Aniline‐nonamer segmented polyurea: A facile electrocatalyst for detection of ascorbic acid

An unprecedented A‐B‐A type block copolymer electroactive polyurea (EPU) is designed and synthesized with tetraaniline dimer and 1,4‐phenylenediamine via an oxidative coupling, where aniline–nonamer and hexamethylene di‐urea constitute two segments. The EPU was characterized by spectral techniques such as Fourier transform infrared spectroscopy, nuclear magnetic resonance, and UV–vis spectra. The structural characterization of the prepared EPU was obtained by powder X‐ray diffraction and X‐ray photoelectron spectroscopy techniques. EPU reorganizes into core–shell microcapsules in presence of aqueous acetic acid/n‐octane interface. These microcapsules exhibited a wide range of pH responses in their absorption spectrum (UV–vis). The EPU is modified as carbon paste electrode which exhibits a remarkable electrocatalytic oxidation of ascorbic acid (AA, Vitamin C) in 0.2 M and pH 7.0 phosphate buffer solution. The carbon paste electrode is useful in sensing as low as 50 µM of ascorbic acid. This can open up new opportunities for fast, simple detection of AA providing a promising platform for sensor/biosensor designs for AA detection. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46630.     

Influence of monomeric concentration on mechanical and electrical properties of poly(styrene-co-acrylonitrile) and poly(styrene-co-acrylonitrile/acrylic acid) yarns electrospun

Two series of copolymers were synthesized by emulsion polymerization: poly(styrene-co-acrylonitrile) P(S:AN) and P(S:AN-acrylic acid) P(S:AN-AA). The monomeric concentrations in both series were: 0:100, 20:80, 40:60, 50:50 (wt%:wt%), and 1 wt% of AA. The copolymers were dissolved in N,N-dimethylformamide (4–10 wt%) and were electrospun. Polymeric yarns were collected using a blade collector. The synthesized and fabricated materials were characterized by known techniques. Mechanical and electrical properties of polymeric yarns indicated a dependence of monomeric concentration. Elastic modulus increases as acrylonitrile concentration increases (up to 30 MPa). Yarns were submitted to degradation process into saline solution, where the acrylic acid content kept a constant elastic modulus at long times. The electrical current into yarns was higher when the concentration is 50:50 wt%:wt% (1.2 mA). The cytotoxicity results showed a cell viability close to 100% for yarns without AA.     

Electrosynthesis,characterization, and application of poly(3,4‐ethylenedioxythiophene) derivative with a chloromethyl functionality

Poly(2‐chloromethyl‐2,3‐dihydrothieno[3,4‐b][1,4]dioxine), a chloromethyl functionalized poly(3,4‐ethylenedioxythiophene) derivative (PEDOT‐MeCl), was synthesized electrochemically via the potentiostatic polymerization of its monomer in dichloromethane solution containing suitable tetrabutylammonium tetrafluoroborate, then it was used for the characterization of film properties and the fabrication of electrochemical sensor. The properties of the resulting PEDOT‐MeCl film were characterized by different methods such as cyclic voltammetry, electrochemical impedance spectroscopy, Fourier transform infrared and ultraviolet–visible techniques, scanning electron microscope, and thermogravimetric analysis. The PEDOT‐MeCl film displayed a good reversible redox activity, remarkable capacitance properties, good thermal stability, rough, and porous structure, especially fluorescent spectra indicated that PEDOT‐MeCl was a blue‐emitter with maximum emission centered at 396 and 398 nm. Finally, the PEDOT‐MeCl film was employed for the fabrication of the sensing electrode, and dopamine was chosen as a model analyte for the application of the electrochemical sensor. Results indicated that the PEDOT‐MeCl film as sensing interface was feasible, and studies of these film properties were very beneficial for studying properties and applications of other poly(3,4‐ethylenedioxythiophene) derivative films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2660–2670, 2013     

Gold nanoparticle patterned on PANI nanowire modified transducer for the simultaneous determination of neurotransmitters in presence of ascorbic acid and uric acid

In the present work, we have electrochemically deposited polyaniline nanowires (PANIS) on glassy carbon electrode (GCE) from its monomer liquid crystalline template of anilinium‐3‐pentadecyl phenyl sulphonic acid (An⁺ PDPSA^?). Further, electrode was modified by the electrochemical patterning of gold nanoparticles on the PANIS/GCE (PANIS/Au/GCE) by electrodeposition through chronoamperometry. Modified electrode characterized by electrochemical impedance, morphology, XRD, electroactive surface area, and later demonstrated its efficacy for the individual and simultaneous sensing of dopamine, ascorbic acid, serotonin, and uric acid. Finally, its performance in the real sample (blood serum) was evaluated. The superior electrocatalytic performance with higher sensitivity suggested that the modified electrode can be used as an excellent transducer for the sensing of neurotransmitters. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 44351.     

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.     

Disposable potentiometric citrate sensor based on polypyrrole‐doped films for indirect determination of sildenafil in pharmaceuticals formulations

A new sensitive and selective disposable potentiometric sensor based on polypyrrole (PPy) films for determination of sildenafil citrate (SC) was proposed. The pyrrole polymerization was performed in presence of citrate ions under galvanostatic conditions which resulted in a membrane of PPy doped with citrate anion at graphite pencil electrode surface. Experimental conditions (e.g., pH and conditioning time) and instrumental parameters (e.g., current density and electrical charge) were evaluated in order to reach the best potentiometric response for the proposed sensor. Under optimized conditions, the device presented a linear dynamic range (LDR) for citrate ions concentrations varying from 0.034 to 1.7 mmol L^?1 with a Nernstian slope of 57.2 mV dec^?1 and a limit of detection (LOD) of 30 µmol L^?1. The developed potentiometric sensor was applied for sildenafil citrate (SC) determination (pharmaceutical formulations) and results compared with an official spectrophotometric method indicating a good agreement for a confidence level of 95%. Effect of concomitants species on the potentiometric response of the proposed device and morphologic characterization using microscopy of atomic force (AFM) were realized. The surface roughness of PPy films (synthesized in citrate solution and chloride) showed poorly affected by changing the doping anion, probably because the polypyrrole nodules grow three‐dimensionally simultaneously. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43762.     

Room temperature CO sensing by polyaniline/Co3O4 nanocomposite

Polyaniline/cobalt oxide (PANI/Co₃O₄) nanocomposites have been investigated for their sensitivity towards carbon monoxide (CO) gas at room temperature. The Co₃O₄ nanoparticles were prepared by ultrasound assisted coprecipitation method and then incorporated into the PANI matrix. Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy, powder X‐ray diffraction, and field emission scanning electron microscopy have been used to characterize the nanomaterials. The PANI/Co₃O₄ nanocomposite sensors were found to be highly selective to CO gas at room temperature. A significantly high response of 0.81 has been obtained for 75 ppm CO concentration with a response time of 40 s. Based on the observations of the sensing study, a mechanism for CO sensing by the nanocomposite has been proposed. Influence of humidity on the sensor response towards CO has also been studied and the results presented. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44115.     

Oxidative solution polymerization of aniline hydrochloride onto electrospun nanofibers mats of polylactic acid: Preparation method and characterization

In this work, we present the preparation of polylactic acid (PLLA)/polyaniline (PANI) conductive composite nanofibers mats. They are prepared by bulk oxidative solution polymerization of PANI onto electrospun non‐woven fibers mats of PLLA. The PANI ratio in the composite is about 70%w/w. Scanning electron microscopy (SEM) shows that PLLA nanofibers are randomly oriented, beads free with diameters of 186 ± 85 nm, The PLLA/PANI composite nanofibers diameter values are 518 ± 128 nm with a good adherence between PANI and PLLA nanofibers. DSC and XRD measurements reveal an amorphous structure of the electrospun PLLA fibers due to the rapid evaporization of the solvent. FTIR and UV–vis spectra reflect good mutual interactions between PANI and PLLA chains. The DC‐conductivities ( ) far better than other published ones for similar composites prepared by bulk oxidative solution polymerization of PANI onto other electrospun nanofiber mats or with electrospun nanofibers from a solution mixture of PLLA and PANI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41618.     

Fabrication of self-functionalized polymeric surfaces and their application in electrochemical acetaminophen detection

Conducting polymer coatings have offered functionalized surfaces having good electrical, mechanical, and physical properties. In this work, electrochemical preparation and characterization of polypyrrole/polypyrrole-3-carboxylic acid (PPy/PPa) copolymer onto single-use pencil graphite electrodes (PGEs) were described and detailed. Then, the application of these electrodes was demonstrated for the detection a commonly used analgesic, acetaminophen (AC) (paracetamol). Copolymer was deposited onto PGEs using cyclic voltammetry (CV) between +0.0 V and +1.0 V versus Ag/AgCl. Experimental conditions such as the effect of monomer ratios (3:1–6:1) and cyclic scans (1 cycle to 10 cycles) on electropolymerization were examined. Coated surfaces were characterized with CV and scanning electron microscopy. Electrochemical response of the electrode in AC at various pH values was evaluated. Then, AC detection was performed based on the oxidation signal of the drug at about +0.55 V versus Ag/AgCl using differential pulse voltammetry in buffer and body fluid (serum).     

A highly selective electrochemical sensor for l‐tryptophan based on a screen‐printed carbon electrode modified with poly‐p‐phenylenediamine and CdS quantum dots

A new highly selective electrochemical sensor for the determination of l ‐tryptophan was proposed by modifying the surface of screen‐printed carbon electrodes (SPCEs). The surface of SPCE was firstly modified by electropolymerization of p‐phenylenediamine (PPD). The polymer film was then covalently linked with cysteamine capped cadmium sulfide quantum dots (Cys‐CdS QDs) by using glutaraldehyde (GA) as a cross‐linker resulted in an organic–inorganic hybrid composite film (QDs/GA/PPD/SPCE). The modified electrode was applied as a working electrode for detecting various amino acids. It was found that the modified electrode gave an electrochemical response selectively to l ‐tryptophan over other amino acids. The experimental parameters, including pH of solution, buffer types, electropolymerization cycles, scan rate, and accumulation time, were studied and optimized. The proposed sensor can be used to detect l ‐tryptophan with a low detection limit of 14.74 µmol L^?1 with good precision and the relative standard deviation less than 3.7%. The modified electrode was used to detect l ‐tryptophan in beverage samples and gave satisfactory recoveries from 91.9 to 104.9%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40356.     

Poly(vinylidene fluoride) nanofiber-based piezoelectric nanogenerators using reduced graphene oxide/polyaniline

Recently, piezoelectric nanogenerators have received great interest as they can convert waste mechanical and radiative energy to electricity and can be used in self-energy generating systems and sensor technologies. In this study, electrospun poly(vinylidene fluoride) (PVDF) nanofiber-based piezoelectric nanogenerators with reduced graphene oxide (rGO), polyaniline (PANI), and PANI-functionalized rGO (rGOPANI) have been developed. Two different types of nanofiber mats were produced: First, rGO- and rGOPANI-doped PVDF nanofiber mats and second, rGO, PANI and rGOPANI-spray-coated PVDF nanofiber mats that have worked as nanogenerators' electrodes. Then, characterizations of samples were performed in terms of piezoelectricity, Fourier transform infrared (FTIR) spectrophotometric, X-ray diffractions (XRD), and scanning electron microscopy analyses. FTIR and XRD results confirmed that piezoelectric β-crystalline phase of PVDF occurred after the electrospinning process. Besides, maximum output voltages were obtained as 7.84 and 10.60 V for rGO-doped PVDF and rGOPANI-coated PVDF nanofiber mats, respectively. As a result, the doped nanofibers were found to be more successful due to the higher device accuracy in sensor technologies compared with spray-coated samples. However, spray-coating method proved to be more suitable technique for the production of nanogenerators on an industrial scale in terms of fast and large-scale applicability. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48517.     

Electrochemical inspection of polypyrrole/chitosan/zinc oxide hybrid composites

Polymer nanocomposite composed of polypyrrole, chitosan, and zinc oxide nanoparticles has been synthesized and it has been evaluated for various electrochemical aspects of the current electrochemical industry. The polypyrrole (PPy) was synthesized by the chemical oxidative polymerization reaction by employing ammonium persulfate as oxidizing agent. Composites of polypyrrole/chitosan (PPy/Chy) and polypyrrole/chitosan/ZnO (PCZ) composites were synthesized by the solution blending method. Detailed structural, morphological, thermal characterization of PPy, PPy/Chy, and PCZ were performed to characterize the specific features of the systems. The composites exhibit better thermal stability and high surface area and the addition of ZnO nanoparticle increase the crystallinity of the composite. Electrochemical characterization of the ITO electrodes modified with PPy, PPy/Chy, and PCZ were performed using cyclic voltammetry, electrochemical impedance spectroscopy, and amperometry techniques. The present study highlights the role of a bio-compatible material with high surface area and conductive constituent for designing of various high performing electronic noninvasive sensors, biosensors, and so forth.     

Smart films based on bacterial cellulose nanofibers modified by conductive polypyrrole and zinc oxide nanoparticles

In this study, we synthesized novel films based on bacterial cellulose (BC), BC modified by polypyrrole (PPy), and a PPy–zinc oxide nanocomposite (BC–PPy–ZnO). The soft polymerization method at room temperature was used to obtain the BC–PPy and BC–PPy–ZnO films. The Combined D‐Optimal design was used to study the effects of the pyrrole monomer concentration, ZnO concentration, and polymerization time on the morphological, physical, color, and electrical conductivity properties of the films. Fourier transform infrared results reflected that some new interactions occurred between BC and PPy and PPy–ZnO. The X‐ray diffraction analysis showed that the crystalline behavior of the BC fiber was hindered because of the complete coating with the amorphous PPy particles. Scanning electron microscopy results show that the ZnO, PPy, and PPy–ZnO nanoparticles were placed between the BC fibers. PPy decreased the water vapor permittivity and total soluble matter percentage. Electrical conductivity studies of the synthesized BC–PPy–ZnO film showed that the film's electrical resistance was changed in different oxidation–reduction or volatile compounds media, so the results suggest that the BC–PPy–ZnO films could be used in antioxidative food active packaging and smart packaging. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46617.     

Impact damage sensing of multiscale composites through epoxy matrix containing carbon nanotubes

Carbon nanotubes are used to provide increased electrical conductivity for polymer matrix materials, thus offering a method to monitor the structure's health. This work investigates the effect of impact damage on the electrical properties of multiscale composite samples, prepared with woven fiberglass reinforcement and epoxy resin modified with as‐received multi‐walled carbon nanotubes (MWCNTs). Moreover, this study addresses potential bias from manufacturing, and investigates the effectiveness of resistance measurements using two‐ and four‐point probe methods. Transmission electron microscopy and static tensile tests results were used to evaluate, respectively, the dispersion of MWCNTs in the epoxy resin and the influence of the incorporation of these nanoparticles on the static tensile properties of the matrix, and interpret results from the resistance measurements on impacted specimens. In this study, the four‐point probe method is shown to be much more repeatable and reliable than the two‐point probe method. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Piezoelectric properties of PVDF-conjugated polymer nanofibers

This study presents the development and characterization of PVDF-conjugated polymer nanofiber-based systems. Five different conducting polymers (CPs) were synthesized successfully and used to create the nanofiber systems. The CPs used are polyaniline (PANI), polypyrrole (PPY), polyindole (PIN), polyanthranilic acid (PANA), and polycarbazole (PCZ). Nanofiber systems were produced utilizing the Forcespinning® technique. The nanofiber systems were developed by mechanical stretching. No electrical field or post-process poling was used in the nanofiber systems. The morphology, structure, electrochemical and piezoelectric performance was characterized. All of the nanofiber PVDF/CP systems displayed higher piezoelectric performance than the fine fiber PVDF systems. The PVDF/PPY nanofiber system displays the highest piezoelectric performance of 15.56 V. The piezoelectric performance of the PVDF/CP nanofiber systems favors potential for an attractive source of energy where highly flexible membranes could be used in power actuators, sensors and portable, and wireless devices to mention some.     

Development of flexible sensors using knit fabrics with conductive polyaniline coating and graphite electrodes

The aim of this study was to develop flexible sensors with cotton and polyester knit fabrics as substrates coated with polyaniline (PAni) doped with hydrochloric acid or phosphoric acid. The deposition of PAni onto the knit, polymerization synthesis, and doping of the aniline monomer were performed via an in situ reaction. Graphite dispersion was used to obtain the electrodes of the sensors, which were prepared differently for each substrate. The main evaluation of the sensors was carried out in a humidity chamber under nitrogen (N₂) with the application of drying and wetting cycles. Significant differences were observed in the responses of the sensory devices to humidity, according to the dopant and substrate types. In all tests, the sensor response to variations in the ambient conditions was very good, with a rapid response to changes in the relative humidity, a good sensitivity (up to 34%), and a high reversibility (ca. 70–100%). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44785.     

Embedded macroporous elastomers by hydrostatic fracturing for flexible strain‐sensor applications

A method is proposed for fabricating flexible materials embedded with macroporous regions by inducing fractures under point loading. Possible use of these structures in strain sensing is demonstrated. Injecting air at high pressure through a needle‐tip generates 3‐dimensional fractures in homogeneously crosslinked polydimethylsiloxane (PDMS) media, whereas a 2‐dimensional planar fracture is generated in a sandwich‐like structure wherein a softer layer is bounded by two stiffer layers. Size‐dependence of 3‐dimensional fractures on stiffness of the media which is controlled by the crosslinker concentration shows a maximum, suggesting an optimal stiffness for generating largest fracture. The size of the 2‐dimensional fractures (～5 cm) generated inside the sandwiched layer is huge as compared to the 3‐dimensional fractures (～1 mm) under the similar conditions. Two dimensional fractured surfaces show ridges with feature length monotonically becoming smaller with stiffness. Embedded rough planar domains are created by introducing 2‐dimensional fractures at distances close enough to overlap. Using this method an embedded 2‐dimensional porous domain of polyaniline nanostructures is realized in flexible PDMS matrix. An Ohmic nature of these embedded polyaniline domains with an ability to change resistance under compression establishes their suitability for developing inexpensive and flexible strain sensors. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43681.     

Two kinds of polyaniline fiber photo sensor with interdigital electrode and flexible hydrogel

In previous studies, polyaniline nanofiber sensor on interdigital electrode is sensitive to light. Herein, we prepared a flexible hydrogel sensor with polyaniline nanofiber as the active material and polyacrylamide hydrogel as the flexible substrate. Comparing the properties of above two different kinds of sensors with polyaniline nanofiber, the photocurrent generated by PANI-hydrogel sensor under external light stimulation is about 1 ~ 2 orders of magnitude higher than interdigital electrode sensor, indicating the PANI-hydrogel sensor is more sensitive. The two sensors can all respond to different wavelengths of monochromatic light, especially sensitive to light of smaller wavelengths such as ultraviolet light (380 nm) and blue light (475 nm). Moreover, the volt-ampere characteristic curve in response to external light stimulation can be clearly distinguished only when the appropriate concentration of proton acid is doped (3 g citric acid, 7 g acetic acid, and 3 ml HCl).     

Molecularly imprinted electrochemical sensor for the determination of ampicillin based on a gold nanoparticle and multiwalled carbon nanotube‐coated pt electrode

A novel molecularly imprinted electrochemical sensor was developed for the sensitive and selective determination of ampicillin (AMP). The sensor was prepared on a platinum electrode modified with multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (AuNPs), and a thin film of molecularly imprinted polymers (MIPs). MWCNTs and AuNPs were introduced to enhance the sensor's electronic transmission and sensitivity. The molecularly imprinted polymer (MIP) was synthesized using AMP as the template molecule, methacrylic acid as functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as cross‐linker. The performance of the proposed imprinted sensor was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The results showed that the imprinted film displayed a fast and sensitive response to AMP. Under optimal conditions, response peak current had a linear relationship with the concentration of AMP in the range of 1.0 × 10^?8 mol/L to 5.0 × 10^?6 mol/L and a detection limit of 1.0 × 10^?9 mol/L (S/N = 3). This imprinted sensor was used to detect AMP in food samples with recoveries of 91.4–105%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40613.     

Novel electrically conducting polyurethanes with oligoanilines: Synthesis,conductivity, and electrochemical properties

New class of conducting polyurethanes (CPUs) containing oligoanilines, namely tetraaniline (TAni) or trianiline (TriAni), in the backbone have been synthesized and characterized by formal spectral techniques. The unique properties of these CPUs, viz., electronic conductivity and electrochemical activity arising from the presence of oligoaniline units have been evaluated. The basic polyurethane backbone is derived from toluene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate, and polypropylene glycols of molecular weight 425 and 2000. In the first category of polyurethanes, the prepolymers obtained from the above reactants were chain terminated by TAni in emeraldine base oxidation state. The conductivity of these CPUs films ranged from 1.2 × 10^?5 to 1.77 × 10^?3 S cm^?1. These polymers showed lower conductivity due to the presence of nonconjugated polyurethane segments. These CPUs exhibited slightly different electrochemical activity than that of TAni. The second category of CPUs is obtained from prepolymers by chain extension with TriAni. The conductivity of these polymers is similar to the TAni analogues but are electrochemically inactive. The anticorrosion properties of two of these polymers have also been evaluated in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40794.