte nanoparticles (United States)

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


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

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

    NARCIS (Netherlands)

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


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

  15. Layer-by-layer deposition of oppositely charged polyelectrolytes on the surface of condensed DNA particles. (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


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

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

    Directory of Open Access Journals (Sweden)

    Jan-Michael Y. Carrillo


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

  18. Coacervation in Symmetric Mixtures of Oppositely Charged Rodlike Polyelectrolytes (United States)

    Kumar, Rajeev; Fredrickson, Glenn


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

  19. Characteristics of model polyelectrolyte multilayer films containing laponite clay nanoparticles. (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

    庹新林; 陈峥; 邓永红; 王晓工; 刘德山


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

  1. The biocompatibility of a polyelectrolyte vitreous body substitute on a high resistance in vitro model of the blood-retinal barrier. (United States)

    Strotmann, Falko; Wolf, Isabel; Galla, Hans-Joachim


    The vitreous body can be regarded as a fascinating simple but important tissue, since it represents the main compartment of the eye and plays a crucial role for proper vision. Several diseases require its removal with following substitution using a liquid artificial vitreous body replacement. We explore the biocompatibility of a poly(AMPS-Na(+))-graft-poly(NIPAAm) polyelectrolyte following the innovative concept of thermo-responsive behaviour, exhibiting enhanced shear viscosity at physiological temperatures. As a powerful model for the blood-retinal barrier, we use the well-established in vitro cell culture model based on highly differentiated porcine brain capillary endothelial cells. Via the quantification of the transendothelial electrical resistance and immunocytochemical staining of tight junction proteins, we are able to show that a barrier integrity affecting impact of the polyelectrolyte was only transient and nearly reversible. Furthermore, the polyelectrolyte hydrogel is characterized by the absence of any acute cell morphology, cell vitality or proliferation affecting impacts. It does not trigger acute apoptotic processes, as can be substantiated via caspase-3 activity and DNA fragmentation assays. In view of the results of this study, it is shown that the polyelectrolyte does not affect the vitality parameters of our porcine brain capillary endothelial cells. It can be suggested that the tested thermo-responsive polyelectrolyte does not affect the sensitive retinal barrier integrity. Thus from the cellular tolerance it might serve as a potential liquid artificial vitreous body replacement to overcome the most prominent difficulties of common vitreal endotamponades.


    Institute of Scientific and Technical Information of China (English)

    张停; 李桂英; 李睿鑫; 陈厚


    以天然高分子壳聚糖(CS)、羧甲基纤维素(CMC)和温度敏感性单体N-异丙基丙烯酰胺(N1PAM)为原料,通过自组装制备了温度敏感性聚电解质复合纳米粒子CS-g-PNIPAM/CMC-g-PNIPAM,并以5-氟尿嘧啶(5-FU)为模型药物研究了纳米粒子对药物的负载与可控释放性能.当CMC-g-PNIPAM与CS-g-PNIPAM的质量比为3∶7时,形成的纳米粒子结构最稳定,动态光散射(DLS)测得其平均粒径为116nm,粒径分布较窄.载药纳米粒子对5-FU具有较高的载药量和包封率.在磷酸盐缓冲溶液中的释药行为表明,其累积药物释放量随pH和温度的增加而增大,表现出良好的pH与温度可控性能.%The self-assembled thermo-sensitive chitosan-graft-poly(N-isopropylacrylamide)/ carboxymethyl cellulose-graft-poly(N-isopropyl-acrylamide) (CS-g-PNIPAM/CMC-g-PNIPAM) polyelectrolyte complex nanoparticles for loading and release of 5-fluorouracil (5-FU) were studied. The highly aggregated nanoparticle was formed at the weight ratio of CMC-g-PNIPAM and CS-g-PNIPAM=3:7 with thermo-sensitive properties as expected. The polyelectrolyte complex nanoparticles showed a narrow size distribution with an average diameter of 116nm by dynamic light scattering (DLS). The 5-FU-loaded nanoparticle was exhibited higher drug loading content and encapsulation efficiency. In terms of the release of 5-FU from nanoparticles in the phosphate buffer solutions, a controlled property of fine pH and temperature was observed. Increasing temperature or pH of the solutions was beneficial to the cumulative release of 5-FU.

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

    DEFF Research Database (Denmark)

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


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

  4. Molecular base of biochemical complex I deficiency.

    NARCIS (Netherlands)

    Hoefs, S.J.G.; Rodenburg, R.J.T.; Smeitink, J.A.M.; Heuvel, L.P.W.J. van den


    The oxidative phosphorylation (OXPHOS) system, consisting of five enzyme complexes (I-V) together with 2 electron carriers, has an important role in the energy metabolism of the cell. With 45 subunits, complex I is the first and largest complex of the respiratory chain. It is under bigenomic control

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

    Directory of Open Access Journals (Sweden)

    Prateek K. Jha


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


    the dynamics especially of the polyelectrolyte within the complexes.

  7. A novel, biodegradable and reversible polyelectrolyte platform for topical-colonic delivery of pentosan polysulphate. (United States)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)



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

  9. Single-chain-in-mean-field simulations of weak polyelectrolyte brushes (United States)

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


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

  10. Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Voisin, David


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

  11. Layer-by-layer coating of textile with two oppositely charged cyclodextrin polyelectrolytes for extended drug delivery. (United States)

    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


    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.

  12. Capturing Complex Multidimensional Data in Location-Based Data Warehouses

    DEFF Research Database (Denmark)

    Timko, Igor; Pedersen, Torben Bach


    Motivated by the increasing need to handle complex multidimensional data inlocation-based data warehouses, this paper proposes apowerful data model that is able to capture the complexities of such data. The model provides a foundation for handling complex transportationinfrastructures and the att......Motivated by the increasing need to handle complex multidimensional data inlocation-based data warehouses, this paper proposes apowerful data model that is able to capture the complexities of such data. The model provides a foundation for handling complex transportationinfrastructures...

  13. Polyelectrolyte stabilized multilayered liposomes for oral delivery of paclitaxel

    DEFF Research Database (Denmark)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


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

  15. Ionizable polyelectrolyte brushes: brush height and electrosteric interaction

    NARCIS (Netherlands)

    Biesheuvel, P.M.


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

  16. Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces (United States)

    Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew


    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).

  17. Formation of surface-attached microstructured polyelectrolyte brushes

    Institute of Scientific and Technical Information of China (English)

    Hai Ning Zhang


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

  18. Polyelectrolyte multilayer surface functionalization of poly(dimethylsiloxane) (PDMS) for reduction of yeast cell adhesion in microfluidic devices


    Schmolke, Hannah; Demming, Stefanie; Edlich, Astrid; Magdanz, Veronika; Büttgenbach, Stephanus; Franco-Lara, Ezequiel; Krull, Rainer; Klages, Claus-Peter


    Polyelectrolyte multilayers (PEMs) based on the combinations poly(diallyldimethylammonium chloride)∕poly(acrylic acid) (PDADMAC∕PAA) and poly(allylamine hydrochloride)∕PAA (PAH∕PAA) were adsorbed on poly(dimethylsiloxane) (PDMS) and tested for nonspecific surface attachment of hydrophobic yeast cells using a parallel plate flow chamber. A custom-made graft copolymer containing poly(ethylene glycol) (PEG) side chains (PAA-g-PEG) was additionally adsorbed on the PEMs as a terminal layer. A suit...

  19. Conformal nano-thin modified polyelectrolyte coatings for encapsulation of cells. (United States)

    Granicka, L H; Antosiak-Iwańska, M; Godlewska, E; Strawski, M; Szklarczyk, M; Maranowski, B; Kowalewski, C; Wiśniewsk, J


    Encapsulation of cells in polymeric shells allows for separation of biological material from produced factors, which may find biotechnological and biomedical applications. Human T-lymphocyte cell line Jurkat as well as rat pancreatic islets were encapsulated using LbL technique within shells of polyelectrolyte modified by incorporation of biotin complexed with avidin to improve cell coating and to create the potential ability to elicit specific biochemical responses. The coating with nano-thin modified shells allowed for maintenance of the evaluated cells' integrity and viability during the 8-day culture. The different PE impact may be observed on different biological materials. The islets exhibited lower mitochondrial activity than the Jurkat cells. Nevertheless, coating of cells with polyelectrolyte modified membrane allowed for functioning of both model cell types: 10 μm leukemia cells or 150 μm islets during the culture. Applied membranes maintained the molecular structure during the culture period. The conclusion is that applied modified membrane conformation may be recommended for coating shells for biomedical purposes.

  20. Forming Reversible Gels with Triblock Polyelectrolytes: a Field-theoretic Study (United States)

    Audus, Debra; Fredrickson, Glenn


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

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

    Institute of Scientific and Technical Information of China (English)

    皮瑛瑛; 尚亚卓; 彭昌军; 刘洪来


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

  2. Insight into the electrical properties and chain conformation of spherical polyelectrolyte brushes by dielectric spectroscopy (United States)

    Guo, Xiaoxia; Zhao, Kongshuang


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

  3. Polyelectrolyte multilayer coatings for the separation of proteins by capillary electrophoresis: Influence of polyelectrolyte nature and multilayer crosslinking. (United States)

    Bekri, Samya; Leclercq, Laurent; Cottet, Hervé


    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.

  4. Structure-based characterization of multiprotein complexes. (United States)

    Wiederstein, Markus; Gruber, Markus; Frank, Karl; Melo, Francisco; Sippl, Manfred J


    Multiprotein complexes govern virtually all cellular processes. Their 3D structures provide important clues to their biological roles, especially through structural correlations among protein molecules and complexes. The detection of such correlations generally requires comprehensive searches in databases of known protein structures by means of appropriate structure-matching techniques. Here, we present a high-speed structure search engine capable of instantly matching large protein oligomers against the complete and up-to-date database of biologically functional assemblies of protein molecules. We use this tool to reveal unseen structural correlations on the level of protein quaternary structure and demonstrate its general usefulness for efficiently exploring complex structural relationships among known protein assemblies.

  5. Low Power Complex Multiplier based FFT Processor

    Directory of Open Access Journals (Sweden)



    Full Text Available High speed processing of signals has led to the requirement of very high speed conversion of signals from time domain to frequency domain. Recent years there has been increasing demand for low power designs in the field of Digital signal processing. Power consumption is the most important aspect while considering the system performance. In order to design high performance Fast Fourier Transform (FFT and realization, efficient internal structure is required. In this paper we present FFT Single Path Delay feedback (SDF pipeline architecture using radix -24 algorithm .The complex multiplier is realized by using Digit Slicing Concept multiplier less architecture. To reduce computation complexity radix 24 algorithms is used. The proposed design has been coded in Verilog HDL and synthesizes by Cadence tool. The result demonstrates that the power is reduced compared with complex multiplication used CSD (Canonic Signed Digit multiplier.

  6. On the scattering properties of polyelectrolyte gels (United States)

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


    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

  7. A Complexity measure based on Requirement Engineering Document

    CERN Document Server

    Sharma, Ashish


    Research shows, that the major issue in development of quality software is precise estimation. Further this estimation depends upon the degree of intricacy inherent in the software i.e. complexity. This paper attempts to empirically demonstrate the proposed complexity which is based on IEEE Requirement Engineering document. It is said that a high quality SRS is pre requisite for high quality software. Requirement Engineering document (SRS) is a specification for a particular software product, program or set of program that performs some certain functions for a specific environment. The various complexity measure given so far are based on Code and Cognitive metrics value of software, which are code based. So these metrics provide no leverage to the developer of the code. Considering the shortcoming of code based approaches, the proposed approach identifies complexity of software immediately after freezing the requirement in SDLC process. The proposed complexity measure compares well with established complexity...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  9. Silanization of polyelectrolyte-coated particles: an effective route to stabilize Raman tagging molecules adsorbed on micrometer-sized silver particles. (United States)

    Kim, Kwan; Lee, Hyang Bong; Shin, Kuan Soo


    Micrometer-sized Ag (microAg) powders are very efficient surface-enhanced Raman scattering (SERS) substrates. To use microAg powders as a core material for molecular sensors operating via SERS, it is necessary to stabilize the tagging (i.e., SERS-marker) molecules adsorbed onto them. We demonstrate in this work that once the tagging molecules are coated with aliphatic polyelectrolytes such as poly(allylamine hydrochloride), the base-catalyzed silanization can be readily carried out to form stable silica shells around the polyelectrolyte layers by a biomimetic process; any particle can therefore be coated with silica since polyelectrolytes can be deposited beforehand via a layer-by-layer deposition method. Even after silanization, the SERS peaks of marker molecules on microAg particles are the only observable peaks since aliphatic polyelectrolytes, as well as silica shells, are intrinsically weak Raman scatterers, and more importantly, the SERS signals must be derived mostly from the first layer of the adsorbates (i.e., the marker molecules) in direct contact with the microAg particles. Silica shells, once fabricated, can further be derivatized to possess biofunctional groups; therefore, the modified microAg particles can be used as platforms of highly stable SERS-based biological sensors, as well as barcoding materials.

  10. Structure formation of soil dispersions in the presence of polyelectrolytes on the basis of allyl alcohol and acryl acid derivatives

    Directory of Open Access Journals (Sweden)

    Amankait Asanov


    Full Text Available Some changes of structural composition and surface properties of soil dispersions in the presence of polyelectrolytes, based on allyl alcohol and acryl acid derivatives, have been studied. The results show, that the changes in the structure of soil dispersions composition are connected with the added concentration and pH value, that depend on mole ratio and nature of functional groups, as well as on the nature of counterions and concomitant electrolytes, changing with the conditions of polymer analogous conversion and neutralization reaction. Experimental data show, that the change in the conformational state and the length of the macromolecule has a significant impact on the structure-forming effect and the amount of polyelectrolyte, needed to achieve the same degree of structure-forming effect of soil dispersions. The causes for the revealed reasons are shown on the basis of the results of the experiment. Along with this, it was found that particular changes of structural composition and surface properties of the soil dispersions depend on the type and concentration of the added polyelectrolyte.


    Institute of Scientific and Technical Information of China (English)

    LI Zhuomei; ZHANG Xuexin; XIE Zhiming; HUANG Yuhui


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

  12. Monte Carlo simulation and equation of state for flexible charged hard-sphere chain fluids: polyampholyte and polyelectrolyte solutions. (United States)

    Jiang, Hao; Adidharma, Hertanto


    The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must therefore be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions.

  13. Complex System Optimization Using Biogeography-Based Optimization

    Directory of Open Access Journals (Sweden)

    Dawei Du


    Full Text Available Complex systems are frequently found in modern industry. But with their multisubsystems, multiobjectives, and multiconstraints, the optimization of complex systems is extremely hard. In this paper, a new algorithm adapted from biogeography-based optimization (BBO is introduced for complex system optimization. BBO/Complex is the combination of BBO with a multiobjective ranking system, an innovative migration approach, and effective diversity control. Based on comparisons with three complex system optimization algorithms (multidisciplinary feasible (MDF, individual discipline feasible (IDF, and collaborative optimization (CO on four real-world benchmark problems, BBO/Complex demonstrates competitive performance. BBO/Complex provides the best performance in three of the benchmark problems and the second best in the fourth problem.

  14. Cellular uptake and distribution of graphene oxide coated with layer-by-layer assembled polyelectrolytes (United States)

    Li, Yiye; Lu, Zhenzhen; Li, Zhongjun; Nie, Guangjun; Fang, Ying


    We report a facile approach for the fabrication of a new class of graphene oxide (GO)-based nanoassemblies by layer-by-layer (LbL) technique. The single-layer thickness and intrinsic negatively charged carboxyl groups of GO nanosheets provide a natural platform for LbL assembly of polyelectrolyte nanofilms by electrostatic forces at mild and aqueous conditions. The general applicability of our approach is demonstrated by the preparation of GO nanoassemblies with sizes of 100-200 nm using various charged polyelectrolytes, including synthetic polymers, polypeptides, and DNA oligonucleotides. Systemic assessment of cytotoxicity and acute stress response show that no discernable signs of cytotoxicity are associated with exposure of GO and its nanoassemblies [GO/PLL (poly ( l-lysine)), GO/PLL/PSS (poly(sodium-4-styrenesulfonate)), GO/PLL-PEG (PEGlayted PLL), GO/PLL/PLGA-PEG (PEGlayted poly ( l-glutamic acid))] up to 1 μg/mL. Studies on cellular uptake and subcellular localization show that a representative nanoassembly, GO/PLL-PEG, can effectively cross cell membranes and localize mainly in lysosomal compartments, without induction of noticeable harmful effects as confirmed by detection of mitochondrial depolarization and lysosomal pH.

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

    Directory of Open Access Journals (Sweden)

    Da Hye Shin


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

  16. Phosphonic acid functionalized poly(pentafluorostyrene) as polyelectrolyte membrane for fuel cell application (United States)

    Atanasov, Vladimir; Oleynikov, Andrey; Xia, Jiabing; Lyonnard, Sandrine; Kerres, Jochen


    In this paper we introduce polyelectrolyte membranes based on phosphonated poly(pentafluorostyrene) (PPFS) and their performances in a fuel cell. The polyelectrolytes were obtained via partial phosphonation of PPFS varying the phosphonation degree from 17 to 66%. These membranes showed a high resistance to temperature (Tdecomp. = 355-381 °C) and radical attack (96-288 h in Fenton's test). A blend membrane consisting of 82 wt% fully phosphonated PPFS and 18 wt% poly(benzimidazole) is compared to the 66% phosphonated membrane having similar ion-conductivity (σ = 57 mS cm-1 at 120 °C, 90% RH). In the fuel cell the blend showed the best performance reaching 0.40 W cm-2 against 0.34 W cm-2 for the 42 wt% phosphonated membrane and 0.35 W cm-2 for Nafion 212. Furthermore, the blend maintained its operation at potentiostatic regime (0.5 V) for 620 h without declining in its performance. The highest power density of 0.78 W cm-2 was reached for the blend with a thickness of 15 μm using humidified oxygen (RH > 90%) at the cathode side. The switch from humidified to dry gasses during operation reduced the current density down to 0.6 A cm-2, but the cell maintained under operation for 66 h.

  17. Encapsulation of the herbicide picloram by using polyelectrolyte biopolymers as layer-by-layer materials. (United States)

    Wang, Xiaojing; Zhao, Jing


    Microcapsules of the herbicide picloram (PLR) were formulated by a layer-by-layer (LbL) self-assembly method using the polyelectrolyte biopolymers of biocompatible chitosan (CS) and the UV-absorbent sodium lignosulfonate (SL) as shell materials. The herbicide PLR was recrystallized and characterized using XRD analysis. The obtained PLR-loaded microcapsules were characterized by using SEM, FTIR, CLSM, and ζ-potential measurements. The herbicide loading and encapsulation efficiency were also analyzed for the PLR-loaded microcapsules. The influence of LbL layer numbers on herbicide release and photodegradation rates was investigated in vitro. The results showed that the release rates and photodegradation rates of PLR in microcapsules decreased with increasing number of CS/SL self-assembly layers. The results demonstrated that polyelectrolyte biopolymer-based LbL multilayer microcapsules can be a promising approach for the controlled release of PLR as well as other pesticides with poor photostability or short half-release time.

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

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


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

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

    Directory of Open Access Journals (Sweden)

    Sabine Frühbeißer


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

  20. Aqueous dispersions of silver nanoparticles in polyelectrolyte solutions

    Indian Academy of Sciences (India)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


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

  3. Ultramicroelectrode studies of oxygen reduction in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

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


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

  4. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes (United States)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui


    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  6. Kinetics of swelling of polyelectrolyte gels: Fixed degree of ionization (United States)

    Sen, Swati; Kundagrami, Arindam


    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.

  7. Multifunctional polyelectrolyte microcapsules as a contrast agent for photoacoustic imaging in blood. (United States)

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


    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.

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

    KAUST Repository

    Ge, Qingchun


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

  9. Forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces. (United States)

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


    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.

  10. Hollow polyelectrolyte multilayer tubes: mechanical properties and shape changes. (United States)

    Mueller, Renate; Daehne, Lars; Fery, Andreas


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

  11. Adsorption of anionic polyelectrolytes to dioctadecyldimethylammonium bromide monolayers (United States)

    Engelking, J.; Menzel, H.

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

  12. A Memristor-Based Hyperchaotic Complex Lü System and Its Adaptive Complex Generalized Synchronization

    Directory of Open Access Journals (Sweden)

    Shibing Wang


    Full Text Available This paper introduces a new memristor-based hyperchaotic complex Lü system (MHCLS and investigates its adaptive complex generalized synchronization (ACGS. Firstly, the complex system is constructed based on a memristor-based hyperchaotic real Lü system, and its properties are analyzed theoretically. Secondly, its dynamical behaviors, including hyperchaos, chaos, transient phenomena, as well as periodic behaviors, are explored numerically by means of bifurcation diagrams, Lyapunov exponents, phase portraits, and time history diagrams. Thirdly, an adaptive controller and a parameter estimator are proposed to realize complex generalized synchronization and parameter identification of two identical MHCLSs with unknown parameters based on Lyapunov stability theory. Finally, the numerical simulation results of ACGS and its applications to secure communication are presented to verify the feasibility and effectiveness of the proposed method.

  13. Nanoassemblies driven by cyclodextrin-based inclusion complexation. (United States)

    Kang, Yang; Guo, Kun; Li, Bang-Jing; Zhang, Sheng


    Nanoscaled supramolecular systems have attracted significant attention because of their promising applications in many fields. This review focuses on recent advances in the construction of nanoassemblies driven by cyclodextrin (CD)-based inclusion complexation and their application in biomedical and biomimetic fields. As a result of the reversibility of the CD-based host-guest interactions, CD-based driving forces provide the opportunity to generate complex and sophisticated nanoassemblies with tunable properties.

  14. Entering and exiting the protein-polyelectrolyte coacervate phase via nonmonotonic salt dependence of critical conditions. (United States)

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


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

  15. Dynamics of polyelectrolyte adsorption on surfaces: Applications in the detection of iron in water (United States)

    Gammana, Madhira N.

    presented in this thesis. It was found that the amount and rate of Fe3+ uptake was dependent on the relative size of each block in the polymer and the degree of reaction of DFB with the adsorbed layer. In particular, higher amounts and higher rates were obtained when the density of DFB was lowered. This shows that the DFB was sterically hindered from forming a hexacoordinate complex with Fe3+ by the presence of neighboring DFB molecules. This is a key factor that needs to be considered in developing Fe3+ detection systems based on siderophores anchored to surfaces.

  16. Comparative Analysis of EEG Signals Based on Complexity Measure

    Institute of Scientific and Technical Information of China (English)


    The aim of this study is to identify the functions and states of the brains according to the values of the complexity measure of the EEG signals. The EEG signals of 30 normal samples and 30 patient samples are collected. Based on the preprocessing for the raw data, a computational program for complexity measure is compiled and the complexity measures of all samples are calculated. The mean value and standard error of complexity measure of control group is as 0.33 and 0.10, and the normal group is as 0.53 an...

  17. Complexity Measurement of Large-Scale Software System Based on Complex Network

    Directory of Open Access Journals (Sweden)

    Dali Li


    Full Text Available With the increase of software system complexity, the traditional measurements can not meet the requirements, for the reason that the developers need control the software quality effectively and guarantee the normal operation of software system. Hence how to measure the complexity of large-scale software system has been a challenge problem. In order to solve this problem, the developers have to obtain a good method to measure the complexity of software system first. Only through this work, the software quality and the software structure could be controlled and optimized. Note that the complex network theory has offered a new theoretical understanding and a new perspective to solve this kind of complexity problem, this work discusses the complexity phenomenon in large-scale software system. Based on this, some complexity measurements of large-scale software system are put forward from static structure and dynamic structure perspectives. Furthermore, we find some potential complexity characteristics in large-scale software networks through the numerical simulations. The proposed measurement methods have a guiding significance on the development for today's large-scale software system. In addition, this paper presents a new technique for the structural complexity measurements of large-scale software system

  18. A fluorescence-Raman dual-imaging platform based on complexes of conjugated polymers and carbon nanotubes. (United States)

    Liu, Yun; Huang, Jun; Sun, Min-Jie; Yu, Ji-Cheng; Chen, Yu-Lei; Zhang, Yu-Qi; Jiang, Shao-Jun; Shen, Qun-Dong


    The present study describes a flexible nanoplatform based on electrostatic assembly of conjugated polyelectrolytes (CPEs) and carboxylated multi-walled carbon nanotubes (cMWNTs). It is demonstrated that the obtained nanocomposites inherit intrinsic optical properties of CPEs and characteristic Raman vibration modes of MWNTs, providing a fluorescence-Raman dual-imaging method for intracellular tracking and locating of MWNTs. We suggest that the cellular internalization of the CPE-cMWNT nanocomposites is a surface charge-dependent process. The strengths of this nanoplatform include satisfying biocompatibility, enhanced protein-repellent property, and ease of implementation, making it available for both in vitro and in vivo applications.

  19. Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex

    Institute of Scientific and Technical Information of China (English)

    Lei Zhang; Xu Feng Ni; Wei Lin Sun; Zhi Quan Shen


    Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 95%) and high molecular weight (ca. 105) in the presence of the triisobutyl aluminium (AliBu3) as cocatalyst. The microstructure of obtained polyisoprene was investigated by FTIR, 1H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.

  20. New diketone based vanadium complexes as insulin mimetics. (United States)

    Sheela, A; Roopan, S Mohana; Vijayaraghavan, R


    Since 1985, when Heyliger et al. first reported the in vivo insulin mimetic activity of oral vanadate, extensive studies exploring vanadium chemistry, including the synthesis of novel complexes and their biological effects both in vitro and in vivo have been pursued. Such complexes have emerged as possible potential agents for diabetes therapy. Among the several existing compounds, diketone based vanadium complexes have been chosen for the current study. Two new complexes namely bisdimethylmalonatooxovanadium(IV) and bisdiethylmalonatooxovanadium(IV) have been synthesized and characterized by UV-visible, FTIR and mass spectral studies. The antidiabetic activity of the complexes was proved by animal study. The results show that the above complexes have comparable antidiabetic potential with respect to the standard drug as well as with bisacetylacetonatooxovanadium(IV) which has been studied earlier by Reul et al.

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

    NARCIS (Netherlands)

    Boehm, J.T.C.


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Roger, G.


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


    Institute of Scientific and Technical Information of China (English)

    吴燕梅; 石建兵; 佟斌; 支俊格; 董宇平


    A conjugated polymer ( P0) containing tetraphenylethene ( TPE) group and benzothiadiazole (BT) group has been designed and synthesized by Suzuki coupling reaction of 1,2-di[4-(6-bromohexyloxy) phenyl]-l ,2-di(4-bromophenyl)ethene (Ml) , 1,2-di[4-(6-bromohexyloxy) phenyl]-1 ,2-di(4-(4,4,5,5-tetramethyl-1 ,3, 2-dioxaborolan-2-yl) phenyl) ethylene ( M2 ) and 4, 7-dibromo-2 , 1 , 3-benzothiadiazole (M3). The ratio of TPE unit to BT unit at 0. 803: 0. 197 was determined by 1H-NMR spectrum. A water-soluble cationic conjugated polyelectrolyte (P1) is obtained by quaternization P0 with trimethylamine,which is completely soluble in water and insoluble in common organic solvents such as THF and acetone. When P1 is aggregated by adding a poor solvent such as THF into P1 aqueous solution, the fluorescence intensity and color of P1 change drastically. The intensity increases up to seven times and the maximum emission peak is red-shifted up to 30 nm. The color is changing from khaki ( no aggregation) to orange ( aggregation) under ultraviolet irradiation. Therefore, dual-channel fluorescence response as the unique properties of P1 was applied to detect heparin, a highly sulfated glycosaminoglycan with the highest negative charge density among the known biological molecules. The fluorescence intensity gradually increased upon addition of heparin into P1 aqueous solution with a linear response to concentration of heparin, and the correlation coefficient was up to 0. 9999. In addition, a linear red shift of the maximum emission peak was observed as the concentration of heparin increased with a correlation coefficient up to 0. 9998. These results indicate that P1 is a potential material for developing dual-channel fluorescence probe for heparin quantification. The UV spectra of P1/ heparin complexing titration don' t show any change. This indicates that there is no inter-chains or intra-chains π-π stacking of P1. DLS result indicates some aggregates can be formed through

  4. Synthesis of Chiral Metal Complexes of Unsymmetrical Schiff Bases

    Institute of Scientific and Technical Information of China (English)


    @@ Recently, in asymmetric catalyst research the great developments of chiral Salen complexes have been made, but the report on unsymmetrical schiff bases is deficient. The unsymmetrical schiff bases complexes are an effective system in catalytically selective Olefin-epoxidations1. At the same time, unsymmetrical schiff bases was immobilized onto polymer supports for heterogenization2. The potential benefits of the catalyst include facilitation of catalyst separation from reagents, simplification of methods for catalyst recycle, and the possible adaptation of the immobilized catalyst to continuous-flow processes. A series of new unsymmetrical schiff bases was synthesized to study the relations between unsymmetry and enantioselectivity and select better catalyst. The following is the route:

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

    CERN Document Server

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


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

  6. Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers (United States)

    White, Nicholas

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

  7. Highly Conductive Graphene and Polyelectrolyte Multilayer Thin Films Produced From Aqueous Suspension. (United States)

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


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

  8. Investigation of metal nanoparticles encapsulated in polyelectrolyte multilayers for catalytic and antibacterial applications (United States)

    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


    Institute of Scientific and Technical Information of China (English)

    Hyuck Joon Kwon; Kazuhiro Shikinaka; Akira Kakugo; Hidemitsu Furukawa; Yoshihito Osada; Jian Ping Gong


    F-actins are semi-flexible polyelectrolytes and can be assembled into large polymer-actin complex with polymorphism through electrostatic interaction with polycations. This study investigates the structural phase behavior and the growth of polymer-actin complexes in terms of its longitudinal and lateral sizes. Our results show that formation of polymer-actin complexes is cooperative, and morphology and growth of polymer-actin complexes depend on polycation species and concentrations of polycation and salt in a constant actin concentration. We found that the longitudinal growth and lateral growth of polymer-actin complexes are dominated by different factors. This induces the structural polymorphism of polymer-actin complexes. Major factors to influence the polymorphism of polymer-actin complexes in polyelectrolyte system have been discussed. Our results indicate that the semi-flexible polyelectrolyte nature of F-actins is important for controlling the morphology and growth of actin architectures in cell.


    Institute of Scientific and Technical Information of China (English)

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


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

  11. Encapsulation of Bacterial Spores in Nanoorganized Polyelectrolyte Shells (Postprint) (United States)


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

  12. Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers. (United States)

    Peyratout, Claire S; Dähne, Lars


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

  13. Towards a Complexity Theory of Randomized Search Heuristics: Ranking-Based Black-Box Complexity

    CERN Document Server

    Doerr, Benjamin


    Randomized search heuristics are a broadly used class of general-purpose algorithms. Analyzing them via classical methods of theoretical computer science is a growing field. A big step forward would be a useful complexity theory for such algorithms. We enrich the two existing black-box complexity notions due to Wegener and other authors by the restrictions that not actual objective values, but only the relative quality of the previously evaluated solutions may be taken into account by the algorithm. Many randomized search heuristics belong to this class of algorithms. We show that the new ranking-based model gives more realistic complexity estimates for some problems, while for others the low complexities of the previous models still hold.

  14. A Knowledge base model for complex forging die machining


    Mawussi, Kwamiwi; Tapie, Laurent


    International audience; Recent evolutions on forging process induce more complex shape on forging die. These evolutions, combined with High Speed Machining (HSM) process of forging die lead to important increase in time for machining preparation. In this context, an original approach for generating machining process based on machining knowledge is proposed in this paper. The core of this approach is to decompose a CAD model of complex forging die in geometric features. Technological data and ...

  15. Safety control program for complex system based on behavior science

    Institute of Scientific and Technical Information of China (English)

    LIANG Mei-jian; YANG Guang; CHEN Da-wei


    To control complex system's safety effectively,safety control program was supported based on the principles of behavioral science that shapes organizational behavior,and organizational behavior produced individual behavior.The program can be structured into a model that consists of three modules including individual behavior rectification,organization behavior diagnosis and model of safety culture.The research result not only reveals the deep cause of complex system accidents but also provides structural descriptions with the accidents cause.

  16. Safety control program for complex system based on behavior science

    Institute of Scientific and Technical Information of China (English)

    LIANG Mei-jian; YANG Guang; CHEN Da-wei


    To control complex system's safety effectively, safety control program was supported based on the principles of behavioral science that shapes organizational be-havior, and organizational behavior produced individual behavior. The program can be structured into a model that consists of three modules including individual behavior rectifi-cation, organization behavior diagnosis and model of safety culture. The research result not only reveals the deep cause of complex system accidents but also provides structural descriptions with the accidents cause.

  17. EPR spectra of four gadolinium complexes with Schiff bases

    Institute of Scientific and Technical Information of China (English)

    姚克敏; 陈德余; 封子先; 李冬成; 冯亚菲; 何玲


    EPR spectra of four new gadolinium complexes with Schiff bases in polycrystalline powder and those of these complexes in three organic solvents were investigated at different temperatures. It has been observed for the first time that their freezing solution spectra are quite different from each other. In THF one peak was observed only, but there were three peaks and typical "U" spectral features appearing in DMF and DMSO at low temperatures. On the basis of spin Hamiltonian of S = 7/2 system, the correlations between crystal field strength in complexes and local symmetry around Gd3+ ions are discussed.

  18. Synthesis, characterization and antimicrobial studies of Schiff base complexes (United States)

    Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali


    The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

  19. Pathway-based analysis tools for complex diseases: a review. (United States)

    Jin, Lv; Zuo, Xiao-Yu; Su, Wei-Yang; Zhao, Xiao-Lei; Yuan, Man-Qiong; Han, Li-Zhen; Zhao, Xiang; Chen, Ye-Da; Rao, Shao-Qi


    Genetic studies are traditionally based on single-gene analysis. The use of these analyses can pose tremendous challenges for elucidating complicated genetic interplays involved in complex human diseases. Modern pathway-based analysis provides a technique, which allows a comprehensive understanding of the molecular mechanisms underlying complex diseases. Extensive studies utilizing the methods and applications for pathway-based analysis have significantly advanced our capacity to explore large-scale omics data, which has rapidly accumulated in biomedical fields. This article is a comprehensive review of the pathway-based analysis methods-the powerful methods with the potential to uncover the biological depths of the complex diseases. The general concepts and procedures for the pathway-based analysis methods are introduced and then, a comprehensive review of the major approaches for this analysis is presented. In addition, a list of available pathway-based analysis software and databases is provided. Finally, future directions and challenges for the methodological development and applications of pathway-based analysis techniques are discussed. This review will provide a useful guide to dissect complex diseases.

  20. Pathway-based Analysis Tools for Complex Diseases: A Review

    Directory of Open Access Journals (Sweden)

    Lv Jin


    Full Text Available Genetic studies are traditionally based on single-gene analysis. The use of these analyses can pose tremendous challenges for elucidating complicated genetic interplays involved in complex human diseases. Modern pathway-based analysis provides a technique, which allows a comprehensive understanding of the molecular mechanisms underlying complex diseases. Extensive studies utilizing the methods and applications for pathway-based analysis have significantly advanced our capacity to explore large-scale omics data, which has rapidly accumulated in biomedical fields. This article is a comprehensive review of the pathway-based analysis methods—the powerful methods with the potential to uncover the biological depths of the complex diseases. The general concepts and procedures for the pathway-based analysis methods are introduced and then, a comprehensive review of the major approaches for this analysis is presented. In addition, a list of available pathway-based analysis software and databases is provided. Finally, future directions and challenges for the methodological development and applications of pathway-based analysis techniques are discussed. This review will provide a useful guide to dissect complex diseases.

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

    Institute of Scientific and Technical Information of China (English)

    张波; 蔡钧; 刘洪来; 胡英


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

  2. Recent advances in agent-based complex automated negotiation

    CERN Document Server

    Ito, Takayuki; Zhang, Minjie; Fujita, Katsuhide; Robu, Valentin


    This book covers recent advances in Complex Automated Negotiations as a widely studied emerging area in the field of Autonomous Agents and Multi-Agent Systems. The book includes selected revised and extended papers from the 7th International Workshop on Agent-Based Complex Automated Negotiation (ACAN2014), which was held in Paris, France, in May 2014. The book also includes brief introductions about Agent-based Complex Automated Negotiation which are based on tutorials provided in the workshop, and brief summaries and descriptions about the ANAC'14 (Automated Negotiating Agents Competition) competition, where authors of selected finalist agents explain the strategies and the ideas used by them. The book is targeted to academic and industrial researchers in various communities of autonomous agents and multi-agent systems, such as agreement technology, mechanism design, electronic commerce, related areas, as well as graduate, undergraduate, and PhD students working in those areas or having interest in them.

  3. The model of a polyelectrolyte solution with explicit account of counterions within a self-consistent field theory (United States)

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


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

  4. Complexation Between Cationic Diblock Copolymers and Plasmid DNA (United States)

    Jung, Seyoung; Reineke, Theresa; Lodge, Timothy

    Deoxyribonucleic acids (DNA), as polyanions, can spontaneously bind with polycations to form polyelectrolyte complexes. When the polycation is a diblock copolymer with one cationic block and one uncharged hydrophilic block, the polyelectrolyte complexes formed with plasmid DNA (pDNA) are often colloidally stable, and show great promise in the field of polymeric gene therapy. While the resulting properties (size, stability, and toxicity to biological systems) of the complexes have been studied for numerous cationic diblocks, the fundamentals of the pDNA-diblock binding process have not been extensively investigated. Herein, we report how the cationic block content of a diblock influences the pDNA-diblock interactions. pDNA with 7164 base pairs and poly(2-deoxy-2-methacrylamido glucopyranose)-block-poly(N-(2-aminoethyl) methacrylamide) (PMAG-b-PAEMA) are used as the model pDNA and cationic diblock, respectively. To vary the cationic block content, two PMAG-b-PAEMA copolymers with similar PMAG block lengths but distinct PAEMA block lengths and a PAEMA homopolymer are utilized. We show that the enthalpy change from pDNA-diblock interactions is dependent on the cationic diblock composition, and is closely associated with both the binding strength and the pDNA tertiary structure.

  5. Local algorithm for computing complex travel time based on the complex eikonal equation (United States)

    Huang, Xingguo; Sun, Jianguo; Sun, Zhangqing


    The traditional algorithm for computing the complex travel time, e.g., dynamic ray tracing method, is based on the paraxial ray approximation, which exploits the second-order Taylor expansion. Consequently, the computed results are strongly dependent on the width of the ray tube and, in regions with dramatic velocity variations, it is difficult for the method to account for the velocity variations. When solving the complex eikonal equation, the paraxial ray approximation can be avoided and no second-order Taylor expansion is required. However, this process is time consuming. In this case, we may replace the global computation of the whole model with local computation by taking both sides of the ray as curved boundaries of the evanescent wave. For a given ray, the imaginary part of the complex travel time should be zero on the central ray. To satisfy this condition, the central ray should be taken as a curved boundary. We propose a nonuniform grid-based finite difference scheme to solve the curved boundary problem. In addition, we apply the limited-memory Broyden-Fletcher-Goldfarb-Shanno technology for obtaining the imaginary slowness used to compute the complex travel time. The numerical experiments show that the proposed method is accurate. We examine the effectiveness of the algorithm for the complex travel time by comparing the results with those from the dynamic ray tracing method and the Gauss-Newton Conjugate Gradient fast marching method.

  6. Local algorithm for computing complex travel time based on the complex eikonal equation. (United States)

    Huang, Xingguo; Sun, Jianguo; Sun, Zhangqing


    The traditional algorithm for computing the complex travel time, e.g., dynamic ray tracing method, is based on the paraxial ray approximation, which exploits the second-order Taylor expansion. Consequently, the computed results are strongly dependent on the width of the ray tube and, in regions with dramatic velocity variations, it is difficult for the method to account for the velocity variations. When solving the complex eikonal equation, the paraxial ray approximation can be avoided and no second-order Taylor expansion is required. However, this process is time consuming. In this case, we may replace the global computation of the whole model with local computation by taking both sides of the ray as curved boundaries of the evanescent wave. For a given ray, the imaginary part of the complex travel time should be zero on the central ray. To satisfy this condition, the central ray should be taken as a curved boundary. We propose a nonuniform grid-based finite difference scheme to solve the curved boundary problem. In addition, we apply the limited-memory Broyden-Fletcher-Goldfarb-Shanno technology for obtaining the imaginary slowness used to compute the complex travel time. The numerical experiments show that the proposed method is accurate. We examine the effectiveness of the algorithm for the complex travel time by comparing the results with those from the dynamic ray tracing method and the Gauss-Newton Conjugate Gradient fast marching method.

  7. Influence of higher valent ions on flexible polyelectrolyte stiffness and counter-ion distribution. (United States)

    Chremos, Alexandros; Douglas, Jack F


    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.

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

    Directory of Open Access Journals (Sweden)

    Miguel A. Zanuttini


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

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

    CERN Document Server

    Wang, Yong-Lei; Lu, Zhong-Yuan; 10.1016/


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

  10. Charge regulation and local dielectric function in planar polyelectrolyte brushes. (United States)

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


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

  11. Study of sporadical properties of crosslinked polyelectrolyte multilayers (United States)

    Balu, Deebika

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

  12. Optimization-based topology identification of complex networks

    Institute of Scientific and Technical Information of China (English)

    Tang Sheng-Xue; Chen Li; He Yi-Gang


    In many cases,the topological structures of a complex network are unknown or uncertain,and it is of significance to identify the exact topological structure.An optimization-based method of identifying the topological structure of a complex network is proposed in this paper.Identification of the exact network topological structure is converted into a minimal optimization problem by using the estimated network.Then,an improved quantum-behaved particle swarm optimization algorithm is used to solve the optimization problem.Compared with the previous adaptive synchronizationbased method,the proposed method is simple and effective and is particularly valid to identify the topological structure of synchronization complex networks.In some cases where the states of a complex network are only partially observable,the exact topological structure of a network can also be identified by using the proposed method.Finally,numerical simulations are provided to show the effectiveness of the proposed method.

  13. [A complexity-based approach to zoonoses in Colombia]. (United States)

    Agudelo-Suárez, Angela N


    The present reflection was aimed at making a contribution towards improving control policy and programs integrality and efficacy in an attempt to answer the following question, "How can understanding zoonoses in Colombia be approached from a complexity-based approach?" The first part of this article examines zoonoses as a complex problem and the reiterated tendency of control policy and programs to deal with them as a simple problem, involving unidisciplinary and reductionist responses. The current status of complexity is synthesized as a paradigm, as are the advantages of using it in analysis and formulating policy and interventions. Possible fields of work are proposed for development when approaching zoonoses in Colombia from a complexity science viewpoint.

  14. Potential Use of Polyelectrolyte Multilayer thin Films in Vascular Tissue Engineering:Evaluation of the Viability and Adhesion of Endothelial Cells

    Institute of Scientific and Technical Information of China (English)

    Cédric; BOURA; Halima; KERDJOUDJ; Vanessa; MOBY; Pierre; SCHAAJ; Jean; Claude; VOEGEL; Jean-Franois; STOLTZ; Patrick; MENU


    1 IntroductionA method in vascular tissue engineering to obtain hemocompatible synthetic prosthesis consists to cover the luminal surface by a monolayer of endothelial cells (ECs). Nevertheless, the surface of current prosthesis does not favour the development of an ECs monolayer. Recently, a new versatile method of self-assembled architectures based on the alternate adsorption of polycations and polyanions has been developed to lead to the build-up of multilayered polyelectrolyte films (MPF). This new type...

  15. Disaster Rescue Simulation based on Complex Adaptive Theory

    Directory of Open Access Journals (Sweden)

    Feng Jiang


    Full Text Available Disaster rescue is one of the key measures of disaster reduction. The rescue process is a complex process with the characteristics of large scale, complicate structure, non-linear. It is hard to describe and analyze them with traditional methods. Based on complex adaptive theory, this paper analyzes the complex adaptation of the rescue process from seven features: aggregation, nonlinearity, mobility, diversity, tagging, internal model and building block. With the support of Repast platform, an agent-based model including rescue agents and victim agents was proposed. Moreover, two simulations with different parameters are employed to examine the feasibility of the model. As a result, the proposed model has been shown that it is efficient in dealing with the disaster rescue simulation and can provide the reference for making decisions.

  16. Novel insights in agent-based complex automated negotiation

    CERN Document Server

    Lopez-Carmona, Miguel; Ito, Takayuki; Zhang, Minjie; Bai, Quan; Fujita, Katsuhide


    This book focuses on all aspects of complex automated negotiations, which are studied in the field of autonomous agents and multi-agent systems. This book consists of two parts. I: Agent-Based Complex Automated Negotiations, and II: Automated Negotiation Agents Competition. The chapters in Part I are extended versions of papers presented at the 2012 international workshop on Agent-Based Complex Automated Negotiation (ACAN), after peer reviews by three Program Committee members. Part II examines in detail ANAC 2012 (The Third Automated Negotiating Agents Competition), in which automated agents that have different negotiation strategies and are implemented by different developers are automatically negotiated in the several negotiation domains. ANAC is an international competition in which automated negotiation strategies, submitted by a number of universities and research institutes across the world, are evaluated in tournament style. The purpose of the competition is to steer the research in the area of bilate...

  17. Field theoretic simulations of the interfacial properties of complex coacervates (United States)

    Riggleman, Robert; Fredrickson, Glenn


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

  18. Synthesis of Chiral Metal Complexes of Unsymmetrical Schiff Bases

    Institute of Scientific and Technical Information of China (English)

    SONG; Bo


    Recently, in asymmetric catalyst research the great developments of chiral Salen complexes have been made, but the report on unsymmetrical schiff bases is deficient. The unsymmetrical schiff bases complexes are an effective system in catalytically selective Olefin-epoxidations1. At the same time, unsymmetrical schiff bases was immobilized onto polymer supports for heterogenization2. The potential benefits of the catalyst include facilitation of catalyst separation from reagents, simplification of methods for catalyst recycle, and the possible adaptation of the immobilized catalyst to continuous-flow processes. A series of new unsymmetrical schiff bases was synthesized to study the relations between unsymmetry and enantioselectivity and select better catalyst. The following is the route:  ……

  19. Polyelectrolyte Conformation, Interactions and Hydrodynamics as Studied by Light Scattering. (United States)

    Ghosh, Snehasish

    Polyelectrolyte conformation, interactions and hydrodynamics show a marked dependence on the ionic strength (C_{rm s}) of the medium, the concentration (C_{rm p}) of the polymer itself and their charge density (xi). The apparent electrostatic persistence length obtained from static light scattering varied approximately as the inverse square root of C _{rm s} for highly pure, high molecular weight hyaluronate (HA) as well as for variably ionized acrylamide/sodium acrylate copolymers (NaPAA), and linearly with xi. The experimental values of persistence length and second virial coefficient (A_2) are compared to predictions from theories based on the Debye-Huckel approximation for the Poisson-Boltzmann equation and on excluded-volume. Although the mean square radius of gyration () depended strongly on C _{rm s}. decreasing with increasing C_{rm s} for both HA and NaPAA indicating clear evidence of polyion expansion, dynamic light scattering values of the translational diffusion coefficient (D) remains constant when extrapolated to infinite polymer concentration for both the polymers. The behavior of D is compared to predictions from coupled mode theory in the linear limit. The effects of NaOH on the conformations, interactions, diffusion and hydrolysis rates of HA are characterized in detail using static, dynamic and time-dependent light scattering supplemented by size exclusion chromatography (SEC). For the HA , A_2 and the hydrolysis rates all resemble superposing titration curves, while the D remains independent of both the concentration of NaOH, and the contraction of . The indication is that the interactions, conformations and the hydrolysis rates are all controlled by the titration of the HA hydroxyl groups by the NaOH to yield -O ^-, which (i) destroys single strand hydrogen bonds, leading to de-stiffening and contraction of the HA coil and a large decrease in intermolecular interaction, and (ii) slowly depolymerizes HA. The experimental results of HA

  20. Mössbauer investigation of novel pentadentate schiff base complexes (United States)

    Heyer, L.; Dreyer, B.; Preiss, A.; Menze, M.; Klimke, S.; Jahns, M.; Sindelar, R.; Klingelhöfer, G.; O. Costa, B. F.; Renz, F.


    We synthesised a series of seven mononuclear and two trinuclear Schiff base coordination compounds. All nine complexes have been analysed by Mössbauer and IR spectroscopy. The Mössbauer spectra reveal a doublet, which are related to the high spin state (S = 5/2) of the iron(III) centres.

  1. Model-based safety architecture framework for complex systems

    NARCIS (Netherlands)

    Schuitemaker, K.; Rajabalinejad, M.; Braakhuis, J.G.; Podofilini, Luca; Sudret, Bruno; Stojadinovic, Bozidar; Zio, Enrico; Kröger, Wolfgang


    The shift to transparency and rising need of the general public for safety, together with the increasing complexity and interdisciplinarity of modern safety-critical Systems of Systems (SoS) have resulted in a Model-Based Safety Architecture Framework (MBSAF) for capturing and sharing architectural

  2. Complexity, Networking, & Effects-Based Approaches to Operations (United States)


    40 Figure 10. Miller’s Living Systems Model ....................................47 Figure 11. State versus Non- State Living Systems...human organizations and to apply it in an effects-based context. State and non- state living systems The model described above extrapolates quite... STATE LIVING SYSTEMS MODEL 52 Complexity, Networking, and Effects-Based Approaches to Operations The living systems model organizations such as the

  3. Novel measures based on the Kolmogorov complexity for use in complex system behavior studies and time series analysis

    CERN Document Server

    Mihailovic, Dragutin T; Nikolic-Djoric, Emilija; Arsenic, Ilija


    We have proposed novel measures based on the Kolmogorov complexity for use in complex system behavior studies and time series analysis. We have considered background of the Kolmogorov complexity and also we have discussed meaning of the physical as well as other complexities. To get better insights into the complexity of complex systems and time series analysis we have introduced the three novel measures based on the Kolmogorov complexity: (i) the Kolmogorov complexity spectrum, (ii) the Kolmogorov complexity spectrum highest value and (iii) the overall Kolmogorov complexity. The characteristics of these measures have been tested using a generalized logistic equation. Finally, the proposed measures have been applied on different time series originating from: the model output (the biochemical substance exchange in a multi-cell system), four different geophysical phenomena (dynamics of: river flow, long term precipitation, indoor 222Rn concentration and UV radiation dose) and economy (stock prices dynamics). Re...

  4. Confidence bounds of recurrence-based complexity measures

    Energy Technology Data Exchange (ETDEWEB)

    Schinkel, Stefan [Interdisciplinary Centre for Dynamics of Complex Systems, University of Potsdam (Germany)], E-mail:; Marwan, N. [Interdisciplinary Centre for Dynamics of Complex Systems, University of Potsdam (Germany); Potsdam Institute for Climate Impact Research (PIK) (Germany); Dimigen, O. [Department of Psychology, University of Potsdam (Germany); Kurths, J. [Potsdam Institute for Climate Impact Research (PIK) (Germany); Department of Physics, Humboldt University at Berlin (Germany)


    In the recent past, recurrence quantification analysis (RQA) has gained an increasing interest in various research areas. The complexity measures the RQA provides have been useful in describing and analysing a broad range of data. It is known to be rather robust to noise and nonstationarities. Yet, one key question in empirical research concerns the confidence bounds of measured data. In the present Letter we suggest a method for estimating the confidence bounds of recurrence-based complexity measures. We study the applicability of the suggested method with model and real-life data.

  5. Disk-like Tiles Derived from Complex Bases

    Institute of Scientific and Technical Information of China (English)

    Jun LUO; Zuo Ling ZHOU


    For each positive integer k, the radix representation of the complex numbers in the base-k + i gives rise to a lattice self-affine tile Tk in the plane, which consists of all the complex numbers that can be expressed in the form ∑j≥1 dj(-k + i)-j, where dj ∈ {0, 1,2,……,k2}. We prove that Tk is homeomorphic to the closed unit disk {z ∈ C: |z| ≤ 1} if and only if k ≠ 2.

  6. Evaluating complex community-based health promotion: addressing the challenges. (United States)

    Jolley, Gwyneth


    Community-based health promotion is poorly theorised and lacks an agreed evidence-base. This paper examines characteristics of community-based health promotion and the challenges they present to evaluation. A review of health promotion evaluation leads to an exploration of more recent approaches, drawing on ideas from complexity theory and developmental evaluation. A reflexive analysis of three program evaluations previously undertaken as an evaluation consultant is used to develop a conceptual model to help in the design and conduct of health promotion evaluation. The model is further explored by applying it retrospectively to one evaluation. Findings suggest that the context-contingent nature of health promotion programs; turbulence in the community context and players; multiple stakeholders, goals and strategies; and uncertainty of outcomes all contribute to the complexity of interventions. Bringing together insights from developmental evaluation and complexity theory can help to address some evaluation challenges. The proposed model emphasises recognising and responding to changing contexts and emerging outcomes, providing rapid feedback and facilitating reflexive practice. This will enable the evaluator to gain a better understanding of the influence of context and other implementation factors in a complex setting. Use of the model should contribute to building cumulative evidence and knowledge in order to identify the principles of health promotion effectiveness that may be transferable to new situations.

  7. A new entropy based method for computing software structural complexity

    CERN Document Server

    Roca, J L


    In this paper a new methodology for the evaluation of software structural complexity is described. It is based on the entropy evaluation of the random uniform response function associated with the so called software characteristic function SCF. The behavior of the SCF with the different software structures and their relationship with the number of inherent errors is investigated. It is also investigated how the entropy concept can be used to evaluate the complexity of a software structure considering the SCF as a canonical representation of the graph associated with the control flow diagram. The functions, parameters and algorithms that allow to carry out this evaluation are also introduced. After this analytic phase follows the experimental phase, verifying the consistency of the proposed metric and their boundary conditions. The conclusion is that the degree of software structural complexity can be measured as the entropy of the random uniform response function of the SCF. That entropy is in direct relation...

  8. Electrodeposition of a palladium nanocatalyst by ion confinement in polyelectrolyte multilayers. (United States)

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


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

  9. Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates. (United States)

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


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

  10. Complex-wave retrieval based on blind signal separation

    Institute of Scientific and Technical Information of China (English)

    Xiaodong Chai; Chengpeng Zhou; Zhaoyan Feng; Yinhua Wang; Yansheng Zuo


    In the process of the reconstruction of digital holography, the traditional methods of diffraction and filtration are commonly adopted to recover the original complex-wave signal. Influenced by twin-image and zero-order terms, the above-mentioned methods, however, either limit the field of vision or result in the loss of the amplitude and phase. A new method for complex-wave retrieval is presented, which is based on blind signal separation. Three frames of holograms are captured by a charge coupled device (CCD)camera to form an observation signal. The term containing only amplitude and phase of complex-wave is separated, by means of independent component analysis, from the observation signal, which effectively eliminates the zero-order term. Finally, the complex-wave retrieval of pure phase wavefront is achieved.Experimental results show that this method can better recover the amplitude and phase of the original complex-wave even when there is a frequency spectrum mixture in the hologram.

  11. Pyrazine-based organometallic complex: synthesis, characterization, and supramolecular chemistry. (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Rajamohanan, P R; Das, Neeladri


    The design, synthesis, and characterization of a new pyrazine-based ditopic platinum(II) organometallic complex are reported. The molecular structure of the organoplatinum pyrazine dipod was determined by single-crystal X-ray crystallography. The potential utility of this organometallic ditopic acceptor as a building block in the construction of neutral metallasupramolecular macrocycles containing the pyrazine motif was explored. Pyrazine motifs containing supramolecules were characterized by multinuclear NMR (including (1)H DOSY), mass spectrometry, and elemental analysis. The geometry of each supramolecular framework was optimized by employing the PM6 semiempirical molecular orbital method to predict its shape and size. The ability of the pyrazine-based organoplatinum complex to act as a host for nitroaromatic guest (2,4-dinitrotoluene and PA) molecules was explored by isothermal titration calorimetry (ITC). The binding stoichiometry and thermodynamic parameters of these host-guest complexation reactions were evaluated using ITC. Theoretical calculations were performed to obtain insight into the binding pattern between the organometallic host and nitroaromatic guests. The preferable binding propensity of the binding sites of complex 1 for both nitroaromatics (PA and 2,4-dinitrotoluene) determined by molecular simulation studies corroborates well with the experimental results as obtained by ITC experiments.

  12. Polyelectrolyte coating of ferumoxytol nanoparticles for labeling of dendritic cells (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  14. Fabrication of ultrathin polyelectrolyte fibers and their controlled release properties. (United States)

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


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

  15. Encapsulation of curcumin in polyelectrolyte nanocapsules and their neuroprotective activity (United States)

    Szczepanowicz, Krzysztof; Jantas, Danuta; Piotrowski, Marek; Staroń, Jakub; Leśkiewicz, Monika; Regulska, Magdalena; Lasoń, Władysław; Warszyński, Piotr


    Poor water solubility and low bioavailability of lipophilic drugs can be potentially improved with the use of delivery systems. In this study, encapsulation of nanoemulsion droplets was utilized to prepare curcumin nanocarriers. Nanosize droplets containing the drug were encapsulated in polyelectrolyte shells formed by the layer-by-layer (LbL) adsorption of biocompatible polyelectrolytes: poly-L-lysine (PLL) and poly-L-glutamic acid (PGA). The size of synthesized nanocapsules was around 100 nm. Their biocompatibility and neuroprotective effects were evaluated on the SH-SY5Y human neuroblastoma cell line using cell viability/toxicity assays (MTT reduction, LDH release). Statistically significant toxic effect was clearly observed for PLL coated nanocapsules (reduction in cell viability about 20%-60%), while nanocapsules with PLL/PGA coating did not evoke any detrimental effects on SH-SY5Y cells. Curcumin encapsulated in PLL/PGA showed similar neuroprotective activity against hydrogen peroxide (H2O2)-induced cell damage, as did 5 μM curcumin pre-dissolved in DMSO (about 16% of protection). Determination of concentration of curcumin in cell lysate confirmed that curcumin in nanocapsules has cell protective effect in lower concentrations (at least 20 times) than when given alone. Intracellular mechanisms of encapsulated curcumin-mediated protection engaged the prevention of the H2O2-induced decrease in mitochondrial membrane potential (MMP) but did not attenuate Reactive Oxygen Species (ROS) formation. The obtained results indicate the utility of PLL/PGA shell nanocapsules as a promising, alternative way of curcumin delivery for neuroprotective purposes with improved efficiency and reduced toxicity.

  16. A Knowledge Based Interactive System for Complex Product Design (United States)

    Gayretli, Ahmet

    This research presents a new Artificial Intelligence (AI) based product development approach for integrating mechanical design with electronic design to improve design and manufacture of electromechanical products by avoiding design conflicts in the early stages of the design process. The proposed approach has been implemented in a Delphi based environment integrated with a CAD system. The system assists designers from different disciplines in evaluating complex systems as far as parts relation, potential effects on each other, conflict management, costs, weight and physical constraints are concerned in the early design stages. This helps the designers to avoid design iterations leading to longer lead-time, hence increased cost. The developed system enables to rapidly develop and evaluate new complex products and add new functions to the existing products within given constraints.

  17. Next frontier in agent-based complex automated negotiation

    CERN Document Server

    Ito, Takayuki; Zhang, Minjie; Robu, Valentin


    This book focuses on automated negotiations based on multi-agent systems. It is intended for researchers and students in various fields involving autonomous agents and multi-agent systems, such as e-commerce tools, decision-making and negotiation support systems, and collaboration tools. The contents will help them to understand the concept of automated negotiations, negotiation protocols, negotiating agents’ strategies, and the applications of those strategies. In this book, some negotiation protocols focusing on the multiple interdependent issues in negotiations are presented, making it possible to find high-quality solutions for the complex agents’ utility functions. This book is a compilation of the extended versions of the very best papers selected from the many that were presented at the International Workshop on Agent-Based Complex Automated Negotiations.

  18. Complexity and agent-based modelling in urban research

    DEFF Research Database (Denmark)

    Fertner, Christian

    Urbanisation processes are results of a broad variety of actors or actor groups and their behaviour and decisions based on different experiences, knowledge, resources, values etc. The decisions done are often on a micro/individual level but resulting in macro/collective behaviour. In urban research...... influence on the bigger system. Traditional scientific methods or theories often tried to simplify, not accounting complex relations of actors and decision-making. The introduction of computers in simulation made new approaches in modelling, as for example agent-based modelling (ABM), possible, dealing...... of complexity for a majority of science, there exists a huge number of scientific articles, books, tutorials etc. to these topics which doesn’t make it easy for a novice in the field to find the right literature. The literature used gives an optimistic outlook for the future of this methodology, although ABM...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Low Complexity for Scalable Video Coding Extension of H.264 based on the Complexity of Video

    Directory of Open Access Journals (Sweden)

    Mayada Khairy


    Full Text Available Scalable Video Coding (SVC / H.264 is one type of video compression techniques. Which provided more reality in dealing with video compression to provide an efficient video coding based on H.264/AVC. This ensures higher performance through high compression ratio. SVC/H.264 is a complexity technique whereas the takes considerable time for computation the best mode of macroblock and motion estimation through using the exhaustive search techniques. This work reducing the processing time through matching between the complexity of the video and the method of selection macroblock and motion estimation. The goal of this approach is reducing the encoding time and improving the quality of video stream the efficiency of the proposed approach makes it suitable for are many applications as video conference application and security application.

  1. Modifying the adsorption properties of anionic surfactants onto hydrophilic silica using the pH dependence of the polyelectrolytes PEI, ethoxylated PEI, and polyamines. (United States)

    Zhang, Xiaoli; Taylor, Diana; Thomas, Robert; Penfold, Jeffrey; Tucker, Ian


    The manipulation of the adsorption of the anionic surfactant, sodium dodecyl sulfate, SDS, onto hydrophilic silica by the polyelectrolytes, polyethyleneimine, PEI, ethoxylated PEI, and the polyamine, pentaethylenehexamine, has been studied using neutron reflectometry. The adsorption of a thin PEI layer onto hydrophilic silica promotes a strong reversible adsorption of the SDS through surface charge reversal induced by the PEI at pH 7. At pH 2.4, a much thicker adsorbed PEI layer is partially swelled by the SDS, and the SDS adsorption is now no longer completely reversible. At pH 10, there is some penetration of SDS and solvent into a thin PEI layer, and the SDS adsorption is again not fully reversible. Ethoxylation of the PEI (PEI-EO(1) and PEI-EO(7)) results in a much weaker and fragile PEI and SDS adsorption at both pH 3 and pH 10, and both polymer and surfactant desorb at higher surfactant concentrations (>critical micellar concentration, cmc). For the polyamine, pentaethylenehexamine, adsorption of a layer of intermediate thickness is observed at pH 10, but at pH 3, no polyamine adsorption is evident; and at both pH 3 and pH 10, no SDS adsorption is observed. The results presented here show that, for the amine-based polyelectrolytes, polymer architecture, molecular weight, and pH can be used to manipulate the surface affinity for anionic surfactant (SDS) adsorption onto polyelectrolyte-coated hydrophilic silica surfaces.

  2. Clustering based segmentation of text in complex color images

    Institute of Scientific and Technical Information of China (English)

    毛文革; 王洪滨; 张田文


    We propose a novel scheme based on clustering analysis in color space to solve text segmentation in complex color images. Text segmentation includes automatic clustering of color space and foreground image generation. Two methods are also proposed for automatic clustering: The first one is to determine the optimal number of clusters and the second one is the fuzzy competitively clustering method based on competitively learning techniques. Essential foreground images obtained from any of the color clusters are combined into foreground images. Further performance analysis reveals the advantages of the proposed methods.

  3. Trajectory-Based Complexity (TBX): A Modified Aircraft Count to Predict Sector Complexity During Trajectory-Based Operations (United States)

    Prevot, Thomas; Lee, Paul U.


    In this paper we introduce a new complexity metric to predict -in real-time- sector complexity for trajectory-based operations (TBO). TBO will be implemented in the Next Generation Air Transportation System (NextGen). Trajectory-Based Complexity (TBX) is a modified aircraft count that can easily be computed and communicated in a TBO environment based upon predictions of aircraft and weather trajectories. TBX is scaled to aircraft count and represents an alternate and additional means to manage air traffic demand and capacity with more consideration of dynamic factors such as weather, aircraft equipage or predicted separation violations, as well as static factors such as sector size. We have developed and evaluated TBX in the Airspace Operations Laboratory (AOL) at the NASA Ames Research Center during human-in-the-loop studies of trajectory-based concepts since 2009. In this paper we will describe the TBX computation in detail and present the underlying algorithm. Next, we will describe the specific TBX used in an experiment at NASA's AOL. We will evaluate the performance of this metric using data collected during a controller-inthe- loop study on trajectory-based operations at different equipage levels. In this study controllers were prompted at regular intervals to rate their current workload on a numeric scale. When comparing this real-time workload rating to the TBX values predicted for these time periods we demonstrate that TBX is a better predictor of workload than aircraft count. Furthermore we demonstrate that TBX is well suited to be used for complexity management in TBO and can easily be adjusted to future operational concepts.

  4. Condensation of nonstochiometric DNA/polycation complexes by divalent cations. (United States)

    Budker, Vladimir; Trubetskoy, Vladimir; Wolff, Jon A


    This study found that divalent cations induced the further condensation of partially condensed DNA within nonstochiometric polycation complexes. The addition of a few mmol of a divalent cation such as calcium reduced by half the inflection point at which DNA became fully condensed by poly-L-lysine (PLL) and a variety of other polycations. The effect on DNA condensation was initially observed using a new method, which is based on the concentration-dependent self-quenching of fluorescent moieties (e.g., rhodamine) covalently linked to the DNA backbone at relatively high densities. Additional analyses, which employed ultracentrifugation, dynamic light scattering, agarose gel electrophoresis, and atomic force microscopy, confirmed the effect of divalent cations. These results provide an additional accounting of the process by which divalent cations induce greater chromatin compaction that is based on the representation of chromatin fibers as a nonstoichiometric polyelectrolyte complex. They also offer a new approach to assemble nonviral vectors for gene therapy.

  5. Polyelectrolytes: Influence on Evaporative Self-Assembly of Particles and Assembly of Multilayers with Polymers, Nanoparticles and Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Tatiana Bukreeva


    Full Text Available Assembling polyelectrolyte multilayers in a bottom-up approach is reported for polymers, particles, nanoparticles, and carbon nanotubes. Effects of polyelectrolyte multilayers on evaporative self-assembly of particles, which are of interest to a number of applications including photonic crystals, films and substrates, are investigated. Polyelectrolyte multilayer coatings bring multifunctionality to spherical particles and planar films. Studying the construction of polyelectrolyte assemblies is convenient in the planar layout: it is reported here for incorporation of gold and magnetic nanoparticles as well as of carbon nanotubes. Gold nanoparticles concentration is controlled within the films. Potential applications of both spherical structures and planar films are highlighted.

  6. Inferring drug-disease associations based on known protein complexes. (United States)

    Yu, Liang; Huang, Jianbin; Ma, Zhixin; Zhang, Jing; Zou, Yapeng; Gao, Lin


    Inferring drug-disease associations is critical in unveiling disease mechanisms, as well as discovering novel functions of available drugs, or drug repositioning. Previous work is primarily based on drug-gene-disease relationship, which throws away many important information since genes execute their functions through interacting others. To overcome this issue, we propose a novel methodology that discover the drug-disease association based on protein complexes. Firstly, the integrated heterogeneous network consisting of drugs, protein complexes, and disease are constructed, where we assign weights to the drug-disease association by using probability. Then, from the tripartite network, we get the indirect weighted relationships between drugs and diseases. The larger the weight, the higher the reliability of the correlation. We apply our method to mental disorders and hypertension, and validate the result by using comparative toxicogenomics database. Our ranked results can be directly reinforced by existing biomedical literature, suggesting that our proposed method obtains higher specificity and sensitivity. The proposed method offers new insight into drug-disease discovery. Our method is publicly available at

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

    Directory of Open Access Journals (Sweden)

    Maximilian Zerball


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

  8. Formation of multilayers by star polyelectrolytes: effect of number of arms on chain interpenetration. (United States)

    Chen, Fenggui; Liu, Guangming; Zhang, Guangzhao


    We have investigated the influence of number of arms on chain interpenetration in the growth of star poly[2-(dimethylamino)ethyl methacrylate] (PDEM)/star poly(acrylic acid) (PAA) multilayers using a quartz crystal microbalance with dissipation (QCM-D). The oscillations in the changes of dissipation and frequency reflect the chain interpenetration and the variation of the mass of multilayer, respectively. The QCM-D results demonstrate that the growth of multilayers has two different mechanisms in terms of chain interpenetration. That is, the arm chains of star PDEM insert into a predeposited PAA layer to form a swollen multilayer, but the complex of star PAA with predeposited star PDEM is an "octopus-like" structure forming a dense multilayer. The transition between these two penetration modes is controlled by the number of arms in the star polyelectrolytes. As the number of arms of either PAA or PDEM increases, it becomes more difficult for star PDEM to penetrate into the PAA layer, but star PAA can more easily penetrate into the PDEM layer. According to atomic force microscopy and water contact angle measurements, all eight-bilayer multilayer surfaces have similar roughness values, and the surface wettability of the multilayers is dominated by the outermost PDEM layer.

  9. Synthesis and Reactivity of Tripodal Complexes Containing Pendant Bases

    Energy Technology Data Exchange (ETDEWEB)

    Blacquiere, Johanna M.; Pegis, Michael L.; Raugei, Simone; Kaminsky, Werner; Forget, Amelie; Cook, Sarah; Taguchi, Taketo; Borovik, Andrew S.; Mayer, James M.


    The synthesis of a new tripodal ligand family is reported, with tertiary-amine groups in the second-coordination sphere. The ligands are tris(amido)amine derivatives, with the pendant amines attached via a peptide coupling strategy. They were designed to be used in new catalysts for the oxygen reduction reaction (ORR), in which the pendant acid/base group could improve catalyst performance. Two members of the new ligand family were each metallated with Co(II) and Zn(II) to afford trigonal monopyramidal complexes. Reaction of the cobalt complexes, [Co(L)]-, with dioxygen reversibly generates a small amount of a Co(III)-superoxo species, which was characterized by EPR. Protonation of the zinc complex Zn[N{CH2CH2NC(O)CH2N(CH2Ph)2}3)-– ([Zn(TNBn)]-) with one equivalent of acid occurs with displacement and dissociation of an amide ligand. Addition of excess acid to the any of the complexes [M(L)]- results in complete proteolysis and formation of the ligands H3L. This decomposition limits the use of these complexes as catalysts for the ORR. An alternative ligand with two pyridyl arms was also prepared but could not be metallated. These studies highlight the importance of stability of the primary-coordination sphere of ORR electrocatalysts to both oxidative and acidic conditions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  10. A complex network-based importance measure for mechatronics systems (United States)

    Wang, Yanhui; Bi, Lifeng; Lin, Shuai; Li, Man; Shi, Hao


    In view of the negative impact of functional dependency, this paper attempts to provide an alternative importance measure called Improved-PageRank (IPR) for measuring the importance of components in mechatronics systems. IPR is a meaningful extension of the centrality measures in complex network, which considers usage reliability of components and functional dependency between components to increase importance measures usefulness. Our work makes two important contributions. First, this paper integrates the literature of mechatronic architecture and complex networks theory to define component network. Second, based on the notion of component network, a meaningful IPR is brought into the identifying of important components. In addition, the IPR component importance measures, and an algorithm to perform stochastic ordering of components due to the time-varying nature of usage reliability of components and functional dependency between components, are illustrated with a component network of bogie system that consists of 27 components.

  11. Langmuir-Blodgett Films from Schiff Base Aluminium ( Ⅲ ) Complex

    Institute of Scientific and Technical Information of China (English)


    The characteristics of the LB films of Schiff base aluminium( Ⅲ ), tris(2-hydroxy-5-nitro N-dodecyl-benzylideneaminato) aluminium ( Ⅲ ) [Al (TA 12) 3], were studied. The surface pres sure-area(r-A) isotherm of Al(TA12)3 in the pure water subphase was investigated. The molec ular area, 0.48 nm2, is one-third of the expected value that indicates the formation of an aggre gate. The Langmuir-Blodgett (LB) films of Al(TA12) 3 were transferred and characterized. The UV-Vis spectra and the AFM image both confirmed that the J-aggregates formed. The polarized UV-Vis spectra indicated that the complex plane had to be oriented with an angle of about 30° to the substrate surface. The IR spectra suggested that the complexation took place between aluminium ions and the oxygen atoms of the ligand rather than the nitrogen atom.

  12. H.264 SVC Complexity Reduction Based on Likelihood Mode Decision

    Directory of Open Access Journals (Sweden)

    L. Balaji


    Full Text Available H.264 Advanced Video Coding (AVC was prolonged to Scalable Video Coding (SVC. SVC executes in different electronics gadgets such as personal computer, HDTV, SDTV, IPTV, and full-HDTV in which user demands various scaling of the same content. The various scaling is resolution, frame rate, quality, heterogeneous networks, bandwidth, and so forth. Scaling consumes more encoding time and computational complexity during mode selection. In this paper, to reduce encoding time and computational complexity, a fast mode decision algorithm based on likelihood mode decision (LMD is proposed. LMD is evaluated in both temporal and spatial scaling. From the results, we conclude that LMD performs well, when compared to the previous fast mode decision algorithms. The comparison parameters are time, PSNR, and bit rate. LMD achieve time saving of 66.65% with 0.05% detriment in PSNR and 0.17% increment in bit rate compared with the full search method.

  13. Community Clustering Algorithm in Complex Networks Based on Microcommunity Fusion

    Directory of Open Access Journals (Sweden)

    Jin Qi


    Full Text Available With the further research on physical meaning and digital features of the community structure in complex networks in recent years, the improvement of effectiveness and efficiency of the community mining algorithms in complex networks has become an important subject in this area. This paper puts forward a concept of the microcommunity and gets final mining results of communities through fusing different microcommunities. This paper starts with the basic definition of the network community and applies Expansion to the microcommunity clustering which provides prerequisites for the microcommunity fusion. The proposed algorithm is more efficient and has higher solution quality compared with other similar algorithms through the analysis of test results based on network data set.

  14. A Knowledge base model for complex forging die machining

    CERN Document Server

    Mawussi, Kwamiwi; 10.1016/j.cie.2011.02.016


    Recent evolutions on forging process induce more complex shape on forging die. These evolutions, combined with High Speed Machining (HSM) process of forging die lead to important increase in time for machining preparation. In this context, an original approach for generating machining process based on machining knowledge is proposed in this paper. The core of this approach is to decompose a CAD model of complex forging die in geometric features. Technological data and topological relations are aggregated to a geometric feature in order to create machining features. Technological data, such as material, surface roughness and form tolerance are defined during forging process and dies design. These data are used to choose cutting tools and machining strategies. Topological relations define relative positions between the surfaces of the die CAD model. After machining features identification cutting tools and machining strategies currently used in HSM of forging die, are associated to them in order to generate mac...

  15. Fractal Analysis Based on Hierarchical Scaling in Complex Systems

    CERN Document Server

    Chen, Yanguang


    A fractal is in essence a hierarchy with cascade structure, which can be described with a set of exponential functions. From these exponential functions, a set of power laws indicative of scaling can be derived. Hierarchy structure and spatial network proved to be associated with one another. This paper is devoted to exploring the theory of fractal analysis of complex systems by means of hierarchical scaling. Two research methods are utilized to make this study, including logic analysis method and empirical analysis method. The main results are as follows. First, a fractal system such as Cantor set is described from the hierarchical angle of view; based on hierarchical structure, three approaches are proposed to estimate fractal dimension. Second, the hierarchical scaling can be generalized to describe multifractals, fractal complementary sets, and self-similar curve such as logarithmic spiral. Third, complex systems such as urban system are demonstrated to be a self-similar hierarchy. The human settlements i...

  16. Fast complex memory polynomial-based adaptive digital predistorter (United States)

    Singh Sappal, Amandeep; Singh Patterh, Manjeet; Sharma, Sanjay


    Today's 3G wireless systems require both high linearity and high power amplifier (PA) efficiency. The high peak-to-average ratios of the digital modulation schemes used in 3G wireless systems require that the RF PA maintain high linearity over a large range while maintaining this high efficiency; these two requirements are often at odds with each other with many of the traditional amplifier architectures. In this article, a fast and easy-to-implement adaptive digital predistorter has been presented for Wideband Code Division Multiplexed signals using complex memory polynomial work function. The proposed algorithm has been implemented to test a Motorola LDMOSFET PA. The proposed technique also takes care of the memory effects of the PA, which have been ignored in many proposed techniques in the literature. The results show that the new complex memory polynomial-based adaptive digital predistorter has better linearisation performance than conventional predistortion techniques.

  17. Design of ANSYS-based Cathode with Complex Groove

    Institute of Scientific and Technical Information of China (English)

    范植坚; 赵刚刚; 张丽娟


    The profile of cathode with complex groove needs to be modified time after time during design of electrochemical machining (ECM) cathode.A design scheme using finite element method (FEM) for cathode with complex profile is put forward to shorten the period of cathode design.Based on Laplace equation,the potential distribution on parameter-transformation model was calculated by using ANSYS,which is compared to the potential distribution calculated by substituting conductivity and current efficiency into Laplace equation.According to the difference between the results calculated and simulated by ANSYS,the cathode profile was modified by adjusting the cathode boundary.The experiments show that the dimensions and shape of workpiece machined by numerically simulated cathode conform well with the blueprint.

  18. Synchronization criteria based on a general complex dynamical network model

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jian-lin; WANG Chang-jian; XU Cong-fu


    Many complex dynamical networks display synchronization phenomena. We introduce a general complex dynamical network model. The model is equivalent to a simple vector model of adopting the Kronecker product. Some synchronization criteria, including time-variant networks and time-varying networks, are deduced based on Lyapunov's stability theory, and they are proven on the condition of obtaining a certain synchronous solution of an isolated cell. In particular, the inner-coupling matrix directly determines the synchronization of the time-invariant network; while for a time-varying periodic dynamical network, the asymptotic stability of a synchronous solution is determined by a constant matrix which is related to the fundamental solution matrices of the linearization system. Finally, illustrative examples are given to validate the results.

  19. Efficient target control of complex networks based on preferential matching

    CERN Document Server

    Zhang, Xizhe; Lv, Tianyang


    Controlling a complex network towards a desire state is of great importance in many applications. Existing works present an approximate algorithm to find the driver nodes used to control partial nodes of the network. However, the driver nodes obtained by this algorithm depend on the matching order of nodes and cannot get the optimum results. Here we present a novel algorithm to find the driver nodes for target control based on preferential matching. The algorithm elaborately arrange the matching order of nodes in order to minimize the size of the driver nodes set. The results on both synthetic and real networks indicate that the performance of proposed algorithm are better than the previous one. The algorithm may have various application in controlling complex networks.

  20. Effect of complexation conditions on microcapsulation of Lactobacillus acidophilus in xanthan-chitosan polyelectrolyte complex gels

    Directory of Open Access Journals (Sweden)

    He Chen


    Full Text Available Background. Lactobacillus acidophilus has become increasingly popular because of their beneficial effects on health of their host, and are called proboscis. In order to exert benefi cial effects for probiotics, they must be able to tolerate the acidic conditions of the stomach environment and the bile in the small intestine. Microencapsulated form has received reasonable attention, since it can protect probiotic organisms against an unfavourable environment, and to allow their release in a viable and metabolically active state in the intestine. The aim of this study was to investigate some factores, such as chitosan solution pH and concentration, xanthan concentration, cell suspension-xanthan ratio, mixed bacteria glue liquid-chitosan ratio, which impacted the process of microencapsulation of L. acidophilus. Material and methods. In this study, L. acidophilus was immobilized with xanthan⁄chitosan gel using extrusion method. The viable counts and encapsulation yield of L. acidophilus encapsulated in different chitosan solution pH (4.5, 5, 5.5 and 6, in different chitosan concentration (0.5%, 0.7%, 0.9% and 1.1%, in different xanthan concentration (0.5%, 0.7%, 0.9% and 1.1%, in different cell suspension-xanthan ratios (1:5, 1:10, 1:15 and 1:20, in different mixed bacteria glue liquid-chitosan ratios (1:3, 1:4, 1:5 and 1:6, have been investigated by single factor experiment method. Results. The optimum conditions of microencapsulated L. acidophilus have been observed. The optimum chitosan solution pH for L. acidophilus was 5.5; the optimum chitosan concentration was 0.9%; the optimum xanthan concentration was 0.7%; the optimum cell suspension-xanthan ratio was 1:10; the optimum mixed bacteria glue liquid-chitosan ratio was 1:3. Conclusions. These results will be helpful to further optimize the process of L. acidophilus microencapsulation, and provide reference for obtaining higher viable counts and entrapped yield of L. acidophilus microcapsules.

  1. Complex coacervates formed across liquid interfaces

    NARCIS (Netherlands)

    Monteillet, H.; Kleijn, J.M.; Sprakel, J.; Leermakers, F.A.M.


    The Scheutjens-Fleer self-consistent field (SF-SCF) theory is used to study complexation between two oppositely charged polyelectrolytes across an interface formed by two solvents, here called oil and water. The focus is on the composition and the lateral stability of such interfacial coacervate. On

  2. Complex coacervates formed across liquid interfaces

    NARCIS (Netherlands)

    Monteillet, H.; Kleijn, J.M.; Sprakel, J.; Leermakers, F.A.M.


    The Scheutjens-Fleer self-consistent field (SF-SCF) theory is used to study complexation between two oppositely charged polyelectrolytes across an interface formed by two solvents, here called oil and water. The focus is on the composition and the lateral stability of such interfacial coacervate.

  3. Airworthiness Compliance Verification Method Based on Simulation of Complex System

    Institute of Scientific and Technical Information of China (English)

    XU Haojun; LIU Dongliang; XUE Yuan; ZHOU Li; MIN Guilong


    A study is conducted on a new airworthiness compliance verification method based on pilot-aircraft-environment complex system simulation.Verification scenarios are established by “block diagram” method based on airworthiness criteria..A pilot-aircraft-environment complex model is set up and a virtual flight testing method based on connection of MATLAB/Simulink and Flightgear is proposed.Special researches are conducted on the modeling of pilot manipulation stochastic parameters and manipulation in critical situation.Unfavorable flight factors of certain scenario are analyzed,and reliability modeling of important system is researched.A distribution function of small probability event and the theory on risk probability measurement are studied.Nonlinear function is used to depict the relationship between the cumulative probability and the extremum of the critical parameter.A synthetic evaluation model is set up,modified genetic algorithm (MGA) is applied to ascertaining the distribution parameter in the model,and amore reasonable result is obtained.A clause about vehicle control functions (VCFs) verification in MIL-HDBK-516B is selected as an example to validate the practicability of the method.

  4. Increased complexity of gene structure and base composition in vertebrates

    Institute of Scientific and Technical Information of China (English)

    Ying Wu; Huizhong Yuan; Shengjun Tan; Jian-Qun Chen; Dacheng Tian; Haiwang Yang


    How the structure and base composition of genes changed with the evolution of vertebrates remains a puzzling question. Here we analyzed 895 orthologous protein-coding genes in six multicellular animals: human, chicken, zebrafish, sea squirt, fruit fly, and worm. Our analyses reveal that many gene regions, particularly intron and 3' UTR, gradually expanded throughout the evolution of vertebrates from their invertebrate ancestors, and that the number of exons per gene increased. Studies based on all protein-coding genes in each genome provide consistent results.We also find that GC-content increased in many gene regions (especially 5' UTR) in the evolution of endotherms, except in coding-exons.Analysis of individual genomes shows that 3′ UTR demonstrated stronger length and CC-content correlation with intron than 5' UTR, and gene with large intron in all six species demonstrated relatively similar GC-content. Our data indicates a great increase in complexity in vertebrate genes and we propose that the requirement for morphological and functional changes is probably the driving force behind the evolution of structure and base composition complexity in multicellular animal genes.

  5. Predicting links based on knowledge dissemination in complex network (United States)

    Zhou, Wen; Jia, Yifan


    Link prediction is the task of mining the missing links in networks or predicting the next vertex pair to be connected by a link. A lot of link prediction methods were inspired by evolutionary processes of networks. In this paper, a new mechanism for the formation of complex networks called knowledge dissemination (KD) is proposed with the assumption of knowledge disseminating through the paths of a network. Accordingly, a new link prediction method-knowledge dissemination based link prediction (KDLP)-is proposed to test KD. KDLP characterizes vertex similarity based on knowledge quantity (KQ) which measures the importance of a vertex through H-index. Extensive numerical simulations on six real-world networks demonstrate that KDLP is a strong link prediction method which performs at a higher prediction accuracy than four well-known similarity measures including common neighbors, local path index, average commute time and matrix forest index. Furthermore, based on the common conclusion that an excellent link prediction method reveals a good evolving mechanism, the experiment results suggest that KD is a considerable network evolving mechanism for the formation of complex networks.

  6. Rate control algorithm based on frame complexity estimation for MVC (United States)

    Yan, Tao; An, Ping; Shen, Liquan; Zhang, Zhaoyang


    Rate control has not been well studied for multi-view video coding (MVC). In this paper, we propose an efficient rate control algorithm for MVC by improving the quadratic rate-distortion (R-D) model, which reasonably allocate bit-rate among views based on correlation analysis. The proposed algorithm consists of four levels for rate bits control more accurately, of which the frame layer allocates bits according to frame complexity and temporal activity. Extensive experiments show that the proposed algorithm can efficiently implement bit allocation and rate control according to coding parameters.

  7. Audiovisual Quality Fusion based on Relative Multimodal Complexity

    DEFF Research Database (Denmark)

    You, Junyong; Korhonen, Jari; Reiter, Ulrich


    In multimodal presentations the perceived audiovisual quality assessment is significantly influenced by the content of both the audio and visual tracks. Based on our earlier subjective quality test for finding the optimal trade-off between audio and video quality, this paper proposes a novel method...... designed auditory and visual features, the relative complexity analysis model across sensory modalities is proposed for deriving the fusion parameter. Experimental results have demonstrated that the content adaptive fusion parameter can improve the prediction accuracy of objective audiovisual quality...

  8. A complexity-based approach to batterer intervention programmes. (United States)

    Medina-Maldonado, Venus E; Medina-Maldonado, Rossana; Parada-Cores, Germán


    This paper was aimed at providing opinion by adopting a complexity-based approach to coordinating nursing science and psychology concerning psycho-educational intervention for batterers regarding their partner or ex-partner. Improving both disciplines' interrelationship should facilitate implementing relevant action, thereby engendering motivation for change in participants and modifying sexist attitudes and beliefs. The document has analyzed the importance of coordinating scientific disciplines' action and defined guidelines for an approach involving intervention as well as highlighting implications for practice and research.

  9. Experience-based exploration of complex energy systems



    In our energy-restricted world, planners and engineers have to cope with problems of CO2 emissions and oil- and gas-shortages. Many planning activities not captured under the heading of “futures studies” share common goals like dealing with an uncertain, complex future. We focus on two novel approaches: agent-based modelling and serious games. These approaches, even though they stem from the same general systems theory roots, allow its users to experience “reality” in different ways. This has...

  10. Intelligent Transportation Control based on Proactive Complex Event Processing

    Directory of Open Access Journals (Sweden)

    Wang Yongheng


    Full Text Available Complex Event Processing (CEP has become the key part of Internet of Things (IoT. Proactive CEP can predict future system states and execute some actions to avoid unwanted states which brings new hope to intelligent transportation control. In this paper, we propose a proactive CEP architecture and method for intelligent transportation control. Based on basic CEP technology and predictive analytic technology, a networked distributed Markov decision processes model with predicting states is proposed as sequential decision model. A Q-learning method is proposed for this model. The experimental evaluations show that this method works well when used to control congestion in in intelligent transportation systems.

  11. Visualization of Complex Networks Based on Dyadic Curvelet Transform

    Directory of Open Access Journals (Sweden)

    Kaoru Hirota


    Full Text Available A visualization method is proposed for understanding the structure of complex networks based on an extended Curvelet transform named Dyadic Curvelet Transform (DClet. The proposed visualization method comes to answer specific questions about structures of complex networks by mapping data into orthogonal localized events with a directional component via the Cartesian sampling sets of detail coefficients. It behaves in the same matter as human visual system, seeing in terms of segments and distinguishing them by scale and orientation. Compressing the network is another fact. The performance of the proposed method is evaluated by two different networks with structural properties of small world networks with N = 16 vertices, and a globally coupled network with size N = 1024 and 523 776 edges. As the most large scale real networks are not fully connected, it is tested on the telecommunication network of Iran as a real extremely complex network with 92 intercity switching vertices, 706 350 E1 traffic channels and 315 525 transmission channels. It is shown that the proposed method performs as a simulation tool for successfully design of network and establishing the necessary group sizes. It can clue the network designer in on all structural properties that network has.

  12. Conformational thermodynamics of biomolecular complexes: The histogram-based method (United States)

    Das, Amit; Sikdar, Samapan; Ghosh, Mahua; Chakrabarti, J.


    Conformational changes in biomacromolecules govern majority of biological processes. Complete characterization of conformational contributions to thermodynamics of complexation of biomacromolecules has been challenging. Although, advances in NMR relaxation experiments and several computational studies have revealed important aspects of conformational entropy changes, efficient and large-scale estimations still remain an intriguing facet. Recent histogram-based method (HBM) offers a simple yet rigorous route to estimate both conformational entropy and free energy changes from same set of histograms in an efficient manner. The HBM utilizes the power of histograms which can be generated as accurately as desired from an arbitrarily large sample space from atomistic simulation trajectories. Here we discuss some recent applications of the HBM, using dihedral angles of amino acid residues as conformational variables, which provide good measure of conformational thermodynamics of several protein-peptide complexes, obtained from NMR, metal-ion binding to an important metalloprotein, interfacial changes in protein-protein complex and insight to protein function, coupled with conformational changes. We conclude the paper with a few future directions worth pursuing.

  13. Poly-electrolytes for fuel cells: tools and methods for characterization; Polyelectrolytes pour piles a combustible: outils et methodes de caracterisation

    Energy Technology Data Exchange (ETDEWEB)

    Marechal, M.


    The research works reported in the manuscript are a contribution to the study of poly-electrolytes for Proton Exchange Membrane Fuel Cells (PEMFC). They are supported by two investigation tools, i.e. the study of model molecules and accurate conductivity measurements. With regard to the material science domain, the optimization of poly-sulfone sulfonation procedure allows chain breaking to be reduced and even eliminated while obtaining reproducible sulfonation degrees. It is thus possible to improve the mechanical properties of the dense membrane elaborated with these poly-electrolytes before performing the tests on the MEA (Membrane Electrode Assembly). In parallel, the functionalization of microporous silicon made it possible to prepare poly-electrolytes reinforced by the mechanical strength of the silicon separator. With regard to the physicochemical and electrochemical characterizations, the model molecules, with the same functions and groups than for associated polymers, make it possible to amplify the electrochemical or thermal phenomena vs. the corresponding polymers. Thus, they simulate an accelerated ageing of the poly-electrolytes. The development of a new conductivity measurement set allows conductivity to be obtained with a great accuracy, in a wide range of temperature and relative humidity. (author)

  14. SVD-based digital image watermarking using complex wavelet transform

    Indian Academy of Sciences (India)

    A Mansouri; A Mahmoudi Aznaveh; F Torkamani Azar


    A new robust method of non-blind image watermarking is proposed in this paper. The suggested method is performed by modification on singular value decomposition (SVD) of images in Complex Wavelet Transform (CWT) domain while CWT provides higher capacity than the real wavelet domain. Modification of the appropriate sub-bands leads to a watermarking scheme which favourably preserves the quality. The additional advantage of the proposed technique is its robustness against the most of common attacks. Analysis and experimental results show much improved performance of the proposed method in comparison with the pure SVD-based as well as hybrid methods (e.g. DWT-SVD as the recent best SVD-based scheme).

  15. Complexity

    CERN Document Server

    Gershenson, Carlos


    The term complexity derives etymologically from the Latin plexus, which means interwoven. Intuitively, this implies that something complex is composed by elements that are difficult to separate. This difficulty arises from the relevant interactions that take place between components. This lack of separability is at odds with the classical scientific method - which has been used since the times of Galileo, Newton, Descartes, and Laplace - and has also influenced philosophy and engineering. In recent decades, the scientific study of complexity and complex systems has proposed a paradigm shift in science and philosophy, proposing novel methods that take into account relevant interactions.

  16. The experimental study of polyelectrolyte coatings suitability for encapsulation of cells. (United States)

    Granicka, L H; Antosiak-Iwańska, M; Godlewska, E; Hoser, G; Strawski, M; Szklarczyk, M; Dudziński, K


    Living cells encapsulated in polymeric shells are receiving increasing attention because of their possible biotechnological and biomedical applications. The aim of this work is to evaluate how different polyelectrolyte coatings, characterized by different numbers of polyelectrolyte layers and by different polyelectrolyte conformations, affect the viability of encapsulated biological material. We demonstrate the ability to individually encapsulate HL-60 cells as well as rat pancreatic islets within polymeric shells consisting of different PE layers using the layer-by-layer process. Coating of HL-60 cells allows for surviving and functioning of cells for all applied PE as well as for different numbers of layers. The islets encapsulated in applied polyelectrolytes exhibited the lower level of mitochondrial activity as compared to non-encapsulated islets. Nevertheless, encapsulated islets exhibited comparable absorbance values during the whole period of culture. Polyelectrolyte coating seems to be a promising way of allowing capsule void volume minimization in a model of encapsulated biological material for local production of biologically active substances.

  17. Alternate drop coating for forming dual biointerfaces composed of polyelectrolyte multilayers. (United States)

    Watanabe, Junji; Shen, Heyun; Akashi, Mitsuru


    Two types of polyelectrolyte multilayers were formed on both sides of a quartz crystal microbalance (QCM) substrate by a novel alternate drop coating process. In this study, poly(diallyldimethylammonium chloride) (PDDA) and poly(sodium 4-styrene sulfonate) (PSS) were used as strong-strong polyelectrolytes. On the other hand, PDDA and poly(acrylic acid) (PAA) were used as strong-weak polyelectrolytes. The novel alternate drop coating process can separately fabricate each polyelectrolyte multilayer on both sides of the substrate. The substrate provides dual biointerfaces, both sides of which comprise different multilayers, by employing a combination of polymers. The formation of the multilayer by alternate drop coating was evaluated in terms of changes in the frequency of the QCM and model protein adsorption for proteins such as bovine serum albumin, and their characteristics were investigated with those of the conventional alternate adsorption process by performing dip coating. There was no significant difference between the surface properties resulting from the two formation conditions. This result strongly supported the fact that the multilayers fabricated by alternate drop coating were similar in quality to those fabricated by conventional dip coating. The resulting dual biointerfaces with polyelectrolyte multilayers provide alternative biofunctions in terms of individual protein loading. In summary, the novel alternate drop coating process for substrates is a good candidate for the preparation of dual biointerfaces in the biomedical field.

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

    Energy Technology Data Exchange (ETDEWEB)

    Celikkin, Nehar; Jakubcová, Lucie; Zenke, Martin [Institute for Biomedical Engineering, Department of Cell Biology, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Helmholtz Institute for Biomedical Engineering, RWTH Aachen University, Pauwelsstrasse 20, 52074 Aachen (Germany); Hoss, Mareike [Institute of Pathology, Electron Microscopy Facility, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Wong, John Erik, E-mail: [Chemical Process Engineering, RWTH Aachen University, Turmstrasse 46, 52056 Aachen (Germany); DWI – Leibniz Institute for Interactive Materials Research, Forckenbeckstrasse 50, Aachen (Germany); Hieronymus, Thomas, E-mail: [Institute for Biomedical Engineering, Department of Cell Biology, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Helmholtz Institute for Biomedical Engineering, RWTH Aachen University, Pauwelsstrasse 20, 52074 Aachen (Germany)


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

  19. Preparation of photoluminescent carbon dots-embedded polyelectrolyte microcapsules

    Institute of Scientific and Technical Information of China (English)

    Xiaoling Yang; Liming Peng; Jie Zong; Yihua Zhu


    Two types of photoluminescent carbon dots (CDs)-embedded polyelectrolyte (PE) microcapsules were successfully prepared via the layer-by-layer (LbL) assembly approach on sacrificial templates.For the first type,the PE microcapsules with CDs embedded in the cavity were produced from assembly of five pairs of poly(sodium 4-styrensulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) on CDs-pre-loaded meso-porous silica.For the second type,the PE microcapsules with CDs embedded in the wall were made of CDs and PAH,which were derived from SiO2 particles as templates.Microscope images confirmed the introduction of CDs into the two CDs-embedded microcapsules.These two microcapsules also retained the optical properties of free CDs.Photoluminescence spectra revealed that the two types of microcapsules had excitation-dependent photoluminescence behavior.When the excitation wavelength changed from 280 to 340 nm,photoluminescence emission peak of the PE microcapsules with CDs embedded in the cavity shifts from 369 to 377 nm,while for microcapsules with CDs embedded in the wall,emission peak shifts from 367 to 390 nm.Due to low toxicity,good hydrophilicity and photoluminescence properties of CDs,these two kinds of photo-luminescent microcapsules have competitive potential for application in carriers for imaging,drug delivery and biosensors.

  20. Polyelectrolyte Layer-by-Layer Assembly on Organic Electrochemical Transistors

    KAUST Repository

    Pappa, Anna-Maria


    Oppositely charged polyelectrolyte multilayers (PEMs) were built up in a layer-by-layer (LbL) assembly on top of the conducting polymer channel of an organic electrochemical transistor (OECT), aiming to combine the advantages of well-established PEMs with a high performance electronic transducer. The multilayered film is a model system to investigate the impact of biofunctionalization on the operation of OECTs comprising a poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) film as the electrically active layer. Understanding the mechanism of ion injection into the channel that is in direct contact with charged polymer films provides useful insights for novel biosensing applications such as nucleic acid sensing. Moreover, LbL is demonstrated to be a versatile electrode modification tool enabling tailored surface features in terms of thickness, softness, roughness, and charge. LbL assemblies built up on top of conducting polymers will aid the design of new bioelectronic platforms for drug delivery, tissue engineering, and medical diagnostics.

  1. Underwater Reversible Adhesion Between Oppositely Charged Weak Polyelectrolytes (United States)

    Alfhaid, Latifah; Geoghegan, Mark; Williams, Nicholas; Seddon, William


    Force-distance data has shown that the adhesion between two oppositely charged polyelectrolytes: poly(methacrylic acid) (PMAA, a polyacid) and poly[2-(diethylamino)ethyl methacrylate] (PDEAEMA, a polybase), was controllable by varying the pH level of their surrounding. Accordingly, adhesive force at the interface between these two polymers was higher inside basic surroundings at pH 6 and 7, and then it started to decrease at pH level below 3 and above 8. Stimulating adhesion between PMAA gel and PDEAEMA brushes by adding salt to their surrounded water has only a limited effect on the adhesive force between them, contradicting previous results. Increasing the molar concentration of sodium chloride (NaCl) in the surrounded water of these two polymers from 0.1 to 1M did not decrease the adhesion forces between a PMAA gel and a grafted PDEAEMA layer (brush). The JKR equation was used to evaluate the adhesion forces between the polymer gel and the brushes and it was observed that the adhesion increased with the elastic modulus of the gel decreased.

  2. Effect of Temperature on Polyelectrolyte Expansion of Lignosulfonate

    Directory of Open Access Journals (Sweden)

    Hao Li


    Full Text Available The temperature effect on the polyelectrolyte expansion of sodium lignosulfonate (SL was studied in the range of 20 to 38 °C. A narrow molecular-weight distribution fraction of sodium lignosulfonate was first obtained by gel column chromatography, which was suitable for the hydrodynamic radius (Rh measurement by dynamic light scattering (DLS. Dynamic light scattering experiments showed that the hydrodynamic radius of sodium lignosulfonate decreased with increasing temperature. Using a quartz crystal microbalance (QCM and atomic force microscopy (AFM, it was found that the adsorbed sodium lignosulfonate film lost water with increasing temperature and reabsorbed water with decreasing temperature. Surface tension and contact angle experiments showed that there were more hydrophobic groups on the surface of the sodium lignosulfonate molecule as the temperature increased. It can be concluded that the sodium lignosulfonate molecule shrank and became more hydrophobic with increasing temperature. Analysis suggests that the decreasing of the hydrogen-bond interactions between the sodium lignosulfonate molecule and water molecules with increasing temperature is the primary reason for the molecular conformation change of sodium lignosulfonate.

  3. Polyelectrolyte Microcapsules: Ion Distributions from a Poisson-Boltzmann Model (United States)

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


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

  4. Polyelectrolyte Multilayers: A Versatile Tool for Preparing Antimicrobial Coatings. (United States)

    Séon, Lydie; Lavalle, Philippe; Schaaf, Pierre; Boulmedais, Fouzia


    The prevention of pathogen colonization of medical implants represents a major medical and financial issue. The development of antimicrobial coatings aimed at protecting against such infections has thus become a major field of scientific and technological research. Three main strategies are developed to design such coatings: (i) the prevention of microorganisms adhesion and the killing of microorganisms (ii) by contact and (iii) by the release of active compounds in the vicinity of the implant. Polyelectrolyte multilayer (PEM) technology alone covers the entire widespread spectrum of functionalization possibilities. PEMs are obtained through the alternating deposition of polyanions and polycations on a substrate, and the great advantages of PEMs are that (i) they can be applied to almost any type of substrate whatever its shape and composition; (ii) various chemical, physicochemical, and mechanical properties of the coatings can be obtained; and (iii) active compounds can be embedded and released in a controlled manner. In this article we will give an overview of the field of PEMs applied to the design of antimicrobial coatings, illustrating the large versatility of the PEM technology.

  5. Lipid monolayers and adsorbed polyelectrolytes with different degrees of polymerization. (United States)

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


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


    Institute of Scientific and Technical Information of China (English)

    Qunying LIAO; Keqin FENG


    A formula on the complexity of the normal bases generated by prime Gauss period over finite fields is presented in terms of cyclotomic numbers. Then, the authors determine explicitly the complexity of such normal bases and their dual bases in several cases where the related cyclotomic numbers have been calculated. Particularly, the authors find several series of such normal bases with low complexity.

  7. In vitro and in vivo characterisation of a novel peptide delivery system: amphiphilic polyelectrolyte-salmon calcitonin nanocomplexes. (United States)

    Cheng, Woei-Ping; Thompson, Colin; Ryan, Sinéad M; Aguirre, Tanira; Tetley, Laurence; Brayden, David J


    The cationic peptide, salmon calcitonin (sCT) was complexed with the cationic amphiphilic polyelectrolyte, poly(allyl)amine, grafted with palmitoyl and quaternary ammonium moieties at pH 5.0 and 7.4 to yield particulates (sCT-QPa). The complexes were approximately 200 nm in diameter, had zeta potentials ranging from +20 to +50 mV, and had narrow polydispersity indices (PDIs). Differential scanning calorimetry revealed the presence of an interaction between sCT and QPa in the complexes. Electron microscopy confirmed the zeta-size data and revealed a vesicular bilayer structure with an aqueous core. Tyrosine- and Nile red fluorescence indicated that the complexes retained gross physical stability for up to 7 days, but that the pH 5.0 complexes were more stable. The complexes were more resistant to peptidases, serum and liver homogenates compared to free sCT. In vitro bioactivity was measured by cAMP production in T47D cells and the complexes had EC50 values in the nM range. While free sCT was unable to generate cAMP following storage for 7 days, the complexes retained approximately 33% activity. When the complexes were injected intravenously to rats, free and complexed sCT (pH 5.0 and 7.4) but not QPa reduced serum calcium over 120 min. Free and complexed sCT but not QPa also reduced serum calcium over 240 min following intra-jejunal administration. In conclusion, sCT-QPa nanocomplexes that have been synthesised are stable, bioactive and resistant to a range of peptidases. These enhanced features suggest that they may have the potential for improved efficacy when formulated for injected and oral delivery.

  8. Structural changes in a polyelectrolyte multilayer assembly investigated by reflection absorption infrared spectroscopy and sum frequency generation spectroscopy. (United States)

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


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

  9. Conjugated Polyelectrolytes with Imidazolium Solubilizing Groups. Properties and Application to Photodynamic Inactivation of Bacteria. (United States)

    Parthasarathy, Anand; Pappas, Harry C; Hill, Eric H; Huang, Yun; Whitten, David G; Schanze, Kirk S


    This article reports an investigation of the photophysical properties and the light- and dark-biocidal activity of two poly(phenyleneethynylene) (PPE)-based conjugated polyelectrolytes (CPEs) bearing cationic imidazolium solubilizing groups. The two polymers feature the same PPE-type backbone, but they differ in the frequency of imidazoliums on the chains: PIM-4 features two imidazolium units on every phenylene repeat, whereas PIM-2 contains two imidazolium units on every other phenylene unit. Both polymers are very soluble in water and polar organic solvents, but their propensity to aggregate in water differs with the density of the imidazolium units. The polymers are highly fluorescent, and they exhibit the amplified quenching effect when exposed to a low concentration of anionic electron-acceptor anthraquinone disulfonate. The CPEs are also quenched by a relatively low concentration of pyrophosphate by an aggregation-induced quenching mechanism. The biocidal activity of the cationic imidazolium CPEs was studied against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria in the dark and under blue-light illumination. Both polymers are effective biocides, exhibiting greater than 3 log kill with 30-60 min of light exposure at concentrations of ≤10 μg mL(-1).

  10. Polyelectrolyte microcapsules as ionic liquid reservoirs within ionomer membrane to confer high anhydrous proton conductivity (United States)

    Zhang, Haoqin; Wu, Wenjia; Li, Yifan; Liu, Yong; Wang, Jingtao; Zhang, Bing; Liu, Jindun


    Herein, novel composite membranes are prepared by embedding methacrylic acid polyelectrolyte microcapsules (PMCs) into sulfonated poly(ether ether ketone) (SPEEK) matrix, followed by impregnating imidazole-type ionic liquids (ILs). Within the composite membrane, the lumens of PMCs act as IL reservoirs, which provide large space for IL storage and thus significantly elevate the IL uptake. The IL leaching measurement suggests that the cross-linked shells of PMCs manipulate the IL release, endowing the composite membrane with high IL retention. Moreover, the high IL retention renders the composite membrane more anhydrous hopping sites (e.g., the imidazole groups on IL and the acid-base pairs between imidazole and sulfonic acid groups), imparting a facilitated proton conduction via Grotthuss mechanism. In particular, the composite membrane containing 12% PMCs achieves a high anhydrous proton conductivity of 33.7 mS cm-1 at 150 °C. The same membrane also exhibits a surprising steady-state IL retention of 36.9% after leaching in liquid water.

  11. Optimal control of complex networks based on matrix differentiation (United States)

    Li, Guoqi; Ding, Jie; Wen, Changyun; Pei, Jing


    Finding the key node set to be connected to external control sources so as to minimize the energy for controlling a complex network, known as the minimum-energy control problem, is of critical importance but remains open. We address this critical problem where matrix differentiation is involved. To this end, the differentiation of energy/cost function with respect to the input matrix is obtained based on tensor analysis, and the Hessian matrix is compressed from a fourth-order tensor. Normalized projected gradient method (NPGM) normalized projected trust-region method (NPTM) are proposed with established convergence property. We show that NPGM is more computationally efficient than NPTM. Simulation results demonstrate satisfactory performance of the algorithms, and reveal important insights as well. Two interesting phenomena are observed. One is that the key node set tends to divide elementary paths equally. The other is that the low-degree nodes may be more important than hubs from a control point of view, indicating that controlling hub nodes does not help to lower the control energy. These results suggest a way of achieving optimal control of complex networks, and provide meaningful insights for future researches.

  12. Proteomics based compositional analysis of complex cellulase-hemicellulase mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Chundawat, Shishir P.; Lipton, Mary S.; Purvine, Samuel O.; Uppugundla, Nirmal; Gao, Dahai; Balan, Venkatesh; Dale, Bruce E.


    Efficient deconstruction of cellulosic biomass to fermentable sugars for fuel and chemical production is accomplished by a complex mixture of cellulases, hemicellulases and accessory enzymes (e.g., >50 extracellular proteins). Cellulolytic enzyme mixtures, produced industrially mostly using fungi like Trichoderma reesei, are poorly characterized in terms of their protein composition and its correlation to hydrolytic activity on cellulosic biomass. The secretomes of commercial glycosyl hydrolase producing microbes was explored using a proteomics approach with high-throughput quantification using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Here, we show that proteomics based spectral counting approach is a reasonably accurate and rapid analytical technique that can be used to determine protein composition of complex glycosyl hydrolase mixtures that also correlates with the specific activity of individual enzymes present within the mixture. For example, a strong linear correlation was seen between Avicelase activity and total cellobiohydrolase content. Reliable, quantitative and cheaper analytical methods that provide insight into the cellulosic biomass degrading fungal and bacterial secretomes would lead to further improvements towards commercialization of plant biomass derived fuels and chemicals.

  13. Structure-based control of complex networks with nonlinear dynamics

    CERN Document Server

    Zañudo, Jorge G T; Albert, Réka


    Given the network of interactions underlying a complex system, what can we learn about controlling such a system solely from its structure? Over a century of research in control theory has given us tools to answer this question, which were widely applied in science and engineering. Yet the current tools do not always consider the inherently nonlinear dynamics of real systems and the naturally occurring system states in their definition of "control", a term whose interpretation varies across disciplines. Here we use a new mathematical framework for structure-based control of networks governed by a broad class of nonlinear dynamics that includes the major dynamic models of biological, technological, and social processes. This framework provides realizable node overrides that steer a system towards any of its natural long term dynamic behaviors and which are guaranteed to be effective regardless of the dynamic details and parameters of the underlying system. We use this framework on several real networks, compar...

  14. Ground-based complex for checking the optical system (United States)

    Grebenyuk, V.; Boreiko, V.; Dmitrotsa, A.; Gorbunov, N.; Khrenov, B.; Klimov, P.; Lavrova, M.; Popescu, E. M.; Sabirov, B.; Tkachenko, A.; Tkachev, L.; Volvach, A.; Yashin, I.


    The purpose TUS space experiment is to study cosmic rays of ultrahigh energies produced by extensive air showers from space. The concentrator is located on satellite, made in the form of the Fresnel mirror towards the earth's atmosphere, the focus of which is a photodetector. The angle of view of the mirror is ±4.5° that for a given height of the orbit corresponds to the area 80 × 80 km2 on ground. The ground complex consisting of a number of stations, to check the optical system of the experiment is created, (their location and the amount will be determined after the launch of the satellite based on its actual orbit).

  15. The Architecture of a Complex GIS & Spreadsheet Based DSS

    Directory of Open Access Journals (Sweden)

    Dinu Airinei


    Full Text Available The decision support applications available on today market use to combine the decision analysis of historical databased on On-Line Analytical Processing (OLAP products or spreadsheet pivot tables with some new reporting facilities as alerts or key performance indicators available in portal dashboards or in complex spreadsheet-like reports, both corresponding to a new approach of the field called Business Intelligence. Moreover the geographical features of GIS added to DSS applications become more and more required by many kinds of businesses. In fact they are more useful this way than as distinctive parts.The paper tries to present a certain DSS architecture based on the association between such approaches and technologies. The particular examples are meant to support all the theoretical arguments and to complete the understanding of the interaction schemas available.

  16. The guitar chord-generating algorithm based on complex network (United States)

    Ren, Tao; Wang, Yi-fan; Du, Dan; Liu, Miao-miao; Siddiqi, Awais


    This paper aims to generate chords for popular songs automatically based on complex network. Firstly, according to the characteristics of guitar tablature, six chord networks of popular songs by six pop singers are constructed and the properties of all networks are concluded. By analyzing the diverse chord networks, the accompaniment regulations and features are shown, with which the chords can be generated automatically. Secondly, in terms of the characteristics of popular songs, a two-tiered network containing a verse network and a chorus network is constructed. With this network, the verse and chorus can be composed respectively with the random walk algorithm. Thirdly, the musical motif is considered for generating chords, with which the bad chord progressions can be revised. This method can make the accompaniments sound more melodious. Finally, a popular song is chosen for generating chords and the new generated accompaniment sounds better than those done by the composers.

  17. Coherent pair production in deformed crystals with a complex base

    CERN Document Server

    Mkrtchyan, A R; Saharian, A A


    We investigate the coherent electron-positron pair creation by high-energy photons in a periodically deformed single crystal with a complex base. The formula for the corresponding differential cross-section is derived for an arbitrary deformation field. The conditions are specified under which the influence of the deformation is considerable. The case is considered in detail when the photon enters into the crystal at small angles with respect to a crystallographic axis. The results of the numerical calculations are presented for $\\mathrm{SiO}_{2}$ single crystal and Moliere parametrization of the screened atomic potentials in the case of the deformation field generated by the acoustic wave of $S$ type. In dependence of the parameters, the presence of deformation can either enhance or reduce the pair creation cross-section. This can be used to control the parameters of the positron sources for storage rings and colliders.

  18. Polyelectrolyte properties of filamentous biopolymers and their consequences in biological fluids. (United States)

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


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

  19. Reversible Self-Assembly of Hydrophilic Inorganic Polyelectrolytes into Highly Conservative, Vesicle-like Structures (United States)

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


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

  20. Recent Progress and Perspectives in the Electrokinetic Characterization of Polyelectrolyte Films

    Directory of Open Access Journals (Sweden)

    Ralf Zimmermann


    Full Text Available The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid films and for a polyelectrolyte bilayer consisting of poly(ethylene imine and poly(acrylic acid. Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers.

  1. Synthesis and characterization of CdS-polyelectrolyte-Bi2S3 thin film by SILAR (United States)

    Desale, Dipalee J.; Shaikh, Shaheed; Siddiqui, Farha; AnilGhule, Ravikiran Birajadar; Sharma, Ramphal


    CdS-Polyelectrolyte-Bi2S3 was grown by cost effective successive ionic layer adsorption and reaction method (SILAR) on glass substrate. The polyelectrolyte used as a protecting layer for excessive ionic loss during the exchange reaction between the cation and anions of the reactants. Thin films was characterized for structural, morphological and an I-V characteristic. The X-ray diffraction pattern (XRD) pattern shows that, CdS-Polyelectrolyte-Bi2S3 thin films have mixed phase of hexagonal and orthorhombic crystal structures corresponding to CdS and Bi2S3 respectively. Scanning electron microscopy (SEM) corresponds deposition of the material along with the presence of bundle like shape is observed in thin film. The I-V measurement under dark and illumination to 100 mW/cm2 shows increase in photoconductivity.

  2. Oxidative peptide /and amide/ formation from Schiff base complexes (United States)

    Strehler, B. L.; Li, M. P.; Martin, K.; Fliss, H.; Schmid, P.


    One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.

  3. Dynamical complexity in the perception-based network formation model (United States)

    Jo, Hang-Hyun; Moon, Eunyoung


    Many link formation mechanisms for the evolution of social networks have been successful to reproduce various empirical findings in social networks. However, they have largely ignored the fact that individuals make decisions on whether to create links to other individuals based on cost and benefit of linking, and the fact that individuals may use perception of the network in their decision making. In this paper, we study the evolution of social networks in terms of perception-based strategic link formation. Here each individual has her own perception of the actual network, and uses it to decide whether to create a link to another individual. An individual with the least perception accuracy can benefit from updating her perception using that of the most accurate individual via a new link. This benefit is compared to the cost of linking in decision making. Once a new link is created, it affects the accuracies of other individuals' perceptions, leading to a further evolution of the actual network. As for initial actual networks, we consider both homogeneous and heterogeneous cases. The homogeneous initial actual network is modeled by Erdős-Rényi (ER) random networks, while we take a star network for the heterogeneous case. In any cases, individual perceptions of the actual network are modeled by ER random networks with controllable linking probability. Then the stable link density of the actual network is found to show discontinuous transitions or jumps according to the cost of linking. As the number of jumps is the consequence of the dynamical complexity, we discuss the effect of initial conditions on the number of jumps to find that the dynamical complexity strongly depends on how much individuals initially overestimate or underestimate the link density of the actual network. For the heterogeneous case, the role of the highly connected individual as an information spreader is also discussed.

  4. Biofunctionalization of polyelectrolyte microcapsules with biotinylated polyethylene glycol-grafted liposomes. (United States)

    Gao, Jie; Reibetanz, Uta; Venkatraman, Subbu; Neu, Björn


    Hollow polyelectrolyte microcapsules (PEMC) are prepared using layer-by-layer self-assembly of polyelectrolytes on melamine formaldehyde templates, followed by template dissolution, and subsequent coating with biotinylated polyethylene glycol-grafted liposomes. These potential site-specific carrier systems show a high specificity for NeutrAvidin binding and a strong resistance against unspecific protein binding. It is concluded that this design with NeutrAvidin as the outermost layer of such capsules provides an ideal platform for the biofunctionalization of PEMC as drug delivery systems or as artificial cell-like structures for biomimetic studies.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  6. Effect of surfactants on the fluorescence spectra of water-soluble MEHPPV derivatives having grafted polyelectrolyte chains

    Indian Academy of Sciences (India)

    Nagesh Kolishetti; S Ramakrishnan


    Poly(2-methoxy-5-[2'-ethylhexyoxy]-1,4-phenylenevinylene) (MEHPPV) derivatives with polyacrylic acid (PAA) chains grafted onto their backbone were found to be water soluble, and they exhibited a dramatic increase in their fluorescence intensity in the presence of a variety of surfactants, even at concentrations far below their critical micelle concentrations (CMC). This increase was accompanied by a blue-shift in the emission maximum. These observations are rationalized based on the postulate that the backbone conformation of the conjugated polymer is modulated upon interaction of the surfactant molecules with the polyelectrolytic tethers, which in turn results in a significant depletion of intra-chain interchromophore interactions that are known to cause red-shifted emission bands with significantly lower emission yields.

  7. Learning-Based Tracking of Complex Non-Rigid Motion

    Institute of Scientific and Technical Information of China (English)

    Qiang Wang; Hai-Zhou Ai; Guang-You Xu


    This paper describes a novel method for tracking complex non-rigid motions by learning the intrinsic object structure.The approach builds on and extends the studies on non-linear dimensionality reduction for object representation,object dynamics modeling and particle filter style tracking.First,the dimensionality reduction and density estimation algorithm is derived for unsupervised learning of object intrinsic representation,and the obtained non-rigid part of object state reduces even to 2-3 dimensions.Secondly the dynamical model is derived and trained based on this intrinsic representation.Thirdly the learned intrinsic object structure is integrated into a particle filter style tracker.It is shown that this intrinsic object representation has some interesting properties and based on which the newly derived dynamical model makes particle filter style tracker more robust and reliable.Extensive experiments are done on the tracking of challenging non-rigid motions such as fish twisting with selfocclusion,large inter-frame lip motion and facial expressions with global head rotation.Quantitative results are given to make comparisons between the newly proposed tracker and the existing tracker.The proposed method also has the potential to solve other type of tracking problems.

  8. Hyperbolic mapping of complex networks based on community information (United States)

    Wang, Zuxi; Li, Qingguang; Jin, Fengdong; Xiong, Wei; Wu, Yao


    To improve the hyperbolic mapping methods both in terms of accuracy and running time, a novel mapping method called Community and Hyperbolic Mapping (CHM) is proposed based on community information in this paper. Firstly, an index called Community Intimacy (CI) is presented to measure the adjacency relationship between the communities, based on which a community ordering algorithm is introduced. According to the proposed Community-Sector hypothesis, which supposes that most nodes of one community gather in a same sector in hyperbolic space, CHM maps the ordered communities into hyperbolic space, and then the angular coordinates of nodes are randomly initialized within the sector that they belong to. Therefore, all the network nodes are so far mapped to hyperbolic space, and then the initialized angular coordinates can be optimized by employing the information of all nodes, which can greatly improve the algorithm precision. By applying the proposed dual-layer angle sampling method in the optimization procedure, CHM reduces the time complexity to O(n2) . The experiments show that our algorithm outperforms the state-of-the-art methods.

  9. Project management for complex ground-based instruments: MEGARA plan (United States)

    García-Vargas, María. Luisa; Pérez-Calpena, Ana; Gil de Paz, Armando; Gallego, Jesús; Carrasco, Esperanza; Cedazo, Raquel; Iglesias, Jorge


    The project management of complex instruments for ground-based large telescopes is a challenge itself. A good management is a clue for project success in terms of performance, schedule and budget. Being on time has become a strict requirement for two reasons: to assure the arrival at the telescope due to the pressure on demanding new instrumentation for this first world-class telescopes and to not fall in over-costs. The budget and cash-flow is not always the expected one and has to be properly handled from different administrative departments at the funding centers worldwide distributed. The complexity of the organizations, the technological and scientific return to the Consortium partners and the participation in the project of all kind of professional centers working in astronomical instrumentation: universities, research centers, small and large private companies, workshops and providers, etc. make the project management strategy, and the tools and procedures tuned to the project needs, crucial for success. MEGARA (Multi-Espectrógrafo en GTC de Alta Resolución para Astronomía) is a facility instrument of the 10.4m GTC (La Palma, Spain) working at optical wavelengths that provides both Integral-Field Unit (IFU) and Multi-Object Spectrograph (MOS) capabilities at resolutions in the range R=6,000-20,000. The project is an initiative led by Universidad Complutense de Madrid (Spain) in collaboration with INAOE (Mexico), IAA-CSIC (Spain) and Universidad Politécnica de Madrid (Spain). MEGARA is being developed under contract with GRANTECAN.

  10. Self-organized topology of recurrence-based complex networks. (United States)

    Yang, Hui; Liu, Gang


    With the rapid technological advancement, network is almost everywhere in our daily life. Network theory leads to a new way to investigate the dynamics of complex systems. As a result, many methods are proposed to construct a network from nonlinear time series, including the partition of state space, visibility graph, nearest neighbors, and recurrence approaches. However, most previous works focus on deriving the adjacency matrix to represent the complex network and extract new network-theoretic measures. Although the adjacency matrix provides connectivity information of nodes and edges, the network geometry can take variable forms. The research objective of this article is to develop a self-organizing approach to derive the steady geometric structure of a network from the adjacency matrix. We simulate the recurrence network as a physical system by treating the edges as springs and the nodes as electrically charged particles. Then, force-directed algorithms are developed to automatically organize the network geometry by minimizing the system energy. Further, a set of experiments were designed to investigate important factors (i.e., dynamical systems, network construction methods, force-model parameter, nonhomogeneous distribution) affecting this self-organizing process. Interestingly, experimental results show that the self-organized geometry recovers the attractor of a dynamical system that produced the adjacency matrix. This research addresses a question, i.e., "what is the self-organizing geometry of a recurrence network?" and provides a new way to reproduce the attractor or time series from the recurrence plot. As a result, novel network-theoretic measures (e.g., average path length and proximity ratio) can be achieved based on actual node-to-node distances in the self-organized network topology. The paper brings the physical models into the recurrence analysis and discloses the spatial geometry of recurrence networks.

  11. Self-organized topology of recurrence-based complex networks

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hui, E-mail:; Liu, Gang [Complex Systems Monitoring, Modeling and Analysis Laboratory, University of South Florida, Tampa, Florida 33620 (United States)


    With the rapid technological advancement, network is almost everywhere in our daily life. Network theory leads to a new way to investigate the dynamics of complex systems. As a result, many methods are proposed to construct a network from nonlinear time series, including the partition of state space, visibility graph, nearest neighbors, and recurrence approaches. However, most previous works focus on deriving the adjacency matrix to represent the complex network and extract new network-theoretic measures. Although the adjacency matrix provides connectivity information of nodes and edges, the network geometry can take variable forms. The research objective of this article is to develop a self-organizing approach to derive the steady geometric structure of a network from the adjacency matrix. We simulate the recurrence network as a physical system by treating the edges as springs and the nodes as electrically charged particles. Then, force-directed algorithms are developed to automatically organize the network geometry by minimizing the system energy. Further, a set of experiments were designed to investigate important factors (i.e., dynamical systems, network construction methods, force-model parameter, nonhomogeneous distribution) affecting this self-organizing process. Interestingly, experimental results show that the self-organized geometry recovers the attractor of a dynamical system that produced the adjacency matrix. This research addresses a question, i.e., “what is the self-organizing geometry of a recurrence network?” and provides a new way to reproduce the attractor or time series from the recurrence plot. As a result, novel network-theoretic measures (e.g., average path length and proximity ratio) can be achieved based on actual node-to-node distances in the self-organized network topology. The paper brings the physical models into the recurrence analysis and discloses the spatial geometry of recurrence networks.

  12. Stabilization of starch-based microgel-lysozyme complexes using a layer-by-layer assembly technique. (United States)

    Zhang, Bao; Pan, Yi; Chen, Hanqing; Liu, Tengfei; Tao, Han; Tian, Yaoqi


    The layer-by-layer assembly of polyelectrolyte multilayers of chitosan (CS) and carboxymethyl starch (CMS) on soft and porous pH- and ionic strength-response microgels was determined by confocal laser scanning microscopy (CLSM) and zeta potential measurements. In vitro release of lysozyme from the stabilized microgels under simulated gastric and intestinal fluids was also investigated. The distribution of CS in the microgels was identified by CLSM, and the optimal molecular weight of CS was 100kDa, which could only be absorbed on the microgel surface. The CS was used as the first layer, while the CMS was used as the second layer, and the zeta potential revealed that the optimal weight ratios of CS and CMS to microgels in the complexes were 0.1 and 0.06, respectively. The in vitro release experiments suggested that the stabilized double-layer microgel complexes could potentially be applied as a carrier system to prevent early release in the stomach to target intestinal delivery.

  13. Synthesis and Complexation of Well-Defined Labeled Poly(N,N-dimethylaminoethyl methacrylates (PDMAEMA

    Directory of Open Access Journals (Sweden)

    Mark Billing


    Full Text Available We present the synthesis and characterization of well-defined polycationic copolymers containing thiazole dyes in the side chain. Atom transfer radical polymerization (ATRP was used for the copolymerization of 3-azidopropyl methacrylate (AzPMA and N,N-dimethylaminoethyl methacrylate (DMAEMA of different composition. Thiazole-based alkyne-functionalized dyes (e.g., 5-methyl-4-(prop-2-yn-1-yloxy-2-(pyridin-2-ylthiazole, (MPPT were afterwards covalently attached using copper catalyzed azide alkyne cycloadditions (CuAAC reaching contents of up to 9 mol % dye. Subsequent quaternization of the tertiary nitrogen of DMAEMA with strong methylation agents (e.g., methyl iodide led to permanently charged polyelectrolytes. The materials were characterized by size exclusion chromatography, as well as NMR- and UV/VIS-spectroscopy. Particular attention is paid to the spectroscopic properties of the dyes in the side chain upon environmental changes such as pH and salinity. We anticipate the application of such precisely functionalized polyelectrolytes as temperature- and pH-responsive sensors in biomedical applications, e.g., within interpolyelectrolyte complexes. Concerning the latter, first complex formation results are demonstrated.

  14. Potential Use of Polyelectrolyte Multilayer thin Films in Vascular Tissue Engineering:Evaluation of the Viability and Adhesion of Endothelial Cells

    Institute of Scientific and Technical Information of China (English)

    Cédric BOURA; Halima KERDJOUDJ; Vanessa MOBY; Pierre SCHAAJ; Jean Claude VOEGEL; Jean-Fran(c)ois STOLTZ; Patrick MENU


    @@ 1 Introduction A method in vascular tissue engineering to obtain hemoeompatible synthetic prosthesis consists to cover the luminal surface by a monolayer of endothelial cells(ECs). Nevertheless, the surface of current prosthesis does not favour the development of an ECs monolayer.Recently, a new versatile method of self-assembled architectures based on the alternate adsorption of polycations and polyanions has been developed to lead to the build-up of multilayered polyelectrolyte films (MPF). This new type of surface modification offers also large possibilities for varying the physico-chemical properties such as roughness or surface charges, film thickness and viscoelastic properties.

  15. Evolution of complexity in a resource-based model (United States)

    Fernández, Lenin; Campos, Paulo R. A.


    Through a resource-based modelling the evolution of organismal complexity is studied. In the model, the cells are characterized by their metabolic rates which, together with the availability of resource, determine the rate at which they divide. The population is structured in groups. Groups are also autonomous entities regarding reproduction and propagation, and so they correspond to a higher biological organization level. The model assumes reproductive altruism as there exists a fitness transfer from the cell level to the group level. Reproductive altruism comes about by inflicting a higher energetic cost to cells belonging to larger groups. On the other hand, larger groups are less prone to extinction. The strength of this benefit arising from group augmentation can be tuned by the synergistic parameter γ. Through extensive computer simulations we make a thorough exploration of the parameter space to find out the domain in which the formation of larger groups is allowed. We show that formation of small groups can be obtained for a low level of synergy. Larger group sizes can only be attained as synergistic interactions surpass a given level of strength. Although the total resource influx rate plays a key role in determining the number of groups coexisting at the equilibrium, its function on driving group size is minor. On the other hand, how the resource is seized by the groups matters.

  16. Structural controllability of complex networks based on preferential matching. (United States)

    Zhang, Xizhe; Lv, Tianyang; Yang, XueYing; Zhang, Bin


    Minimum driver node sets (MDSs) play an important role in studying the structural controllability of complex networks. Recent research has shown that MDSs tend to avoid high-degree nodes. However, this observation is based on the analysis of a small number of MDSs, because enumerating all of the MDSs of a network is a #P problem. Therefore, past research has not been sufficient to arrive at a convincing conclusion. In this paper, first, we propose a preferential matching algorithm to find MDSs that have a specific degree property. Then, we show that the MDSs obtained by preferential matching can be composed of high- and medium-degree nodes. Moreover, the experimental results also show that the average degree of the MDSs of some networks tends to be greater than that of the overall network, even when the MDSs are obtained using previous research method. Further analysis shows that whether the driver nodes tend to be high-degree nodes or not is closely related to the edge direction of the network.

  17. Developing a theoretical framework for complex community-based interventions. (United States)

    Angeles, Ricardo N; Dolovich, Lisa; Kaczorowski, Janusz; Thabane, Lehana


    Applying existing theories to research, in the form of a theoretical framework, is necessary to advance knowledge from what is already known toward the next steps to be taken. This article proposes a guide on how to develop a theoretical framework for complex community-based interventions using the Cardiovascular Health Awareness Program as an example. Developing a theoretical framework starts with identifying the intervention's essential elements. Subsequent steps include the following: (a) identifying and defining the different variables (independent, dependent, mediating/intervening, moderating, and control); (b) postulating mechanisms how the independent variables will lead to the dependent variables; (c) identifying existing theoretical models supporting the theoretical framework under development; (d) scripting the theoretical framework into a figure or sets of statements as a series of hypotheses, if/then logic statements, or a visual model; (e) content and face validation of the theoretical framework; and (f) revising the theoretical framework. In our example, we combined the "diffusion of innovation theory" and the "health belief model" to develop our framework. Using the Cardiovascular Health Awareness Program as the model, we demonstrated a stepwise process of developing a theoretical framework. The challenges encountered are described, and an overview of the strategies employed to overcome these challenges is presented.

  18. Synthesis of a base-stabilized silanone-coordinated complex by oxygenation of a (silyl)(silylene)tungsten complex. (United States)

    Muraoka, Takako; Abe, Keisuke; Haga, Youhei; Nakamura, Tomoko; Ueno, Keiji


    Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.

  19. Mesogenic copper(II) complexes with [1,2,3]-triazole-based bidentate Schiff bases

    Indian Academy of Sciences (India)

    Guan-Yeow Yeap; Boon-Teck Heng


    The first mesogenic Cu(II) complex with [1,2,3]-triazole-based bidentate Schiff bases with flexible terminal alkyl chain, CnH2n+1 (even parity of n = 10-18) has been successfully synthesized. The heterocyclic triazole core was introduced into the target compound through the click reaction between azidoalkane and propargyl aldehyde. All the uncoordinated ligands and target complexes were characterized by elemental analysis, FT-IR, 1H-NMR and UV-visible spectroscopic techniques. The observation under the polarized light and differential scanning calometry (DSC) shows that the triazole-based ligands exhibit unstable SmA phase which are not reproducible upon subsequent heating and cooling. Interestingly, the whole homologues of Cu(II) complexes show exclusively stable focal conic fan-shaped texture characteristic of SmA phase. This can be ascribed to the presence of Cu-N and Cu-O coordination modes which enhance the collinearity and molecular anisotropy. On the other hand, the Cu(II) complexes are thermally more stable as compared to their corresponding ligands.

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

    Directory of Open Access Journals (Sweden)

    Xiaozheng Duan


    Full Text Available We employ Monte Carlo simulations to investigate the interaction between an adsorbing linear flexible cationic polyelectrolyte and a binary fluid membrane. The membrane contains neutral phosphatidyl–choline, PC and multivalent anionic (phosphatidylinositol, PIP2 lipids. We systematically study the influences of the solution ionic strength, the chain length and the bead charge density of the polyelectrolyte on the lateral rearrangement and the restricted mobility of the multivalent anionic lipids in the membrane. Our findings show that, the cooperativity effect and the electrostatic interaction of the polyelectrolyte beads can significantly affect the segregation extent and the concentration gradients of the PIP2 molecules, and further cooperate to induce the complicated hierarchical mobility behaviors of PIP2 molecules. In addition, when the polyelectrolyte brings a large amount of charges, it can form a robust electrostatic well to trap all PIP2 and results in local overcharge of the membrane. This work presents a mechanism to explain the membrane heterogeneity formation induced by the adsorption of charged macromolecule.

  1. Charge Density Quantification of Polyelectrolyte Polysaccharides by Conductometric Titration: An Analytical Chemistry Experiment (United States)

    Farris, Stefano; Mora, Luigi; Capretti, Giorgio; Piergiovanni, Luciano


    An easy analytical method for determination of the charge density of polyelectrolytes, including polysaccharides and other biopolymers, is presented. The basic principles of conductometric titration, which is used in the pulp and paper industry as well as in colloid and interface science, were adapted to quantify the charge densities of a…

  2. Incorporation of a Cationic Conjugated Polyelectrolyte CPE within an Aqueous Poly(vinyl alcohol) Sol

    DEFF Research Database (Denmark)

    Knaapila, Matti; Stewart, Beverly; Costa, Telma


    We report on a multiscale polymer-within-polymer structure of the cationic conjugated polyelectrolyte poly{[9,9-bis(6-N,N,N-trimethylammonium)hexyl]fluorene phenylene} (HTMAPFP) in aqueous poly(vinyl alcohol).(PVA) sol. Molecular dynamics simulations and small-angle neutron scattering (SANS) data...

  3. Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

    NARCIS (Netherlands)

    Zielinska, K.; Leeuwen, van H.P.


    In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimet

  4. Mechanism of rate enhancement of wood fiber saccharification by cationic polyelectrolytes. (United States)

    Mora, Sandeep; Lu, Jian; Banerjee, Sujit


    Cationic polyelectrolytes can increase the cellulase-induced hydrolysis rates of bleached wood fiber. We show that the polymer associates mainly with the amorphous region of fiber and acts principally on endoglucanase. Fiber/water partitioning of the enzyme follows a Langmuir isotherm for the untreated fiber but a Freundlich isotherm is obeyed for the polymer-treated fiber.

  5. The solvation and ion condensation properties for sulfonated polyelectrolytes in different solvents—a computational study (United States)

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


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

  6. The photoluminescent lifetime of polyelectrolytes in thin films formed via layer by layer self-assembly. (United States)

    Reilly, Roseanne S; Smyth, Ciarán A; Rakovich, Yury P; McCabe, Eithne M


    We present results on luminescence lifetime studies of thin multilayer films of polyelectrolyte molecules produced via layer by layer (LbL) electrostatic assembly. We found that, in contrast to common assumptions, LbL films show measurable photoluminescent lifetimes with an average value of 6 ns. Scanning fluorescence lifetime imaging microscopy studies combined with steady-state photoluminescence measurements imply that this lifetime may be due to aggregation of polyelectrolyte molecules during preparation of LbL films. This conclusion has been further confirmed by atomic force microscopy (AFM). AFM images clearly show the presence of 100-200 nm high aggregates on the surface of these films. This aggregation of polyelectrolyte molecules contributes significantly to the experimentally detected luminescence decays of any light-emitting samples attached to LbL film, especially in a single molecule detection regime. To demonstrate this effect we compare photoluminescence lifetime results for CdTe quantum dots deposited on the surface of LbL polyelectrolyte films.

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

    NARCIS (Netherlands)

    Hoogeveen, N.G.


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

  8. A modified box model including charge regulation for protein adsorption in a spherical polyelectrolyte brush

    NARCIS (Netherlands)

    Biesheuvel, P.M.; Wittemann, A.


    Recent experiments showed significant adsorption of bovine serum albumin (BSA) in spherical polyelectrolyte brushes (SPB) consisting of polyacrylic acid, even for pH values above the isoelectric point of the protein, when both protein and polyion are negatively charged. To describe these experimenta


    Directory of Open Access Journals (Sweden)

    Beata Bień


    Full Text Available The article presents the results of research on the impact of inorganic coagulants and polyelectrolytes and their common action on sonicated digested sludge. Sonication of sludge samples was carried out under static conditions for 60, 120 and 180 seconds. The ultrasonic wave of f = 20 kHz and two different amplitudes of A = 15.25 μm was used in tests. The coagulant PIX123 and the polyelectrolyte Zetag 8160 were used for conditioning. On the basis of CST test the doses of chemical reagents were chosen for conditioning. The results showed the effect of application of the PIX123 and Zetag 8160 and their combination on non-sonicated and sonicated sludge. The lowest CST was achieved for non-sonicated sludge while polyelectrolyte was applied. For sonicated sludge better results were achieved when PIX123 was used. The combination of coagulant and polyelectrolyte allowed to achieve COD reduction, but the best results were achieved for sludge prepared by PIX123. The application of Zetag8160 in this case was not satisfactory.

  10. Investigation of interpolymer complexes based on methylcellulose and polyacrylic acid

    Directory of Open Access Journals (Sweden)

    Zh. Nurpeysova


    Full Text Available In the given work the patterns of formation interpolymer complexes in the methylcellulose and polyacrylic acid system were studied by turbidimetry. It is shown that the increase in molecular weight and concentration of polymers promotes efficient formation of interpolymer complexes.

  11. Team-Based Complex Problem Solving: A Collective Cognition Perspective (United States)

    Hung, Woei


    Today, much problem solving is performed by teams, rather than individuals. The complexity of these problems has exceeded the cognitive capacity of any individual and requires a team of members to solve them. The success of solving these complex problems not only relies on individual team members who possess different but complementary expertise,…

  12. Knowledge based method for solving complexity in design problems

    NARCIS (Netherlands)

    Vermeulen, B.


    The process of design aircraft systems is becoming more and more complex, due to an increasing amount of requirements. Moreover, the knowledge on how to solve these complex design problems becomes less readily available, because of a decrease in availability of intellectual resources and reduced kno

  13. Detection of K-complexes based on the wavelet transform

    DEFF Research Database (Denmark)

    Krohne, Lærke K.; Hansen, Rie B.; Christensen, Julie Anja Engelhard;


    Sleep scoring needs computational assistance to reduce execution time and to assure high quality. In this pilot study a semi-automatic K-Complex detection algorithm was developed using wavelet transformation to identify pseudo-K-Complexes and various feature thresholds to reject false positives...

  14. Antioxidant activity of bovine serum albumin binding amino acid Schiff-bases metal complexes

    Institute of Scientific and Technical Information of China (English)


    Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin (BSA), which afforded BSA binding Schiff-base metal complexes (BSA-SalGluM, M=Cu, Co, Ni, Zn). The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.

  15. Polyelectrolyte multilayers promote stent-mediated delivery of DNA to vascular tissue. (United States)

    Saurer, Eric M; Jewell, Christopher M; Roenneburg, Drew A; Bechler, Shane L; Torrealba, Jose R; Hacker, Timothy A; Lynn, David M


    We report an approach to deliver DNA to vascular tissue in vivo using intravascular stents coated with degradable, DNA-containing polyelectrolyte multilayers (PEMs). Ionically cross-linked multilayers ∼120 nm thick were fabricated layer-by-layer on the surfaces of balloon-mounted stainless steel stents using plasmid DNA and a hydrolytically degradable poly(β-amino ester) (polymer 1). Characterization of stents coated using a fluorescently end-labeled analog of polymer 1 revealed film erosion to be uniform across the surfaces of the stents; differential stresses experienced upon balloon expansion did not lead to faster film erosion or dose dumping of DNA in areas near stent joints when stents were incubated in physiologically relevant media. The ability of film-coated stents to transfer DNA and transfect arterial tissue in vivo was then investigated in pigs and rabbits. Stents coated with films fabricated using fluorescently labeled DNA resulted in uniform transfer of DNA to sub-endothelial tissue in the arteries of pigs in patterns corresponding to the locations and geometries of stent struts. Stents coated with films fabricated using polymer 1 and plasmid DNA encoding EGFP resulted in expression of EGFP in the medial layers of stented tissue in both pigs and rabbits two days after implantation. The results of this study, combined with the modular and versatile nature of layer-by-layer assembly, provide a polymer-based platform that is well suited for fundamental studies of stent-mediated gene transfer. With further development, this approach could also prove useful for the design of nonviral, gene-based approaches for prevention of complications that arise from the implantation of stents and other implantable interventional devices.

  16. Phase behavior and molecular thermodynamics of coacervation in oppositely charged polyelectrolyte/surfactant systems: a cationic polymer JR 400 and anionic surfactant SDS mixture. (United States)

    Li, Dongcui; Kelkar, Manish S; Wagner, Norman J


    Coacervation in mixtures of polyelectrolytes and surfactants with opposite charge is common in nature and is also technologically important to consumer health care products. To understand the complexation behavior of these systems better, we combine multiple experimental techniques to systematically study the polymer/surfactant binding interactions and the phase behavior of anionic sodium dodecyl sulfate (SDS) surfactant in cationic JR 400 polymer aqueous solutions. The phase-behavior study resolves a discrepancy in the literature by identifying a metastable phase between the differing redissolution phase boundaries reported in the literature for the surfactant-rich regime. Isothermal titration calorimetry analyzed within the framework of the simple Satake-Yang model identifies binding parameters for the surfactant-lean phase, whereas a calculation for polymer-bound micelles coexisting with free micelles is analyzed in the surfactant-rich redissolution regime. This analysis provides a preliminary understanding of the interactions governing the observed phase behavior. The resulting thermodynamic properties, including binding constants and the molar Gibbs free energies, enthalpies, and entropies, identify the relative importance of both hydrophobic and electrostatic interactions and provide a first approximation for the corresponding microstructures in the different phases. Our study also addresses the stability and metastability of oppositely charged polyelectrolytes and surfactant mixtures.

  17. Structural assembly of molecular complexes based on residual dipolar couplings. (United States)

    Berlin, Konstantin; O'Leary, Dianne P; Fushman, David


    We present and evaluate a rigid-body molecular docking method, called PATIDOCK, that relies solely on the three-dimensional structure of the individual components and the experimentally derived residual dipolar couplings (RDCs) for the complex. We show that, given an accurate ab initio predictor of the alignment tensor from a protein structure, it is possible to accurately assemble a protein-protein complex by utilizing the RDCs' sensitivity to molecular shape to guide the docking. The proposed docking method is robust against experimental errors in the RDCs and computationally efficient. We analyze the accuracy and efficiency of this method using experimental or synthetic RDC data for several proteins, as well as synthetic data for a large variety of protein-protein complexes. We also test our method on two protein systems for which the structure of the complex and steric-alignment data are available (Lys48-linked diubiquitin and a complex of ubiquitin and a ubiquitin-associated domain) and analyze the effect of flexible unstructured tails on the outcome of docking. The results demonstrate that it is fundamentally possible to assemble a protein-protein complex solely on the basis of experimental RDC data and the prediction of the alignment tensor from 3D structures. Thus, despite the purely angular nature of RDCs, they can be converted into intermolecular distance/translational constraints. Additionally, we show a method for combining RDCs with other experimental data, such as ambiguous constraints from interface mapping, to further improve structure characterization of protein complexes.

  18. Cytotoxicity and antibacterial property of titanium alloy coated with silver nanoparticle-containing polyelectrolyte multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xinming [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Li, Zhaoyang [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Yuan, Xubo [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Cui, Zhenduo [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Bao, Huijing; Li, Xue; Liu, Yunde [School of Laboratory Medicine, Tianjin Medical University, Tianjin, 300203 (China); Yang, Xianjin, E-mail: [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China)


    Silver nanoparticle (AgNP) was incorporated into dopamine-modified alginate/chitosan (DAL/CHI) polyelectrolyte multilayer to modify the surface of titanium alloy and improve its antibacterial property. Scanning electron microscopy showed that AgNP with the size of 50 nm embedded in DAL/CHI multilayers homogeneously. X-ray photoelectron spectroscopy analysis indicated that the nanoparticles were silver (0) with peaks at 368.4 and 374.4 eV, respectively. The formation of silver (0) without the addition of reductants was due to the self-polymerization of dopamine, which can reduce the silver cation into neutral metal. The polyelectrolyte multilayer coating enhanced the wettability of titanium alloy and promoted the fibroblast proliferation significantly, which could be attributed to the excellent biocompatibility of DAL/CHI. Despite the slight fall of L929 cell activity after AgNP incorporation, AgNP-DAL/CHI multilayer inhibited the growth of both Escherichia coli and Staphylococcus aureus. The above results demonstrate that dopamine decoration is a simple and effective way to induce the in-situ formation of AgNP within polyelectrolyte multilayer. Furthermore, the AgNP-containing multilayer considerably enhances the antibacterial activity of titanium alloy. The fabrication of AgNP-DAL/CHI multilayer on the surface of titanium implant might have great potential in orthopedic use. - Highlights: • Polyelectrolyte multilayer was fabricated through layer-by-layer assembly. • AgNP was formed in-situ and embedded within polyelectrolyte multilayer. • Surface of titanium was modified by AgNP-DAL/CHI multilayer with a facile method. • AgNP-DAL/CHI multilayer enhanced antibacterial activity of titanium alloy.

  19. Transport rectification in nanopores with outer membranes modified with surface charges and polyelectrolytes. (United States)

    Tagliazucchi, Mario; Rabin, Yitzhak; Szleifer, Igal


    This work reports a comprehensive theoretical study of the transport-rectification properties of cylindrical nanopores with neutral inner walls and chemically modified outer membrane. The chemical species on the two outer sides of the membrane have charges of opposite sign and can be either surface-confined species (i.e., surface charges) or polyelectrolyte brushes. The advantage of this design over other types of rectifying nanopores is that it requires controlling the composition of the outer walls of the pore (which are easy to access) rather than the inner walls, thus simplifying the fabrication process. Ion-current rectification in nanopores with charged outer walls is ascribed to applied-potential-induced changes in the ionic concentration within the pore. The rectification efficiency is studied as a function of pore length, radius, surface charge and bulk electrolyte concentration. An analytical model is derived for the case of surface-confined charges that predicts the current-potential curves in very good agreement with the numerical calculations. Neutral nanopores with polyelectrolyte-modified outer walls have two distinct advantages compared to surface-charged systems: (i) they exhibit higher rectification factors due to the large charge density immobilized by the polyelectrolyte brushes, and (ii) the applied potential deforms the polyelectrolyte chains toward the oppositely charged electrode. This deformation brings the polyelectrolyte brushes into the pore in the low conductivity state and expels them from the pore in the high conductivity regime. Calculations of the potentials of mean-force suggest that the applied-field-induced conformational changes can be used to control the translocation of cargoes larger than ions, such as proteins and nanoparticles.

  20. BlenX-based compositional modeling of complex reaction mechanisms

    CERN Document Server

    Zámborszky, Judit; 10.4204/EPTCS.19.6


    Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model buildin...

  1. New Trends in Agent-Based Complex Automated Negotiations

    CERN Document Server

    Zhang, Minjie; Robu, Valentin; Fatima, Shaheen; Matsuo, Tokuro


    Complex Automated Negotiations represent an important, emerging area in the field of Autonomous Agents and Multi-Agent Systems. Automated negotiations can be complex, since there are a lot of factors that characterize such negotiations. These factors include the number of issues, dependencies between these issues,  representation of utilities, the negotiation protocol, the number of parties in the negotiation (bilateral or multi-party), time constraints, etc. Software agents can support automation or simulation of such complex negotiations on the behalf of their owners, and can provide them with efficient bargaining strategies. To realize such a complex automated negotiation, we have to incorporate advanced Artificial Intelligence technologies includes search, CSP, graphical utility models, Bayes nets, auctions, utility graphs, predicting and learning methods. Applications could include e-commerce tools, decision-making support tools, negotiation support tools, collaboration tools, etc. This book aims to pro...

  2. Radar Emitter Signal Recognition Based on Complexity Features

    Institute of Scientific and Technical Information of China (English)

    张葛祥; 金炜东; 胡来招


    Intra-pulse characteristics of different radar emitter signals reflect on signal waveform by way of changing frequency, phase and amplitude. A novel approach was proposed to extract complexity features of radar emitter signals in a wide range of signal-to-noise ratio ( SNR), and radial basis probability neural network (RBPNN) was used to recognize different radar emitter signals. Complexity features, including Lempel-Ziv complexity (LZC) and correlation dimension (CD), can measure the complexity and irregularity of signals, which mirrors the intra-pulse modulation laws of radar emitter signals. In an experiment, LZC and CD features of 10 typical radar emitter signals were extracted and RBPNN was applied to identify the 10 radar emitter signals. Simulation results show that the proposed approach is effective and has good application values because average accurate recognition rate is high when SNR varies in a wide range.

  3. Block-based test data adequacy measurement criteria and test complexity metrics

    Institute of Scientific and Technical Information of China (English)


    On the basis of software testing tools we developed for programming languages, we firstly present a new control flowgraph model based on block. In view of the notion of block, we extend the traditional program-based software test data adequacy measurement criteria, and empirically analyze the subsume relation between these measurement criteria. Then, we define four test complexity metrics based on block. They are J-complexity 0; J-complexity 1; J-complexity 1 +; J-complexity 2. Finally, we show the Kiviat diagram that makes software quality visible.

  4. Block-based test data adequacy measurement criteria and test complexity metrics

    Institute of Scientific and Technical Information of China (English)

    陈卫东; 杨建军; 叶澄清; 潘云鹤


    On the basis of software testing tools we developed for progrmnming languages, we firstly present a new control flowgraph model based on block. In view of the notion of block, we extend the traditional program-based software test data adequacy measurement criteria, and empirically analyze the subsume relation between these measurement criteria. Then, we define four test complexity metrics based on block. They are J-complexity 0; J-complexity 1 ; J-complexity 1 + ; J-complexity 2. Finally, we show the Kiviat diagram that makes software quality visible.

  5. Adaptive growth factor delivery from a polyelectrolyte coating promotes synergistic bone tissue repair and reconstruction. (United States)

    Shah, Nisarg J; Hyder, Md Nasim; Quadir, Mohiuddin A; Dorval Courchesne, Noémie-Manuelle; Seeherman, Howard J; Nevins, Myron; Spector, Myron; Hammond, Paula T


    Traumatic wounds and congenital defects that require large-scale bone tissue repair have few successful clinical therapies, particularly for craniomaxillofacial defects. Although bioactive materials have demonstrated alternative approaches to tissue repair, an optimized materials system for reproducible, safe, and targeted repair remains elusive. We hypothesized that controlled, rapid bone formation in large, critical-size defects could be induced by simultaneously delivering multiple biological growth factors to the site of the wound. Here, we report an approach for bone repair using a polyelectrolye multilayer coating carrying as little as 200 ng of bone morphogenetic protein-2 and platelet-derived growth factor-BB that were eluted over readily adapted time scales to induce rapid bone repair. Based on electrostatic interactions between the polymer multilayers and growth factors alone, we sustained mitogenic and osteogenic signals with these growth factors in an easily tunable and controlled manner to direct endogenous cell function. To prove the role of this adaptive release system, we applied the polyelectrolyte coating on a well-studied biodegradable poly(lactic-co-glycolic acid) support membrane. The released growth factors directed cellular processes to induce bone repair in a critical-size rat calvaria model. The released growth factors promoted local bone formation that bridged a critical-size defect in the calvaria as early as 2 wk after implantation. Mature, mechanically competent bone regenerated the native calvaria form. Such an approach could be clinically useful and has significant benefits as a synthetic, off-the-shelf, cell-free option for bone tissue repair and restoration.

  6. Elucidating the Role of Conjugated Polyelectrolyte Interlayers for High-Efficiency Organic Photovoltaics. (United States)

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


    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 %.

  7. Introducing a high gravity field to enhance infiltration of small molecules into polyelectrolyte multilayers. (United States)

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


    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.

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

    Oćwieja, M; Adamczyk, Z; Morga, M


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

  9. Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation (United States)

    Malekzadeh Moghani, Mahdy; Khomami, Bamin


    Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ˜ cs-0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

  10. Biological Properties Of Benzopyran-Based Platinum (Ii Complexes

    Directory of Open Access Journals (Sweden)

    Malinowska Katarzyna


    Full Text Available The aim of the study was to analyze the physicochemical synthesized complex 3 [(1,3- thiazol -2- ylimino methyl]-4H- chromene -4 -one with tetrachloroplatinate(II dipotassium and determination peroxidase activity and glutathione (GPX in red blood cells of cancer patients and healthy subjects. Materials and methods. Tests were carried out with the approval of the Bioethics Committee No. RNN/260/08/KB. Blood was collected into tubes with anticoagulant (heparin lithium. Determination of glutathione peroxidase activity was performed by methods of Little and O’Brien in 20 person groups hospitalized at the Department of General and Colorectal Surgery Veterans General Hospital in Łódź. Results. The study was an increase of activity in the control without the compound and after the introduction of the complex relative to the treatment groups. In healthy subjects, without the use of glutathione peroxidase complex averaged 73.25 ± 23.88 U / g Hb after application of the compound corresponds to the reference group 81.01 ± 25.94 U / g Hb. In contrast, in patients without the use of the complex activity amounted to 42.85 ± 27.49 U / g Hb. In the study group, which uses synthesized complex GPX activity corresponds to 67.72 ± 13.44 U / g Hb. Conclusions. The obtained results underline that the introduction of significant blood antioxidant complex research has a significant impact on the results of the determinations. Statistically significant (p < 0.05 difference occurred in both test and no relation to the administration of the complex in relation to the control of 1. 2.

  11. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Vasudevan, Kalyan V.; Zhang, Guoqi; Hanson, Susan K.


    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions ( C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  12. An Agent Based Software Approach towards Building Complex Systems

    Directory of Open Access Journals (Sweden)

    Latika Kharb


    Full Text Available Agent-oriented techniques represent an exciting new means of analyzing, designing and building complex software systems. They have the potential to significantly improve current practice in software engineering and to extend the range of applications that can feasibly be tackled. Yet, to date, there have been few serious attempts to cast agent systems as a software engineering paradigm. This paper seeks to rectify this omission. Specifically, points to be argued include:firstly, the conceptual apparatus of agent-oriented systems is well-suited to building software solutions for complex systems and secondly, agent-oriented approaches represent a genuine advance over the current state of the art for engineering complex systems. Following on from this view, the major issues raised by adopting an agentoriented approach to software engineering are highlighted and discussed in this paper.

  13. Catalytic hydrogenation using complexes of base metals with tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Hanson, Susan K.; Zhang, Guoqi; Vasudevan, Kalyan V.


    Complexes of cobalt and nickel with tridentate ligand PNHP.sup.R are effective for hydrogenation of unsaturated compounds. Cobalt complex [(PNHP.sup.Cy)Co(CH.sub.2SiMe.sub.3)]BAr.sup.F.sub.4 (PNHP.sup.Cy=bis[2-(dicyclohexylphosphino)ethyl]amine, BAr.sup.F.sub.4=B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4)) was prepared and used with hydrogen for hydrogenation of alkenes, aldehydes, ketones, and imines under mild conditions ( C., 1-4 atm H.sub.2). Nickel complex [(PNHP.sup.Cy)Ni(H)]BPh.sub.4 was used for hydrogenation of styrene and 1-octene under mild conditions. (PNP.sup.Cy)Ni(H) was used for hydrogenating alkenes.

  14. Ruthenium(II) cluster complexes: a series of homooligonuclear complexes based on bidentate bridging ligands

    Energy Technology Data Exchange (ETDEWEB)

    Sahai, R.; Morgan, L.; Rillema, D.P.


    The preparation and properties of trimetallic and tetrametallic cluster complexes containing ruthenium(II) metal centers bridged by 2,2'-bipyrimidine (bpm) and 2,3-bis(2-pyridyl)quinoxaline (bpq) are reported. The tetrametallic clusters are symmetrical complexes containing a central ruthenium(II) coordinated to three (BL)Ru(bpy)/sub 2//sup 2 +/ ligands, where BL is bpm or bpq and bpy is 2,2'-bipyridine. The trimetallic clusters are asymmetric and are of the general formula ((bpy)Ru(BLRu(bpy)/sub 2/)/sub 2/)/sup 6 +/. The complexes exhibit low-energy MLCT transitions assigned as d..pi..(Ru(outer)) ..-->.. ..pi..*(BL). The MLCT maxima of the tetrametallic complexes were at slightly higher energies than those for their trimetallic analogues. For example, lambda/sub max/ for (Ru(bpqRu(bpy)/sub 2/)/sub 3/)/sup 8 +/ was located at 618 nm; that of ((bpy)Ru(bpqRu(bpy)/sub 2/)/sub 2/)/sup 3 +/ was located at 621 nm. The E/sub 1/2/ values were determined by cyclic voltammetry. The first oxidation in the case of ((bpy)Ru(bpqRu(bpy)/sub 2/)/sub 2/)/sup 6 +/ was located at E/sub 1/2/(1) = 1.57 V, and the second, at E/sub 1/2/(2) = 1.83 V vs. SSCE. The wave associated with E/sub 1/2/(1) had about twice the peak current as the wave at E/sub 1/2/(2) and, hence, was assigned to the Ru(III/II) redox couple of the outer ruthenium(II) components. The low-energy MLCT transitions for the mononuclear precursors (Ru(bpy)/sub x/(BL)/sub 3-x/, x = 1-3) and the multimetallic complexes were found to parallel 1/2/, the difference between E/sub 1/2/ values for the first oxidation and the first reduction. The excellent correlation (slope 1, correlation coefficient 0.99) indicates that either the energy of the lowest MLCT transition or 1/2/ can be used to measure the energy gap between the d..pi.. and ..pi..* energy levels. 32 references, 5 figures, 2 tables.

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

    KAUST Repository

    Ezzeddine, Alaa


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

  16. Influence of Layer-by-Layer Polyelectrolyte Deposition and EDC/NHS Activated Heparin Immobilization onto Silk Fibroin Fabric


    M. Fazley Elahi; Guoping Guan; Lu Wang; Martin W. King


    To enhance the hemocompatibility of silk fibroin fabric as biomedical material, polyelectrolytes architectures have been assembled through the layer-by-layer (LbL) technique on silk fibroin fabric (SFF). In particular, 1.5 and 2.5 bilayer of oppositely charged polyelectrolytes were assembled onto SFF using poly(allylamine hydrochloride) (PAH) as polycationic polymer and poly(acrylic acid) (PAA) as polyanionic polymer with PAH topmost. Low molecular weight heparin (LMWH) activated with 1-ethyl...

  17. Research and Measurement of Software Complexity Based on Wuli, Shili, Renli (WSR and Information Entropy

    Directory of Open Access Journals (Sweden)

    Rong Jiang


    Full Text Available Complexity is an important factor throughout the software life cycle. It is increasingly difficult to guarantee software quality, cost and development progress with the increase in complexity. Excessive complexity is one of the main reasons for the failure of software projects, so effective recognition, measurement and control of complexity becomes the key of project management. At first, this paper analyzes the current research situation of software complexity systematically and points out existing problems in current research. Then, it proposes a WSR framework of software complexity, which divides the complexity of software into three levels of Wuli (WL, Shili (SL and Renli (RL, so that the staff in different roles may have a better understanding of complexity. Man is the main source of complexity, but the current research focuses on WL complexity, and the research of RL complexity is extremely scarce, so this paper emphasizes the research of RL complexity of software projects. This paper not only analyzes the composing factors of RL complexity, but also provides the definition of RL complexity. Moreover, it puts forward a quantitative measurement method of the complexity of personnel organization hierarchy and the complexity of personnel communication information based on information entropy first and analyzes and validates the scientificity and rationality of this measurement method through a large number of cases.

  18. Stacking interaction in metal complexes with compositions of DNA and heteroaromatic N-bases

    Institute of Scientific and Technical Information of China (English)


    The current development in the intramolecular aromatic-ring stacking i nteractions in the complexes with compositions of DNA and heteroaromatic N-bases has been reviewed to a great extent, especially the significant contributions i n several important systems about ternary mixed-ligand complexes, including nucl eotide-metal ion-po- lyaromatic amine, amino acid-metal ion-polyaromatic amine, nucleotide-metal ion-pyridine-like aromatic amine, nucleotide-metal ion-amino ac id, nucleotide-metal ion-nucleic acid base, nucleic acid base-metal ion, and the important factors affecting the intramolecular aromatic-ring stacking interacti ons in the complexes. Based on the study of stacking interaction in the complexe s, the mechanism of interaction between DNA molecules and complexes of heteroaro matic N-bases has been established, which is crucial for the design and synthesi s of the complexes acting as molecular devices of DNA.

  19. BlenX-based compositional modeling of complex reaction mechanisms

    Directory of Open Access Journals (Sweden)

    Judit Zámborszky


    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  20. Experience-based exploration of complex energy systems

    NARCIS (Netherlands)

    Ligtvoet, A.; Chappin, E.J.L.


    In our energy-restricted world, planners and engineers have to cope with problems of CO2 emissions and oil- and gas-shortages. Many planning activities not captured under the heading of “futures studies” share common goals like dealing with an uncertain, complex future. We focus on two novel approac

  1. High energy density battery based on complex hydrides (United States)

    Zidan, Ragaiy


    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  2. Dissipative particle dynamics simulations of weak polyelectrolyte adsorption on charged and neutral surfaces as a function of the degree of ionization

    CERN Document Server

    Alarcón, F; Goicochea, A Gama


    The influence of the chain degree of ionization on the adsorption of weak polyelectrolytes on neutral and on oppositely and likely charged surfaces is investigated for the first time, by means of Monte Carlo simulations with the mesoscopic interaction model known as dissipative particle dynamics. The electrostatic interactions are calculated using the three-dimensional Ewald sum method, with an appropriate modification for confined systems. Effective wall forces confine the linear polyelectrolytes, and electric charges on the surfaces are included. The solvent is included explicitly also and it is modeled as an athermal solvent for the polyelectrolytes. The number of solvent particles is allowed to fluctuate. The results show that the polyelectrolytes adsorb both onto neutral and charged surfaces, with the adsorption regulated by the chain degree of ionization, being larger at lower ionization degrees, where polyelectrolytes are less charged. Furthermore, polyelectrolyte adsorption is strongly modulated by th...

  3. Synthesis and Application of Zeolite-encapsulated Nickel Schiff-base Complex

    Institute of Scientific and Technical Information of China (English)

    FENG; HuiXi


    Transition-metal complex-catalyzed oxidation of organic substrates with molecular oxygen is gaining importance as a viable alternative to the environmentally hazardous metal-oxide-based reagents. The complexes have received much attention recently due to the potential application of these complexes as oxidation catalysts for the oxidation of alkene, enolizable, aldehydes and other organic substrates. Recent studies of our group showed that metal complexes catalyzed the oxidation of organic substrates selectively in the presence of molecular oxygen 1,5. Here, it is reported that zeolite-encapsulated Ni (I) Schiff-base complex exhibit a catalytic activity and selectivity for the oxidation of styrene.  ……

  4. Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes. (United States)

    Asadi, Zahra; Shorkaei, Mohammad Ranjkesh


    Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible.

  5. Synthesis and Application of Zeolite-encapsulated Nickel Schiff-base Complex

    Institute of Scientific and Technical Information of China (English)


    @@ Transition-metal complex-catalyzed oxidation of organic substrates with molecular oxygen is gaining importance as a viable alternative to the environmentally hazardous metal-oxide-based reagents. The complexes have received much attention recently due to the potential application of these complexes as oxidation catalysts for the oxidation of alkene, enolizable, aldehydes and other organic substrates. Recent studies of our group showed that metal complexes catalyzed the oxidation of organic substrates selectively in the presence of molecular oxygen 1,5. Here, it is reported that zeolite-encapsulated Ni (I) Schiff-base complex exhibit a catalytic activity and selectivity for the oxidation of styrene.

  6. Complex coacervate core micelles. (United States)

    Voets, Ilja K; de Keizer, Arie; Cohen Stuart, Martien A


    In this review we present an overview of the literature on the co-assembly of neutral-ionic block, graft, and random copolymers with oppositely charged species in aqueous solution. Oppositely charged species include synthetic (co)polymers of various architectures, biopolymers - such as proteins, enzymes and DNA - multivalent ions, metallic nanoparticles, low molecular weight surfactants, polyelectrolyte block copolymer micelles, metallo-supramolecular polymers, equilibrium polymers, etcetera. The resultant structures are termed complex coacervate core/polyion complex/block ionomer complex/interpolyelectrolyte complex micelles (or vesicles); i.e., in short C3Ms (or C3Vs) and PIC, BIC or IPEC micelles (and vesicles). Formation, structure, dynamics, properties, and function will be discussed. We focus on experimental work; theory and modelling will not be discussed. Recent developments in applications and micelles with heterogeneous coronas are emphasized.

  7. Efficient white organic light-emitting diodes based on iridium complex sensitized copper complex

    Energy Technology Data Exchange (ETDEWEB)

    Su Zisheng; Li Wenlian; Chu Bei; Xu Maoliang; Che Guangbo; Wang Dan; Han Liangliang; Li Xiao; Zhang Dongyu; Bi Defeng; Chen Yiren [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033 (China)], E-mail:


    Efficient double emission-layer white organic light-emitting diodes comprising a yellow emission from bis[(4,6-difluorophenyl)-pyridinato-N,C{sup 2}](picolinato)Ir(III) (FIrpic) sensitized [Cu(bis[2-(diphenylphosphino)phenyl]ether) (6,7-Dicyanodipyrido[2,2-d : 2', 3'-f] quinoxaline)]BF{sub 4}(Cu{sup I} complex) and a blue emission from 4, 4'-bis(2,2'-diphenylvinyl)-1, 1'-biphenyl (DPVBi) were demonstrated. The emission spectrum can be fine tuned by effectively controlling the thicknesses of the two emission layers. The optimized device with 18 nm FIrpic and the Cu{sup I} complex codoped 4, 4'-N,N'-dicarbazole-biphenyl layer and 12 nm DPVBi layer shows a maximum current efficiency of 8.5 cd A{sup -1}, a maximum power efficiency of 5.3 lm W{sup -1} and a maximum luminance of 3290 cd m{sup -2}. Moreover, the device exhibits a CIE coordinate of (0.345, 0.357) at a bias of 8 V and a slight colour variation with increased voltage from 6 to 16 V.

  8. Mixed polyelectrolyte coatings on glassy carbon electrodes: Ion-exchange, permselectivity properties and analytical application of poly-l-lysine-poly(sodium 4-styrenesulfonate)-coated mercury film electrodes for the detection of trace metals. (United States)

    Monterroso, Sandra C C; Carapuça, Helena M; Duarte, Armando C


    The present work describes the preparation, optimization and characterization of mixed polyelectrolyte coatings of poly-l-lysine (PLL) and poly(sodium 4-styrenesulfonate) (PSS) for the modification of thin mercury film electrodes (MFEs). The novel-modified electrodes were applied in the direct analysis of trace metals in estuarine waters by square-wave anodic stripping voltammetry (SWASV). The effects of the coating morphology and thickness and also of the monomeric molar ratio PLL/PSS on the cation-exchange ability of the PLL-PSS polyelectrolyte coatings onto glassy carbon (GC) were evaluated using target cationic species such as dopamine (DA) or lead cation. Further, the semi-permeability of the PLL-PSS-coated electrodes based both on electrostatic interactions and on molecular size leads to an improved anti-fouling ability against several tensioactive species. The analytical usefulness of the PLL-PSS-mixed polyelectrolyte coatings on thin mercury film electrodes is demonstrated via SWASV measurements of trace metals (lead, copper and cadmium at the low nanomolar level; accumulation time of 180s) in estuarine waters containing moderate levels of dissolved organic matter, resulting in a fast and direct methodology requiring no sample pretreatment.

  9. Large scale molecular dynamics study of polymer-surfactant complex (United States)

    Goswami, Monojoy; Sumpter, Bobby


    In this work, we study the self-assembly of cationic polyelectrolytes mediated by anionic surfactants in dilute or semi-dilute and gel states. The understanding of the dilute system is a requirement for the understanding of gel states. The importance of polyelectrolyte with oppositely charged colloidal particles can be found in biological systems, such as immobilization of enzymes in polyelectrolyte complexes or nonspecific association of DNA with protein. With the same understanding, interaction of surfactants with polyelectrolytes shows intriguing phenomena that are important for both in academic research as well as industrial applications. Many useful properties of PE surfactant complexes come from the highly ordered structures of surfactant self-assembly inside the PE aggregate. We do large scale molecular dynamics simulation using LAMMPS to understand the structure and dynamics of PE-surfactant systems. Our investigation shows highly ordered ring-string structures that have been observed experimentally in biological systems. We will investigate many different properties of PE-surfactant complexation which will be helpful for pharmaceutical, engineering and biological applications.

  10. Organic versus hybrid coacervate complexes: co-assembly and adsorption properties (United States)

    Qi, Ling; Chapel, Jean-Paul; Castaing, Jean-Christophe; Fresnais, Jérôme; Berret, Jean-François

    We report the co-assembly and adsorption properties of coacervate complexes made from polyelectrolyte-neutral block copolymers and oppositely charged nanocolloids. The nanocolloids put under scrutiny were ionic surfactant micelles and highly charged 7 nm cerium oxide (CeO2) nanoparticles. Static and dynamic light scattering was used to investigate the microstructure and stability of the organic and hybrid complexes. The microstructure of the CeO2-based complexes was resolved using cryogenic transmission electronic microscopy (Cryo-TEM), and it revealed that the cores were clusters made from densely packed nanoparticles. In the concentration range of interest, c = 10-4 - 1 wt. %, the surfactant-based complexes were shown to exhibit a critical association concentration (cac) whereas the nanoparticle-polymer hybrids did not. The adsorption properties of the same complexes were investigated above the cac by stagnation point adsorption reflectometry. The adsorbed amount was measured as a function of time for polymers and complexes using anionically charged silica and hydrophobic poly(styrene) substrates. It was found that all complexes adsorbed readily on both types of substrates up to a level of 1 - 2 mg m-2 at stationary state. Upon rinsing however, the adsorbed layer was removed for the surfactant-based systems, but not for the cerium oxide clusters. As for the solution properties, these finding were interpreted in terms of a critical association concentrations which are very different for organic and hybrid complexes.

  11. Controller Design of Complex System Based on Nonlinear Strength

    Directory of Open Access Journals (Sweden)

    Rongjun Mu


    Full Text Available This paper presents a new idea of controller design for complex systems. The nonlinearity index method was first developed for error propagation of nonlinear system. The nonlinearity indices access the boundary between the strong and the weak nonlinearities of the system model. The algorithm of nonlinearity index according to engineering application is first proposed in this paper. Applying this method on nonlinear systems is an effective way to measure the nonlinear strength of dynamics model over the full flight envelope. The nonlinearity indices access the boundary between the strong and the weak nonlinearities of system model. According to the different nonlinear strength of dynamical model, the control system is designed. The simulation time of dynamical complex system is selected by the maximum value of dynamic nonlinearity indices. Take a missile as example; dynamical system and control characteristic of missile are simulated. The simulation results show that the method is correct and appropriate.

  12. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.


    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  13. Prediction of Software Requirements Stability Based on Complexity Point Measurement Using Multi-Criteria Fuzzy Approach

    Directory of Open Access Journals (Sweden)

    D. Francis Xavier Christopher


    Full Text Available Many software projects fail due to instable requirements and lack of managing the requirements changesefficiently. Software Requirements Stability Index Metric (RSI helps to evaluate the overall stability ofrequirements and also keep track of the project status. Higher the stability, less changes tends topropagate. The existing system use Function Point modeling for measuring the Requirements Stability.However, the main drawback of the existing modeling is that the complexity of non-functional requirementshas not been measured for Requirements Stability. The Non-Functional Factors plays a vital role inassessing the Requirements Stability. Numerous Measurement methods have been proposed for measuringthe software complexity. This paper proposes Multi-criteria Fuzzy Based approach for finding out thecomplexity weight based on Requirement Complexity Attributes such as Functional RequirementComplexity, Non-Functional Requirement Complexity, Input Output Complexity, Interface and FileComplexity. Based on the complexity weight, this paper computes the software complexity point. And thenpredict the Software Requirements Stability based on Software Complexity Point changes. The advantageof this model is that it is able to estimate the software complexity early which in turn predicts the SoftwareRequirement Stability during the software development life cycle.

  14. Photo-reactive charge trapping memory based on lanthanide complex. (United States)

    Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V A L


    Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 10(4) s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

  15. Synthesis, structures, and reactivity of the base-stabilized silanone molybdenum complexes. (United States)

    Muraoka, Takako; Abe, Keisuke; Kimura, Haruhiko; Haga, Youhei; Ueno, Keiji; Sunada, Yusuke


    Base-stabilized silanone molybdenum complexes were synthesized by the oxygenation of the M=Si bond in the silyl(silylene)molybdenum complex with 1 eq. of PNO in the presence of Lewis base L. The PNO-coordinated silanone complex (L = PNO) was converted to cis-[Cp*(OC)2Mo{OSiMes2(OSiMe3)}(PMe3)] in the presence of excess PMe3.

  16. Preparation and Electronic Property Investigation of Zinc(II)-Schiff Base Complexes in the Confined Space


    Peng Shang; Lei Zhang


    Metal-Schiff base complexes have attracted continued research interest regarding their intriguing and useful features, while the electronic properties of these complexes in the confined space have not been sufficiently addressed in previous studies. In this work, a new zinc(II)-Schiff base complex bis(N-dodecyl salicylideneiminato)Zn(II) (1) was synthesized and subsequently loaded in an inorganic solid host. A large red shift (~40 nm) of the absorption onset was recorded, when the microenviro...

  17. Synthesis and Characterization of Binuclear Schiff Base Complexes of Nickel, Copper, and Manganese. (United States)



  18. Design of polyelectrolyte multilayer membranes for ion rejection and wastewater effluent treatment (United States)

    Sanyal, Oishi

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

  19. Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents. (United States)

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


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

  20. Local pH and effective pKA of weak polyelectrolytes - insights from computer simulations. (United States)

    Nová, Lucie; Uhlík, Filip; Košovan, Peter


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

  1. Suitability of polyelectrolyte shells modified with fullerene derivate for immunoisolation of cells. Experimental study. (United States)

    Borkowska, M; Godlewska, E; Antosiak-Iwańska, M; Kinasiewicz, J; Strawski, M; Szklarczyk, M; Granicka, L H


    The polymeric permiselective membranes application for immunoisolation of cells separating the transplanted cells from the host immunological system may eliminate immunosuppressive therapy during transplantation. The suitability of polyelectrolyte modified nanocoatings for immunoisolation of cells was assessed. The polymeric shells modified with incorporated fullerene derivate were applied for encapsulation of human T-lymphocyte cell line Jurkat or rat pancreatic islets of Langerhans using layer-by-layer technique. Hydroxylated fullerene was incorporated to the polyelectrolyte shell for hydrophility increase as well as for layer stability improvement. Evaluation with AFM, FTIR, fluorescence microscopy confirmed the nanocoating presence on the encapsulated cells. It was observed that polylysine-polyethyleneimine membrane with incorporated fullerenol allowed for encapsulated cells functioning in vitro. Membrane conformation applied for encapsulation of pancreatic rat islets allowed for glucose level decline during xenotransplantation into mice. The elaborated nanocoating may be recommended as the possible alternative to the space consuming microencapsulation for biomedical purposes.

  2. Persistence length of a polyelectrolyte in salty water: Monte Carlo study. (United States)

    Nguyen, T T; Shklovskii, B I


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

  3. Interferometry study of aqueous lubrication on the surface of polyelectrolyte brush. (United States)

    Kobayashi, Motoyasu; Tanaka, Hiroyoshi; Minn, Myo; Sugimura, Joichi; Takahara, Atsushi


    The water lubrication behavior of a polyelectrolyte brush was investigated by using double-spacer-layer ultra-thin-film interferometry to determine the thickness of the aqueous lubrication layer present at the interface between the brush and a spherical glass lens. A hydrophilic poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride} brush was prepared on an optical glass disk coated with layers of semireflective chromium and silica. The thickness of the hydrodynamic lubrication layer was estimated interferometrically. On increasing the sliding velocity from 10(-5) to 10(-1) m·s(-1), the gap between the rotating disk and loading sphere glass lens showed a marked increase to 130 nm at 2×10(-2) m·s(-1), and the friction coefficient simultaneously decreased to 0.01-0.02, indicating that the polyelectrolyte brush promoted the formation of a fluid lubrication layer that separates the rubbing surfaces, preventing direct contact and providing a low friction coefficient.

  4. Spherical polyelectrolyte brushes as a nanoreactor for synthesis of ultrafine magnetic nanoparticles (United States)

    Zhu, Yan; Chen, Kaimin; Wang, Xiang; Guo, Xuhong


    Ultrafine magnetic nanoparticles (MNP, 1.4-5.8 nm) were generated within a nanoreactor of spherical polyelectrolyte brushes (SPB). SPB consist of a solid polystyrene (PS) core and densely grafted poly(acrylic acid) (PAA) chains. Due to strong chemical coordination between carboxyl groups in PAA and MNP surfaces, the obtained magnetic spherical polyelectrolyte brushes (MSPB) kept excellent stability and maintained pH sensitivity. The magnetic properties of MSPB were confirmed by a vibrating sample magnetometer (VSM). The size and the size dispersion of MNP can be modulated by varying adding sequences (conventional coprecipitation or reverse coprecipitation), or nanoreactor structure (with or without crosslinking). MNP content in MSPB could be adjusted by multicycle reactions. This new strategy makes it possible to synthesize ultrafine inorganic nanoparticles with tunable size in SPB.

  5. A new approach for automatic sleep scoring: Combining Taguchi based complex-valued neural network and complex wavelet transform. (United States)

    Peker, Musa


    Automatic classification of sleep stages is one of the most important methods used for diagnostic procedures in psychiatry and neurology. This method, which has been developed by sleep specialists, is a time-consuming and difficult process. Generally, electroencephalogram (EEG) signals are used in sleep scoring. In this study, a new complex classifier-based approach is presented for automatic sleep scoring using EEG signals. In this context, complex-valued methods were utilized in the feature selection and classification stages. In the feature selection stage, features of EEG data were extracted with the help of a dual tree complex wavelet transform (DTCWT). In the next phase, five statistical features were obtained. These features are classified using complex-valued neural network (CVANN) algorithm. The Taguchi method was used in order to determine the effective parameter values in this CVANN. The aim was to develop a stable model involving parameter optimization. Different statistical parameters were utilized in the evaluation phase. Also, results were obtained in terms of two different sleep standards. In the study in which a 2nd level DTCWT and CVANN hybrid model was used, 93.84% accuracy rate was obtained according to the Rechtschaffen & Kales (R&K) standard, while a 95.42% accuracy rate was obtained according to the American Academy of Sleep Medicine (AASM) standard. Complex-valued classifiers were found to be promising in terms of the automatic sleep scoring and EEG data.

  6. Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: a comparative approach. (United States)

    Raman, N; Sakthivel, A; Pravin, N


    A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 10(2) to 10(5) indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

  7. Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: A comparative approach (United States)

    Raman, N.; Sakthivel, A.; Pravin, N.

    A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 102 to 105 indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

  8. Energetic Ionic Liquids Based on Lanthanide Nitrate Complex Anions (Postprint) (United States)


    xH2O (x=27–44) [5a] and lanthanide complexes of the pseudohalide SCN in the hydrolytically unstable [ bmim ]4Ln ACHTUNGTRENNUNG(SCN)7·H2O ( bmim =1-butyl-3...Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim These are not the final page numbers! &1& FULL PAPER cal ionic liquids. The instability of [ bmim ]4Ln... bmim ]4Ln ACHTUNGTRENNUNG(SCN)7·H2O ionic liquids by displacing the isothiocyanate ligand.[5b] In our syntheses, guanidinium ni- trate and lanthanum or

  9. Photo-functional materials based on copper(Ⅰ) complexes

    Institute of Scientific and Technical Information of China (English)

    WANG Yuanmin; TENG Feng; XU Zheng; QIAN Lei; ZHANG Ting; LIU Deang


    Copper(Ⅰ) complexes are attractive photo-functional materials due to their rich photochemical and photophysical properties. It has been proved that these new materials have potential application in many fields, such as organic light-emitting diodes, optical sensor, nonlinear optics and dye sensitized solar cells. The goal of this review is to outline the progress in this field. Many aspects, including new ligands, stereochemical control and the construction of supramolecules, design of the excited states, the high-energy emission and low-energy emission, the Cu-Cu bonding interactions and applications, are discussed.

  10. Fuzzy nodes recognition based on spectral clustering in complex networks (United States)

    Ma, Yang; Cheng, Guangquan; Liu, Zhong; Xie, Fuli


    In complex networks, information regarding the nodes is usually incomplete because of the effects of interference, noise, and other factors. This results in parts of the network being blurred and some information having an unknown source. In this paper, a spectral clustering algorithm is used to identify fuzzy nodes and solve network reconstruction problems. By changing the fuzzy degree of placeholders, we achieve various degrees of credibility and accuracy for the restored network. Our approach is verified by experiments using open source datasets and simulated data.

  11. Chemistry and applications of organotin(IV) complexes of Schiff bases. (United States)

    Nath, Mala; Saini, Pramendra K


    Schiff bases are the most widely used versatile ligands, able to coordinate many elements and to stabilize them in various oxidation states. Recently, this class of compounds has been employed as models for biological systems, and in control of stereochemistry in six-coordinate transition metal complexes. Recently, the chemistry of organotin(IV) complexes of Schiff bases has also stemmed from their antitumour, antimicrobial, antinematicidal, anti-insecticidal and anti-inflammatory activities. Furthermore, organotin(IV) complexes of Schiff bases present a wide variety of interesting structural possibilities. Both aliphatic and aromatic Schiff bases in their neutral and deprotonated forms have been used to yield adducts and chelates with variable stoichiometry and different modes of coordination. This critical review (>155 references) focuses upon the chemistry and biological applications of organotin(IV) complexes of Schiff bases reported in the past 15 years. Thermal behavior of these complexes is also discussed.

  12. Charge regulation of weak polyelectrolytes at low- and high-dielectric-constant substrates

    CERN Document Server

    Netz, R R


    As is well known, the effective charge of weak polyelectrolytes (PEs) decreases with decreasing salt concentration due to the electrostatic repulsion between dissociated charges. Close to dielectric boundaries, image-charge effects influence the dissociation equilibrium. At low-dielectric-constant substrates, one finds a further charge decrease and repulsion from the interface, while at high-dielectric-constant (e.g. metallic) substrates, the effective charge increases and the PE is attracted to the interface.

  13. Improved pharmacokinetics and enhanced tumor growth inhibition using a nanostructured lipid carrier loaded with doxorubicin and modified with a layer-by-layer polyelectrolyte coating (United States)

    Mussi, Samuel V.; Parekh, Gaurav; Pattekari, Pravin; Levchenko, Tatyana; Lvov, Yuri; Ferreira, Lucas A.M.; Torchilin, Vladimir P.


    A nanostructured lipid carrier (NLC) loaded with doxorubicin (DOX) has been shown to be cytotoxic against the human cancer cell lines A549 and MCF-7/Adr. In attempts to improve formulation characteristics, enhance pharmacokinetics and antitumor effects, we modified the surface of these NLC with an alternating layer-by-layer (LbL) assembly of polycation and polyanion polyelectrolytes and an additional coating with PEG using a simple method of core shell attachment. The formulation had a narrow size distribution, longer residence in the blood, lower accumulation in the liver, higher accumulation in tumors and a significant tumor growth inhibition effect. Thus, NLC-DOX nanopreparations complexes modified by LbL coating have the potential to enhance the anticancer effects of DOX against tumors. PMID:26325314

  14. Lysozyme complexes with thermo- and pH-responsive PNIPAM- b-PAA block copolymer (United States)

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


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


    Directory of Open Access Journals (Sweden)

    S.P Li.


    Full Text Available This research demonstrated development and properties of detoxicants of integrated effect based on humic derivatives. Set of samples of humic-based derivatives including carbonylated, hydrophobizated, oxygenated, cryodestructed and biosolubilized have been synthesized. It has been demonstrated that all the produced detoxicants possessed plant growth promoting activity and detoxifying potential in relation to heavy metals.

  16. Efficient prediction of co-complexed proteins based on coevolution.

    Directory of Open Access Journals (Sweden)

    Damien M de Vienne

    Full Text Available The prediction of the network of protein-protein interactions (PPI of an organism is crucial for the understanding of biological processes and for the development of new drugs. Machine learning methods have been successfully applied to the prediction of PPI in yeast by the integration of multiple direct and indirect biological data sources. However, experimental data are not available for most organisms. We propose here an ensemble machine learning approach for the prediction of PPI that depends solely on features independent from experimental data. We developed new estimators of the coevolution between proteins and combined them in an ensemble learning procedure.We applied this method to a dataset of known co-complexed proteins in Escherichia coli and compared it to previously published methods. We show that our method allows prediction of PPI with an unprecedented precision of 95.5% for the first 200 sorted pairs of proteins compared to 28.5% on the same dataset with the previous best method.A close inspection of the best predicted pairs allowed us to detect new or recently discovered interactions between chemotactic components, the flagellar apparatus and RNA polymerase complexes in E. coli.

  17. Text Classification Retrieval Based on Complex Network and ICA Algorithm

    Directory of Open Access Journals (Sweden)

    Hongxia Li


    Full Text Available With the development of computer science and information technology, the library is developing toward information and network. The library digital process converts the book into digital information. The high-quality preservation and management are achieved by computer technology as well as text classification techniques. It realizes knowledge appreciation. This paper introduces complex network theory in the text classification process and put forwards the ICA semantic clustering algorithm. It realizes the independent component analysis of complex network text classification. Through the ICA clustering algorithm of independent component, it realizes character words clustering extraction of text classification. The visualization of text retrieval is improved. Finally, we make a comparative analysis of collocation algorithm and ICA clustering algorithm through text classification and keyword search experiment. The paper gives the clustering degree of algorithm and accuracy figure. Through simulation analysis, we find that ICA clustering algorithm increases by 1.2% comparing with text classification clustering degree. Accuracy can be improved by 11.1% at most. It improves the efficiency and accuracy of text classification retrieval. It also provides a theoretical reference for text retrieval classification of eBook

  18. Solid polyelectrolyte fuel cell power supply system; Kotai kobunshigata nenryo denchi dengen system

    Energy Technology Data Exchange (ETDEWEB)

    Aoki, T. [Kanagawa (Japan); Kadoma, H. [Yokohama (Japan); Hashizaki, K.; Tani, T. [Mitsubishi Heavy Industries Ltd., Tokyo (Japan)


    When a previous solid polyelectrolyte fuel cell power supply system is used underwater, the water generated by the cell reaction is stored in a water storage tank and it is necessary that the system is suspended in case the generated water is full in the water storage tank to take the system out of water and the water in the tank is discharged in the atmosphere. The solid polyelectrolyte fuel cell power supply system of this invention is equipped with a discharge pump to exhaust the generated water out of the closed vessel accommodating the system or equipped with a device to exhaust the generated water into the outside water accompanied with gushing of high-pressure gas into the outside water. As a result, the water generated by the cell reaction can be exhausted from the system into the outside water at any required time so that the fuel cell power supply system can be operated continuously as far as the supply of the fuel or the oxidizer last. By the installment of this function, a solid polyelectrolyte fuel cell power supply system can be used as an independent underwater power source or as a power source for an underwater moving body. 4 figs.

  19. Densely charged polyelectrolyte-stuffed nanochannel arrays for power generation from salinity gradient (United States)

    Kwak, Su Hong; Kwon, Seung-Ryong; Baek, Seol; Lim, Seung-Min; Joo, Young-Chang; Chung, Taek Dong


    We devised anodized aluminium oxide (AAO) frame-supported polyelectrolytic ion-exchange membranes for the application of electrical power generation systems where salinity differences are present. A series of polyelectrolytic AAO membranes (PAMs) were fabricated as a function of concentration of monomers and cross-linkers. Of the ion-selective PAMs as made, the membranes from the most concentrated monomers and cross-linkers, C-PAM100 and A-PAM100, showed the highest area resistances and permselectivities (the resistances were 4.9 and 2.9 Ω · cm2, the permseletivities for C-PAM100 and A-PAM100 were 99 and 89%, respectively). The measured resistances and permselectivities allowed the power density to be estimated for C-PAM100 and A-PAM100, 3.5 W/m2, and experimentally obtained power density using a reverse electrodialysis (RED) stack was 17.3 mW/m2. In addition, we investigated the influence of an AAO framework on a membrane resistance by comparing the PAMs with polyelectrolyte-stuffed capillaries, revealing that the resistance of the PAM has plenty of potential to be further reduced by optimizing the AAO pore spaces. PMID:27194475

  20. Molecular-dynamics simulations and x-ray analysis of dye precipitates in the polyelectrolyte microcapsules (United States)

    Saphiannikova, Marina; Radtchenko, Igor; Sukhorukov, Gleb; Shchukin, Dmitri; Yakimansky, Alexander; Ilnytskyi, Jaroslav


    The precipitate of the Disperse Red-1 dye in bulk and in confined microsized volumes was investigated by x-ray powder diffraction and molecular-dynamics simulations. The diffraction patterns exhibited two different precipitation regimes: In bulk when dye molecules form a distinct crystallite structure and inside polyelectrolyte capsules with a diameter up to 8 μm when the precipitate presumably represents a very fine polycrystalline powder. The latter result was further supported by molecular-dynamics simulations carried out for up to 640 dye molecules in the NVT ensemble. Calculations have also shown that effects of confined geometry and steric restrictions arising due to encapsulated polyelectrolyte molecules can not prohibit dye nucleation and subsequent crystallization. However, nonspecific interactions between Disperse Red-1 and encapsulated polyelectrolyte could cause the onset of heterogeneous nucleation resulting in formation of a fine polycrystalline powder. The formation process was directly observed building configuration snapshots and calculating the Gay-Berne orientational order parameter and radial distribution function resolved parallel and perpendicular to the director. Comparison of powder diagrams derived from simulation data indicates that it is nearly impossible to distinguish a fine polycrystalline powder from the isotropic system.