Electrochemical preparation of epinephrine/Nafion chemically modified electrodes and their electrocatalytic oxidation of ascorbic acid and dopamine

Two types of epinephrine and cyclized epinephrine quinone films have been prepared using cyclic voltammetry from the epinephrine in the strong acidic solutions and neutral aqueous solutions over different scanning potential ranges. The cyclic voltammogram of the epinephrine film is characterized by one redox couple at about +0.5 V (versus Ag|AgCl) and cyclized epinephrine quinone film exhibits one redox couples at about −0.15 V (versus Ag|AgCl) .In addition to cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM) were used to study the growth mechanism of the epinephrine and cyclized epinephrine quinone molecules. The electrocatalytic oxidation of catecholamines (dopamine and norepinephrine) and also ascorbic acid were investigated in acidic aqueous solutions using epinephrine films. The rotating ring-disk electrode technique was used to investigate the mechanism of electrochemical oxidation of dopamine and ascorbic acid.     

Electrocatalytic properties of NDGA and NDGA/FAD hybrid film modified electrodes for NADH/NAD redox reaction

The fabrication of monolayers composed of nordihydroguaiaretic acid (NDGA), and hybrid films composed of NDGA-flavin adenine dinucleotide (FAD) adsorbed films was performed in neutral aqueous solutions to produce electrochemically active thin films exhibiting one and two redox couples, respectively. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the NDGA and hybrid NDGA/FAD film monolayers. The NDGA modified film electrocatalytically oxidized NADH, ascorbic acid, dopamine, and N₂H₄ in neutral aqueous solutions. Well-separated voltammetric peaks were observed for dopamine and uric acid mixtures, and also for ascorbic acid and uric acid mixtures using the NDGA/GC modified electrode. When transferred to various aqueous buffered solutions, the two redox couples of the NDGA/FAD hybrid film and their formal potentials were observed to be pH-dependent. The electrocatalytic oxidation and reduction of NADH and NAD⁺ by a NDGA/FAD hybrid film in neutral aqueous solutions was carried out, and the electrocatalytic oxidation of NADH was performed using a NDGA/FAD hybrid film.     

Electrocatalytic reduction of hydrogen peroxide and its determination in antiseptic and soft-glass cleaning solutions at phosphotungstate-doped-glutaraldehyde-cross-linked poly-l-lysine film electrodes

The present work describes the electrocatalytic behavior of phosphotungstate-doped glutaraldehyde-cross-linked poly-l-lysine (PLL-GA-PW) film electrode towards reduction of hydrogen peroxide (H₂O₂) in acidic medium. The modified electrode was prepared by means of electrostatically trapping the phosphotungstate anion into the cationic PLL-GA coating on glassy carbon electrode. The PLL-GA-PW film electrode showed excellent electrocatalytic activity towards H₂O₂ reduction in 0.1 M H₂SO₄. Under the optimized conditions, the electrochemical sensor exhibited a linear response for H₂O₂ concentration over the range 2.5 × 10⁻⁶ to 6.85 × 10⁻³ M with a sensitivity of 1.69 μA mM⁻¹. The curvature in the calibration curve at high concentration is explained in terms of Michaelis-Menten (MM) saturation kinetics, and the kinetics parameters calculated by three different methods were compared. The PLL-GA-PW film electrode did not respond to potential interferents such as dopamine, ascorbic acid and uric acid. This unique feature of PLL-GA-PW film electrode allowed selective determination of H₂O₂. Finally, the proposed electrochemical sensor was successfully applied to determine H₂O₂ in commercially available antiseptic solution and soft-contact lenses cleaning solution and the method has been validated using independent estimation by classical potassium permanganate titration method. Major advantages of the method are simple electrode fabrication, stability and high selectivity towards hydrogen peroxide.     

一种基于模糊粗糙集知识获取方法

本文介绍了粗糙集和模糊粗糙集的上下近似。并且利用模糊粗糙上下近似算子,论述了在不完备模糊信息系统中知识获取的一种方法。应用这种方法能够让隐藏在不完备模糊信息系统中的知识,以决策规则的形式表示出来。最后给出了一种实现算法和实例。     

POPS: an off-peak precomputing scheme for privacy-preserving computing

Emerging privacy-preserving technologies help protect sensitive data during application executions. Recently, the secure two-party computing (TPC) scheme has demonstrated its potential, especially for the secure model inference of a deep learning application by protecting both the user input data and the model parameters. Nevertheless, existing TPC protocols incur excessive communications during the program execution, which lengthens the execution time. In this work, we propose the precomputing scheme, POPS, to address the problem, which is done by shifting the required communications from during the execution to the time prior to the execution. Particular, the multiplication triple generation is computed beforehand with POPS to remove the overhead at runtime. We have analyzed the TPC protocols to ensure that the precomputing scheme conforms the existing secure protocols. Our results show that POPS takes a step forward in the secure inference by delivering up to \(20\times \) and \(5\times \) speedups against the prior work for the microbenchmark and the convolutional neural network experiments, respectively.

     

Green synthesized Au–Ag bimetallic nanoparticles modified electrodes for the amperometric detection of hydrogen peroxide

Simple and eco-friendly electro deposition method was employed for the fabrication of Au–Ag bimetallic nanoparticles modified glassy carbon electrode. Nano Au–Ag film modified glassy carbon electrode surface morphology has been examined using atomic force microscopy. Electrodeposited Au–Ag bimetallic nanoparticles were found in the average size range of 15–50 nm. The electrochemical investigations of nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion film have been carried out using cyclic voltammetry and electrochemical impedance spectroscopy. The nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion film modified glassy carbon electrode holds the good electrochemical behavior and stability in pH 7.0 phosphate buffer solutions. The nano Au–Ag/1-butyl-3-methylimidazolium tetrafluoroborate-nafion modified glassy carbon electrode was successfully employed for the detection of H₂O₂ in the linear range of 1–250 μM in lab samples, and 1 × 10⁻³–2 × 10⁻² M in real samples, respectively.     

Electrochemical fabrication of Rh–Pd particles and electrocatalytic applications

Electrochemical deposition method was employed for the fabrication of rhodium–palladium (Rh–Pd) particles on the glassy carbon electrode (GCE) and indium tin oxide (ITO) electrode surface. Surface morphological analysis of Rh–Pd film has been carried out using scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. Here, the electrodeposited Rh–Pd particles were found in the average size range of 30–200 nm. The electrochemical activities of the Rh–Pd film have been investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopic (EIS) analysis. The Rh–Pd particles-modified GCE successfully detects the hydrogen peroxide (H₂O₂) (in pH 7.0 phosphate buffer solution (PBS)) in the linear range in the lab (10–460 μM) and real samples (10–340 μM). The Rh–Pd particles-modified GCE possesses the good sensitivity and selectivity for the detection of H₂O₂ in lab and real samples.     

Preparation and characterization of osmium hexacyanoferrate films and their electrocatalytic properties

Osmium hexacyanoferrate films have been prepared using repeated cyclic voltammetry, and the deposition process and the films’ electrocatalytic properties in electrolytes containing various cations have been investigated. The cyclic voltammograms recorded the deposition of osmium hexacyanoferrate films directly from the mixing of Os³⁺ and Fe(CN)₆³⁻ ions from solutions containing various cations. An electrochemical quartz crystal microbalance, cyclic voltammetry, and UV-visible spectroscopy were used to study the growth mechanism of the osmium hexacyanoferrate films. The osmium hexacyanoferrate films showed a single redox couple, and the redox reactions included “electron transfer” and “proton transfer” with a formal potential that demonstrates a proton effect in acidic solutions up to a 12 M aqueous HCl solution. The electrochemical and electrochemical quartz crystal microbalance results indicate that the redox process was confined to the immobilized osmium hexacyanoferrate film. The electrocatalytic reduction of dopamine, epinephrine, norepinephrine, S₂O₃²⁻, and SO₅²⁻ by the osmium hexacyanoferrate films was performed. The preparation and electrochemical properties of co-deposited osmium(III) hexacyanoferrate and copper(II) hexacyanoferrate films were determined, and their two redox couples showed formal potentials that demonstrated a proton effect and an alkaline cation effect, respectively. Electrocatalytic reactions on the hybrid films were also investigated.     

The interaction of water-soluble iron porphyrins with DNA films and the electrocatalytic properties for inorganic and organic nitro compounds

The electrochemistry of water-soluble iron porphyrins (Fe(n-TMPyP)) (where n=2 and 4) was studied as an electrochemically active film on DNA modified glassy carbon, gold, platinum, and transparent semiconductor tin oxide electrodes in solutions of various pH values. The two layers of the modified electrode containing the iron porphyrin and the DNA film were prepared by depositing the iron porphyrin on a DNA film modified electrode. The Fe(4-TMPyP)/DNA film was electrocatalytic reductive for p-nitrobenzoic acid in a weak acidic, or neutral aqueous solution through an Fe^II species, and the electrocatalytic reduction peak potential became more negative than the cathodic peak of the Fe^III/II redox couple. The electrocatalytic reduction properties by the Fe(2-TMPyP)/DNA film as catalysts for nitrite reduction have also been determined, and shown to be active through an Fe^I species and to be pH-dependent. The electrocatalytic oxidation properties of nitrite by Fe(n-TMPyP)/DNA (for n=2 and 4) film have also been determined and shown to be active through an Fe^IV species with the electrocatalytic oxidation efficiency of NO₂⁻ with Fe^IV(O)(n-TMPyP) being higher than with (HO)Fe^IV(O)(n-TMPyP). The electrocatalytic oxidation efficiency of NO₂⁻ by iron porphyrin is pH-dependent. The electrocatalytic reduction of p-nitrophenol by Fe(2-TMPyP)/DNA film are also discussed.     

The bioelectrocatalytic properties of cytochrome C by direct electrochemistry on DNA film modified electrode

The direct electrochemistry of cytochrome C can be performed in weak acidic and basic aqueous solutions. Cytochrome C can be deposited as a stable and electrochemically active film on a deoxyribonucleic acid (DNA) modified glassy carbon electrode. These films can also be produced on gold, platinum, and transparent semiconducting tin oxide electrodes. Two-layer modified electrodes containing cytochrome C and a DNA film were prepared by the deposition of cytochrome C on a DNA film modified electrode. The cytochrome C/DNA film was electrocatalytically oxidation active for l-cysteine in a pH 8.3 tris(hydroxymethyl)aminomethane (TRIS)-buffered aqueous solution through both Fe^III and Fe^IV species. The electrocatalytic oxidation current developed from the anodic peak of the redox couple. The electrocatalytic oxidation properties of ascorbic acid, NH₂OH, N₂H₄, and SO₃²⁻ by a cytochrome C/DNA film were also determined, and shown to be electrocatalytically active. An electrochemical quartz crystal microbalance, cyclic voltammetry, and direct spectroelectrochemistry were used to study in situ DNA deposition on a gold disc electrode and cytochrome C deposition on DNA/Au and DNA/GC films. The direct electrochemistry of cytochrome C can also be performed, and it can be deposited as a stable and electrochemically active film on polyvinyl sulfonate, polystyrene sulfonate, TiO₂, and polyethylene glycol modified glassy carbon electrodes. The results show that cytochrome C interacts with, and deposits on, a DNA film modified electrode, and that the cytochrome C (Fe^III) oxidized form is more easily deposited on a DNA film than the cytochrome C (Fe^II) reduced form.