Amperometric detection of amino acids with a passivated copper electrode

The amperometric behaviour of a copper electrode towards amino acids is studied by means of a rotating disc electrode. A theoretical model describing the anodic background current in a buffer solution and the increase of the current caused by amino acids is checked experimentally. The influences of the amino acid concentration, the rotation speed of the electrode and the composition of the buffer solution are studied. It is proved that chemical dissolution of a passivating film on the electrode surface, which is enhanced by the complexation reaction between the amino acid and copper(II) ions, is the principle of the phenomena observed. The applicability to flow systems is demonstrated.     

Flow injection sample processing with nickel oxide electrode amperometric detection of amino acids separated by ion-exchange chromatography

A new automatic post-column sampler has been designed and used for interfacing the column outlet to a flow injection system. Segments of the effluent from the column are injected into the flow injection apparatus at regular intervals. Separation and detection of several amino acids are described. A nickel oxide electrode detector yields characteristic, useful signals for concentrations as low as 10^-6 M. Samples containing 20–35 μg of total amino acids in 1 ml were chromatographed.     

Amperometric detection of amino acids in a flow-injection system with a nickel(II)-modified electrode with an Eastman-AQ polymer film

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l⁻¹ KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 × 10⁻⁶-0.1 mol l⁻¹ with a detection limit of 1.0×10⁻⁶ mol l⁻¹. A 1 × 10⁻⁴ mol l⁻¹ mixture of serine and tyrosine was also detected after separation on an Nucleosil C₁₈ column.     

Determination of ethanol by air-stream separation with flow injection and electrochemical detection at a nickel oxide electrode

Ethanol is separated by an air stream from a 1-ml sample with collection in 1 ml of 0.2 mol l^-1 sodium hydroxide. Measurement is by voltammetry at a tubular, catalytic nickel oxide electrode with 30-μl sample injected into a continuous flow stream. Relative standard deviation for repetitive measurements is 1.8% for synthetic samples. Serum samples extracted for 100 s and then measured yielded linear results for concentrations of 2 × 10^-4–5 × 10^-2 mol l^-1 ethanol (0.001–0.23%), with relative standard deviation of 2.0%. The time per determination was about 2 min.     

Amperometric carbohydrate detection in flow systems by means of a bismuth modified platinum electrode

Bismuth modified platinum electrodes are used for constant-potential amperometric determination of carbohydrates in flow systems. The monitored response is stable and reproducible over more than two days. An attempt is made to gain more detailed information about the characteristics of the modified layer by electrochemical methods and X-ray photoelectron spectroscopy. The response proved to be linear over the investigated concentration range (1.1–1200 mol/L) and detection limits for glucose and fructose were found to be 1.1 mol/L.     

Amperometric detection for capillary flow injection analysis

Ultrasmall-volume measurements of oxidizable compounds have been accomplished by coupling a capillary flow injection system with amperometric detection. Remarkably low (femtomole) mass detection limits result from the combination of nanoliter sample volume and the inherent sensitivity of the wall-jet detector. A substantial economy of reagent consumption and disposal accrues from the operation of the nl/min flow regime. Variables influencing the physical dispersion in the capillary flow injection system, including capillary length, sample volume or flow rate, are explored and optimized.     

Selective determination of amino acids using flow injection analysis coupled with chemiluminescence detection

The determination of the amino acids proline, histidine, tyrosine, arginine, phenylalanine and tryptophan using flow injection analysis (FIA) with chemiluminescence detection is described. Proline was the only amino acid to exhibit chemiluminescence with the tris(2,2-bipyridyl)ruthenium(III) reaction at pH 10. While, histidine was found to selectively enhance the reaction of luminol with Mn(II) salts in a basic medium. Acidic potassium permanganate chemiluminescence was able to selectively determine tyrosine at pH 6.75. Low pressure separations using a C18 guard column allowed the simultaneous determination of tyrosine and tryptophan or phenylalanine and tryptophan with acidic potassium permanganate and copper(II)-amino acid-hydrogen peroxide chemiluminescence, respectively. Precision for each method was less than 3.9% (R.S.D.) for five replicates of a standard (1×10⁻⁵ M) and the detection limits ranged between 4×10⁻⁹ and 7×10⁻⁶ M. Preliminary investigations revealed that the methodology developed was able to selectively determine the individual amino acids in an equimolar mixture of the 20 naturally occurring amino acids.     

Amperometric detection of hydroxypurines at an electrode modified with a composite based on mixed-valence ruthenium and cobalt oxides in flow injection analysis

A composite material based on mixed-valence ruthenium and cobalt oxides, electrodeposited on the surface of a screen printed electrode, exhibits high catalytic activity in the electrooxidation of uric acid, xanthine, and hypoxanthine. Catalysis manifests itself as a decrease in the substrate oxidation overvoltage and an increase in current at the potential of modifier oxidation. A method is proposed for the simultaneous amperometric detection of two-component systems uric acid–xanthine, xanthine–hypoxanthine, and uric acid–hypoxanthine using a screen printed electrode with two working electrodes modified by this composite. The dependence of the analytical signal on the concentration of analytes is linear in the range 5 × 10^–8 to 5 × 10^–3 M for uric acid and xanthine and from 5 × 10^–7 to 5 × 10^–3 M for hypoxanthine.     

Amperometric determination of underivatized amino acids at a nickel-modified gold electrode by anion-exchange chromatography

A nickel-based composite electrode obtained by anodic electrodeposition of nickel (III) oxyhydroxide film on the gold electrode substrate was characterized as an amperometric sensor and successfully applied to the determination of underivatised amino acids in flow-through systems. The electrodeposition of nickel oxyhydroxide films was obtained by cycling a gold electrode between 0.0 V and +1.0 V vs. a saturated calomel electrode in a 80 microM Ni2+ solution buffered at pH 10 with NaHCO3/Na2CO3. The resulting Au-Ni composite electrode exhibits good stability in alkaline medium and can be used as an amperometric sensor of underivatised amino acids at a fixed applied potential (+0.55 V vs. Ag/AgCl). The detection limits (S/N=3) for all investigated compounds ranged between 5 and 30 pmol injected, while the linear ranges spanned over two or three orders of magnitude. The contents of several free amino acids in two sample cheeses from different brands were evaluated by calibration graphs.     

Adsorption of dicarboxylic acids on lithiated nickel oxide electrode

Adsorption of dicarboxylic acids on NiO electrodes was studied by means of the galvanostatic transient method, mainly for oxalic acid. The oxalate or hydrogen oxalate anion or both were concluded to adsorb on the electrode. The adsorption was maximal at a potential less positive than the flat-band potential of the electrode, owing to preferential adsorption of hydroxyl anion in the region above the maximum adsorption potential. The quantity of adsorption was dependent on carrier concentration of the electrode, and high for the electrode of high carrier concentration. This phenomenon is connected to the charged condition of the electrode that when the maximum adsorption takes place, positively charged sites remain on the surface of the electrode which is charged negatively as a whole and the amount of the sites is much more different between the electrodes of different N than their bulk carrier concentrations. Adsorptions of malonic and succinic acid were distinctly low compared with that of oxalic acid. The adsorbability was in the order; oxalic acid>malonic acid>succinic acid. This order was in accord with the stability constants of nickel dicarboxylic acid chelates.     

Amperometric measurements with ion-selective electrode membranes in a flow system

Calcium and salicylate sensitive electrode membranes based on plasticized PVC were used for selective amperometric detection in a flow injection system. The peak current was found to depend linearly on concentration and the working range extended well below the potentiometric detection limit.Dedicated to Professor W. Simon on the occasion of his 60th birthday     

Amperometric nonenzymatic determination of glucose via a glassy carbon electrode modified with nickel hydroxide and N-doped reduced graphene oxide

The authors describe a nonenzymatic glucose sensor that was obtained by electrochemical deposition and oxidization of metallic nickel on the surface of nitrogen-doped reduced graphene oxide (N-RGO) placed on a glassy carbon electrode (GCE). An analysis of the morphology and chemical structure indicated the composite to possess a well-defined vermicular Ni(OH)₂ nanorods combined with N-RGO. The electrochemical performance of the modified GCE with respect to the detection of glucose in 0.1 M NaOH was investigated by cyclic voltammetry and amperometry. The wrinkle and protuberance of N-RGO for loading of nanostructured Ni(OH)₂ are found to increase electrical conductivity, surface area, electrocatalytical activity and stability. The modified GCE displays a high electrocatalytic activity towards the oxidation of glucose in 0.1 M NaOH solution. The lower detection limit is 0.12 μM at an applied potential of +0.45 V (vs Ag/AgCl) (S/N=3), and the sensitivity is 3214 μA mM^?1 cm^?2. The modified GCE possesses long-term stability, good reproducibility and high selectivity over fructose, sucrose and lactose.

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Graphical abstract The composite of vermicular Ni(OH)₂ nanorods combined with N-doped reduced graphene oxide is a viable catalyst for non-enzymatic electrochemical sensing of glucose.

     

Sheath-flow electrochemical detection of amino acids with a copper wire electrode in capillary electrophoresis

Here, we report the detection of native amino acids using a sheath-flow electrochemical detector with a working electrode made of copper wire. A separation capillary that was inserted into a platinum tube in the detector acted as a grounded electrode for electrophoresis and as a flow channel for sheath liquid. Sheath liquid flowed outside the capillary to support the transport of the separated analytes to the working electrode for electrochemical detection. The copper wire electrode was aligned at the outlet of the capillary in a wall-jet configuration. Amino acids injected into the capillary were separated following elution from the end of the capillary and detection by the copper electrode. Three kinds of copper electrodes with different diameters-50, 125, and 300 μm-were examined to investigate the effect of the electrode diameter on sensitivity. The peak widths of the analytes were independent of the diameter of the working electrode, while the 300-μm electrode led to a decrease in the signal-to-noise ratio compared with the 50- and 125-μm electrodes, which showed no significant difference. The flow rate of the sheath liquid was also varied to optimize the detection conditions. The limits of detection for amino acids ranged from 4.4 to 27 μM under optimal conditions.     

Amperometric method for rapid detection of Escherichia coli by flow injection analysis using a bismuth nano-film modified glassy carbon electrode

A new method for rapid detection of Escherichia coli (E. coli) was developed by flow injection analysis (FIA) using bismuth nano-film modified glassy carbon electrode (BiNFE) in this paper. The method depended on a good marker β-d-glucuronidase which is found in E. coli strains. β-d-Glucuronidase was produced by the induction of methyl-β-d-glucuronide sodium (MetGlu), then released from E. coli cells through the permeabilization of cell membrane caused by polymyxin B nonapeptide and lysozyme. The released β-d-glucuronidase could catalyze the hydrolysis of the substrate 4-nitrophenyl β-d-glucuronide (PNPG) in the culture medium to produce 4-nitrophenol. Since 4-nitrophenol is electroactive and its quantity is proportional to the concentration of E. coli, E. coli could be determined by electroanalysis of 4-nitrophenol. The BiNFE was fabricated by an electrodeposition of metallic bismuth onto a glassy carbon electrode, which showed a high sensitivity in determination of 4-nitrophenol when used in conjunction with FIA system. Experimental results showed that the amplified response current of 4-nitrophenol obtained at the BiNFE was linear with the concentration of E. coli ranging from 1.5 × 10² to 1.0 × 10⁶ cfu/ml, the detection limit of this method for E. coli is 100 cfu/ml, and the complete assay was performed in 3 h.     

Amperometric determination of sulfide at a pre-oxidised nickel electrode in acidic media

The electrochemical response of a pre-oxidised nickel electrode to increasing additions of sulfide has been examined and shown to produce a stripping-like voltammetric wave. A mechanism is described based on the formation of nickel sulfide at the electrode surface from a non-electroactive nickel oxide layer. The analytical utility of the approach has been examined and a linear range from 1 to 140 microM and a limit of detection of 0.8 microM is achievable, depending on the accumulation time.     

A nickel oxide amperometric detector in the chromatographic separation of amino acids

Reverse-phase ion-pair chromatography with a nickel oxide amperometric detector is evaluated for separation and detection of several amino acids. A simple T-junction allows post-column mixing of detector electrolyte. Mixer and detector dimensions are shown to contribute negligibly to band spreading. Picomole amounts of some amino acids can be detected. The system is evaluated for determination of amino acids in hydrolyzed bovine A-chain insulin and urine samples.     

Amperometry of thiols in a flow-injection system with a nickel oxide electrode

The electrochemical oxidation of a series of thils on the surface of a nickel oxide electrode is investigated in a flow-injection system. The background electrolyte is 0.1 M NaOH containing 5 × 10^?65 M NiSO₄ and the injected sample volume is 25 μl. The net peak current is observed at +0.46 V vs. SCE for thiols dissolved in pH 3.0 phthalate buffer. The upper limit of linearity extends to 10^?3 M. The relative standard deviation for ten replicate measurements on 10^?4 M ethanethiol is 1.6%. The lower limits of detection are between 3 × 10^?5 and 2 × 10^?4 M for a series of thiols. Peak shapes indicate that thiolate oxidation mediated by a higher oxide layer on the electrode rather than mass transport or adsorption / rearrangement is the rate-determining step.     

Amperometric detection of nitric oxide using a glassy carbon electrode modified with gold nanoparticles incorporated into a nanohybrid composed of reduced graphene oxide and Nafion

Microchimica Acta - The authors show that the electrocatalytic performance toward the detection of nitric oxide (NO) can be enhanced by making use of gold nanoparticles (AuNP) in a matrix...