Cobalt sulfide flower-like derived from metal organic frameworks on nickel foam as an electrode for fabrication of asymmetric supercapacitors.

Metal-organic frameworks, as a kind of advanced nanoporous materials with metal centers and organic linkers, have been applied as promising electrode materials in energy storage devices. In this study, we are successfully prepared cobalt sulfide nanosheets (CoS) derived from the metal-organic framework on nickel foam (NF). The prepared electrodes are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller and Barrett-Joyner-Halenda and electrochemical methods like voltammetry, galvanostatic charge-discharge curve and electrochemical impedance spectroscopy. The CoS/NF electrode demonstrates a high specific capacity of 377.5 mA h g-1 (1359 C g-1) at the current density of 2 A g-1, considerable rate performance and excellent durability (89.4% after 4000 cycles). A hybrid supercapacitor is assembled using CoS/NF as the positive electrode and activated carbon as the negative electrode, it shows a high energy density of 57.4 W h kg-1 at a power density of 405.2 W kg-1. The electrochemical results suggest that the CoS nanosheet arrays would possess excellent potential for applications in energy storage devices.

A multichannel closed bipolar platform to visual electrochemiluminescence sensing of caffeic acid as a model: Potential for multiplex detection.

In this study, a fully-featured electrochemiluminescence (ECL) sensing platform based on a multichannel closed bipolar system (closed-BP, C-BP) for the determination of caffeic acid (CA) was successfully developed. The system comprises three individual reservoirs connected to each other by two pairs of gold rods as bipolar electrodes. Moreover, a single pair of gold rods functions as the driving electrodes. Due to configuration consisting of three channels and double-bipolar electrodes, the detection of CA was accomplished in two oxidation and reduction pathways within a single device. Firstly, through close observation of the reactions occurring within the device and utilizing a universal pH indicator and bipolar electrodes, a precise mechanism for the current bipolar systems was initially proposed. Then, the concentration of CA was monitored in the reporting chamber through the following ECL intensities resulting from luminol oxidation and H2O2. The monitoring process was performed using both a photomultiplier tube (PMT) and a digital camera. In the process of analyte oxidation, the PMT and visual (camera)-based detection exhibited a linear response from 5 µmol L-1 to 700 µmol L-1 (limit of detection (LOD) 1.2 µmol L-1) and 50 µmol L-1 to 600 µmol L-1 (LOD 14.8 µmol L-1), respectively. In the analyte reduction pathway, the respective values were 30 µmol L-1 to 450 µmol L-1 (LOD 8.6 µmol L-1) and 55 µmol L-1 to 400 µmol L-1 (LOD 21.2 µmol L-1), for the PMT and visual-based detection, respectively. Our experiments have demonstrated the practical application of the sensor array for efficient and high-performance analysis. This innovative design holds significant potential for diverse fields and paves the way for the development of a user-friendly device.

In situ electrosynthesis of a copper-based metal-organic framework as nanosorbent for headspace solid-phase microextraction of methamphetamine in urine with GC-FID analysis.

For the first time, a fiber coating based on copper metal-organic framework was fabricated on an anodized stainless steel wire by an in situ electrosynthesis approach. The fiber was used for the preconcentration and determination of methamphetamine by headspace solid-phase microextraction followed by gas chromatography-flame ionization detection. The electrosynthesis of the fiber coating was performed under a constant potential of - 1.7 V by controlling the electrogeneration of OH- in a solution containing sodium nitrate as the probase, 1,2,4,5-benzenetetracarboxylate acid as the ligand and copper nitrate as the cation source. The coating was characterized using field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The effective parameters on the electrosynthesis, extraction, and desorption processes were thoroughly optimized. Under the optimized conditions, metamphetamine (MAP) was quantified over a linear range of 0.90-1000.0 ng mL-1 with R2 > 0.997. A limit of detection of 0.1 ng mL-1 was achieved, and intra- and inter-day relative standard deviations were found within the range 3.0-4.4% and 2.8-3.9%, respectively. Finally, the method was successfully applied to determination of MAP in urine samples with good recoveries in the range 85.0-102.5%. Graphical abstract Schematic representation of the in-situ electrochemical synthesis of a Cu-based metal-organic framework and its application in a headspace SPME procedure for the measuring methamphetamine in urine samples followed by GC-MS analysis.

An electrochemical sensor based on an Eriochrome Black T polymer and deep eutectic solvent for the simultaneous determination of omeprazole and lansoprazole.

Here we report the fabrication of an electrochemical sensor for the simultaneous determination of the concentrations of omeprazole (OMZ) and lansoprazole (LAN) in biological fluids and pharmaceuticals in Britton-Robinson buffer solution (pH 6.0). The sensor was prepared by bulk modifying a carbon paste electrode with deep eutectic solvent (DES), followed by carrying out electropolymerization of Eriochrome Black T (EBT) at this electrode. The presence of DES increased the extent of the polymerization of EBT on the surface of the electrode, and this increase led to better OMZ and LAN electron transfer kinetics at the electrode surface. The modified electrode was evaluated and characterized by performing cyclic voltammetry, electrochemical impedance spectroscopy, scanning electronic microscopy, and Fourier-transform infrared spectroscopy. The best responses were obtained in drug-free Britton-Robinson buffer solution (pH 6.0) after 600 s of stirring at the open circuit potential. Linear relationships were obtained between the anodic peak currents and the concentrations of OMZ and LAN in the ranges of 0.010-0.276 and 0.010-0.300 µM, with detection limits of 0.006 and 0.009 µM, respectively. Satisfactory results were also obtained for the analysis of OMZ and LAN in real samples. The excellent sensitivity and easy regeneration and modification of this electrode with DES followed by the polymerization of EBT make this electrode relatively highly applicable for flow methods.

Introduction of electropolymerization of pyrrole as a coating method for stir bar sorptive extraction of estradiol followed by gas chromatography.

In this study, fabrication of a stir bar sorbent is presented by electropolymerization of pyrrole via cyclic voltametry for the first time. The fabricated stir bar was applied as an efficient sorbent for extraction and pre-concentration of trace amounts of estradiol in urine samples through stir bar sorptive extraction (SBSE) method followed by gas chromatography-flame ionization detector. For this purpose, first the surface of stainless steel rod was modified by hyroxide functional group. Then electropolymerization of pyrrole monomers took place on the surface of functionalized steel rod under the optimized conditions including pyrrole concentration of 0.03 mol L-1, equal concentration ratio of pyrrole to sodium dodecyl sulfate, 10 cycles of cyclic voltammetry and potential scan rate of 10 mV s-1. Characterization of the produced sorbent was confirmed by scanning electron microscope imaging and energy-dispersive X-ray and infrared spectroscopy. Evantually, under the optimized conditions, the stir bar sorbent was used for extraction of estradiol from human urine samples. The presented SBSE method showed a good linearity range of 50-700 ng mL-1 with coefficient of determination 0.9910, limit of detection 10 ng mL-1 and theoretical limit of quantification 33 ng mL-1. Moreover, better enrichment factor (87) and extraction recovery (43%) were obtained using the fabricated stir bar compared with two commercial stir bars for estradiol. The intra- and inter-bar relative recoveries were obtained 92.0% and their coefficient of variations were less than 5.4%.

Voltammetric determination of adefovir dipivoxil by using a nanocomposite prepared from molecularly imprinted poly(o-phenylenediamine), multi-walled carbon nanotubes and carbon nitride.

An electrochemical sensor for adefovir dipivoxil (ADV) detection was prepared by electropolymerization of o-phenylenediamine in the presence of ADV on a glassy carbon electrode modified with multi-walled carbon nanotubes and carbon nitride. The electrode was characterized by field emission scanning electron microscopy and differential pulse voltammetry. The performance was optimized by response surface methodology. The changes in differential pulse voltammetric peak currents of the redox probe, ferricyanide, were linear to ADV concentrations in the range from 0.1 to 9.9 µmol L-1, with the detection limit of 0.05 µmol L-1 (S/N = 3). The sensor was applied to the determination of ADV in drug formulations, human serum and urine samples. It is selective due to the use of an imprinted material, well reproducible, long-term stable, and regenerable. Graphical abstract By merging the unique properties of carbon nitride with intrinsic properties of MWCNTs, and molecularly imprinted polymers, a novel electrochemical sensor with selective binding sites was prepared for determination of adefovir dipivoxil in pharmaceutical and biological samples.

Electrochemically Induced Michael Addition Reaction: An Overview.

Due to its high potential for the formation of carbon-carbon bonds, Michael addition reaction is one of the closest reactions to the heart of synthetic organic chemists. Electrochemistry presents a very stimulating and divergent resource for selective oxidation and reduction in organic chemistry, generating activated species, for example radical anions or radical cations. In this review, we try to underscore usefulness of electrogenerated Michael addition reaction with the hope of encouraging synthetic organic chemists to contemplate it, as an efficient and green strategy when it is required in their designed multi-step reaction pathways.

Recent Progress in the Development of Conducting Polymer-Based Nanocomposites for Electrochemical Biosensors Applications: A Mini-Review.

Among various immobilizing materials, conductive polymer-based nanocomposites have been widely applied to fabricate the biosensors, because of their outstanding properties such as excellent electrocatalytic activity, high conductivity, and strong adsorptive ability compared to conventional conductive polymers. Electrochemical biosensors have played a significant role in delivering the diagnostic information and therapy monitoring in a rapid, simple, and low cost portable device. This paper reviews the recent developments in conductive polymer-based nanocomposites and their applications in electrochemical biosensors. The article starts with a general and concise comparison between the properties of conducting polymers and conducting polymer nanocomposites. Next, the current applications of conductive polymer-based nanocomposites of some important conducting polymers such as PANI, PPy, and PEDOT in enzymatic and nonenzymatic electrochemical biosensors are overviewed. This review article covers an 8-year period beginning in 2010.

Enhancement of corrosion resistance of polypyrrole using metal oxide nanoparticles: Potentiodynamic and electrochemical impedance spectroscopy study.

We introduce a simple and facile strategy for dispersing of nanoparticles within a p-type conducting polymer matrix by in situ electropolymerization using oxalic acid as the supporting electrolyte. Coatings prepared from polypyrrole-nano-metal oxide particles synthesized by in situ polymerization were found to exhibit excellent corrosion resistance much superior to polypyrrole (Ppy) in aggressive environments. The anti-corrosion behavior of polypyrrole films in different states and the presence of TiO2, Mn2O3 and ZnO nanoparticles synthesized by electropolymerization on Al electrodes have been investigated in corrosive solutions using potentiodynamic polarization and electrochemical impedance spectroscopy. The electrochemical response of the coated electrodes in polymer and nanocomposite state was compared with bare electrodes. The use of TiO2 nanoparticles has proved to be a great improvement in the performances of polypyrrole films for corrosion protection of Al samples. The polypyrrole synthesized in the presence of TiO2 nanoparticles coated electrodes offered a noticeable enhancement of protection against corrosion processes. The exceptional improvement of performance of these coatings has been associated with the increase in barrier to diffusion, prevention of charge transport by the nanosize TiO2, redox properties of polypyrrole as well as very large surface area available for the liberation of dopant due to nano-size additive.

Facile electrosynthesis of nano flower like metal-organic framework and its nanocomposite with conjugated polymer as a novel and hybrid electrode material for highly capacitive pseudocapacitors.

The [Cu(btec)0.5DMF] (H4btec=1,2,4,5-benzenetetracarboxylate acid) was electrosynthesized on the graphite working electrode by applying catholic potential. The [Cu(btec)0.5DMF] grows on a graphite surface which results from the coordination of 1,2,4,5-benzenetetracarboxylate anions with Cu2+ cations. The electrosynthesized [Cu(btec)0.5DMF] was characterized by X-ray diffraction, scanning electron microscopy. Furthermore, POAP/Cu(btec)0.5DMF nanocomposite film electrosynthesized on the surface of the carbon paste electrode by cyclic voltammetry. Different electrochemical methods including galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. This work introduces new nanocomposite materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area and stability in an aqueous electrolyte.

Novel electroactive nanocomposite of POAP for highly efficient energy storage and electrocatalyst: Electrosynthesis and electrochemical performance.

In this work, we presented facile route for fabrication of poly ortho aminophenol (POAP) POAP and POAP/ZnO nanocomposite on the surface of the working electrode. The fractal dimension of nanocomposite films in the presence of counter ions was investigated. Surface morphology of the composite film was studied by surface microscopy techniques (SEM). The presence of ZnO in the films was confirmed by EDS analysis. The results indicate that a strong interaction exist at the interface of POAP and nano-ZnO. Different electrochemical methods including galvanostatic charge discharge experiments and cyclic voltammetry have been applied to study the system performance. This work introduces new nanocomposite materials for electrochemical redox capacitors with such advantages as the ease of synthesis, high active surface area and stability in an aqueous electrolyte. Furthermore, comparison with a Ni-POAP the Ni-POAP/ZnO electrode shows a better catalytic performance for the electrocatalytic oxidation of methanol in alkaline solution. It is observed that the in the presence of ZnO nanoparticles current density of electro-oxidation of methanol is almost constant in 400 cycles due to the stability of electrocatalyst in this cycle number and indicating that methanol reacted with the surface and no poisoning effect on the surface was observed.

Recent Electroanalytical Studies of Metal-Organic Frameworks: A Mini-Review.

Metal-organic frameworks (MOFs) are attracting considerable attention because of their unique structural properties, such as high surface areas, tunable pore sizes, and open metal sites, which enable them to have potential applications in gas storage, catalysis, sensors, drug release, and separation. Also, MOFs can be fabricated and functionalized as electrochemically functional frameworks with perfect electrochemical properties and electrocatalytic activities. This review focuses on the electroanalytical applications of MOFs between 2010 and 2014 years.

A study of the interaction tyrosine and DNA using voltammetry and spectroscopy methods.

The interaction of tyrosine (Tyr) with double stranded DNA was studied by cyclic voltammetry, fluorescence emission spectroscopy, and UV-vis spectroscopy. The presence of DNA on a single-walled carbon nanotubes (DNA/SWCNT/GCE) and multi-walled carbon nanotubes (DNA/MWCNT/GCE) modified glassy carbon electrode showed a decrease in the current and a positive shift in the Tyr oxidation peak, indicating the intercalative interaction. The transfer coefficient (α), heterogeneous rate constant (k(s)), and surface concentration (Γ) were calculated in the absence and presence of DNA. The corresponding binding constant of Tyr with DNA and Hill coefficient were obtained from cooperative Hill model. The UV spectroscopic data confirmed the interaction between Tyr and DNA is intercalative with the binding constant of 3.98×10(3) mol(-1) L. Furthermore, the mechanism of fluorescence quenching has been discussed and the binding constant and numbers of binding sites were obtained as 3.37×10(3) mol(-1) L and 2, respectively from the Stern-Volmer plot.

Interaction of ciprofloxacin with DNA studied by spectroscopy and voltammetry at MWCNT/DNA modified glassy carbon electrode.

The interaction of ciprofloxacin (Cf) with double-stranded DNA was studied by cyclic voltammetry, fluorescence emission spectroscopy, and UV-Vis spectroscopy. The presence of DNA results in a decrease in the current and a positive shift in the Cf oxidation peak indicates the intercalative interaction. The corresponding heterogeneous rate constant (k(s)) and the electron transfer coefficient (α) were calculated for free Cf and the bound Cf-DNA complex. The UV spectroscopic data confirmed the interaction between Cf and DNA is intercalative. Besides, the fluorescence emitted by Cf at 420 nm could be quenched in Britton-Robinson (B-R) buffer solution (pH 7.0, 0.04 mol L(-1)) when DNA was added. The mechanism of fluorescence quenching was a static quenching; the binding constant and numbers of binding sites were obtained from the Stern-Volmer plot. The calibration curve was found to be linear between F(0)/F and the DNA concentration is lied in the two dynamic ranges of 0.8-96.0 and 96.0-223 µg mL(-1) with the detection limit of 0.33 µg mL(-1). The method was efficaciously applied to analyze DNA in the serum sample.

Interaction of sulfadiazine with DNA on a MWCNT modified glassy carbon electrode: determination of DNA.

The interactions of sulfadiazine (SD), an antimicrobial drug, with double-stranded calf thymus DNA on the multi-walled carbon nanotubes modified glassy carbon electrode (MWCNT-GCE) have been studied by cyclic voltammetry and UV-vis spectroscopy. In the presence of DNA, the oxidation peak current of SD decreases and the peak potential shifts to a positive potential which indicates the interaction of SD with DNA. The binding of SD with DNA shows both electrostatic and intercalative modes. The binding of SD with DNA, when analyzed in terms of the cooperative Hill model, yields the binding constant, K(a)=2.87 × 10(3)M(-1) and a Hill coefficient m=1.9 in Britton-Robinson (B-R) buffer solution, pH=6.5. This electrochemical method was further applied to the determination of DNA. Under the selected conditions, two linear calibration curves for DNA detection were obtained in the concentration ranges from 0.03 to 0.13 µgmL(-1) and 0.60-3.50 µgmL(-1) with detection limit 0.03 µgmL(-1). The method was also applied to the determination of DNA in human blood plasma sample.

Comparison of conventional hollow fiber based liquid phase microextraction and electromembrane extraction efficiencies for the extraction of ephedrine from biological fluids.

In the present study, hollow fiber liquid phase microextraction (HF-LPME) based on pH gradient and electromembrane extraction (EME) coupled with high-performance liquid chromatography (HPLC) was compared for the extraction of ephedrine from biological samples. The influences of fundamental parameters affecting the extraction efficiency of ephedrine were studied and optimized for both methods. Under the optimized conditions, preconcentration factors of 120 and 35 for urine and 51 and 8 for human plasma were obtained using EME and HF-LPME, respectively. The calibration curves showed good linearity for urine and plasma samples by both methods with the coefficient of estimations higher than 0.98. The limits of detection were obtained 5 and 10 ng mL(-1) using EME and 60 and 200 ng mL(-1) by HF-LPME for urine and plasma samples respectively. The relative standard deviations of the analysis were found in the range of 5.2-8.6% (n=3). The results showed that in comparison with HF-LPME based on pH gradient, EME is a much more effective transport process, providing high extraction efficiencies in very short time.

Microextraction of mebendazole across supported liquid membrane forced by pH gradient and electrical field.

In the present study, extraction of mebendazole across a supported-liquid membrane (SLM) was performed based on two different driving forces: (1) pH gradient over the SLM, and (2) electrical field sustained over the SLM. The extracted drug concentration was studied using reversed-phase HPLC-UV. At passive extraction conditions, mebendazole was extracted from alkaline samples (0.01 mmol L(-1) NaOH) into 1-undecanol immobilized in the pores of a porous hollow fiber of polypropylene (SLM), and then transported into 25 µL of 100mM HCl as the acceptor solution. Under electrokinetic migration conditions, mebendazole transported under applied voltage from acidic solutions (100 mmol L(-1) HCl) through 2-nitrophenyl octyl ether (NPOE) immobilized in the pores of hollow fiber, into 25 µL of 100 mmol L(-1) HCl as the acceptor solution. The effects of several factors including the nature of organic solvent, pH of donor and acceptor solutions, extraction time and stirring speed on the extraction efficiency of the drug were investigated and optimized. Under optimal conditions, preconcentration factors (PF) of 211 and 190 were obtained for the drug based on passive transport and electromembrane extraction (EME), respectively. Also, linear range of 0.5-1000 µg L(-1) with estimation of coefficient higher than 0.994 was obtained for both of the proposed methods. The results showed that EME has higher speed in comparison with simple passive transport. The methods were successfully applied to extract mebendazole from plasma and urine samples and satisfactory results were obtained.

Electrochemical behavior and analytical application of ciprofloxacin using a multi-walled nanotube composite film-glassy carbon electrode.

A simple, rapid and applicable electrochemical method was developed for the determination of ciprofloxacin (Cf) based on a multi-wall carbon nanotubes film-modified glassy carbon electrode (MWCNT/GCE). The constructed electrode (MWCNT/GCE) exhibited excellent electrocatalytic behavior in the oxidation of Cf as evidenced by the enhancement of the oxidation peak current and the shift in the oxidation potential to lower values (by 130 mV) in comparison with the bare GCE. A detailed analysis of cyclic voltammograms and chronoamperograms gave fundamental electrochemical parameters including the electroactive surface coverage (Gamma), the transfer coefficient (alpha), the standard rate constant (k(s)) and diffusion coefficient (D). Under optimized conditions in voltammetric method, the dynamic linear calibration curve for Cf was obtained in the concentration range of 40-1000 micromol/L with the detection limit of 6 micromol/L. The analytical performance of this sensor has been evaluated for detection of the analyte in urine and serum samples.

Electrochemistry of the interaction of furazolidone and bovine serum albumin.

The electrochemical behavior of the interaction of furazolidone (Fu) with bovine serum albumin (BSA) was investigated by cyclic voltammetry and differential pulse voltammetry at a glassy carbon electrode. Fu shows an irreversible reduction at -0.34 V in pH 4.0 Britton-Robinson buffer (B-R) buffer-10% DMF solution. After the addition of BSA into the Fu solution, the reductive peak currents decreased without any significant shift of the peak potential and the appearance of new peaks. The electrochemical parameters of the interaction system were calculated in the absence and presence of BSA. This electrochemical method was further applied to the determination of BSA samples and the results were in good agreement with the traditional cellulose acetate electrophoresis. The linear dynamic range was between 10.0 and 80.0 mg l(-1). The detection limit was 7.6 mg l(-1) and the recoveries were obtained from 97.0% to 104.0%.

Electrochemical synthesis of 4-(dihydroxyphenylthio)-2H-chromen-2-one derivatives.

The 4-(dihydroxyphenylthio)-2H-chromen-2-one derivatives have been synthesized by direct electrochemical oxidation of catechols in the presence of 4-mercaptocoumarin as a nucleophile in water/acetonitrile (50/50) solution, in a one-pot process, at carbon rod electrode, in an undivided cell and in constant current conditions, through an EC mechanism. The products are characterized by spectra data. Besides, the difference in electrochemical oxidation of catechol in the presence of 4-hydroxycoumarin and 4-mercaptocoumarin explained by computational structure, natural bond orbital (NBO) analysis and density functional theory (DFT: B3LYP/6-31G*//B3LYP/6-31G*) based methods, using the GAUSSIAN 98 package of programs.