Surface graft polymerization of conducting polyaniline on waterborne poyurethane‐urea film and its phenol sensing

Waterborne polyurethane‐ureas (pristine WBPUs: WBPU‐19 and WBPU‐24, fixed soft segment content: 60 wt %) containing dimethylol propionic acid (DMPA)/ethylene diamine (EDA) contents (19/16.8 and 24/11.4 mol %) were prepared. The polyaniline (PANI)‐graft‐WBPU (PANI‐graft‐WBPU) films were prepared by oxidative graft polymerization of aniline on the surface layer of WBPU films. This study focused on the effects of reaction conditions (concentrations/treating times/temperatures of aniline and APS) and DMPA content on the %grafting, conductivity, and mechanical properties of PANI‐graft‐WBPU films. To obtain the maximum %grafting (PANI‐graft‐WBPU‐19: 6.2, and PANI‐graft‐WBPU‐24: 7.4) and conductivity (PANI‐graft‐WBPU‐19: 3.6 × 10^?2S/cm, and PANI‐graft‐WBPU‐24: 4.7 × 10^?2S/cm), the optimum concentrations/treating times/temperatures of aniline and APS, were found to be 0.35M/10 min/25°C and 0.2M/10 min/0°C, respectively. The tensile strength of film samples was found to be increased in the order of PANI‐graft‐WBPU‐19>pristine WBPU‐19>PANI‐graft‐WBPU‐24>pristine WBPU‐24. The PANI‐graft‐WBPU‐19 (%grafting: 6.2) films on exposure to 0–10,000 ppm phenol solutions showed a well‐defined response behavior, demonstrating high promise for application in aqueous phenol sensors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrochemical preparation of poly(N‐acetylaniline)/poly‐(4‐styrenesulfonic acid‐co‐maleic acid) composite film towards ascorbic acid sensing

Poly(N‐acetylaniline)/poly(4‐styrenesulfonic acid‐co‐maleic acid) (PNAANI/PSSMA) composite film was prepared by cyclic voltammetry (CV), and was characterized by FTIR and X‐ray photoelectron spectrum (XPS). The electroactivity of the composite film was high in neutral and basic solutions, and it had been used for amperometric determination of ascorbic acid (AA). Compared with pure PNAANI film, the catalytic activity of the composite film was much better. AA was detected amperometrically in sodium citrate buffer at a potential of 0.3 V (versus SCE). The response current was proportional to the concentration of ascorbic acid in the range of 4.7 × 10^?6 to 5.0 × 10^?5M and 5.0 × 10^?5 to 2.5 × 10^?3M, respectively, with the detection limit of 1.9 × 10^?6 mol L^?1 at a signal to noise ratio 3. In addition, the stability and reusability of the composite film were performed well, and it was satisfying to be used for determination of AA in real fruit juice samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and morphology of carboxylated polyether‐block‐polydimethylsiloxane and the supermolecule self‐assembled from it

In this research, hydroxyl‐terminated polyether‐block‐polydimethylsiloxane (PESO) was synthesized as an intermediate through the hydrosilylation of Si? H‐terminated polydimethylsiloxane with allyl polyoxyethylene polyoxypropylene ether. Then, carboxylated polyether‐block‐polydimethylsiloxane (CPES) was prepared through the reaction of maleic anhydride with PESO. First, the chemical structures of the synthesized polysiloxanes were characterized with IR and ¹H‐NMR spectroscopy, and then the film morphology of CPES and the supermolecule self‐assembled from CPES and N‐β‐aminoethyl‐γ‐aminopropyl polydimethylsiloxane (ASO‐1) was investigated by atomic force microscopy in detail. Experimental results indicated that the superpolysiloxane that self‐assembled from CPES and ASO‐1 showed a film morphology very different from those of CPES and ASO‐1. There were not only many small, bright dots but also some big and marvelous dots circled by dots on the film surface. The morphology of dots circled by dots was estimated to result from aggregates of CPES micelles adsorbed onto the curled ASO‐1 molecule interface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of block copolymers via metal‐free visible‐light‐induced ATRP for the detection of lead ions

Polyacrylamide‐b‐poly(methacrylic acid) was prepared on the surface of Au electrode (Au/PAM/PMAA) for Pb²⁺ ion electrochemical sensing via metal‐free visible‐light‐induced atom transfer radical polymerization, which was very simple, convenient, and environmentally friendly. Au/PAM/PMAA was carefully examined by cyclic voltammetry, electrochemical impedance spectroscopy, and X‐ray photoelectron spectroscopy. Further, Au/PAM/PMAA was successfully used for the determination of Pb²⁺ ion by differential pulse anodic stripping voltammetry. Under the optimal conditions, a linear response from 1.0 × 10^?11 to 1.0 × 10^?4 mol/L with detection limit of 2.5 × 10^?12 mol/L (S/N = 3) was achieved from the results of experiments. Comparing with similar Pb²⁺ sensors, the broader linear range and lower detection limit suggested the promising prospect of Au/PAM/PMAA. In a word, the work of this article had an important significance for the polymer‐modified electrodes and the sensitive detection of Pb²⁺. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45863.     

Development of an amperometric biosensor based on a redox‐mediator‐doped polypyrrole film

An amperometric biosensor was developed for the quantitative estimation of phenolic compounds in aqueous media. The enzyme tyrosinase [poly(phenol oxidase) (PPO)] was adsorbed onto a hexacyanoferrate(II)‐ion‐doped conducting polypyrrole (PPY) film deposited on an indium tin oxide (ITO) coated glass‐plate support. The PPO activity in the PPO/Fe²⁺‐PPY/ITO film was assayed as a function of the concentration of phenolic compounds. Cyclic voltammetric studies were carried out on this enzyme electrode, and the surface morphology of the enzyme‐immobilized polymer film was studied with scanning electron microscopy. The results of the amperometric response of the PPO/Fe²⁺‐PPY/ITO film showed sensitivities of 0.14, 0.21, and 0.36 A M^?1cm^?2 and linear response ranges of 9.9–84.7, 6.7–72.6, and 3.9–48.8 μM for phenol, catechol, and p‐chlorophenol, respectively. The PPO/Fe²⁺‐PPY/ITO electrode exhibited a response time of about 50 s and was stable for about 12 weeks at 4°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 927–933, 2004     

Facile synthesis of graphene/polypyrrole 3D composite for a high‐sensitivity non‐enzymatic dopamine detection

One kind of nanocomposite consisting of graphene and polypyrrole was synthesized via a facile and mild way with the assistant of microwave irradiation. The synthesis route was embedding the polypyrrole into the graphene flakes to form a 3D structure, to achieve larger active surface and higher electro‐catalysis property. Structures and components of the composite were measured by X‐ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared spectroscopy. A stronger electrochemical response of electrode with modified resultant was observed in the electrochemical test. Dopamine sensor based on the composite showed a sensitivity of 363 μA mM ^?1 cm^?2, a linear range of 1 × 10^?4 M to 1 × 10^?3 M , and a detection limit of 2.3 × 10^?6 M (S/N = 3). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44840.     

Enhanced Thermal and Mechanical Properties in Polyurethane/Au Nanocomposites

Summary: We have prepared waterborne polyurethane (WBPU) thin films containing gold nanoparticles by casting WBPU/Au solutions. The effect of the Au nanoparticle contents on the microstructure and properties of the composite films was investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), transmittance electron microscopy (TEM), FTIR spectroscopy (FTIR) and dynamic mechanical analysis (DMA). The Au nanoparticles initially in the WBPU solution were well dispersed in the WBPU films cast and dried at 60 °C. The thermostability and mechanical properties of the polymer increased with Au contents up to 4.35 × 10^?2 wt.‐%, which was believed to be a result of induced crystallization in the presence of Au nanoparticles. The Au/WBPU nanocomposite containing with 6.5 × 10^?2 wt.‐% of Au resulted in the aggregation of Au particles, which leads to a worsening of the thermal and mechanical properties.

TEM micrograph of nanocomposites filled with 4.35 × 10^?2 wt.‐% of Au nanoparticles.     

Highly stretchable,tough, and self‐recoverable and self‐healable dual physically crosslinked hydrogels with synergistic “soft and hard” networks

Strength, toughness and self‐recoverability are among the most important properties of hydrogels for tissue‐engineering applications. Yet, it remains a challenge to achieve these desired properties from the synthesis of a single‐polymer hydrogel. Here, we report our one‐pot, a monomer‐polymerization approach to addressing the challenge by creating dual physically crosslinked hybrid networks, in particular, synergistic “soft and hard” polyacrylic acid‐Fe³⁺ hydrogels (SHPAAc‐Fe³⁺). Favorable mechanical properties achieved from such SHPAAc‐Fe³⁺ hydrogels included high tensile strength (about 1.08 MPa), large elongation at break (about 38 times), excellent work of extension (about 19 MJ m^?3), and full self‐recoverability (100% recovery of initial properties within 15 min at 50°C and within 60 min in ambient conditions, respectively). In addition, the hydrogels exhibited good self‐healing capabilities at ambient conditions (about 40% tensile strength recovery without any external stimuli). This work demonstrates that dual physical crosslinking combining hydrophobic interaction and ionic association can be achieved in single‐polymer hydrogels with significantly improved mechanical performance but without sacrificing favorable properties. POLYM. ENG. SCI., 59:145–154, 2019. © 2018 Society of Plastics Engineers     

Affinity‐tuned peroxidase‐like activity of hydrogel‐supported Fe3O4 nanozyme through alteration of crosslinking concentration

In this work, we evaluated the effect of crosslinking concentration on the affinity of poly (2‐acrylamido‐2‐methyl‐1‐propansulfonic acid) (PAMPS) hydrogel‐supported Fe₃O₄ nanozyme towards substrates (tetramethylbenzidine (TMB) and H₂O₂). The peroxidase‐like catalytic activity of PAMPS/Fe₃O₄ nanozyme was discussed with respect to crosslinking concentration of PAMPS hydrogel for the oxidation of TMB in the presence of H₂O₂ at room temperature. High catalytic activity was achieved due to good dispersion of Fe₃O₄ nanozyme in the hydrogel network and strong affinity of PAMPS hydrogel‐supported Fe₃O₄ nanozyme towards substrates. The affinity between the hydrogel‐supported Fe₃O₄ nanozyme and substrates can be improved by regulating the crosslinking concentration of PAMPS hydrogel without other trenchant experimental conditions. In addition, the result indicated that H₂O₂ can be detected even at a concentration as low as 1.5 × 10^?6 mol L^?1 with a linear detection range of 1.5–9.8 × 10^?6 mol L^?1. Such investigations not only showed a new approach to improve the affinity and peroxidase‐like activity of Fe₃O₄ nanozyme, but also verified its potential application in bio‐detection and environmental chemistry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43065.     

Effect of side‐chain functionality on the organic field‐effect transistor performance of oligo(p‐phenylenevinylene) derivatives

In order to observe the effects of the substitution of electronegative flourine with aromatic groups in oligo(p ‐phenylenevinylene) compounds on their packing, morphology, and charge carrier mobility, we have synthesized napthol‐substituted oligo(p ‐phenylenevinylene) compounds and examined their solubility, redox properties, thin film morphologies, and charge carrier properties. To date, very few examples of conjugated oligomers bearing napthol side groups have been reported in the literature. After annealing at 150 °C, the mobility of S1, S2, and S3 was 4.0 × 10^?2 cm² V^?1 s^?1, 1.2 × 10^?2 cm² V^?1 s^?1, and 2.6 × 10^?3 cm² V^?1 s^?1, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44825.     

Preparation and characterization of polyaniline‐DBSNa/Fe2O3 and polyaniline‐DBSNa/CoO nanocomposites using surfactive dopant sodium dodecylbenzenesulfonate (DBSNa)

Nanocomposites of polyaniline (PAn) containing nanometer‐size Fe₂O₃ and CoO were synthesized by a chemical method using sodium dodecylbenzenesulfonate (DBSNa) as a surfactant. Characteristics of the products such as morphology, particle size, and conductivity were studied. The results indicated that these properties were dependent on the surfactant and the type and content of metallic oxide used. When the concentration of Fe₂O₃ and CoO increased from 1 to 5 g/L in the PAn‐DBSNa/Fe₂O₃ and PAn‐DBSNa/CoO composites, the conductivity decreased from 1.3 × 10^?4 to 5.1 × 10^?5 and from 1.4 × 10^?4 to 5.1 × 10^?5 S/cm, respectively, while the particle size increased from 92 to 103 and from 104 to 117 nm, respectively. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

A study toward the physicochemical properties of graft copolymer (partially carboxymethylated guar gum‐g‐N,N′‐dimethylacrylamide): Synthesis and characterization

Unreported graft copolymer of N,N′‐dimethylacrylamide (DMA) with partially carboxymethylated guar gum (CmgOH) has been synthesized and the reaction conditions have been optimized for affording maximum grafting using a potassium peroxymonosulphate (PMS)/thiourea (TU) redox initiators under nitrogen atmosphere. The study of graft copolymerization has been performed to observe maximum value of grafting parameters except percentage of homopolymer by varying the concentrations of DMA, PMS, and TU. The grafting parameters increase continuously on increasing the concentration of DMA from 8 × 10^?2 to 24 × 10^?2 mol dm^?3, PMS from 5 × 10^?3 to 21 × 10^?3 mol dm^?3, and TU from 1.6 × 10^?3 to 4.8 × 10^?3 mol dm^?3. The optimum temperature and time for grafting of DMA onto CmgOH were found to be 35°C and 120 min, respectively. The water‐swelling capacity of graft copolymer is investigated. Flocculation property for both coking and noncoking coals is studied for the treatment of coal mine waste water. The graft copolymer is characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of Nano‐γ‐Ferric Oxide by Thermolysis of the 2‐Mercapto‐5‐Methylpyridine‐N‐Oxide‐Iron(III) Complex via Factorial Design

2‐Mercapto‐5‐methylpyridine‐N‐oxide (MMPNO) and its sodium salt (NaMMPNO) were synthesized. The reaction of the latter with Fe³⁺ generates Fe(MMPNO)₃ chelate. The thermolysis of this chelate at 350 °C yielded highly pure reddish‐brown γ‐Fe₂O₃ nanocrystallites with an average particle size of 6.2 nm, a particle size range of 4.2 to 14.8 nm, and a specific surface area of 51.5 m²g^–1. The thermolysis process was optimized using the 2² fractional design. Quantitative tests and characterization of products were carried out by UV‐vis spectroscopy, XRD, LLS, SEM, TGA, BET, TEM, FT‐IR, elemental microanalysis, and classical analytical measurements.     

Determination of epigallocatechin‐3‐gallate with a high‐efficiency electrochemical sensor based on a molecularly imprinted poly(o‐phenylenediamine) film

An electrochemical molecularly imprinted polymer (MIP) sensor for detecting the existence of epigallocatechin‐3‐gallate (EGCG) in tea and its products was successfully developed on the basis of a glassy carbon electrode modified with an electropolymerized nonconducting poly(o‐phenylenediamine) film. The properties of the electrode were characterized by cyclic voltammetry, differential pulse voltammetry, and infrared spectroscopy. The template molecules could be rapidly and thoroughly removed by methanol/acetic acid. The linear response range for EGCG was 5.0 × 10^?7–1.0 × 10^?4 mol/L, and the limit of detection was as low as 1.6 × 10^?7 mol/L. The prepared MIP sensor could discriminate between EGCG and its analogs. In addition, satisfactory results were obtained in the detection of real tea samples. The results of our investigation indicate that the MIP sensor was useful for the determination of EGCG with excellent selectivity, high sensitivity, repeatability, and reproducibility. This MIP sensor provides the potential for monitoring the variation of EGCG content during the industrial processes and for predicting the quality of tea and its products. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of poly(acrylic acid)–Fe3+/gelatin/poly(vinyl alcohol) triple‐network supramolecular hydrogels with high toughness,high strength and self‐healing properties

Hydrogels with good mechanical and self‐healing properties are of great importance for various applications. Poly(acrylic acid)–Fe³⁺/gelatin/poly(vinyl alcohol) (PAA‐Fe³⁺/Gelatin/PVA) triple‐network supramolecular hydrogels were synthesized by a simple one‐pot method of copolymerization, cooling and freezing/thawing. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels exhibit superior toughness, strength and recovery capacity compared to single‐ and double‐network hydrogels. The mechanical properties of the synthesized hydrogels could be tailored by adjusting the compositions. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogel with 0.20 mmol Fe³⁺, 3% gelatin and 15% PVA could achieve good mechanical properties, the tensile strength and elongation at break being 239.6 kPa and 12.8 mm mm^?1, respectively, and the compression strength reaching 16.7 MPa under a deformation of about 91.5%. The synthesized PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels have good self‐healing properties owing to metal coordination between Fe³⁺ and carboxylic groups, hydrogen bonding between the gelatin chains and hydrogen bonding between the PVA chains. Healed PAA‐Fe³⁺(0.20)/Gelatin3%/PVA15% triple‐network hydrogels sustain a tensile strength of up to 231.4 kPa, which is around 96.6% of the tensile strength of the original samples. Therefore, the synthesized triple‐network supramolecular hydrogels would provide a new strategy for gel research and expand the potential for their application. © 2019 Society of Chemical Industry     

A Dual‐Crosslinked Strategy to Construct Physical Hydrogels with High Strength,Toughness, Good Mechanical Recoverability,and Shape‐Memory Ability

A novel type of physical hydrogel based on dual‐crosslinked strategy is successfully synthesized by micellar copolymerization of stearyl methacrylate, acrylamide, and acrylic acid, and subsequent introduction of Fe³⁺. Strong hydrophobic associations among poly(stearyl methacrylate) blocks form the first crosslinking point and ionic coordination bonds between carboxyl groups and Fe³⁺ serve as the second crosslinking point. The mechanical properties of the hydrogel can be tuned in a wide range by controlling the densities of two crosslinks. The optimal hydrogel shows excellent mechanical properties (tensile strength of ≈6.8 MPa, elastic modulus of ≈8.0 MPa, elongation of ≈1000%, toughness of 53 MJ m^?3) and good self‐recovery property. Furthermore, owing to stimuli responsiveness of physical interaction, this hydrogel also shows a triple shape memory effect. The combination of two different physical interactions in a single network provides a general strategy for designing of high‐strength hydrogels with functionalities.     

Bimetallic ions synergistic cross‐linking high‐strength rapid self‐healing antibacterial hydrogel

In this work, a novel PAA‐Fe³⁺‐Al³⁺ hydrogel with triple network structure (TN) was synthesized via bimetallic ions synergistic cross‐linking strategy. As‐synthesized samples were characterized by scanning electron microscope, Fourier transform infrared analysis, and X‐ray diffractometer. The relevant experiment results demonstrated that the hydrogel can rapidly self‐heal in ambient temperature without any external stimulus with 95% healing efficiency in 60 s. Simultaneously, the relatively rapid self‐healing of PAA‐Fe³⁺‐Al³⁺ polymer can be obtained through the coordination of metal ions with the ? COO^? in PAA and the oxygen of agar in the TN hydrogel system. And the prepared hydrogels demonstrate excellent mechanical properties—high tensile strength (the tensile strain ≈ 1.011 mm/mm, tensile stress ≈ 0.34 MPa) and large elasticity (the elongation at break ≈ 74%). Especially, the antimicrobial activity of the novel hydrogel against Staphylococcus aureus and Escherichia coli bacteria was investigated using the inhibition zone method, showing remarkable antibacterial activity. POLYM. ENG. SCI., 59:919–927, 2019. © 2018 Society of Plastics Engineers     

Characteristics of waterborne polyurethane/poly(N‐vinylpyrrolidone) composite films for wound‐healing dressings

For ideal wound‐healing dressings, a series of waterborne polyurethane (WBPU)/poly(N‐vinylpyrrolidone) (PVP) composite films (transparent film dressings) were prepared by in situ polymerization in an aqueous medium. Stable WBPU/PVP composites, which had a high remaining weight greater than 98.4%, were obtained. The maximum content of PVP for stable WBPU/PVP dispersions was found to be about 15 wt %. The water absorption (%) and equilibrium water content (%) of the WBPU/PVP composite films remarkably increased in proportion to the PVP content and the time of water immersion. The maximum water absorption and equilibrium water content of the WBPU/PVP composite films were in the range of 21–158 and 22–56%, respectively. The water vapor transmission rate of the WBPU/PVP composite films was in the range of 1816–2728 g/m²/day. These results suggest that WBPU/PVP composite films may have high potential as new wound‐dressing materials that provide and maintain the moist environment needed to prevent scab formation and dehydration of the wound bed. By a wound‐healing evaluation using a full‐thickness rat model experiment, it was found that a wound covered with a typical WBPU/PVP composite film (15 wt % PVP) was completely filled with new epithelium without any significant adverse reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Oxygen permeability and structural stability of a novel tantalum‐doped perovskite BaCo0.7Fe0.2Ta0.1O3−δ

Dense BaCo_0.7Fe_0.2Ta_0.1O_3?δ (BCFT) perovskite membranes were successfully synthesized by a simple solid state reaction. In situ high‐temperature X‐ray diffraction indicated the good structure stability and phase reversibility of BCFT at high temperatures. The thermal expansion coefficient (TEC) of BCFT was determined to amount 1.02 × 10^?5 K^?1, which is smaller than those of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) (1.15 × 10^?5 K^?1), SrCo_0.8Fe_0.2O_3?δ (SCF) (1.79 × 10^?5 K^?1), and BaCo_0.4Fe_0.4Zr_0.2O_3?δ (BCFZ) (1.03 × 10^?5 K^?1). It can be seen that the introduction of Ta ions into the perovskite framework could effectively lower the TEC. Thickness dependence studies of oxygen permeation through the BCFT membrane indicated that the oxygen permeation process was controlled by bulk diffusion. A membrane reactor made from BCFT was successfully operated for the partial oxidation of methane to syngas at 900°C for 400 h without failure and with the relatively high, stable oxygen permeation flux of about 16.8 ml/min cm². © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Multiple Shape Memory,Self‐Healable,and Supertough PAA‐GO‐Fe3+ Hydrogel

A multiple shape memory and self‐healing poly(acrylic acid)‐graphene oxide‐Fe³⁺ (PAA‐GO‐Fe³⁺) hydrogel with supertough strength is synthesized containing dual physically cross‐linked PAA network by GO and Fe³⁺. The first GO cross‐linked hydrogel can be reversibly reinforced by immersing in FeCl₃/HCl and pure water and softened by immersing in HCl. The tensile strength is 2.5 MPa with the break strain of 700%. Multiple shape memory capability is found depending on this unique feature, the hydrogel can be fixed in four temporary shapes by adjusting the immersing time in FeCl₃/HCl and pure water, and recovered in sequence by immersing in HCl. This hydrogel also exhibits perfect self‐healing behavior, the cut as‐prepared hydrogel is almost completely healed by immersing in FeCl₃/HCl. Besides, the hydrogel shows enhanced electrical conductivity with the presence of GO and Fe³⁺. This supertough hydrogel provides a new way to design soft actuators.