Sample records for nanoparticle-fluorescent polymer complexes

  1. Phase Equilibria for Complex Polymer Solutions

    Lindvig, Thomas; Hestkjær, L. L.; Hansen, A. F.


    the content of organic solvents. This work presents an investigation of the three polymer models Entropic-FV (EFV). UNIFAC-FV (UFV) and GC-Flory (GCF) for their capability of predicting solvent activity coefficients in binary systems containing complex polymers. It is possible to obtain good predictions...... at finite concentrations and satisfactory predictions at infinite dilution, particularly with the EFV model. The investigation shows that EFV is the most robust and stable of the models, which indicates that it is the most well suited model for further development of methods for predicting the miscibility...

  2. 50th Anniversary Perspective: Polymers with Complex Architectures

    Polymeropoulos, George; Zapsas, George; Ntetsikas, Konstantinos; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos


    The scope of this Perspective is to highlight innovative contributions in the synthesis of well-defined complex macromolecular architectures and to emphasize the importance of these materials to polymer physical chemistry, physics, theory

  3. 50th Anniversary Perspective: Polymers with Complex Architectures

    Polymeropoulos, George


    The scope of this Perspective is to highlight innovative contributions in the synthesis of well-defined complex macromolecular architectures and to emphasize the importance of these materials to polymer physical chemistry, physics, theory, and applications. In addition, this Perspective tries to enlighten the past and show possible pathways for the future. Among the plethora of polymerization methods, we briefly report the impact of the truly living and controlled/living polymerization techniques focusing mainly on anionic polymerization, the mother of all living and controlled/living polymerizations. Through anionic polymerization well-defined model polymers with complex macromolecular architectures having the highest molecular weight, structural and compositional homogeneity can be achieved. The synthesized structures include star, comb/graft, cyclic, branched and hyberbranched, dendritic, and multiblock multicomponent polymers. In our opinion, in addition to the work needed on the synthesis, properties, and application of copolymers with more than three chemically different blocks and complex architecture, the polymer chemists in the future should follow closer the approaches Nature, the perfect chemist, uses to make functional complex macromolecular structures by noncovalent chemistry. Moreover, development of new analytical methods for the characterization/purification of polymers with complex macromolecular architectures is essential for the synthesis and properties study of this family of polymeric materials.

  4. From precision polymers to complex materials and systems

    Lutz, Jean-François; Lehn, Jean-Marie; Meijer, E. W.; Matyjaszewski, Krzysztof


    Complex chemical systems, such as living biological matter, are highly organized structures based on discrete molecules in constant dynamic interactions. These natural materials can evolve and adapt to their environment. By contrast, man-made materials exhibit simpler properties. In this Review, we highlight that most of the necessary elements for the development of more complex synthetic matter are available today. Using modern strategies, such as controlled radical polymerizations, supramolecular polymerizations or stepwise synthesis, polymers with precisely controlled molecular structures can be synthesized. Moreover, such tailored polymers can be folded or self-assembled into defined nanoscale morphologies. These self-organized macromolecular objects can be at thermal equilibrium or can be driven out of equilibrium. Recently, in the latter case, interesting dynamic materials have been developed. However, this is just a start, and more complex adaptive materials are anticipated.

  5. Synthesis of conjugated polymers with complex architecture for photovoltaic applications

    Kiriy, Anton; Krebs, Frederik C


    A common approach to bulk heterojunction solar cells involves a “trialand- error” approach in finding optimal kinetically unstable morphologies. An alternative approach assumes the utilization of complex polymer architectures, such as donor–acceptor block copolymers. Because of a covalent preorga...... preorganization of the donor and acceptor components, these materials may form desirable morphologies at thermodynamic equilibrium. This chapter reviews synthetic approaches to such architectures and shows the first photovoltaic results....

  6. Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers.

    Fares, Hadi M; Schlenoff, Joseph B


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

  7. A new synthesis route for Os-complex modified redox polymers for potential biofuel cell applications.

    Pöller, Sascha; Beyl, Yvonne; Vivekananthan, Jeevanthi; Guschin, Dmitrii A; Schuhmann, Wolfgang


    A new synthesis route for Os-complex modified redox polymers was developed. Instead of ligand exchange reactions for coordinative binding of suitable precursor Os-complexes at the polymer, Os-complexes already exhibiting the final ligand shell containing a suitable functional group were bound to the polymer via an epoxide opening reaction. By separation of the polymer synthesis from the ligand exchange reaction at the Os-complex, the modification of the same polymer backbone with different Os-complexes or the binding of the same Os-complex to a number of different polymer backbones becomes feasible. In addition, the Os-complex can be purified and characterized prior to its binding to the polymer. In order to further understand and optimize suitable enzyme/redox polymer systems concerning their potential application in biosensors or biofuel cells, a series of redox polymers was synthesized and used as immobilization matrix for Trametes hirsuta laccase. The properties of the obtained biofuel cell cathodes were compared with similar biocatalytic interfaces derived from redox polymers obtained via ligand exchange reaction of the parent Os-complex with a ligand integrated into the polymer backbone during the polymer synthesis. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Moessbauer spectroscopic study of polymer-bound heme complexes

    Tsuchida, Eishun; Nishide, Hiroyuki; Yokoyama, Hiroyuki; Inoue, Hidenari; Shirai, Tsuneo.


    Moessbauer spectra were measured on the heme complexes of poly(1-vinyl- and 1-vinyl-2-methylimidazole)(PVI and PMI) and heme derivatives with covalently bound imidazoleligand (IH) and 2-methylimidazole-ligand (MIH) embedded in poly(1-vinyl-2-pyrrolidone) film. Quadrupole splitting (ΔE sub(Q)) for the carbon monoxide adduct of PMI-heme indicated large electronic field gradient at the iron nucleus, probably due to steric hindrance of the polymer chain, and this behavior agreed with its low affinity with carbon monoxide. PMI-heme formed an oxygen adduct and its isomer shift and ΔE sub(Q) values were obtained. (author)

  9. Manipulating interfacial polymer structures through mixed surfactant adsorption and complexation.

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


    The effects of a nonionic alcohol ethoxylate surfactant, C(13)E(7), on the interactions between PVP and SDS both in the bulk and at the silica nanoparticle interface are studied by photon correlation spectroscopy, solvent relaxation NMR, SANS, and optical reflectometry. Our results confirmed that, in the absence of SDS, C(13)E(7) and PVP are noninteracting, while SDS interacts strongly both with PVP and C(13)E(7) . Studying interfacial interactions showed that the interfacial interactions of PVP with silica can be manipulated by varying the amounts of SDS and C(13)E(7) present. Upon SDS addition, the adsorbed layer thickness of PVP on silica increases due to Coulombic repulsion between micelles in the polymer layer. When C(13)E(7) is progressively added to the system, it forms mixed micelles with the complexed SDS, reducing the total charge per micelle and thus reducing the repulsion between micelle and the silica surface that would otherwise cause the PVP to desorb. This causes the amount of adsorbed polymer to increase with C(13)E(7) addition for the systems containing SDS, demonstrating that addition of C(13)E(7) hinders the SDS-mediated desorption of an adsorbed PVP layer. © 2012 American Chemical Society

  10. Self-consistent field theory of polymer-ionic molecule complexation

    Nakamura, Issei; Shi, An-Chang


    A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C_(i)^(a)(kΔ)(= 0 or 1), whose average determines the number of adsorbed molecules, nBI. Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for nBI are obtained, depending...

  11. Influence of complexing on physicochemical properties of polymer-salt solutions

    Ostroushko, A.A.; Yushkova, S.M.; Koridze, N.V.; Skobkoreva, N.V.; Zhuravleva, L.I.; Palitskaya, T.A.; Antropova, S.V.; Ostroushko, I.P.; AN SSSR, Moscow


    Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated

  12. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei


    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Preparation and characterization of PAN–KI complexed gel polymer ...

    The conductivity-temperature dependence of these polymer electrolyte films obeys Arrhenius behaviour with activa- ... oxide (PEO), polyvinyl alcohol, polyvinyl pyrrolidone (PVP) ... chemical, flame resistance and electrochemical stability.

  14. Removal of waterborne microorganisms by filtration using clay-polymer complexes.

    Undabeytia, Tomas; Posada, Rosa; Nir, Shlomo; Galindo, Irene; Laiz, Leonila; Saiz-Jimenez, Cesareo; Morillo, Esmeralda


    Clay-polymer composites were designed for use in filtration processes for disinfection during the course of water purification. The composites were formed by sorption of polymers based on starch modified with quaternary ammonium ethers onto the negatively charged clay mineral bentonite. The performance of the clay-polymer complexes in removal of bacteria was strongly dependent on the conformation adopted by the polycation on the clay surface, the charge density of the polycation itself and the ratio between the concentrations of clay and polymer used during the sorption process. The antimicrobial effect exerted by the clay-polymer system was due to the cationic monomers adsorbed on the clay surface, which resulted in a positive surface potential of the complexes and charge reversal. Clay-polymer complexes were more toxic to bacteria than the polymers alone. Filtration employing our optimal clay-polymer composite yielded 100% removal of bacteria after the passage of 3L, whereas an equivalent filter with granular activated carbon (GAC) hardly yielded removal of bacteria after 0.5L. Regeneration of clay-polymer complexes saturated with bacteria was demonstrated. Modeling of the filtration processes permitted to optimize the design of filters and estimation of experimental conditions for purifying large water volumes in short periods. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Plasticisation and complexation of certain polymers in supercritical CO2

    Labuschagne, Philip W


    Full Text Available A polymer system (polyvinylpyrrolidone + polyvinyl acetate-co-crotonic acid) was successfully identified for use as encapsulation material for sensitive actives using supercritical CO2 as plasticisation medium, having the following properties: 1...

  16. Synthesis and characterization of variable-architecture thermosensitive polymers for complexation with DNA.

    Pennadam, Sivanand S; Ellis, James S; Lavigne, Matthieu D; Górecki, Dariusz C; Davies, Martyn C; Alexander, Cameron


    Copolymers of N-isopropylacrylamide with a fluorescent probe monomer were grafted to branched poly(ethyleneimine) to generate polycations that exhibited lower critical solution temperature (LCST) behavior. The structures of these polymers were confirmed by spectroscopy, and their phase transitions before and after complexation with DNA were followed using ultraviolet and fluorescence spectroscopy and light scattering. Interactions with DNA were investigated by ethidium bromide displacement assays, while temperature-induced changes in structure of both polymers and polymer-DNA complexes were evaluated by fluorescence spectroscopy, dynamic light scattering, laser Doppler anemometry, and atomic force microscopy (AFM) in water and buffer solutions. The results showed that changes in polymer architecture were mirrored by variations in the architectures of the complexes and that the overall effect of the temperature-mediated changes was dependent on the graft polymer architecture and content, as well as the solvent medium, concentrations, and stoichiometries of the complexes. Furthermore, AFM indicated subtle changes in polymer-DNA complexes at the microstructural level that could not be detected by light scattering techniques. Uniquely, variable-temperature aqueous-phase AFM was able to show that changes in the structures of these complexes were not uniform across a population of polymer-DNA condensates, with isolated complexes compacting above LCST even though the sample as a whole showed a tendency for aggregation of complexes above LCST over time. These results indicate that sample heterogeneities can be accentuated in responsive polymer--DNA complexes through LCST-mediated changes--a factor that is likely to be important in cellular uptake and nucleic acid transport.

  17. Advances in Biomagnetic Interfacing Concepts Derived from Polymer-Magnetic Particle Complexes

    Riffle, Judy S


    Our research on the development and characterization of magnetic nanoparticle-polymer complexes for tile project period 6/1/03-12/31/04 has yielded approximately 10-nm diameter cobalt particles coated...

  18. Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

    Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.


    We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

  19. Polymers with complexing properties. Simple poly(amino acids)

    Roque, J. M.


    The free amino (0.3 equiv/residue) and carboxyl (0.5 equiv/residue) groups of thermal polylysine increased dramatically on treatment with distilled water. The total hydrolysis of such a polymer was abnormal in that only about 50% of the expected amino acids were recovered. Poly (lysine-co-alanine-co-glycine) under usual conditions hydrolyzed completely in 8 hours; whereas, when it was pretreated with diazomethane, a normal period of 24 hours was required to give (nearly) the same amounts of each free amino acid as compared with those obtained from the untreated polymer. The amino groups of the basic thermal poly(amino acids) were sterically hindered. The existence of nitrogen atoms linking two or three chains and reactive groups (anhydride, imine) were proposed.

  20. Synthesis and photocatalytic activity of TiO2/conjugated polymer complex nanoparticles

    Shi Xiong Min; Fang Wang; Lei Feng; Yong Chun Tong; Zi Rong Yang


    A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light (λ=190-800nm). Methylene blue (MB) could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃>300℃>340℃>220℃>180℃.

  1. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.


    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

  2. New transition metal complexes and their ring-opened polymers

    Apodaca, Paula

    An exciting new class of metallacycle (eta5-C5 H4Fe) (CO)2CH2SiR2 that undergoes ring-opening polymerization was recently reported by Sharma et al. [1]. We are interested in further expanding this research area by synthesizing related cyclopentadienyl derivatives containing Fe, Mo, and W in combination with other elements of the group 14. We report here the synthesis and crystal structure characterization of new germa-metallacyclobutanes of Mo and W. In addition, we have successfully synthesized and characterized new ring-opening polymers of the related germanium systems [(eta5-C5 H4Fe)(CO) 2(CH2GeR2)] n. The new polymers were characterized using various spectroscopic techniques and gel permeation chromatography. The recent report on the synthesis of a new class of siloxane polymers based upon base-catalyzed ring opening of phenylene-bridged cyclic siloxanes [2] encouraged us to investigate the related ferrocenyl (Fc, (C5H 5)Fe(C5H4)) siloxane systems. The incorporation of ferrocene could provide new materials with all the interesting properties usually associated with these groups such as thermal and photochemical stability, electrochemical activity and potentially conducting materials. Thus far a new required organometallic monomer containing Fc-R, where R = disilaoxacyclopentene 5 has been synthesized and completely characterized. Based-induced ring-opening polymerizations of 5 were attempted under different reaction conditions and produced, inter alia: (C5H5)Fe(C 5H4)C(SiMe2OH)=CH(SiMe2R), R = nBu (2), tBu (3), Ph (4). The single crystal X-ray structures and full spectroscopic analysis of such products has been accomplished. Furthermore, the reactivity of the ferrocenyl silanols concerning condensation and their behavior under acidic conditions has been investigated. 1Sharma, H.; Cervantes-Lee, F.; Pannell, K. H. J. Am. Chem. Soc. 2004, 126, 1326. 2 Loy, A. D.; Rahimian, K.; Samara, M. Angew. Chem. 1999, 38, 45.

  3. Self-consistent field theory of polymer-ionic molecule complexation.

    Nakamura, Issei; Shi, An-Chang


    A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

  4. Evaluating polymer degradation with complex mixtures using a simplified surface area method.

    Steele, Kandace M; Pelham, Todd; Phalen, Robert N


    Chemical-resistant gloves, designed to protect workers from chemical hazards, are made from a variety of polymer materials such as plastic, rubber, and synthetic rubber. One material does not provide protection against all chemicals, thus proper polymer selection is critical. Standardized testing, such as chemical degradation tests, are used to aid in the selection process. The current methods of degradation ratings based on changes in weight or tensile properties can be expensive and data often do not exist for complex chemical mixtures. There are hundreds of thousands of chemical products on the market that do not have chemical resistance data for polymer selection. The method described in this study provides an inexpensive alternative to gravimetric analysis. This method uses surface area change to evaluate degradation of a polymer material. Degradation tests for 5 polymer types against 50 complex mixtures were conducted using both gravimetric and surface area methods. The percent change data were compared between the two methods. The resulting regression line was y = 0.48x + 0.019, in units of percent, and the Pearson correlation coefficient was r = 0.9537 (p ≤ 0.05), which indicated a strong correlation between percent weight change and percent surface area change. On average, the percent change for surface area was about half that of the weight change. Using this information, an equivalent rating system was developed for determining the chemical degradation of polymer gloves using surface area.

  5. Polymer brushes infiltrated by nanoparticles and applications to the nuclear pore complex

    Opferman, Michael G.

    Systems of grafted polymers in the presence of additives are useful in a variety of contexts including industrial applications, solar cells, organic electronics, drug delivery, and nucleocytoplasmic transport. In this thesis, we will consider the morphologies that polymer brushes attain when exposed to a solution of additives (which we generically term "nanoparticles"), particularly when those nanparticles interact attractively with the polymers. We find that nanoparticles of this type can have a dramatic effect on the height of the polymer chains above the grafting surface, and they can induce highly non-uniform morphologies, including ones in which a dense layer of nanoparticles and monomers forms near the grafting surface. We consider especially the relevance of the system to several experiments performed on biopolymers in the nuclear pore complex when they interact attractively with transport factors that regulate nucleocytoplasmic transport. We find that, although these experiments appear to give inconsistent results, the inconsistencies can be reconciled through two simple models: the Alexander-de Gennes polymer brush, and the Milner-Witten-Cates polymer brush. Our findings should contribute to the understanding of the nuclear pore complex in that experiments can be better understood in the context of their relevant control parameters.

  6. From precision polymers to complex materials and systems

    Lutz, J.F.; Lehn, J.M.; Meijer, E.W.; Matyjaszewski, K.


    Complex chemical systems, such as living biological matter, are highly organized structures based on discrete molecules in constant dynamic interactions. These natural materials can evolve and adapt to their environment. By contrast, man-made materials exhibit simpler properties. In this Review, we

  7. Fourier-transform infrared spectroscopic study of a fractional-complexed polymer blend

    Šturcová, Adriana; Kratochvíl, Jaroslav; Dybal, Jiří; Sikora, Antonín


    Roč. 59, October (2014), s. 200-207 ISSN 0014-3057 R&D Projects: GA ČR GAP108/12/0703 Institutional support: RVO:61389013 Keywords : miscible blend * inter-polymer complex * associative phase separation Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.005, year: 2014

  8. Leaching of irradiated polymers: solution characterization and actinides complexation

    Fromentin, Elodie


    The first aim of this work is to study the degradation of an industrial poly-esterurethane (PURm) by radio-oxidation and then by leaching in an alkaline aqueous solution. The second aim is to measure the complexing power of hydro-soluble degradation products (HDP) with actinides. To reach these goals, PURm was first characterized and then radio-oxidized at room temperature with γ rays up to 10 MGy. Second, it was leached at pH 13.3 at different temperature values. Numerous analytical techniques were employed in order to characterize the HDP which were obtained. Europium(III) was used as an analogue of actinides(III) and the behavior of HDP with europium(III) was analyzed by time-resolved luminescence spectroscopy (TRLS). Whatever the dose received by PURm, adipic acid and butane-1,4-diol are the two main HDP in leachates. The leaching data acquired at 40 and 60 C, on the 1 MGy radio-oxidized PURm, correlate with the model given by Yoon et al. (1997). However, the data at room temperature (22 C in average) are not in agreement with the model. Nevertheless, it seems that the plateau which was reached at long-term leaching is the same whatever the temperature used in this study. The results allow to conclude that the predominant mechanism occurring during the leaching of unirradiated and radio-oxidized PURm in an alkaline medium is the hydrolysis of the soft segments ester groups. The complexation of europium(III) by HDP in alkaline medium was demonstrated. The measurement of the complexing power and the identification of ligands was achieved under certain conditions. (author) [fr

  9. Fabrication of Superhydrophobic and Luminescent Rare Earth/Polymer complex Films.

    Wang, Zefeng; Ye, Weiwei; Luo, Xinran; Wang, Zhonggang


    The motivation of this work is to create luminescent rare earth/polymer films with outstanding water-resistance and superhydrophobicity. Specifically, the emulsion polymerization of styrene leads to core particles. Then core-shell-structured polymer nanoparticles are synthesized by copolymerization of styrene and acrylic acid on the core surface. The coordination reaction between carboxylic groups and rare earth ions (Eu(3+) and Tb(3+)) generates uniform spherical rare earth/polymer nanoparticles, which are subsequently complexed with PTFE microparticles to obtain micro-/nano-scaled PTFE/rare earth films with hierarchical rough morphology. The films exhibit large water contact angle up to 161° and sliding angle of about 6°, and can emit strong red and green fluorescence under UV excitation. More surprisingly, it is found that the films maintain high fluorescence intensity after submersed in water and even in aqueous salt solution for two days because of the excellent water repellent ability of surfaces.

  10. Incorporation of Znq2 complexes into mesoporous silica and their transparent polymer luminescent nanocomposites

    Du Yaying; Fu Yuqin; Shi Yongli; Lue Xiaodan; Lue Changli; Su Zhongmin


    Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent nanocomposites were prepared by in situ bulk polymerization. CMS nanoparticles or nanorods with hydroxyl-, mercapto- and sulfonic-functionalized interiors were obtained by different synthetic routes in the nanosize dimensions between 50 and 500 nm. The luminescent Znq 2 complex was successfully introduced in the pores of different mesoporous silicas by chemical adsorption as the driving force. The different internal circumstances of mesoporous silicas had an obvious effect on the luminescence and lifetime of Znq 2 complex. The transparent fluorescent nanocomposites were fabricated from different Znq 2 -CMS and suitable monomers. The Znq 2 -CMS were uniformly dispersed in the polymer matrix without evident aggregation. The photoluminescence properties of Znq 2 -CMS in the transparent matrix exhibited a dependence on the inner surrounding of CMS due to the interaction between Znq 2 -CMS and polymers. The maximum emission peak of the nanocomposites had a red-shift of 28 nm as compared to pure Znq 2 -CMS. - Graphical abstract: Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent fluorescent nanocomposites were prepared by in situ bulk polymerization. The figure shows the synthetic scheme for the Znq 2 -CMS and their transparent bulk nanocomposites.

  11. Estimation of apparent kinetic parameters of polymer pyrolysis with complex thermal degradation behavior

    Srimachai, Taranee; Anantawaraskul, Siripon


    Full text: Thermal degradation behavior during polymer pyrolysis can typically be described using three apparent kinetic parameters (i.e., pre-exponential factor, activation energy, and reaction order). Several efficient techniques have been developed to estimate these apparent kinetic parameters for simple thermal degradation behavior (i.e., single apparent pyrolysis reaction). Unfortunately, these techniques cannot be directly extended to the case of polymer pyrolysis with complex thermal degradation behavior (i.e., multiple concurrent reactions forming single or multiple DTG peaks). In this work, we proposed a deconvolution method to determine the number of apparent reactions and estimate three apparent kinetic parameters and contribution of each reaction for polymer pyrolysis with complex thermal degradation behavior. The proposed technique was validated with the model and experimental pyrolysis data of several polymer blends with known compositions. The results showed that (1) the number of reaction and (2) three apparent kinetic parameters and contribution of each reaction can be estimated reasonably. The simulated DTG curves with estimated parameters also agree well with experimental DTG curves. (author)

  12. ToF-SIMS and Laser-SNMS Imaging of Heterogeneous Topographically Complex Polymer Systems.

    Pelster, Andreas; Körsgen, Martin; Kurosawa, Takako; Morita, Hiromi; Arlinghaus, Heinrich F


    Heterogeneous polymer coatings, such as those used in organic electronics and medical devices, are of increasing industrial importance. In order to advance the development of these types of systems, analytical techniques are required which are able to determine the elemental and molecular spatial distributions, on a nanometer scale, with very high detection efficiency and sensitivity. The goal of this study was to investigate the suitability of laser postionization secondary neutral mass spectrometry (Laser-SNMS) with a 157 nm postionization laser beam to image structured polymer mixtures and compare the results with time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements using Bi 3 + primary ions. The results showed that Laser-SNMS is better suited than ToF-SIMS for unambiguous detection and submicrometer imaging of the wide range of polymers investigated. The data also showed that Laser-SNMS has the advantage of being much more sensitive (in general higher by more than an order of magnitude and peaking at up to 3 orders of magnitude) than ToF-SIMS while also showing superior performance on topographically complex structured insulating surfaces, due to significantly reduced field effects and a higher dynamic range as compared to ToF-SIMS. It is concluded that Laser-SNMS is a powerful complementary technique to ToF-SIMS for the analysis of heterogeneous polymers and other complex structured organic mixtures, providing submicrometer resolution and high sensitivity.

  13. Novel polymer anchored Cr(III) Schiff base complexes: Synthesis, characterization and antimicrobial properties

    Selvi, Canan; Nartop, Dilek


    New polymer-bound Schiff bases and Cr(III) complexes have been synthesized by the reaction of 4-benzyloxybenzaldehyde, polymer-bound with 2-aminophenol, 2-amino-4-chlorophenol and 2-amino-4-methylphenol. The structure of polymeric-Schiff bases and their Cr(III) complexes have been characterized by elemental analyses, magnetic measurements, IR, UV-Vis, TG-DTA and 1H-NMR. All these compounds have also been investigated for antibacterial activity by the well-diffusion method against Staphylococcus aureus (RSKK-07035), Shigella dysenteria type 10 (RSKK 1036), Listeria monocytogenes 4b(ATCC 19115, Escherichia coli (ATCC 1230), Salmonella typhi H (NCTC 901.8394), Staphylococcus epidermis (ATCC 12228), Brucella abortus (RSKK-03026), Micrococcs luteus (ATCC 93419, Bacillus cereus sp., Pseudomonas putida sp. and for antifungal activity against Candida albicans (Y-1200-NIH).

  14. Prevention of the wind migration of Semipalatinsk test site contaminated topsoil by inter-polymer complexes

    Kudaibergenov, S.E.


    Full text: It is well known that Semipalatinsk Test Site has been contaminated by radionuclides mainly as a result of atmospheric, aboveground and underground intensive nuclear tests during more than 40 years. Survey of residual radioactivity in the soil at ten Semipalatinsk Test Site areas showed that a great number of Plutonium-239, 240, Strontium-90 and Cesium-137 are concentrated in the depth of soil layer 0-8 cm. The residual radioactivity within the Semipalatinsk Test Site is tightly bound to the topsoil as a result of extreme heating and melting of the soils during the tests. The maximal amount of radionuclides is accumulated on the fine soil particles having 0.1-1.0 mm size. Wind erosion is responsible for suspension of contaminated soil particles in the air and further spreading of contamination far away. For instance, dust particles of diameter 0,05-0,1 mm are dropped within a couple of kilometers of the erosion site, while particles of about 0.005-0.01 mm diameter can move hundreds and thousands of kilometers. According to the results of the Institute of Radiation Safety and Ecology, Kazakhstan, in “Degelen” massive, where the intensive nuclear tests were carried out, the concentration of radionuclides in air increases for Sr-90 up to 5 times, for Pu-239,240 up to 100-250 times during the elevation of thin dust from the ground surface. In this connection agglomeration of thin dust containing radionuclides is of primary importance to protect the population from inhalation of re-suspended dust. Inter-polymer complexes are water-insoluble, moisture and gas permeable substances that form a “cobweb” on the surface of soil particles and consequently leading to formation of protective crust. Inter-polymer complexes enhance the intrusion of water into the soil, resulting in increased soil moisture to promote seed germination and plant growth. Inter-polymer complexes are also able to accumulate radionuclides via inclusion of metal ions into the Inter-polymer

  15. Silver-tellurolate polynuclear complexes: from isolated cluster units to extended polymer chains

    Corrigan, J.F.; Fenske, D.; Power, W.P.


    In the presence of tertiary phosphanes, AgCl reacts readily with the reagent Te(Ph)SiMe 3 to yield silver - tellurolate polynuclear complexes. In the case of PMe 3 , the polymer [Ag 10 (μ 3 -TePh) 10 (PMe 3 ) 2 ] ∞ (shown below) is formed, in which the TePh ligands seve as both inter- and intracluster bridges. (orig.)

  16. The effective complex permittivity stability in filled polymer nanocomposites studied above the glass transition temperature

    Elhaouzi F.


    Full Text Available The temperature effecton the dielectric response of nanocomposite at low frequencies range is reported. The investigated samples are formed by a semi-crystalline ethylene-co-butyl acrylate (EBA polymer filled with three concentrations of the dispersed conducting carbon black (CB nanoparticles. The temperature dependence of the complex permittivity has been analyzedabove the glass transition temperature of the neat polymer matrix Tg=-75°C. For all CB concentrations, the dielectric spectra follow a same trend in frequency range 100-106Hz. More interestingly, the stability of the effective complex permittivity ɛ=ɛ' -iɛ'' with the temperature range of 10-70°C is explored. While the imaginary part of the complex permittivity ɛ'' exhibits a slight decreasewith temperature, the real part ɛ' shows a significant reduction especially for high loading samples. The observed dielectric response may be related to the breakup of the three-dimensional structurenetwork formed by the aggregation of CB particles causing change at the interfaceEBA-CB.This interface is estimated bythe volume fraction of constrained polymer chain according to loss tangent data of dynamic mechanical analysis.

  17. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun


    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

  18. Complex-shaped ceramic composites obtained by machining compact polymer-filler mixtures

    Rosa Maria da Rocha


    Full Text Available Research in the preparation of ceramics from polymeric precursors is giving rise to increased interest in ceramic technology because it allows the use of several promising polymer forming techniques. In this work ceramic composite pieces were obtained by pyrolysis of a compacted mixture of a polysiloxane resin and alumina/silicon powder. The mixture consists of 60 vol% of the polymer phase and 40 vol% of the filler in a 1:1 ratio for alumina/silicon, which was hot pressed to crosslink the polymer, thus forming a compact body. This green body was trimmed into different geometries and pyrolised in nitrogen atmosphere at temperatures up to 1600 °C. X-ray diffraction analysis indicated the formation of phases such as mullite and Si2ON2 during pyrolysis, that result from reactions between fillers, polymer decomposition products and nitrogen atmosphere. The porosity was found to be less than 20% and the mass loss around 10%. The complex geometry was maintained after pyrolysis and shrinkage was approximately 8%, proving pyrolisis to be a suitable process to form near-net-shaped bulk ceramic components.

  19. Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

    El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.


    The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

  20. Influence of intensive light exposure on the complex impedance of polymer light-emitting diodes

    Fábio Rogério Cury


    Full Text Available In this work we investigated the effect of visible radiation on the electrical properties of poly[(2-methoxy-5-hexyloxy-p-phenylenevinylene]- MH-PPV films and light emitting diodes. Complex impedance measurements of (Au or ITO/MH-PPV/(Au or Al samples were carried out at room temperature and exposed to white light. Over the frequency range from 100 mHz to 2 MHz, the electrical results of Au/MH-PPV/Au was dominated by the Cole-Cole approach, where the electrode influence is negligible. However, some additional influence of the interface was observed to occur when Al was used as electrode. These effects were observed under both dark and visible-light illumination conditions. A simple model based on resistor-capacitor parallel circuits was developed to represent the complex impedance of the samples, thereby separating bulk and interface contributions. We observed that the polymer electrical resistivity decreased while the dielectric constant of the polymer and the thickness of the Al/MH-PPV layer were almost constant with increasing light intensity. The decrease of the polymer layer resistance comes from a better charge injection due to a light induced dissociation of positive charge carriers at the electrode.

  1. Preparation and Evaluation of Taste Masked Famotidine Formulation Using Drug/β-cyclodextrin/Polymer Ternary Complexation Approach

    Patel, Ashok R.; Vavia, Pradeep R.


    The main aim of the present study was to evaluate potential of ternary complexation (comprising of drug, cyclodextrin and polymer) as an approach for taste masking. For this purpose famotidine with property of bitter taste was selected as a model drug. Improvement in taste masking capability of cyclodextrin towards famotidine was evaluated by formulating a ternary complex including hydrophilic polymer hydroxyl propyl methyl cellulose (HPMC 5 cps) as the third component. Phase solubility analy...

  2. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)


    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  3. A look at the effect of sequence complexity on pressure destabilisation of DNA polymers.

    Rayan, Gamal; Macgregor, Robert B


    Our previous studies on the helix-coil transition of double-stranded DNA polymers have demonstrated that molar volume change (ΔV) accompanying the thermally-induced transition can be positive or negative depending on the experimental conditions, that the pressure-induced transition is more cooperative than the heat-induced transition [Rayan and Macgregor, J Phys Chem B2005, 109, 15558-15565], and that the pressure-induced transition does not occur in the absence of water [Rayan and Macgregor, Biophys Chem, 2009, 144, 62-66]. Additionally, we have shown that ΔV values obtained by pressure-dependent techniques differ from those obtained by ambient pressure techniques such as PPC [Rayan et al. J Phys Chem B2009, 113, 1738-1742] thus shedding light on the effects of pressure on DNA polymers. Herein, we examine the effect of sequence complexity, and hence cooperativity on pressure destabilisation of DNA polymers. Working with Clostridium perfringes DNA under conditions such that the estimated ΔV of the helix-coil transition corresponds to -1.78 mL/mol (base pair) at atmospheric pressure, we do not observe the pressure-induced helix-coil transition of this DNA polymer, whereas synthetic copolymers poly[d(A-T)] and poly[d(I-C)] undergo cooperative pressure-induced transitions at similar ΔV values. We hypothesise that the reason for the lack of pressure-induced helix-coil transition of C. perfringens DNA under these experimental conditions lies in its sequence complexity. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Cellobiose dehydrogenase entrapped within specifically designed Os-complex modified electrodeposition polymers as potential anodes for biofuel cells

    Shao, Minling; Guschin, Dmitrii A.; Kawah, Zahma; Beyl, Yvonne; Stoica, Leonard; Ludwig, Roland; Schuhmann, Wolfgang; Chen, Xingxing


    Electron-transfer pathways between cellobiose dehydrogenase from Myriococcum thermophilum (MtCDH) and the related flavodehydrogenase domain (FAD-MtCDH) and electrodes were evaluated using specifically designed Os-complex modified electrodeposition paints (EDPs). The properties of the Os-complex modified EDPs were varied by variation of the monomer composition, the coordination sphere of the polymer-bound Os-complexes, and the length and flexibility of the spacer chain between Os complex and polymer backbone. The MtCDH-to-EDP weight ratio, the pH value, as well as the operational temperature have been optimized

  5. Hepatoma targeting peptide conjugated bio-reducible polymer complexed with oncolytic adenovirus for cancer gene therapy.

    Choi, Joung-Woo; Kim, Hyun Ah; Nam, Kihoon; Na, Youjin; Yun, Chae-Ok; Kim, SungWan


    Despite adenovirus (Ad) vector's numerous advantages for cancer gene therapy, such as high ability of endosomal escape, efficient nuclear entry mechanism, and high transduction, and therapeutic efficacy, tumor specific targeting and antiviral immune response still remain as a critical challenge in clinical setting. To overcome these obstacles and achieve cancer-specific targeting, we constructed tumor targeting bioreducible polymer, an arginine grafted bio-reducible polymer (ABP)-PEG-HCBP1, by conjugating PEGylated ABP with HCBP1 peptides which has high affinity and selectivity towards hepatoma. The ABP-PEG-HCBP1-conjugated replication incompetent GFP-expressing ad, (Ad/GFP)-ABP-PEG-HCBP1, showed a hepatoma cancer specific uptake and transduction compared to either naked Ad/GFP or Ad/GFP-ABP. Competition assays demonstrated that Ad/GFP-ABP-PEG-HCBP1-mediated transduction was specifically inhibited by HCBP1 peptide rather than coxsackie and adenovirus receptor specific antibody. In addition, ABP-PEG-HCBP1 can protect biological activity of Ad against serum, and considerably reduced both innate and adaptive immune response against Ad. shMet-expressing oncolytic Ad (oAd; RdB/shMet) complexed with ABP-PEG-HCBP1 delivered oAd efficiently into hepatoma cancer cells. The oAd/ABP-PEG-HCBP1 demonstrated enhanced cancer cell killing efficacy in comparison to oAd/ABP complex. Furthermore, Huh7 and HT1080 cancer cells treated with oAd/shMet-ABP-PEG-HCBP1 complex had significantly decreased Met and VEGF expression in hepatoma cancer, but not in non-hepatoma cancer. In sum, these results suggest that HCBP1-conjugated bioreducible polymer could be used to deliver oncolytic Ad safely and efficiently to treat hepatoma. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. New polymer-supported ion-complexing agents: Design, preparation and metal ion affinities of immobilized ligands

    Alexandratos, Spiro D.


    Polymer-supported reagents are comprised of crosslinked polymer networks that have been modified with ligands capable of selective metal ion complexation. Applications of these polymers are in environmental remediation, ion chromatography, sensor technology, and hydrometallurgy. Bifunctional polymers with diphosphonate/sulfonate ligands have a high selectivity for actinide ions. The distribution coefficient for the uranyl ion from 1 M nitric acid is 70,000, compared to 900 for the monophosphonate/sulfonate polymer and 200 for the sulfonic acid ion-exchange resin. A bifunctional trihexyl/triethylammonium polymer has a high affinity and selectivity for pertechnetate and perchlorate anions from groundwater. In one example, its distribution coefficient for perchlorate ions in the presence of competing anions is 3,300,000, compared to 203,180 for a commercially available anion-exchange resin. Polystyrene modified with N-methyl-D-glucamine ligands is capable of selectively complexing arsenate from groundwater. It complexes 99% of the arsenate present in a solution of 100 mg/L arsenate with 560 mg/L sulfate ions. Its selectivity is retained even in the presence of 400 mg/L phosphate. There is no affinity for arsenate above pH 9, allowing for the polymer to be regenerated with moderate alkali solution. In studies aimed at developing a Hg(II)-selective resin, simple amine resins were found to have a high Hg(II) affinity and that affinity is dependent upon the solution pH and the counterion

  7. Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

    Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P


    In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

  8. Numerical investigation of complex flooding schemes for surfactant polymer based enhanced oil recovery

    Dutta, Sourav; Daripa, Prabir


    Surfactant-polymer flooding is a widely used method of chemical enhanced oil recovery (EOR) in which an array of complex fluids containing suitable and varying amounts of surfactant or polymer or both mixed with water is injected into the reservoir. This is an example of multiphase, multicomponent and multiphysics porous media flow which is characterized by the spontaneous formation of complex viscous fingering patterns and is modeled by a system of strongly coupled nonlinear partial differential equations with appropriate initial and boundary conditions. Here we propose and discuss a modern, hybrid method based on a combination of a discontinuous, multiscale finite element formulation and the method of characteristics to accurately solve the system. Several types of flooding schemes and rheological properties of the injected fluids are used to numerically study the effectiveness of various injection policies in minimizing the viscous fingering and maximizing oil recovery. Numerical simulations are also performed to investigate the effect of various other physical and model parameters such as heterogeneity, relative permeability and residual saturation on the quantities of interest like cumulative oil recovery, sweep efficiency, fingering intensity to name a few. Supported by the grant NPRP 08-777-1-141 from the Qatar National Research Fund (a member of The Qatar Foundation).

  9. Properties of grafted polymer metal complexes as ion exchangers and its electrical conductivity

    El-Arnaouty, M.B.; Abdel Ghaffar, A.M.; Eid, M.


    The polyelectrolyte has been prepared as a potential proton exchanger polymer by grafting of acrylic acid/acrylamide and acrylic acid/acrylonitrile comonomer onto low density polyethylene film via gamma radiation. The influence of grafting percent on the electrical conductivity was studied. The resulting polymers were then characterized by evaluating their physico-chemical properties such as ion exchange capacity, and electrical conductivity as a function of grafting yield. The grafted films at different compositions was characterized by FTIR, TGA and SEM. The ion exchange capacity (IEC) of the grafted film at grafting % (191) and monomer concentration ratio 50:50 for (LDPE-g-AAc/AAm) was found to be more than that for (LDPE-g-AAc/AN). The electrical conductivity was found to be greatly affected by the comonomer composition where it increased as the degree of grafting increased for all grafted films. After alkaline treatment with 3% KOH, the electrical conductivity of the grafted films found to be increased. The presence of potassium as counter ion maximized the electrical conductivity of the grafted films. The electrical conductivity of Cu-membrane complexes was higher than that of both Co and Ni complexes. The electrical conductivity increases by increasing both Cu ions content and temperature

  10. Optimization of Temperature Sensing with Polymer-Embedded Luminescent Ru(II Complexes

    Nelia Bustamante


    Full Text Available Temperature is a key parameter in many fields and luminescence-based temperature sensing is a solution for those applications in which traditional (mechanical, electrical, or IR-based thermometers struggle. Amongst the indicator dyes for luminescence thermometry, Ru(II polyazaheteroaromatic complexes are an appealing option to profit from the widespread commercial technologies for oxygen optosensing based on them. Six ruthenium dyes have been studied, engineering their structure for both photostability and highest temperature sensitivity of their luminescence. The most apt Ru(II complex turned out to be bis(1,10-phenanthroline(4-chloro-1,10-phenanthrolineruthenium(II, due to the combination of two strong-field chelating ligands (phen and a substituent with electron withdrawing effect on a conjugated position of the third ligand (4-Clphen. In order to produce functional sensors, the dye has been best embedded into poly(ethyl cyanoacrylate, due to its low permeability to O2, high temperature sensitivity of the indicator dye incorporated into this polymer, ease of fabrication, and excellent optical quality. Thermosensitive elements have been fabricated thereof as optical fiber tips for macroscopic applications (water courses monitoring and thin spots for microscopic uses (temperature measurements in cell culture-on-a-chip. With such dye/polymer combination, temperature sensing based on luminescence lifetime measurements allows 0.05 °C resolution with linear response in the range of interest (0–40 °C.

  11. Preparation and characterization of complex ferrite nanoparticles by a polymer-pyrolysis route

    Liu Xianming; Fu Shaoyun; Xiao Hongmei; Zhu Luping


    The polymer-pyrolysis route used in this work was to synthesize the copolymeric precursor of the mixed metallic ions and then to pyrolyze the precursor into complex spinel ferrite nanoparticles. Thermogravimetric analysis (TGA) showed that the complex ferrite nanoparticles could be obtained by calcination of their precursors at 500 deg. C. The structures, elemental analyses and particle morphology of the as-calcined products were characterized by powder X-ray diffraction (XRD), ICP-AES, transmission electron microscope (TEM) and electron diffraction (ED) pattern. The results revealed that the as-calcined powders were complex spinel ferrites and the size of those nanoparticles ranged from 10 to 20 nm. Magnetic measurements were carried out at room temperature using a vibrating sample magnetometer (VSM). The saturation magnetization of the Mn-Zn ferrites was related to the molar ratio of Mn to Zn and increased with the increase of Mn. The complex Co-Mn-Zn ferrite nanoparticles showed a high magnetization of 58 emu/g at the applied field of 10 kOe and a low coercivity of 30 Oe, which indicated that this materials exhibited characteristics of soft ferromagnetism

  12. Hemocompatibility of ultrafine systems on the basis of chitosan and its derivatives polymer-colloid complexes

    M.V. Bazunova


    Full Text Available This article presents the results of the development process for the preparation of micro and nano-sized polymer-colloid com-plexes (РСС on the basis of water-soluble natural polymer chitosan (СTZ and the sodium salt of chitosan succinylamid (SСTZ with silver halide sols in aqueous media. Results of research of СTZ, sodium salt of SСTZ solutions and PСС of CTZ and SСTZ with colloidal parti-cles of silver iodide influence on structurally-functional properties of erythrocytes’ membranes on model of acidic hemolisis are presented in the article. Their influence on the nature of erythrocytes distribution by degree of their stability and on kinetic parameters (the beginning, intensity and completion of process of their destruction under the influence of the damaging agent (HCl is shown. The comparative analysis of results convinces that СTZ, SСTZ solutions and disperse systems on the basis of PСС of СTZ and SСTZ with colloidal particles of the silver iodide are capable of modulating variously matrix properties of erythrocytes of blood.

  13. Studies on the antifungal activities of the novel synthesized chelating co-polymer emulsion lattices and their silver complexes

    Abd-El-Ghaffar M.A.


    Full Text Available The novel binary chelating co-polymers of butyl acrylate with itaconic and maleic acids were prepared by emulsion polymerization process. The chelating co-polymers of butyl acrylate-co-itaconic acid (BuA/IA and butyl acrylate-co-maleic acid (BuA/MA and their silver complexes were characterized and identified using IR spectroscopy and differential scanning calorimetry (DSC measurements. The biological activities of these compounds were studied against various types of fungal species. The dose and the rate of leached silver ions were controlled by the type of the co-polymers used and the solubility in the medium. The results provided laboratory support for the concept that the polymers containing chemically bound biocide are useful for controlling microbial growth. The silver uptake by strains of different fungal species was studied to determine their difference in behavior to the antifungal activities of these compounds. The uptake strategy was examined by transmission electron microscopy (TEM.

  14. In situ X-ray polymerization: from swollen lamellae to polymer-surfactant complexes.

    Agzenai, Yahya; Lindman, Björn; Alfredsson, Viveka; Topgaard, Daniel; Renamayor, Carmen S; Pacios, Isabel E


    The influence of the monomer diallyldimethylammonium chloride (D) on the lamellar liquid crystal formed by the anionic surfactant aerosol OT (AOT) and water is investigated, determining the lamellar spacings by SAXS and the quadrupolar splittings by deuterium NMR, as a function of the D or AOT concentrations. The cationic monomer D induces a destabilization of the AOT lamellar structure such that, at a critical concentration higher than 5 wt %, macroscopic phase separation takes place. When the monomer, which is dissolved in the AOT lamellae, is polymerized in situ by X-ray initiation, a new collapsed lamellar phase appears, corresponding to the complexation of the surfactant with the resulting polymer. A theoretical model is employed to analyze the variation of the interactions between the AOT bilayers and the stability of the lamellar structure.

  15. Effect of complexing salt on conductivity of PVC/PEO polymer blend ...


    composite polymer, a blend-based polymer electrolyte, composed of two conductive ... LiClO4 electrolytes with various methacrylic and acrylic polymers used as additives .... Z real vs Z imaginary plot for PVC : PEO : LiBF4 at room temperature.

  16. Influence of complexing on physicochemical properties of polymer-salt solutions. Vliyanie kompleksoobrazovaniya na fiziko-khimicheskie svojstva polimerno-solevykh rastvorov

    Ostroushko, A A; Yushkova, S M; Koridze, N V; Skobkoreva, N V; Zhuravleva, L I; Palitskaya, T A; Antropova, S V; Ostroushko, I P [Ural' skij Gosudarstvennyj Univ., Sverdlovsk (Russian Federation) AN SSSR, Moscow (Russian Federation). Inst. Obshchej i Neorganicheskoj Khimii


    Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated.

  17. Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

    Carpio, M.M.; Kerr, J.B.


    Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

  18. Manufacturing of ionic polymer-metal composites (IPMCs) that can actuate into complex curves

    Stoimenov, Boyko L.; Rossiter, Jonathan M.; Mukai, Toshiharu


    Ionic polymer-metal composites (IPMC) are soft actuators with potential applications in the fields of medicine and biologically inspired robotics. Typically, an IPMC bends with approximately constant curvature when voltage is applied to it. More complex shapes were achieved in the past by pre-shaping the actuator or by segmentation and separate actuation of each segment. There are many applications for which fully independent control of each segment of the IPMC is not required and the use of external wiring is objectionable. In this paper we propose two key elements needed to create an IPMC, which can actuate into a complex curve. The first is a connection between adjacent segments, which enables opposite curvature. This can be achieved by reversing the polarity applied on each side of the IPMC, for example by a through-hole connection. The second key element is a variable curvature segment. The segment is designed to bend with any fraction of its full bending ability under given electrical input by changing the overlap of opposite charge electrodes. We demonstrated the usefulness of these key elements in two devices. One is a bi-stable buckled IPMC beam, also used as a building block in a linear actuator device. The other one is an IPMC, actuating into an S-shaped curve with gradually increasing curvature near the ends. The proposed method of manufacturing holds promise for a wide range of new applications of IPMCs, including applications in which IPMCs are used for sensing.

  19. Inert Layered Silicate Improves the Electrochemical Responses of a Metal Complex Polymer.

    Eguchi, Miharu; Momotake, Masako; Inoue, Fumie; Oshima, Takayoshi; Maeda, Kazuhiko; Higuchi, Masayoshi


    A chemically inert, insulating layered silicate (saponite; SP) and an iron(II)-based metallo-supramolecular complex polymer (polyFe) were combined via electrostatic attraction to improve the electrochromic properties of polyFe. Structural characterization indicated that polyFe was intercalated into the SP nanosheets. Interestingly, the redox potential of polyFe was lowered by combining it with SP, and the current was measurable despite the insulating nature of SP. X-ray photoelectron spectroscopy showed that the decrease in the redox potential observed in the SP-polyFe hybrid was caused by the electrostatic neutralization of the Fe cation in polyFe by the negative charge on SP. Electrochemical analyses indicated that electron transfer occurred through electron hopping across the SP-polyFe hybrid. Control experiments using a metal complex composed of Fe and two 2,2':6',2''-terpyridine ligands (terpyFe) showed that SP contributes to the effective electron hopping. This modulation of the electrochemical properties by the layered silicates could be applied to other electrochemical systems, including hybrids of the redox-active ionic species and ion-exchangeable adsorbents.

  20. An AAA-DDD triply hydrogen-bonded complex easily accessible for supramolecular polymers.

    Han, Yi-Fei; Chen, Wen-Qiang; Wang, Hong-Bo; Yuan, Ying-Xue; Wu, Na-Na; Song, Xiang-Zhi; Yang, Lan


    For a complementary hydrogen-bonded complex, when every hydrogen-bond acceptor is on one side and every hydrogen-bond donor is on the other, all secondary interactions are attractive and the complex is highly stable. AAA-DDD (A=acceptor, D=donor) is considered to be the most stable among triply hydrogen-bonded sequences. The easily synthesized and further derivatized AAA-DDD system is very desirable for hydrogen-bonded functional materials. In this case, AAA and DDD, starting from 4-methoxybenzaldehyde, were synthesized with the Hantzsch pyridine synthesis and Friedländer annulation reaction. The association constant determined by fluorescence titration in chloroform at room temperature is 2.09×10(7)  M(-1) . The AAA and DDD components are not coplanar, but form a V shape in the solid state. Supramolecular polymers based on AAA-DDD triply hydrogen bonded have also been developed. This work may make AAA-DDD triply hydrogen-bonded sequences easily accessible for stimuli-responsive materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Conformation Control of a Conjugated Polymer through Complexation with Bile Acids Generates Its Novel Spectral and Morphological Properties.

    Tsuchiya, Youichi; Noguchi, Takao; Yoshihara, Daisuke; Roy, Bappaditya; Yamamoto, Tatsuhiro; Shinkai, Seiji


    Control of higher-order polymer structures attracts a great deal of interest for many researchers when they lead to the development of materials having various advanced functions. Among them, conjugated polymers that are useful as starting materials in the design of molecular wires are particularly attractive. However, an equilibrium existing between isolated chains and bundled aggregates is inevitable and has made their physical properties very complicated. As an attempt to simplify this situation, we previously reported that a polymer chain of a water-soluble polythiophene could be isolated through complexation with a helix-forming polysaccharide. More recently, a covalently self-threading polythiophene was reported, the main chain of which was physically protected from self-folding and chain-chain π-stacking. In this report, we wish to report a new strategy to isolate a water-soluble polythiophene and to control its higher-order structure by a supramolecular approach: that is, among a few bile acids, lithocholate can form stoichiometric complexes with cationic polythiophene to isolate the polymer chain, and the higher-order structure is changeable by the molar ratio. The optical and morphological studies have been thoroughly performed, and the resultant complex has been applied to the selective recognition of two AMP structural isomers.

  2. Charge transfer processes on electrodes modified by polymer films of metal complexes with Schiff bases

    Levin, O.V.; Karushev, M.P.; Timonov, A.M.; Alekseeva, E.V.; Zhang, Shuanghua; Malev, V.V.


    Electrochemical properties of glassy carbon electrodes modified by two polymer films of different nickel complexes with Schiff base ligands containing methoxy substituents in their aromatic parts were studied in acetonitrile solutions with cyclic voltammetry, quartz crystal microbalance, atomic force microscopy, and impedance spectroscopy. It was observed that introduction of such substituents leads to a noticeable splitting of cycling voltammetric curves into at least two ox/red transitions. In addition, solvent flows accompanying the counter-ions ones during charging/discharge processes within the films appeared significantly greater than those observed in the case of non-substituted ligands. The obtained impedance results as a whole were satisfactorily treated in scope of the so-called model of homogeneous films with two kinds of charge carriers. However, determinations of the Warburg constant as a function of the electrode potential require additional verifications, at least in the ranges of overlapping ox/red transitions. In particular, it was established that in this region the impedance frequency dependence was some superposition of the diffusion (Warburg) and the pseudo-capacitive constituents. This, most likely, resulted from the presence of three kinds of charge carriers in the film interior

  3. Hydrogen-Bonded Polymer-Small Molecule Complexes with Tunable Mechanical Properties.

    Liu, Tianqi; Peng, Xin; Chen, Ya-Nan; Bai, Qing-Wen; Shang, Cong; Zhang, Lin; Wang, Huiliang


    A novel type of polymeric material with tunable mechanical properties is fabricated from polymers and small molecules that can form hydrogen-bonded intermolecular complexes (IMCs). In this work, poly(vinyl alcohol) (PVA)-glycerol hydrogels are first prepared, and then they are dried to form IMCs. The tensile strengths and moduli of IMCs decrease dramatically with increasing glycerol content, while the elongations increase gradually. The mechanical properties are comparable with or even superior to those of common engineering plastics and rubbers. The IMCs with high glycerol content also show excellent flexibility and cold-resistance at subzero temperatures. Cyclic tensile and stress relaxation tests prove that there is an effective energy dissipation mechanism in IMCs and dynamic mechanical analysis confirms their physical crosslinking nature. FTIR and NMR characterizations prove the existence of hydrogen bonding between glycerol and PVA chains, which suppresses the crystallization of PVA from X-ray diffraction measurement. These PVA-glycerol IMCs may find potential applications in barrier films, biomedical packaging, etc., in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Synthesis and green electrophosphorescence of a novel cyclometalated iridium complex in polymer light-emitting diodes

    Wu Lilan [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan 70101 (China); Tsai Sunghao [Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 70101 (China); Guo Tzungfang [Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 70101 (China); Yang Chenghsien [Carbon Nanocapsules Research Department, Nano-Powder and Thin Film Technology Center, ITRI South, Tainan, Taiwan 709 (China)]. E-mail:; Sun, I-W. [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan 70101 (China)]. E-mail:


    Abstact: In this paper, we synthesized a new complex bis(dibenzo[f,h]quinolinato-N,C {sup 2'}) iridium(III) acetylactonate ((DBQ){sub 2}Ir(acac)) having a longer conjugate system than bis(2-phenylpyridinato-N,C {sup 2'}) iridium(III) acetylacetonate ((PPY){sub 2}Ir(acac)). Interestingly (DBQ){sub 2}Ir(acac) emits at the same wavelength as (photoluminescence of 530 nm) (PPY){sub 2}Ir(acac). A high-efficiency electrophosphorescent polymer light-emitting diodes was constructed by using (DBQ){sub 2}Ir(acac) as the dopant, and a blend of poly(vinylcarbazole) (PVK) with 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazol (PBD) as the host material. The electroluminescence efficiency of 9.5 cd/A is reported for the device doped with 3 wt% of (DBQ){sub 2}Ir(acac). In this device, the emission from the PVK or PBD host was effectively inhibited with the using (DBQ){sub 2}Ir(acac) . Emission from the dopant molecules in such devices involve localization of the injected electron and hole on the metal-organic center. This can occur by a variety of mechanisms, including Foerster and Dexter energy transfer from the host transport material to the dopant, and direct trapping of both electrons and holes on the metal-organic center.

  5. Physico-chemical properties of modified inter-polymer complexes and composites

    Khafizov, M.M.


    Full text: Inter-polymer complexes (IC) are rather perspective and can occupy the important place in technology of materials, as find out a number of the most valuable properties. In essence, they are new polymeric materials with a complex of new qualities and operational characteristics. In the present work the influence of a nature and structure of cooperating components both on structure, and on properties of received final products is investigated. It is shown new opportunities of use of the IC for reception composite materials formed IC on the physical properties, rather close to amorphous compounds. The opportunity of reception polymeric composite materials with the given properties and structure is shown; the purposeful regulation of process of hardening inter-polymeric composite materials with disperse fillers of a various nature and contents is established. The properties of such composite materials are determined by amount of entered components, both their distribution and chemical nature of a filler, that allows to increase stability properties in 2.5-3 times. By using phenomenological analysis of the contact phenomena the differential equations are made which are used for the analysis of VAC sandwich-structures metal-IC-metal. In a range of voltage V=0 -1 -10 2 V the experimental VAC are described by dependences close to Ohmic J∼V n , n=1. It is shown that the presence of breaks σ=f(T) at temperature ∼ 300 K specifies on ionic character of conductivity of samples. The chemical resistance of inter-polymeric composites in relation to water, to a solution of NaCl and 'to aggressive environment' is comprehensively characterized. The optimum degree of filling of the fillers Cv=2-3 is determined at a specific surface of fillers 0.2-0.3 m 2 /g

  6. A supramolecular miktoarm star polymer based on porphyrin metal complexation in water.

    Hou, Zhanyao; Dehaen, Wim; Lyskawa, Joël; Woisel, Patrice; Hoogenboom, Richard


    A novel supramolecular miktoarm star polymer was successfully constructed in water from a pyridine end-decorated polymer (Py-PmDEGA) and a metalloporphyrin based star polymer (ZnTPP-(PEG) 4 ) via metal-ligand coordination. The Py-PmDEGA moiety was prepared via a combination of reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequent aminolysis and Michael addition reactions to introduce the pyridine end-group. The ZnTPP(PEG) 4 star-polymer was synthesized by the reaction between tetrakis(p-hydroxyphenyl)porphyrin and toluenesulfonyl-PEG, followed by insertion of a zinc ion into the porphyrin core. The formation of a well-defined supramolecular AB 4 -type miktoarm star polymer was unambiguously demonstrated via UV-Vis spectroscopic titration, isothermal titration calorimetry (ITC) and diffusion ordered NMR spectroscopy (DOSY).

  7. Machine learning-based screening of complex molecules for polymer solar cells

    Jørgensen, Peter Bjørn; Mesta, Murat; Shil, Suranjan; García Lastra, Juan Maria; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer; Schmidt, Mikkel N.


    Polymer solar cells admit numerous potential advantages including low energy payback time and scalable high-speed manufacturing, but the power conversion efficiency is currently lower than for their inorganic counterparts. In a Phenyl-C_61-Butyric-Acid-Methyl-Ester (PCBM)-based blended polymer solar cell, the optical gap of the polymer and the energetic alignment of the lowest unoccupied molecular orbital (LUMO) of the polymer and the PCBM are crucial for the device efficiency. Searching for new and better materials for polymer solar cells is a computationally costly affair using density functional theory (DFT) calculations. In this work, we propose a screening procedure using a simple string representation for a promising class of donor-acceptor polymers in conjunction with a grammar variational autoencoder. The model is trained on a dataset of 3989 monomers obtained from DFT calculations and is able to predict LUMO and the lowest optical transition energy for unseen molecules with mean absolute errors of 43 and 74 meV, respectively, without knowledge of the atomic positions. We demonstrate the merit of the model for generating new molecules with the desired LUMO and optical gap energies which increases the chance of finding suitable polymers by more than a factor of five in comparison to the randomised search used in gathering the training set.

  8. Temperature dependence of the luminescence lifetime of a europium complex immobilized in different polymer matrices

    Basu, Bharathi Bai J. [Surface Engineering Division, National Aerospace Laboratories, Bangalore 560017 (India)], E-mail:; Vasantharajan, N. [Surface Engineering Division, National Aerospace Laboratories, Bangalore 560017 (India)


    The temperature dependence of the luminescence lifetime of temperature sensor films based on europium (III) thenoyltrifluoroacetonate (EuTTA) as sensor dye in various polymer matrices such as polystyrene (PS), polymethylmethacrylate (PMMA), polyurethane (PU) and model airplane dope was studied and compared. The luminescence lifetime of EuTTA was found to depend on the polymer matrix. The temperature sensitivity of lifetime was maximum for EuTTA-PS coating in the temperature range of 10-60 deg. C. The effect of concentration of the sensor dye in the polymer on the lifetime and temperature sensitivity was also studied.

  9. Red polymer light-emitting devices based on an oxadiazole-functionalized europium(III) complex

    Liu, Yu; Wang, Yafei; Li, Chun; Huang, Ying; Dang, Dongfeng; Zhu, Meixiang; Zhu, Weiguo; Cao, Yong


    A novel tris(dibenzoylmethanato)[5-(2-(4-tert-butylbenzenyl)-5-benzenyl-1,3, 4-oxadiazole-4′)-1,10-phenanthroline]europium(III) [Eu(DBM) 3 (BuOXD-Phen)] containing an electron-transporting oxadiazole-functionalized phenanthroline ligand was synthesized and characterized. Its UV–vis absorption and photoluminescence (PL), as well as the electroluminescence (EL) in polymer light-emitting devices (PLEDs) were investigated. The double-layer PLEDs with a configuration of ITO/PEDOT:PSS (50 nm)/PVK (40 nm)/PFO:PBD (30%):Eu(DBM) 3 (BuOXD-Phen) (1–8 wt %) (80 nm)/Ba (4 nm)/Al (150 nm) were fabricated. Saturated red Eu 3+ ion emission, based on the 5 D 0 → 7 F 2 transition, is centered at a wavelength of 614 nm with a full width at half maximum (FWHM) of 10 nm. The highest external quantum efficiency (QE ext ) of 1.26% at current density of 1.65 mA cm −2 , with a maximum brightness of 568 cd m −2 at 137.8 mA cm −2 was achieved from the device at 1 wt % dopant concentration. - Highlights: • An oxadiazole-functionalized europium(III) complex of Eu(DBM) 3 (BuOXD-Phen) was presented. • The optophysical properties of Eu(DBM) 3 (BuOXD-Phen) were investigated. • Saturated red emission was observed in the PLEDs. • An external quantum efficiency of 1.26% was obtained in these devices

  10. Free energy landscape of siRNA-polycation complexation: Elucidating the effect of molecular geometry, polymer flexibility, and charge neutralization.

    Gianvito Grasso

    Full Text Available The success of medical threatments with DNA and silencing interference RNA is strongly related to the design of efficient delivery technologies. Cationic polymers represent an attractive strategy to serve as nucleic-acid carriers with the envisioned advantages of efficient complexation, low cost, ease of production, well-defined size, and low polydispersity index. However, the balance between efficacy and toxicity (safety of these polymers is a challenge and in need of improvement. With the aim of designing more effective polycationic-based gene carriers, many parameters such as carrier morphology, size, molecular weight, surface chemistry, and flexibility/rigidity ratio need to be taken into consideration. In the present work, the binding mechanism of three cationic polymers (polyarginine, polylysine and polyethyleneimine to a model siRNA target is computationally investigated at the atomistic level. In order to better understand the polycationic carrier-siRNA interactions, replica exchange molecular dynamic simulations were carried out to provide an exhaustive exploration of all the possible binding sites, taking fully into account the siRNA flexibility together with the presence of explicit solvent and ions. Moreover, well-tempered metadynamics simulations were employed to elucidate how molecular geometry, polycation flexibility, and charge neutralization affect the siRNA-polycations free energy landscape in term of low-energy binding modes and unbinding free energy barriers. Significant differences among polymer binding modes have been detected, revealing the advantageous binding properties of polyarginine and polylysine compared to polyethyleneimine.

  11. Preparation of polymer-rare earth complex using salicylic acid-containing polystyrene and its fluorescence emission property

    Gao Baojiao, E-mail: [Department of Chemical Engineering, North University of China, Taiyuan 030051 (China); Zhang Wei; Zhang Zhengguo; Lei Qingjuan [Department of Chemical Engineering, North University of China, Taiyuan 030051 (China)


    Salicylic acid (SA) was first bonded onto the side chains of polystyrene (PS), obtaining functional macromolecule SAPS. Using the salicylic acid-containing polystyrene as a macromolecular ligand, a polymer-rare earth complex, SAPS-Eu(III), was prepared. The structure of SAPS-Eu(III) was characterized, and the fluorescence properties of SAPS-Eu(III) were mainly investigated. The experimental results show that the complex SAPS-Eu(III) has fine chemical stability because of the bidentate chelating effect of salicylic acid ligand. More important, the ligand SA on the side chains of PS can strongly sensitize the fluorescence emission of the center ion, Eu{sup 3+} ion, and it enables the complex SAPS-Eu(III) to produce the apparent 'Antenna Effect'. In the diluted solution of the functional macromolecule SAPS, the formed complex SAPS-Eu(III) belongs to an intramolecular complex, or an intrachain complex. For the binary intramolecular complex SAPS-Eu(III), the apparent saturated coordination number of SA of SAPS towards Eu{sup 3+} ion is equal to 10, and here the binary intrachain complex SAPS-Eu(III) has the strongest fluorescence emission. On this basis, small-molecule 1,10-phenanthroline (Phen) acting as a co-ligand is added and the ternary complex SAPS-Eu(III)-Phen will be formed. As long as a small amount of Phen is added (in the molar ratio 1:1 (n(Phen):n(Eu))), the coordination of the two kinds of ligands, SA of SAPS and Phen, to Eu{sup 3+} ion will reach complete saturation, and here the fluorescence emission of the ternary complex will be further enhanced via the complementary coordination effect in comparison with that of the binary complex SAPS-Eu(III). - Highlights: Black-Right-Pointing-Pointer We prepared the functional polystyrene, SAPS, on whose side chain salicylic acid ligand was bonded. Black-Right-Pointing-Pointer The polymer-rare earth complex, SAPS-Eu(III), was prepared and a stronger 'antenna effect' was produced. Black

  12. Studies on polymer electrolyte poly(vinyl) pyrrolidone (PVP) complexed with ionic liquid: Effect of complexation on thermal stability, conductivity and relaxation behaviour

    Saroj, A.L. [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India); Singh, R.K., E-mail: [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India); Chandra, S. [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India)


    Highlights: Black-Right-Pointing-Pointer PVP + IL based polymer electrolyte films have been prepared and studied. Black-Right-Pointing-Pointer The complexation/interaction of PVP with IL has been confirmed by FT-IR analysis. Black-Right-Pointing-Pointer The conductivity and relaxation frequency increases with increasing IL content. Black-Right-Pointing-Pointer Two relaxation peaks for complexed and uncomplexed PVP with IL have been observed. - Abstract: Polymer electrolyte films of PVP + x wt% ionic liquid (IL) (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF{sub 4}]) for x = 0, 5, 10, 15, 20, 25 wt% have been prepared using solution cast technique. These films were characterized by TGA, DSC, FT-IR and ac impedance spectroscopy techniques. From XRD studies it is found that the inclusion of IL increases the amorphocity of polymeric membranes. DSC thermograms show that the glass transition (T{sub g}) and melting temperatures (T{sub m}) of PVP shift upon complexation with IL. FT-IR analysis shows the complexation of PVP with IL. Thermogravimetric studies show that PVP decomposes in a single step while PVP/IL membranes exhibit two step decomposition; lower value of decomposition temperature corresponds to the decomposition of PVP/IL complex while the higher decomposition temperature has been attributed to the decomposition of PVP. The decomposition temperature of PVP/IL complex decreases with the increasing amount of IL in the PVP membrane. Temperature dependence of conductivity and dielectric relaxation frequencies have also been studied for PVP and PVP/IL membranes. Both show thermally activated Arrhenius behaviour.

  13. A functional monomer is not enough: principal component analysis of the influence of template complexation in pre-polymerization mixtures on imprinted polymer recognition and morphology.

    Golker, Kerstin; Karlsson, Björn C G; Rosengren, Annika M; Nicholls, Ian A


    In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

  14. A Functional Monomer Is Not Enough: Principal Component Analysis of the Influence of Template Complexation in Pre-Polymerization Mixtures on Imprinted Polymer Recognition and Morphology

    Kerstin Golker


    Full Text Available In this report, principal component analysis (PCA has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA-crosslinked polymers had either methacrylic acid (MAA or methyl methacrylate (MMA as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

  15. Synthesis And Characterization Of An Ion Imprinted Polymer For Cadmium Using Quinaldic Acid As Complexing Agent And Applying By Microwave



    Full Text Available Abstract A Cd2 Ion Imprinted Polymer Cd-IIP has been synthesized by copolymerizaton of cadmium ion quinaldic acid complexing agent 4-vynil pyridine monomer dimethyl sulfoxide solvent ethyleneglycoldimethacrylate EGDMA cross-linker and 22-azobis-isobutyronitrile AIBN initiator. Polymerization was conducted using a microwave at a temperature of 70 oC with heating times of 45 minutes. The template Cd2 was removed by leaching the template with ethanol and 4 M HCl washed by aquabidest and dried in an oven at the temperature of 60oC. The polymer particles imprinted and nonimprinted were characterized using fourir transform infrared FTIR spectroscopy scanning electron microscopy SEM and energy dispersive spectroscopy EDS. The result showed that using heating time 45 minutes at temperature 70 oC the particle morphology is viewed like as the large homogeneous. So the imprinted polymer had bands at 3483 cm-1 1726 cm-1 and 1155 cm-1 indicating the presence of OH CO and C-O respectively.

  16. A nanosized cadmium(II)-imprinted polymer for use in selective trace determination of cadmium in complex matrices

    Behbahani, Mohammad; Bagheri, Akbar; Barati, Mozhgan; Pourali, Ali Reza; Tapeh, Nasim Akbari Ghareh; Bojdi, Majid Kalate


    We describe a nanosized Cd(II)-imprinted polymer that was prepared from 4-vinyl pyridine (the functional monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator), neocuproine (the ligand), and Cd(II) (the template ion) by precipitation polymerization in acetonitrile as the solvent. The imprinted polymer was characterized by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, and scanning electron microscopy. The maximum adsorption capacity of the nanosized sorbent was calculated to be 64 mg g −1 . Cadmium(II) was then quantified by FAAS. The relative standard deviation and limit of detection are 4.2 % and 0.2 μg L −1 , respectively. The imprinted polymer displays improve selectivity for Cd(II) ions over a range of competing metal ions with the same charge and similar ionic radius. This nanosized sorbent is an efficient solid phase for selective extraction and preconcentration of Cd(II) in complex matrices. The method was successfully applied to the trace determination of Cd(II) in food and water samples. (author)

  17. Polymer-free nanofibers from vanillin/cyclodextrin inclusion complexes: high thermal stability, enhanced solubility and antioxidant property.

    Celebioglu, Asli; Kayaci-Senirmak, Fatma; İpek, Semran; Durgun, Engin; Uyar, Tamer


    Vanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HPβCD, HPγCD and MβCD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (∼12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (∼5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/MβCD-IC NFs which is up to ∼85% w/w, besides, a considerable amount of vanillin (∼75% w/w) was also preserved for vanillin/HPβCD-IC NFs and vanillin/HPγCD-IC NFs. Phase solubility studies suggested a 1 : 1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin : CD complexation was strongest for MβCD when compared to HPβCD and HPγCD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced

  18. Structuring and capturing of radioactive strontium-90 from the polluted soil of Semipalatinsk nuclear test site by inter-polymer complexes

    Bimendina, L.A.; Kudaibergenov, S.E.; Orazzhanova, L.K.; Yashkarova, M.G.; Kaliaskarova, B.


    The model and experiments on application of polymer-polymer complexes stabilized by hydrogen and ionic bonds for structuring of Semipalatinsk nuclear test site soils in order to prevent the wind and water erosion of radionuclides from contaminated soil are considered. It is expected that the treatment by inter-polymer complexes (IPC) would cause the structuring of soil particle. Besides IPSs are able to form thin films on the soil particles surface, aggregate and considerably protect the migration of radionuclides. Both the water soluble polymer-polyacrylic acid (PAA), polyethylene glycol (PEG), poly-N,N,-dimethyldiallylammonium chloride (PDMDAACI) and the PAA-PEG, PAA-PDMDAACI inter-polymer complexes were used as structuring agents. The treatment of soil particles was carried out by two methods: the first method is uniform splash of polymer solution and mixing with soil; the second one is pouring of soil surface by polymer solution. The obtained results are summarized as follows: - Optimal concentration of polymer solutions are arranged between 10 -4 -10 -2 mol·l -1 . The best results corresponds to concentration 10 -2 mol·l -1 ; - Pouring of soil surface is most preferential in comparison with splash of polymer solution and mixing with soil; - Both the individual polymers (PAA, PEG and PDMDAACI) and the PAA-PEG, PAA-PDMDAACI inter-polymer complexes show the structuring effect. However the best results were observed for IPC solution. The best structuring effect has been obtained for equimolar [PAA]:[PEG]=1:1 complex solution with 10 -2 mol·l -1 and at p H=3.0 when the IPC solution is poured through the soil surface. The similar results were obtained for [PAA]:[PDMDAACI]=1:1 system. The capillary moisture capacity and water stability at optimal soil treatment conditions of soil is given. Since PAA, PEG and PAA-PEG complexes form polymer-metal complexes with Sr 2+ ions the possibility of capture of soil radionuclides by means of binding into the complex particles

  19. Theory of interfacial charge-transfer complex photophysics in π-conjugated polymer-fullerene blends

    Aryanpour, K.; Psiachos, D.; Mazumdar, S.


    We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes [1]. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component π-conjugated polymers [2], we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend [3], observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component π-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground state charge-transfer to the case of excited state charge-transfer. [1] K. Aryanpour, D. Psiachos, and S. Mazumdar, arXiv:0908.0366 [2] D. Psiachos and S. Mazumdar, Phys. Rev. B. 79 155106 (2009) [3] T. Drori et al., Phys. Rev. Lett. 101, 037402 (2008)

  20. Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

    Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu


    We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

  1. In vitro and in vivo studies on the complexes of glipizide with water-soluble β-cyclodextrin-epichlorohydrin polymers.

    Nie, Shufang; Zhang, Shu; Pan, Weisan; Liu, Yanli


    The purpose of this study was to evaluate the potential of a newly modified cyclodextrin derivative, water-soluble β-cyclodextrin-epichlorohydrin polymer (β-CDP), as an effective drug carrier to enhance the dissolution rate and oral bioavailability of glipizide as a poorly water-soluble model drug. Inclusion complexes of glipizide with β-CDP were prepared by the co-evaporation method and characterized by phase solubility, dissolution, and differential scanning calorimetry. The solubility curve was classified as type A(L), which indicated the formation of 1:1 complex between glipizide and β-CDP. β-CDP had better properties of increasing the aqueous solubility of glipizide compared with HP-β-CD. The dissolution rate of drug from the β-CDP complexes was significantly greater than that of the corresponding physical mixtures indicating that the formation of amorphous complex increased the solubility of glipizide. Moreover, the increment in drug dissolution rate from the glipizide/β-CDP systems was higher than that from the corresponding ones with HP-β-CD, which indicated that β-CDP could provide greater capability of solubilization for poorly soluble drugs. Furthermore, in vivo study revealed that the bioavailability of glipizide was significantly improved by glipizide /β-CDP inclusion complex after oral administration to beagle dogs.

  2. The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

    Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina


    Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    Vidal, Fernando


    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  4. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.


    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  5. Synthesis and photoluminescence properties of novel Schiff base type polymer-rare earth complexes containing furfural-based bidentate Schiff base ligands

    Gao, Baojiao; Zhang, Dandan; Li, Yanbin


    Luminescent polymer-rare earth complexes are an important class of photoluminescence and electroluminescence materials. Via molecular design, two furfural-based bidentate Schiff base ligands, furfural-aniline (FA) type ligand and furfural-cyclohexylamine (FC) type ligand, were bonded on the side chains of polysulfone (PSF), respectively, forming two functionalized macromolecules, PSF-FA and PSF-FC. And then through respective coordination reactions of the two functionalized macromolecules with Eu(Ⅲ) ion and Tb(Ⅲ) ion, novel luminescent binary and ternary (with 1,10-phenanthroline as the second ligand) polymer-rare earth complexes were synthesized. For these complexes, on basis of the characterization of their chemical structures, they photoluminescence properties were main researched, and the relationship between their luminescent properties and structures was explored. The experimental results show that the complexes coming from PSF-FA and Eu(Ⅲ) ion including binary and ternary complexes emit strong red luminescence, indicating that the bonded bidentate Schiff base ligand FA can sensitize the fluorescence emission of Eu(III) ion. While the complexes coming from PSF-FC and Tb(Ⅲ) ion produce green luminescence, displaying that the bonded bidentate Schiff base ligand FC can sensitize the fluorescence emission of Tb(Ⅲ) ion. The fluorescence emission intensities of the ternary complexes were stronger than that of binary complexes, reflecting the important effect of the second ligand. The fluorescence emission of the solid film of complexes is much stronger than that of the solutions of complexes. Besides, by comparison, it is found that the furfural (as a heteroaromatic compound)-based Schiff base type polymer-rare earth complexes have stronger fluorescence emission and higher energy transfer efficiency than salicylaldehyde (as a common aromatic compound)-based Schiff base type polymer-rare earth complexes.

  6. A sensor for acetaminophen in a blood medium using a Cu(II)-conducting polymer complex modified electrode

    Boopathi, Mannan; Won, Mi-Sook; Shim, Yoon-Bo


    Complexation of Cu ions in a terthiophene carboxylic acid (TTCA) polymer film resulted an enhanced anodic current for acetaminophen oxidation when compared to polymer coated and bare glassy carbon electrodes in human blood and buffer media. Scanning electron microscopy (SEM) and ESCA experiments indicate the involvement of copper in the electrocatalytic oxidation of acetaminophen. No interference was observed from other biologically important and phenolic compounds used with this modified electrode. Especially, the non-interference from N-acetylcysteine, an antidote for the treatment of acetaminophen poisoning, reveals the proposed method's superiority in medicinal applications. In addition, the present modified electrode avoids surface fouling at higher concentrations of acetaminophen. The calibration range obtained with CV was based between 2.0x10 -5 and 5.0x10 -3 M [r 2 =0.997 (n=5, R.S.D.=2.5%); DL=5.0x10 -6 M (S/N=3)]. The analytical utility of the modified electrode was achieved by analyzing the content of acetaminophen in different drugs without pretreatment using CV and amperometric techniques

  7. Star Polymers.

    Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G


    Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

  8. Electrospun Polymer Nanofibers Reinforced by Tannic Acid/Fe+++ Complexes

    Yang, Weiqiao; Sousa, Ana M. M.; Thomas-Gahring, Audrey; Fan, Xuetong; Jin, Tony; Li, Xihong; Tomasula, Peggy M.; Liu, LinShu


    We report the successful preparation of reinforced electrospun nanofibers and fibrous mats of polyvinyl alcohol (PVA) via a simple and inexpensive method using stable tannic acid (TA) and ferric ion (Fe+++) assemblies formed by solution mixing and pH adjustment. Changes in solution pH change the number of TA galloyl groups attached to the Fe+++ from one (pH PVA and TA. At pH ~ 5.5, the morphology and fiber diameter size (FDS) examined by SEM are determinant for the mechanical properties of the fibrous mats and depend on the PVA content. At an optimal 8 wt % concentration, PVA becomes fully entangled and forms uniform nanofibers with smaller FDS (p mechanical properties when compared to mats of PVA alone and of PVA with TA (p mechanical properties (p 0.05) suggesting the potential of TA-Fe+++ assemblies to reinforce polymer nanofibers with high functionality for use in diverse applications including food, biomedical and pharmaceutical. PMID:28773876

  9. Preparation and luminescent properties of the novel polymer-rare earth complexes composed of Poly(ethylene-co-acrylic acid) and Europium ions

    Wu, Yuewen; Hao, Haixia; Wu, Qingyao; Gao, Zihan; Xie, Hongde


    A series of novel polymer-rare earth complexes with Eu3+ ions have been synthesized and investigated successfully, including the binary complexes containing the single ligand poly(ethylene-co-acrylic acid) (EAA) and the ternary complexes using 1,10-phenanthroline (phen), dibenzoylmethane (DBM) or thenoyltrifluoroacetone (TTA) as the second ligand. Their structures have been characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis and X-ray diffraction (XRD), which confirm that both EAA and small molecules participate in the coordination reaction with rare earth ions, and they can disperse homogeneously in the polymer matrixes. Both ultraviolet-visible (UV-vis) absorption and photoluminescence tests for the complexes have been recorded. The relationship between fluorescence intensity of polymer-rare earth complexes and the quantity of ligand EAA has been studied and discussed. The films casted from the complexes solution can emit strong characteristic red light under UV light excitation. All these results suggest that the complexes possess potential application as luminescent materials.

  10. New soluble functional polymers by free-radical copolymerization of methacrylates and bipyridine ruthenium complexes

    Holder, E.; Meier, M.A.R.; Marin, V.N.; Schubert, U.S.


    The luminescent complex [4-(3-hydroxypropyl)-4-methyl-2,2-bipyridine]-bis(2,2-bipyridine)-ruthenium(II)-bis(hexafluoroantimonate) and its methacrylate derivative were successfully synthesized and fully characterized by two-dimensional 1H and 13C{1H} NMR techniques [correlation spectroscopy (COSY)

  11. Fractional complexation in a miscible polymer blend. Calorimetry and size exclusion chromatography

    Kratochvíl, Jaroslav; Šturcová, Adriana; Sikora, Antonín; Dybal, Jiří


    Roč. 63, č. 8 (2014), s. 1406-1413 ISSN 0959-8103 R&D Projects: GA AV ČR IAA200500903; GA ČR GAP108/12/0703 Institutional support: RVO:61389013 Keywords : miscible blend * interpolymer complex * residual phase Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.409, year: 2014

  12. Macromolecules containing bipyridine and terpyridine metal complexes: towards metallo-supramolecular polymers

    Schubert, U.S.; Eschbaumer, C.


    The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular

  13. A viscoelastic-viscoplastic model for short-fibre reinforced polymers with complex fibre orientations

    Nciri M.


    Full Text Available This paper presents an innovative approach for the modelling of viscous behaviour of short-fibre reinforced composites (SFRC with complex distributions of fibre orientations and for a wide range of strain rates. As an alternative to more complex homogenisation methods, the model is based on an additive decomposition of the state potential for the computation of composite’s macroscopic behaviour. Thus, the composite material is seen as the assembly of a matrix medium and several linear elastic fibre media. The division of short fibres into several families means that complex distributions of orientation or random orientation can be easily modelled. The matrix behaviour is strain-rate sensitive, i.e. viscoelastic and/or viscoplastic. Viscoelastic constitutive laws are based on a generalised linear Maxwell model and the modelling of the viscoplasticity is based on an overstress approach. The model is tested for the case of a polypropylene reinforced with short-glass fibres with distributed orientations and subjected to uniaxial tensile tests, in different loading directions and under different strain rates. Results demonstrate the efficiency of the model over a wide range of strain rates.

  14. Synthesis and optical properties of a new fluorinated erbium complex/polymer composite material

    Song Limei; Wang Jianshe; Hu Jin; Liu Xinhou; Zhen Zhen


    A new fluorinated erbium complex with pentafluorobenzoate groups and triphenylphosphine oxide ligands, Er(PFBZ) 3 (TPPO) 2 (PFBZ: pentafluorobenzoate, TPPO: triphenylphosphine oxide), was synthesized and characterized. And Er(PFBZ) 3 (TPPO) 2 /PMMA (polymethyl methacrylate) composite material was made by bulk polymerization. Both emission properties of the pure complex in the solid and that embedded in PMMA matrix were investigated upon excitation at different wavelengths. The luminescent intensity of the complex embedded in PMMA was enhanced strongly through the indirect excitation of the ligands absorption. Judd-Ofelt theory is used to analyze the absorption spectrum of Er 3+ in PMMA matrix and obtain the intensity parameters: Ω 2 = 11.343 x 10 -20 cm 2 , Ω 4 = 1.474 x 10 -20 cm 2 and Ω 6 = 1.001 x 10 -20 cm 2 . Based on these parameters, the radiative lifetime of the excited 4 I 13/2 level and the stimulated emission cross-section for the 4 I 13/2 → 4 I 15/2 transition are also evaluated

  15. Evidence of solvent-dependent complexation in non-ionic polymer-salt systems

    Hakem, I.F.; Lal, J.


    Small angle neutron scattering measurements have been performed on polyethylene oxide (PEO)-salt solutions. An attempt is made to characterize experimentally the scattering behavior of aqueous (D 2 O) polyethylene oxide and PEO-methanol solutions in the presence of potassium iodide (KI). In water solution, no interactions were observed with KI and PEO. However, in methanol a definite indication of complex formation was found. Addition of KI to a solution of PEO in methanol shows a large change in interchain interaction and chain conformation. (orig.)

  16. Direct Synthesis of Polymer Nanotubes by Aqueous Dispersion Polymerization of a Cyclodextrin/Styrene Complex.

    Chen, Xi; Liu, Lei; Huo, Meng; Zeng, Min; Peng, Liao; Feng, Anchao; Wang, Xiaosong; Yuan, Jinying


    A one-step synthesis of nanotubes by RAFT dispersion polymerization of cyclodextrin/styrene (CD/St) complexes directly in water is presented. The resulted amphiphilic PEG-b-PS diblock copolymers self-assemble in situ into nanoparticles with various morphologies. Spheres, worms, lamellae, and nanotubes were controllably obtained. Because of the complexation, the swelling degree of polystyrene (PS) blocks by free St is limited, resulting in limited mobility of PS chains. Consequently, kinetically trapped lamellae and nanotubes were obtained instead of spherical vesicles. During the formation of nanotubes, small vesicles first formed at the ends of the tape-like lamellae, then grew and fused into nanotubes with a limited chain rearrangement. The introduction of a host-guest interaction based on CDs enables the aqueous dispersion polymerization of water-immiscible monomers, and produces kinetically trapped nanostructures, which could be a powerful technique for nanomaterials synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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


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

  18. Charge transfer complex states in diketopyrrolopyrrole polymers and fullerene blends: Implications for organic solar cell efficiency

    Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.


    The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT:PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT:PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

  19. Transparent conducting polymer electrolyte by addition of lithium to the molecular complex chitosane-poly(aminopropyl siloxane)

    Fuentes, S.; Retuert, P.J.; Gonzalez, Guillermo


    Transparent lithium-ion conducting films were prepared by adding lithium perchlorate to a mixture of chitosane (CHI) and poly(aminopropylsiloxane) (pAPS) in a molar ratio 0.6:1 by sol-gel methods. The morphological and molecular properties, determined by scanning electron microscopy and FT-IR, respectively, depend on the lithium salt concentration. The same techniques were also used for performing a 'titration' of the capacity of the film for incorporating lithium salt. Results show that about 0.8 mol lithium salt per mol chitosane can be added before the product losses the transparence and molecular compatibility characteristic of the pristine CHI/pAPS polymer complex. When lithium salt addition reaches the tolerance limit, anisotropically oriented patterns are observed in the hybrid films. Both transparence and ionic conductivity of the product appear to be related to the layered nature of formed nanocomposites. The properties of obtained films may be furthermore rationalized considering the chemical functionality and the Lewis donor-acceptor affinity of the components.

  20. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    Ramos-Gonzá lez, R.; Garcí a-Cerda, L. A.; Alshareef, Husam N.; Gnade, Bruce E.; Quevedo-Ló pez, Manuel Angel Quevedo


    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  1. Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

    Ramos-González, R.


    This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

  2. A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS

    Zambrzycka, Elżbieta; Godlewska-Żyłkiewicz, Beata


    A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2′-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L−1 aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL −1 . The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %. (author)

  3. Stability effect of cholesterol-poly(acrylic acid) in a stimuli-responsive polymer-liposome complex obtained from soybean lecithin for controlled drug delivery.

    Simões, M G; Alves, P; Carvalheiro, Manuela; Simões, P N


    The development of polymer-liposome complexes (PLCs), in particular for biomedical applications, has grown significantly in the last decades. The importance of these studies comes from the emerging need in finding intelligent controlled release systems, more predictable, effective and selective, for applications in several areas, such as treatment and/or diagnosis of cancer, neurological, dermatological, ophthalmic and orthopedic diseases, gene therapy, cosmetic treatments, and food engineering. This work reports the development and characterization of a pH sensitive system for controlled release based on PLCs. The selected hydrophilic polymer was poly(acrylic acid) (PAA) synthesized by atom transfer radical polymerization (ATRP) with a cholesterol (CHO) end-group to improve the anchoring of the polymer into the lipid bilayer. The polymer was incorporated into liposomes formulated from soybean lecithin and stearylamine, with different stearylamine/phospholipid and polymer/phospholipid ratios (5, 10 and 20%). The developed PLCs were characterized in terms of particle size, polydispersity, zeta potential, release profiles, and encapsulation efficiency. Cell viability studies were performed to assess the cytotoxic potential of PLCs. The results showed that the liposomal formulation with 5% of stearylamine and 10% of polymer positively contribute to the stabilization of the complexes. Afterwards, the carboxylic acid groups of the polymer present at the surface of the liposomes were crosslinked and the same parameters analyzed. The crosslinked complexes showed to be more stable at physiologic conditions. In addition, the release profiles at different pHs (2-12) revealed that the obtained complexes released all their content at acidic conditions. In summary, the main accomplishments of this work are: (i) innovative synthesis of cholesterol-poly(acrylic acid) (CHO-PAA) by ATRP; (ii) stabilization of the liposomal formulation by incorporation of stearylamine and CHO

  4. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    Zong-Cheng Chen


    Full Text Available In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP to atom transfer self-condensing vinyl polymerization (AT-SCVP through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy in a mixture of styrene (St, 4-vinyl benzyl chloride (VBC, and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC macroinitiator (name as: hbPSt MI with either St or tBA (tert-butyl acrylate. The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98; hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid segments.

  5. Reusable Polymer-Supported Terpyridine Palladium Complex for Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost Reaction in Water

    Takuya Nagamine


    Full Text Available A novel heterogeneous transition-metal catalyst comprising a polymer-supported terpyridine palladium(II complex was prepared and found to promote the Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost, reactions in water under aerobic conditions with a high to excellent yield. The catalyst was recovered by simple filtration and directly reused several times without loss of catalytic activity.

  6. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure

    Biswas, S.; Singh, G. P.; Ram, S.; Fecht, H.-J.


    Stable anisotropic nanorods of surface modified CrO2 (˜18 nm diameter) with a correlated diamagnetic layer (2-3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr4+ ions by Ag atoms on the CrO2 surface (topotactic surface layer) via an etching reaction of a CrO2-polymer complex with Ag+ ions in hot water followed by heating the dried sample at 300-400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO2 such that it no longer converts to Cr2O3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d5/2 and 3d3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (-) 7.6% at 77 K, than reported values in compacted CrO2 powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO2 nanorods.

  7. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure

    Biswas, S.; Singh, G.P.; Ram, S.; Fecht, H.-J.


    Stable anisotropic nanorods of surface modified CrO 2 (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr 4+ ions by Ag atoms on the CrO 2 surface (topotactic surface layer) via an etching reaction of a CrO 2 -polymer complex with Ag + ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO 2 such that it no longer converts to Cr 2 O 3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO 2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d 5/2 and 3d 3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO 2 powders or composites. Such a large MR-value in the Coulomb blockade regime ( 2 nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO 2 . • Tailoring useful GMR property in CrO 2 nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO 2 nanorods

  8. Polymer-bound oxidovanadium(IV) and dioxidovanadium(V) complexes as catalysts for the oxidative desulfurization of model fuel diesel.

    Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Kuznetsov, Maxim L; Avecilla, Fernando; Costa Pessoa, João


    The Schiff base (Hfsal-dmen) derived from 3-formylsalicylic acid and N,N-dimethyl ethylenediamine has been covalently bonded to chloromethylated polystyrene to give the polymer-bound ligand, PS-Hfsal-dmen (I). Treatment of PS-Hfsal-dmen with [V(IV)O(acac)(2)] in the presence of MeOH gave the oxidovanadium(IV) complex PS-[V(IV)O(fsal-dmen)(MeO)] (1). On aerial oxidation in methanol, complex 1 was oxidized to PS-[V(V)O(2)(fsal-dmen)] (2). The corresponding neat complexes, [V(IV)O(sal-dmen)(acac)] (3) and [V(V)O(2)(sal-dmen)] (4) were similarly prepared. All these complexes are characterized by various spectroscopic techniques (IR, electronic, NMR, and electron paramagnetic resonance (EPR)) and thermal as well as field-emission scanning electron micrographs (FE-SEM) studies, and the molecular structures of 3 and 4 were determined by single crystal X-ray diffraction. The EPR spectrum of the polymer supported V(IV)O-complex 1 is characteristic of magnetically diluted V(IV)O-complexes, the resolved EPR pattern indicating that the V(IV)O-centers are well dispersed in the polymer matrix. A good (51)V NMR spectrum could also be measured with 4 suspended in dimethyl sulfoxide (DMSO), the chemical shift (-503 ppm) being compatible with a VO(2)(+)-center and a N,O binding set. The catalytic oxidative desulfurization of organosulfur compounds thiophene, dibenzothiophene, benzothiophene, and 2-methyl thiophene (model of fuel diesel) was carried out using complexes 1 and 2. The sulfur in model organosulfur compounds oxidizes to the corresponding sulfone in the presence of H(2)O(2). The systems 1 and 2 do not loose efficiency for sulfoxidation at least up to the third cycle of reaction, this indicating that they preserve their integrity under the conditions used. Plausible intermediates involved in these catalytic processes are established by UV-vis, EPR, (51)V NMR, and density functional theory (DFT) studies, and an outline of the mechanism is proposed. The (51)V NMR spectra

  9. Coordination Nature of 4-Mercaptoaniline to Sn(II Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV Complex

    Eon S. Burkett


    Full Text Available The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV complex was previously reported, crystal structure of this compound was redetermined.

  10. New Textile Sensors for In Situ Structural Health Monitoring of Textile Reinforced Thermoplastic Composites Based on the Conductive Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Polymer Complex.

    Jerkovic, Ivona; Koncar, Vladan; Grancaric, Ana Marija


    Many metallic structural and non-structural parts used in the transportation industry can be replaced by textile-reinforced composites. Composites made from a polymeric matrix and fibrous reinforcement have been increasingly studied during the last decade. On the other hand, the fast development of smart textile structures seems to be a very promising solution for in situ structural health monitoring of composite parts. In order to optimize composites' quality and their lifetime all the production steps have to be monitored in real time. Textile sensors embedded in the composite reinforcement and having the same mechanical properties as the yarns used to make the reinforcement exhibit actuating and sensing capabilities. This paper presents a new generation of textile fibrous sensors based on the conductive polymer complex poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) developed by an original roll to roll coating method. Conductive coating for yarn treatment was defined according to the preliminary study of percolation threshold of this polymer complex. The percolation threshold determination was based on conductive dry films' electrical properties analysis, in order to develop highly sensitive sensors. A novel laboratory equipment was designed and produced for yarn coating to ensure effective and equally distributed coating of electroconductive polymer without distortion of textile properties. The electromechanical properties of the textile fibrous sensors confirmed their suitability for in situ structural damages detection of textile reinforced thermoplastic composites in real time.

  11. New Textile Sensors for In Situ Structural Health Monitoring of Textile Reinforced Thermoplastic Composites Based on the Conductive Poly(3,4-ethylenedioxythiophene-poly(styrenesulfonate Polymer Complex

    Ivona Jerkovic


    Full Text Available Many metallic structural and non-structural parts used in the transportation industry can be replaced by textile-reinforced composites. Composites made from a polymeric matrix and fibrous reinforcement have been increasingly studied during the last decade. On the other hand, the fast development of smart textile structures seems to be a very promising solution for in situ structural health monitoring of composite parts. In order to optimize composites’ quality and their lifetime all the production steps have to be monitored in real time. Textile sensors embedded in the composite reinforcement and having the same mechanical properties as the yarns used to make the reinforcement exhibit actuating and sensing capabilities. This paper presents a new generation of textile fibrous sensors based on the conductive polymer complex poly(3,4-ethylenedioxythiophene-poly(styrenesulfonate developed by an original roll to roll coating method. Conductive coating for yarn treatment was defined according to the preliminary study of percolation threshold of this polymer complex. The percolation threshold determination was based on conductive dry films’ electrical properties analysis, in order to develop highly sensitive sensors. A novel laboratory equipment was designed and produced for yarn coating to ensure effective and equally distributed coating of electroconductive polymer without distortion of textile properties. The electromechanical properties of the textile fibrous sensors confirmed their suitability for in situ structural damages detection of textile reinforced thermoplastic composites in real time.

  12. Surface stabilized GMR nanorods of silver coated CrO{sub 2} synthesized via a polymer complex at ambient pressure

    Biswas, S., E-mail: [The LNM Institute of Information Technology, Jaipur-302031 (India); Singh, G.P. [Centre for Nanotechnology, Central University of Jharkhand, Ranchi-835205 (India); Ram, S. [Materials Science Centre, Indian Institute of Technology, Kharagpur-721302 (India); Fecht, H.-J. [Insitut für Micro-und Nanomaterialien, Universität Ulm, Albert Einstein Allee-47, Ulm, D-89081, and Forschungszentrum Karlsruhe, Institute of Nanotechnology, Karlsruhe, D-76021 (Germany)


    Stable anisotropic nanorods of surface modified CrO{sub 2} (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr{sup 4+} ions by Ag atoms on the CrO{sub 2} surface (topotactic surface layer) via an etching reaction of a CrO{sub 2}-polymer complex with Ag{sup +} ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO{sub 2} such that it no longer converts to Cr{sub 2}O{sub 3} in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO{sub 2} structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d{sub 5/2} and 3d{sub 3/2} X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO{sub 2} powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO{sub 2} nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO{sub 2}. • Tailoring useful GMR property in CrO{sub 2} nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO{sub 2} nanorods.

  13. Formation of a ground-state charge-transfer complex in Polyfluorene//[6,6]-Phenyl-C61 butyric acid methyl ester (PCBM) blend films and its role in the function of polymer/PCBM solar cells

    Benson-Smith, J.J.; Bradley, D.D.C.; Nelson, J. [Department of Physics, Imperial College London, London SW7 2BW (United Kingdom); Goris, L.; Vandewal, K.; Haenen, K.; Manca, J.V.; Vanderzande, D. [Institute for Materials Research, Limburgs Universitair Centrum, Wetenschapspark 1, 3590 Diepenbeek (Belgium)


    Evidence is presented for the formation of a weak ground-state charge-transfer complex in the blend films of poly[9,9-dioctylfluorene-co-N-(4-methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]-phenyl-C{sub 61} butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground-state charge-transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge-transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge-transfer complex may be involved in charge separation. Possible mechanisms for this charge-transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  14. A novel gel based on an ionic complex from a dendronized polymer and ciprofloxacin: Evaluation of its use for controlled topical drug release

    García, Mónica C. [Unidad de Investigación y Desarrollo en Tecnología Farmacéutica (UNITEFA), CONICET and Departamento de Farmacia, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Cuggino, Julio C. [Instituto de Desarrollo Tecnológico para la Industria Química (INTEC), CONICET, Colectora Ruta Nac. N° 168, km. 0, Pje. El Pozo, 3000 Santa Fe (Argentina); Rosset, Clarisa I.; Páez, Paulina L. [Unidad de Investigación y Desarrollo en Tecnología Farmacéutica (UNITEFA), CONICET and Departamento de Farmacia, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Strumia, Miriam C. [Instituto Multidisciplinario de Biología Vegetal (IMBIV), CONICET and Laboratorio de Materiales Poliméricos (LAMAP), Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); and others


    The development and characterization of a novel, gel-type material based on a dendronized polymer (DP) loaded with ciprofloxacin (CIP), and the evaluation of its possible use for controlled drug release, are presented in this work. DP showed biocompatible and non-toxic behaviors in cultured cells, both of which are considered optimal properties for the design of a final material for biomedical applications. These results were encouraging for the use of the polymer loaded with CIP (as a drug model), under gel form, in the development of a new controlled-release system to be evaluated for topical administration. First, DP-CIP ionic complexes were obtained by an acid-base reaction using the high density of carboxylic acid groups of the DP and the amine groups of the CIP. The complexes obtained in the solid state were broadly characterized using FTIR spectroscopy, XRP diffraction, DSC-TG analysis and optical microscopy techniques. Gels based on the DP-CIP complexes were easily prepared and presented excellent mechanical behaviors. In addition, optimal properties for application on mucosal membranes and skin were achieved due to their high biocompatibility and acute skin non-irritation. Slow and sustained release of CIP toward simulated physiological fluids was observed in the assays (in vitro), attributed to ion exchange phenomenon and to the drug reservoir effect. An in vitro bacterial growth inhibition assay showed significant CIP activity, corresponding to 38 and 58% of that exhibited by a CIP hydrochloride solution at similar CIP concentrations, against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. However, CIP delivery was appropriate, both in terms of magnitude and velocity to allow for a bactericidal effect. In conclusion, the final product showed promising behavior, which could be exploited for the treatment of topical and mucosal opportunistic infections in human or veterinary applications. - Highlights: • A novel hydrogel based on

  15. A novel gel based on an ionic complex from a dendronized polymer and ciprofloxacin: Evaluation of its use for controlled topical drug release

    García, Mónica C.; Cuggino, Julio C.; Rosset, Clarisa I.; Páez, Paulina L.; Strumia, Miriam C.


    The development and characterization of a novel, gel-type material based on a dendronized polymer (DP) loaded with ciprofloxacin (CIP), and the evaluation of its possible use for controlled drug release, are presented in this work. DP showed biocompatible and non-toxic behaviors in cultured cells, both of which are considered optimal properties for the design of a final material for biomedical applications. These results were encouraging for the use of the polymer loaded with CIP (as a drug model), under gel form, in the development of a new controlled-release system to be evaluated for topical administration. First, DP-CIP ionic complexes were obtained by an acid-base reaction using the high density of carboxylic acid groups of the DP and the amine groups of the CIP. The complexes obtained in the solid state were broadly characterized using FTIR spectroscopy, XRP diffraction, DSC-TG analysis and optical microscopy techniques. Gels based on the DP-CIP complexes were easily prepared and presented excellent mechanical behaviors. In addition, optimal properties for application on mucosal membranes and skin were achieved due to their high biocompatibility and acute skin non-irritation. Slow and sustained release of CIP toward simulated physiological fluids was observed in the assays (in vitro), attributed to ion exchange phenomenon and to the drug reservoir effect. An in vitro bacterial growth inhibition assay showed significant CIP activity, corresponding to 38 and 58% of that exhibited by a CIP hydrochloride solution at similar CIP concentrations, against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. However, CIP delivery was appropriate, both in terms of magnitude and velocity to allow for a bactericidal effect. In conclusion, the final product showed promising behavior, which could be exploited for the treatment of topical and mucosal opportunistic infections in human or veterinary applications. - Highlights: • A novel hydrogel based on

  16. A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

    Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon


    Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

  17. A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation.

    Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon


    Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors' knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

  18. Recyclable Polymer-Supported Terpyridine–Palladium Complex for the Tandem Aminocarbonylation of Aryl Iodides to Primary Amides in Water Using NaN3 as Ammonia Equivalent

    Toshimasa Suzuka


    Full Text Available Primary aromatic amides are valuable compounds, which are generally prepared via Beckmann rearrangement of oximes and the hydration of nitriles in organic solvents. We investigated the environmentally friendly catalytic aminocarbonylation in water. Thus, a novel heterogeneous transition-metal catalyst, a polymer-supported terpyridine–palladium(II complex, was prepared and found to promote azidocarbonylation of aryl iodides with NaN3 and to reduce the generated benzoyl azides in water under CO gas to yield primary aryl amides with high to excellent yield in a one-pot reaction. The catalyst was recovered and reused several times with no loss of catalytic activity.

  19. Bispecific antibody complex pre-targeting and targeted delivery of polymer drug conjugates for imaging and therapy in dual human mammary cancer xenografts. Targeted polymer drug conjugates for cancer diagnosis and therapy

    Khaw, Ban-An; Gada, Keyur S.; Patil, Vishwesh; Panwar, Rajiv; Mandapati, Savitri [Northeastern University, Department of Pharmaceutical Sciences, Bouve College of Health Sciences, School of Pharmacy, Boston, MA (United States); Hatefi, Arash [Rutgers University, Department of Pharmaceutics, New Brunswick, NJ (United States); Majewski, Stan [West Virginia University, Department of Radiology, Morgantown, WV (United States); Weisenberger, Andrew [Thomas Jefferson National Accelerator Facility, Jefferson Lab, Newport News, VA (United States)


    Doxorubicin, a frontline chemotherapeutic agent, limited by its cardiotoxicity and other tissue toxicities, was conjugated to N-terminal DTPA-modified polyglutamic acid (D-Dox-PGA) to produce polymer pro-drug conjugates. D-Dox-PGA or Tc-99 m labeled DTPA-succinyl-polylysine polymers (DSPL) were targeted to HER2-positive human mammary carcinoma (BT-474) in a double xenografted SCID mouse model also hosting HER2-negative human mammary carcinoma (BT-20). After pretargeting with bispecific anti-HER2-affibody-anti-DTPA-Fab complexes (BAAC), anti-DTPA-Fab or only phosphate buffered saline, D-Dox-PGA or Tc-99 m DSPL were administered. Positive therapeutic control mice were injected with Dox alone at maximum tolerated dose (MTD). Only BT-474 lesions were visualized by gamma imaging with Tc-99 m-DSPL; BT-20 lesions were not. Therapeutic efficacy was equivalent in mice pretargeted with BAAC/targeted with D-Dox-PGA to mice treated only with doxorubicin. There was no total body weight (TBW) loss at three times the doxorubicin equivalent MTD with D-Dox-PGA, whereas mice treated with doxorubicin lost 10 % of TBW at 2 weeks and 16 % after the second MTD injection leading to death of all mice. Our cancer imaging and pretargeted therapeutic approaches are highly target specific, delivering very high specific activity reagents that may result in the development of a novel theranostic application. HER/2 neu specific affibody-anti-DTPA-Fab bispecific antibody pretargeting of HER2 positive human mammary xenografts enabled exquisite targeting of polymers loaded with radioisotopes for molecular imaging and doxorubicin for effective therapy without the associating non-tumor normal tissue toxicities. (orig.)

  20. Polymer films

    Granick, Steve; Sukhishvili, Svetlana A.


    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  1. Surface functionalization of quantum dots with fine-structured pH-sensitive phospholipid polymer chains.

    Liu, Yihua; Inoue, Yuuki; Ishihara, Kazuhiko


    To add novel functionality to quantum dots (QDs), we synthesized water-soluble and pH-responsive block-type polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were composed of cytocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer segments, which contain a small fraction of active ester groups and can be used to conjugate biologically active compounds to the polymer, and pH-responsive poly(2-(N,N-diethylamino) ethyl methacrylate (DEAEMA)) segments. One terminal of the polymer chain had a hydrophobic alkyl group that originated from the RAFT initiator. This hydrophobic group can bind to the hydrophobic layer on the QD surface. A fluorescent dye was conjugated to the polymer chains via the active ester group. The block-type polymers have an amphiphilic nature in aqueous medium. The polymers were thus easily bound to the QD surface upon evaporation of the solvent from a solution containing the block-type polymer and QDs, yielding QD/fluorescence dye-conjugated polymer hybrid nanoparticles. Fluorescence resonance energy transfer (FRET) between the QDs (donors) and the fluorescent dye molecules (acceptors) was used to obtain information on the conformational dynamics of the immobilized polymers. Higher FRET efficiency of the QD/fluorescent dye-conjugated polymer hybrid nanoparticles was observed at pH 7.4 as compared to pH 5.0 due to a stretching-shrinking conformational motion of the poly(DEAEMA) segments in response to changes in pH. We concluded that the block-type MPC polymer-modified nanoparticles could be used to evaluate the pH of cells via FRET fluorescence based on the cytocompatibility of the MPC polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Application of Nanoparticle Technology to Reduce the Anti-Microbial Resistance through β-Lactam Antibiotic-Polymer Inclusion Nano-Complex.

    Salamanca, Constain H; Yarce, Cristhian J; Roman, Yony; Davalos, Andrés F; Rivera, Gustavo R


    Biocompatible polymeric materials with potential to form functional structures in association with different therapeutic molecules have a high potential for biological, medical and pharmaceutical applications. Therefore, the capability of the inclusion of nano-Complex formed between the sodium salt of poly(maleic acid- alt -octadecene) and a β-lactam drug (ampicillin trihydrate) to avoid the chemical and enzymatic degradation and enhance the biological activity were evaluated. PAM-18Na was produced and characterized, as reported previously. The formation of polymeric hydrophobic aggregates in aqueous solution was determined, using pyrene as a fluorescent probe. Furthermore, the formation of polymer-drug nano-complexes was characterized by Differential Scanning Calorimetry-DSC, viscometric, ultrafiltration/centrifugation assays, zeta potential and size measurements were determined by dynamic light scattering-DLS. The PAM-18Na capacity to avoid the chemical degradation was studied through stress stability tests. The enzymatic degradation was evaluated from a pure β-lactamase, while the biological degradation was determined by different β-lactamase producing Staphylococcus aureus strains. When ampicillin was associated with PAM-18Na, the half-life time in acidic conditions increased, whereas both the enzymatic degradation and the minimum inhibitory concentration decreased to a 90 and 75%, respectively. These results suggest a promissory capability of this polymer to protect the β-lactam drugs against chemical, enzymatic and biological degradation.

  3. Novel siRNA delivery system using a ternary polymer complex with strong silencing effect and no cytotoxicity.

    Kodama, Yukinobu; Shiokawa, Yumi; Nakamura, Tadahiro; Kurosaki, Tomoaki; Aki, Keisei; Nakagawa, Hiroo; Muro, Takahiro; Kitahara, Takashi; Higuchi, Norihide; Sasaki, Hitoshi


    We developed a novel small interfering RNA (siRNA) delivery system using a ternary complex with polyethyleneimine (PEI) and γ-polyglutamic acid (γ-PGA), which showed silencing effect and no cytotoxicity. The binary complexes of siRNA with PEI were approximately 73-102 nm in particle size and 45-52 mV in ζ-potential. The silencing effect of siRNA/PEI complexes increased with an increase of PEI, and siRNA/PEI complexes with a charge ratio greater than 16 showed significant luciferase knockdown in a mouse colon carcinoma cell line regularly expressing luciferase (Colon26/Luc cells). However, strong cytotoxicity and blood agglutination were observed in the siRNA/Lipofectamine complex and siRNA/PEI16 complex. Recharging cationic complexes with an anionic compound was reported to be a promising method for overcoming these toxicities. We therefore prepared ternary complexes of siRNA with PEI (charge ratio 16) by the addition of γ-PGA to reduce cytotoxicity and deliver siRNA. As expected, the cytotoxicity of the ternary complexes decreased with an increase of γ-PGA content, which decreased the ζ-potential of the complexes. A strong silencing effect comparable to siRNA/Lipofectamine complex was discovered in ternary complexes including γ-PGA with an anionic surface charge. The high incorporation of ternary complexes into Colon26/Luc cells was confirmed with fluorescence microcopy. Having achieved knockdown of an exogenously transfected gene, the ability of the complex to mediate knockdown of an endogenous housekeeping gene, glyceraldehyde 3-phosphate dehydrogenase (GAPDH), was assessed in B16-F10 cells. The ternary complex (siRNA/PEI16/γ-PGA12 complex) exhibited a significant GAPDH knockdown effect. Thus, we developed a useful siRNA delivery system.

  4. Study the effect of ion-complex on the properties of composite gel polymer electrolyte based on Electrospun PVdF nanofibrous membrane

    Li, Weili; Xing, Yujin; Wu, Yuhui; Wang, Jiawei; Chen, Lizhuang; Yang, Gang; Tang, Benzhong


    In this paper, nanofibrous membranes based on poly(vinylidene fluoride) (PVdF) doped with ion-complex (SiO 2 -PAALi) were prepared by electrospinning technique and the corresponding composite gel-polymer electrolytes (CGPEs) were obtained after being activated in liquid electrolyte. The microstructure, physical and electrochemical performances of the nanofibrous membranes and the corresponding CGPEs were studied by various measurements such as Fourier Transform Infrared Spectroscopy(FTIR), Scanning Electron Microscope (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Stress-strain test, Linear Sweep Voltammetry (LSV), AC impedance measurement and Charge/discharge cycle test. As to the ion-complex doped nanofibrous membranes, PVdF can provide mechanical support with network structure composed of fully interconnection; while the ion-complexes are absorbed onto the surface of the PVdF nanofibers evenly instead of being aggregated. With the help of doped ion-complex, the prepared nanofibrous membranes present good liquid electrolyte absorbability, excellent mechanical performance, and high decomposition temperature. For the corresponding CGPEs, they possess high ionic conductivity, wide electrochemical window, and good charge/discharge cycle performance

  5. New carboxy-functionalized terpyridines as precursors for zwitterionic ruthenium complexes for polymer-based solar cells

    Duprez, V.; Krebs, Frederik C


    New carboxy-terpyridines selectively functionalized at the 4-, 4'- and 4"-positions were prepared in a three-step procedure with good yields using, the Krohnke reaction followed by saponification. Their complexation with ruthenium led to symmetric and unsymmetric terpyridinyl zwitterionic complexes...

  6. Artificially Engineered Protein Polymers.

    Yang, Yun Jung; Holmberg, Angela L; Olsen, Bradley D


    Modern polymer science increasingly requires precise control over macromolecular structure and properties for engineering advanced materials and biomedical systems. The application of biological processes to design and synthesize artificial protein polymers offers a means for furthering macromolecular tunability, enabling polymers with dispersities of ∼1.0 and monomer-level sequence control. Taking inspiration from materials evolved in nature, scientists have created modular building blocks with simplified monomer sequences that replicate the function of natural systems. The corresponding protein engineering toolbox has enabled the systematic development of complex functional polymeric materials across areas as diverse as adhesives, responsive polymers, and medical materials. This review discusses the natural proteins that have inspired the development of key building blocks for protein polymer engineering and the function of these elements in material design. The prospects and progress for scalable commercialization of protein polymers are reviewed, discussing both technology needs and opportunities.

  7. Modeling the influence of silver nanoparticles on the f–f luminescence of the EuEDTA complex in the polyvinylpirrolidone polymer

    Couto dos Santos, M.A., E-mail: [Departamento de Física, Universidade Federal de Sergipe/CCET, São Cristóvão, SE 49100-000 (Brazil); Malta, O.L. [Departamento de Química Fundamental, Universidade Federalde Pernambuco/CCEN, Cidade Universitária, Recife, PE 50670-901 (Brazil); Reisfeld, R. [The Hebrew University of Jerusalem, Chemistry Institute, E. Safra Campus, 91904 Jerusalem (Israel)


    A theoretical analysis on experimental results previously obtained on the influence of silver nanoparticles in a polyvinylpirrolidone (PVP) polymer film containing a trivalent europium complex with EDTA ligand is made. Depending on the excitation source (at 393 nm with a xenon lamp or at 532 nm with a focused diode laser) the characteristic Eu{sup 3+} luminescence is observed to be enhanced by factors between 5 and 50. The theoretical analysis presumes a migration process of the EuEDTA complex units towards the silver nanoparticles, during the synthesis of the composite samples, and subsequently the treatment of the competition between local high field gradient effects and Eu{sup 3+} ion to the silver nanoparticles energy transfer successfully accounts for the observed luminescence enhancement factors. - Highlights: • Unusual luminescence enhancement of EuEDTA–silver nanoparticles–polyvinylpyrrolidone is treated theoretically. • A migration process of the EuEDTA complex units towards the silver nanoparticles is assumed. • The local high field gradient effects successfully accounts for the observed unusual luminescence enhancement factor of 50.

  8. Biodegradable Polymers

    Vroman, Isabelle; Tighzert, Lan


    Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources) or from biological resources (renewable resources). In general natural polymers offer fewer advantages than synthetic polymers. ...

  9. Use of hydroxypropyl-beta-cyclodextrin ad polymer matrix for formation of inclusion complex with drug nifedipine

    Carneiro, Elisa F.; Araujo, Marcia V.G. de; Barbosa, Ronilson V.; Silva, Caroline W.P. da; Barisson, Andersson; Zawadzki, Sonia F.; Andrade, George Ricardo S.; Costa Junior, Nivan B. da


    In this work it was prepared and characterized an inclusion complex between the polymeric matrix hydroxypropyl-beta cyclodextrin and nifedipine, a hydrophobic drug calcium antagonistic, used for the cardiovascular diseases treatment. The study of the phase- solubility diagram showed an increase of the aqueous solubility of the drug after inclusion, was observed and The differential scanning calorimetry analysis did not show the melting point temperature of the drug in the formed complex. This fact is considered as an evidence of the encapsulation process. 1 H NMR studies suggested that the non-aromatic ring of the nifedipine would be inserted in the cavity of the hydroxypropyl-beta-cyclodextrin.This orientation was also proposed by the used molecular modelling methods. (author)

  10. Fabrication of an ionic-liquid-based polymer monolithic column and its application in the fractionation of proteins from complex biosamples.

    Zhang, Doudou; Zhang, Qian; Bai, Ligai; Han, Dandan; Liu, Haiyan; Yan, Hongyuan


    An ionic-liquid-based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless-steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross-linking agent, and polyethylene glycol 200 and isopropanol as co-porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption-desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic-liquid-based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m 2 /g. Compared to a non-ionic-liquid-based monolith prepared under the same conditions, the ionic-liquid-based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Porous rod-like MgO complex membrane with good anti-bacterial activity directed by conjugated linolenic acid polymer

    Wang, Hua-Jie, E-mail:; Chen, Meng [Henan Normal University, College of Chemistry and Chemical Engineering (China); Mi, Li-Wei, E-mail: [Zhongyuan University of Technology, Center for Advanced Materials Research (China); Shi, Li-Hua [Anyang 101 Education Center (China); Cao, Ying, E-mail: [Zhongyuan University of Technology, Center for Advanced Materials Research (China)


    The problem of infection in the tissue engineering substitutes is driving us to seek new coating materials. We previously found that conjugated linolenic acid (CLnA) has well biocompatibility and excellent membrane-forming property. The objective of this study is to endow the anti-bacterial activity to CLnA membra ne by linking with MgO. The results showed that the CLnA polymer membrane can be loaded with porous rod-like MgO and such complex membrane showed anti-bacterial sensitivity against gram-positive bacteria (Staphylococcus aureus) even at the low concentration (0.15 μg/mm{sup 2}). In the present study, the best zone of inhibition got to 18.2 ± 0.8 mm when the amount of MgO reach 2.42 ± 0.58 μg/mm{sup 2}. It was deduced that the porous rod-like structure of MgO was directed by CLnA in its polymerization process. Such CLnA/MgO complex membrane can be helpful in the tissue engineering, medicine, food engineering, food preservation, etc. on the basis of its good anti-bacterial activity.

  12. Polymer compound


    A Polymer compound comprising a polymer (a) that contains cyclic imidesgroups and a polymer (b) that contains monomer groups with a 2,4-diamino-1,3,5-triazine side group. According to the formula (see formula) whereby themole percentage ratio of the cyclic imides groups in the polymer compoundwith

  13. Hybrid white organic light-emitting diodes combining blue-fluorescent polymer and red phosphorescent Pt(II) complexes as active layer

    Germino, Jose Carlos; Faleiros, Marcelo Meira; Moraes, Emmanuel Santos; Atvars, Teresa Dib Zambon, E-mail: [Universidade Estadual de Campinas (UNICAMP), SP (Brazil); Domingues, Raquel Aparecida [Universidade Federal de Sao Paulo (UNIFESP), SP (Brazil); Quites, Fernando Junior [Universidade Federal de Mato Grosso (UFMT), Cuiaba, MT (Brazil); Freitas, Jilian Nei de [Centro de Tecnologia da Informacao Renato Archer, Campinas, SP (Brazil)


    Full text: In this work we proposed a PFO composite with two salicylidene based Pt(II) coordination compounds, the [Pt(salophen)] and [Pt(sal-3,4-ben)] (red emitters), as emissive layer (EML) for Organic Light-emitting Diodes (OLEDs), combining a blue-fluorescent polymer (PFO) with red-phosphorescent Pt(II) coordination complexes in order to obtain an efficient white electroluminescent EML for WOLEDs application. Firstly, [Pt(salophen)] and [Pt(sal-3,4-ben)] were synthesized, purified and characterized by single crystal X-ray diffraction, yielding their respective expected molecular structures. The photoluminescence properties of the devices were evaluated by steady-state (electronic absorption and emission spectroscopies) and transient (fluorescence decays and TRES) measurements. It was observed the presence of non-radiative energy transfer processes between the PFO derivative and Pt(II) complexes. Posteriorly, the Pt(II) complexes were blended with PVK at 1% mol:mol ratio and OLEDs were made, leading to red-emitting devices with high color purity for the two coordination compounds. However, the two devices present low current efficiency values. In order to improve the electroluminescence properties of Pt(II) complexes PhOLEDs, PVK host was substituted by PFO at 0.5, 1.0 and 2.5% mol:mol ratios of complex and it was observed a great improvement of their optical-electronic properties in terms of luminance, voltage, current density and current efficiency in comparison to PVK composites or pure PFO devices. At 2.5% concentration, predominant bands of Pt(II) complexes were observed at low and high voltages. For the other concentrations, a different behavior was observed: the emission bands and device color were function of applied electrical field, exhibiting a red color at lower voltages (5 to 9V) and the PFO characteristic emission between 9 and 13V, leading to a white light emission at 13V. The best results were obtained for [Pt(sal-3,4-ben)] coordination compound

  14. Cellular interactions of a water-soluble supramolecular polymer complex of carbon nanotubes with human epithelial colorectal adenocarcinoma cells.

    Lee, Yeonju; Geckeler, Kurt E


    Water-soluble, PAX-loaded carbon nanotubes are fabricated by employing a synthetic polyampholyte, PDM. To investigate the suitability of the polyampholyte and the nanotubes as drug carriers, different cellular interactions such as the human epithelial Caco-2 cells viability, their effect on the cell growth, and the change in the transepithelial electrical resistance in Caco-2 cells are studied. The resulting complex is found to exhibit an effective anti-cancer effect against colon cancer cells and an increased the reduction of the electrical resistance in the Caco-2 cells when compared to the precursor PAX. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Polymer electronics

    Hsin-Fei, Meng


    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  16. Synthesis of a red electrophosphorescent heteroleptic iridium complex and its application in efficient polymer light-emitting diodes

    Zhang Xiuju; Xu Yunhua; Sun Yiheng; Shi Huahong; Zhu Xuhui; Cao Yong


    The preparation and characterization of a heteroleptic iridium complex [2-(benzo[b]thiophen-2-yl)pyridine]Ir(III)[2-(4H-1,2,4-triazol-3-yl) pyridine] [(Btp) 2 Ir(PZ)] were reported (2-(benzo[b]thiophen-2-yl)pyridine = Btp; 2-(4H-1,2,4-triazol-3-yl)pyridine = PZ). Electrophosphorescence was investigated in the device structure [indium-tin-oxide (ITO)/poly(ethlenedioxythiophene) (PEDOT)/poly(vinylcarbazole)(PVK)/Poly(9,9-dioctylfluorenyl-2,7-diyl) end capped with dimethylphenyl (PFO): (Btp) 2 Ir(PZ)/Ba/Al] by using this iridium complex as guest and PFO as host. The red electrophosphorescent devices showed a peak emission at approximately 604 nm and shoulder at 654 nm with the Commission International de'Eclairage (CIE) coordinates of (0.64, 0.35) and external quantum efficiency of 7.7% at a doping concentration of 8 wt.% without an electron-transporting material in the emitting layer

  17. Fast-Dissolving, Prolonged Release, and Antibacterial Cyclodextrin/Limonene-Inclusion Complex Nanofibrous Webs via Polymer-Free Electrospinning.

    Aytac, Zeynep; Yildiz, Zehra Irem; Kayaci-Senirmak, Fatma; San Keskin, Nalan Oya; Kusku, Semran Ipek; Durgun, Engin; Tekinay, Turgay; Uyar, Tamer


    We have proposed a new strategy for preparing free-standing nanofibrous webs from an inclusion complex (IC) of a well-known flavor/fragrance compound (limonene) with three modified cyclodextrins (HPβCD, MβCD, and HPγCD) via electrospinning (CD/limonene-IC-NFs) without using a polymeric matrix. The experimental and computational modeling studies proved that the stoichiometry of the complexes was 1:1 for CD/limonene systems. MβCD/limonene-IC-NF released much more limonene at 37, 50, and 75 °C than HPβCD/limonene-IC-NF and HPγCD/limonene-IC-NF because of the greater amount of preserved limonene. Moreover, MβCD/limonene-IC-NF has released only 25% (w/w) of its limonene, whereas HPβCD/limonene-IC-NF and HPγCD/limonene-IC-NF released 51 and 88% (w/w) of their limonene in 100 days, respectively. CD/limonene-IC-NFs exhibited high antibacterial activity against E. coli and S. aureus. The water solubility of limonene increased significantly and CD/limonene-IC-NFs were dissolved in water in a few seconds. In brief, CD/limonene-IC-NFs with fast-dissolving character enhanced the thermal stability and prolonged the shelf life along with antibacterial properties could be quite applicable in food and oral care applications.

  18. Liposome-based polymer complex as a novel adjuvant: enhancement of specific antibody production and isotype switch

    Chen CH


    Full Text Available Chia-Hung Chen1,*, Yu-Ling Lin1,*, Yen-Ku Liu1, Pei-Juin He2, Ching-Min Lin1, Yi-Han Chiu2, Chang-Jer Wu3, Tian-Lu Cheng4, Shih-Jen Liu5,6,**, Kuang-Wen Liao1,2,**1Institute of Molecular Medicine and Bioengineering, 2Department of Biological Science and Technology, National Chiao Tung University, Hsinchu, 3Department of Food Science, National Taiwan Ocean University, Keelung, 4Department of Biomedical Science and Environmental Biology, Kaohsiung Medical University, Kaohsiung, 5National Institute of Infectious Diseases and Vaccinology, National Health Research Institutes, Miaoli, 6Graduate Institute of Immunology, China Medical University, Taichung, Taiwan, , *Chia-Hung Chen and Yu-Ling Lin contributed equally to this work**Kuang-Wen Liao and Shih-Jen Liu contributed equally to this workAbstract: The aim of vaccination is to induce appropriate immunity against pathogens. Antibody-mediated immunity is critical for protection against many virus diseases, although it is becoming more evident that coordinated, multifunctional immune responses lead to the most effective defense. Specific antibody (Ab isotypes are more efficient at protecting against pathogen invasion in different locations in the body. For example, compared to other Ab isotypes, immunoglobulin (Ig A provides more protection at mucosal areas. In this study, we developed a cationic lipopolymer (liposome-polyethylene glycol-polyethyleneimine complex [LPPC] adjuvant that strongly adsorbs antigens or immunomodulators onto its surface to enhance or switch immune responses. The results demonstrate that LPPC enhances uptake ability, surface marker expression, proinflammatory cytokine release, and antigen presentation in mouse phagocytes. In contrast to Freund's adjuvant, LPPC preferentially activates Th1-immunity against antigens in vivo. With lipopolysaccharides or CpG oligodeoxynucleotides, LPPC dramatically enhances the IgA or IgG2A proportion of total Ig, even in hosts that have developed

  19. Imaging small human prostate cancer xenografts after pretargeting with bispecific bombesin-antibody complexes and targeting with high specific radioactivity labeled polymer-drug conjugates

    Patil, Vishwesh; Gada, Keyur; Panwar, Rajiv; Ferris, Craig; Khaw, Ban-An; Varvarigou, Alexandra; Majewski, Stan; Weisenberger, Andrew; Tekabe, Yared


    Pretargeting with bispecific monoclonal antibodies (bsMAb) for tumor imaging was developed to enhance target to background activity ratios. Visualization of tumors was achieved by the delivery of mono- and divalent radiolabeled haptens. To improve the ability to image tumors with bsMAb, we have combined the pretargeting approach with targeting of high specific activity radiotracer labeled negatively charged polymers. The tumor antigen-specific antibody was replaced with bombesin (Bom), a ligand that binds specifically to the growth receptors that are overexpressed by many tumors including prostate cancer. Bom-anti-diethylenetriaminepentaacetic acid (DTPA) bispecific antibody complexes were used to demonstrate pretargeting and imaging of very small human prostate cancer xenografts targeted with high specific activity 111 In- or 99m Tc-labeled negatively charged polymers. Bispecific antibody complexes consisting of intact anti-DTPA antibody or Fab' linked to Bom via thioether bonds (Bom-bsCx or Bom-bsFCx, respectively) were used to pretarget PC-3 human prostate cancer xenografts in SCID mice. Negative control mice were pretargeted with Bom or anti-DTPA Ab. 111 In-Labeled DTPA-succinyl polylysine (DSPL) was injected intravenously at 24 h (7.03 ± 1.74 or 6.88 ± 1.89 MBq 111 In-DSPL) after Bom-bsCx or 50 ± 5.34 MBq of 99m Tc-DSPL after Bom-bsFCx pretargeting, respectively. Planar or single photon emission computed tomography (SPECT)/CT gamma images were obtained for up to 3 h and only planar images at 24 h. After imaging, all mice were killed and biodistribution of 111 In or 99m Tc activities were determined by scintillation counting. Both planar and SPECT/CT imaging enabled detection of PC-3 prostate cancer lesions less than 1-2 mm in diameter in 1-3 h post 111 In-DSPL injection. No lesions were visualized in Bom or anti-DTPA Ab pretargeted controls. 111 In-DSPL activity in Bom-bsCx pretargeted tumors (1.21 ± 0.36%ID/g) was 5.4 times that in tumors pretargeted with

  20. Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

    Ou, Yiwei


    The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

  1. Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

    Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari


    The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

  2. Water Soluble Polymers for Pharmaceutical Applications

    Veeran Gowda Kadajji


    Full Text Available Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers are available. In the present paper, only water soluble polymers are described. They have been explained in two categories (1 synthetic and (2 natural. Drug polymer conjugates, block copolymers, hydrogels and other water soluble drug polymer complexes have also been explained. The general properties and applications of different water soluble polymers in the formulation of different dosage forms, novel delivery systems and biomedical applications will be discussed.

  3. Optical Properties of ZnO Nanoparticles Capped with Polymers

    Atsushi Noguchi


    Full Text Available Optical properties of ZnO nanoparticles capped with polymers were investigated. Polyethylene glycol (PEG and polyvinyl pyrrolidone (PVP were used as capping reagents. ZnO nanoparticles were synthesized by the sol-gel method. Fluorescence and absorption spectra were measured. When we varied the timing of the addition of the polymer to the ZnO nanoparticle solution, the optical properties were drastically changed. When PEG was added to the solution before the synthesis of ZnO nanoparticles, the fluorescence intensity increased. At the same time, the total particle size increased, which indicated that PEG molecules had capped the ZnO nanoparticles. The capping led to surface passivation, which increased fluorescence intensity. However, when PEG was added to the solution after the synthesis of ZnO nanoparticles, the fluorescence and particle size did not change. When PVP was added to the solution before the synthesis of ZnO nanoparticles, aggregation of nanoparticles occurred. When PVP was added to the solution after the synthesis of ZnO nanoparticles, fluorescence and particle size increased. This improvement of optical properties is advantageous to the practical usage of ZnO nanoparticles, such as bioimaging


    Morichere, D; Malliaras, G.G; Krasnikov, V.V.; Bolink, H.J; Hadziioannou, G

    The use of polymers as photorefractive materials offers many advantages : flexibility in synthesis, doping, processing and low cost. The required functionalities responsible for photorefractivity, namely charge generation, transport, trapping and linear electrooptic effect are given in the polymer

  5. Photorefractive polymers

    Bolink, Hendrik Jan; Hadziioannou, G


    This thesis describes the synthesis and properties of photorefractive polymers. Photorefractive polymers are materials in which the refractive index can be varied by the interaction with light. Unlike in numerous other photosensitive materials, in photorefractive materials this occurs via

  6. Polymer Brushes

    Vos, de W.M.; Kleijn, J.M.; Keizer, de A.; Cosgrove, T.; Cohen Stuart, M.A.


    A polymer brush can be defined as a dense array of polymers end-attached to an interface that stretch out into the surrounding medium. Polymer brushes have been investigated for the past 30 years and have shown to be an extremely useful tool to control interfacial properties. This review is intended

  7. Nanoparticles from Renewable Polymers

    Frederik Roman Wurm


    Full Text Available The use of polymers from natural resources can bring many benefits for novel polymeric nanoparticle systems. Such polymers have a variety of beneficial properties such as biodegradability and biocompatibility, they are readily available on large scale and at low cost. As the amount of fossil fuels decrease, their application becomes more interesting even if characterization is in many cases more challenging due to structural complexity, either by broad distribution of their molecular weights polysaccharides, polyesters, lignin or by complex structure (proteins, lignin. This review summarizes different sources and methods for the preparation of biopolymer-based nanoparticle systems for various applications.

  8. Rheology of Supramolecular Polymers

    Shabbir, Aamir

    Supramolecular polymers are a broad class of materials that include all polymerscapable of associating via secondary interactions. These materials represent an emerging class of systems with superior versatility compared to classical polymers with applications in food stuff, coatings, cost...... efficient processes or biomedical areas. Design and development of supramolecular polymers using ionic, hydrogen bonding or transition metal complexes with tailored properties requires deep understanding of dynamics both in linear and non-linear deformations. While linear rheology is important to understand...... the dynamics under equilibrium conditions, extensional rheology is relevant during the processing or in the usage of polymers utilizing supramolecular associations for example, acrylic based pressure sensitive adhesives are subjected to extensional deformations during the peeling where strain hardening...

  9. Polymer Electrolytes

    Hallinan, Daniel T.; Balsara, Nitash P.


    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  10. Polymer chemistry (revised edition)

    Kim, Jae Mum


    This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

  11. Water-soluble building blocks for terpyridine-containing supramolecular polymers : synthesis, complexation, and pH stability studies of poly(ethylene oxide) moieties

    Lohmeijer, B.G.G.; Schubert, U.S.


    Poly(ethylene oxide) of various molecular weights ([bar M ]n = 3 000, 5 200, 10 000, 16 500 g · mol-1) has been modified with terpyridine end groups as building blocks for water-soluble metallo-supramolecular polymers. Metallo-supramolecular A-A homopolymers have been prepared and characterized by

  12. Multifunctional e-spun colloidal nanofiber structures from various dispersed blends of PVA/ODA-MMT with PVP/ODA-MMT, poly(VP-alt-MA and AgNPs incorporated polymer complexes as electro-active platforms

    U. Bunyatova


    Full Text Available This work presented a new approach to fabricate polymer nanocomposites films with nanofiber structures from solution blends of poly(vinyl alcohol + octadecyl amine-montmorillonite (ODA-MMT (matrix with poly(N-vinylpyrrolidone + ODA-MMT (partner-1, poly(N-vinylpyrrolidone-alt-maleic anhydride ((poly(VP-alt-MA + (ODA-MMT (partner-2 and their silver (Ag-carrying polymer complexes by electrospinning. Chemical and physical structures, surface morphologies, thermal behaviors, electrical conductivity and thermal resistance parameters of nanofiber structures were investigated. Poly(VP-alt-MA was used both as a crosslinker and a donor of the hydrophilic groups such as ‒COOH and ‒NH–C=O amide from pyrrolidone ring. Reactive poly(VP-alt-MA, in situ generated Ag nanoparticles (AgNPs and original partner polymer had an significant effect on the morphology and diameter distribution of nanofibers. High and excellent conductive behaviors were observed for the homopolymer and copolymer of VP based fiber structures, respectively. Upon successive chemical cross-linking of the nanofiber structures by reactive partner copolymer, the conductivity of nanofiber films as electro-active platforms dramatically increased to 3.90·10–2 S·cm–1 at room temperature. Comparative analysis results also indicated that electrical properties strongly depended on the loaded reactive organoclay and in situ generated AgNPs.

  13. Synthetic approaches to uniform polymers.

    Ali, Monzur; Brocchini, Steve


    Uniform polymers are characterised by a narrow molecular weight distribution (MWD). Uniformity is also defined by chemical structure in respect of (1) monomer orientation, sequence and stereo-regularity, (2) polymer shape and morphology and (3) chemical functionality. The function of natural polymers such as polypeptides and polynucleotides is related to their conformational structure (e.g. folded tertiary structure). This is only possible because of their high degree of uniformity. While completely uniform synthetic polymers are rare, polymers with broad structure and MWD are widely used in medicine and the biomedical sciences. They are integral components in final dosage forms, drug delivery systems (DDS) and in implantable devices. Increasingly uniform polymers are being used to develop more complex medicines (e.g. delivery of biopharmaceuticals, enhanced formulations or DDS's for existing actives). In addition to the function imparted by any new polymer it will be required to meet stringent specifications in terms of cost containment, scalability, biocompatibility and performance. Synthetic polymers with therapeutic activity are also being developed to exploit their polyvalent properties, which is not possible with low molecular weight molecules. There is need to utilise uniform polymers for applications where the polymer may interact with the systemic circulation, tissues or cellular environment. There are also potential applications (e.g. stimuli responsive coatings) where uniform polymers may be used for their more defined property profile. While it is not yet practical to prepare synthetic polymers to the same high degree of uniformity as proteins, nature also effectively utilises many polymers with lower degrees of uniformity (e.g. polysaccharides, poly(amino acids), polyhydroxyalkanoates). In recent years it has become possible to prepare with practical experimental protocols sufficient quantities of polymers that display many aspects of uniformity. This

  14. Novel High-Viscosity Polyacrylamidated Chitosan for Neural Tissue Engineering: Fabrication of Anisotropic Neurodurable Scaffold via Molecular Disposition of Persulfate-Mediated Polymer Slicing and Complexation

    Viness Pillay


    Full Text Available Macroporous polyacrylamide-grafted-chitosan scaffolds for neural tissue engineering were fabricated with varied synthetic and viscosity profiles. A novel approach and mechanism was utilized for polyacrylamide grafting onto chitosan using potassium persulfate (KPS mediated degradation of both polymers under a thermally controlled environment. Commercially available high molecular mass polyacrylamide was used instead of the acrylamide monomer for graft copolymerization. This grafting strategy yielded an enhanced grafting efficiency (GE = 92%, grafting ratio (GR = 263%, intrinsic viscosity (IV = 5.231 dL/g and viscometric average molecular mass (MW = 1.63 × 106 Da compared with known acrylamide that has a GE = 83%, GR = 178%, IV = 3.901 dL/g and MW = 1.22 × 106 Da. Image processing analysis of SEM images of the newly grafted neurodurable scaffold was undertaken based on the polymer-pore threshold. Attenuated Total Reflectance-FTIR spectral analyses in conjugation with DSC were used for the characterization and comparison of the newly grafted copolymers. Static Lattice Atomistic Simulations were employed to investigate and elucidate the copolymeric assembly and reaction mechanism by exploring the spatial disposition of chitosan and polyacrylamide with respect to the reactional profile of potassium persulfate. Interestingly, potassium persulfate, a peroxide, was found to play a dual role initially degrading the polymers—“polymer slicing”—thereby initiating the formation of free radicals and subsequently leading to synthesis of the high molecular mass polyacrylamide-grafted-chitosan (PAAm-g-CHT—“polymer complexation”. Furthermore, the applicability of the uniquely grafted scaffold for neural tissue engineering was evaluated via PC12 neuronal cell seeding. The novel PAAm-g-CHT exhibited superior neurocompatibility in terms of cell infiltration owing to the anisotropic porous architecture, high molecular mass mediated robustness

  15. Polymer Nanocomposites

    methods for the synthesis of polymer nanocomposites. In this article we .... ers, raw materials recovery, drug delivery and anticorrosion .... region giving rise to dose-packed absorption bands called an IR ... using quaternary ammonium salts.

  16. Homogeneous crystal nucleation in polymers.

    Schick, C; Androsch, R; Schmelzer, J W P


    The pathway of crystal nucleation significantly influences the structure and properties of semi-crystalline polymers. Crystal nucleation is normally heterogeneous at low supercooling, and homogeneous at high supercooling, of the polymer melt. Homogeneous nucleation in bulk polymers has been, so far, hardly accessible experimentally, and was even doubted to occur at all. This topical review summarizes experimental findings on homogeneous crystal nucleation in polymers. Recently developed fast scanning calorimetry, with cooling and heating rates up to 10 6 K s -1 , allows for detailed investigations of nucleation near and even below the glass transition temperature, including analysis of nuclei stability. As for other materials, the maximum homogeneous nucleation rate for polymers is located close to the glass transition temperature. In the experiments discussed here, it is shown that polymer nucleation is homogeneous at such temperatures. Homogeneous nucleation in polymers is discussed in the framework of the classical nucleation theory. The majority of our observations are consistent with the theory. The discrepancies may guide further research, particularly experiments to progress theoretical development. Progress in the understanding of homogeneous nucleation is much needed, since most of the modelling approaches dealing with polymer crystallization exclusively consider homogeneous nucleation. This is also the basis for advancing theoretical approaches to the much more complex phenomena governing heterogeneous nucleation.

  17. Mo-II Cluster Complex-Based Coordination Polymer as an Efficient Heterogeneous Catalyst in the Suzuki–Miyaura Coupling Reaction

    Bůžek, Daniel; Hynek, Jan; Kučeráková, Monika; Kirakci, Kaplan; Demel, Jan; Lang, Kamil


    Roč. 2016, č. 28 (2016), s. 4668-4673 ISSN 1434-1948 R&D Projects: GA ČR GA13-05114S; GA ČR GA15-12653S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:61388980 ; RVO:68378271 Keywords : C–C coupling * Heterogeneous catalysis * Molybdenum * Palladium * Polymers Subject RIV: CA - Inorganic Chemistry ; CF - Physical ; Theoretical Chemistry (FZU-D) Impact factor: 2.444, year: 2016

  18. Polymer nanocomposites: polymer and particle dynamics

    Kim, Daniel; Srivastava, Samanvaya; Narayanan, Suresh; Archer, Lynden A.


    Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has

  19. Antimocrobial Polymer

    McDonald, William F.; Huang, Zhi-Heng; Wright, Stacy C.


    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from quaternary ammonium compounds, gentian violet compounds, substituted or unsubstituted phenols, biguanide compounds, iodine compounds, and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)3P wherein A is hydroxyalkyl; and the antimicrobial agent is chlorhexidine, dimethylchlorophenol, cetyl pyridinium chloride, gentian violet, triclosan, thymol, iodine, and mixtures thereof.

  20. Polymer electronics

    Geoghegan, Mark


    Polymer electronics is the science behind many important new developments in technology, such as the flexible electronic display (e-ink) and many new developments in transistor technology. Solar cells, light-emitting diodes, and transistors are all areas where plastic electronics is likely to, or is already having, a serious impact on our daily lives. With polymer transistors and light-emitting diodes now being commercialised, there is a clear need for a pedagogic text thatdiscusses the subject in a clear and concise fashion suitable for senior undergraduate and graduate students. The content

  1. Approaches for Making High Performance Polymer Materials from Commodity Polymers

    Xu Xi


    blending it with small amount of degraded PVC, fulfilling the idea of plasticizing PVC by itself.Through co-milling of PS and TiO2 with the pan-mill designed by our Lab, the co-milled PS/TiO2 is easier to process and has higher impact strength than that of the blended PS/TiO2.3. Stress induced reactions and irradiation processing technique were utilized for making polymer nanomaterials. PMMA microlatex, polyamiline nanoparticles, PBA/SiO2 nano-composite latex,ultra-fine PA6 filled PP blend, ultra-fine waste tire rubber (WTR) filled PP and Fe/PP nanocomposite were successfully prepared.4. The superstructure and properties of polymer might be improved through hydrogen bonding.Intermacromolecular complexation is a physical way to control the supermolecular structure of polymers at the molecular level and may be treated as a molecular design at higher structure level.A series of high performance polymer materials: PC/EAA complex, P(MMA-MAA)/PEO-LiClO4 complex, P(AN-AM-AA)/PVA complex, UV-irradiated PET/PVA complex and UV-irradiated HDPE/PA6 complex were prepared through hydrogen bonding.

  2. Entangled Polymer Melts in Extensional Flow

    Hengeller, Ludovica

    Many commercial materials derived from synthetic polymers exhibit a complex response under different processing operations such as fiber formation, injection moulding,film blowing, film casting or coatings. They can be processed both in the solid or in the melted state. Often they may contain two...... or more different polymers in addition to additives, fillers or solvents in order to modify the properties of the final product. Usually, it is also desired to improve the processability. For example the supplement of a high molecular weight component improves the stability in elongational flows....... Understanding the behaviour of polymer melts and solutions in complex non-linearflows is crucial for the design of polymeric materials and polymer processes. Through rheological characterization, in shear and extensional flow, of model polymer systems,i.e. narrow molar mass distribution polymer melts...

  3. Luminescent lanthanide coordination polymers

    Ma, L.; Evans, O.R.; Foxman, B.M.; Lin, W.


    One-dimensional lanthanide coordination polymers with the formula Ln(isonicotinate){sub 3}(H{sub 2}O){sub 2} (Ln = Ce, Pr, Nd, Sm, Eu, Tb; 1a-f) were synthesized by treating nitrate or perchlorate salts of Ln(III) with 4-pyridinecarboxaldehyde under hydro(solvo)thermal conditions. Single-crystal and powder X-ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. While Ce(III), Pr(III), and Nd(III) complexes adopt a chain structure with alternating Ln-(carboxylate){sub 2}-Ln and Ln-(carboxylate){sub 4}-Ln linkages, Sm(III), Eu(III), and Tb(III) complexes have a doubly carboxylate-bridged infinite-chain structure with one chelating carboxylate group on each metal center. In both structures, the lanthanide centers also bind to two water molecules to yield an eight-coordinate, square antiprismatic geometry. The pyridine nitrogen atoms of the isonicotinate groups do not coordinate to the metal centers in these lanthanide(III) complexes; instead, they direct the formation of Ln(III) coordination polymers via hydrogen bonding with coordinated water molecules. Photoluminescence measurements show that Tb(isonicotinate){sub 3}(H{sub 2}O){sub 2} is highly emissive at room temperature with a quantum yield of {approximately}90%. These results indicate that highly luminescent lanthanide coordination polymers can be assembled using a combination of coordination and hydrogen bonds. Crystal data for 1a: monoclinic space group P2{sub 1}/c, a = 9.712(2) {angstrom}, b = 19.833(4) {angstrom}, c = 11.616(2) {angstrom}, {beta} = 111.89(3){degree}, Z = 4. Crystal data for 1f: monoclinic space group C2/c, a = 20.253(4) {angstrom}, b = 11.584(2) {angstrom}, c = 9.839(2) {angstrom}, {beta} = 115.64(3){degree}, Z = 8.

  4. A novel solid fluorescence method for the fast determination of quercetin in biological samples based on the quercetin-Al(III) complex imprinted polymer

    Hu, Yufei; Feng, Ting; Li, Gongke


    In this work, a novel solid fluorescence method was proposed and applied to the fast determination of quercetin in urine and onion skin samples by using metal coordination imprinted polymer membrane, which was regarded as a recognition element. The quercetin-Al(III) imprinted polymer was immobilized in the microporous polypropylene fiber membrane via consecutive in situ polymerization. The CIP membrane had the porous, loose and layer upon layer structure. The CIP membrane was characterized by electron microscope photographs, infrared spectra, thermogravimetric analysis and solvent-resistant investigation. The extraction conditions including extraction solvent, extraction time, desorption solvent were optimized. Compared with MIP and NIP membrane, CIP membrane had been proved to be peculiar selective for quercetin even in presence of the structurally similar compounds such as kaempferol, rutin, naringenin and alpinetin. The CIP membrane was characteristic of high selectivity, stable and sensitive response to quercetin in polar environment. Under the optimum condition, there was a linear relationship between the state fluorescent response and the concentration of quercetin. The linear calibration range was over 0.02 mg L-1-0.80 mg L-1 with a detection limit of 5 μg L-1. The method was characteristic of flexible and good repeatability with relative standard deviation (RSD) of 4.1%. The proposed method was also successfully applied for the determination of quercetin in urine and onion skin samples without complicated pretreatment. The recoveries were 84.0-112.4% and RSDs varied from 1.5% to 6.8%. The results obtained by the proposed method agreed well with those obtained by HPLC method.

  5. Polymer physics

    Gedde, Ulf W


    This book is the result of my teaching efforts during the last ten years at the Royal Institute of Technology. The purpose is to present the subject of polymer physics for undergraduate and graduate students, to focus the fundamental aspects of the subject and to show the link between experiments and theory. The intention is not to present a compilation of the currently available literature on the subject. Very few reference citations have thus been made. Each chapter has essentially the same structure: starling with an introduction, continuing with the actual subject, summarizing the chapter in 30D-500 words, and finally presenting problems and a list of relevant references for the reader. The solutions to the problems presented in Chapters 1-12 are given in Chapter 13. The theme of the book is essentially polymer science, with the exclusion of that part dealing directly with chemical reactions. The fundamentals in polymer science, including some basic polymer chemistry, are presented as an introduction in t...

  6. Antimicrobial polymers.

    Jain, Anjali; Duvvuri, L Sailaja; Farah, Shady; Beyth, Nurit; Domb, Abraham J; Khan, Wahid


    Better health is basic requirement of human being, but the rapid growth of harmful pathogens and their serious health effects pose a significant challenge to modern science. Infections by pathogenic microorganisms are of great concern in many fields such as medical devices, drugs, hospital surfaces/furniture, dental restoration, surgery equipment, health care products, and hygienic applications (e.g., water purification systems, textiles, food packaging and storage, major or domestic appliances etc.) Antimicrobial polymers are the materials having the capability to kill/inhibit the growth of microbes on their surface or surrounding environment. Recently, they gained considerable interest for both academic research and industry and were found to be better than their small molecular counterparts in terms of enhanced efficacy, reduced toxicity, minimized environmental problems, resistance, and prolonged lifetime. Hence, efforts have focused on the development of antimicrobial polymers with all desired characters for optimum activity. In this Review, an overview of different antimicrobial polymers, their mechanism of action, factors affecting antimicrobial activity, and application in various fields are given. Recent advances and the current clinical status of these polymers are also discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Nonlinear optical and G-Quadruplex DNA stabilization properties of novel mixed ligand copper(II) complexes and coordination polymers: Synthesis, structural characterization and computational studies

    Rajasekhar, Bathula; Bodavarapu, Navya; Sridevi, M.; Thamizhselvi, G.; RizhaNazar, K.; Padmanaban, R.; Swu, Toka


    The present study reports the synthesis and evaluation of nonlinear optical property and G-Quadruplex DNA Stabilization of five novel copper(II) mixed ligand complexes. They were synthesized from copper(II) salt, 2,5- and 2,3- pyridinedicarboxylic acid, diethylenetriamine and amide based ligand (AL). The crystal structure of these complexes were determined through X-ray diffraction and supported by ESI-MAS, NMR, UV-Vis and FT-IR spectroscopic methods. Their nonlinear optical property was studied using Gaussian09 computer program. For structural optimization and nonlinear optical property, density functional theory (DFT) based B3LYP method was used with LANL2DZ basis set for metal ion and 6-31G∗ for C,H,N,O and Cl atoms. The present work reveals that pre-polarized Complex-2 showed higher β value (29.59 × 10-30e.s.u) as compared to that of neutral complex-1 (β = 0.276 × 10-30e.s.u.) which may be due to greater advantage of polarizability. Complex-2 is expected to be a potential material for optoelectronic and photonic technologies. Docking studies using AutodockVina revealed that complex-2 has higher binding energy for both G-Quadruplex DNA (-8.7 kcal/mol) and duplex DNA (-10.1 kcal/mol). It was also observed that structure plays an important role in binding efficiency.

  8. Synthesis and photoluminescent properties of Sr{sub (1−x)}Si{sub 2}O{sub 2}N{sub 2}: xEu{sup 2+} phosphor prepared by polymer metal complex method for WLEDs applications

    Hassan, Dhia A., E-mail: [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Department of Chemistry, College of Education for Pure Science, University of Basrah, Basrah 61004 (Iraq); Xu, Jian; Chen, Yibin; Li, Langkai [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Zeng, Renjie, E-mail: [Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005 (China); Fujian Key Lab of Advanced Special Materials, Xiamen University, Xiamen 361005 (China)


    Highlights: • SrSi{sub 2}O{sub 2}N{sub 2}: Eu{sup 2+} phosphor was prepared by polymer metal complex (pechini method). • The annealing time was decreased from 6 h in solid state method to 3 h. • The particles are crystalline and dispersed well with average size 6.5 μm. - Abstract: Green emitting Sr{sub (1−x)}Si{sub 2}O{sub 2}N{sub 2}: xEu{sup 2+} (x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1) phosphors were synthesized by polymer metal complex or pechini method. The XRD results confirm the formation of a pure phase at 1400 °C for 3 h. The SEM and particles size results indicate that the prepared phosphor consists of a polyhedral crystalline shape with well dispersed and the average particle size around 6.5 μm. The maximum PL intensity was found at 0.04% Eu{sup 2+} with a wide emission band between 460 and 640 nm and a green emission peak at 531.4 nm. The external quantum efficiency of 0.04% Eu{sup 2+} sample was 43.13%. The results indicate that pechini method is an alternative way and close in efficiency to the solid state method to prepare SrSi{sub 2}O{sub 2}N{sub 2} phosphor with higher homogeneity and more uniform size distribution for near UV and blue region applications for white light emitting diodes WLEDs.

  9. Polymer Physics Prize Talk

    Olvera de La Cruz, Monica

    Polymer electrolytes have been particularly difficult to describe theoretically given the large number of disparate length scales involved in determining their physical properties. The Debye length, the Bjerrum length, the ion size, the chain length, and the distance between the charges along their backbones determine their structure and their response to external fields. We have developed an approach that uses multi-scale calculations with the capability of demonstrating the phase behavior of polymer electrolytes and of providing a conceptual understanding of how charge dictates nano-scale structure formation. Moreover, our molecular dynamics simulations have provided an understanding of the coupling of their conformation to their dynamics, which is crucial to design self-assembling materials, as well as to explore the dynamics of complex electrolytes for energy storage and conversion applications.

  10. Examination of nanoformulated crosslinked polymers complexed with copper/zinc superoxide dismutase as a therapeutic strategy for angiotensin II-mediated hypertension

    Savalia, Krupa

    Excessive generation of superoxide (O2·-) has been extensively implicated as a signaling molecule in cardiovascular pathologies, including hypertension. As a major risk factor for myocardial infarction, stroke, and heart failure, the morbidity and mortality associated with hypertension is a worldwide epidemic. Although there are several standard therapies that effectively lower blood pressure, many hypertensive patients have uncontrolled blood pressure despite taking available medications. Thus, there is a necessity to develop new pharmacotherapies that target novel molecular effectors (e.g. O2·-) that have been implicated to be integral in the pathogenesis of hypertension. To overcome the failed therapeutic impact of currently available antioxidants in cardiovascular disease, we developed a nanomedicine-based delivery system for the O2 ·- scavenging enzyme, copper/zinc superoxide dismutase (CuZnSOD), in which CuZnSOD protein is electrostatically bound to poly-L-lysine (PLL 50)-polyethylene glycol (PEG) block co-polymer to form CuZnSOD nanozyme. Different formulations of CuZnSOD nanozyme are covalently stabilized by either reducible or non-reducible crosslinked bonds between the PLL50-PEG polymers. Herein, we tested the overall hypothesis that PLL50-PEG CuZnSOD nanozyme delivers active CuZnSOD protein to neurons and decreases blood pressure in a model of Angll-dependent hypertension. As determined by electron paramagnetic resonance (EPR) spectroscopy, nanozymes retain full SOD enzymatic activity. Furthermore, non-reducible crosslinked nanozyme delivers active CuZnSOD protein to central neurons in culture (CATH.a neurons) without inducing significant neuronal toxicity. In vivo studies conducted in Angll-mediated hypertensive adult male C57BL/6 mice demonstrate that the non-reducible crosslinked nanozyme significantly attenuates blood pressure when given directly into the brain and prevents the further increase in hypertension when intravenously (IV) administered

  11. Dispersions of Carbon nanotubes in Polymer Matrices

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


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

  12. Polymer blends

    Allen, Scott D.; Naik, Sanjeev


    The present invention provides, among other things, extruded blends of aliphatic polycarbonates and polyolefins. In one aspect, provided blends comprise aliphatic polycarbonates such as poly(propylene carbonate) and a lesser amount of a crystalline or semicrystalline polymer. In certain embodiments, provided blends are characterized in that they exhibit unexpected improvements in their elongation properties. In another aspect, the invention provides methods of making such materials and applications of the materials in applications such as the manufacture of consumer packaging materials.

  13. bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers.

    Islamova, Regina M; Dobrynin, Mikhail V; Ivanov, Daniil M; Vlasov, Andrey V; Kaganova, Elena V; Grigoryan, Galina V; Kukushkin, Vadim Yu


    cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C₅H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl2(NCCH2Ph)2] exhibits the best catalytic activity (room temperature, c = 1.0 × 10(-4) mol/L, τpot-life 60 min, τcuring 6 h). Although cis-[PtCl₂(NCCH2Ph)2] is less active than the widely used Karstedt's catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10(-4) mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10(-4)-1.0 × 10(-5) mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl2(NCR)2] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking.

  14. Synthesis, characterization and applications of polymer-metal ...

    Abstract. 4-Acryloxy acetophenone was prepared and subjected to suspension polymerization with divinyl- benzene as a cross-linking agent. The resulting network polymer was ligated with benzoyl hydrazone. The functional polymer was treated with metal ions [Cu(II), Fe(II)]. The polymer-metal complexes obtained.

  15. Electrospun complexes - functionalised nanofibres

    Meyer, T.; Wolf, M.; Dreyer, B.; Unruh, D.; Krüger, C.; Menze, M. [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany); Sindelar, R. [University of Applied Science Hannover, Faculty II (Germany); Klingelhöfer, G. [Gutenberg-University, Institute of Inorganic and Analytic Chemistry (Germany); Renz, F., E-mail: [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany)


    Here we present a new approach of using iron-complexes in electro-spun fibres. We modify poly(methyl methacrylate) (PMMA) by replacing the methoxy group with Diaminopropane or Ethylenediamine. The complex is bound covalently via an imine-bridge or an amide. The resulting polymer can be used in the electrospinning process without any further modifications in method either as pure reagent or mixed with small amounts of not functionalised polymer resulting in fibres of different qualities (Fig. 1).

  16. Complex shaped ZnO nano- and microstructure based polymer composites: mechanically stable and environmentally friendly coatings for potential antifouling applications.

    Hölken, Iris; Hoppe, Mathias; Mishra, Yogendra K; Gorb, Stanislav N; Adelung, Rainer; Baum, Martina J


    Since the prohibition of tributyltin (TBT)-based antifouling paints in 2008, the development of environmentally compatible and commercially realizable alternatives is a crucial issue. Cost effective fabrication of antifouling paints with desired physical and biocompatible features is simultaneously required and recent developments in the direction of inorganic nanomaterials could play a major role. In the present work, a solvent free polymer/particle-composite coating based on two component polythiourethane (PTU) and tetrapodal shaped ZnO (t-ZnO) nano- and microstructures has been synthesized and studied with respect to mechanical, chemical and biocompatibility properties. Furthermore, antifouling tests have been carried out in artificial seawater tanks. Four different PTU/t-ZnO composites with various t-ZnO filling fractions (0 wt%, 1 wt%, 5 wt%, 10 wt%) were prepared and the corresponding tensile, hardness, and pull-off test results revealed that the composite filled with 5 wt% t-ZnO exhibits the strongest mechanical properties. Surface free energy (SFE) studies using contact angle measurements showed that the SFE value decreases with an increase in t-ZnO filler amounts. The influence of t-ZnO on the polymerization reaction was confirmed by Fourier transform infrared-spectroscopy measurements and thermogravimetric analysis. The immersion tests demonstrated that fouling behavior of the PTU/t-ZnO composite with a 1 wt% t-ZnO filler has been decreased in comparison to pure PTU. The composite with a 5 wt% t-ZnO filler showed almost no biofouling.

  17. Efficient near-infrared emission of π-extended cyclometalated iridium complexes based on pyrene in solution-processed polymer light-emitting diode

    Liu, Yu; Hao, Zhaoran; Meng, Fanyuan; Wang, Pu; Yang, Liang; Wang, Yafei; Pei, Yong; Su, Shijian


    A novel iridium complex grafting hole-transporting triphenylamine (TPA) unit onto cyclometalated ligand, namely t-BuPyrPyTPA)2Ir(acac), was successfully synthesized and characterized. The photophysical, electrochemical and DFT/TD-DFT calculation, as well as electroluminescence properties of this iridium complex were fully investigated. Meanwhile, the PLEDs employing (t-BuPyrPyTPA)2Ir(acac) as dopant presented stable NIR emission peaked at 697 nm and a shoulder at 764 nm with a highest external quantum efficiency (EQE) of 0.56% at 4 wt% dopant concentration. These results demonstrate that expanding the conjugation length of the ligand is an effective way to achieve NIR emission.

  18. Simultaneous determination of trace amounts of metals by high-performance liquid chromatography after preconcentration with adsorption on chlorotrifluoroethylene polymer as their hexamethylenedithiocarbamate complexes

    Shijo, Yoshio; Yoshida, Hideaki; Uehara, Nobuo; Kitamura, Teruo; Yoshimoto, Eiji.


    A method for the simultaneous determination of Bi, Cd, Cu, In, Ni and Pb by high-performance liquid chromatography is presented. These metals are preconcentrated on poly(chlorotrifluoroethylene) resin particles as their hexamethylenedithiocarbamate (HMDC) complexes, and eluted with dimethyl sulfoxide, followed by HPLC separation and determination using an ODS column. The conditions for the adsorption of metal-HMDC complexes, such as the pH, HMDC concentration, amount of the resin particles and elution times with dimethyl sulfoxide, are discussed. The resulting solution is suitable for injection into reversed-phase HPLC. The detection limits for the metals were found to be at sub μgl -1 levels. The application of this principle to the trace analysis of Bi, Cd, Cu, In, Ni and Pb in high-purity aluminum is demonstrated. (author)

  19. The hydrodynamic size of polymer stabilized nanocrystals

    Krueger, Karl M; Al-Somali, Ali M; Mejia, Michelle; Colvin, Vicki L [Department of Chemistry, Rice University, MS-60 6100 Main Street, Houston, TX 77005 (United States)


    For many emerging applications, nanocrystals are surface functionalized with polymers to control self-assembly, prevent aggregation, and promote incorporation into polymer matrices and biological systems. The hydrodynamic diameter of these nanoparticle-polymer complexes is a critical factor for many applications, and predicting this size is complicated by the fact that the structure of the grafted polymer at a nanocrystalline interface is not generally established. In this work we evaluate using size-exclusion chromatography the overall hydrodynamic diameter of nanocrystals (Au, CdSe, d<5 nm) surface coated with polystyrene of varying molecular weight. The polymer is tethered to the nanoparticles via a terminal thiol to provide strong attachment. Our data show that at full coverage the polymer assumes a brush conformation and is 44% longer than the unbound polymer in solution. The brush conformation is confirmed by comparison with models used to describe polymer brushes at flat interfaces. From this work, we suggest an empirical formula which predicts the hydrodynamic diameter of polymer coated nanoparticles based on the size of the nanoparticle core and the size of the randomly coiled unbound polymer in solution.

  20. Foaming behaviour of polymer-surfactant solutions

    Cervantes-MartInez, Alfredo; Maldonado, Amir


    We study the effect of a non-ionic amphiphilic polymer (PEG-100 stearate also called Myrj 59) on the foaming behaviour of aqueous solutions of an anionic surfactant (sodium dodecyl sulfate or SDS). The SDS concentration was kept fixed while the Myrj 59 concentration was varied. Measurements of foamability, surface tension and electrical conductivity were carried out. The results show two opposite effects depending on the polymer concentration: foamability is higher when the Myrj 59 concentration is low; however, it decreases considerably when the polymer concentration is increased. This behaviour is due to the polymer adsorption at the air/liquid interface at lower polymer concentrations, and to the formation of a polymer-surfactant complex in the bulk at higher concentrations. The results are confirmed by surface tension and electrical conductivity measurements, which are interpreted in terms of the microstructure of the polymer-surfactant solutions. The observed behaviour is due to the amphiphilic nature of the studied polymer. The increased hydrophobicity of Myrj 59, compared to that of water-soluble polymers like PEG or PEO, increases its 'reactivity' towards SDS, i.e. the strength of its interaction with this anionic surfactant. Our results show that hydrophobically modified polymers have potential applications as additives in order to control the foaming properties of surfactant solutions

  1. Biochemical synthesis of water soluble conducting polymers

    Bruno, Ferdinando F.; Bernabei, Manuele


    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  2. Biochemical synthesis of water soluble conducting polymers

    Bruno, Ferdinando F., E-mail: [US Army Natick Soldier Research, Development and Engineering Center, Natick, MA 01760 (United States); Bernabei, Manuele [ITAF, Test Flight Centre, Chemistry Dept. Pratica di Mare AFB, 00071 Pomezia (Rome), Italy (UE) (Italy)


    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  3. Biochemical synthesis of water soluble conducting polymers

    Bruno, Ferdinando F.; Bernabei, Manuele


    An efficient biomimetic route for the synthesis of conducting polymers/copolymers complexed with lignin sulfonate and sodium (polystyrenesulfonate) (SPS) will be presented. This polyelectrolyte assisted PEG-hematin or horseradish peroxidase catalyzed polymerization of pyrrole (PYR), 3,4 ethyldioxithiophene (EDOT) and aniline has provided a route to synthesize water-soluble conducting polymers/copolymers under acidic conditions. The UV-vis, FTIR, conductivity and cyclic voltammetry studies for the polymers/copolymer complex indicated the presence of a thermally stable and electroactive polymers. Moreover, the use of water-soluble templates, used as well as dopants, provided a unique combination of properties such as high electronic conductivity, and processability. These polymers/copolymers are nowadays tested/evaluated for antirust features on airplanes and helicopters. However, other electronic applications, such as photovoltaics, for transparent conductive polyaniline, actuators, for polypyrrole, and antistatic films, for polyEDOT, will be proposed.

  4. Natural polymers: an overview

    John, MJ


    Full Text Available The scarcity of natural polymers during the world war years led to the development of synthetic polymers like nylon, acrylic, neoprene, styrene-butadiene rubber (SBR) and polyethylene. The increasing popularity of synthetic polymers is partly due...


    Hiemstra, C.; Zhong, Zhiyuan; Feijen, Jan


    The Invention relates to a stereo photo hydrogel formed by stereo complexed and photo cross-linked polymers, which polymers comprise at least two types of polymers having at least one hydrophilic component, at least one hydrophobic mutually stereo complexing component, and at least one of the types

  6. Quality assurance of polymer concrete

    Schulz, H.


    With polymer concrete, a whole range of organisational and functional measures have to be met in order to assure the required quality with an economic expenditure. Quality assurance begins in the design and does not end in the production, rather includes all fields of the enterprise. The following deals with a particular range of the total complex, the inspection methods for assuring the quality of machine components of polymer concrete, particularly machine tool bases, this being through the control of the raw material, the production and the finished product. (orig.) [de

  7. Polymer dynamics from synthetic polymers to proteins

    Keywords. Polymer dynamics; reptation; domain dynamics biomolecules. Abstract. Starting from the standard model of polymer motion - the Rouse model - we briefly present some key experimental results on the mesoscopic dynamics of polymer systems. We touch the role of topological confinement as expressed in the ...

  8. [New polymer-drug systems based on natural and synthetic polymers].

    Racoviţă, Stefania; Vasiliu, Silvia; Foia, Liliana


    The great versatility of polymers makes them very useful in the biomedical and pharmaceutical fields. The combination of natural and synthetic polymers leads to new materials with tailored functional properties. The aim of this work consists in the preparation of new drug delivery system based on chitosan (natural polymer) and polybetaines (synthetic polymers), by a simple process, well known in the literature as complex coacervation methods. Also, the adsorption and release studies of two antibiotics as well as the preservation of their bactericidal capacities were performed.

  9. Flexible Photonics: Polymer LEDs Made from Monochromatic Red Emitting Lanthanide/Polymer Blends. Phase 1

    O'Regan, Marie


    .... Spectrally pure, red emitting flexible LEDs have been fabricated. Close to a four-fold increase in device efficiency is obtained when a suitable lanthanide complex is blended with the semi-conducting host polymer...

  10. Shape memory polymers

    Wilson, Thomas S.; Bearinger, Jane P.


    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  11. Shape memory polymers

    Wilson, Thomas S.; Bearinger, Jane P.


    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  12. Slippery self-lubricating polymer surfaces

    Aizenberg, Joanna; Aizenberg, Michael; Cui, Jiaxi; Dunn, Stuart; Hatton, Benjamin; Howell, Caitlin; Kim, Philseok; Wong, Tak Sing; Yao, Xi


    The present disclosure describes a strategy to create self-healing, slippery self-lubricating polymers. Lubricating liquids with affinities to polymers can be utilized to get absorbed within the polymer and form a lubricant layer (of the lubricating liquid) on the polymer. The lubricant layer can repel a wide range of materials, including simple and complex fluids (water, hydrocarbons, crude oil and bodily fluids), restore liquid-repellency after physical damage, and resist ice, microorganisms and insects adhesion. Some exemplary applications where self-lubricating polymers will be useful include energy-efficient, friction-reduction fluid handling and transportation, medical devices, anti-icing, optical sensing, and as self-cleaning, and anti-fouling materials operating in extreme environments.

  13. Synthesis and study of conjugated polymers containing Di- or Triphenylamine

    Sukwattanasinitt, M.


    This thesis consists of two separate parts. The first part addresses the synthesis and study of conjugated polymers containing di- or triphenylamine. Two types of polymers: linear polymers and dendrimers, were synthesized. The polymers were characterized by NMR, IR, UV, GPC, TGA and DSC. Electronic and optical properties of the polymers were studied through the conductivity measurements and excitation- emission spectra. the second part of this thesis deals with a reaction of electron-rich acetylenes with TCNE. The discovery of the reaction from charge transfer complex studies and the investigation of this reaction on various electron-rich acetylenes are presented.

  14. Polymer nanocomposites: polymer and particle dynamics

    Kim, Daniel


    Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has been hypothesized that these unusual properties result from fast diffusion of the nanostructures in the host polymer, which facilitates polymer chain relaxation by constraint release and other processes. In this study, the effects of addition of sterically stabilized inorganic nanoparticles to entangled cis-1,4-polyisoprene and polydimethylsiloxane on the overall rheology of nanocomposites are discussed. In addition, insights about the relaxation of the host polymer chains and transport properties of nanoparticles in entangled polymer nanocomposites are presented. The nanoparticles are found to act as effective plasticizers for their entangled linear hosts, and below a critical, chemistry and molecular-weight dependent particle volume fraction, lead to reduced viscosity, glass transition temperature, number of entanglements, and polymer relaxation time. We also find that the particle motions in the polymer host are hyperdiffusive and at the nanoparticle length scale, the polymer host acts like a simple, ideal fluid and the composites\\' viscosity rises with increasing particle concentration. © 2012 The Royal Society of Chemistry.

  15. Electrical characterization of proton conducting polymer electrolyte based on bio polymer with acid dopant

    Kalaiselvimary, J.; Pradeepa, P.; Sowmya, G.; Edwinraj, S.; Prabhu, M. Ramesh, E-mail: [Department of Physics, Alagappa University, Karaikudi – 630 004, India. (India)


    This study describes the biodegradable acid doped films composed of chitosan and Perchloric acid with different ratios (2.5 wt %, 5 wt %, 7.5 wt %, 10 wt %) was prepared by the solution casting technique. The temperature dependence of the proton conductivity of complex electrolytes obeys the Arrhenius relationship. Proton conductivity of the prepared polymer electrolyte of the bio polymer with acid doped was measured to be approximately 5.90 × 10{sup −4} Scm{sup −1}. The dielectric data were analyzed using Complex impedance Z*, Dielectric loss ε’, Tangent loss for prepared polymer electrolyte membrane with the highest conductivity samples at various temperature.

  16. Cycloadditions in modern polymer chemistry.

    Delaittre, Guillaume; Guimard, Nathalie K; Barner-Kowollik, Christopher


    Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes started to give access to a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. A few years later, the concept of click chemistry revolutionized the way polymer chemists approached synthetic routes. Among the few reactions that could qualify as click, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) initially stood out. Soon, many old and new reactions, including cycloadditions, would further enrich the synthetic macromolecular chemistry toolbox. Whether click or not, cycloadditions are in any case powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes, responsiveness. Here, we wish to describe cycloaddition methodologies that have been reported in the last 10 years in the context of macromolecular engineering, with a focus on those developed in our laboratories. The overarching structure of this Account is based on the three most commonly encountered cycloaddition subclasses in organic and macromolecular chemistry: 1,3-dipolar cycloadditions, (hetero-)Diels-Alder cycloadditions ((H)DAC), and [2+2] cycloadditions. Our goal is to briefly describe the relevant reaction conditions, the advantages and disadvantages, and the realized polymer applications. Furthermore, the orthogonality of most of these reactions is highlighted because it has proven highly beneficial for generating unique, multifunctional polymers in a one-pot reaction. The overview on 1,3-dipolar cycloadditions is mostly centered on the application of CuAAC as the most travelled route, by far. Besides illustrating the capacity of CuAAC to generate complex polymeric architectures, alternative 1,3-dipolar cycloadditions operating without the need for a catalyst are described. In the area of (H)DA cycloadditions

  17. Prebiotic polymers and infrared spectra of galactic sources

    Wickramasinghe, N.C.; Hoyle, F.; Brooks, J.; Shaw, G.


    It is stated that infrared absorption features characteristic of molecular dust clouds in the Galaxy may be assigned to complex organic polymers or prebiotic polymers. It could be argued that such highly stable, complex polymers evolve due to radiation processing of molecular mantles on interstellar grains - essentially by a type of natural selection which operates in the interstellar medium. A large fraction of all C, N, O elements in the interstellar medium could be condensed in the form of these stable polymers. Such interstellar material may also account for a significant fraction of the 'insoluble organic matter' which is found in carbonaceous chondrites. (author)

  18. Microgel polymer composite fibres

    Kehren, Dominic


    In this thesis some novel ideas and advancements in the field of polymer composite fibres, specifically microgel-based polymer composite fibres have been achieved. The main task was to investigate and understand the electrospinning process of microgels and polymers and the interplay of parameter influences, in order to fabricate reproducible and continuously homogenous composite fibres. The main aim was to fabricate a composite material which combines the special properties of polymer fibres ...

  19. Physics of Complex Polymeric Molecules

    Kelly, Joshua Walter

    The statistical physics of complex polymers with branches and circuits is the topic of this dissertation. An important motivation are large, single-stranded (ss) RNA molecules. Such molecules form complex ``secondary" and ``tertiary" structures that can be represented as branched polymers with circuits. Such structures are in part directly determined by the nucleotide sequence and in part subject to thermal fluctuations. The polymer physics literature on molecules in this class has mostly focused on randomly branched polymers without circuits while there has been minimal research on polymers with specific structures and on polymers that contain circuits. The dissertation is composed of three parts: Part I studies branched polymers with thermally fluctuating structure confined to a potential well as a simple model for the encapsidation of viral RNA. Excluded volume interactions were ignored. In Part II, I apply Flory theory to the study of the encapsidation of viral ss RNA molecules with specific branched structures, but without circuits, in the presence of excluded volume interaction. In Part III, I expand on Part II and consider complex polymers with specific structure including both branching and circuits. I introduce a method based on the mathematics of Laplacian matrices that allows me to calculate density profiles for such molecules, which was not possible within Flory theory.

  20. Thermosetting Phthalocyanine Polymers

    Fohlen, G.; Parker, J.; Achar, B.


    Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.

  1. based gel polymer electrolytes

    (PVdF) as a host polymer, lithium perchlorate (LiClO4), lithium triflate ... TG/DTA studies showed the thermal stability of the polymer electrolytes. .... are observed while comparing pure XRD spectra with .... batteries as its operating temperature is normally in the .... chain ion movements and the conductivity of the polymer.

  2. Aerogel / Polymer Composite Materials

    Williams, Martha K. (Inventor); Smith, Trent M. (Inventor); Fesmire, James E. (Inventor); Roberson, Luke B. (Inventor); Clayton, LaNetra M. (Inventor)


    The invention provides new composite materials containing aerogels blended with thermoplastic polymer materials at a weight ratio of aerogel to thermoplastic polymer of less than 20:100. The composite materials have improved thermal insulation ability. The composite materials also have better flexibility and less brittleness at low temperatures than the parent thermoplastic polymer materials.

  3. Organic thin film transistors and polymer light-emitting diodes patterned by polymer inking and stamping

    Li Dawen; Guo, L Jay


    To fully realize the advantages of organic flexible electronics, patterning is very important. In this paper we show that a purely additive patterning technique, termed polymer inking and stamping, can be used to pattern conductive polymer PEDOT and fabricate sub-micron channel length organic thin film transistors. In addition, we applied the technique to transfer a stack of metal/conjugated polymer in one step and fabricated working polymer light-emitting devices. Based on the polymer inking and stamping technique, a roll-to-roll printing for high throughput fabrication has been demonstrated. We investigated and explained the mechanism of this process based on the interfacial energy consideration and by using the finite element analysis. This technique can be further extended to transfer more complex stacked layer structures, which may benefit the research on patterning on flexible substrates

  4. Polymer dynamics driven by a helical filament

    Balin, Andrew; Shendruk, Tyler; Zoettl, Andreas; Yeomans, Julia

    Microbial flagellates typically inhabit complex suspensions of extracellular polymeric material which can impact the swimming speed of motile microbes, filter-feeding of sessile cells, and the generation of biofilms. There is currently a need to better understand how the fundamental dynamics of polymers near active cells or flagella impacts these various phenomena. We study the hydrodynamic and steric influence of a rotating helical filament on suspended polymers using Stokesian Dynamics simulations. Our results show that as a stationary rotating helix pumps fluid along its long axis, nearby polymers migrate radially inwards and are elongated in the process. We observe that the actuation of the helix tends to increase the probability of finding polymeric material within its pervaded volume. At larger Weissenberg numbers, this accumulation of polymers within the vicinity of the helix is greater. Further, we have analysed the stochastic work performed by the helix on the polymers and we show that this quantity is positive on average and increases with polymer contour length. Our results provide a basis for understanding the microscopic interactions that govern cell dynamics in complex media. This work was supported through funding from the ERC Advanced Grant 291234 MiCE and we acknowledge EMBO funding to TNS (ALTF181-2013).

  5. Tandem catalysis: a new approach to polymers.

    Robert, Carine; Thomas, Christophe M


    The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

  6. Electroluminescence of Multicomponent Conjugated Polymers. 1. Roles of Polymer/Polymer Interfaces in Emission Enhancement and Voltage-Tunable Multicolor Emission in Semiconducting Polymer/Polymer Heterojunctions

    Zhang, Xuejun, Ph.D


    Effects of the electronic structure of polymer/polymer interfaces on the electroluminescence efficiency and tunable multicolor emission of polymer heterojunction light-emitting diodes were explored...


    Kaur Jasmeet; Harikumar S.L.; Kaur Amanpreet


    In the current scenario, polymers as carriers have revolutionized the drug delivery system. A more successful approach, to exploit the different properties of polymers in a solitary system is the complexation of polymers to form polyelectrolyte complexes. These complexes circumvent the use of chemical crosslinking agents, thereby reducing the risk of toxicity. The complex formed is generally applied in different dosage forms for the formulation of stable aggregated macromolecules. There are t...

  8. Nanoporous polymer electrolyte

    Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO


    A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

  9. Polymer friction Molecular Dynamics

    Sivebæk, Ion Marius; Samoilov, Vladimir N.; Persson, Bo N. J.

    We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively...... independent of molecular length. For polymer sliding on polymer the friction is significantly larger, and dependent on the molecular chain length. In both cases, the shear stresses are proportional to the squeezing pressure and finite at zero load, indicating an adhesional contribution to the friction force....

  10. Biostable glucose permeable polymer


    A new biostable glucose permeable polymer has been developed which is useful, for example, in implantable glucose sensors. This biostable glucose permeable polymer has a number of advantageous characteristics and, for example, does not undergo hydrolytic cleavage and degradation, thereby providing...... a composition that facilitates long term sensor stability in vivo. The versatile characteristics of this polymer allow it to be used in a variety of contexts, for example to form the body of an implantable glucose sensor. The invention includes the polymer composition, sensor systems formed from this polymer...

  11. Advanced polymer chemistry of organometallic anions

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.


    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes

  12. Fluorination of polymers

    Du Toit, F.J.


    Polyethylene and polypropylene were reacted with elemental fluorine under carefully controlled conditions to produce fluorocarbon polymers. Fluorination of polymer films resulted in fluorination of only the outer surfaces of the films, while the reaction of elemental fluorine with powdered hydrocarbon polymers produced perfluorocarbon polymers. Existing and newly developed techniques were used to characterize the fluorinated polymers. It was shown that the degree of fluorination was influenced by the surface area of the hydrocarbon material, the concentration, of the fluorine gas, and the time and temperature of fluorination. A fluidized-bed reactor used for the fluorination of polymer powders effectively increased the reaction rate. The surface tension and the oxygen permeability of the fluorinated polymers were studied. The surface tension of hydrocarbon polymers was not influenced by different solvents, but the surface tension of fluorinated polymers was affected by the type of solvent that was used. There were indications that the surface tension was affected by oxygen introduced into the polymer surface during fluorination. Fluorination lowered the permeability of oxygen through hydrocarbon polymers. 55 refs., 51 figs., 26 tabs

  13. Advanced polymers in medicine

    Puoci, Francesco


    The book provides an up-to-date overview of the diverse medical applications of advanced polymers. The book opens by presenting important background information on polymer chemistry and physicochemical characterization of polymers. This serves as essential scientific support for the subsequent chapters, each of which is devoted to the applications of polymers in a particular medical specialty. The coverage is broad, encompassing orthopedics, ophthalmology, tissue engineering, surgery, dentistry, oncology, drug delivery, nephrology, wound dressing and healing, and cardiology. The development of polymers that enhance the biocompatibility of blood-contacting medical devices and the incorporation of polymers within biosensors are also addressed. This book is an excellent guide to the recent advances in polymeric biomaterials and bridges the gap between the research literature and standard textbooks on the applications of polymers in medicine.

  14. Antiviral Polymer Therapeutics

    Smith, Anton Allen Abbotsford


    polymerized in a controlled manner with carrier monomers of historically proven biocompatible polymers. The carrier polymers, the loading of ribavirin as well as the size of the polymer were varied systematically with the aid of an automated synthesis platform. These polymers were tested in a cellular assay...... of reversible-addition-fragmentation chain transfer polymerization, which not only controls the size of polymer, but also allows the introduction of a terminal amine on the polymer which can be used for further conjugation. This has allowed for not only fluorescent labeling of the polymer, but also protein...... is mediated through specific transporters, it is thought that the accumulation can be alleviated through the attachment of ribavirin to a macromolecule. To this end, ribavirin was enzymatically modified into a monomer compatible with controlled polymerization techniques. The ribavirin monomers were...

  15. Polymer reaction engineering, an integrated approach

    Meyer, T.; Keurentjes, J.T.F.; Meyer, T.; Keurentjes, J.T.F.


    Summary This chapter contains sections titled: Polymer Materials A Short History of Polymer Reaction Engineering The Position of Polymer Reaction Engineering Toward Integrated Polymer Reaction Engineering The Disciplines in Polymer Reaction Engineering The Future: Product-inspired Polymer Reaction

  16. Segmental dynamics in polymer electrolytes

    Triolo, A; Lo Celso, F; Triolo, R; Passerini, S; Arrighi, V; Frick, B


    Polymer dynamics in poly(ethylene oxide) (PEO)-salt mixtures is investigated by means of quasi-elastic neutron scattering (QENS). In a previous study, we reported QENS data from the NEAT spectrometer (BENSC) that evidenced, for the first time, a dynamic heterogeneity in PEO-salt mixtures induced by salt addition. This finding is supported by molecular dynamics (MD) simulations carried out by Borodin et al. In agreement with MD simulations, our QENS data revealed two distinct processes: a fast motion corresponding to the bulk polymer and a slower relaxation, which we attribute to formation of PEO-cation complexes. In this paper we present new QENS data from the high-resolution spectrometer IN16 that further support MD simulations as well as our previous data interpretation. (orig.)

  17. Removal of Cu(II) in water by polymer enhanced ultrafiltration: Influence of polymer nature and pH.

    Kochkodan, Olga D; Kochkodan, Viktor M; Sharma, Virender K


    This study presents an efficient removal of Cu(II) in water using the polymer enhanced ultrafiltration (PEUF) method. Polymer of different molecular weight (MW) (polyethyleneimine (PEI), sodium lignosulfonates (SLS) and dextrans) were investigated to evaluate efficiency in removal of Cu(II) in water by the PEUF method. The decomposition of Cu(II)-polymer complex was also evaluated in order to reuse polymers. Cu(II) complexation depends on the MW of chelating polymer and the pH of feed solution. It was found that the Cu(II) rejection increased with the polymer dosage with high removal of Cu(II) when using PEI and SLS at a 10:20 (mg/mg) ratio ([Cu(II)]:[polymer]). It was found that the maximum chelating capacity was 15 mg of Cu(II) per 20 mg of PEI. The Cu(II)-PEI complex could be decomposed by acid addition and the polymer could be efficiently reused with multiple complexation-decomplexation cycles. A conceptual flow chart of the integrated process of efficient removal of Cu(II) by PEUF method is suggested.

  18. Star-Branched Polymers (Star Polymers)

    Hirao, Akira; Hayashi, Mayumi; Ito, Shotaro; Goseki, Raita; Higashihara, Tomoya; Hadjichristidis, Nikolaos


    The synthesis of well-defined regular and asymmetric mixed arm (hereinafter miktoarm) star-branched polymers by the living anionic polymerization is reviewed in this chapter. In particular, much attention is being devoted to the synthetic

  19. Polymer dynamics from synthetic polymers to proteins

    Abstract. Starting from the standard model of polymer motion – the Rouse model – .... reptation and the escape processes (creep motion) from the tube. .... scattering curves from an arrangement of small mesoscopic spheres also allows a.

  20. Quantum dot doped solid polymer electrolyte for device application

    Singh, Pramod K.; Kim, Kang Wook; Rhee, Hee-Woo [Department of Chemical and Biomolecular Engineering, Sogang University, Mapo-Gu, Seoul 121-742 (Korea)


    ZnS capped CdSe quantum dots embedded in PEO:KI:I{sub 2} polymer electrolyte matrix have been synthesized and characterized for dye sensitized solar cell (DSSC) application. The complex impedance spectroscopy shows enhance in ionic conductivity ({sigma}) due to charges provide by quantum dots (QD) while AFM affirm the uniform distribution of QD into polymer electrolyte matrix. Cyclic voltammetry revealed the possible interaction between polymer electrolyte, QD and iodide/iodine. The photovoltaic performances of the DSSC containing quantum dots doped polymer electrolyte was also found to improve. (author)


    Carbas, Buket Bezgin; Odabas, Serhat; Türksoy, Figen; Tanyeli, Cihangir


    Highlights: • A novel tetraphenylethylene containing tetrakis carbazole electropolymerized polymer was synthesized. • The polymer displayed transparent colored to dark green coloration upon oxidation. • A neutral state colorless electrochromic device was constructed. - Abstract: Poly-1,1,2,2-tetrakis(4-9H-carbazol-9-yl)phenyl)ethene P(TCP) was successfully synthesized by electrochemical oxidation of corresponding monomer, namely, 1,1,2,2-tetrakis(4-9H-carbazol-9-yl)phenyl)ethene (TCP) using dichloromethane as the solvent and tetrabutylammonium hexafluorophosphate (TBAPF 6 ) as supporting electrolyte. Spectroelectrochemical properties of P(TCP) were investigated in situ recording the electronic absorption spectra of the polymer film coated on indium-tin oxide (ITO) at various potentials. P(TCP) displayed transparent to military green color in 1.80 s with an optical contrast of 23.0% (at 770 nm) and an optical band gap of 3.1 eV. The objective evaluation of the colors of P(TCP) at various potentials was performed through colorimetry studies on the basis of “Commission Internationale de l′Eclairage” (CIE) standards. The morphology of the polymer film was investigated by AFM analysis. A dual type electrochromic device based on P(TCP) was constructed and its spectroelectrochemical properties were investigated. The electrochromic device exhibits color change from transparent to dark blue with a good open circuit memory.

  2. Star-Branched Polymers (Star Polymers)

    Hirao, Akira


    The synthesis of well-defined regular and asymmetric mixed arm (hereinafter miktoarm) star-branched polymers by the living anionic polymerization is reviewed in this chapter. In particular, much attention is being devoted to the synthetic development of miktoarm star polymers since 2000. At the present time, the almost all types of multiarmed and multicomponent miktoarm star polymers have become feasible by using recently developed iterative strategy. For example, the following well-defined stars have been successfully synthesized: 3-arm ABC, 4-arm ABCD, 5-arm ABCDE, 6-arm ABCDEF, 7-arm ABCDEFG, 6-arm ABC, 9-arm ABC, 12-arm ABC, 13-arm ABCD, 9-arm AB, 17-arm AB, 33-arm AB, 7-arm ABC, 15-arm ABCD, and 31-arm ABCDE miktoarm star polymers, most of which are quite new and difficult to synthesize by the end of the 1990s. Several new specialty functional star polymers composed of vinyl polymer segments and rigid rodlike poly(acetylene) arms, helical polypeptide, or helical poly(hexyl isocyanate) arms are introduced.

  3. Dynamics in Complex Coacervates

    Perry, Sarah

    Understanding the dynamics of a material provides detailed information about the self-assembly, structure, and intermolecular interactions present in a material. While rheological methods have long been used for the characterization of complex coacervate-based materials, it remains a challenge to predict the dynamics for a new system of materials. Furthermore, most work reports only qualitative trends exist as to how parameters such as charge stoichiometry, ionic strength, and polymer chain length impact self-assembly and material dynamics, and there is little information on the effects of polymer architecture or the organization of charges within a polymer. We seek to link thermodynamic studies of coacervation phase behavior with material dynamics through a carefully-controlled, systematic study of coacervate linear viscoelasticity for different polymer chemistries. We couple various methods of characterizing the dynamics of polymer-based complex coacervates, including the time-salt superposition methods developed first by Spruijt and coworkers to establish a more mechanistic strategy for comparing the material dynamics and linear viscoelasticity of different systems. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  4. The Role of Nanofillers in Polymer Nanocomposites

    Xu, Di

    Polymer nanocomposites have been widely used in many fields. By introducing nanoparticles as fillers, researchers are able to get reinforced materials and new materials with novel properties, such as stronger mechanics, enhanced optical properties and improved conductivity. Though experimental techniques have rapidly advanced to enable better control of materials at atomic level, there is still a lack of a fundamental understanding of the dynamics and structure-properties relations in polymer nanocomposites. In this thesis, we use computer simulations to study the molecular structure and connections between microstate to macro properties of a variety of nanocomposites. Our goal is to understand the role of nanofillers in complex nanocomposite systems and to assist nanocomposite design. Nanoplatelet fillers, such as clays, have shown superior effects on the properties of polymer gels. We used molecular dynamic simulation to study nanoplatelet-filled composite gel system, in which short-range attraction exists between the polymer and nanoplatelet fillers. We show that the polymers and nanoplatelet fillers formed organic-inorganic networks with nanoplatelets acting as crosslink junctions, and the network eventually percolates the system as fillers reached a critical concentration. Stress auto-correlation and step-strain test were applied to investigate the mechanical properties; the results show the simulated composites changed from fluid-like to solid-like. The mechanical changes were consistent with the percolation transition, and gelation mechanism was therefore believed to be similar to those pure polymer physical gels. It was observed platelets aggregated into a local intercalation structure, which significantly differs from typical spherical fillers. This unique intercalation structure was examined by radial distribution function and ordering parameters. We discussed how intercalation would affect the properties of the platelet composites by comparing them with

  5. Internally plasticised cellulose polymers

    Burnup, M.; Hayes, G.F.; Fydelor, P.J.


    Plasticised cellulose polymers comprise base polymer having a chain of β-anhydroglucose units joined by ether linkages, with at least one of said units carrying at least one chemically unreactive side chain derived from an allylic monomer or a vinyl substituted derivative of ferrocene. The side chains are normally formed by radiation grafting. These internally plasticised celluloses are useful in particular as inhibitor coatings for rocket motor propellants and in general wherever cellulose polymers are employed. (author)

  6. pi-Conjugated polymers for photovoltaics

    Zoombelt, A.P.


    Polymer solar cells employ a nanoscopic phase separation or bulk heterojunction (BHJ) between two complementary molecular based p and n-type organic semiconductors to convert sunlight directly into electricity. The operational principle involves a complex sequence of events, starting with the

  7. Drug delivery's quest for polymers: Where are the frontiers?

    Merkle, Hans P


    Since the legendary 1964 article of Folkman and Long entitled "The use of silicone rubber as a carrier for prolonged drug therapy" the role of polymers in controlled drug delivery has come a long way. Today it is evident that polymers play a crucial if not the prime role in this field. The latest boost owes to the interest in drug delivery for the purpose of tissue engineering in regenerative medicine. The focus of this commentary is on a selection of general and personal observations that are characteristic for the current state of polymer therapeutics and carriers. It briefly highlights selected examples for the long march of synthetic polymer-drug conjugates from bench to bedside, comments on the ambivalence of selected polymers as inert excipients versus biological response modifiers, and on the yet unsolved dilemma of cationic polymers for the delivery of nucleic acid therapeutics. Further subjects are the complex design of multifunctional polymeric carriers including recent concepts towards functional supramolecular polymers, as well as observations on stimuli-sensitive polymers and the currently ongoing trend towards natural and naturally-derived biopolymers. The final topic is the discovery and early development of a novel type of biodegradable polyesters for parenteral use. Altogether, it is not the basic and applied research in polymer therapeutics and carriers, but the translational process that is the key hurdle to proceed towards an authoritative approval of new polymer therapeutics and carriers. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Characterisation of polymers, 1

    Crompton, Roy


    This essential guide to Polymer Characterisation is a complete compendium of methodologies that have evolved for the determination of the chemical composition of polymers. This 478-page book gives an up-to-date and thorough exposition of the state-of-the-art theories and availability of instrumentation needed to effect chemical and physical analysis of polymers. This is supported by approximately 1200 references. Volume 1 covers the methodology used for the determination of metals, non-metals and organic functional groups in polymers, and for the determination of the ratio in which different m

  9. Electroactive polymers for healthcare and biomedical applications

    Bauer, Siegfried


    Electroactivity was noticed early in biological substances, including proteins, polynucleotides and enzymes, even piezoand pyroelectricity were found in wool, hair, wood, bone and tendon. Recently, ferroelectricity has been identified in a surprisingly large number of biologically relevant materials, including hydroxyapatite, aortic walls and elastin. Inspired by the variety of natural electroactive materials, a wealth of new elastomers and polymers were designed recently, including an all organic elastomer electret and self-healing dielectric elastomers. Let's further draw inspiration from nature and widen the utilization of electroactive polymers towards (mobile) healthcare and biomedical applications. Ferroelectrets, internally charged polymer foams with a strong piezoelectric thickness coefficient are employed in biomedical sensing, for example as blood pressure and pulse sensor, as vital signs monitor or for the detection of tonicclonic seizures. Piezo- and pyroelectric polymers are booming in printed electronics research. They provide electronic skin the ability to "feel" pressure and temperature changes, or to generate electrical energy from vibrations and motions, even from contractile and relaxation motions of the heart and lung. Dielectric elastomers are pioneered by StretchSense as wearable motion capture sensors, monitoring pressure, stretch, bend and shear, quantifying comfort in sports and healthcare. On the cellular level, electroactive polymer arrays are used to study mechanotransduction of individual cells. Ionic electroactive polymers show potential to be used in implantable electroactive biomedical devices. Already with the currently available science and technology, we are at the verge of witnessing the demonstration of truly complex bionic systems.

  10. 3D Printing of Biocompatible Supramolecular Polymers and their Composites.

    Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne


    A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure.

  11. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J


    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  12. Inclusion and Functionalization of Polymers with Cyclodextrins: Current Applications and Future Prospects

    Christian Folch-Cano


    Full Text Available The numerous hydroxyl groups available in cyclodextrins are active sites that can form different types of linkages. They can be crosslinked with one another, or they can be derivatized to produce monomers that can form linear or branched networks. Moreover, they can form inclusion complexes with polymers and different substrates, modifying their physicochemical properties. This review shows the different applications using polymers with cyclodextrins, either by forming inclusion complexes, ternary complexes, networks, or molecularly imprinted polymers (MIPs. On one hand, the use of cyclodextrins enhances the properties of each polymer, and on the other the use of polymers decreases the amount of cyclodextrins required in different formulations. Both cyclodextrins and polymers contribute synergistically in several applications such as pharmacological, nutritional, environmental, and other industrial fields. The use of polymers based on cyclodextrins is a low cost easy to use potential tool with great future prospects.

  13. Binary Polymer Brushes of Strongly Immiscible Polymers.

    Chu, Elza; Babar, Tashnia; Bruist, Michael F; Sidorenko, Alexander


    The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

  14. NATO Advanced Research Workshop on Computational Methods for Polymers and Liquid Crystalline Polymers

    Pasini, Paolo; Žumer, Slobodan; Computer Simulations of Liquid Crystals and Polymers


    Liquid crystals, polymers and polymer liquid crystals are soft condensed matter systems of major technological and scientific interest. An understanding of the macroscopic properties of these complex systems and of their many and interesting peculiarities at the molecular level can nowadays only be attained using computer simulations and statistical mechanical theories. Both in the Liquid Crystal and Polymer fields a considerable amount of simulation work has been done in the last few years with various classes of models at different special resolutions, ranging from atomistic to molecular and coarse-grained lattice models. Each of the two fields has developed its own set of tools and specialized procedures and the book aims to provide a state of the art review of the computer simulation studies of polymers and liquid crystals. This is of great importance in view of a potential cross-fertilization between these connected areas which is particularly apparent for a number of experimental systems like, e.g. poly...

  15. Polymer gels and networks

    Osada, Yoshihito; Khokhlov, A. R


    ... or magnetic field, etc.). It was realized that not only can polymer gels absorb and hold a considerable volume of liquids, but they can also be forced to expel the absorbed liquid in a controlled manner. Of particular interest are hydrogels, i.e., polymer gels, which swell extensively in water. The most common hydrogels are polyelectrolyte gels: ...

  16. SANS studies of polymers

    Wignall, G.D.


    Some information provided by the application of small-angle neutron scattering concerning polymer structure is reviewed herein. Information about the polymer structure as examined in H 2 O/D 2 O mixtures is also provided. Examples of results of experiments performed at the National Center for Small-Angle Scattering Research are included

  17. Polymer based tunneling sensor

    Cui, Tianhong (Inventor); Wang, Jing (Inventor); Zhao, Yongjun (Inventor)


    A process for fabricating a polymer based circuit by the following steps. A mold of a design is formed through a lithography process. The design is transferred to a polymer substrate through a hot embossing process. A metal layer is then deposited over at least part of said design and at least one electrical lead is connected to said metal layer.

  18. Polymers for Combating Biocorrosion

    Jing Guo


    Full Text Available Biocorrosion has been considered as big trouble in many industries and marine environments due to causing of great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anticorrosion and antimicrobial properties have been widely accepted as a novel and effective approach to prevent biocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbial corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: (i traditional polymers incorporated with biocides, (ii antibacterial polymers containing quaternary ammonium compounds, and (iii conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting antibacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization, and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

  19. Polymer light emitting diodes

    Gautier-Thianche, Emmmanuelle


    We study sandwich type semiconducting polymer light emitting diodes; anode/polymer/cathode. ITO is selected as anode, this polymer is a blend of a commercially available polymer with a high hole transport ability: polyvinyl-carbazole and a laser dye: coumarin-515. Magnesium covered with silver is chosen for the anode. We study the influence of polymer thickness and coumarin doping ratio on electroluminescence spectrum, electric characteristics and quantum efficiency. An important drawback is that diodes lifetime remains low. In the second part of our study we determine degradations causes with X-Ray reflectivity experiments. It may be due to ITO very high roughness. We realize a new type of planar electroluminescent device: a channel type electroluminescent device in which polymer layer is inserted into an aluminium channel. Such a device is by far more stable than using classical sandwich structures with the same polymer composition: indeed, charges are generated by internal-field ionization and there is no injection from the electrode to the polymer. This avoids electrochemical reactions at electrodes, thus reducing degradations routes. (author) [fr

  20. Polymers targeting habitual diseases

    The use of polymeric drug conjugates mainly for the treatment for cancer therapy has been addressed, but these polymers also find their way in treatment of various lifestyle disorders like diabetes, hypertension, cardiovascular diseases etc. The focus is being laid to develop biodegradable polymer ...

  1. Stiff quantum polymers

    Kleinert, H.


    At ultralow temperatures, polymers exhibit quantum behavior, which is calculated here for the second and fourth moments of the end-to-end distribution in the large-stiffness regime. The result should be measurable for polymers in wide optical traps.

  2. Conducting polymer hydrogels

    Stejskal, Jaroslav


    Roč. 71, č. 2 (2017), s. 269-291 ISSN 0366-6352 R&D Projects: GA ČR(CZ) GA16-02787S Institutional support: RVO:61389013 Keywords : aerogel * conducting polymers * conductivity Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 1.258, year: 2016

  3. Theory of polymer blends

    Curro, J.G.; Schweizer, K.S.


    We have recently developed a new theoretical approach to the study of polymer liquids. The theory is based on the ''reference interaction site model'' (RISM theory) of Chandler and Andersen, which has been successful in describing the structure of small molecule liquids. We have recently extended our polymer RISM theory to the case of polymer blends. In the present investigation we have applied this theory to two special binary blends: (1) the athermal mixture where we isolate structural effects, and (2) the isotopic mixture in which structurally identical polymer chains interact with dissimilar attractive interactions. By studying these two special cases we are able to obtain insights into the molecular factors which control the miscibility in polymer mixtures. 18 refs., 2 figs

  4. Ion Implantation of Polymers

    Popok, Vladimir


    The current paper presents a state-of-the-art review in the field of ion implantation of polymers. Numerous published studies of polymers modified by ion beams are analysed. General aspects of ion stopping, latent track formation and changes of structure and composition of organic materials...... are discussed. Related to that, the effects of radiothermolysis, degassing and carbonisation are considered. Specificity of depth distributions of implanted into polymers impurities is analysed and the case of high-fluence implantation is emphasised. Within rather broad topic of ion bombardment, the focus...... is put on the low-energy implantation of metal ions causing the nucleation and growth of nanoparticles in the shallow polymer layers. Electrical, optical and magnetic properties of metal/polymer composites are under the discussion and the approaches towards practical applications are overviewed....

  5. All Polymer Micropump

    Hansen, Thomas Steen


    In this thesis an all polymer micropump, and the fabrication method required to fabricate this, are examined. Polymer microfluidic. devices are of major scientific interest because they can combine complicated chemical and biological analys~s in cheap and disposable devices. The electrode system...... in the micropump is based on the conducting polymer poly(3,4 ethylenedioxythiophene) (PEDOT). The majority of the work conducted was therefore aimed at developing methods for patterning and processing PEDOT. First a method was developed, where the conducting polymer PEDOT can be integrated into non...... of the substrate, the PEDOT is integrated into the non-conductive polymer. The result is a material that retains the good conductivity of PEDOT, but gains the mechanical stability of the substrate. The best results were obtained for PEDOTjPMMA. The new mechanically stable PEDOTjPMMA was micro-patterned using clean...

  6. Polymer wear evaluation

    Lagerbon, Mikkel; Sivebæk, Ion Marius


    Polymer wear plays an increasing role in manufacturing of machine parts for e.g. medical devices. Some of these have an expected lifetime of five to eight years during which very little wear of the components is acceptable. Too much wear compromises the dosage accuracy of the device and thereby...... the safety of the patients. Prediction of the wear of polymers is complicated by the low thermal conductivity of this kind of material. It implies that any acceleration of testing conditions by increased contact pressure and/or sliding velocity will make the polymer fail due to exaggerated heat buildup....... This is not the kind of wear observed in medical devices. In the present work a method was developed capable of evaluating the wear progression in polymer-polymer contacts. The configuration of the setup is injection moulded specimens consisting of an upper part having a toroid shape and a lower flat part. The sliding...

  7. Study of Hydrophobic and Ionizable Hydrophilic Copolymers at Polymer/Solid and Polymer/Liquid Interfaces

    Perahia, Dvora


    Joint experimental-computational efforts were set to characterize the interfacial effects on the structure and dynamics of polymers consisting of highly rigid hydrophilic-ionizable and hydrophobic sub-units within one polymeric chain casted into thin films of several molecular dimensions. Focusing on the ultra thin film region we separate out the interfacial effects from bulk characteristics. Specifically, the study sought to: identify the parameters that control the formation of a stable polymer-solid interface. The study consists of two components, experimental investigations and computational efforts. The experimental component was designed to derive empirical trends that can be used to correlate the set of coupled polymer molecular parameters with the interfacial characteristics of these polymers, and their response to presence of solvents. The computational study was designed to provide molecular insight into the ensemble averages provided by the experimental efforts on multiple length scales from molecular dimensions, to the nanometer lengths to a macroscopic understanding of solvent interactions with structured polymers. With the ultimate goal of correlating molecular parameters to structure, dynamics and properties of ionic polymers, the first stage of the research began with the study of two systems, one which allowed tailoring the flexibility of the backbone without the presence of ionic groups, but with a potential to sulfonate groups at a later stage, and a polymer whose backbone is rigid and the density of the ionic group can be varied. The combined experimental and computational studies significantly extended the understanding of polymers at interfaces from model systems to polydispersed copolymers with blocks of varying nature and complexity. This new insight directly affects the design of polymers for sustainable energy applications from batteries and fuel cells to solar energy.

  8. Imprinted Polymers in Wastewater Treatment

    Eastman, Christopher; Goodrich, Scott; Gartner, Isabelle; Mueller, Anja


    In wastewater treatment, a method that specifically recognizes a variety of impurities in a flexible manner would be useful for treatment facilities with varying needs. Current purification techniques (i.e. bacteria, oxidation, reduction, precipitation and filtration) are nonspecific and difficult to control in complex mixtures. Heavy metal removal is particularly important in improving the efficiency of wastewater treatment, as they inhibit or even destroy the bacteria used for filtration. Imprinting polymerization is a technique that allows for the efficient removal of specific compounds and has been used in purification of enantiomers. It has potential to be applied in wastewater systems with the impurities acting as the template for the imprinting polymerization. The polymer with the bound impurities intact can then be removed via precipitation. After removal of the impurity the polymer can be reused. Data for the imprinting polymerization of polyacrylates and polyacrylamides for several metal complexes will be presented. Imprinting polymerization in combination with emulsion polymerization to improve the removal of hydrophobic contaminants will be described. Removal efficiencies will be presented and compared with conventional wastewater treatment methods.

  9. A numerical model to simulate foams during devolatilization of polymers

    Khan, Irfan; Dixit, Ravindra


    Customers often demand that the polymers sold in the market have low levels of volatile organic compounds (VOC). Some of the processes for making polymers involve the removal of volatiles to the levels of parts per million (devolatilization). During this step the volatiles are phase separated out of the polymer through a combination of heating and applying lower pressure, creating foam with the pure polymer in liquid phase and the volatiles in the gas phase. The efficiency of the devolatilization process depends on predicting the onset of solvent phase change in the polymer and volatiles mixture accurately based on the processing conditions. However due to the complex relationship between the polymer properties and the processing conditions this is not trivial. In this work, a bubble scale model is coupled with a bulk scale transport model to simulate the processing conditions of polymer devolatilization. The bubble scale model simulates the nucleation and bubble growth based on the classical nucleation theory and the popular ``influence volume approach.'' As such it provides the information of bubble size distribution and number density inside the polymer at any given time and position. This information is used to predict the bulk properties of the polymer and its behavior under the applied processing conditions. Initial results of this modeling approach will be presented.

  10. Additive manufacturing of polymer-derived ceramics

    Eckel, Zak C.; Zhou, Chaoyin; Martin, John H.; Jacobsen, Alan J.; Carter, William B.; Schaedler, Tobias A.


    The extremely high melting point of many ceramics adds challenges to additive manufacturing as compared with metals and polymers. Because ceramics cannot be cast or machined easily, three-dimensional (3D) printing enables a big leap in geometrical flexibility. We report preceramic monomers that are cured with ultraviolet light in a stereolithography 3D printer or through a patterned mask, forming 3D polymer structures that can have complex shape and cellular architecture. These polymer structures can be pyrolyzed to a ceramic with uniform shrinkage and virtually no porosity. Silicon oxycarbide microlattice and honeycomb cellular materials fabricated with this approach exhibit higher strength than ceramic foams of similar density. Additive manufacturing of such materials is of interest for propulsion components, thermal protection systems, porous burners, microelectromechanical systems, and electronic device packaging.

  11. Photoluminescence in conjugated polymers

    Furst, J.E.; Laugesen, R.; Dastoor, P.; McNeill, C.


    Full text: Conjugated polymers combine the electronic and optical properties of semiconductors with the processability of polymers. They contain a sequence of alternate single and double carbon bonds so that the overlap of unhybridised p z orbitals creates a delocalised ρ system which gives semiconducting properties with p-bonding (valence) and p* -antibonding (conduction) bands. Photoluminesence (PL) in conjugated polymers results from the radiative decay of singlet excitons confined to a single chain. The present work is the first in a series of studies in our laboratory that will characterize the optical properties of conjugated polymers. The experiment involves the illumination of thin films of conjugated polymer with UV light (I=360 nm) and observing the subsequent fluorescence using a custom-built, fluorescence spectrometer. Photoluminesence spectra provide basic information about the structure of the polymer film. A typical spectrum is shown in the accompanying figure. The position of the first peak is related to the polymer chain length and resolved multiple vibronic peaks are an indication of film structure and morphology. We will also present results related to the optical degradation of these materials when exposed to air and UV light

  12. Radiation modification of polymers: fundamentals and applications

    Clough, R.L.


    When polymers were first exposed to ionizing radiation some 50 years ago, the resultant changes were found to be complex and relatively non-selective. Most importantly, irradiation was seen to give a mix of bond forming and bond breaking processes, and different polymer types were classified into two groups according to which process predominated. For polymers in the 'crosslinking' category, large industrial applications emerged within the first two decades of the initiation of this field, including heat shrink products, high performance wire insulation and tire manufacturing. There has been continuing work toward development of a wide range of new applications based on polymers and radiation, and this field remains quite active today. One approach to finding new commercial processes has been to take advantage of a variety of different radiation-induced phenomena (for example, uses for chain scission have emerged for enhancing the processing properties of various bulk polymers, for recycling of rubber, and for microlithography and LIGA). Another approach has taken advantage of progress in the science of radiation chemistry, by employing our increasing knowledge to enhance and/or reduce competing processes through the use of additives, the design of specialized resins, controlling gaseous atmospheres, varying processing conditions such as temperature, post-irradiation treatments, etc. This presentation will survey some of the exciting developments in polymer radiation processing, and will point out some of the underlying phenomena that are being manipulated to further their success. We will finish by describing progress on fundamental isotope-labeling studies of one longstanding mechanistic complexity, oxidation chemistry, which is critical in many radiation processing applications, such as retarding post-irradiation degradation problems, enhancing chain scission where desired, altering surface polarity, and providing a useful pretreatment in grafting schemes

  13. Biomedical applications of polymers

    Gebelein, C G


    The biomedical applications of polymers span an extremely wide spectrum of uses, including artificial organs, skin and soft tissue replacements, orthopaedic applications, dental applications, and controlled release of medications. No single, short review can possibly cover all these items in detail, and dozens of books andhundreds of reviews exist on biomedical polymers. Only a few relatively recent examples will be cited here;additional reviews are listed under most of the major topics in this book. We will consider each of the majorclassifications of biomedical polymers to some extent, inclu

  14. SANS studies of polymers

    Wignall, G.D.


    Before small-angle neutron scattering (SANS), chain conformation studies were limited to light and small angle x-ray scattering techniques, usually in dilute solution. SANS from blends of normal and labeled molecules could give direct information on chain conformation in bulk polymers. Water-soluble polymers may be examined in H 2 O/D 2 O mixtures using contrast variation methods to provide further information on polymer structure. This paper reviews some of the information provided by this technique using examples of experiments performed at the National Center for Small-Angle Scattering Research (NCSASR)

  15. Development of Silicate Polymers

    Søgaard, Erik Gydesen; Simonsen, Morten Enggrob

      The development of inorganic polymers is a new promising technology that may be used in many applications. The syntheses of inorganic polymers are normally carried out either by mixing an amorphous material for example silicium dioxide with a mineral base or dissolving metal oxids or metal...... hydroxide in acid and increase pH to saturation of the metal hydroxide. It is assumed that the syntheses of the inorganic polymer are carried out through polymerisation of oligomers (dimer, trimer) which provide the actual unit structures of the three dimensional macromolecular structure. In this work...

  16. Soluble porphyrin polymers

    Gust, Jr., John Devens; Liddell, Paul Anthony


    Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) ##STR00001## are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.

  17. Statistical properties of curved polymer

    respective ground states decide the conformational statistics of the polymer. For semiflexible polymers, the relevant non-dimensional quantity is lp/L, where lp is the persistence length (which is proportional to the bending modulus k) and L is the contour length of the polymer. In the limit, lp/L ≪ 1, the polymer behaves as.

  18. Electroluminescence from GaN-polymer heterojunction

    Chitara, Basant; Lal, Nidhi; Krupanidhi, S.B.; Rao, C.N.R.


    Inorganic and organic semiconductor devices are generally viewed as distinct and separate technologies. Herein we report a hybrid inorganic-organic light-emitting device employing the use of an air stable polymer, Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction, avoiding the use of p-type GaN, which is difficult to grow, being prone to the complex and expensive fabrication techniques that characterises it. I-V characteristics of the GaN-polymer heterojunction fabricated by us exhibits excellent rectification. The luminescence onset voltage is typically about 8-10 V. The device emits yellowish white electroluminescence with CIE coordinates (0.42, 0.44). - Highlights: → We use a polymer Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction. → I-V characteristics of the device fabricated by us exhibits excellent rectification. → The p-type polymer also emits yellow light, which when combined in proper composition with GaN, give rise to white light. → Device can be readily fabricated by just spin coating the polymer over GaN reducing the cost of the device.

  19. Electroactive polymers for sensing


    Electromechanical coupling in electroactive polymers (EAPs) has been widely applied for actuation and is also being increasingly investigated for sensing chemical and mechanical stimuli. EAPs are a unique class of materials, with low-moduli high-strain capabilities and the ability to conform to surfaces of different shapes. These features make them attractive for applications such as wearable sensors and interfacing with soft tissues. Here, we review the major types of EAPs and their sensing mechanisms. These are divided into two classes depending on the main type of charge carrier: ionic EAPs (such as conducting polymers and ionic polymer–metal composites) and electronic EAPs (such as dielectric elastomers, liquid-crystal polymers and piezoelectric polymers). This review is intended to serve as an introduction to the mechanisms of these materials and as a first step in material selection for both researchers and designers of flexible/bendable devices, biocompatible sensors or even robotic tactile sensing units. PMID:27499846

  20. Superabsorbent polymer; Kokyushusei porima

    Fujita, M. [Sanyo Kasei Kogyo K.K., Tokyo (Japan)


    Superabsorbent polymer (SAP) which has the absorbing ability from several hundreds to thousand times of the dead weight possesses many other functions in addition to the absorbing function, and studies on its application to various fields have been carried on very actively. Particularly, about 90% of the demand is for the application to body fluid absorber in the fields of sanitary materials. Basic water absorption mechanism, kinds, production methods, special features and applied cases of superabsorbent polymer are introduced. SAP is structured by loosely bridged water soluble polymer, particularly polymer electrolyte, to provide water unsoluble and water swelling properties. The kinds and production methods of SAP are described. SAP has respiration property in addition to the high water absorbing power and water holding ability. It has carboxyl ions, and has ammonia absorption ability and polyvalent metal ion adsorption ability. Paper diapers, water holding materials for soil, and cold reserving materials are discussed as examples of SAP application. 3 refs., 2 figs., 1 tab.

  1. Piezoelectricity in polymers

    Kepler, R.G.; Anderson, R.A.


    Piezoelectricity and related properties of polymers are reviewed. After presenting a historical overview of the field, the mathematical basis of piezo- and pyroelectricity is summarized. We show how the experimentally measured quantities are related to the changes in polarization and point out the serious inequlity between direct and converse piezoelectric coefficients in polymers. Theoretical models of the various origins of piezo- and pyroelectricity, which include piezoelectricity due to inhomogeneous material properties and strains, are reviewed. Relaxational effects are also considered. Experimental techniques are examined and the results for different materials are presented. Because of the considerable work in recent years polyimylidene fluoride, this polymer receives the majority of the attention. The numerous applications of piezo-and pyroelectric polymers are mentioned. This article concludes with a discussion of the possible role of piezo- and pyroelectricity in biological system

  2. Conjugated Polymer Solar Cells

    Paraschuk, Dmitry Y


    This report results from a contract tasking Moscow State University as follows: Conjugated polymers are promising materials for many photonics applications, in particular, for photovoltaic and solar cell devices...

  3. Polymers for Protein Conjugation

    Gianfranco Pasut


    Full Text Available Polyethylene glycol (PEG at the moment is considered the leading polymer for protein conjugation in view of its unique properties, as well as to its low toxicity in humans, qualities which have been confirmed by its extensive use in clinical practice. Other polymers that are safe, biodegradable and custom-designed have, nevertheless, also been investigated as potential candidates for protein conjugation. This review will focus on natural polymers and synthetic linear polymers that have been used for protein delivery and the results associated with their use. Genetic fusion approaches for the preparation of protein-polypeptide conjugates will be also reviewed and compared with the best known chemical conjugation ones.

  4. Reactive polymer fused deposition manufacturing

    Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander


    Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

  5. Sensitive determination of nucleic acids using organic nanoparticle fluorescence probes

    Zhou, Yunyou; Bian, Guirong; Wang, Leyu; Dong, Ling; Wang, Lun; Kan, Jian


    This paper describes the preparation of organic nanoparticles by reprecipitation method under sonication and vigorous stirring. Transmission electron microscopy (TEM) was used to characterize the size and size distribution of the luminescent nanoparticles. Their average diameter was about 25 nm with a size variation of ±18%. The fluorescence decay lifetime of the nanoparticles also was determined on a self-equipped fluorospectrometer with laser light source. The lifetime (˜0.09 μs) of nanoparticles is about three times long as that of the monomer. The nanoparticles were in abundant of hydrophilic groups, which increased their miscibility in aqueous solution. These organic nanoparticles have high photochemical stability, excellent resistance to chemical degradation and photodegradation, and a good fluorescence quantum yield (25%). The fluorescence can be efficiently quenched by nucleic acids. Based on the fluorescence quenching of nanoparticles, a fluorescence quenching method was developed for determination of microamounts of nucleic acids by using the nanoparticles as a new fluorescent probe. Under optimal conditions, maximum fluorescence quenching is produced, with maximum excitation and emission wavelengths of 345 and 402 nm, respectively. Under optimal conditions, the calibration graphs are linear over the range 0.4-19.0 μg ml -1 for calf thymus DNA (ct-DNA) and 0.3-19.0 μg ml -1 for fish sperm DNA (fs-DNA). The corresponding detection limits are 0.25 μg ml -1 for ct-DNA and 0.17 μg ml -1 for fs-DNA. The relative standard deviation of six replicate measurements is 1.3-2.1%. The method is simple, rapid and sensitive with wide linear range. The recovery and relative standard deviation are very satisfactory.

  6. Radiation treated propylene polymers

    Hoffman, W.A. III; Baum, G.A.


    A method is provided for imparting improved strength and discoloration resistance to a stabilized propylene polymer that is to be exposed to a sterilizing dose of radiation. From 200 to 400 ppm of a phenolic antioxidant containing an isocyanurate group in its molecular structure, and a thiosynergist in an amount at least 6 times the weight of the antioxidant, are incorporated into the polymer before irradiation

  7. Interfaced conducting polymers

    Stejskal, Jaroslav; Bober, Patrycja; Trchová, Miroslava; Nuzhnyy, Dmitry; Bovtun, Viktor; Savinov, Maxim; Petzelt, Jan; Prokeš, J.


    Roč. 224, February (2017), s. 109-115 ISSN 0379-6779 R&D Projects: GA ČR(CZ) GA16-02787S Institutional support: RVO:61389013 ; RVO:68378271 Keywords : polyaniline * polypyrrole * poly(p-phenylenediamine) Subject RIV: CD - Macromolecular Chemistry; CD - Macromolecular Chemistry (FZU-D) OBOR OECD: Polymer science; Polymer science (FZU-D) Impact factor: 2.435, year: 2016

  8. Sulfur polymer cement concrete

    Weber, H.H.; McBee, W.C.


    Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

  9. Radiation chemistry of polymers

    Charlesby, A.


    There are several and quite distinct major fields of interest discussed in this paper. The first deals with the modification of existing polymers either by main-chain scission or by cross-linking; the theories of these patterns of behavior are summarized here, and typical examples of polymers that show these alternative reactions are given. These are not comprehensive to avoid this presentation becoming a catalog of similar patterns of behavior

  10. Rapid Polymer Sequencer

    Stolc, Viktor (Inventor); Brock, Matthew W (Inventor)


    Method and system for rapid and accurate determination of each of a sequence of unknown polymer components, such as nucleic acid components. A self-assembling monolayer of a selected substance is optionally provided on an interior surface of a pipette tip, and the interior surface is immersed in a selected liquid. A selected electrical field is impressed in a longitudinal direction, or in a transverse direction, in the tip region, a polymer sequence is passed through the tip region, and a change in an electrical current signal is measured as each polymer component passes through the tip region. Each of the measured changes in electrical current signals is compared with a database of reference electrical change signals, with each reference signal corresponding to an identified polymer component, to identify the unknown polymer component with a reference polymer component. The nanopore preferably has a pore inner diameter of no more than about 40 nm and is prepared by heating and pulling a very small section of a glass tubing.

  11. New anion-exchange polymers for improved separations

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.


    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials

  12. Conducting Polymers Functionalized with Phthalocyanine as Nitrogen Dioxide Sensors

    S. D. Deshpande


    Full Text Available The conducting polymers such as polyaniline, polypyrrole and polythiophene were functionalized with copper phthalocyanine using chemical oxidation method. The obtained polymers viz. PANI-CuPc, PPy-CuPc and PT-CuPc were studied as chemical sensors by their response characteristics after exposure to various chemical vapors such as methanol, ammonia and nitrogen dioxide. The results obtained showed that these polymers have moderate sensitivity towards the methanol as well as ammonia vapors whereas they show tremendous sensitivity towards nitrogen dioxide vapors. The sensitivity factor of as high as 50,000 was obtained for PT-CuPc polymers in nitrogen dioxide. In comparison to this, the sensitivity factors of about 100 and 40 were obtained, when these polymers were exposed to ammonia and methanol vapors. The very high selectivity towards the nitrogen dioxide was explained on the basis of charge transfer complex formed between, the phthalocyanine donor and nitrogen dioxide acceptor molecules. On the other hand, ammonia becomes a competing electron donor in CuPc containing conducting polymers. The very low response towards the methanol may be explained on the basis very little charge transfer / interaction between CuPc containing polymers and methanol. Thus, CuPc incorporated conducting polymers have much higher selectivity than their original homopolymer.

  13. Branched-linear and agglomerate protein polymers as vaccine platforms.

    Wang, Leyi; Xia, Ming; Huang, Pengwei; Fang, Hao; Cao, Dianjun; Meng, Xiang-Jin; McNeal, Monica; Jiang, Xi; Tan, Ming


    Many viral structural proteins and their truncated domains share a common feature of homotypic interaction forming dimers, trimers, and/or oligomers with various valences. We reported previously a simple strategy for construction of linear and network polymers through the dimerization feature of viral proteins for vaccine development. In this study, technologies were developed to produce more sophisticated polyvalent complexes through both the dimerization and oligomerization natures of viral antigens. As proof of concept, branched-linear and agglomerate polymers were made via fusions of the dimeric glutathione-s-transferase (GST) with either a tetrameric hepatitis E virus (HEV) protruding protein or a 24-meric norovirus (NoV) protruding protein. Furthermore, a monomeric antigen, either the M2e epitope of influenza A virus or the VP8* antigen of rotavirus, was inserted and displayed by the polymer platform. All resulting polymers were easily produced in Escherichia coli at high yields. Immunization of mice showed that the polymer vaccines induced significantly higher specific humoral and T cell responses than those induced by the dimeric antigens. Additional evidence in supporting use of polymer vaccines included the significantly higher neutralization activity and protective immunity of the polymer vaccines against the corresponding viruses than those of the dimer vaccines. Thus, our technology for production of polymers containing different viral antigens offers a strategy for vaccine development against infectious pathogens and their associated diseases. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Precursor polymer compositions comprising polybenzimidazole

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.


    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  15. Characterization of Creases in Polymers for Adaptive Origami Structures (Postprint)


    in space. Shape change is seen in origami when a flat sheet of paper is folded into a complex geometry or model. Origami is not limited to artistic...AFRL-RX-WP-JA-2015-0036 CHARACTERIZATION OF CREASES IN POLYMERS FOR ADAPTIVE ORIGAMI STRUCTURES (POSTPRINT) Philip R. Buskohl UES, Inc. Richard...From – To) 08 June 2011 – 08 September 2014 4. TITLE AND SUBTITLE CHARACTERIZATION OF CREASES IN POLYMERS FOR ADAPTIVE ORIGAMI STRUCTURES

  16. Simple Room Temperature Method for Polymer Optical Fibre Cleaving

    Saez-Rodriguez, David; Nielsen, Kristian; Bang, Ole


    In this paper, we report on a new method to cleave polymer optical fibre. The most common way to cut a polymer optical fibre is chopping it with a razor blade; however, in this approach both the fibre and the blade must be preheated in order to turn the material ductile, and thus, prevent crazing...... of similar quality to those produced by more complex and expensive heated systems....

  17. Characterization of functional polymers by NMR

    Neto, Oscar H.S. A.S.; San Gil, Rosane A.S.; Nakayama, T.; Costa Neto, Claudio


    Several synthetic polymers are used in the chemical analysis of complexes mixtures aiming to extract certain specific functional groups for further identification. This work describes the utilization of NMR in the characterization of one of the above mentioned compounds which will be used as reagent for the synthesis of another compound of the same type, which will be further used in the chemical analysis of alcohols and phenols. The methodology is described. The results are described and discussed

  18. Can polymer thermal oxidative ageing be modelled?

    Audouin, L.; Colin, X.; Fayolle, B.; Richaud, E.; Verdu, J.


    It has been supposed, for a long time, that kinetic modelling of polymer ageing for nonempirical lifetime prediction was out of reach for two main reasons: hyper-complexity of mechanisms and heterogeneity of reactions. The arguments relative to both aspects are examined here. It is concluded that, thanks to recent advances, especially the introduction of numerical methods, kinetic modelling is possible in various important practical cases. (authors)

  19. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    Li, Xiu-Hua; Zhang, Qi; Hu, Ping


    A multifunctional homochiral coordination polymer, [Co(H 2 O)(BDC)(4,4′-BPY)]∙3H 2 O (1) (H 2 BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions

  20. New Polymer Electrolyte Cell Systems

    Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.


    PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

  1. Polymer gel dosimetry

    Baldock, C [Institute of Medical Physics, School of Physics, University of Sydney (Australia); De Deene, Y [Radiotherapy and Nuclear Medicine, Ghent University Hospital (Belgium); Doran, S [CRUK Clinical Magnetic Resonance Research Group, Institute of Cancer Research, Surrey (United Kingdom); Ibbott, G [Radiation Physics, UT M D Anderson Cancer Center, Houston, TX (United States); Jirasek, A [Department of Physics and Astronomy, University of Victoria, Victoria, BC (Canada); Lepage, M [Centre d' imagerie moleculaire de Sherbrooke, Departement de medecine nucleaire et de radiobiologie, Universite de Sherbrooke, Sherbrooke, QC (Canada); McAuley, K B [Department of Chemical Engineering, Queen' s University, Kingston, ON (Canada); Oldham, M [Department of Radiation Oncology, Duke University Medical Center, Durham, NC (United States); Schreiner, L J [Cancer Centre of South Eastern Ontario, Kingston, ON (Canada)], E-mail:, E-mail:


    Polymer gel dosimeters are fabricated from radiation sensitive chemicals which, upon irradiation, polymerize as a function of the absorbed radiation dose. These gel dosimeters, with the capacity to uniquely record the radiation dose distribution in three-dimensions (3D), have specific advantages when compared to one-dimensional dosimeters, such as ion chambers, and two-dimensional dosimeters, such as film. These advantages are particularly significant in dosimetry situations where steep dose gradients exist such as in intensity-modulated radiation therapy (IMRT) and stereotactic radiosurgery. Polymer gel dosimeters also have specific advantages for brachytherapy dosimetry. Potential dosimetry applications include those for low-energy x-rays, high-linear energy transfer (LET) and proton therapy, radionuclide and boron capture neutron therapy dosimetries. These 3D dosimeters are radiologically soft-tissue equivalent with properties that may be modified depending on the application. The 3D radiation dose distribution in polymer gel dosimeters may be imaged using magnetic resonance imaging (MRI), optical-computerized tomography (optical-CT), x-ray CT or ultrasound. The fundamental science underpinning polymer gel dosimetry is reviewed along with the various evaluation techniques. Clinical dosimetry applications of polymer gel dosimetry are also presented. (topical review)

  2. Polymer Directed Protein Assemblies

    Patrick van Rijn


    Full Text Available Protein aggregation and protein self-assembly is an important occurrence in natural systems, and is in some form or other dictated by biopolymers. Very obvious influences of biopolymers on protein assemblies are, e.g., virus particles. Viruses are a multi-protein assembly of which the morphology is dictated by poly-nucleotides namely RNA or DNA. This “biopolymer” directs the proteins and imposes limitations on the structure like the length or diameter of the particle. Not only do these bionanoparticles use polymer-directed self-assembly, also processes like amyloid formation are in a way a result of directed protein assembly by partial unfolded/misfolded biopolymers namely, polypeptides. The combination of proteins and synthetic polymers, inspired by the natural processes, are therefore regarded as a highly promising area of research. Directed protein assembly is versatile with respect to the possible interactions which brings together the protein and polymer, e.g., electrostatic, v.d. Waals forces or covalent conjugation, and possible combinations are numerous due to the large amounts of different polymers and proteins available. The protein-polymer interacting behavior and overall morphology is envisioned to aid in clarifying protein-protein interactions and are thought to entail some interesting new functions and properties which will ultimately lead to novel bio-hybrid materials.

  3. Supercritical transitiometry of polymers.

    Randzio, S L; Grolier, J P


    Employing supercritical fluids (SCFs) during polymers processing allows the unusual properties of SCFs to be exploited for making polymer products that cannot be obtained by other means. A new supercritical transitiometer has been constructed to permit study of the interactions of SCFs with polymers during processing under well-defined conditions of temperature and pressure. The supercritical transitiometer allows pressure to be exerted by either a supercritical fluid or a neutral medium and enables simultaneous determination of four basic parameters of a transition, i.e., p, T, Δ(tr)H and Δ(tr)V. This permits determination of the SCF effect on modification of the polymer structure at a given pressure and temperature and defines conditions to allow reproducible preparation of new polymer structures. Study of a semicrystalline polyethylene by this method has defined conditions for preparation of new microfoamed phases with good mechanical properties. The low densities and microporous structures of the new materials may make them useful for applications in medicine, pharmacy, or the food industry, for example.

  4. Multifunctional Polymer Nanocomposites

    Galaska, Alexandra Maria; Song, Haixiang; Guo, Zhanhu

    With more awareness of energy conversion/storage and saving, different strategies have been developed to utilize the sustainable and renewable energy. Introducing nanoscale fillers can make inert polymer matrix possess unique properties to satisfy certain functions. For example, alumina nanoparticles have strengthened the weak thermosetting polymers. A combined mixture of carbon nanofibers and magnetite nanoparticles have made the inert epoxy sensitive for magnetic field for sensing applications. Introducing silica nanoparticles into conductive polymers such as polyaniline has enhanced the giant magnetoresistance behaviors. The introduced nanoparticles have made the transparent polymer have the electromagnetic interference (EMI) shielding function while reduce the density significantly. With the desired miniaturization, the materials combining different functionalities have become importantly interesting. In this talk, methodologies to prepare nanocomposites and their effects on the produced nanocomposites will be discussed. A variety of advanced polymer nanocomposites will be introduced. Unique properties including mechanical, electrical, magnetoresistance etc. and the applications for environmental remediation, energy storage/saving, fire retardancy, electromagnetic interference shielding, and electronic devices will be presented.

  5. Flame spraying of polymers

    Varacalle, D.J. Jr.; Zeek, D.P.; Couch, K.W.; Benson, D.M.; Kirk, S.M.


    Statistical design-of-experiment studies of the thermal spraying of polymer powders are presented. Studies of the subsonic combustion (i.e., Flame) process were conducted in order to determine the quality and economics of polyester and urethane coatings. Thermally sprayed polymer coatings are of interest to several industries for anticorrosion applications, including the chemical, automotive, and aircraft industries. In this study, the coating design has been optimized for a site-specific application using Taguchi-type fractional-factorial experiments. Optimized coating designs are presented for the two powder systems. A substantial range of thermal processing conditions and their effect on the resultant polymer coatings is presented. The coatings were characterized by optical metallography, hardness testing, tensile testing, and compositional analysis. Characterization of the coatings yielded the thickness, bond strength, Knoop microhardness, roughness, deposition efficiency, and porosity. Confirmation testing was accomplished to verify the coating designs

  6. Nanostructured silicate polymer concrete

    Figovskiy Oleg L'vovich


    Full Text Available It has been known that acid-resistant concretes on the liquid glass basis have high porosity (up to 18~20 %, low strength and insufficient water resistance. Significant increasing of silicate matrix strength and density was carried out by incorporation of special liquid organic alkali-soluble silicate additives, which block superficial pores and reduce concrete shrinkage deformation. It was demonstrated that introduction of tetrafurfuryloxisilane additive sharply increases strength, durability and shock resistance of silicate polymer concrete in aggressive media. The experiments showed, that the strength and density of silicate polymer concrete increase in case of decreasing liquid glass content. The authors obtained optimal content of silicate polymer concrete, which possesses increased strength, durability, density and crack-resistance. Diffusive permeability of concrete and its chemical resistance has been investigated in various corroding media.

  7. Semi-metallic polymers

    Bubnova, Olga; Khan, Zia Ullah; Wang, Hui


    Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report...... that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being...... a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics....

  8. 'Stuffed' conducting polymers

    Winther-Jensen, Bjørn; Chen, Jun; West, Keld


    Conducting polymers (CP) obtained by oxidative polymerization using iron(III) salts shrink when Fe(II) and the excess counter ions are washed out after polymerization. This phenomenon can be used to incorporate active molecules into the CP matrix via their addition to the wash liquid. In the pres......Conducting polymers (CP) obtained by oxidative polymerization using iron(III) salts shrink when Fe(II) and the excess counter ions are washed out after polymerization. This phenomenon can be used to incorporate active molecules into the CP matrix via their addition to the wash liquid....... In the present work we demonstrate this principle on three different CP's: polypyrrole (PPy), poly-terthiophene (PTTh) and poly(3,4-ethylenedioxy thiophene) (PEDT), using ferrocene as a model molecule to be trapped in the polymer films. (c) 2005 Elsevier Ltd. All rights reserved....

  9. New insights into the mechanism of interaction between CO2 and polymers from thermodynamic parameters obtained by in situ ATR-FTIR spectroscopy.

    Gabrienko, Anton A; Ewing, Andrew V; Chibiryaev, Andrey M; Agafontsev, Alexander M; Dubkov, Konstantin A; Kazarian, Sergei G


    This work reports new physical insights of the thermodynamic parameters and mechanisms of possible interactions occurring in polymers subjected to high-pressure CO2. ATR-FTIR spectroscopy has been used in situ to determine the thermodynamic parameters of the intermolecular interactions between CO2 and different functional groups of the polymers capable of specific interactions with sorbed CO2 molecules. Based on the measured ATR-FTIR spectra of the polymer samples subjected to high-pressure CO2 (30 bar) at different temperatures (300-340 K), it was possible to characterize polymer-polymer and CO2-polymer interactions. Particularly, the enthalpy and entropy of the formation of the specific non-covalent complexes between CO2 and the hydroxy (-OH), carbonyl (C[double bond, length as m-dash]O) and hydroxyimino ([double bond, length as m-dash]N-OH) functional groups of the polymer samples have been measured. Furthermore, the obtained spectroscopic results have provided an opportunity for the structure of these complexes to be proposed. An interesting phenomenon regarding the behavior of CO2/polymer systems has also been observed. It has been found that only for the polyketone, the value of enthalpy was negative indicating an exothermic process during the formation of the CO2-polymer non-covalent complexes. Conversely, for the polyoxime and polyalcohol samples there is a positive enthalpy determined. This is a result of the initial polymer-polymer interactions requiring more energy to break than is released during the formation of the CO2-polymer complex. The effect of increasing temperature to facilitate the breaking of the polymer-polymer interactions has also been observed. Hence, a mechanism for the formation of CO2-polymer complexes was suggested based on these results, which occurs via a two-step process: (1) the breaking of the existing polymer-polymer interactions followed by (2) the formation of new CO2-polymer non-covalent interactions.

  10. Electric field induced dewetting at polymer/polymer interfaces

    Lin, Z.Q.; Kerle, T.; Russell, T.P.; Schäffer, E.; Steiner, U


    External electric fields were used to amplify interfacial fluctuations in the air/polymer/polymer system where one polymer dewets the other. Two different hydrodynamic regimes were found as a function of electric field strength. If heterogeneous nucleation leads to the formation of holes before the

  11. Polymer containing functional end groups is base for new polymers

    Hirshfield, S. M.


    Butadiene is polymerized with lithium-p-lithiophenoxide to produce linear polymer containing oxy-lithium group at one end and active carbon-lithium group at other end. Living polymers represent new approach to preparation of difunctional polymers in which structural features, molecular weight, type and number of end groups are controlled.

  12. Understanding Molecular Interactions within Chemically Selective Layered Polymer Assemblies

    Gary J. Blanchard


    This work focuses on two broad issues. These are (1) the molecular origin of the chemical selectivity achieved with ultrathin polymer multilayers, and (2) how the viscoelastic properties of the polymer layers are affected by exposure to solvent and analytes. These issues are inter-related, and to understand them we need to design experiments that probe both the energetic and kinetic aspects of interfacial adsorption processes. This project focuses on controling the chemical structure, thickness, morphology and sequential ordering of polymer layers bound to interfaces using maleimide-vinyl ether and closely related alternating copolymerization chemistry and efficient covalent cross-linking reactions that allow for layer-by-layer polymer deposition. This chemistry has been developed during the funding cycle of this Grant. We have measure the equilibrium constants for interactions between specific layers within the polymer interfaces and size-controlled, surface-functionalized gold nanoparticles. The ability to control both size and functionality of gold nanoparticle model analytes allows us to evaluate the average “pore size” that characterizes our polymer films. We have measured the “bulk” viscosity and shear modulus of the ultrathin polymer films as a function of solvent overlayer identity using quartz crystal microbalance complex impedance measurements. We have measured microscopic viscosity at specific locations within the layered polymer interfaces with time-resolved fluorescence lifetime and depolarization techniques. We combine polymer, cross-linking and nanoparticle synthetic expertise with a host of characterization techniques, including QCM gravimetry and complex impedance analysis, steady state and time-resolved spectroscopies.

  13. Raw and renewable polymers

    Joseph, S


    Full Text Available in the permeability of the membrane and HO H3C H3C H2C H2C HO OH NH NH OH O OC C n O O O O Fig. 4 Structure of Chitin Raw and Renewable Polymers promoting internal osmotic imbalances. This results in leaching of electrolytes and proteins. 2... is often lost. In most cases this denaturation is not reversible. R-CH-COOH NH2 w Amino acid H2N COOHR a Amino acid Fig. 5 Structure of amino acid Raw and Renewable Polymers The solubilities of proteins vary considerably based on compositions...

  14. Delocalization in polymer models

    Jitomirskaya, S Yu; Stolz, G


    A polymer model is a one-dimensional Schroedinger operator composed of two finite building blocks. If the two associated transfer matrices commute, the corresponding energy is called critical. Such critical energies appear in physical models, an example being the widely studied random dimer model. Although the random models are known to have pure-point spectrum with exponentially localized eigenstates for almost every configuration of the polymers, the spreading of an initially localized wave packet is here proven to be at least diffusive for every configuration.

  15. Polymers at cryogenic temperatures

    Fu, Shao-Yun


    Kalia and Fu's novel monograph covers cryogenic treatment, properties and applications of cryo-treated polymer materials. Written by numerous international experts, the twelve chapters in this book offer the reader a comprehensive picture of the latest findings and developments, as well as an outlook on the field. Cryogenic technology has seen remarkable progress in the past few years and especially cryogenic properties of polymers are attracting attention through new breakthroughs in space, superconducting, magnetic and electronic techniques. This book is a valuable resource for researchers, educators, engineers and graduate students in the field and at technical institutions.

  16. Polymers and colloids

    Schurtenberger, P.


    A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs

  17. Polymers and colloids

    Schurtenberger, P [ETH Zurich, Inst. fuer Polymere, Zurich (Switzerland)


    A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs.

  18. Ballistic nanoindentation of polymers

    Gotsmann, B.; Rothuizen, H.; Duerig, U.


    Indentation of a sharp (20 nm) cantilevered silicon tip into a polymer (SU8) surface is analyzed experimentally and through finite-element simulations. A rate effect on the microsecond scale that eases indentation is found, in contrast to the commonly observed hardening at high strain rates. The observed rate effect is discussed in terms of adiabatic heating and inertial force overshoot. The estimated magnitude of adiabatic heating is marginal, but the force overshoot itself is large enough to explain the data. The data imply that topographic patterning of a polymer at megahertz rates is feasible.

  19. Mechanically Invisible Polymer Coatings


    phase comprises particles, said particles comprising a filler material and an encapsulating coating of a second polymeric material, wherein the backbones of the first and second polymeric materials are the same. The composition may be used in electroactive polymers (EAPs) in order to obtain mechanically......The present invention relates to a composition comprising encapsulated particles in a polymeric material. The composition comprises a continuous phase and a discontinuous phase incorporated therein, wherein the continuous phase comprises a first polymeric material and wherein the discontinuous...... invisible polymer coatings....

  20. Antibacterial polymer coatings.

    Wilson, Mollye C.; Allen, Ashley N.; Barnhart, Meghan; Tucker, Mark David; Hibbs, Michael R.


    A series of poly(sulfone)s with quaternary ammonium groups and another series with aldehyde groups are synthesized and tested for biocidal activity against vegetative bacteria and spores, respectively. The polymers are sprayed onto substrates as coatings which are then exposed to aqueous suspensions of organisms. The coatings are inherently biocidal and do not release any agents into the environment. The coatings adhere well to both glass and CARC-coated coupons and they exhibit significant biotoxicity. The most effective quaternary ammonium polymers kills 99.9% of both gram negative and gram positive bacteria and the best aldehyde coating kills 81% of the spores on its surface.

  1. Polymer architecture and drug delivery.

    Qiu, Li Yan; Bae, You Han


    Polymers occupy a major portion of materials used for controlled release formulations and drug-targeting systems because this class of materials presents seemingly endless diversity in topology and chemistry. This is a crucial advantage over other classes of materials to meet the ever-increasing requirements of new designs of drug delivery formulations. The polymer architecture (topology) describes the shape of a single polymer molecule. Every natural, seminatural, and synthetic polymer falls into one of categorized architectures: linear, graft, branched, cross-linked, block, star-shaped, and dendron/dendrimer topology. Although this topic spans a truly broad area in polymer science, this review introduces polymer architectures along with brief synthetic approaches for pharmaceutical scientists who are not familiar with polymer science, summarizes the characteristic properties of each architecture useful for drug delivery applications, and covers recent advances in drug delivery relevant to polymer architecture.

  2. Fabrication of multilayered conductive polymer structures via selective visible light photopolymerization

    Cullen, Andrew T.; Price, Aaron D.


    Electropolymerization of pyrrole is commonly employed to fabricate intrinsically conductive polymer films that exhibit desirable electromechanical properties. Due to their monolithic nature, electroactive polypyrrole films produced via this process are typically limited to simple linear or bending actuation modes, which has hindered their application in complex actuation tasks. This initiative aims to develop the specialized fabrication methods and polymer formulations required to realize three-dimensional conductive polymer structures capable of more elaborate actuation modes. Our group has previously reported the application of the digital light processing additive manufacturing process for the fabrication of three-dimensional conductive polymer structures using ultraviolet radiation. In this investigation, we further expand upon this initial work and present an improved polymer formulation designed for digital light processing additive manufacturing using visible light. This technology enables the design of novel electroactive polymer sensors and actuators with enhanced capabilities and brings us one step closer to realizing more advanced electroactive polymer enabled devices.

  3. Conducting polymer 3D microelectrodes

    Sasso, Luigi; Vazquez, Patricia; Vedarethinam, Indumathi


    Conducting polymer 3D microelectrodes have been fabricated for possible future neurological applications. A combination of micro-fabrication techniques and chemical polymerization methods has been used to create pillar electrodes in polyaniline and polypyrrole. The thin polymer films obtained...... showed uniformity and good adhesion to both horizontal and vertical surfaces. Electrodes in combination with metal/conducting polymer materials have been characterized by cyclic voltammetry and the presence of the conducting polymer film has shown to increase the electrochemical activity when compared...

  4. Shape memory polymer medical device

    Maitland, Duncan [Pleasant Hill, CA; Benett, William J [Livermore, CA; Bearinger, Jane P [Livermore, CA; Wilson, Thomas S [San Leandro, CA; Small, IV, Ward; Schumann, Daniel L [Concord, CA; Jensen, Wayne A [Livermore, CA; Ortega, Jason M [Pacifica, CA; Marion, III, John E.; Loge, Jeffrey M [Stockton, CA


    A system for removing matter from a conduit. The system includes the steps of passing a transport vehicle and a shape memory polymer material through the conduit, transmitting energy to the shape memory polymer material for moving the shape memory polymer material from a first shape to a second and different shape, and withdrawing the transport vehicle and the shape memory polymer material through the conduit carrying the matter.

  5. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    Andernach, Rolf


    We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple timescales and investigated the mechanism of triplet exciton formation. During sensitization, single exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and find that 60% of the complex triplet excitons are transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and up-conversion layers.

  6. Frictional properties of confined polymers

    Sivebæk, Ion Marius; Samoilov, Vladimir N; Persson, Bo N J


    We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively i...

  7. New polymers for phase partitioning

    Harris, J. M.


    The synthesizing of several polyethylene glycols having crown ethers attached is reported. This work led to the identification of three new polymer types which promise to be more effective at selectively binding specific cell types. Work was completed on identification of chemical properties of the new polymer crowns and on development of new techniques for determination of polymer-phase composition.

  8. Nonlinear microstructured polymer optical fibres

    Frosz, Michael Henoch

    is potentially the case for microstructured polymer optical fibres (mPOFs). Another advantage is that polymer materials have a higher biocompatibility than silica, meaning that it is easier to bond certain types of biosensor materials to a polymer surface than to silica. As with silica PCFs, it is difficult...

  9. Reversible networks in supramolecular polymers

    Havermans - van Beek, D.J.M.


    Non–covalent interactions between low molecular weight polymers form the basis of supramolecular polymers. The material properties of such polymers are determined by the strength and lifetime of the non–covalent reversible interactions. Due to the reversibility of the interactions between the low

  10. White polymer light-emitting diode based on polymer blending

    Lee, Yong Kyun; Kwon, Soon Kab; Kim, Jun Young; Park, Tae Jin; Song, Dae Ho; Kwon, Jang Hyuk; Choo, Dong Jun; Jang, Jin; Jin, Jae Kyu; You, Hong


    A series of white polymer light emitting devices have been fabricated by using a polymer blending system of polyfluorene-based blue and MEH-PPV red polymers. A device structure of ITO/PEDOT:PSS/polymer/LiF/Al was employed. The white polymer device exhibited a current efficiency of 4.33 cd/A (4,816 cd/m 2 , Q.E. = 1.9 %) and a maximum luminance of 21,430 cd/m 2 at 9.2 V. The CIE coordinates were (0.35, 0.37) at 5 V and (0.29, 0.30) at 9 V.

  11. Fludized-bed process for complex municipal sewage treatment systems using micro-organisms immobilized on heterogenous polymer structures (biocompounds); Wirbelbettverfahren zur komplexen kommunalen Abwasserreinigung unter Verwendung von auf heterogenen Polymerstrukturen (Biocompounds) immobilisierten Mikroorganismen

    Ochmann, C.


    Within the context of the present work, novel carriers for immobilizing microorganisms have been developed and tested both in the laboratory and on a semi-industrial scale. It was the primary target to optimize the known processes in deep biofilms such that, besides carbon compounds decomposition and nitrification, a directed (and sufficient) denitrification would also become possible. Prerequisite for purposefully influencing denitrification processes is to realize biofilms of a definite thickness. This cannot be ensured by means of the carriers used hitherto in practice. The approach consists in the use of heterogeneous polymer structures (biocompounds) made of two differently rapidly degradable biopolymers. The biopolymer that is more slowly degradable forms a matrix into which the rapidly degradable biopolymer is inserted in form of particles arranged from one another at a distance. Based on the primary biological decomposition of the more rapidly degradable component (''biocorrosion''), porosity is generated in the substrate, releasing carbon at the same time. In this way, anoxic zones are formed based on the existent material gradient, besides protection of the biofilm forming in the pores from mechanical wear and tear. Simultaneously this ensures the supply of carbon to the anoxic zone for denitrification. In examinations (laboratory and semi-technology), it has been shown that simultaneous and continuous degradation of carbon and nitrogen compounds can be achieved in a completely and steadily aerated reaction space through the use of biocompounds. No problems arose both in carbon compounds degradation and nitrification. The removal of nitrogen compounds from wastewater was limited by the denitrification performance, which allowed to identify denitrification as the limiting process within the total process. It was possible to show that the N{sub tot} elimination rate is a function of the C/N ratio in crude wastewater. (orig.)

  12. Polymers of phenylenediamines

    Stejskal, Jaroslav


    Roč. 41, February (2015), s. 1-31 ISSN 0079-6700 R&D Projects: GA ČR(CZ) GA13-00270S Institutional support: RVO:61389013 Keywords : polyphenylenediamine * phenylenediamine * conducting polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 27.184, year: 2015

  13. Nanoporous thermosetting polymers.

    Raman, Vijay I; Palmese, Giuseppe R


    Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

  14. Characterization of healable polymers

    Nielsen, C.; Weizman, Or; Nemat-Nasser, Sia


    Materials with an internal mechanism for damage repair would be valuable in isolated environments where access is difficult or impossible. Current work is focused on characterizing neat polymers with reformable cross-linking bonds. These bonds are thermally reversible, the result of a Diels-Alder cycloaddition between furan and maleimide monomers. Candidate polymers are examined using modulated differential scanning calorimetry (DSC) to confirm the presence of reversible bonding. One polymer, 2MEP3FT, was expected to have these bonds, but none were observed. A second polymer, 2MEP4FS, with a modified furan monomer does exhibit reversible bonding. Further DSC testing and dynamic mechanical thermal analyses (DMA) are conducted to determine material properties such as glass transition temperature, storage modulus and quality of the polymerization. Healing efficiency is established using the double cleavage drilled compression (DCDC) fracture test. A column of material with a central hole is subjected to axial compression, driving cracks up and down the sample. After unloading, the cracks are healed, and the sample is retested. Comparing the results gives a quantitative evaluation of healing.

  15. Knots in polymers

    Abstract. Knots and topological entanglements play an important role in the statistical mechanics of polymers. While topological entanglement is a global property, it is possible to study the size of a knotted region both numerically and analytically. It can be shown that long-range repulsive interactions, as well as entropy ...

  16. Polyester polymer concrete overlay.


    Polyester polymer concrete (PPC) was used in a trial application on a section of pavement that suffers from extensive studded tire wear. The purpose of the trial section is to determine if PPC is a possible repair strategy for this type of pavement d...

  17. Conductive polymer composition


    The present invention relates to a process for the preparation of a conductive polymer composition comprising graphene and the articles obtained by this process. The process comprises the following steps: A) contacting graphite oxide in an aqueous medium with a water-soluble or dispersible

  18. BEAM applications to polymer materials

    Tagawa, Seiichi


    Recently papers about beam applications to polymers have been increasing rapidly both in the fundamental and applied fields. Fairly large number of papers have been published in the fundamental aspects of radiation effects of beam applications to polymers such as pulse radiolysis and high density electronic excitation effects. A number of papers have been published in the more applied aspects of beam applications to polymers such as radiation processing and curing. The present paper describes recent beam applications to polymers. 1. Radiation Effects on Polymers; Radiation effects on polymers have been studied for more than 40 years. Most of work on radiation effects on polymers has been carried out by using high energy photon (gamma-ray) and electron beams, since polymers are sensitive to any kinds of ionizing radiation. Even non-ionizing radiation such as ultraviolet and visible light excites electronic excited states of polymers and then photo-chemical reactions of polymers are induced from the electronic excited states. Studies on radiation effects of other ionizing radiation on polymers have not been so popular for a long time. Recently application of new radiation such as ion beams to polymers have been worthy of remark in fields of advanced science and technology, since new radiation beams induce different radiation effects from those induced by high energy gamma-rays and electrons. 2. Beam Applications of Polymers; Recent progress in beam applications to polymers such as radiation processing and curing, x-ray and electron beam microlithography, and applications of new beams such as ion beams to polymers has been reviewed. (author)

  19. Selective separation of Eu3+ using polymer-enhanced ultrafiltration

    Norton, M.V.


    A process to selectively remove 241 Am from liquid radioactive waste was investigated as an actinide separation method applicable to Hanford and other waste sites. The experimental procedures involved removal of Eu, a nonradioactive surrogate for Am, from aqueous solutions at pH 5 using organic polymers in conjunction with ultrafiltration. Commercially available polyacrylic acid (60,000 MW) and Pacific Northwest Laboratory's (PNL) synthesized E3 copolymer (∼10,000 MW) were tested. Test solutions containing 10 μg/mL of Eu were dosed vath each polymer at various concentrations in order to bind Eu (i.e., by complexation and/or cation exchange) for subsequent rejection by an ultrafiltration coupon. Test solutions were filtered with and without polymer to determine if enhanced Eu separation could be achieved from polymer treatment. Both polymers significantly increased Eu removal. Optimum concentrations were 20 μg/mL of polyacrylic acid and 100 μg/mL of E3 for 100% Eu rejection by the Amicon PM10 membrane at 55 psi. In addition to enhancement of removal, the polymers selectively bound Eu over Na, suggesting that selective separation of Eu was possible. This suggests that polymer-enhanced ultrafiltration is a potential process for separation of 241 Am from Hanford tank waste, further investigation of binding agents and membranes effective under very alkaline and high ionic strength is warranted. This process also has potential applications for selective separation of toxic metals from industrial process streams

  20. Coherent states field theory in supramolecular polymer physics

    Fredrickson, Glenn H.; Delaney, Kris T.


    In 1970, Edwards and Freed presented an elegant representation of interacting branched polymers that resembles the coherent states (CS) formulation of second-quantized field theory. This CS polymer field theory has been largely overlooked during the intervening period in favor of more conventional "auxiliary field" (AF) interacting polymer representations that form the basis of modern self-consistent field theory (SCFT) and field-theoretic simulation approaches. Here we argue that the CS representation provides a simpler and computationally more efficient framework than the AF approach for broad classes of reversibly bonding polymers encountered in supramolecular polymer science. The CS formalism is reviewed, initially for a simple homopolymer solution, and then extended to supramolecular polymers capable of forming reversible linkages and networks. In the context of the Edwards model of a non-reacting homopolymer solution and one and two-component models of telechelic reacting polymers, we discuss the structure of CS mean-field theory, including the equivalence to SCFT, and show how weak-amplitude expansions (random phase approximations) can be readily developed without explicit enumeration of all reaction products in a mixture. We further illustrate how to analyze CS field theories beyond SCFT at the level of Gaussian field fluctuations and provide a perspective on direct numerical simulations using a recently developed complex Langevin technique.

  1. Processing and characterization of ceramic superconductor/polymer composites

    Kander, R.G.; Namboodri, S.L.


    One way to more easily process a brittle high-temperature ceramic superconductor into a useful structure is to combine it with a polymer to form a composite material. Processing of polymer-based composites into complex shapes is well established and relatively easy when compared with traditional ceramic processing unit operations. In addition, incorporating a ceramic superconductor into a polymer matrix can improve mechanical performance as compared with a monolithic ceramic. Finally, because ceramic superconductors are susceptible to attack by moisture, a polymer-based composite structure can also provide protection from deleterious environmental effects. This paper focuses on the processing and subsequent characterization of ceramic superconductor/polymer composites designed primarily for electromagnetic shielding and diamagnetic applications. YBa 2 Cu 3 O 7-x [YBCO] ceramic superconductor is combined with poly(methyl methacrylate) [PMMA] to form novel composite structures. Composite structures have been molded with both a discontinuous superconducting phase (i.e., ceramic particulate reinforced polymers) and with a continuous superconducting phase (i.e., polymer infiltrated porous ceramics). Characterization of these composite structures includes the determination of diamagnetic strength, electromagnetic shielding effectiveness, mechanical performance, and environmental resistance. The goal of this program is to produce a composite structure with increased mechanical integrity and environmental resistance at liquid nitrogen temperatures without compromising the electromagnetic shielding and diamagnetic properties of the superconducting phase. Composites structures of this type are potentially useful in numerous magnetic applications including electromagnetic shielding, magnetic sensors, energy storage, magnetic levitation, and motor windings

  2. Conception et réactivité de complexes mono- et polymétalliques d'éléments f en bas degré d'oxydation

    Camp , Clément


    Beyond its importance in nuclear industry the redox chemistry uranium is attracting increasinginterest because complexes of low-valent uranium can promote unusual reductive chemistrythrough unusual reaction pathways, including attractive examples of CO, CO2, N2, arenes andazides activation in mild condition. Due to the unique coordination and bonding properties ofuranium, its compounds could provide an attractive alternative to transition metals for thecatalytic transformation of small molecu...

  3. Conducting Polymers for Neutron Detection

    Clare Kimblin; Kirk Miller; Bob Vogel; Bill Quam; Harry McHugh; Glen Anthony; Steve Jones; Mike Grover


    Conjugated polymers have emerged as an attractive technology for large-area electronic applications. As organic semiconductors, they can be used to make large-area arrays of diodes or transistors using fabrication techniques developed for polymer coatings, such as spraying and screen-printing. We have demonstrated both neutron and alpha detection using diodes made from conjugated polymers and have done preliminary work to integrate a boron carbide layer into the conventional polymer device structure to capture thermal neutrons. The polymer devices appear to be insensitive to gamma rays, due to their small physical thickness and low atomic number

  4. Gel polymer electrolytes for batteries

    Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William


    Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at C.

  5. Chemistry of the metal-polymer interfacial region.

    Leidheiser, H; Deck, P D


    In many polymer-metal systems, chemical bonds are formed that involve metal-oxygen-carbon complexes. Infrared and Mössbauer spectroscopic studies indicate that carboxylate groups play an important role in some systems. The oxygen sources may be the polymer, the oxygen present in the oxide on the metal surface, or atmospheric oxygen. Diffusion of metal ions from the substrate into the polymer interphase may occur in some systems that are cured at elevated temperatures. It is unclear whether a similar, less extensive diffusion occurs over long time periods in systems maintained at room temperature. The interfacial region is dynamic, and chemical changes occur with aging at room temperature. Positron annihilation spectroscopy may have application to characterizing the voids at the metal-polymer interface.

  6. Bistable collective behavior of polymers tethered in a nanopore

    Osmanovic, Dino; Bailey, Joe; Harker, Anthony H.; Fassati, Ariberto; Hoogenboom, Bart W.; Ford, Ian J.


    Polymer-coated pores play a crucial role in nucleo-cytoplasmic transport and in a number of biomimetic and nanotechnological applications. Here we present Monte Carlo and Density Functional Theory approaches to identify different collective phases of end-grafted polymers in a nanopore and to study their relative stability as a function of intermolecular interactions. Over a range of system parameters that is relevant for nuclear pore complexes, we observe two distinct phases: one with the bulk of the polymers condensed at the wall of the pore, and the other with the polymers condensed along its central axis. The relative stability of these two phases depends on the interpolymer interactions. The existence the two phases suggests a mechanism in which marginal changes in these interactions, possibly induced by nuclear transport receptors, cause the pore to transform between open and closed configurations, which will influence transport through the pore.

  7. Investigation of a thiolated polymer in gene delivery

    Bacalocostantis, Irene

    Thiol-containing bioreducible polymers show significant potential as delivery vectors in gene therapy, a rapidly growing field which seeks to treat genetic-based disorders by delivering functional synthetic genes to diseased cells. Studies have shown that thiolated polymers exhibit improved biodegradability and prolonged in vivo circulation times over non-thiolated polymers. However, the extent to which thiol concentrations impact the carrier's delivery potential has not been well explored. The aim of this dissertation is to investigate how relative concentrations of free thiols and disulfide crosslinks impact a polymeric carriers delivery performance with respect to DNA packaging, complex stability, cargo protection, gene release, internalization efficiency and cytotoxicity. To accomplish this goal, several fluorescent polymers containing varying concentrations of thiol groups were synthesized by conjugating thiol-pendant chains onto the primary amines of cationic poly(allylamine). In vitro delivery assays and characterization techniques were employed to assess the effect of thiols in gene delivery.

  8. Lithium secondary batteries: Role of polymer cathode morphology

    Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.


    Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

  9. Photonic polymer-blend structures and method for making

    Barnes, Michael D.


    The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

  10. Study on dissolution behavior of polymer-bound and polymer-blended photo-acid generator (PAG) resists

    Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi


    The requirements for the next generation resist materials are so challenging that it is indispensable for feasibility of EUV lithography to grasp basic chemistry of resist matrices in all stage of resist processes. Under such circumstances, it is very important to know dissolution characteristics of the resist film into alkaline developer though the dissolution of exposed area of resist films in alkaline developer to form a pattern is a complex reactive process. In this study, the influence of EUV and KrF exposure on the dissolution behavior of polymer bound PAG and polymer blended PAG was studied in detail using quartz crystal microbalance (QCM) methods. The difference in swelling formation between KrF and EUV exposure was observed. It is likely that difference of reaction mechanism induces the difference of these swelling. Also, it is observed that the swelling of polymer-bound PAG is less than that of polymer blended PAG in both KrF and EUV exposure. This result indicates that polymer-bound PAG suppresses swelling very well and showed an excellent performance. Actually, the developed polymer bound-PAG resist showed an excellent performance (half pitch 50 nm line and space pattern). Thus, polymer bound PAG is one of the promising candidate for 16 nm EUV resist.

  11. Polymers at interfaces and in colloidal dispersions.

    Fleer, Gerard J


    This review is an extended version of the Overbeek lecture 2009, given at the occasion of the 23rd Conference of ECIS (European Colloid and Interface Society) in Antalya, where I received the fifth Overbeek Gold Medal awarded by ECIS. I first summarize the basics of numerical SF-SCF: the Scheutjens-Fleer version of Self-Consistent-Field theory for inhomogeneous systems, including polymer adsorption and depletion. The conformational statistics are taken from the (non-SCF) DiMarzio-Rubin lattice model for homopolymer adsorption, which enumerates the conformational details exactly by a discrete propagator for the endpoint distribution but does not account for polymer-solvent interaction and for the volume-filling constraint. SF-SCF corrects for this by adjusting the field such that it becomes self-consistent. The model can be generalized to more complex systems: polydispersity, brushes, random and block copolymers, polyelectrolytes, branching, surfactants, micelles, membranes, vesicles, wetting, etc. On a mean-field level the results are exact; the disadvantage is that only numerical data are obtained. Extensions to excluded-volume polymers are in progress. Analytical approximations for simple systems are based upon solving the Edwards diffusion equation. This equation is the continuum variant of the lattice propagator, but ignores the finite segment size (analogous to the Poisson-Boltzmann equation without a Stern layer). By using the discrete propagator for segments next to the surface as the boundary condition in the continuum model, the finite segment size can be introduced into the continuum description, like the ion size in the Stern-Poisson-Boltzmann model. In most cases a ground-state approximation is needed to find analytical solutions. In this way realistic analytical approximations for simple cases can be found, including depletion effects that occur in mixtures of colloids plus non-adsorbing polymers. In the final part of this review I discuss a



    A method for preparing polybenzimidazole or polybenzimidazole blend membranes and fabricating gas diffusion electrodes and membrane-electrode assemblies is provided for a high temperature polymer electrolyte membrane fuel cell. Blend polymer electrolyte membranes based on PBI and various...... thermoplastic polymers for high temperature polymer electrolyte fuel cells have also been developed. Miscible blends are used for solution casting of polymer membranes (solid electrolytes). High conductivity and enhanced mechanical strength were obtained for the blend polymer solid electrolytes....... With the thermally resistant polymer, e.g., polybenzimidazole or a mixture of polybenzimidazole and other thermoplastics as binder, the carbon-supported noble metal catalyst is tape-cast onto a hydrophobic supporting substrate. When doped with an acid mixture, electrodes are assembled with an acid doped solid...

  13. Approaches in biotechnological applications of natural polymers

    José A. Teixeira


    Full Text Available Natural polymers, such as gums and mucilage, are biocompatible, cheap, easily available and non-toxic materials of native origin. These polymers are increasingly preferred over synthetic materials for industrial applications due to their intrinsic properties, as well as they are considered alternative sources of raw materials since they present characteristics of sustainability, biodegradability and biosafety. As definition, gums and mucilages are polysaccharides or complex carbohydrates consisting of one or more monosaccharides or their derivatives linked in bewildering variety of linkages and structures. Natural gums are considered polysaccharides naturally occurring in varieties of plant seeds and exudates, tree or shrub exudates, seaweed extracts, fungi, bacteria, and animal sources. Water-soluble gums, also known as hydrocolloids, are considered exudates and are pathological products; therefore, they do not form a part of cell wall. On the other hand, mucilages are part of cell and physiological products. It is important to highlight that gums represent the largest amounts of polymer materials derived from plants. Gums have enormously large and broad applications in both food and non-food industries, being commonly used as thickening, binding, emulsifying, suspending, stabilizing agents and matrices for drug release in pharmaceutical and cosmetic industries. In the food industry, their gelling properties and the ability to mold edible films and coatings are extensively studied. The use of gums depends on the intrinsic properties that they provide, often at costs below those of synthetic polymers. For upgrading the value of gums, they are being processed into various forms, including the most recent nanomaterials, for various biotechnological applications. Thus, the main natural polymers including galactomannans, cellulose, chitin, agar, carrageenan, alginate, cashew gum, pectin and starch, in addition to the current researches about them

  14. Binning of shallowly sampled metagenomic sequence fragments reveals that low abundance bacteria play important roles in sulfur cycling and degradation of complex organic polymers in an acid mine drainage community

    Dick, G. J.; Andersson, A.; Banfield, J. F.


    not expected to reflect the tetranucleotide frequency signature of the host genome. Four unknown tetranucleotide frequency clusters with significant sequence (6 Mb total) were noted and analyzed further. Based on phylogenetic markers and BLAST results, these clusters represent low abundance bacteria including Acintobacteria, Firmicutes, and Proteobacteria. Functional analysis of these clusters revealved that the low- abundance bacteria harbor genes that could potentially encode important ecosystem functions such as sulfur utilization (e.g. polysulfide reductase) and polymer degradation (e.g. chitinase and glycoside hydrolase). We conclude that ESOM clustering of tetranucleotide frequency patterns is an effective method for rapidly binning shotgun community genomic sequences and a valuable tool for analyzing minor community members, which despite their low abundance may play crucial ecological roles.

  15. Redox-active porous coordination polymers prepared by trinuclear heterometallic pivalate linking with the redox-active nickel(II) complex: synthesis, structure, magnetic and redox properties, and electrocatalytic activity in organic compound dehalogenation in heterogeneous medium.

    Lytvynenko, A S; Kolotilov, S V; Kiskin, M A; Cador, O; Golhen, S; Aleksandrov, G G; Mishura, A M; Titov, V E; Ouahab, L; Eremenko, I L; Novotortsev, V M


    Linking of the trinuclear pivalate fragment Fe2CoO(Piv)6 by the redox-active bridge Ni(L)2 (compound 1; LH is Schiff base from hydrazide of 4-pyridinecarboxylic acid and 2-pyridinecarbaldehyde, Piv(-) = pivalate) led to formation of a new porous coordination polymer (PCP) {Fe2CoO(Piv)6}{Ni(L)2}1.5 (2). X-ray structures of 1 and 2 were determined. A crystal lattice of compound 2 is built from stacked 2D layers; the Ni(L)2 units can be considered as bridges, which bind two Fe2CoO(Piv)6 units. In desolvated form, 2 possesses a porous crystal lattice (SBET = 50 m(2) g(-1), VDR = 0.017 cm(3) g(-1) estimated from N2 sorption at 78 K). At 298 K, 2 absorbed a significant quantity of methanol (up to 0.3 cm(3) g(-1)) and chloroform. Temperature dependence of molar magnetic susceptibility of 2 could be fitted as superposition of χMT of Fe2CoO(Piv)6 and Ni(L)2 units, possible interactions between them were taken into account using molecular field model. In turn, magnetic properties of the Fe2CoO(Piv)6 unit were fitted using two models, one of which directly took into account a spin-orbit coupling of Co(II), and in the second model the spin-orbit coupling of Co(II) was approximated as zero-field splitting. Electrochemical and electrocatalytic properties of 2 were studied by cyclic voltammetry in suspension and compared with electrochemical and electrocatalytic properties of a soluble analogue 1. A catalytic effect was determined by analysis of the catalytic current dependency on concentrations of the substrate. Compound 1 possessed electrocatalytic activity in organic halide dehalogenation, and such activity was preserved for the Ni(L)2 units, incorporated into the framework of 2. In addition, a new property occurred in the case of 2: the catalytic activity of PCP depended on its sorption capacity with respect to the substrate. In contrast to homogeneous catalysts, usage of solid PCPs may allow selectivity due to porous structure and simplify separation of product.

  16. Using Sodium Hydrogen Carbonate for Foaming Polymers

    Satin Lukáš


    Full Text Available All plastics products are made of the essential polymer mixed with a complex blend of materials known collectively as additives. Without additives, plastics would not work, but with them, they can be made safer, cleaner, tougher and more colourful. Additives cost money, but by reducing production costs and making products live longer, they help us save money and conserve the world's precious raw material reserves. In fact, our world would be a lot less safe, a lot more expensive and a great deal duller without the additives that turn basic polymers into useful plastics. One of these additives is sodium bicarbonate. Influence of sodium bicarbonate on properties of the product made of polystyrene was observed in the research described in this paper. Since polystyrene is typically used as a material for electrical components, the mechanical properties of tensile strength and inflammability were measured as a priority. Inflammability parameters were measured using a cone calorimeter.

  17. Adsorption and flocculation by polymers and polymer mixtures.

    Gregory, John; Barany, Sandor


    Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Lignins : natural polymers from oxidative coupling of 4-hydroxyphenyl-propanoids

    John Ralph; Knut Lundquist; Gosta Brunow; Fachuang Lu; Hoon Kim; Paul F. Schatz; Jane M. Marita; Ronald D. Hatfield; Sally A. Ralph; Jorgen Holst Christensen; Wout Boerjan


    Lignins are complex natural polymers resulting from oxidative coupling of, primarily, 4-hydroxyphenylpropanoids. An understanding of their nature is evolving as a result of detailed structural studies, recently aided by the availability of lignin-biosynthetic-pathway mutants and transgenics. The currently accepted theory is that the lignin polymer is formed by...

  19. Deformation and degradation of polymers in ultra-high-pressure liquid chromatography

    Uliyanchenko, E.; van der Wal, S.; Schoenmakers, P.J.


    Ultra-high-pressure liquid chromatography (UHPLC) using columns packed with sub-2 μm particles has great potential for separations of many types of complex samples, including polymers. However, the application of UHPLC for the analysis of polymers meets some fundamental obstacles. Small particles

  20. Polymer dual ring resonators for label-free optical biosensing using microfluidics.

    Salleh, Muhammad H M; Glidle, Andrew; Sorel, Marc; Reboud, Julien; Cooper, Jonathan M


    We demonstrate a polymer resonator microfluidic biosensor that overcomes the complex manufacturing procedures required to fabricate traditional devices. In this new format, we show that a gapless light coupling photonic configuration, fabricated in SU8 polymer, can achieve high sensitivity, label-free chemical sensing in solution and high sensitivity biological sensing, at visible wavelengths.

  1. m-Carboranylphosphinate as Versatile Building Blocks To Design all Inorganic Coordination Polymers.

    Oleshkevich, Elena; Viñas, Clara; Romero, Isabel; Choquesillo-Lazarte, Duane; Haukka, Matti; Teixidor, Francesc


    The first examples of coordination polymers of manganese(II) and a nickel(II) complex with a purely inorganic carboranylphosphinate ligand are reported, together with its exhaustive characterization. X-ray analysis revealed 1D polymeric chains with carboranylphosphinate ligands bridging two manganese(II) centers. The reactivity of polymer 1 with water and Lewis bases has also been studied.

  2. Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

    Archer, Lynden

    Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

  3. Nanoscale Reinforced, Polymer Derived Ceramic Matrix Coatings

    Rajendra Bordia


    The goal of this project was to explore and develop a novel class of nanoscale reinforced ceramic coatings for high temperature (600-1000 C) corrosion protection of metallic components in a coal-fired environment. It was focused on developing coatings that are easy to process and low cost. The approach was to use high-yield preceramic polymers loaded with nano-size fillers. The complex interplay of the particles in the polymer, their role in controlling shrinkage and phase evolution during thermal treatment, resulting densification and microstructural evolution, mechanical properties and effectiveness as corrosion protection coatings were investigated. Fe-and Ni-based alloys currently used in coal-fired environments do not possess the requisite corrosion and oxidation resistance for next generation of advanced power systems. One example of this is the power plants that use ultra supercritical steam as the working fluid. The increase in thermal efficiency of the plant and decrease in pollutant emissions are only possible by changing the properties of steam from supercritical to ultra supercritical. However, the conditions, 650 C and 34.5 MPa, are too severe and result in higher rate of corrosion due to higher metal temperatures. Coating the metallic components with ceramics that are resistant to corrosion, oxidation and erosion, is an economical and immediate solution to this problem. Good high temperature corrosion protection ceramic coatings for metallic structures must have a set of properties that are difficult to achieve using established processing techniques. The required properties include ease of coating complex shapes, low processing temperatures, thermal expansion match with metallic structures and good mechanical and chemical properties. Nanoscale reinforced composite coatings in which the matrix is derived from preceramic polymers have the potential to meet these requirements. The research was focused on developing suitable material systems and

  4. A 3d-4f complex constructed by the assembly of a cationic template, [Cu(en){sub 2}]{sup 2+}, and a 3D anionic coordination polymer, [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-}

    Ke, Szu-Yu; Yeh, Chang-Tsung; Wang, Chih-Chieh [Department of Chemistry, Soochow University, Taipei, Taiwan (China); Lee, Gene-Hsiang [Instrumentation Center, National Taiwan University, Taipei, Taiwan (China); Sheu, Hwo-Shuenn [National Synchrotron Radiation Research Center, Hsinchu, Taiwan (China)


    A three-dimensional (3D) 3d-4f complex, [Cu(en){sub 2}][Sm{sub 2}(C{sub 5}O{sub 5})(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 2}].8H{sub 2}O (1) (en = ethylenediamine, C{sub 5}O{sub 5}{sup 2-} = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), were prepared via the in-situ ring-opening oxidation reaction of croconate in the presence of the template-directed complex, [Cu(en){sub 2}]{sup 2+} cation. The structural characterization determined by X-ray diffraction determination reveals that the 3D anionic coordination polymer of [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}(C{sub 5}O{sub 5})(H{sub 2}O){sub 2}]{sup 2-} in 1 can be describe in terms of in-plane 2D honeycomb-like [Sm{sub 2}(C{sub 2}O{sub 4}){sub 3}] layered frameworks bridged by oxalate with bis-chelating mode, being mutually interlinked via the bridge of μ{sub 1,2,3,4}-croconate ligands with bis-chelating coordination mode to complete the 3D open framework, which gives rise to 1D channels with pore size of 14.023 x 11.893 Aa (longest atom-atom contact distances) along the b axis. The structure-directing complex, [Cu(en){sub 2}]{sup 2+}, and solvated water molecules are resided into these honeycomb-type hexagonal channels. The thermal stability of 1 was further studied by TGA and in-situ powder X-ray diffraction measurement. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. How do polymers degrade?

    Lyu, Suping


    Materials derived from agricultural products such as cellulose, starch, polylactide, etc. are more sustainable and environmentally benign than those derived from petroleum. However, applications of these polymers are limited by their processing properties, chemical and thermal stabilities. For example, polyethylene terephthalate fabrics last for many years under normal use conditions, but polylactide fabrics cannot due to chemical degradation. There are two primary mechanisms through which these polymers degrade: via hydrolysis and via oxidation. Both of these two mechanisms are related to combined factors such as monomer chemistry, chain configuration, chain mobility, crystallinity, and permeation to water and oxygen, and product geometry. In this talk, we will discuss how these materials degrade and how the degradation depends on these factors under application conditions. Both experimental studies and mathematical modeling will be presented.

  6. Dielectric Actuation of Polymers

    Niu, Xiaofan

    Dielectric polymers are widely used in a plurality of applications, such as electrical insulation, dielectric capacitors, and electromechanical actuators. Dielectric polymers with large strain deformations under an electric field are named dielectric elastomers (DE), because of their relative low modulus, high elongation at break, and outstanding resilience. Dielectric elastomer actuators (DEA) are superior to traditional transducers as a muscle-like technology: large strains, high energy densities, high coupling efficiency, quiet operation, and light weight. One focus of this dissertation is on the design of DE materials with high performance and easy processing. UV radiation curing of reactive species is studied as a generic synthesis methodology to provide a platform for material scientists to customize their own DE materials. Oligomers/monomers, crosslinkers, and other additives are mixed and cured at appropriate ratios to control the stress-strain response, suppress electromechanical instability of the resulting polymers, and provide stable actuation strains larger than 100% and energy densities higher than 1 J/g. The processing is largely simplified in the new material system by removal of the prestretching step. Multilayer stack actuators with 11% linear strain are demonstrated in a procedure fully compatible with industrial production. A multifunctional DE derivative material, bistable electroactive polymer (BSEP), is invented enabling repeatable rigid-to-rigid deformation without bulky external structures. Bistable actuation allows the polymer actuator to have two distinct states that can support external load without device failure. Plasticizers are used to lower the glass transition temperature to 45 °C. Interpenetrating polymer network structure is established inside the BSEP to suppress electromechanical instability, providing a breakdown field of 194 MV/m and a stable bistable strain as large as 228% with a 97% strain fixity. The application of BSEP

  7. Rheo-NMR: nuclear magnetic resonance and the rheology of complex fluids

    Callaghan, Paul T.


    The application of nuclear magnetic resonance methods to the study of complex fluids under shearing and extensional flows is reviewed. Both NMR velocimetry and spectroscopy approaches are discussed while specific systems studied include polymer melts, rigid rod and random coil polymers in solution, lyotropic and thermotropic liquid crystals and liquid crystalline polymers, and wormlike micelles. Reference is made to food systems. (author)

  8. Conjugated polymer nanoparticles, methods of using, and methods of making

    Habuchi, Satoshi


    Embodiments of the present disclosure provide for conjugated polymer nanoparticle, method of making conjugated polymer nanoparticles, method of using conjugated polymer nanoparticle, polymers, and the like.

  9. Conjugated polymer nanoparticles, methods of using, and methods of making

    Habuchi, Satoshi; Piwonski, Hubert Marek; Michinobu, Tsuyoshi


    Embodiments of the present disclosure provide for conjugated polymer nanoparticle, method of making conjugated polymer nanoparticles, method of using conjugated polymer nanoparticle, polymers, and the like.

  10. Polymerization of lanthanide acrylonitrile complexes.

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A


    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  11. Solid polymer electrolytes

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.


    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.


    I. I. Karpunin


    Full Text Available The executed investigations have made it possible to ascertain that a morphological structure of starch granules mainly determine technological peculiarities of starch isolation from raw material, its modification and its later use. Morphological structure of starch granules primarily depends on type of plant starch-containing raw material which has been used for its isolation. Class of raw material exerts a strong impact on the shape and size of the granules. Linear “light” amylose chains and “heavy” amylopectin branch chains form a starch granule ultrastructure. X-ray research has proved that starch granules are characterized by presence of interlacing amorphous and crystalline regions. In this case polymer orientation using stretching of the obtained end product influences on its physical and mechanical  indices which are increasing due to polymer orientation. For the purpose of packaging orientation of polymer films can solve such important problems as significant improvement of operational properties, creation of  thermosetting film materials, improvement of qualitative indices of the recycled film.Results of the conducted research have proved the fact that it is necessary to make changes in technology in order to increase biological degradability of the recycled packaging made from polymers and improve physical and mechanical indices. In this regard film production technology presupposes usage of such substances as stark and others which are characterized by rather large presence of branch chains of molecules and interlacing amorphous and crystalline regions. Such approach makes it possible to obtain after-use package which is strong and quickly degradable by micro-organisms.

  13. Dynamics of polymers

    Buchenau, U [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energieverfahrenstechnik


    Neutron scattering from amorphous polymers allows to switch from incoherent to coherent scattering in the same substance. The power of the tool for the study of the picosecond dynamics of disordered matter is illustrated for polybutadiene, polycarbonate and polystyrene. The results suggest a mixture of sound waves and localized modes, strongly interacting with each other, in the picosecond range. (author) 8 figs., tabs., 39 refs.

  14. Conjugated Polymer Solar Cells


    thermal gravimetry analysis (TGA)............... 12 2.6 Photoluminescence (PL) spectroscopy... gravimetry analysis (TGA) Thermal analysis of polymer films has been accomplished by TGA and DSC methods with the aid of Perkin-Elmer Series 7 Analysers...The MEH-PPV/acceptor films were prepared by spin-casting of the resulting mixture (with or without precipitate ) on glass substrates of diameter 23 mm

  15. Absorbable and biodegradable polymers

    Shalaby, Shalaby W


    INTRODUCTION NOTES: Absorbable/Biodegradable Polymers: Technology Evolution. DEVELOPMENT AND APPLICATIONOF NEW SYSTEMS: Segmented Copolyesters with Prolonged Strength Retention Profiles. Polyaxial Crystalline Fiber-Forming Copolyester. Polyethylene Glycol-Based Copolyesters. Cyanoacrylate-Based Systems as Tissue Adhesives. Chitosan-Based Systems. Hyaluronic Acid-Based Systems. DEVELOPMENTS IN PREPARATIVE, PROCESSING, AND EVALUATION METHODS: New Approaches to the Synthesis of Crystalline. Fiber-Forming Aliphatic Copolyesters. Advances in Morphological Development to Tailor the Performance of Me

  16. Mechanoresponsive Healing Polymers

    Gordon, Keith L. (Inventor); Siochi, Emilie J. (Inventor)


    Methods are provided to produce new mechanoresponsive healing systems. Additionally, various embodiments provide a two tier self-healing material system concept that provides a non-intrusive method to mitigate impact damage in a structure ranging from low velocity impact damage (e.g., crack damage) to high velocity impact damage (e.g., ballistic damage.) The various embodiments provide the mechanophore linked polymer PBG-BCB-PBG. The various embodiments provide methods for synthesizing PBG-BCB-PBG.

  17. Electrochemical polymer electrolyte membranes

    Fang, Jianhua; Wilkinson, David P


    Electrochemical Polymer Electrolyte Membranes covers PEMs from fundamentals to applications, describing their structure, properties, characterization, synthesis, and use in electrochemical energy storage and solar energy conversion technologies. Featuring chapters authored by leading experts from academia and industry, this authoritative text: Discusses cutting-edge methodologies in PEM material selection and fabricationPoints out important challenges in developing PEMs and recommends mitigation strategies to improve PEM performanceAnalyzes the cur

  18. Investigation of Thermal and Viscoelastic Properties of Polymers Relevant to Hot Melt Extrusion, IV: Affinisol™ HPMC HME Polymers.

    Gupta, Simerdeep Singh; Solanki, Nayan; Serajuddin, Abu T M


    Most cellulosic polymers cannot be used as carriers for preparing solid dispersion of drugs by hot melt extrusion (HME) due to their high melt viscosity and thermal degradation at high processing temperatures. Three HME-grade hydroxypropyl methylcelluloses, namely Affinisol™ HPMC HME 15 cP, Affinisol™ HPMC HME 100 cP, and Affinisol™ HPMC HME 4 M, have recently been introduced by The Dow Chemical Co. to enable the preparation of solid dispersion at lower and more acceptable processing temperatures. In the present investigation, physicochemical properties of the new polymers relevant to HME were determined and compared with that of Kollidon(®) VA 64. Powder X-ray diffraction (PXRD), modulated differential scanning calorimetry (mDSC), thermogravimetric analysis (TGA), moisture sorption, rheology, and torque analysis by melt extrusion were applied. PXRD and mDSC showed that the Affinisol™ polymers were amorphous in nature. According to TGA, the onset of degradation for all polymers was >220°C. The Affinisol™ polymers exhibited less hygroscopicity than Kollidon(®) VA 64 and another HPMC polymer, Methocel™ K100LV. The complex viscosity profiles of the Affinisol™ polymers as a function of temperature were similar. The viscosity of the Affinisol™ polymers was highly sensitive to the shear rate applied, and unlike Kollidon(®) VA 64, the viscosity decreased drastically when the angular frequency was increased. Because of the very high shear rate encountered during melt extrusion, Affinisol™ polymers showed capability of being extruded at larger windows of processing temperatures as compared to that of Kollidon(®) VA 64.

  19. BioArtificial polymers

    Szałata, Kamila; Gumi, Tania


    Nowadays, the polymer science has impact in practically all life areas. Countless benefits coming from the usage of materials with high mechanical and chemical resistance, variety of functionalities and potentiality of modification drive to the development of new application fields. Novel approaches of combining these synthetic substances with biomolecules lead to obtain multifunctional hybrid conjugates which merge the bioactivity of natural component with outstanding properties of artificial polymer. Over the decades, an immense progress in bioartificial composites domain allowed to reach a high level of knowledge in terms of natural-like systems engineering, leading to diverse strategies of biomolecule immobilization. Together with different available options, including covalent and noncovalent attachment, come various challenges, related mainly with maintaining the biological activity of fixed molecules. Even though the amount of applications that achieve commercial status is still not substantial, and is expanding continuously in the disciplines like "smart materials," biosensors, delivery systems, nanoreactors and many others. A huge number of remarkable developments reported in the literature present a potential of bioartificial conjugates as a fabrics with highly controllable structure and multiple functionalities, serving as a powerful nanotechnological tool. This novel approach brings closer biologists, chemists and engineers, who sharing their effort and complementing the knowledge can revolutionize the field of bioartificial polymer science.

  20. Development of technology for the large-scale preparation of 60Co polymer film source

    Udhayakumar, J.; Pardeshi, G.S.; Gandhi, Shymala S.; Chakravarty, Rubel; Kumar, Manoj; Dash, Ashutosh; Venkatesh, Meera


    60 Co sources (∼37 kBq) in the form of a thin film are widely used in position identification of perforation in offshore oil-well explorations. This paper describes the large-scale preparation of such sources using a radioactive polymer containing 60 Co. 60 Co was extracted into chloroform containing 8-hydroxyquinoline. The chloroform layer was mixed with polymethyl methacrylate (PMMA) polymer. A large film was prepared using the polymer solution containing the complex. The polymer film was then cut into circular sources, mounted on a source holder and supplied to various users

  1. Luminescent sensing of organophosphates using europium(III) containing imprinted polymers prepared by RAFT polymerization

    Southard, Glen E.; Van Houten, Kelly A.; Ott, Edward W.; Murray, George M.


    Molecularly imprinted polymers capable of sensing organophosphorous compounds by luminescence have been prepared by reversible addition fragmentation chain transfer (RAFT) polymerization. The polymer contained a dithiobenzoate substituted tris(β-diketonate) europium(III) complex which served as a polymerization substrate and as a luminescent binding site for pinacolyl methylphosphonate (PMP), the hydrolysis product of the nerve agent Soman. The resultant polymer allowed quantitation of PMP in the low ppb range with minimal interference from similar compounds. Polymers were characterized by luminescence spectroscopy and scanning electron microscopy

  2. Modular Assembly of Hierarchically Structured Polymers

    Leophairatana, Porakrit

    The synthesis of macromolecules with complex yet highly controlled molecular architectures has attracted significant attention in the past few decades due to the growing demand for specialty polymers that possess novel properties. Despite recent efforts, current synthetic routes lack the ability to control several important architectural variables while maintaining low polydispersity index. This dissertation explores a new synthetic scheme for the modular assembly of hierarchically structured polymers (MAHP) that allows virtually any complex polymer to be assembled from a few basic molecular building blocks using a single common coupling chemistry. Complex polymer structures can be assembled from a molecular toolkit consisting of (1) copper-catalyzed azide-alkyne cycloaddition (CuAAC), (2) linear heterobifunctional macromonomers, (3) a branching heterotrifunctional molecule, (4) a protection/deprotection strategy, (5) "click" functional solid substrates, and (6) functional and responsive polymers. This work addresses the different challenges that emerged during the development of this synthetic scheme, and presents strategies to overcome those challenges. Chapter 3 investigates the alkyne-alkyne (i.e. Glaser) coupling side reactions associated with the atom transfer radical polymerization (ATRP) synthesis of alkyne-functional macromonomers, as well as with the CuAAC reaction of alkyne functional building blocks. In typical ATRP synthesis of unprotected alkyne functional polymers, Glaser coupling reactions can significantly compromise the polymer functionality and undermine the success of subsequent click reactions in which the polymers are used. Two strategies are reported that effectively eliminate these coupling reactions: (1) maintaining low temperature post-ATRP upon exposure to air, followed by immediate removal of copper catalyst; and (2) adding excess reducing agents post-ATRP, which prevents the oxidation of Cu(I) catalyst required by the Glaser coupling

  3. Polymer crowding and shape distributions in polymer-nanoparticle mixtures

    Lim, Wei Kang; Denton, Alan R., E-mail: [Department of Physics, North Dakota State University, Fargo, North Dakota 58108-6050 (United States)


    Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments.

  4. Polymer crowding and shape distributions in polymer-nanoparticle mixtures

    Lim, Wei Kang; Denton, Alan R.


    Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments

  5. Dynamics in thin folded polymer films

    Croll, Andrew; Rozairo, Damith

    Origami and Kirigami inspired structures depend on a complex interplay between geometry and material properties. While clearly important to the overall function, very little attention has focused on how extreme curvatures and singularities in real materials influence the overall dynamic behaviour of folded structures. In this work we use a set of three polymer thin films in order to closely examine the interaction of material and geometry. Specifically, we use polydimethylsiloxane (PDMS), polystyrene (PS) and polycarbonate (PC) thin films which we subject to loading in several model geometries of varying complexity. Depending on the material, vastly different responses are noted in our experiments; D-cones can annihilate, cut or lead to a crumpling cascade when pushed through a film. Remarkably, order can be generated with additional perturbation. Finally, the role of adhesion in complex folded structures can be addressed. AFOSR under the Young Investigator Program (FA9550-15-1-0168).

  6. Building-up novel coordination polymer with Zn(II) porphyrin dimer ...

    mer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between ... porphyrin polymers by self-assembly is fascinating ..... ture determination. ..... J K M 2000 In The Porphyrin Handbook Kadish K M,.

  7. Biomolecule-functionalized polymer brushes.

    Jiang, Hui; Xu, Fu-Jian


    Functional polymer brushes have been utilized extensively for the immobilization of biomolecules, which is of crucial importance for the development of biosensors and biotechnology. Recent progress in polymerization methods, in particular surface-initiated atom transfer radical polymerization (ATRP), has provided a unique means for the design and synthesis of new biomolecule-functionalized polymer brushes. This current review summarizes such recent research activities. The different preparation strategies for biomolecule immobilization through polymer brush spacers are described in detail. The functional groups of the polymer brushes used for biomolecule immobilization include epoxide, carboxylic acid, hydroxyl, aldehyde, and amine groups. The recent research activities indicate that functional polymer brushes become versatile and powerful spacers for immobilization of various biomolecules to maximize their functionalities. This review also demonstrates that surface-initiated ATRP is used more frequently than other polymerization methods in the designs of new biomolecule-functionalized polymer brushes.

  8. Claisen thermally rearranged (CTR) polymers

    Tena, Alberto; Rangou, Sofia; Shishatskiy, Sergey; Filiz, Volkan; Abetz, Volker


    Thermally rearranged (TR) polymers, which are considered the next-generation of membrane materials because of their excellent transport properties and high thermal and chemical stability, are proven to have significant drawbacks because of the high temperature required for the rearrangement and low degree of conversion during this process. We demonstrate that using a [3,3]-sigmatropic rearrangement, the temperature required for the rearrangement of a solid glassy polymer was reduced by 200°C. Conversions of functionalized polyimide to polybenzoxazole of more than 97% were achieved. These highly mechanically stable polymers were almost five times more permeable and had more than two times higher degrees of conversion than the reference polymer treated under the same conditions. Properties of these second-generation TR polymers provide the possibility of preparing efficient polymer membranes in a form of, for example, thin-film composite membranes for various gas and liquid membrane separation applications. PMID:27482538

  9. Terminology of Polymers Containing Ionizable or Ionic Groups and of Polymers Containing Ions, VII.3

    Jarm, V.


    Full Text Available The class of ionic polymers has widespread application in many areas of everyday life, in industrial production, and in the processes of living matter. The properties of ionic polymers depend on the polymer structure, and the nature, content, and location of the ionic groups. To clear differences among various ionic polymers, the IUPAC recommendations present 34 definitionsfor the ionomer, polyacid, polybase, polyampholytic polymer, ion-exchange polymer, polybetaine, polyelectrolyte, intrinsically conducting polymer, solid polymer electrolyte, etc

  10. The synthesis and luminescence quenching of the water-soluble polymer-supported tris(2,2'-bipyridine)ruthenium(II) analogue

    Kurimura, Yoshimi; Shinozaki, Norio; Ito, Fumio; Uratani, Yasuyo; Shigehara, Kiyotaka; Tsuchida, Eishun; Kaneko, Masao; Yamada, Akira.


    The p-aminostyrene-N-vinylpyrrolidone copolymer-supported tris(2,2'-bipyridine)ruthenium (II) analogue, [Ru(bpy) 2 (pbyCOOH)] 2 + (bpy = 2,2'-bipyridine and pbyCOOH = polymeric bipyridine ligand), has been prepared, and the luminescence behavior of the polymer complex has been investigated in an aqueous solution. The efficiency of the quenching of the excited state of the polymer complex with [Fe(CN) 6 ] 4 - , [Co(phen) 3 ] 2 + , and Cu 2 + is compared with that of [Ru(bpy) 3 ] 2 + . The quenching of the excited state of the polymer complex by Cu 2 + is strongly enhanced by the effect of the polymer chains. In the polymer complex/Cu 2 + system, the quenching by Cu 2 + in the presence of poly(p-styrenesulfonate) is much more effective than in the absence of the polyion. The characteristics of the polymer complex in terms of the luminescence behavior are discussed. (author)

  11. Pending templates imprinted polymers-hypothesis, synthesis, adsorption, and chromatographic properties.

    Yang, Chun; Luan, Xinjie; Zhao, Meifeng; Liu, Guofeng; Wang, Jian; Qu, Qishu; Hu, Xiaoya


    This is the first time when protein-imprinted polymers are prepared with "pending templates." The polymers were synthesized in the presence of a real sample (chicken egg white), rather than any known commercial proteins. Compared with a simultaneously synthesized nonimprinted control polymer, the polymers show higher adsorption capacity for abundant components (as "pending templates") in the original sample. Chromatography experiments indicated that the columns made of the imprinted polymers could retain abundant species (imprinted) and separate them from those not imprinted. Thus, the sample could be split into dimidiate subfractions with reduced complexities. "Pending template imprinting" suggests a new way to investigate molecular imprinting, especially to dissect, simplify, and analyze complicated samples through a series of polymers just imprinted by the samples per se. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Integration of molecular machines into supramolecular materials: actuation between equilibrium polymers and crystal-like gels.

    Mariani, Giacomo; Goujon, Antoine; Moulin, Emilie; Rawiso, Michel; Giuseppone, Nicolas; Buhler, Eric


    In this article, the dynamic structure of complex supramolecular polymers composed of bistable [c2]daisy chain rotaxanes as molecular machines that are linked by ureidopyrimidinones (Upy) as recognition moieties was studied. pH actuation of the integrated mechanically active rotaxanes controls the contraction/extension of the polymer chains as well as their physical reticulation. Small-angle neutron and X-ray scattering were used to study in-depth the nanostructure of the contracted and extended polymer aggregates in toluene solution. The supramolecular polymers comprising contracted nanomachines were found to be equilibrium polymers with a mass that is concentration dependent in dilute and semidilute regimes. Surprisingly, the extended polymers form a gel network with a crystal-like internal structure that is independent of concentration and reminiscent of a pearl-necklace network.

  13. Solid polymer electrolyte lithium batteries

    Alamgir, Mohamed; Abraham, Kuzhikalail M.


    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  14. Vacuum ultraviolet photochemistry of polymers

    Skurat, Vladimir


    The interaction of vacuum UV radiation (wavelength range from 1 to 200 nm) with polymers is interesting for fundamental and applied sciences. This interest is stimulated by various reasons: - Wide applications of polymeric materials in semiconductor technology, where they are used as photoresist materials in combination with VUV light sources (lasers, excimer lamps, synchrotron radiation and others). - Polymers are widely used as spacecraft materials in the last 20 years. On near-Earth orbits, the polymeric materials of spacecraft surfaces are destroyed by solar radiation. - VUV radiation is one of the components of gas discharge plasmas, which are used for treatment of polymer, with the aim of modifying their surface properties. The main features of interaction of VUV radiation with polymers are discussed. The spectra of intrinsic absorption of saturated polymers (polyethylene, polypropylene, polytetrafluoroethylene and others) are situated mainly in the VUV region. The photochemistry of polymers in the VUV region is very different from their photochemistry at wavelengths longer than 200 nm, where the absorption spectra belong to impurities and polymer defects. The polymer photochemistry in the VUV region is wavelength-dependent. At wavelengths longer than about 140 nm, the main role is played by transformations of primary-formed singlet excited molecules. At shorter wavelengths the role of photoionization increases progressively and the main features of VUV photolysis become similar to the picture of radiolysis, with significant contributions of charge pairs and triplet excited molecules. Very important features of VUV light absorption in polymers are high absorption coefficients. Because of this, the surface layers absorb large doses of energy. This leads to very profound transformation of material on the polymer surface. In particular for polymers which are considered destroyed by radiation (for example, perfluoropolymers), this leads to VUV-induced erosion

  15. Planar-Processed Polymer Transistors.

    Xu, Yong; Sun, Huabin; Shin, Eul-Yong; Lin, Yen-Fu; Li, Wenwu; Noh, Yong-Young


    Planar-processed polymer transistors are proposed where the effective charge injection and the split unipolar charge transport are all on the top surface of the polymer film, showing ideal device characteristics with unparalleled performance. This technique provides a great solution to the problem of fabrication limitations, the ambiguous operating principle, and the performance improvements in practical applications of conjugated-polymer transistors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. High-Permeability Magnetic Polymer Additives for Lightweight Electromagnetic Shielding


    incorporation) or chemical incorporation as part of the polymer chain backbone or linked as pendant groups.13 Many transition-metal organometallic...10.1002/9781119951438. 15. Poli R. Open-shell organometallics as a bridge between Werner-type and low-valent organometallic complexes: the effect

  17. Modelling the permeability of polymers: a neural network approach

    Wessling, Matthias; Mulder, M.H.V.; Bos, A.; Bos, A.; van der Linden, M.K.T.; Bos, M.; van der Linden, W.E.


    In this short communication, the prediction of the permeability of carbon dioxide through different polymers using a neural network is studied. A neural network is a numeric-mathematical construction that can model complex non-linear relationships. Here it is used to correlate the IR spectrum of a

  18. Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

    Andernach, Rolf; Utzat, Hendrik; Dimitrov, Stoichko; McCulloch, Iain; Heeney, Martin; Durrant, James; Bronstein, Hugo


    We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin

  19. Syntheses, crystal structures and Hirshfeld surface analysis of a coordination polymer of Cu(II) chlorido and a tris-octahedral complex of Ni(II) containing isonicotinoylhydrazone blockers

    Mahmoudi, Ghodrat; Chowdhury, Habibar; Ghosh, Barindra K.; Lofland, Samuel E.; Maniukiewicz, Waldemar


    One-pot reactions of pre-assigned molar ratios of appropriate metal (II) salts and HL1 (2-acetylpyridine nicotinoylhydrazone) or HL2 (2-acetylpyridine isonicotinoylhydrazone) in MeOH solutions at room temperature afford 1D coordination polymeric chain [Cu(μ-L1) (Cl)]n (1) and a mononuclear complex [Ni(L2)2] (2). The compounds (1) and (2) were characterized using elemental analyses, spectral and other physicochemical methods. Single crystal X-ray diffraction measurements for (1) and (2) have been made to define the molecular aggregates and crystalline architectures. In (1), each copper (II) center adopts a distorted square pyramidal geometry with a CuN3OCl chromophore linked through μ-L1 to form the 1D polymeric chain. While in (2) each Ni(II) cation is six-coordinate with octahedral structure having NiN4O2 chromophore containing two L2 units each functioning as a classical tridentate (N,N,O) chelator. Different weak non-covalent interactions promote dimensionalities in the compounds. A Hirshfeld surface analysis was employed to gain additional insight into interactions responsible for packing of (1) and (2). Magnetic susceptibility measurement of (1) in the 4-300 K range reveals simple paramagnetism.

  20. Conjugated Polymers for Energy Production

    Livi, Francesco

    This dissertation is aimed at developing materials for flexible, large area, ITO-free polymer solar cells (PSCs) fully printed under ambient conditions. A large screening of conjugated polymers, both novel and well-known materials, has been carried out in order to find suitable candidates...... polymerization method for industrial production of polymers. Several DArP protocols have been employed for the synthesis of PPDTBT leading to polymers with high structural regularity and photovoltaic performances comparable with the same materials synthesized via Stille cross-coupling polymerization...

  1. Multifunctional Polymer/Inorganic Nanocomposites

    Manias, E


    ... in multifunctional nanocomposite materials. Understanding the structure/property relations in polymer/clay nanocomposites is of great importance in designing materials with desired sets of properties...

  2. Wear of polymers and composites

    Abdelbary, Ahmed


    In the field of tribology, the wear behaviour of polymers and composite materials is considered a highly non-linear phenomenon. Wear of Polymers and Composites introduces fundamentals of polymers and composites tribology. The book suggests a new approach to explore the effect of applied load and surface defects on the fatigue wear behaviour of polymers, using a new tribometer and thorough experiments. It discusses effects of surface cracks, under different static and cyclic loading parameters on wear, and presents an intelligent algorithm, in the form of a neural network, to map the relations

  3. Application of Composite Polymer Electrolytes

    Scrosati, Bruno


    ...)PEO-based composite polymer electrolytes, by a series of specifically addressed electrochemical tests which included the determination of the conductivity and of the lithium transference number...

  4. Sustainable polymers from renewable resources.

    Zhu, Yunqing; Romain, Charles; Williams, Charlotte K


    Renewable resources are used increasingly in the production of polymers. In particular, monomers such as carbon dioxide, terpenes, vegetable oils and carbohydrates can be used as feedstocks for the manufacture of a variety of sustainable materials and products, including elastomers, plastics, hydrogels, flexible electronics, resins, engineering polymers and composites. Efficient catalysis is required to produce monomers, to facilitate selective polymerizations and to enable recycling or upcycling of waste materials. There are opportunities to use such sustainable polymers in both high-value areas and in basic applications such as packaging. Life-cycle assessment can be used to quantify the environmental benefits of sustainable polymers.

  5. Phenomenology of polymer solution dynamics

    Phillies, George D. J


    ... solutions, not dilute solutions or polymer melts. From centrifugation and solvent dynamics to viscosity and diffusion, experimental measurements and their quantitative representations are the core of the discussion...

  6. Small angle scattering and polymers

    Cotton, J.P.


    The determination of polymer structure is a problem of interest for both statistical physics and industrial applications. The average polymer structure is defined. Then, it is shown why small angle scattering, associated with isotopic substitution, is very well suited to the measurement of the chain conformation. The corresponding example is the old, but pedagogic, measurement of the chain form factor in the polymer melt. The powerful contrast variation method is illustrated by a recent determination of the concentration profile of a polymer interface. (author) 12 figs., 48 refs

  7. Polymer Processing and Characterization Laboratory

    Federal Laboratory Consortium — The purpose is to process and evaluate polymers for use in nonlinear optical, conductive and structural Air Force applications. Primary capabilities are extrusion of...

  8. Determination of the glass transition temperature of cyclodextrin polymers.

    Tabary, Nicolas; Garcia-Fernandez, Maria Jose; Danède, Florence; Descamps, Marc; Martel, Bernard; Willart, Jean-François


    The aim of this work was to determine the main physical characteristics of β-cyclodextrin polymers, well known for improving complexation capacities and providing enhanced and sustained release of a large panel of drugs. Two polymers were investigated: a polymer of β-cyclodextrin (polyβ-CD) and a polymer of partially methylated (DS=0.57) β-cyclodextrin (polyMe-β-CD). The physical characterizations were performed by powder X-ray diffraction and differential scanning calorimetry. The results indicate that these polymers are amorphous and that their glass transition is located above the thermal degradation point of the materials preventing their direct observation and thus their full characterization. We could however estimate the virtual glass transition temperatures by mixing the polymers with different plasticizers (trehalose and mannitol) which decreases Tg sufficiently to make the glass transition observable. Extrapolation to zero plasticizer concentration then yield the following Tg values: Tg (polyMe-β-CD)=317°C±5°C and Tg (polyβ-CD)=418°C±6°C. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Injection molded polymer optics in the 21st Century

    Beich, William S.


    Precision polymer optics, manufactured by injection molding techniques, has been a key enabling technology for several decades now. The technology, which can be thought of as a subset of the wider field of precision optics manufacturing, was pioneered in the United States by companies such as Eastman Kodak, US Precision Lens, and Polaroid. In addition to suppliers in the U.S. there are several companies worldwide that design and manufacture precision polymer optics, for example Philips High Tech Plastics in Europe and Fujinon in Japan. Designers who are considering using polymer optics need a fundamental understanding of exactly how the optics are created. This paper will survey the technology and processes that are employed in the successful implementation of a polymer optic solution from a manufacturer's perspective. Special emphasis will be paid to the unique relationship between the molds and the optics that they produce. We will discuss the key elements of production: molding resins, molds and molding equipment, and metrology. Finally we will offer a case study to illustrate just how the optics designer carries a design concept through to production. The underlying theme throughout the discussion of polymer optics is the need for the design team to work closely with an experienced polymer optics manufacturer with a solid track record of success in molded optics. As will be seen shortly, the complex interaction between thermoplastics, molds, and molding machines dictates the need for working closely with a supplier who has the critical knowledge needed to manage all aspects of the program.

  10. Hybrid protein-synthetic polymer nanoparticles for drug delivery.

    Koseva, Neli S; Rydz, Joanna; Stoyanova, Ekaterina V; Mitova, Violeta A


    Among the most common nanoparticulate systems, the polymeric nanocarriers have a number of key benefits, which give a great choice of delivery platforms. Nevertheless, polymeric nanoparticles possess some limitations that include use of toxic solvents in the production process, polymer degradation, drug leakage outside the diseased tissue, and polymer cytotoxicity. The combination of polymers of biological and synthetic origin is an appealing modern strategy for the production of novel nanocarriers with unprecedented properties. Proteins' interface can play an important role in determining bioactivity and toxicity and gives perspective for future development of the polymer-based nanoparticles. The design of hybrid constructs composed of synthetic polymer and biological molecules such as proteins can be considered as a straightforward tool to integrate a broad spectrum of properties and biofunctions into a single device. This review discusses hybrid protein-synthetic polymer nanoparticles with different structures and levels in complexity and functionality, in view of their applications as drug delivery systems. © 2015 Elsevier Inc. All rights reserved.

  11. Hybrid Polymer-Network Hydrogels with Tunable Mechanical Response

    Sebastian Czarnecki


    Full Text Available Hybrid polymer-network gels built by both physical and covalent polymer crosslinking combine the advantages of both these crosslinking types: they exhibit high mechanical strength along with excellent fracture toughness and extensibility. If these materials are extensively deformed, their physical crosslinks can break such that strain energy is dissipated and irreversible fracturing is restricted to high strain only. This mechanism of energy dissipation is determined by the kinetics and thermodynamics of the physical crosslinking contribution. In this paper, we present a poly(ethylene glycol (PEG based material toolkit to control these contributions in a rational and custom fashion. We form well-defined covalent polymer-network gels with regularly distributed additional supramolecular mechanical fuse links, whose strength of connectivity can be tuned without affecting the primary polymer-network composition. This is possible because the supramolecular fuse links are based on terpyridine–metal complexation, such that the mere choice of the fuse-linking metal ion adjusts their kinetics and thermodynamics of complexation–decomplexation, which directly affects the mechanical properties of the hybrid gels. We use oscillatory shear rheology to demonstrate this rational control and enhancement of the mechanical properties of the hybrid gels. In addition, static light scattering reveals their highly regular and well-defined polymer-network structures. As a result of both, the present approach provides an easy and reliable concept for preparing hybrid polymer-network gels with rationally designed properties.

  12. Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

    Fish, D.


    The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished

  13. Growth and gelation of inorganic polymers

    Kallala, Mohamed


    This research thesis reports a study during which gels, sols and precipitates are obtained by hydrolysis and condensation of titanium tetra-n-butoxide diluted in n-butanol. The condensation of the non-modified precursor always results in a precipitate. Small angle X-ray scattering shows that these precipitates are made of dense polymers with rough surfaces. Due to the condensation selective inhibition by protons or by organic complexes, polymers must grow in an anisotropic way. When these accumulations reach a macroscopic size, a gel is formed. The inner structure of these accumulations is continuously varying with the inhibition rate. For high inhibitions, the final state is a sol or a transparent gel with a fractal dimension equal to 2. For intermediate inhibition rates, the gel becomes turbid. Precipitation occurs when fractal dimension reaches 3. The author shows that the final state of the aggregation results from a difference of reactivity of monomers with respect to their environment. Depending on this reactivity, the reaction bath changes its regime during aggregation, and passes from a recombination of branch polymers to the precipitation of dense objects. This explains the role of some chemical modifiers in the control of aggregation processes, notably in the sol-gel process [fr

  14. Laser etching of polymer masked leadframes

    Ho, C. K.; Man, H. C.; Yue, T. M.; Yuen, C. W.


    A typical electroplating production line for the deposition of silver pattern on copper leadframes in the semiconductor industry involves twenty to twenty five steps of cleaning, pickling, plating, stripping etc. This complex production process occupies large floor space and has also a number of problems such as difficulty in the production of rubber masks and alignment, generation of toxic fumes, high cost of water consumption and sometimes uncertainty on the cleanliness of the surfaces to be plated. A novel laser patterning process is proposed in this paper which can replace many steps in the existing electroplating line. The proposed process involves the application of high speed laser etching techniques on leadframes which were protected with polymer coating. The desired pattern for silver electroplating is produced by laser ablation of the polymer coating. Excimer laser was found to be most effective for this process as it can expose a pattern of clean copper substrate which can be silver plated successfully. Previous working of Nd:YAG laser ablation showed that 1.06 μm radiation was not suitable for this etching process because a thin organic and transparent film remained on the laser etched region. The effect of excimer pulse frequency and energy density upon the removal rate of the polymer coating was studied.

  15. Topology of polymer chains under nanoscale confinement.

    Satarifard, Vahid; Heidari, Maziar; Mashaghi, Samaneh; Tans, Sander J; Ejtehadi, Mohammad Reza; Mashaghi, Alireza


    Spatial confinement limits the conformational space accessible to biomolecules but the implications for bimolecular topology are not yet known. Folded linear biopolymers can be seen as molecular circuits formed by intramolecular contacts. The pairwise arrangement of intra-chain contacts can be categorized as parallel, series or cross, and has been identified as a topological property. Using molecular dynamics simulations, we determine the contact order distributions and topological circuits of short semi-flexible linear and ring polymer chains with a persistence length of l p under a spherical confinement of radius R c . At low values of l p /R c , the entropy of the linear chain leads to the formation of independent contacts along the chain and accordingly, increases the fraction of series topology with respect to other topologies. However, at high l p /R c , the fraction of cross and parallel topologies are enhanced in the chain topological circuits with cross becoming predominant. At an intermediate confining regime, we identify a critical value of l p /R c , at which all topological states have equal probability. Confinement thus equalizes the probability of more complex cross and parallel topologies to the level of the more simple, non-cooperative series topology. Moreover, our topology analysis reveals distinct behaviours for ring- and linear polymers under weak confinement; however, we find no difference between ring- and linear polymers under strong confinement. Under weak confinement, ring polymers adopt parallel and series topologies with equal likelihood, while linear polymers show a higher tendency for series arrangement. The radial distribution analysis of the topology reveals a non-uniform effect of confinement on the topology of polymer chains, thereby imposing more pronounced effects on the core region than on the confinement surface. Additionally, our results reveal that over a wide range of confining radii, loops arranged in parallel and cross

  16. Radiation preparation of drug carriers based polyacrylic acid (PAAc) using poly(vinyl pyrrolidone) (PVP) as a template polymer

    Abd El-Rehim, H. A.; Hegazy, E. A.; Khalil, F. H.; Hamed, N. A.


    The present study deals with the radiation synthesis of stimuli response hydrophilic polymers from polyacrylic acid (PAAc). To maintain the property of PAAc and control the water swellibility for its application as a drug delivery system, radiation polymerization of AAc in the presence of poly(vinyl pyrrolidone) (PVP) as a template polymer was carried out. Characterization of the prepared PAA/PVP inter-polymer complex was investigated by determining gel content, swelling property, hydrogel microstructure and the release rate of caffeine as a model drug. The release rate of caffeine from the PAA/PVP inter-polymer complexes showed pH-dependency, and seemed to be mainly controlled by the dissolution rate of the complex above a p Ka of PAAc. The prepared inter-polymer complex could be used for application as drug carriers.

  17. Clickable antifouling polymer brushes for polymer pen lithography

    Bog, U.; de los Santos Pereira, Andres; Mueller, S. L.; Havenridge, S.; Parrillo, Viviana; Bruns, M.; Holmes, A. E.; Rodriguez-Emmenegger, C.; Fuchs, H.; Hirtz, M.


    Roč. 9, č. 13 (2017), s. 12109-12117 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GJ15-09368Y Institutional support: RVO:61389013 Keywords : antifouling * biofunctional interfaces * polymer brushes Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 7.504, year: 2016

  18. Enhancement of Polymer Cytocompatibility by Nanostructuring of Polymer Surface

    Slepička, P.; Kasálková-Slepičková, N.; Bačáková, Lucie; Kolská, Z.; Švorčík, V.


    Roč. 2012, č. 2012 (2012), ID527403 ISSN 1687-4110 R&D Projects: GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:67985823 Keywords : polymer cytocompatibility * polymer surface * nanotechnology Subject RIV: EI - Biotechnology ; Bionics Impact factor: 1.547, year: 2012

  19. Radiation Synthesis of Superabsorbent Polymers Based on Natural Polymers

    Sen, Murat; Hayrabolulu, Hande


    The objectives of proposed research contract were first synthesize superabsorbent polymers based on natural polymers to be used as disposable diapers and soil conditioning materials in agriculture, horticulture and other super adsorbent using industries. We have planned to use the natural polymers; locust beam gum, tara gum, guar gum and sodium alginate on the preparation of natural superabsorbent polymers(SAP). The aqueous solution of natural polymers and their blends with trace amount of monomer and cross-linking agents will be irradiated in paste like conditions by gamma rays for the preparation of cross-linked superabsorbent systems. The water absorption and deswellling capacity of prepared super adsorbents and retention capacity, absorbency under load, suction power, swelling pressure and pet-rewet properties will be determined. Use of these materials instead of synthetic super absorbents will be examined by comparing the performance of finished products. The experimental studies achieved in the second year of project mainly on the effect of radiation on the chemistry of sodium alginate polymers in different irradiation conditions and structure-property relationship particularly with respect to radiation induced changes on the molecular weight of natural polymers and preliminary studies on the synthesis of natural-synthetic hydride super adsorbent polymers were given in details

  20. Polymer Crowding in Confined Polymer-Nanoparticle Mixtures

    Davis, Wyatt J.; Denton, Alan R.

    Crowding can influence the conformations and thus functionality of macromolecules in quasi-two-dimensional environments, such as DNA or proteins confined to a cell membrane. We explore such crowding within a model of polymers as penetrable ellipses, whose shapes are governed by the statistics of a 2D random walk. The principal radii of the polymers fluctuate according to probability distributions of the eigenvalues of the gyration tensor. Within this coarse-grained model, we perform Monte Carlo simulations of mixtures of polymers and hard nanodisks, including trial changes in polymer conformation (shape and orientation). Penetration of polymers by nanodisks is incorporated with a free energy cost predicted by polymer field theory. Over ranges of size ratio and nanodisk density, we analyze the influence of crowding on polymer shape by computing eigenvalue distributions, mean radius of gyration, and mean asphericity of the polymer. We compare results with predictions of free-volume theory and with corresponding results in three dimensions. Our approach may help to interpret recent (and motivate future) experimental studies of biopolymers interacting with cell membranes, with relevance for drug delivery and gene therapy. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

  1. Lattice cluster theory for polymer melts with specific interactions

    Xu, Wen-Sheng; Freed, Karl F.


    Despite the long-recognized fact that chemical structure and specific interactions greatly influence the thermodynamic properties of polymer systems, a predictive molecular theory that enables systematically addressing the role of chemical structure and specific interactions has been slow to develop even for polymer melts. While the lattice cluster theory (LCT) provides a powerful vehicle for understanding the influence of various molecular factors, such as monomer structure, on the thermodynamic properties of polymer melts and blends, the application of the LCT has heretofore been limited to the use of the simplest polymer model in which all united atom groups within the monomers of a species interact with a common monomer averaged van der Waals energy. Thus, the description of a compressible polymer melt involves a single van der Waals energy. As a first step towards developing more realistic descriptions to aid in the analysis of experimental data and the design of new materials, the LCT is extended here to treat models of polymer melts in which the backbone and side groups have different interaction strengths, so three energy parameters are present, namely, backbone-backbone, side group-side group, and backbone-side group interaction energies. Because of the great algebraic complexity of this extension, we retain maximal simplicity within this class of models by further specializing this initial study to models of polymer melts comprising chains with poly(n-α-olefin) structures where only the end segments on the side chains may have different, specific van der Waals interaction energies with the other united atom groups. An analytical expression for the LCT Helmholtz free energy is derived for the new model. Illustrative calculations are presented to demonstrate the degree to which the thermodynamic properties of polymer melts can be controlled by specific interactions

  2. Polymer solidification national program

    Kalb, P.D.; Colombo, P.


    Brookhaven National Laboratory (BNL) has developed several new and innovative polymer processes for the solidification of low-level radioactive, hazardous and mixed wastes streams. Polyethylene and modified sulfur cement solidification technologies have undergone steady, gradual development at BNL over the past nine years. During this time they have progressed through each of the stages necessary for logical technology maturation: from process conception, parameter optimization, waste form testing, evaluation of long-term durability, economic analysis, and scale-up feasibility. This technology development represents a significant investment which can potentially provide DOE with both short- and long-term savings

  3. Monte Carlo simulations of confined polymer systems

    Vliet, Johannes Henricus van


    This thesis considers confined polymer systems. These systems are of considerable interest, e.g., thin polymer films, chromotography of polymer solutions, drag reduction, enhanced oil recovery, stabilization of colloidal dispersions, lubrication and biolubrication. The method used to study these

  4. Processing of polymers using reactive solvents

    Lemstra, P.J.; Kurja, J.; Meijer, H.E.H.; Meijer, H.E.H.


    A review with many refs. on processing of polymers using reactive solvents including classification of synthetic polymers, guidelines for the selection of reactive solvents, basic aspects of processing, examples of intractable and tractable polymer/reactive solvent system

  5. Complexity explained

    Erdi, Peter


    This book explains why complex systems research is important in understanding the structure, function and dynamics of complex natural and social phenomena. Readers will learn the basic concepts and methods of complex system research.

  6. Zotarolimus-eluting durable-polymer-coated stent versus a biolimus-eluting biodegradable-polymer-coated stent in unselected patients undergoing percutaneous coronary intervention (SORT OUT VI)

    Raungaard, Bent; Jensen, Lisette Okkels; Tilsted, Hans-Henrik


    BACKGROUND: New-generation drug-eluting coronary stents have reduced the risk of coronary events, especially in patients with complex disease or lesions. To what extent different stent platforms, polymers, and antiproliferative drugs affect outcomes, however, is unclear. We investigated the safety...... and efficacy of a third-generation stent by comparing a highly biocompatible durable-polymer-coated zotarolimus-eluting stent with a biodegradable-polymer-coated biolimus-eluting stent. METHODS: This open-label, randomised, multicentre, non-inferiority trial was done at three sites across western Denmark. All......-polymer zotarolimus-eluting stent or the biodegradable-polymer biolimus-eluting stent. The primary endpoint was a composite of safety (cardiac death and myocardial infarction not clearly attributable to a non-target lesion) and efficacy (target-lesion revascularisation) at 12 months, analysed by intention to treat...

  7. Entanglements in Conjugated Polymers

    Xie, Renxuan; Lee, Youngmin; Aplan, Melissa; Caggiano, Nick; Gomez, Enrique; Colby, Ralph

    Conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly-((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT), are widely used as hole and electron transport materials in a variety of electronic devices. However, fundamental knowledge regarding chain entanglements and nematic-to-isotropic transition is still lacking and are crucial to maximize charge transport properties. A systematic melt rheology study on P3HT with various molecular weights and regio regularities was performed. We find that the entanglement molecular weight Me is 5.0 kg/mol for regiorandom P3HT, but the apparent Me for regioregular P3HT is significantly higher. The difference is postulated to arise from the presence of a nematic phase only in regioregular P3HT. Analogously, PFTBT shows a clear rheological signature of the nematic-to-isotropic transition as a reversible sharp transition at 278 C. Shearing of this nematic phase leads to anisotropic crystalline order in PFTBT. We postulate that aligning the microstructure will impact charge transport and thereby advance the field of conducting polymers. National Science Foundation.

  8. Polymer article of manufacture

    Newlove, J.C.; McDougall, L.A.


    It is an object of this invention to provide an article and its use to enhance the production of hydrocarbons from geologial reservoirs, more particularly from fractured formations. It has been an additional object to devise a composition for providing controlled release of a reagent downhole, in a pipeline, in other oil-containing environments or fluids. It has been discovered that it is possible to provide for the introduction of an additive reagent into a liquid hydrocarbon by providing solid polymeric bodies each comprising a polymeric matrix containing a substantially water insoluble reagent such as a wax crystal modifier, demulsifier, scale inhibitor, corrosion inhibitor, biocide, ashless dispersant, antioxidant and mixtures thereof. These bodies are, in use, positioned at a location where it is desired to release the reagent into the substantially hydrocarbon fluid and, upon contact with fluid in this location, active reagent is released into the fluid. Thus in accordance with this invention there is provided a solid polymeric body comprising a polymer matrix containing a substantially water-insoluble reagent leachable into a substantially hydrocarbon liquid environment. The object of this invention has been realized in specific form by beads comprising a copolymeric matrix of methylmethacrylate and methacrylic acid containing the behenyl half ester of a C/sub 24/-C/sub 28/ alkenyl succinic anhydride polymer and having a diameter ranging from 0.2 to 1 mm. Such beads, when introduced downhole in a hydraulic fracturing operation, were found to inhibit paraffin wax deposition.

  9. Polymer dye lasers

    Balslev, Søren


    , elektronstrålelithografi og Röntgenstrålelithografi. Andre polymerer er også blevet formgivet via ”nanoimprint” lithografi for at skabe laserresonatorer. En række lasere, både baseret på et flydende forstærkningsmedium og et faststof forstærkningsrmedium er blevet udviklet. Laserne giver både lys i flere ”modes” og i een......Formålet med dette Ph.D. arbejde har været at udvikle miniaturiserede polymer farvestoflasere, egnet til at blive integreret i mikrochips som også indeholder andre polymerstrukturer – som for eksempel kan findes i ”Laboratorie-på-en-chip” kredsløb. Lasernes funktion skal være at levere lys til...... meget følsomme sensorformål, og at undgå at skulle opliniere eksterne lyskilder til sensorer på polymerchips. En enkelt type gennemsigtig ”resist” (SU-8) er blevet brugt til at udvikle en række laserresonatorer i polymer. ”Resisten” er blevet formgivet via en række lithografiske teknikker: UV lithografi...

  10. Developments in polymer degradation - 7

    Grassie, N.


    A selection of topics which are representative of the continually expanding area of polymer degradation is presented. The aspects emphasised include the products of degradation of specific polymers, degradation by high energy radiation and mechanical forces, fire retardant studies and the special role of small radicals in degradation processes. (author)

  11. Wood and concrete polymer composites

    Singer, K.


    There are several ways to prepare and use wood and concrete polymer composites. The most important improvements in the case of concrete polymer composites are obtained for compressive and tensile strengths. The progress in this field in United States and other countries is discussed in this rview. (M.S.)

  12. All-Polymer Electrochemical Sensors

    Kafka, Jan Robert

    This thesis presents fabrication strategies to produce different types of all-polymer electrochemical sensors based on electrodes made of the highly conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT). Three different systems are presented, fabricated either by using microdrilling or by hot...

  13. Degradable polymers for tissue engineering

    van Dijkhuizen-Radersma, Riemke; Moroni, Lorenzo; van Apeldoorn, Aart A.; Zhang, Zheng; Grijpma, Dirk W.; van Blitterswijk, Clemens A.


    This chapter elaborates the degradable polymers for tissue engineering and their required scaffold material in tissue engineering. It recognizes the examples of degradable polymers broadly used in tissue engineering. Tissue engineering is the persuasion of the body to heal itself through the

  14. Graphene-based polymer nanocomposites

    Tkalya, E.


    The main reason for the rapid development of polymer composite materials is that the traditional "pure" polymers have largely played out its performance capabilities whereas technology requires materials with new properties and advances. There are a number of advantages polymeric composites have

  15. Contact mechanics in glassy polymers

    Breemen, van L.C.A.


    Polymers, primarily semi-crystalline, are widely used in applications where low friction is required; examples are cups in artificial hip joints, bearings and gears. Until now there is no clear indication why some polymers display low friction and others don’t. In this thesis a systematic

  16. Radiation synthesis of polymer polyol

    Guo Jianmei; Zeng Xinmiao; Zhou Chengfei; Cao Wei; Zhai Tong; Wu Dezhen


    The polymer polyol was synthesized by γ irradiation. The properties of polymer polyol synthesized with different radiation dose were studied. The experiment result showed the radiation dose hadn't significant influence on the hydroxyl value of polymer polyol. The sample with different solid content had different hydroxyl value. When the radiation dose is between 1 to 12 kGy, the viscosity and hydroxyl value of polymer polyol were increased with the increment of radiation dose. When radiation dose is between 1 to 12 kGy, with the increment of radiation dose, viscosity of polymer polyol was rapidly increased, and the content solid of sample has few change. When radiation dose is higher than 20 kGy, the viscosity and hydroxyl value of polymer polyol have gradually increase with the increment of radiation dose. The size of polymer particles is 0.1-0.6 μm. The value of 150 mesh filter was 100%. The polymer polyol may be used as PU foam and elastomer. (authors)


    Jensen, Jens Oluf; Qingfeng, Li; He, Ronghuan


    This paper will report recent results from our group on polymer fuel cells (PEMFC) based on the temperature resistant polymer polybenzimidazole (PBI), which allow working temperatures up to 200°C. The membrane has a water drag number near zero and need no water management at all. The high working...

  18. Fifty years of polymer science

    Du Prez, Filip; Hoogenboom, Richard; Klumperman, Bert; Meier, Michael; Monteiro, Michael; Müller, Alejandro; Vancso, Gyula J.


    The European Polymer Journal (EPJ) has been serving the scientific community for 50 years, which makes it one of the older macromolecular journals with a broad focus. Since its launch 50 years ago, EPJ has provided a distinguished forum for publications in polymer research, including chemistry,

  19. Complex chemistry

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon


    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  20. Control of Macromolecular Architectures for Renewable Polymers: Case Studies

    Tang, Chuanbing

    The development of sustainable polymers from nature biomass is growing, but facing fierce competition from existing petrochemical-based counterparts. Controlling macromolecular architectures to maximize the properties of renewable polymers is a desirable approach to gain advantages. Given the complexity of biomass, there needs special consideration other than traditional design. In the presentation, I will talk about a few case studies on how macromolecular architectures could tune the properties of sustainable bioplastics and elastomers from renewable biomass such as resin acids (natural rosin) and plant oils.

  1. Characterization of ethyl cellulose polymer.

    Mahnaj, Tazin; Ahmed, Salah U; Plakogiannis, Fotios M


    Ethyl cellulose (EC) polymer was characterized for its property before considering the interactions with the plasicizer. Ethocel Std.10 FP Premium from Dow chemical company USA was tested for its solubility, morphology and thermal properties. Seven percentage of EC solution in ethanol was found to be the right viscosity used to prepare the film. The EC polymer and EC film without any plasticizers showed almost identical thermal behavior, but in X-ray diffraction showed different arrangements of crystallites and amorphous region. Dynamic mechanical analysis of film showed that without a plasticizer, EC film was not flexible and had very low elongation with high applied force. The aim of the work was to avoid using the commercially available EC dispersions Surelease® and Aquacoat®; both already have additives on it. Instead, Ethocel EC polymer (powder) was characterized in our laboratory in order to find out the properties of polymer before considering the interactions of the polymer with various plasticizers.

  2. Accelerated Characterization of Polymer Properties

    R. Wroczynski; l. Brewer; D. Buckley; M. Burrell; R. Potyrailo


    This report describes the efforts to develop a suite of microanalysis techniques that can rapidly measure a variety of polymer properties of industrial importance, including thermal, photo-oxidative, and color stability; as well as ductility, viscosity, and mechanical and antistatic properties. Additional goals of the project were to direct the development of these techniques toward simultaneous measurements of multiple polymer samples of small size in real time using non-destructive and/or parallel or rapid sequential measurements, to develop microcompounding techniques for preparing polymers with additives, and to demonstrate that samples prepared in the microcompounder could be analyzed directly or used in rapid off-line measurements. These enabling technologies are the crucial precursors to the development of high-throughput screening (HTS) methodologies for the polymer additives industry whereby the rate of development of new additives and polymer formulations can be greatly accelerated.

  3. Controlled Release from Recombinant Polymers

    Price, Robert; Poursaid, Azadeh; Ghandehari, Hamidreza


    Recombinant polymers provide a high degree of molecular definition for correlating structure with function in controlled release. The wide array of amino acids available as building blocks for these materials lend many advantages including biorecognition, biodegradability, potential biocompatibility, and control over mechanical properties among other attributes. Genetic engineering and DNA manipulation techniques enable the optimization of structure for precise control over spatial and temporal release. Unlike the majority of chemical synthetic strategies used, recombinant DNA technology has allowed for the production of monodisperse polymers with specifically defined sequences. Several classes of recombinant polymers have been used for controlled drug delivery. These include, but are not limited to, elastin-like, silk-like, and silk-elastinlike proteins, as well as emerging cationic polymers for gene delivery. In this article, progress and prospects of recombinant polymers used in controlled release will be reviewed. PMID:24956486

  4. Direct Photopatterning of Electrochromic Polymers

    Jensen, Jacob; Dyer, Aubrey L.; Shen, D. Eric


    Propylenedioxythiophene (ProDOT) polymers are synthesized using an oxidative polymerization route that results in methacrylate substituted poly(ProDOTs) having a Mn of 10–20 kDa wherein the methacrylate functionality constitutes from 6 to 60% of the total monomer units. Solutions of these polymers...... show excellent film forming abilities, with thin films prepared using both spray‐casting and spin‐coating. These polymers are demonstrated to crosslink upon UV irradiation at 350 nm, in the presence of an appropriate photoinitiator, to render the films insoluble to common organic solvents....... Electrochemical, spectroelectrochemical, and colorimetric analyses of the crosslinked polymer films are performed to establish that they retain the same electrochromic qualities as the parent polymers with no detriment to the observed properties. To demonstrate applicability for multi‐film processing...

  5. Polymer research by neutron scattering

    Richter, D.


    Polymer physics aims on an understanding of the macroscopic behavior of polymer systems on the basis of their molecular structure and dynamics. For this purpose neutrons serve as a unique probe, allowing a simultaneous investigation of polymer structure and dynamics on a molecular scale. Furthermore, hydrogen deuterium exchange facilitates molecular labeling and offers the possibility to observe selected chains or chain parts in dense systems. Neutron small angle scattering reveals information on the conformation and possible aggregation of polymer chains. Data on linear and star like molecules are shown as examples. High resolution neutron spin-echospectroscopy observes the molecular dynamics of long chain molecules. Results on the large scale motion of chins in polymer melts are presented. finally, experiments on chain relaxation close to the glass transition are displayed. Three distinctly different relaxation processes are revealed. (author)

  6. Polymer materials for fusion reactors

    Yamaoka, H.


    The radiation-resistant polymer materials have recently drawn much attention from the viewpoint of components for fusion reactors. These are mainly applied to electrical insulators, thermal insulators and structural supports of superconducting magnets in fusion reactors. The polymer materials used for these purposes are required to withstand the synergetic effects of high mechanical loads, cryogenic temperatures and intense nuclear radiation. The objective of this review is to summarize the anticipated performance of candidate materials including polymer composites for fusion magnets. The cryogenic properties and the radiation effects of polymer materials are separately reviewed, because there is only limited investigation on the above-mentioned synergetic effects. Additional information on advanced polymer materials for fusion reactors is also introduced with emphasis on recent developments. (orig.)

  7. Ion beam modification of polymers

    Sofield, C.J.; Sugden, S.; Ing, J.; Bridwell, L.B.; Wang, Y.Q.


    The implantation of polymers has received considerable attention in recent years, primarily to examine doping of conducting polymers and to increase the surface conductivity (by many orders of magnitude) of highly insulating polymers. The interest in these studies was partly motivated by possible applications to microelectronic device fabrication. More recently it has been observed that ion implantation can under some conditions lead to the formation of a hard (e.g. as hard as steel, ca. 3 MPa) and conducting surface layer. This paper will review the ion beam modification of polymers resulting from ion implantation with reference to fundamental ion-solid interactions. This leads us to examine whether or not implantation of polymers is a contradiction in terms. (Author)

  8. A microfluidic dialysis device for complex biological mixture SERS analysis

    Perozziello, Gerardo; Candeloro, Patrizio; Gentile, Francesco T.; Coluccio, Maria Laura; Tallerico, Marco; De Grazia, Antonio; Nicastri, Annalisa; Perri, Angela Mena; Parrotta, Elvira; Pardeo, Francesca; Catalano, Rossella; Cuda, Giovanni; Di Fabrizio, Enzo M.


    In this paper, we present a microfluidic device fabricated with a simple and inexpensive process allowing rapid filtering of peptides from a complex mixture. The polymer microfluidic device can be used for sample preparation in biological

  9. High-Temperature Shape Memory Polymers

    Yoonessi, Mitra; Weiss, Robert A.


    physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing

  10. Shape-tailored polymer colloids on the road to become structural motifs for hierarchically organized materials.

    Plüisch, Claudia Simone; Wittemann, Alexander


    Anisometric polymer colloids are likely to behave differently when compared with centrosymmetric particles. Their study may not only shine new light on the organization of matter; they may also serve as building units with specific symmetries and complexity to build new materials from them. Polymer colloids of well-defined complex geometries can be obtained by packing a limited number of spherical polymer particles into clusters with defined configurations. Such supracolloidal architectures can be fabricated at larger scales using narrowly dispersed emulsion droplets as templates. Assemblies built from at least two different types of particles as elementary building units open perspectives in selective targeting of colloids with specific properties, aiming for mesoscale building blocks with tailor-made morphologies and multifunctionality. Polymer colloids with defined geometries are also ideal to study shape-dependent properties such as the diffusion of complex particles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Polymers – A New Open Access Scientific Journal on Polymer Science

    Shu-Kun Lin


    Full Text Available Polymers is a new interdisciplinary, Open Access scientific journal on polymer science, published by Molecular Diversity Preservation International (MDPI. This journal welcomes manuscript submissions on polymer chemistry, macromolecular chemistry, polymer physics, polymer characterization and all related topics. Both synthetic polymers and natural polymers, including biopolymers, are considered. Manuscripts will be thoroughly peer-reviewed in a timely fashion, and papers will be published, if accepted, within 6 to 8 weeks after submission. [...

  12. EDITORIAL: Electroactive polymer materials

    Bar-Cohen, Yoseph; Kim, Kwang J.; Ryeol Choi, Hyouk; Madden, John D. W.


    Imitating nature's mechanisms offers enormous potential for the improvement of our lives and the tools we use. This field of the study and imitation of, and inspiration from, nature's methods, designs and processes is known as biomimetics. Artificial muscles, i.e. electroactive polymers (EAPs), are one of the emerging technologies enabling biomimetics. Polymers that can be stimulated to change shape or size have been known for many years. The activation mechanisms of such polymers include electrical, chemical, pneumatic, optical and magnetic. Electrical excitation is one of the most attractive stimulators able to produce elastic deformation in polymers. The convenience and practicality of electrical stimulation and the continual improvement in capabilities make EAP materials some of the most attractive among activatable polymers (Bar-Cohen Y (ed) 2004 Electroactive Polymer (EAP) Actuators as Artificial Muscles—Reality, Potential and Challenges 2nd edn, vol PM136 (Bellingham, WA: SPIE Press) pp 1-765). As polymers, EAP materials offer many appealing characteristics that include low weight, fracture tolerance and pliability. Furthermore, they can be configured into almost any conceivable shape and their properties can be tailored to suit a broad range of requirements. These capabilities and the significant change of shape or size under electrical stimulation while being able to endure many cycles of actuation are inspiring many potential possibilities for EAP materials among engineers and scientists in many different disciplines. Practitioners in biomimetics are particularly excited about these materials since they can be used to mimic the movements of animals and insects. Potentially, mechanisms actuated by EAPs will enable engineers to create devices previously imaginable only in science fiction. For many years EAP materials received relatively little attention due to their poor actuation capability and the small number of available materials. In the last fifteen

  13. Anomalous polymer collapse winding angle distributions

    Narros, A.; Owczarek, A. L.; Prellberg, T.


    In two dimensions polymer collapse has been shown to be complex with multiple low temperature states and multi-critical points. Recently, strong numerical evidence has been provided for a long-standing prediction of universal scaling of winding angle distributions, where simulations of interacting self-avoiding walks show that the winding angle distribution for N-step walks is compatible with the theoretical prediction of a Gaussian with a variance growing asymptotically as Clog N . Here we extend this work by considering interacting self-avoiding trails which are believed to be a model representative of some of the more complex behaviour. We provide robust evidence that, while the high temperature swollen state of this model has a winding angle distribution that is also Gaussian, this breaks down at the polymer collapse point and at low temperatures. Moreover, we provide some evidence that the distributions are well modelled by stretched/compressed exponentials, in contradistinction to the behaviour found in interacting self-avoiding walks. Dedicated to Professor Stu Whittington on the occasion of his 75th birthday.


    KALB, P.


    Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ((approx)$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

  15. Physical Properties of Polymers (Ultrastructure Processing of Polymers)


    vinyl benzene Network-Diluent Systems". 17. J . Appl. Polym. Sci. 28, 219-224 (1983) (with R. Vukovic and W.J. MacKnight) "Compatibility of Some...Temperature of Polymer Networks by Dil uents". 23. J . Appl. Polym. Sci. 28, 1379-1389 (1983) (with R. Vukovic , V. Kuresevic, N. Segudovic, and W.J...AFOSR 80-0101 IV. DATES: 1 January 1980 - 30 September 1982 V. SENIOR RESEARCH PERSONNEL*: Dr. C. Crosby Dr. G. ten Brinke Dr. T. Ellis Dr. R. Vukovic

  16. Conjugated polymer zwitterions and solar cells comprising conjugated polymer zwitterions

    Emrick, Todd; Russell, Thomas; Page, Zachariah; Liu, Yao


    A conjugated polymer zwitterion includes repeating units having structure (I), (II), or a combination thereof ##STR00001## wherein Ar is independently at each occurrence a divalent substituted or unsubstituted C3-30 arylene or heteroarylene group; L is independently at each occurrence a divalent C1-16 alkylene group, C6-30arylene or heteroarylene group, or alkylene oxide group; and R1 is independently at each occurrence a zwitterion. A polymer solar cell including the conjugated polymer zwitterion is also disclosed.

  17. Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

    Arya, Anil; Sharma, A. L.


    Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a

  18. Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

    Kilbinger, Andreas F M


    In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

  19. Temperature-induced phase separation and hydration in aqueous polymer solutions studied by NMR and IR spectroscopy: comparison of poly(N-vinylcaprolactam) and acrylamide-based polymers

    Spěváček, Jiří; Dybal, Jiří


    Roč. 336, č. 1 (2014), s. 39-46 ISSN 1022-1360. [International IUPAC Conference on Polymer-Solvent Complexes and Intercalates /9./ - POLYSOLVAT-9. Kiev, 11.09.2012-14.09.2012] R&D Projects: GA ČR GA202/09/1281 Institutional support: RVO:61389013 Keywords : aqueous polymer solutions * FT-IR * NMR Subject RIV: CD - Macromolecular Chemistry

  20. Protein Polymers and Amyloids

    Risør, Michael Wulff


    Several human disorders are caused by a common general disease mechanism arising from abnormal folding and aggregation of the underlying protein. These include the prevalent dementias like Alzheimer’s and Parkinson’s, where accumulation of protein fibrillar structures, known as amyloid fibrils......, is a general hallmark. They also include the α1-antitrypsin deficiency, where disease-causing mutations in the serine protease inhibitor, α1-antitrypsin (α1AT), leads to accumulation of the aberrant protein in the liver of these patients. The native metastable structure of α1AT constitutes a molecular trap...... that inhibits its target protease through a large conformational change but mutations compromise this function and cause premature structural collapse into hyperstable polymers. Understanding the conformational disorders at a molecular level is not only important for our general knowledge on protein folding...

  1. Sodium conducting polymer electrolytes

    Skaarup, S.; West, K. (eds.)


    This section deals with the aspects of ionic conduction in general as well as specific experimental results obtained for sodium systems. The conductivity as a function of temperature and oxygen/metal ratio are given for the systems NaI, NaCF/sub 3/SO/sub 3/ and NaClO/sub 4/ plus polyethylene oxide. Attempts have been made to produce mixed phase solid electrolytes analogous to the lithium systems that have worked well. These consist of mixtures of polymer and a solid electrolyte. The addition of both nasicon and sodium beta alumina unexpectedly decreases the ionic conductivity in contrast to the lithium systems. Addition of the nonconducting silica AEROSIL in order to increase the internal surface area has the effect of retarding the phase transition at 60 deg. C, but does not enhance the conductivity. (author) 23 refs.

  2. Conducting Polymer Based Nanobiosensors

    Chul Soon Park


    Full Text Available In recent years, conducting polymer (CP nanomaterials have been used in a variety of fields, such as in energy, environmental, and biomedical applications, owing to their outstanding chemical and physical properties compared to conventional metal materials. In particular, nanobiosensors based on CP nanomaterials exhibit excellent performance sensing target molecules. The performance of CP nanobiosensors varies based on their size, shape, conductivity, and morphology, among other characteristics. Therefore, in this review, we provide an overview of the techniques commonly used to fabricate novel CP nanomaterials and their biosensor applications, including aptasensors, field-effect transistor (FET biosensors, human sense mimicking biosensors, and immunoassays. We also discuss prospects for state-of-the-art nanobiosensors using CP nanomaterials by focusing on strategies to overcome the current limitations.

  3. Photorefractivity of triphenylamine polymers

    Tsujimura, S.; Kinashi, K.; Sakai, W.; Tsutsumi, N.


    We present here the enhanced photorefractive performance and dynamic holographic image of poly(4-diphenylamino)styrene (PDAS)-based photorefractive polymeric composites (PPCs). PDAS and FDCST were synthesized as a photoconductive polymer and a nonlinear optical (NLO) dye, respectively. PPC films including PDAS, TPA (or ECZ), FDCST, and PCBM were investigated. The photorefractive quantities of the PDAS-based PPCs were measured by a degenerate four-wave mixing (DFWM) technique. Additionally, the dynamic holographic images were recorded through an appropriate PDAS-based PPC. Those dynamic holographic images clearly duplicate the original motion with high-speed quality. The present approach provides a promising candidate for the future application of dynamic holographic displays.

  4. Self-healing polymers

    Klein, Daniel J. (Inventor)


    A three dimensional structure fabricated from a self-healing polymeric material, comprising poly(ester amides) obtained from ethylene glycol, azelaic acid and 1,1-aminoundecanoic acid, wherein polymeric material has a melt index above 2.5 g/10 min. as determined by ASTM D1238 at C. and 2.16kg, impact resistance and ductility sufficient to resist cracking and brittle fracture upon impact by a 9 mm bullet fired at a temperature of about C. at subsonic speed in a range from about 800 feet/sec to about 1000 feet/sec. It has been determined that the important factors necessary for self-healing behavior of polymers include sufficient impact strength, control of the degree of crystallinity, low melting point and the ability to instantly melt at impacted area.

  5. Cyborg cells: functionalisation of living cells with polymers and nanomaterials.

    Fakhrullin, Rawil F; Zamaleeva, Alsu I; Minullina, Renata T; Konnova, Svetlana A; Paunov, Vesselin N


    Living cells interfaced with a range of polyelectrolyte coatings, magnetic and noble metal nanoparticles, hard mineral shells and other complex nanomaterials can perform functions often completely different from their original specialisation. Such "cyborg cells" are already finding a range of novel applications in areas like whole cell biosensors, bioelectronics, toxicity microscreening, tissue engineering, cell implant protection and bioanalytical chemistry. In this tutorial review, we describe the development of novel methods for functionalisation of cells with polymers and nanoparticles and comment on future advances in this technology in the light of other literature approaches. We review recent studies on the cell viability and function upon direct deposition of nanoparticles, coating with polyelectrolytes, polymer assisted assembly of nanomaterials and hard shells on the cell surface. The cell toxicity issues are considered for many practical applications in terms of possible adverse effects of the deposited polymers, polyelectrolytes and nanoparticles on the cell surface.

  6. Semiflexible polymer conformation, distribution and migration in microcapillary flows

    Chelakkot, Raghunath; Gompper, Gerhard; Winkler, Roland G


    The flow behavior of a semiflexible polymer in microchannels is studied using multiparticle collision dynamics, a particle-based hydrodynamic simulation technique. Conformations, distributions, and radial cross-streamline migration are investigated for various bending rigidities, with persistence lengths L p in the range 0.5 ≤ L p /L r ≤ 30. The flow behavior is governed by the competition between a hydrodynamic lift force and steric repulsion from the wall, which lead to migration away from the wall, and a locally varying flow induced orientation, which drives the polymer away from the channel center and towards the wall. The different dependences of these effects on the polymer bending rigidity and the flow velocity results in a complex dynamical behavior. However, a generic effect is the appearance of a maximum in the monomer and the center-of-mass distributions, which occurs at the channel center for small flow velocities, but moves off-center at higher velocities.

  7. Development of Speciality polymer to extract uranium from sea water

    Tabushi, Iwao


    Polymer adsorbents were designed to extract uranium efficiently from sea water. The unique coordination structure of uranyl ion was suggested from x-ray crystallography and determining factors influencing equilibrium constants were elucidated. A quantitative estimation of the ligand efficiency was obtained. Based on these considerations on the coordination chemistry of uranyl ion, new polymer adsorbents were prepared and found to show excellent adsorption characteristics. The macrocyclic ligands mimicking crystallographic structure of the complex: planer headentate, were found to show large equilibrium constants as well as high selectivities toward metal ions. Direct usage of sea current was proposed as a most economical way of treating a huge amount of sea water. The polymer adsorbent could recover uranium with large adsorption rate just by immersing the resin into Kuroshio. (author)

  8. Electrochromic in conjugated polymers

    Picado Valenzuela, Alfredo


    This revision considered object the description of one of the materials with the greatest potential in the field of electrochromic (mainly in the visible region): the conjugated polymers (CP), area of enormous potential both now and in a short time ahead. The CP are insulating materials and organic semiconductors in a state not doped. They can be doped positively or negatively being observed a significant increase in the conductivity and being generated a color change in these materials. The understanding of how optical properties vary based on the chemical structure of the polymer or its mixtures and more precisely of the alternatives that can be entered into the conjugated system or π system to obtain a material that besides to be flexible, environmentally stable, presents the colored states. The revision was centred chiefly in the polypyrrole (Ppy), the polythiophene (PTh) and their derivatives such as poly (3.4-ethylenedioxythiophene) (PEDOT). The advantage of using monomers with variable structure, to adjust the composition of the copolymer, or to blend with the PC, allows to obtain a variety of colored states that can be modulated through the visible spectrum and even with applications to wavelengths outside of this region. Because the PC presented at least two different colored states can be varied continuously as a function of the voltage applied. In some cases, they may submit multicoloured statements, which offers a range of possibilities for their application in flexible electronic devices type screens and windows. Applications include smart windows, camouflage clothing and data screens. This type of material is emerging as one of the substitutes of the traditional inorganic semiconductor, with the advantage of its low cost, high flexibility and the possibility to generate multiple colors through the handling of the monomers in the structure and control of energy of his band gap. (author) [es

  9. Cationic polymers for DNA origami coating - examining their binding efficiency and tuning the enzymatic reaction rates.

    Kiviaho, Jenny K; Linko, Veikko; Ora, Ari; Tiainen, Tony; Järvihaavisto, Erika; Mikkilä, Joona; Tenhu, Heikki; Nonappa; Kostiainen, Mauri A


    DNA origamis are fully tailored, programmable, biocompatible and readily functionalizable nanostructures that provide an excellent foundation for the development of sophisticated drug-delivery systems. However, the DNA origami objects suffer from certain drawbacks such as low cell-transfection rates and low stability. A great deal of studies on polymer-based transfection agents, mainly focusing on polyplex formation and toxicity, exists. In this study, the electrostatic binding between a brick-like DNA origami and cationic block-copolymers was explored. The effect of the polymer structure on the binding was investigated and the toxicity of the polymer-origami complexes evaluated. The study shows that all of the analyzed polymers had a suitable binding efficiency irrespective of the block structure. It was also observed that the toxicity of polymer-origami complexes was insignificant at the biologically relevant concentration levels. Besides brick-like DNA origamis, tubular origami carriers equipped with enzymes were also coated with the polymers. By adjusting the amount of cationic polymers that cover the DNA structures, we showed that it is possible to control the enzyme kinetics of the complexes. This work gives a starting point for further development of biocompatible and effective polycation-based block copolymers that can be used in coating different DNA origami nanostructures for various bioapplications.

  10. EPR spin probe and spin label studies of some low molecular and polymer micelles

    Wasserman, A. M.; Kasaikin, V. A.; Timofeev, V. P.


    The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5-2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed.

  11. Monitoring of polymer melt processing

    Alig, Ingo; Steinhoff, Bernd; Lellinger, Dirk


    The paper reviews the state-of-the-art of in-line and on-line monitoring during polymer melt processing by compounding, extrusion and injection moulding. Different spectroscopic and scattering techniques as well as conductivity and viscosity measurements are reviewed and compared concerning their potential for different process applications. In addition to information on chemical composition and state of the process, the in situ detection of morphology, which is of specific interest for multiphase polymer systems such as polymer composites and polymer blends, is described in detail. For these systems, the product properties strongly depend on the phase or filler morphology created during processing. Examples for optical (UV/vis, NIR) and ultrasonic attenuation spectra recorded during extrusion are given, which were found to be sensitive to the chemical composition as well as to size and degree of dispersion of micro or nanofillers in the polymer matrix. By small-angle light scattering experiments, process-induced structures were detected in blends of incompatible polymers during compounding. Using conductivity measurements during extrusion, the influence of processing conditions on the electrical conductivity of polymer melts with conductive fillers (carbon black or carbon nanotubes) was monitored. (topical review)

  12. Spatial Rearrangement and Mobility Heterogeneity of an Anionic Lipid Monolayer Induced by the Anchoring of Cationic Semiflexible Polymer Chains

    Xiaozheng Duan


    Full Text Available We use Monte Carlo simulations to investigate the interactions between cationic semiflexible polymer chains and a model fluid lipid monolayer composed of charge-neutral phosphatidyl-choline (PC, tetravalent anionic phosphatidylinositol 4,5-bisphosphate (PIP2, and univalent anionic phosphatidylserine (PS lipids. In particular, we explore how chain rigidity and polymer concentration influence the spatial rearrangement and mobility heterogeneity of the monolayer under the conditions where the cationic polymers anchor on the monolayer. We find that the anchored cationic polymers only sequester the tetravalent PIP2 lipids at low polymer concentrations, where the interaction strength between the polymers and the monolayer exhibits a non-monotonic dependence on the degree of chain rigidity. Specifically, maximal anchoring occurs at low polymer concentrations, when the polymer chains have an intermediate degree of rigidity, for which the PIP2 clustering becomes most enhanced and the mobility of the polymer/PIP2 complexes becomes most reduced. On the other hand, at sufficiently high polymer concentrations, the anchoring strength decreases monotonically as the chains stiffen—a result that arises from the pronounced competitions among polymer chains. In this case, the flexible polymers can confine all PIP2 lipids and further sequester the univalent PS lipids, whereas the stiffer polymers tend to partially dissociate from the monolayer and only sequester smaller PIP2 clusters with greater mobilities. We further illustrate that the mobility gradient of the single PIP2 lipids in the sequestered clusters is sensitively modulated by the cooperative effects between anchored segments of the polymers with different rigidities. Our work thus demonstrates that the rigidity and concentration of anchored polymers are both important parameters for tuning the regulation of anionic lipids.

  13. Degradation of Polymers by Ultra-Violet Light

    Turner, D. T. [Camille Dreyfus Laboratory, Research Triangle Institute, Research Triangle Park, NC (United States)


    To reach an understanding of the complex processes which occur when polymers are degraded by ultra-violet light under service conditions it is first judicious to try to elucidate the photochemistry of relatively simple polymer reactions. For this reason, emphasis is given to studies in which purified polymers, in bulk, were exposed to monochromatic radiations in the absence of oxygen. In respect of product analysis, emphasis is given to methods for estimating quantum yields for fractures and crosslinks. Photochemical mechanisms are illustrated by discussion of polystyrene, polytethylene terephthalate) and cellulose. Special emphasis is given to the role of free radicals. Attention is drawn to reports that the course of photolysis may be changed by application of an external pressure of a chemically inert gas, such as nitrogen. The explanation suggested in the literature is that this depends on the ease of escape of hydrogen atoms which, alternatively, might react with trapped polymer radicals. The course of photolysis may also be affected by polymer radicals acting as strongly absorbing chromophores and consequently undergoing further chemical reaction. This is illustrated by reference to the conversion of allyl radicals to alkyl radicals in polyethylene and also by changes observed in the ESR spectrum of polymer radicals trapped in poly (ethylene terephthalate) as a result of exposure to light. It is suggested that this effect is primarily responsible for the evolution of hydrocarbon gases on photolysis of polyethylene or natural rubber. In contrast, radiolysis of these polymers yields almost pure hydrogen because, in this case, energy is absorbed by relatively non-selective processes, i.e. free radicals do not absorb high energy radiation much more strongly than does their polymeric environment. (author)

  14. Highly selective determination of methylmercury with methylmercury-imprinted polymers

    Liu Yongwen [Department of Chemistry, Shanxi Datong University, Datong 037009 (China)]. E-mail:; Zai Yunhui [School of Chemistry and Chemical Engineering of Lanzhou University, Lanzhou 730000 (China); Chang Xijun [School of Chemistry and Chemical Engineering of Lanzhou University, Lanzhou 730000 (China); Guo Yong [Department of Chemistry, Shanxi Datong University, Datong 037009 (China); Meng Shuangming [Department of Chemistry, Shanxi Datong University, Datong 037009 (China); Feng Feng [Department of Chemistry, Shanxi Datong University, Datong 037009 (China)


    Methylmercury-imprinted and non-imprinted polymers were prepared by formation monomer complex of methylmercury with (4-ethenylphenyl)-4-formate-6-phenyl-2,2'-bipyridine and thermally polymerizing with divinylbenzene (crosslinker) in the presence of 2,2'-azobisisobutyronitrile as initiator and subsequently leached with the acidic thiourea solution (1.0 mol L{sup -1} of thiourea and 4.0 mol L{sup -1} of HCl). In the same way, non-imprinted copolymers were prepared without methylmercury chloride added. The separation and preconcentration characteristics of the polymers for methylmercury were investigated by batch and column procedures. The results demonstrated that the methylmercury-imprinted polymers had higher adsorption capacity (170 {mu}mol g{sup -1} of dry microbeads) and good selectivity for methylmercury compared to non-imprinted polymers. The distribution ratio (D) values of the methylmercury-imprinted polymers increased for methylmercury with respect to both D values of Hg(II), Cu(II), Zn(II), Cd(II) and non-imprinted polymers. The relatively selective factor ({alpha} {sub r}) values of CH{sub 3}Hg{sup +}/Hg(II), CH{sub 3}Hg{sup +}/Cu(II), CH{sub 3}Hg{sup +}/Zn(II), and CH{sub 3}Hg{sup +}/Cd(II) are 24.0, 46.7, 50.7, and 40.2, which are greater than 1. The methylmercury-imprinted polymers can be used at least twenty times with recoveries no less than 95%. Based on the packed columns with methylmercury-imprinted polymers, a highly selective solid-phase extraction (SPE) and preconcentration method for methylmercury was developed. The metal ion imprinted polymer solid-phase extraction (MIIP-SPE) preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 22 {mu}g L{sup -1}. The detection limit and quantification limit were 0.041 and 0.093 {mu}g L{sup -1} (3{sigma}) for cold vapor atomic absorption spectrometry (CVAAS). The relative standard deviation of the 10 replicate determinations was 3.5% for the

  15. Insight into the Broad Field of Polymer Nanocomposites: From Carbon Nanotubes to Clay Nanoplatelets, via Metal Nanoparticles

    Cristina Stefanescu


    Full Text Available Highly ordered polymer nanocomposites are complex materials that display a rich morphological behavior owing to variations in composition, structure, and properties on a nanometer length scale. Metal-polymer nanocomposite materials are becoming more popular for applications requiring low cost, high metal surface areas. Catalytic systems seem to be the most prevalent application for a wide range of metals used in polymer nanocomposites, particularly for metals like Pt, Ni, Co, and Au, with known catalytic activities. On the other hand, among the most frequently utilized techniques to prepare polymer/CNT and/or polymer/clay nanocomposites are approaches like melt mixing, solution casting, electrospinning and solid-state shear pulverization. Additionally, some of the current and potential applications of polymer/CNT and/or polymer/clay nanocomposites include photovoltaic devices, optical switches, electromagnetic interference (EMI shielding, aerospace and automotive materials, packaging, adhesives and coatings. This extensive review covers a broad range of articles, typically from high impact-factor journals, on most of the polymer-nanocomposites known to date: polymer/carbon nanotubes, polymer/metal nanospheres, and polymer/clay nanoplatelets composites. The various types of nanocomposites are described form the preparation stages to performance and applications. Comparisons of the various types of nanocomposites are conducted and conclusions are formulated.

  16. Thermoresponsive Polymers for Biomedical Applications

    Theoni K. Georgiou


    Full Text Available Thermoresponsive polymers are a class of “smart” materials that have the ability to respond to a change in temperature; a property that makes them useful materials in a wide range of applications and consequently attracts much scientific interest. This review focuses mainly on the studies published over the last 10 years on the synthesis and use of thermoresponsive polymers for biomedical applications including drug delivery, tissue engineering and gene delivery. A summary of the main applications is given following the different studies on thermoresponsive polymers which are categorized based on their 3-dimensional structure; hydrogels, interpenetrating networks, micelles, crosslinked micelles, polymersomes, films and particles.

  17. Physics of photorefraction in polymers

    West, Dave


    Photorefractive polymer composites are an unusually sensitive class of photopolymers. Physics of Photorefraction in Polymers describes our current understanding of the physical processes that produce a photorefractive effect in key composite materials. Topics as diverse as charge generation, dispersive charge transport, charge compensation and trapping, molecular diffusion, organic composite structure, and nonlinear optical wave coupling are all developed from a physical perspective. Emphasis is placed on explaining how these physical processes lead to observable properties of the polymers, and the authors discuss various applications, including holographic archiving.

  18. Multilayer Electroactive Polymer Composite Material

    Harrison, Joycelyn S. (Inventor); Holloway, Nancy M. (Inventor); Park, Cheol (Inventor); Draughon, Gregory K. (Inventor); Ounaies, Zoubeida (Inventor)


    An electroactive material comprises multiple layers of electroactive composite with each layer having unique dielectric, electrical and mechanical properties that define an electromechanical operation thereof when affected by an external stimulus. For example, each layer can be (i) a 2-phase composite made from a polymer with polarizable moieties and an effective amount of carbon nanotubes incorporated in the polymer for a predetermined electromechanical operation, or (ii) a 3-phase composite having the elements of the 2-phase composite and further including a third component of micro-sized to nano-sized particles of an electroactive ceramic incorporated in the polymer matrix.

  19. Polymer liquids fracture like solids

    Huang, Qian; Hassager, Ole


    While fracture in brittle solids has been studied for centuries until today, there are few studies on fracture in polymer liquids. Recent developments in experimental techniques, especially the combination of controlled filament stretching rheometry and high speed imaging, have opened new windows...... into the detailed study of fracture processes for polymer liquids. High speed imaging shows that polymer liquids fracture like solids with initiation and propagation of an edge fracture. However, remarkable features such as highly reproducible critical stress, independent appearance of multiple fractures...

  20. Bridging scales in polymer physics and processing

    Hütter, M.; Kröger, M.; Öttinger, H.C.; Schweizer, T.


    Understanding both the flow behavior of polymers during processing and the end-use properties offinished plastic products from a molecular picture of the constituent polymers has been a long-standing dreamin polymer engineering and science. It is the goal of our work in the Polymer Physics Group to

  1. Statistical thermodynamics of equilibrium polymers at interfaces

    Gucht, van der J.; Besseling, N.A.M.


    The behavior of a solution of equilibrium polymers (or living polymers) at an interface is studied, using a Bethe-Guggenheim lattice model for molecules with orientation dependent interactions. The density profile of polymers and the chain length distribution are calculated. For equilibrium polymers

  2. Performance limitations of polymer electrolytes based on ethylene oxide polymers

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger


    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

  3. Nonequilibrium thermodynamics of dilute polymer solutions in flow.

    Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M


    Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

  4. Lattice cluster theory for dense, thin polymer films.

    Freed, Karl F


    While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L - 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential "transport" constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.

  5. Lattice cluster theory for dense, thin polymer films

    Freed, Karl F.


    While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L − 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential “transport” constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends

  6. Nano-Star-Shaped Polymers for Drug Delivery Applications.

    Yang, Da-Peng; Oo, Ma Nwe Nwe Linn; Deen, Gulam Roshan; Li, Zibiao; Loh, Xian Jun


    With the advancement of polymer engineering, complex star-shaped polymer architectures can be synthesized with ease, bringing about a host of unique properties and applications. The polymer arms can be functionalized with different chemical groups to fine-tune the response behavior or be endowed with targeting ligands or stimuli responsive moieties to control its physicochemical behavior and self-organization in solution. Rheological properties of these solutions can be modulated, which also facilitates the control of the diffusion of the drug from these star-based nanocarriers. However, these star-shaped polymers designed for drug delivery are still in a very early stage of development. Due to the sheer diversity of macromolecules that can take on the star architectures and the various combinations of functional groups that can be cross-linked together, there remain many structure-property relationships which have yet to be fully established. This review aims to provide an introductory perspective on the basic synthetic methods of star-shaped polymers, the properties which can be controlled by the unique architecture, and also recent advances in drug delivery applications related to these star candidates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Interpolymer reactions of nonionic polymers with polyacrylic acid in aqueous solutions

    E. Shaikhutdinov


    Full Text Available Results of fundamental investigations in the intermacromolecular reactions and interpolymer complexes to be performed by authors with co-workes within last 20 years have been intergrated and summarized in the present review. The raw of fundamental regularities in the effect of factors of different nature (pH, ionic strength, temperature, hydrophilic-hydrophobic balance of macrochain, etc. on the complexation of nonionic polymers with polycarboxylic acids in aqueous solutions has been revealed. Critical pH upon complexation (pHcrit. has been used for evaluation of the complexing ability of the polymers. It was shown tha tdepending on pHcrit. all systems can be divided into 2 groups, namely, weak complexing and strongly complexing. The existence of two critical pH upon complexation responsible for formation typical interpolymer complexes and hydrophilic associations has been demonstrated by the method of luminescence spectroscopy.

  8. Soft condensed matter: Polymers, complex fluids, and biomaterials

    Schaefer, D.


    Historians often characterize epochs through their dominant materials, clay, bronze, iron, and steel. From this perspective, the modern era is certainly the age of plastics. The progression from hard to soft materials suggests that the emerging era will be the age of open-quotes soft condensed matter.close quotes

  9. Preparation and characterization of PAN–KI complexed gel polymer

    The structural, miscibility and the chemical rapport between PAN and KI are investigated using X-ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry methods. The conductivity is enhanced with the increase in KI concentration and temperature. The maximum conductivity at 30 ∘ C is ...

  10. Transition Metal Complex/Polymer Systems as Optical Limiting Materials


    set of Ru and Os compounds at 800 nm wavelength using a z-scan method. Extinction coefficients for the compounds at 800 nm are also shown...visioned. It lts have bee escribing th ency 2DIR oiety and c E4C shows nds on the e succinimid function of on the gra rgy transpor s provide a fer

  11. Polymer and Polymer Gel of Liquid Crystalline Semiconductors

    Teppei Shimakawa; Naoki Yoshimoto; Jun-ichi Hanna


    It prepared a polymer and polymer gel of a liquid crystalline (LC) semiconductor having a 2-phenylnaphthalene moiety and studied their charge carrier transport properties by the time-of-flight technique. It is found that polyacrylate having the mesogenic core moiety of 2-phenylnaphtalene (PNP-acrylate) exhibited a comparable mobility of 10-4cm2/Vs in smectic A phase to those in smectic A (SmA) phase of small molecular liquid crystals with the same core moiety, e.g., 6-(4'-octylphenyl)- 2-dodecyloxynaphthalene (8-PNP-O12), and an enhanced mobility up to 10-3cm2/Vs in the LC-glassy phase at room temperature, when mixed with a small amount of 8-PNP-O12. On the other hand, the polymer gel consisting of 20 wt %-hexamethylenediacrylate (HDA)-based cross-linked polymer and 8-PNP-O12 exhibited no degraded mobility when cross-linked at the mesophase. These results indicate that the polymer and polymer composite of liquid crystalline semiconductors provide us with an easy way to realize a quality organic semiconductor thin film for the immediate device applications.

  12. New developments in thermally stable polymers

    Hergenrother, Paul M.


    Advances in high-temperature polymers since 1985 are discussed with the emphasis on the chemistry. High-temperature polymers refer to materials that exhibit glass-transition temperatures greater than 200 C and have the chemical structure expected to provide high thermooxidative stability. Specific polymers or series of polymers were selected to show how the chemical structure influences certain properties. Poly(arylene ethers) and polyimides are the two principal families of polymers discussed. Recent work on poly(arylene ethers) has concentrated on incorporating heterocyclic units within the polymer backbone. Recent polyimide work has centered on the synthesis of new polymers from novel monomers, several containing the trifluoromethyl group strategically located on the molecule. Various members in each of these polymer families display a unique combination of properties, heretofore unattainable. Other families of polymers are also briefly discussed with a polymer from an AB maleimidobenzocyclobutene exhibiting an especially attractive combination of properties.

  13. Vinyl Flanked Difluorobenzothiadiazole-Dithiophene Conjugated Polymer for High Performance Organic Field-Effect Transistors.

    Liang, Xianfeng; Sun, Wandong; Chen, Yanlin; Tan, Luxi; Cai, Zheng-Xu; Liu, Zitong; Wang, Lin; Li, Jing; Chen, Wei; Dong, Lichun


    Fluorine containing conjugated polymers have been widely applied in high performance organic solar cells, but their use in field-effect transistors is still quite limited. In this work, a conjugated polymer PTFBTV based on difluorobenzothiadiazole (DFBT) and dithiophene was synthesized, utilizing multiple vinylene as linkers. The polymer exhibits a relatively high hole mobility up to 2.0 cm(2) V-1 s(-1) compared with the reported DFBT-oligothiophene based polymers, yet its structural complexity is much simpler. The polymer thin film exhibits a typical 'face on' molecular orientation. A single crystal of its monomer revealed a non-covalent intramolecular contact between fluorine and the neighbouring proton, which strengthens the backbone co-planarity. Meanwhile an intermolecular F...F contact was also observed, which might cause rather scattered lamellar crystallinity for PTFBTV in the solid state.

  14. Structural, vibrational and electrical characterization of PVA-NH4Br polymer electrolyte system

    Hema, M.; Selvasekerapandian, S.; Sakunthala, A.; Arunkumar, D.; Nithya, H.


    Polymer electrolyte based on PVA doped with different concentrations of NH 4 Br has been prepared by solution casting technique. The complexation of the prepared polymer electrolytes has been studied using X-ray diffraction (XRD) and Fourier transform infra red (FTIR) spectroscopy. The maximum ionic conductivity (5.7x10 -4 S cm -1 ) has been obtained for 25 mol% NH 4 Br-doped PVA polymer electrolyte. The temperature dependence of ionic conductivity of the prepared polymer electrolytes obeys Arrhenius law. The ionic transference number of mobile ions has been estimated by dc polarization method and the results reveal that the conducting species are predominantly ions. The dielectric behavior of the polymer electrolytes has been analyzed using dielectric permittivity and electric modulus spectra

  15. Analysis of polymer grafted inside the porous hydrogel using confocal laser scanning microscopy


    Full Text Available Graft polymerization of glycidyl methacrylate onto the pore surface of polyacrylamide macroporous gel was implemented in DMSO-aqueous solution using diperiodatocuprate(III complexes as an initiator. The grafting densities up to 410% were achieved. The graft polymerization was confirmed by gravimetrical methods and FTIR. The graft polymerization of polymer inside the pores of the macroporous gel resulted in increased flow resistance through the gel matrix. The distribution of grafted polymer on the gel pore surface material was studied by scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM. CLSM is an alternative method for studying morphology of gel surface with grafted polymer having the advantages over the SEM allowing to investigate the distribution of grafted polymer inside the hydrogel in a native hydrated state. The microscopic techniques demonstrated uneven distribution of the grafted polymer inside the gel pores as a result of initiating the graft polymerization by insoluble initiator deposited on the pore surface.

  16. Selective removal of heavy metal ions by disulfide linked polymer networks

    Ko, Dongah; Sung Lee, Joo; Patel, Hasmukh A.


    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has...... a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal...... sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions―copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water....

  17. Thermal degradation of biocidal organic N-halamines and N-halamine polymers

    Chylińska, Marta; Kaczmarek, Halina, E-mail:


    Highlights: • Novel biocidal N-halamines have been substituted to poly(p-methyl styrene). • Thermal stability of all obtained compounds has been studied by thermogravimetry. • Stabilization of selected polymer has been achieved using octyl tin mercaptide. • The mechanism of thermal degradation of N-halamine polymers has been proposed. - Abstract: Novel biocidal organic N-halamines (based on imidazoline dione rings) were used as a substituents for poly(p-methyl styrene). The biocidal polymers and substituents have been investigated using thermogravimetric analysis. The thermal resistance of investigated compounds was compared to those of non-halogenated precursors. The introduction of chlorine atoms to polymers decreases their thermal resistance comparing to precursors but efficient stabilization is possible by using octyl tin mercaptide. The complex mechanism of thermal decomposition of polymers has been discussed.

  18. Recent advances in photorefractive polymers

    Thomas, Jayan; Christenson, C. W.; Lynn, B.; Blanche, P.-A.; Voorakaranam, R.; Norwood, R. A.; Yamamoto, M.; Peyghambarian, N.


    Photorefractive composites derived from conducting polymers offer the advantage of dynamically recording holograms without the need for processing of any kind. Thus, they are the material of choice for many cutting edge applications, such as updatable three-dimensional (3D) displays and 3D telepresence. Using photorefractive polymers, 3D images or holograms can be seen with the unassisted eye and are very similar to how humans see the actual environment surrounding them. Absence of a large-area and dynamically updatable holographic recording medium has prevented realization of the concept. The development of a novel nonlinear optical chromophore doped photoconductive polymer composite as the recording medium for a refreshable holographic display is discussed. Further improvements in the polymer composites could bring applications in telemedicine, advertising, updatable 3D maps and entertainment.

  19. Layered plasma polymer composite membranes

    Babcock, Walter C.


    Layered plasma polymer composite fluid separation membranes are disclosed, which comprise alternating selective and permeable layers for a total of at least 2n layers, where n is .gtoreq.2 and is the number of selective layers.

  20. Polymer electronic devices and materials.

    Schubert, William Kent; Baca, Paul Martin; Dirk, Shawn M.; Anderson, G. Ronald; Wheeler, David Roger


    Polymer electronic devices and materials have vast potential for future microsystems and could have many advantages over conventional inorganic semiconductor based systems, including ease of manufacturing, cost, weight, flexibility, and the ability to integrate a wide variety of functions on a single platform. Starting materials and substrates are relatively inexpensive and amenable to mass manufacturing methods. This project attempted to plant the seeds for a new core competency in polymer electronics at Sandia National Laboratories. As part of this effort a wide variety of polymer components and devices, ranging from simple resistors to infrared sensitive devices, were fabricated and characterized. Ink jet printing capabilities were established. In addition to promising results on prototype devices the project highlighted the directions where future investments must be made to establish a viable polymer electronics competency.

  1. Culture experiments on conductive polymers

    Onoda, Mitsuyoshi


    Fibroblast L929 and myoblast C2C12 cells of the mouse connective tissue origin were sown on the surface of conductive polymer films (polypyrrole, PPy and poly(3,4-ethylenedioxythiophene), PEDOT) in the cell culture medium, and the proliferative process of these cells was observed. Without changing the form, fibroblast L929 and myoblast C2C12 cells were observed to proliferate almost similarly to the cell which cultured on a dish on the market and to maintain compatibility. In other word, it has been understood these two kinds of conductive polymers used in this study, the PEDOT films maintain the secretion function of the cell cultured on the surface of these polymers. Therefore, the PPy- and the PEDOT-coated electrode suggested the possibility usable as a nerve stimulation electrode with biocompatibility, because these polymers were effective to culture the cell.

  2. Finely divided, irradiated tetrafluorethylene polymers

    Brown, M.T.; Rodway, W.G.


    Dry non-sticky fine lubricant powders are made by γ-irradiation of unsintered coagulated dispersion grade tetrafluoroethylene polymers. These powders may also be dispersed in an organic medium for lubricating purposes

  3. Conducting Polymer 3D Microelectrodes

    Jenny Emnéus


    Full Text Available Conducting polymer 3D microelectrodes have been fabricated for possible future neurological applications. A combination of micro-fabrication techniques and chemical polymerization methods has been used to create pillar electrodes in polyaniline and polypyrrole. The thin polymer films obtained showed uniformity and good adhesion to both horizontal and vertical surfaces. Electrodes in combination with metal/conducting polymer materials have been characterized by cyclic voltammetry and the presence of the conducting polymer film has shown to increase the electrochemical activity when compared with electrodes coated with only metal. An electrochemical characterization of gold/polypyrrole electrodes showed exceptional electrochemical behavior and activity. PC12 cells were finally cultured on the investigated materials as a preliminary biocompatibility assessment. These results show that the described electrodes are possibly suitable for future in-vitro neurological measurements.

  4. NMR Studies of Polymer Nanocomposites

    Greenbaum, Steve


    ... of their kind ever published. Standard ambient pressure results for lithium ion conducting polymer electrolytes containing nanoscopic silica are included, as well as the description of a novel scheme to produce highly conducting...

  5. Polyphosphazine-based polymer materials

    Fox, Robert V.; Avci, Recep; Groenewold, Gary S.


    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  6. Water Soluble Polymers for Pharmaceutical Applications

    Veeran Gowda Kadajji; Guru V. Betageri


    Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers are available. In the present paper, only water soluble polymers are described. They have been explained in two categories (1) synthetic and (2) natural. Drug polymer conjugates, block copolymers, hydrogel...

  7. Comparison of acidic polymers for the removal of cobalt from water solutions by polymer assisted ultrafiltration

    Dambies, Laurent, E-mail: [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland); Jaworska, Agnieszka, E-mail: [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland); Zakrzewska-Trznadel, Grazyna; Sartowska, Bozena [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland)


    In this study, three sulfonated water-soluble polymers based on poly(vinyl alcohol) of different molecular weights (10,000, 50,000 and 100,000 Da) were prepared and tested against commercially available poly(acrylic acid) for the removal of cobalt using polymer assisted ultrafiltration. High rejection rates were obtained between pH 3 and 6 with sulfonated poly(vinyl alcohol) (PVA 10,000 and 50,000 Da) whereas poly(acrylic acid) (PAA) of similar molecular weights performed rather poorly in this pH range. Sulfonation improved significantly sorption capability of PVA. Sulfonated PVA 10,000 was the best complexing agent with rejection rate above 95% between pH 3 and 6. For unmodified PVA the rejection rate was only 30-45% at pH 6 and there was no rejection at pH 3 at all. PAA rejection rate was above 90% at pH 6 and only about 10% at pH 3. Large scale experiment in cross-flow, continuous apparatus conducted by using PVA-SO{sub 3}H 10,000 Da to remove {sup 60}Co radioisotope from water solutions showed excellent results demonstrating the potential of this polymer to purify acidic radioactive wastes containing cobalt radioisotopes.

  8. Coarse-grained simulation of polymer-filler blends

    Legters, Gregg; Kuppa, Vikram; Beaucage, Gregory; Univ of Dayton Collaboration; Univ of Cincinnati Collaboration

    The practical use of polymers often relies on additives that improve the property of the mixture. Examples of such complex blends include tires, pigments, blowing agents and other reactive additives in thermoplastics, and recycled polymers. Such systems usually exhibit a complex partitioning of the components. Most prior work has either focused on fine-grained details such as molecular modeling of chains at interfaces, or on coarse, heuristic, trial-and-error approaches to compounding (eg: tire industry). Thus, there is a significant gap in our understanding of how complex hierarchical structure (across several decades in length) develops in these multicomponent systems. This research employs dissipative particle thermodynamics in conjunction with a pseudo-thermodynamic parameter derived from scattering experiments to represent polymer-filler interactions. DPD simulations will probe how filler dispersion and hierarchical morphology develops in these complex blends, and are validated against experimental (scattering) data. The outcome of our approach is a practical solution to compounding issues, based on a mutually validating experimental and simulation methodology. Support from the NSF (CMMI-1636036/1635865) is gratefully acknowledged.

  9. Chelating water-soluble polymers for waste minimization

    Smith, B.; Cournoyer, M.; Duran, B.; Ford, D.; Gibson, R.; Lin, M.; Meck, A.; Robinson, P.; Robison, T.


    Within the DOE complex and in industry there is a tremendous need for advanced metal ion recovery and waste minimization techniques. This project sought to employ capabilities for ligand-design and separations chemistry in which one can develop and evaluate water- soluble chelating polymers for recovering actinides and toxic metals from various process streams. Focus of this work was (1) to develop and select a set of water-soluble polymers suitable for a selected waste stream and (2) demonstrate this technology in 2 areas: removal of (a) actinides and toxic RCRA metals from waste water and (b) recovery of Cu and other precious metals from industrial process streams including from solid catalysts and aqueous waste streams. The R ampersand D was done in 4 phases for each of the 2 target areas: polymer synthesis for scaleup, equipment assembly, process demonstration at a DOE or industrial site, and advanced ligand/polymer synthesis. The TA- 50 site at Los Alamos was thought to be appropriate due to logistics and to its being representative of similar problems throughout the DOE complex

  10. Optical response of heterogeneous polymer layers containing silver nanostructures

    Miriam Carlberg


    Full Text Available This work is focused on the study of the optical properties of silver nanostructures embedded in a polymer host matrix. The introduction of silver nanostructures in polymer thin films is assumed to result in layers having adaptable optical properties. Thin film layers with inclusions of differently shaped nanoparticles, such as nanospheres and nanoprisms, and of different sizes, are optically characterized. The nanoparticles are produced by a simple chemical synthesis at room temperature in water. The plasmonic resonance peaks of the different colloidal solutions range from 390 to 1300 nm. The non-absorbing, transparent polymer matrix poly(vinylpyrrolidone (PVP was chosen because of its suitable optical and chemical properties. The optical studies of the layers include spectrophotometry and spectroscopic ellipsometry measurements, which provide information about the reflection, transmission, absorption of the material as well as the complex optical indices, n and k. Finite difference time domain simulations of nanoparticles in thin film layers allow the visualization of the nanoparticle interactions or the electric field enhancement on and around the nanoparticles to complete the optical characterization. A simple analysis method is proposed to obtain the complex refractive index of nanospheres and nanoprisms in a polymer matrix.

  11. Ring closure in actin polymers

    Sinha, Supurna, E-mail: [Raman Research Institute, Bangalore 560080 (India); Chattopadhyay, Sebanti [Doon University, Dehradun 248001 (India)


    We present an analysis for the ring closure probability of semiflexible polymers within the pure bend Worm Like Chain (WLC) model. The ring closure probability predicted from our analysis can be tested against fluorescent actin cyclization experiments. We also discuss the effect of ring closure on bend angle fluctuations in actin polymers. - Highlights: • Ring closure of biopolymers. • Worm like chain model. • Predictions for experiments.

  12. Stochastic Models of Polymer Systems


    Distribution Unlimited Final Report: Stochastic Models of Polymer Systems The views, opinions and/or findings contained in this report are those of the...ADDRESS. Princeton University PO Box 0036 87 Prospect Avenue - 2nd floor Princeton, NJ 08544 -2020 14-Mar-2014 ABSTRACT Number of Papers published in...peer-reviewed journals: Number of Papers published in non peer-reviewed journals: Final Report: Stochastic Models of Polymer Systems Report Title

  13. High cation transport polymer electrolyte

    Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL; Klingler, Robert J [Westmont, IL


    A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

  14. Radiation processing of natural polymer

    Khairul Zaman; Kamaruddin Hashim; Zulkafli Ghazali; Mohd Hilmi Mahmood; Jamaliah Sharif


    Radiation processing of natural polymer has been the subject of interest of countries in this region in the past 5 ∼ 7 years. Although some of the output of the research have been commercialized in particular for the applications in the agriculture and healthcare sectors, the potential applications of radiation processing of natural polymers in the medical sector are yet to be fully understood and developed. (author)

  15. Nanoporous polymer liquid core waveguides

    Gopalakrishnan, Nimi; Christiansen, Mads Brøkner; Ndoni, Sokol


    We demonstrate liquid core waveguides defined by UV to enable selective water infiltration in nanoporous polymers, creating an effective refractive index shift Δn=0.13. The mode confinement and propagation loss in these waveguides are presented.......We demonstrate liquid core waveguides defined by UV to enable selective water infiltration in nanoporous polymers, creating an effective refractive index shift Δn=0.13. The mode confinement and propagation loss in these waveguides are presented....

  16. Graphene-Based Polymer Nanocomposites


    polymerize in-situ around the fillers or even graft to them [71], thus it overcomes the problem of dramatically increased viscosity of the polymer...filler dispersion, increased polymer viscosity during processing and filler damage due to thermal degradation or strong shear forces [3, 82]. At...123, 124]. Figure 1.12 (a) SEM image of the fracture surface of GO/PVA nanocomposite film [85]. (b) TEM image of a clay reinforced Nylon-6

  17. (II) complexes

    activities of Schiff base tin (II) complexes. Neelofar1 ... Conclusion: All synthesized Schiff bases and their Tin (II) complexes showed high antimicrobial and ...... Singh HL. Synthesis and characterization of tin (II) complexes of fluorinated Schiff bases derived from amino acids. Spectrochim Acta Part A: Molec Biomolec.

  18. Polymer Brushes: Synthesis, Characterization, Applications

    Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen


    Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

  19. Osmotic load from glucose polymers.

    Koo, W W; Poh, D; Leong, M; Tam, Y K; Succop, P; Checkland, E G


    Glucose polymer is a carbohydrate source with variable chain lengths of glucose units which may result in variable osmolality. The osmolality of two commercial glucose polymers was measured in reconstituted powder infant formulas, and the change in osmolality of infant milk formulas at the same increases in energy density (67 kcal/dL to 81 and 97 kcal/dL) from the use of additional milk powder or glucose polymers was compared. All samples were prepared from powders (to nearest 0.1 mg), and osmolality was measured by freezing point depression. For both glucose polymers the within-batch variability of the measured osmolality was less than 3.5%, and between-batch variability of the measured osmolality was less than 9.6%. The measured osmolality varies linearly with energy density (p less than 0.001) and was highest in infant formula reconstituted from milk powder alone. However, there exist significant differences in the measured osmolality between different glucose polymer preparations. At high energy densities (greater than or equal to 97 kcal/dL), infant milk formulas prepared with milk powder alone or with the addition of certain glucose polymer preparation may have high osmolality (greater than or equal to 450 mosm/kg) and theoretically predispose the infant to complications of hyperosmotic feeds.

  20. UV-cured polymer optics

    Piñón, Victor; Santiago, Freddie; Vogelsberg, Ashten; Davenport, Amelia; Cramer, Neil


    Although many optical-quality glass materials are available for use in optical systems, the range of polymeric materials is limited. Polymeric materials have some advantages over glass when it comes to large-scale manufacturing and production. In smaller scale systems, they offer a reduction in weight when compared to glass counterparts. This is especially important when designing optical systems meant to be carried by hand. We aimed to expand the availability of polymeric materials by exploring both crown-like and flint-like polymers. In addition, rapid and facile production was also a goal. By using UV-cured thiolene-based polymers, we were able to produce optical materials within seconds. This enabled the rapid screening of a variety of polymers from which we down-selected to produce optical flats and lenses. We will discuss problems with production and mitigation strategies in using UV-cured polymers for optical components. Using UV-cured polymers present a different set of problems than traditional injection-molded polymers, and these issues are discussed in detail. Using these produced optics, we integrated them into a modified direct view optical system, with the end goal being the development of drop-in replacements for glass components. This optical production strategy shows promise for use in lab-scale systems, where low-cost methods and flexibility are of paramount importance.