The effect of polypyrrole-bound anthraquinonedisulphonate dianion on cathodic reduction of oxygen

Functionalized polypyrrole (PPy) films were prepared by incorporation of anthraquinonedisulphonate (AQDS) as doping anion during the electropolymerization of pyrrole (Py) monomer at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the PPy-bound AQDS modified electrode and cathodic reduction of oxygen on the resulting polymer film were studied. An obvious surface redox reaction corresponding to AQ/H₂AQ was observed and the dependence of this reaction on the solution pH was also illustrated. The electrocatalytic ability of the PPy-bound AQDS modified electrode was demonstrated by the electroreduction of oxygen at the optimized pH of 6.3 in a phosphate buffer. The reduced AQDS (H₂AQ) is responsible for the extraordinary catalytic activity to the oxygen reduction reaction. The PPy layers not only act as an electron mediator, but also facilitate the stability of the modified electrode. It was found that the catalytic reaction occurred in the presence of the bound AQDS and O₂ is in agreement with an electrochemical–chemical (EC) mechanism. The kinetic parameters of oxygen reduction were determined using Koutecky–Levich equation and Tafel polarization technique.     

Structural,mechanical, and antibacterial features of curcumin/polyurethane nanocomposites

Various types of bacteria inhabit many surfaces thus causing problems which can have very strong impact on human health. Here we present a study of photophysical, mechanical, and antibacterial properties of curcumin/polyurethane nanocomposites prepared by swell-encapsulation-shrink method. The prepared nanocomposites have been characterized for degree of swelling, surface morphology, mechanical properties, chemical contents, photoluminescence, hydrophobicity, potentials for singlet oxygen generation, and antibacterial activity. Dynamic mechanical analysis has shown slight changes of glass temperature of curcumin/polyurethane nanocomposites due to blue light irradiation. It was found that nanocomposites have very strong photoluminescence, become photoactive upon blue light irradiation at 470 nm and generate singlet oxygen. Conducted antibacterial tests have shown very strong activity of these nanocomposites especially toward Escherichia coli. These bacteria strains have been eliminated completely only after 1 h irradiation by blue light. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47283.     

Permeability of oxygen through polymers. I. A novel spectrophotochemical method

A novel method for the measurement of oxygen permeability through polymer membranes is described. It is based on monitoring the sensitized photo-oxygenation of a singlet oxygen acceptor in a detector layer sandwiched between a support and the polymer layer under test. The detector layer contains a sensitizer which on irradiation produces singlet excited oxygen from the ground-state oxygen available. The singlet oxygen reacts with an oxygen acceptor, the disappearance of which can be followed by spectrophotometry. In the photostationary state, changes in the acceptor absorbance are directly related to the overall flux of oxygen through the polymer membrane. It can be shown that the permeation coefficient P of oxygen is proportional to the rate of change in acceptor absorbance and to the inverse of the oxygen concentration in the surrounding atmosphere. It is given by the expression where ? is the molar extinction coefficient, ΔC is the difference in the oxygen concentration on the two sides of the polymer membrane, ΔD is the change in optical density during the time interval Δt, and l is the thickness of the polymer membrane. The method is comparatively simple and rapid and provides data for polymers that are difficult to study by more conventional methods. Oxygen permeabilities were measured for a group of water-soluble polymers.     

Formation and characterization of perfluorocyclobutyl polymer thin films

Perfluorocyclobutyl (PFCB) polymers are a new class of materials that show promise as selective layer materials in the development of composite membranes for gas separations, such as carbon dioxide/methane (α_{pure gas} = 38.6) and oxygen/nitrogen (α_{pure gas} = 4.8) separations. In many of the flat sheet applications, a thin film of the selective layer that is free of major defects must be coated onto a support membrane. A focus of this study was to elucidate the impacts of solvents, polymer concentration, and dip‐coating withdrawal speed on PFCB thin film thickness and uniformity. An extension was proposed to the Landau–Levich model to estimate the polymer film thickness. The results show that the extended model fits the thickness‐withdrawal speed data well above about 55 mm/min, but, at lower withdrawal speeds, the data deviated from the model. This deviation could be explained by the phenomenon of polymer surface excess. Static surface excesses of polymer solutions were estimated by applying the Gibbs adsorption equation using measured surface tension data. Prepared films were characterized by ellipsometry. Refractive index was found to increase with decreasing film thickness below about 50 nm, indicating densification of ultrathin films prepared from PFCB solutions below the overlap concentration. Atomic force microscopy was used to characterize surface morphologies. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymer–gold nanoparticle composite films for topical application: Evaluation of physical properties and antibacterial activity

The biocompatible polymer films show potential as an alternative to gels and patches used for topical delivery of therapeutics and cosmetics. The physical strength and antimicrobial activity of polymer films are important attributes for their topical applicability. Here, we have investigated the physical properties and antibacterial activity of six commonly used film forming polymers before and after formation of nanocomposites with gold nanoparticles (AuNP). The blank and AuNP loaded polymer films were prepared by solvent casting method and characterized for thickness, tensile strength, burst strength, skin adhesion strength, degree of swelling, and porosity. The antibacterial activity of the composite films was evaluated by zone‐of‐inhibition and spectrophotometric growth inhibition method against Staphylococcus aureus and Escherichia coli . The physical characterization showed that chitosan films casted using 1.5% w/w resulted in 76 MPa of tensile strength, while zein films required 40% w/w to show 23 MPa of tensile strength. The AuNP (250 μM; 35 nm) loaded polymer films showed significantly (p < 0.05) greater burst strength and skin adhesion strength compared with respective blank films. Among the polymers tested, only blank films of chitosan and zein showed antibacterial activity. On the other hand, all the AuNP loaded polymer films showed significantly (p < 0.05) greater antibacterial activity. The AuNP loaded chitosan film showed E. coli growth inhibition similar to tetracycline. Taken together, chitosan‐ and zein‐AuNP nanocomposite films showed better physical properties and antibacterial activity. POLYM. COMPOS., 38:2829–2840, 2017. © 2015 Society of Plastics Engineers     

Preparation of PVA/PAN bicomponent nanofiber via electrospinning and selective dissolution

Bicomponent polymer solutions were prepared from two immiscible polymers, poly(vinylalcohol) (PVA) and polyacrylonitrile (PAN), and then used to prepare films and electrospun fibers. The miscibility and the surface morphology of the bicomponent polymer systems were determined. There was a strong relationship between the diameter of the electrospun fibers and the blend ratio used. By applying selective dissolution, using solvents such as hot water, acetic acid, or N,N‐dimethylformamide, to the films and fibers, one polymer component was removed selectively without affecting the other component. This resulted in a decrease in the diameter of the electrospun fibers and the formation of grooves, pores, and craters on the fiber surface. The width of the grooves decreased as the bicomponent polymer content increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

Viscoelastic properties have been determined for poly(glycerol‐co‐glutaric acid) films synthesized from Lewis acid‐catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125°C to form polymer films. The polymers were evaluated for the extent of reaction before and after curing by Fourier transform infrared spectroscopy. They were subsequently immersed in dimethylsulfoxide, tetrahydrofuran, water, methanol, and hexane for 24 h. The amounts of solvent absorbed were monitored and recorded. Dependent up the solvent used, the polymers were able to absorb 9.5–261% of its weight. The effects of the solvent absorption on the viscoelastic properties of the polyester films were evaluated by determining their elastic modulus (G′), viscous modulus (G″), tan δG″/G′, and complex viscosity (η*) by performing oscillatory frequency sweep experiments. The elastic modulus (G′) and viscous modulus (G″) were both higher for the dry polymers than the solvent‐absorbed polymers. However, the polymer films were all higher in elastic (G′) character than viscous (G″) character. Therefore, tan δG″/G′ < 1 before and after immersion in solvents. Values for η* decreased with angular frequency for all of the polyesters tested in this study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrical properties of polymer films prepared from mixture of tetramethylsilane and oxygen by glow discharge polymerization

Summary The electrical properties of polymer films prepared from tetramethylsilane (TMS) and the mixture of TMS and oxygen by glow discharge polymerization were investigated in connection with the chemical structure of the polymers. The polymer films showed two different electrical properties which depended on the strength of electrical field. Under the electrical field of less than 10⁴ V/cm, the polymers showed ohmic behaviour, and their resistivity was approximately 10¹⁴ · cm being independent of the chemical structure of the polymers. Under the electrical field of above 10⁴ V/cm, non-ohmic behaviour was observed, and the current increased exponentially with increasing of the applied field. To explain this enhanced current the contribution of the Poole-Frenkel emission was assumed. The dielectric breakdown of the polymer films (1000–5000 angstroms) occured at the electrical field as high as 3 MV/cm. This indicates that these thin films may be deposited on substrates without pinhole.     

Synthesis and characterization of porous poly(methacrylic acid‐co‐triethylene glycol dimethacrylate) by seed emulsion polymerization

Porous poly(methacrylic acid‐co‐triethylene glycol dimethacrylate) (poly MAA‐co‐3G) particles in the size range of 10–40 μm were prepared via seed emulsion polymerization. Mixtures of linear polymer, solvent, and/or nonsolvent were used as inert diluents. The prepared porous polymer was converted using hydroxylamine hydrochloride and sodium methoxide into the corresponding poly(hydroxamic acid). The surface area of the porous copolymer particles was determined colorimetrically. The effect of the diluent type and concentration on the surface area of the prepared porous polymer was examined. The metal ion absorption capacity of the resin toward the different metal ions was examined using an atomic absorption spectrophotometer. The thermal stability of the polymers was examined by thermal gravimetric analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1209–1215, 2000     

Synthesis of polyblends from polypropylene and poly(R,S)‐β‐hydroxybutyrate,and their characterization

Blends of modified polypropylene (PP) with poly(R,S)‐β‐hydroxybutyrate (PHB) were prepared by casting polymer solutions, followed by compression molding into thin films. The modified polypropylene was obtained by oxidation with hydrogen peroxide. Oxidation of polypropylene produced new functional groups such as carbonyl and hydroxyl groups on the polymer chain, and a decrease in molecular weight and crystallinity of the polymers. Maximum crystallinity and mechanical properties of the polyblends were found with a PP/PHB ratio of 90/10 (w/w), and then decreased with increasing PHB content in the polyblends. Biodegradability of the polyblends was lower than that of bacterial and synthetic PHBs. Furthermore, an increase of PHB proportion in the polyblends resulted in highly non‐compatible polyblends. Hence only PHB and small parts of the polyblends were decomposed by microorganisms. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of novel benzhydrol-containing poly(amide-imide)s

A series of novel benzhydrol-containing poly(amide-imide)s (PAIs) have been prepared from a new diimide-dicarboxylic acid, N,N′-bis(4-hydroxycarbonyl)-benzhydrol-3,3′,4,4′-tetracarboxydiimide (BHTDA-DIA), with various diamines by direct polycondensation using triphenyl phosphite and pyridine as condensing agents. The polymers obtained had inherent viscosities of 0.35–0.96 dl g⁻¹. All these PAIs, except polymer PAI-2, were soluble in N-methyl-2-pyrrolidinone and N,N-dimethylacetamide containing LiCl (1 wt%). Tough and flexible PAI films could be obtained by casting PAIs from their DMAc or NMP solutions, except for polymer PAI-2. The polymer films had a tensile strength of 93–111 MPa, an elongation at break range of 4–6%, and an initial modulus range of 2.7–3.8 GPa. The glass transition temperatures of most polymers were found to be above 255 °C. These polymers were fairly stable up to a temperature around or above 400 °C, and lost 10% weight in the range 426–507 °C in nitrogen and 423–515 °C in air. © 1999 Society of Chemical Industry     

Influence of different types of acidic dopant on the electrodeposition and properties of polyaniline films

The effect of different types of acidic dopant namely, poly(vinyl sulfonic) (PVS), camphor sulfonic (CSA) and hydrochloric acids on the electrodeposition of polyaniline (PANI) films by cyclic voltammetry has been investigated and correlated with the morphology and properties of the polymers produced. The polymer films were studied by cyclic voltammetry, electron microscopy, u.v.–visible spectroscopy, X-ray diffraction and conductivity measurements. The nucleation step of the electrodeposition of PANI depends on the counter-ion of the dopant and significantly affects polymer growth as well as the morphology of the polymers produced. The properties of the polymeric films were also greatly influenced by the type of acid dopant used in the electrodeposition. Although all dopants used were protonic acids the conductivity of the polymer was affected by the counter-ion and could be enhanced by exposition to m-cresol due to secondary doping effects.     

Films of chitosan and N‐carboxymethylchitosan. Part II: effect of plasticizers on their physiochemical properties

Chitosan (Ch) and N‐carboxymethylchitosan (N‐CMCh) films were prepared by the casting method at concentrations of 1% and 2% of polymer, with or without plasticizer: polyethylene glycol (PEG‐400) and glycerol (G), at 15% (w/w). The influence of composition on mechanical properties, water vapour transmission rate (WVTR), water saturation, and aqueous dissolution of the films was analysed. The thermal stability of the mixture (polymer:plasticizer, 1:1) was evaluated by thermogravimetric analysis (TGA). In general, all the properties were affected by the plasticizers. The plasticized films showed lower strength and a higher percentage of elongation (%E), in the following order: G > PEG‐400 > unplasticized film. The total WVTR increased with Ch concentration, with a different WVTR profile for Ch and N‐CMCh. While the PEG‐400 addition did not significantly modify the WVTR profile of films, the glycerol enhanced the transport of water vapour through both polymers. The plasticizer addition increased the time of water film saturation, in the following order: G > PEG‐400 > unplasticized film; this was more pronounced in the N‐CMCh films, probably due to the formation of hydrogen bonds. The solubility of the films was also affected by their composition. Copyright © 2006 Society of Chemical Industry     

Preparation of siloxane-like films by glow discharge polymerization

Glow discharge polymerizations of tetramethoxysilane (TMOS), tetramethylsilane/oxygen mixture (½ molar ratio) (TMS/O₂), hexamethyldisiloxane (HMDSO), and tetramethyldisiloxane (TMDSO) were carried out for the preparation of thin, polymeric films with siloxane structures. The chemical composition of the formed polymers was examined by elemental analysis, infrared spectroscopy, and electron spectroscopy for chemical analysis (ESCA) in connection with polymerization conditions, especially, a level of the radiofrequency (rf) input power per mass of the monomers (W/FM value). The polymers prepared from HMDSO at fairly low W/FM values resembled in chemical composition the conventionally polymerized polydimethylsiloxane. The surface properties of the formed polymers also were evaluated by the measurement of surface energy.     

Breath figure templated semifluorinated block copolymers with tunable surface properties and binding capabilities

Patterning of functionalized polymeric surfaces enables the adjustment of their characteristics and use in novel applications. We prepared breath figure (BF) films from three semifluorinated diblock copolymers, which all are composed of a polystyrene block and a semifluorinated one to compare their surface properties. “Click” chemistry was employed to one of the polymers, containing a poly(pentafluorostyrene) block to incorporate hydrophilic sugar or carboxylic acid moieties. The structure of the polymer alters the obtained porous morphology of the films. Contact angle (CA) analyses of the BF films reveals that the surface porosity increases water CAs compared with solvent cast films, and, in the case of hydrophobic polymers, leads to significant increase in the CAs of dodecane. The hydrophobicity of the BF films is further amplified by the removal of the topmost layer which leads in some cases to superhydrophobic surfaces. BF films containing glucose units are hydrophilic exhibiting water CAs below 90°. These glycosylated porous surfaces are shown to bind lectin Con A‐FITC or can be labelled with isothiocyanate marker. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41225.     

Controlled dispersion of a porphyrin/fullerene donor‐acceptor complex in semiconducting polymer thin films: Intermolecular interactions of polymers with porphyrin and fullerene

Thin films composed of semiconducting polymers [poly(2‐vinyl naphthalene), poly(4‐diphenyl aminostyrene), poly(1‐vinyl pyrene), and poly(3‐hexyl thiophene‐2,5‐diyl)], zinc(II)?5,10,15,20‐tetra‐(2‐naphthyl)porphyrin, and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blends were prepared to investigate the controlled dispersion of porphyrin molecules in semiconducting polymer thin films. Tailoring the intermolecular interactions between the polymer/fullerene, polymer/porphyrin, and porphyrin/fullerene systems was found to be an effective method of controlling the dispersion. When the polymer/porphyrin interactions were enhanced, intermixed porphyrin/fullerene donor–acceptor complex domains were formed, whereas under conditions where the polymer/porphyrin interactions were weakened, the complex assembled at the borders between the polymer and fullerene phases. This concept could potentially be applied to various combinations of porphyrin/fullerene systems in semiconducting polymer thin films to develop polymer solar cells with excellent performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41629.     

Study of electrical properties of polymeric materials using electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy (EIS) has been used to determine the water absorption characteristics of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyaromatic amide (Aramid), and amine–quinone polyurethane (AQ) free-standing polymer films. A method for calculating percent moisture uptake is presented based on capacitance measurements via EIS, which requires initial or “dry” capacitance values, C₀. Three different methods for obtaining C₀ values were described and employed, but the most reliable values were obtained via EIS measurement using Hg contacts. C₀ values obtained by this method resulted in calculated water uptake values nearly identical to those obtained by measured weight gain. Lower capacitance values were observed for films immersed in distilled water compared to 0.1M NaCl, which indicates that water uptake is greater in NaCl than in pure water. The four polymers examined in this study can be listed in order of decreasing resistance to moisture absorption as AQ > PET > PEN > Aramid. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 553–560, 1998     

Evaluation of aminoquinoline‐imprinted polymers and the recognition mechanism

Three molecularly imprinted polymers P(2‐AQ), P(3‐AQ), and P(8‐AQ) based on methacrylic acid (MAA)–ethylene glycol dimethacrylate were prepared using isomers 2‐aminoquinoline (2‐AQ), 3‐aminoquinoline (3‐AQ), and 8‐aminoquinoline (8‐AQ) as template, respectively, by non‐covalent bulk polymerization technique. Neither P(3‐AQ) nor P(8‐AQ) exhibited imprinting effect for 3‐AQ or 8‐AQ, whereas P(2‐AQ) showed significant imprinting effect for 2‐AQ. This indicates that the position of amino group on the quinoline ring has crucial influence on imprinting effect. The recognition mechanism of P(2‐AQ) was investigated extensively by such methods as selective experiments, comparative study with 2‐aminopyridine‐imprinted polymer, and effect of different kinds of mobile phases. It is confirmed that there are complementary cavities in P(2‐AQ) both in size and in the arrangement of functional groups to 2‐AQ, and MAA binds 2‐AQ via cyclic hydrogen bond. Furthermore, the influence of synthetic conditions on 2‐AQ‐imprinted polymers was explored. We found 2‐AQ‐imprinted polymer synthesized in acetonitrile porogen showed higher imprinting effect for 2‐AQ than that prepared in chloroform. It is deduced that the morphology of the former might be more favorable to 2‐AQ binding, which is also supported indirectly by the fluorimetric experiments estimating the interaction of 2‐AQ with MAA in these two porogens. Additionally, 2‐AQ‐imprinted polymers prepared using two different amounts of acetonitrile exhibited very different imprinting effects, which suggested that porogen amount used in the imprinting process exerted significant influence. In addition to the in‐depth elucidation of the recognition mechanism of 2‐AQ‐imprinted polymer, this article provides the basis for the separation and enrichment of bioactive 2‐AQ. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterisation of flame retardant plasma polymer deposited BOPP film

Abstract

Flame retardancy of polypropylene films was studied by plasma polymerisation technique. The surface of BOPP film was modified by boron containing plasma polymers at different plasma conditions. Plasma polymer coated polypropylene films were examined by flame retardancy test (limiting oxygen index, LOI) and TGA. Boron containing plasma polymer deposition on the film surface showed an improvement of flame retardancy. Furthermore, TGA thermograms pointed out that the first degradation temperature of treated polypropylene film was increased from 331 to 396°C, and the second degradation temperature was shifted from 401 to 455°C. Also, the plasma polymers were characterised by FTIR spectroscopy and XPS. According to XPS results, the BOPP surfaces treated with TMB showed significant difference in the composition with respect to the untreated sample. The FTIR spectra of plasma polymers obtained indicated that when the treatment time was increased to 60 min with a constant discharge power at 80 W, the absorption intensities of all the functional groups increased. As a result, boron containing plasma polymer treatment was found to be an effective method in enhancing the flame retardancy of BOPP film.     

Protein adsorption materials based on conducting polymers: polypyrrole modified with ω‐(N‐pyrrolyl)‐octylthiol

In order to fabricate a new polymer matrix for application in biochips and to understand the mechanism of adsorption of proteins on conducting polymers, we prepared polypyrrole (PPy) functionalized with ω‐(N‐pyrrolyl)‐octylthiol moieties. The chemical structure of the polymer could be controlled by varying the concentration of pyrrole added as the monomer. Initially, ω‐(N‐pyrrolyl)‐octylthiol was self‐assembled into a monolayer on a gold surface. Thereafter, a layer of uniform and smooth PPy was obtained by the chemical copolymerization of pyrrole and the ω‐(N‐pyrrolyl)‐octylthiol. Bovine serum albumin (BSA) adsorption on the polymer was investigated using surface plasmon resonance spectroscopy and cyclic voltammograms. The chemical structure and monomer components of the as‐prepared films were characterized using Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Water contact angle measurements were used to assess the surface wettability of the films throughout the preparative procedure. The kinetics of BSA adsorption onto the polymer could be controlled by varying the copolymer thickness and the pH value of the buffer solutions used. Moreover, the electroactivity was changed upon BSA binding. The results suggest that the new conducting polymer may potentially be applied as a more sensitive and reliable matrix in protein sensors. Copyright © 2011 Society of Chemical Industry