Investigation of the behavior of hydrogen‐bonded phenolic compounds and their determination by using poly(vinylferrocenium)–polyaniline composite film

The hydrogen bonding between phenolic compounds (phenol (Ph), catechol (Ct), resorcinol (Rs), and hydroquinone (Hq)) is investigated at pH 4. The oxidation behaviors of total phenolic compounds (TotPh) are different from their individual behaviors due to the existence of intermolecular hydrogen‐bonded oligomeric clusters. Theoretical calculations and voltammetric and spectroscopic evidences support the intermolecular hydrogen bonding. The interaction of the phenolic compounds with polyaniline (PANI) and poly(vinylferrocenium) (PVF⁺) films are also investigated electrochemically and spectroscopically. The phenolic molecules are immobilized in both polymers due to the construction of hydrogen bonds by PANI and the complexation with PVF⁺. In addition, Ct and Hq are catalytically oxidized by PANI. Determinations of Ct and TotPh are performed on PVF⁺–PANI composite ‐ coated Pt electrode using amperometric I–t method. Composite coating exhibits significant electrochemical activity toward Ct and TotPh, with high sensitivity and a wide linearity range. The steady‐state currents versus concentration of Ct and TotPh are found to be linear in the range of 1.35 × 10^?3?50.0 mM and 4.10 × 10^?4?560 mM for two linear regions, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43596.     

Electrochemical detection of avian influenza virus H5N1 gene sequence using a DNA aptamer immobilized onto a hybrid nanomaterial-modified electrode

A sensitive electrochemical method for the detection of avian influenza virus (AIV) H5N1 gene sequence using a DNA aptamer immobilized onto a hybrid nanomaterial-modified electrode was developed. To enhance the selectivity and sensitivity, the modified electrode was assembled with multi-wall carbon nanotubes (MWNT), polypyrrole nanowires (PPNWs) and gold nanoparticles (GNPs). This electrode offered a porous structure with a large effective surface area, highly electrocatalytic activities and electronic conductivity. Therefore, the amount of DNA aptamer immobilized onto the electrode was increased while the accessibility of the detection target was maintained. The biosensor is based on the hybridization and preferred orientation of a DNA aptamer immobilized onto a modified electrode surface with its target (H5N1 specific sequence) present in solution. It is selective for the H5N1 specific sequence, and the signal of the indicator was approximately linear to log(concentration) of the H5N1 specific sequence from 5.0 × 10⁻¹² to 1.0 × 10⁻⁹ M (R = 0.9863) with a detection limit of 4.3 × 10⁻¹³ M. These studies showed that the new hybrid nanomaterial (MWNT/PPNWs/GNPs) and the DNA aptamer could be used to fabricate an electrochemical biosensor for gene sequence detection. Furthermore, this design strategy is expected to have extensive applications in other biosensors.     

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.     

Electrochemical gold deposition from sulfite solution: application for subsequent polyaniline layer formation

Electrochemical gold deposition from sulfite solutions was studied by means of voltammetry, EIS and EQCM. A gold film electrode was used for polyaniline layer formation by electrochemical oxidation of aniline. The standard electrochemical reduction potential of the reaction [Au(SO₃)₂]³⁻ + e⁻ = Au + 2 SO₃²⁻ was determined, and is equal to 0.116 V (vs. NHE). Both solution stirring and temperature increase accelerate the electrochemical reduction of gold, when the electrode potential is below −0.55 V. When the potential is above −0.55 V the electrochemical reduction proceeds via passive layer formation. Our study suggests that the passive layer consists of chemically adsorbed sulfite ions and sulfur. The gold film deposited from sulfite solution is a high quality substrate suitable for conducting polymer layer formation. This technique, where a polymer layer electrode is prepared by thin gold film deposition onto a metal surface and by subsequent polymer layer formation, can be applied in sensor research and technology.     

Gold nanoparticles/water-soluble carbon nanotubes/aromatic diamine polymer composite films for highly sensitive detection of cellobiose dehydrogenase gene

An electrochemical sensor based on gold nanoparticles (GNPs)/multiwalled carbon nanotubes (MWCNTs)/poly (1,5-naphthalenediamine) films modified glassy carbon electrode (GCE) was fabricated. The effectiveness of the sensor was confirmed by sensitive detection of cellobiose dehydrogenase (CDH) gene which was extracted from Phanerochaete chrysosporium using polymerase chain reaction (PCR). The monomer of 1,5-naphthalenediamine was electropolymerized on the GCE surface with abundant free amino groups which enhanced the stability of MWCNTs modified electrode. Congo red (CR)-functionalized MWCNTs possess excellent conductivity as well as high solubility in water which enabled to form the uniform and stable network nanostructures easily and created a large number of binding sites for electrodeposition of GNPs. The continuous GNPs together with MWCNTs greatly increased the surface area, conductivity and electrocatalytic activity. This electrode structure significantly improved the sensitivity of sensor and enhanced the DNA immobilization and hybridization. The thiol modified capture probes were immobilized onto the composite films-modified GCE by a direct formation of thiol–Au bond and horseradish peroxidase–streptavidin (HRP–SA) conjugates were labeled to the biotinylated detection probes through biotin–streptavidin bond. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the film assembly and DNA hybridization processes. The amperometric current response to HRP-catalyzed reaction was linearly related to the common logarithm of the target nucleic acid concentration in the range of 1.0 × 10⁻¹⁵–1.0 × 10⁻¹⁰ M, with the detection limit of 1.2 × 10⁻¹⁶ M. In addition, the electrochemical biosensor exhibited high sensitivity, selectivity, stability and reproducibility.     

A novel polymer‐based genosensor for the detection and quantification of Streptococcus pneumoniae in genomic DNA sample

The Streptococcus pneumoniae detection plays an important role in the diagnosis and monitoring of pneumococcal diseases. A genosensor based on graphite electrodes modified with polymer was developed for such detection. First, the poly(4‐aminophenol) film was electrochemically deposited on a graphite electrode. Afterward, an S. pneumoniae‐specific oligonucleotide (Strep1), isolated from conserved regions of the bacterial genome, was immobilized onto the modified electrode surface and used for the test with complementary target oligonucleotide (Strep2) or genomic DNA. The genosensor was evaluated using electrochemical techniques and atomic force microscopy. Poly(4‐aminophenol) film caused an increase in probe immobilization, monitoring the guanine oxidation peak. The detection limits obtained using differential pulse voltammetry and electrochemical spectroscopy impedance were 54 and 28 ng mL^?1, respectively. The novel genosensor was efficient for the immobilization and detection of S. pneumoniae genomic DNA. POLYM. ENG. SCI., 58:1308–1314, 2018. © 2017 Society of Plastics Engineers     

<Emphasis Type="Italic">Meso</Emphasis>-Tetra-(3,5-Dibromo-4-Hydroxydroxyphenyl) Porphyrin Copper (II) Self-Assembled Modified Gold Electrode Through <Emphasis Type="SmallCaps">l</Emphasis>-Cysteine: The Preparation,Electrochemical Behavior and its Application

In this study, a sensor for the sensitive determination of ascorbic acid (AA) has been fabricated based on meso-tetra-(3,5-dibromo-4-hydroxydroxyphenyl) porphyrin copper (II) (T(DBHP)P-Cu) modified Au electrode through l-cysteine (l-cys). Firstly, l-cys modified Au electrode was prepared through self-assembled technology. Then T(DBHP)P-Cu was adsorbed on l-cys/Au through covalent binding. The fabrication process and electrochemical behavior of T(DBHP)P-Cu/l-cys/Au were studied by cyclic voltammetry and differential pulse voltammetry. The results showed that AA exhibited good electrochemical activity at T(DBHP)P-Cu/l-cys/Au. The oxidation peak current increased linearly with AA concentration in the range of 1.00 × 10⁻³–1.02 × 10⁻⁵ mol L⁻¹ with a detection limit of 5.41 × 10⁻⁷ mol L⁻¹. Additionally, the modified electrode could be applied to the detect AA in practical samples.     

A DNA electrochemical sensor with poly-l-lysine/single-walled carbon nanotubes films and its application for the highly sensitive EIS detection of PAT gene fragment and PCR amplification of NOS gene

A sensitive and novel DNA electrochemical biosensor for the detection of the transgenic plants gene fragment by electrochemical impedance spectroscopy (EIS) was presented. The well-dispersed carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) were dripped onto the carbon paste electrode (CPE) surface firstly, and poly-l-lysine films (pLys) were subsequently electropolymerized by cyclic voltammetry (CV) to prepare pLys/SWNTs/CPE. The morphology of pLys/SWNTs films was examined using a field emission scanning electron microscope (SEM). The pLys/SWNTs films modified electrode exhibited very good conductivity. DNA probes were easily immobilized on the poly-l-lysine films via electrostatic adsorption. The hybridization events were monitored with electrochemical impedance spectroscopy using [Fe(CN)₆]^3−/4− as indicator. The PAT gene fragment from phosphinothricin acetyltransferase gene was detected by this DNA electrochemical sensor. The dynamic detection range of this sensor to the PAT gene fragment was from 1.0 × 10⁻¹² to 1.0 × 10⁻⁷ mol/L. A detection limit of 3.1 × 10⁻¹³ mol/L could be estimated. The PCR amplification of NOS gene from the sample of a kind of transgenic modified bean was also detected satisfactorily by EIS.     

A conducting polymer/ferritin anode for biofuel cell applications

An enzyme anode for use in biofuel cells (BFCs) was constructed using an electrically connected bilayer based on a glassy carbon (GC) electrode immobilized with the conducting polymer polypyrrole (Ppy) as electron transfer enhancer, and with horse spleen ferritin protein (Frt) as electron transfer mediator. The surface-coupled redox system of nicotinamide adenine dinucleotide (NADH) catalyzed with diaphorase (Di) was used for the regeneration of NAD⁺ in the inner layer and the NAD⁺-dependent enzyme catalyst glucose dehydrogenase (GDH) in the outer layer. The outer layer of the GC-Ppy-Frt-Di-NADH-GDH electrode effectively catalyzes the oxidation of glucose biofuel continuously; using the NAD⁺ generated at the inner layer of the Di-catalyzed NADH redox system mediated by Frt and Ppy provides electrical communication with enhancement in electron transport. The electrochemical characteristics of the electrodes were investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). This anode provides a current density of 1.2 mA cm⁻² in a 45 mM glucose solution and offers a good possibility for application in biofuel cells.     

Simultaneous determination of paracetamol and ascorbic acid using tetraoctylammonium bromide capped gold nanoparticles immobilized on 1,6-hexanedithiol modified Au electrode

Tetraoctylammonium bromide stabilized gold nanoparticles (TOAB-AuNPs) attached to 1,6-hexanedithiol (HDT) modified Au electrode was used for the simultaneous determination of paracetamol (PA) and ascorbic acid (AA) at physiological pH. The attachment of TOAB-AuNPs on HDT modified Au surface was confirmed by attenuated total reflectance (ATR)-FT-IR spectroscopy and atomic force microscope (AFM). The ATR-FT-IR spectrum of TOAB-AuNPs attached to the HDT monolayer showed a characteristic stretching modes corresponding to -CH₂ and -CH₃ of TOAB, confirming the immobilization of AuNPs with surface-protecting TOAB ions on the surface of the AuNPs after being attached to HDT modified Au electrode. AFM image showed that the immobilized AuNPs were spherical in shape and densely packed to a film of ca. 7 nm thickness. Interestingly, TOAB-AuNPs modified electrode shifted the oxidation potential of PA towards less positive potential by 70 mV and enhanced its oxidation current twice when compared to bare Au electrode. In addition, the AuNPs modified electrode separated the oxidation potentials of AA and PA by 210 mV, whereas bare Au electrode failed to resolve them. The amperometry current of PA was increased linearly from 1.50 × 10⁻⁷ to 1.34 × 10⁻⁵ M with a correlation coefficient of 0.9981 and the lowest detection limit was found to be 2.6 nM (S/N = 3). The present method was successfully used to determine the concentration of PA in human blood plasma and commercial drugs.     

Electrochemical synthesis of Pd particles on poly(vinylferrocenium)

Electrochemical synthesis of Pd particles on poly(vinylferrocenium) (PVF⁺) support was described. K₂PdCl₄ was used as the metal particle precursor. Pd particles were incorporated into the polymer matrix electrochemically either by cyclic voltammetric scans (between +1.0 V and −0.8 V vs. SCE) or by reduction at constant potential (at −0.8 V vs. SCE) from aqueous solution of K₂PdCl₄. Scanning electron microscopy (SEM) studies showed that the Pd particles were well dispersed in the polymer matrix. Experimental parameters such as polymer film thickness, number of cycles during cyclic voltammetric scans in K₂PdCl₄ and electrolysis time in K₂PdCl₄ were studied. The Pd/PVF⁺ system showed catalytic activity towards hydrazine oxidation and appreciable results were obtained when compared with the related studies.     

Synergistic effect of TiO2 and iron oxide supported on fluorocarbon films. Part 1: Effect of preparation parameters on photocatalytic degradation of organic pollutant at neutral pH

Iron oxide and TiO₂ were immobilized on modified polyvinyl fluoride films in a sequential process. Synergic effects of iron oxide and TiO₂ on the polymer film were observed during the heterogeneous degradation of hydroquinone (HQ) in the presence of H₂O₂ at pH close to neutrality and under simulated solar irradiation. Within the degradation period, little iron leaching (<0.5 mg/L) was observed.The surface of commercial polyvinyl fluoride (PVF) film was modified by TiO₂ under light inducing oxygen group (C–OH, CO, COOH) formation on the film surface. During this treatment, TiO₂ nanoparticles simultaneously bind to the film, leading to PVF^f–TiO₂. The possible mechanistic pathway for the TiO₂ deposition and the nature of the polymer–TiO₂ interaction are discussed. Furthermore PVF and PVF^f–TiO₂ were immersed in an aqueous solution for the deposition of iron oxide layer by hydrolysis of FeCl₃, leading to PVF–Fe oxide and to PVF^f–TiO₂–Fe oxide respectively.HQ degradation and mineralization mediated by PVF^f–TiO₂, PVF–Fe oxide and PVF^f–TiO₂–Fe oxide were investigated under different conditions. Remarkable synergistic effects were observed for PVF^f–TiO₂–Fe oxide possibly due to Fe(II) regeneration, accelerated by electron transfer from TiO₂ to the iron oxide under light.     

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.     

Studies on the electrochemical reduction processes of HTeO<Subscript>2</Subscript><Superscript>+</Superscript> by CV and EIS

Electrochemical characterizations of the underpotential deposition of tellurium on Au substrate were investigated by cyclic voltammetry (CV) in this paper. The results showed that the irreversible underpotential deposition of Te could take place once the Au electrode was immersed into the HTeO₂ ⁺ solution. The redox behaviors of adsorbed HTeO₂ ⁺ were also studied and the results revealed that HTeO₂ ⁺ could only adsorb on Au electrode surface. The kinetics relating to the reduction of adsorbed HTeO₂ ⁺ could be affected by HTeO₂ ⁺ concentration but the charge consumed by the reduction of adsorbed HTeO₂ ⁺ was concentration-independent. Electrochemical impedance spectroscopy (EIS) analyses about the bulk formation process of Te⁰ indicated that during the bulk reduction of HTeO₂ ⁺ to Te⁰, four electrons were not obtained simultaneously in only one electrochemical step, some intermediate products, which need to be further detected and investigated in the future researches, might emerged in the intermediate processes.     

Electrochemical oxidation of hydrogen peroxide at a bromine adatom-modified gold electrode in alkaline media

Bromine (Br)-adatom (Br_(ads)) was in situ fabricated onto polycrystalline gold (Au (poly)) electrode in Br⁻-containing alkaline media. The surface coverage of Br_(ads) (Γ_Br) varied only in the submonolayer coverage within the investigated potential window under potentiodynamic condition because of the coadsorption of hydroxyl ion (OH⁻) in alkaline media. The in situ fabricated Br_(ads)-submonolayer-coated Au (poly) electrode was successfully used for the electrochemical oxidation of hydrogen peroxide (H₂O₂). About five times higher oxidation current was achieved at the modified electrode as compared with the bare electrode. The enhancement of the electrode activity towards the electrochemical oxidation of H₂O₂ was explained based on the enhanced electrostatic attraction between the anionic HO₂⁻ molecules and Br_(ads)-adlayer-induced positively polarized Au (poly) electrode surface.     

Gold nanoparticle ensemble on polydopamine/graphene nanohybrid as a novel electrocatalyst for determination of baicalein

A facile and green approach is used to synthesize polydopamine (PDA) functionalized reduced graphene oxide (RGO) via the self‐polymerization of dopamine (DA) under alkaline conditions. The obtained reduced RGO/PDA composite facilitate Au precursor adsorption. Then Au nanoparticles are reduced and assemble onto the surface of RGO/PDA composite form reduced RGO/PDA/gold (RGO/PDA/Au) nanocatalysts. After that, a sensitive electrochemical sensor for baicalein is fabricated based on RGO/PDA/Au nanocatalysts. In this method, the hydroxyl units of PDA can form hydrogen bonding with the phenolic hydroxyl groups of baicalein, making baicalein easily adsorb on the modified electrode surface to enhance the electrochemical response. The electrochemical mechanism of baicalein on the RGO/PDA/Au nanocatalysts modified GCE is thoroughly investigated by cyclic voltammetry. The fabricated electrochemical sensor show good electrochemical activity for baicalein. The linear range of baicalein is 1 × 10^?8 to 15 × 10^?6 mol L^?1 with the detection limit of 3.1 × 10^?9 mol L^?1. Furthermore, the proposed electrochemical sensor can be used to detect real sample. The results reveal that this method provides a new avenue for electrochemical investigation of baicalein in biochemical, pharmaceutical, and clinical research. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 46720.     

Enhancement of electrochemical ion/electron-transfer reaction at solid|liquid interface by polymer coating on solid surface

Controlling the ion/electron-transfer reaction at the electrode|electrolyte (solid/liquid) interface is a necessary and vitally important point for improving the operation of various electrochemical devices. In this paper, we propose a polymer coating technique which enhances the Li⁺ ion-transfer reaction at the LiCoO₂|electrolyte interface, and confirm the effects of the polymer coating by cyclic voltammetry (CV) and AC impedance techniques. The results from the experiments indicated that the application of an F-introduced polymer on the LiCoO₂ (LCO) surface decreased the activation barrier for Li⁺ ion transfer. Besides the electrochemical studies, the present computational results indicated that the Li⁺ exchange process between two states, which are both solved with ethylene carbonate (EC) and coordinated with an F-introduced polymer, might occur due to the close energy levels of Li⁺ stability. Accordingly, we inferred that the transition state of this exchange process promotes the observed decrease in activation energy for the interfacial Li⁺-transfer reaction.     

Study of a gold electrode modified by trans-[Ru(NH3)4(Ist)SO4] to produce an electrochemical sensor for nitric oxide

The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH₃)₄(Ist)SO₄]⁺ to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH₃)₄(Ist)SO₄]⁺ complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO.     

Hexacyanoferrate ion adsorbed on propylpyridiniumsilsesquioxane polymer film-coated SiO2/Al2O3: use in an electrochemical oxidation study of cysteine

Hexacyanoferrate ion, [Fe(CN)₆]⁴⁻, was immobilized by an ion-exchange reaction on the propylpyridiniumsilsesquioxane chloride polymer thin-film-coated SiO₂/Al₂O₃ surface. The amount of [Fe(CN)₆]⁴⁻ immobilized was 0.22 mmol g⁻¹ with a surface coverage of 9.6×10⁻⁶ mmol cm⁻². A carbon paste electrode made with this material was prepared and its electrochemical properties studied. The electrode presented two well-defined redox peaks with midpoint potentials, E_m, of 0.152 V vs SCE. This potential was not significantly affected by pH changes between 2 and 9.5. The electrode showed much reproducible responses and was successfully used to study the electrochemical oxidation of cysteine.     

Voltammetric determination of paraquat at DNA-gold nanoparticle composite electrodes

A novel electroanalytical method for the detection of paraquat using DNA modified gold nanoparticles immobilized at a gold electrode is demonstrated. The electrode surface was first modified using the self-assembly of gold nanoparticles (NPs) followed by the simple adsorption of DNA onto the NPs, which was straightforward, fast and cost effective. The DNA-nanoparticle composite sensor was then characterized in terms of electrochemical responses both in the absence and in the presence of paraquat using cyclic voltammetry, differential pulse voltammetry and square wave voltammetry. The DNA-NPs composite electrode proved to work adequately as a biosensor for the quantitative analysis of paraquat concentrations, taking advantage of utilizing both the modified gold nanoparticles and the interaction between DNA with paraquat molecules. In addition, the NPs modified electrode demonstrated good sensitivity and stability towards the first reversible reduction step of the double charged paraquat ion. Good linearity between paraquat concentration and peak current was observed for the concentration range of 5.0 × 10⁻⁶ to 1.0 × 10⁻³ M when using differential pulse voltammetry. The use of modified electrodes improves the performance of the biosensor in the presence of interfering species in particular when square wave voltammetry is used.