The formation and properties of polypyrrole doped with an immobile antibiotic

Journal of Solid State Electrochemistry - Oxacillin, a semisynthetic penicillinase-resistant penicillin, was incorporated as a dopant within polypyrrole. The oxacillin-doped polymer was deposited...     

Surfactant-directed polypyrrole/CNT nanocables: synthesis, characterization, and enhanced electrical properties.

We describe here a new approach to the synthesis of size-controllable polypyrrole/carbon nanotube (CNT) nanocables by in situ chemical oxidative polymerization directed by the cationic surfactant cetyltrimethylammonium bromide (CTAB) or the nonionic surfactant polyethylene glycol mono-p-nonylphenyl ether (Opi-10). When carbon nanotubes are dispersed in a solution containing a certain concentration of CTAB or Opi-10, the surfactant molecules are adsorbed and arranged regularly on the CNT surfaces. On addition of pyrrole, some of the monomer is adsorbed at the surface of CNTs and/or wedged between the arranged CTAB or Opi-10 molecules. When ammonium persulfate (APS) is added, pyrrole is polymerized in situ at the surfaces of the CNTs (core layer) and ultimately forms the outer shell of the nanocables. Such polypyrrole/CNT nanocables show enhanced electrical properties; a negative temperature coefficient of resistance at 77-300 K and a negative magnetoresistance at 10-200 K were observed.     

Synthesis,core-shell structures and properties of fluorene/polypyrrole composite

In the current study, fluorene/polypyrrole composite with the core-shell structure has been synthesized by in situ oxidative polymerization of pyrrole in the presence of fluorene. Composite was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. Electrical performance of the composite prepared at various reaction conditions was tested. The composite has the best performance of electrical conductivity when FeCl₃–pyrrole molar ratio is equal to 3 and the reaction time is 18 h. It was found that polypyrrole could be formed on the surface of fluorene due to strong π–π interactions between the fluorene core and the polypyrrole shell.     

Latex and hollow particles of reactive polypyrrole: preparation, properties, and decoration by gold nanospheres

Polypyrrole-coated polystyrene latex particles bearing reactive N-amino functional groups (PS-PPyNH2) were prepared by the in-situ copolymerization of pyrrole (Py) and the active amino-functionalized pyrrole (PyNH2) in the presence of 1.33 microm-diameter polystyrene (PS) latex particles. These particles were prepared by dispersion polymerization of styrene using poly(N-vinylpyrrolidone), PNVP, as a steric stabilizer. The functionalized polypyrrole-coated PS particles (PS-PPyNH2) were characterized in terms of their particle size and surface morphology using transmission electron microscopy (TEM). Infrared and X-ray photoelectron spectroscopy (XPS) detected pyrrole-NH2 repeat units at the surface of the latex particles, indicating that this monomer had indeed copolymerized with pyrrole. The core-shell structure of the PS-PPyNH2 particles was confirmed by etching the polystyrene core in THF, leading to the formation of hollow conducting polymer capsules. The PS-PPyNH2 particles were then decorated with citrate-stabilized gold nanoparticles via electrostatic interactions. Furthermore, etching of the polystyrene core resulted in the formation of gold-decorated PPyNH2 hollow capsules.     

Complexing properties of cation-exchangers grafted with carboxyl moieties

The complexing properties of CM-52, Olvagel-COOH, MacroPrep 50 CM, and hypercrosslinked polystyrene MN (carboxyl-grafted sorbents) toward Cu²⁺, Co²⁺, Ni²⁺, Cd²⁺, Zn²⁺, Mn²⁺, and Pb²⁺ have been studied. The optimal parameters for the sorption of these metal ions from solution have been determined. The pH effect on the ion uptake has been studied. The uptake is maximal at pHs higher than 5–6. When pH is lower than 2, the indicated ions are quantitatively desorbed. Olvagel-COOH is most selective toward these ions.     

Preparation,properties and analytical application of silica with chemically grafted hydroxamic acid groups

The synthesis of silica chemically modified with propanohydroxamic acid groups and salicylhydroxamic acid is described. Sorption of 13 metal ions is studied as a function of pH. The composition of the sorbed complexes is determined and the apparent stability constants of the complexes in the sorbent phase are calculated. A correlation between the stabilities of the complexes in the sorbent phase and in aqueous solution is observed in some cases. Some analytical applications of the sorbents are demonstrated: trace amounts of elements can be concentrated from large volumes; molybdenum(VI) and zirconium(IV) can be separated from 10⁴-fold amounts of accompanying elements, and vanadium(V) can be determined in the sorbent phase by using diffuse reflection and photoacoustic spectrometric techniques.     

Covalently linked nanocomposites of polypyrrole with graphene: Strategic design toward optimized properties

Graphene‐based nanocomposites with conducting polymers have attracted increasing interest due to the enhanced synergistic properties, which can potentiate and broaden applications. In this context, covalent functionalization stands out as a strategic designing tool, which optimizes the interaction between the nanocomposites components. Herein, covalently linked polymeric nanocomposites were obtained between graphene derivatives and polypyrrole (Ppy) under mild routes (i.e., aqueous, room temperature). First, pyrrole was covalently functionalized on graphene oxide (GO) through stable amide bonds and further polymerization with FeCl₃ led to the polymeric nanocomposites. Finally, to improve conductivity, GO was reduced using NaBH₄. Similarly, analogous non‐covalent nanocomposites were obtained for comparison purposes. All samples were thoroughly characterized by thermogravimetric analysis, scanning electron microscopy, and infrared and Raman spectroscopy, confirming the targeted functionalization, polymerization, and reduction processes. Moreover, the covalent link effectively enhances the interaction of the nanocomposite's components as evidenced by its improved electrochemical stability (300 cycles), compared to the non‐covalent composites which loses conductivity in the initial stages. Indeed, Ppy is known for its low stability, limiting its applications. Overall, the results herein evidence that covalently linked nanocomposites can be successfully obtained with optimized electrochemical response, promising for applications as supercapacitors and artificial muscles. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 579–588     

Biofunctional properties of polyester fibers grafted with chitosan and collagen

Poly(ethylene terephthalate) (PET) fiber was treated with ⁶⁰Co-γ-ray and grafted with acrylic acid (AA). The resulting fibers were further grafted with chitosan (CS) via esterification. Afterward collagen (COL) was immobilized onto CS-grafting fibers. The antibacterial activity of CS against Staphylococus aureus, Escherichia coli, and Pseudomonas aeruginosa was preserved after COL-immobilization. After immobilizing COL, the L929 fibroblasts cell proliferation was promoted than CS-grafting PET fiber. The results indicate that by grafting with CS and immobilizing with COL, PET fibers exhibited both antibacterial activity against four pathological bacteria and improvement in the proliferation of fibroblast. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,thermal stability,heats of formation,and explosive properties of cyano-substituted di-, tri-, and tetraazidopyridines

A method of synthesis of 2,6-diazido-3,5-dicyanopyridine, 2,4,6-triazido-3,5-dicyanopyridine, and 2,3,4,5-tetraazido-6-cyanopyridine was developed. The heats of formation and explosive properties of compounds obtained were determined; kinetics and the composition of the gaseous thermolysis products were studied. The replacement of endocyclic nitrogen atoms by C-CN fragments in the aromatic ring of polyazides strongly reduces the explosive risk of these compounds with retention of the energetic properties of the molecules.     

Synthesis and properties of hydrophilic polymers, 6. Water-soluble polypyrrole graft copolymers with electrical conductivity

A novel method for the preparation of water-soluble polypyrrole graft copolymers with polyamines or polyimines is described. The polyreaction is performed in acidic solution by using chemical oxidants, e.g. iron(III) chloride or ammonium peroxodisulfate. The graft copolymers showed electrical semiconductivity in the undoped state which can be placed between the high conductivity of polypyrrole and the nonconductivity of the polyimine. Their thermal stability at 250°C is improved compared to polypyrrole. The novel graft copolymers are soluble in water over a wide pH range and have a good processability.     

Microstructure, distribution and properties of conductive polypyrrole/cellulose fiber composites

Highly intrinsic conductive polypyrrole/cellulose fiber composites (CF) were successfully prepared through in situ chemical oxidation polymerization simply by increasing fiber concentration at the same dosage of pyrrole, oxidant and dopant (based on the weight of dry fiber). FeCl₃ and anthraquinone-2-sulfonic acid sodium salt (AQSNa) were utilized as oxidant and dopant. As fiber concentration increased from 1 % (CF1) to 20 % (CF20), N and S content increased from 0.24 and 0.25 % to 1.24 and 0.89 %, and great increase in the retention of PPy and AQSNa was confirmed by elemental analysis. In addition, on the surface of conductive fiber, PPy of compact fibroid structure was detected instead of interconnected globular structure at higher fiber concentration. Furthermore, scanning transmission electron microscope and X-ray photoelectron spectroscopy (XPS)-depth profile analysis demonstrated denser and more uniformly distributed PPy inside fiber wall for CF20, while PPy tended to deposit on the surface of fiber for CF1. Fourier transform infrared spectroscopy, together with XPS certified that the PPy with longer conjugation length and higher doping level across the conductive fiber was obtained at higher fiber concentration. The doping level for CF10 decreased from 21.55 to 16.39 % with increasing fiber wall thickness, while that of CF20 decreased slightly from 30.73 to 24.10 %. The resulting CF20 showed lowest surface resistivity of 0.433 KΩ/square, as well as improved electro-conductivity stability. The incorporation of more PPy in CF improved the thermal stability.     

Synthesis,characterisation and transport properties of layered conducting electroactive polypyrrole membranes

A novel method for producing asymmetric membranes based on conducting polymers is described. Two layers of different polypyrrole films (PPy–p-toluene sulphonate and PPy–dodecyl sulphate) were electrodeposited onto an electrode to form a sandwich or layer structure. The films produced could be removed from the electrode and had sufficiently good mechanical properties to be used as free-standing membranes in simple transport experiments. Using electrochemically induced transport utilising technology described previously it was shown that a highly asymmetric membrane had been formed with a ratio of up to 35:1 in terms of the flux in one direction compared with another. This was for the transport of simple salts such as KCl and NaCl. In mixtures of these salts it was still possible to derive some reasonable selectivity between cations with selectivity of K⁺ over Na⁺ in ratios up to 4.5:1.     

特殊微形貌聚吡咯的合成及吸附性能

聚吡咯(PPy)是一种性能优异的导电高分子材料,近年来的研究热点集中于PPy及其复合材料在电化学方面的应用,而对于PPy复合材料的特殊微形貌以及吸附性能的关注较少。本文介绍了关于PPy微观形貌的合成方法,综述了采用硬模板和软模版法合成纤维状、管状、球状、多孔状和其他不同特殊微形貌的PPy及其复合材料,包括PPy/金属单质、PPy/金属氧化物、PPy/染料以及PPy/非金属单质等复合材料,并进一步分析了PPy及其复合材料不同形貌之间的差异,得出微形貌的差异可以影响材料性能的结论。简述了目前将PPy复合材料应用于吸附领域的报道,介绍了不同微形貌聚吡咯材料对于其吸附性能的影响,分析了特殊形貌PPy及其复合材料对染料、重金属展示出来的优良吸附性能,指出PPy复合材料在吸附领域的巨大应用前景与商业价值。     

Synthesis,characterization, and electrical properties of polypyrrole/multiwalled carbon nanotube composites

Size‐controllable polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites have been synthesized by in situ chemical oxidation polymerization directed by various concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB). Raman spectra, FTIR, SEM, and TEM were used to characterize their structure and morphology. These results showed that the composites are core (MWCNT)–shell (PPy) tubular structures with the thickness of the PPy layer in the range of 20–40 nm, depending on the concentration of CTAB. Raman and FTIR spectra of the composites are almost identical to those of PPy alone. The electrical conductivities of these composites are 1–2 orders of magnitude higher than those of PPy without MWCNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6449–6457, 2006     

Nanostructure and mechanical properties of polybutylacrylate filled with grafted silica particles

We investigate the nanostructure and the linear rheological properties of polybutylacrylate (PBA) filled with St?ber silica particles grafted with PBA chains. The silica volume fractions range from 1.8 to 4.7%. The nanostructure of these suspensions is investigated by small-angle neutron scattering (SANS), and we determine their spectromechanical behavior in the linear region. SANS measurements performed on low volume fraction composites show that the grafted silica particles are spherical, slightly polydisperse, and do not form aggregates during the synthesis process. These composites thus constitute model filled polymers. The rheological results show that introducing grafted silica particles in a polymer matrix results in the appearance of a secondary process at low frequency: for the lowest volume fractions, we observe a secondary relaxation that we attribute to the diffusion of the particles in the polymeric matrix. By increasing the silica volume fraction up to a critical value, we obtain gellike behavior at low frequency as well as the appearance of a structure factor on the scattering intensity curves obtained by SANS. Further increasing the silica particle concentration leads to composites exhibiting solidlike low-frequency behavior and to an enhanced structure peak on the SANS diagrams. This quantitative correlation between the progressive appearance of a solidlike rheological behavior, on one hand, and a structure factor, on the other hand, supports the idea that the viscoelastic behavior of filled polymers is governed by the spatial organization of the fillers in the matrix.     

Structural and electrical properties of doped polypyrrole and its composite with montmorillonite clay

Polypyrrole is synthesized and doped with Dodecylbenzenesulphonic acid. The doped Polypyrrole with Dodecylbenzenesulphonic acid is intercalated into the layers of Montmorillonite clay successfully by in situ polymerization. The structural properties of synthesized doped Polypyrrole and intercalated doped Polypyrrole were studied by XRD analysis. The crystallinity of intercalated doped Polypyrrole into the layers of Montmorillonite clay is confirmed by means of X-rays diffraction studies, which is more than the doped Polypyrrole. Enhanced d-spacing of Montmorillonite confirmed that doped Polypyrrole is interclated into the layers of Montmorillonite clay at nanoscale. The scanning electron micrographs also confirm the formation of dual phase of platelet as well as of flaky structure of intercalated doped Polypyrrole. Temperature dependant conductivity showed three dimensional variable ranges hopping model. Activation energy, density of states and hopping length are calculated and found to be influenced by intercalating Doped Polypyrole into the layers of Montmorillonite clay.     

Morphology,microhardness, and electrical properties of composites based on polypropylene,montmorillonite, and polypyrrole

The morphology, microhardness, and electrical properties of composites consisting of conductive polypyrrole (PPy) dispersed into a nonconductive polypropylene matrix (PP) as pure component or in form of a sodium montmorillonite/PPy (MMT/PPy) composite have been studied. For comparison, also PP/MMT composites were studied. All types of composites were processed by compression molding or by melt mixing followed by compression molding into plates, which were used for characterization. Scanning electron microscopy and transmission electron microscopy was used to examine the morphology of the prepared materials. The investigation of electrical and dielectric properties was done by dielectric relaxation spectroscopy in a wide frequency range and was related to the composite composition and processing method. The analysis of the conductivity as a function of temperature indicated that the charge transfer mechanism could be described by the variable range hopping model in three dimensions. The microhardness of PP/MMT/PPy composites with different content of MMT or PPy was determined and the creep rate has been estimated. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 407–423, 2009     

Wet foams: Formation,properties and mechanism of stability

Overall picture of phenomena occuring during formation and existence of the wet foams is presented. Properties and mechanism of stability are discussed on the example of the wet foams obtained from solutions of two homologous series of surface active substances; the fatty acids and n-alkanols. In general three physical processes which contribute to foam stability can be distinguished: drainage of liquid out of the foam, coalescence and/or rupture of bubbles, and disproportionation (which may be called Ostwald ripening or gas diffusion from one bubble to another). Dynamic and non-equilibrium character of the wet foams is stressed.Motion of a bubble through the solution causes disequilibration of the surface concentration alongside the bubble surface. The surface concentration on the upstream part of the bubble is much smaller than the equilibrium concentration. Thus, the bubbles arrive at the solution surface with non-equilibrium surface concentration, and these actual non-equilibrium surface coverages determine possibility of formation and properties of the foams.Solution content ϕ in the volume of wet foam is high (of an order 307.), while in top foam layer it is much smaller (ϕ≅5%) . It shows that rupture of the wet foam takes place practically only in the top layer of bubbles and durability of these top foam films determine stability and volume of the whole foam column. On the basis of measurements of liquid content ϕ and lifetimes of bubbles in the top foam layer it was estimated that thicknesses of rupture of these top films were of an order of a few micrometers. At such thicknesses the force of disjoining pressure do not attain yet any meaningful value.Influence of kinetics of adsorption, frequency of external disturbances, surface activity of the solute and lifetime of the foam films on magnitude of the surface elasticity forces induced in the systems studied is discussed. It is shown that stability of the wet foams can be explained in terms of the effective elasticity farces, i.e. the surface elasticity forces which are induced at an actual non-equilibrium surface coverage. There is agreement between the courses of the dependences of the foamability parameter (retention time, rt) and the effective elasticity forces as a function of the number n of carbon atoms in the fatty acid and n-alkanol molecule. This shows that the effective elasticity forces are decisive parameter in formation and stability of the wet foams. It also explains why the foamability of a substance with a stronger surface activity can be lower than that of a substance with a weaker surface activity. The foamability, especially under dynamic conditions, cannot simply be correlated with the surface activity.     

Plasma protein adsorption and thrombus formation on surface functionalized polypyrrole with and without electrical stimulation

A surface modification technique was developed in which heparin was covalently immobilized onto electrically conductive polypyrrole (PPY) film through poly(ethylene glycol) methacrylate (PEGMA) graft copolymerization and subsequent cyanuric chloride activation. In vitro plasma protein adsorption and thrombus formation experiments were carried out on the various films. The PEGMA-graft-copolymerized PPY surfaces with immobilized heparin have good bioactivity indicated by low level of protein adsorption, high ratio of albumin to fibrinogen adsorption, and low thrombus formation, making them potentially good candidates for biomedical applications. Since the PPY film retained significant electrical conductivity after surface modification, the effect of electrical stimulation on protein adsorption and thrombus formation was also evaluated. The covalently immobilized heparin on the PPY film was able to retain its bioactivity after 4 days of immersion in PBS. The film after long-term immersion in PBS also retained sufficient electrical conductivity for electrical stimulation still to be effective for reducing protein adsorption.