A novel solid-contact potentiometric sensor for ascorbic acid based on cobalt phthalocyanine nanoparticles (NanoCoPc) as ionophore was fabricated without any need of auxiliary materials (such as membrane matrix, plasticizer, and other additives). The electrode was prepared by simple drop-coating NanoCoPc colloid on the surface of a glassy carbon electrode. A smooth, bright and blue thin film was strongly attached on the surface of the glassy carbon electrode. The electrode showed high selectivity for ascorbic acid, as compared with many common anions. The influences of the amount of NanoCoPc at the electrode surface and pH on the response characteristics of the electrode were investigated. To overcome the instability of the formal potential of the coated wire electrode, a novel electrochemical pretreatment method was proposed for the potentiometric sensor based on redox mechanism. This resulting sensor demonstrates potentiometric response over a wide linear range of ascorbic acid concentration (5.5 × 10−7 to 5.5 × 10−2 M) with a fast response (<15 s), lower detection limit (ca. 1.0 × 10−7 M), and a long-term stability. Furthermore, microsensors based on different conductors (carbon fiber and Cu wire) were also successfully fabricated for the determination of practical samples. 相似文献
This work presents a comparative study between two different methods for the preparation of mediator-modified screen-printed electrodes, to be used as detectors in a reliable flow injection system for the determination of the nicotinamide adenine dinucleotide (NADH) coenzyme. The best strategy was selected for the final development of compact biosensors based on dehydrogenase enzymes. For the first immobilisation strategy, different redox mediators were electropolymerised onto the SPE surface. The second immobilisation strategy was carried out using polysulfone–graphite composites, which were deposited by screen-printing technology onto the screen-printed electrode (SPE) surface. Both methods achieved an effective and reliable incorporation of redox mediators to the SPE configuration. Finally, a flow system for ammonium determination was developed using a glutamate dehydrogenase (GlDH)-Meldola's Blue (MB)-polysulfone-composite film-based biosensor.
The stability of the redox mediators inside the composite films as well as the negligible fouling effect observed on the electrode surface improve the repeatability and reproducibility of the sensors, important features for continuous analysis in flow systems. Furthermore, the optimised bio/sensors, incorporated in a flow injection system, showed good sensitivities and short response times. Such a good analytical performance together with the simple and fast sensor construction are interesting characteristics to consider the polysulfone-composite films as attractive electrochemical transducer materials for the development of new dehydrogenase-based SPEs. 相似文献
The widely accepted theory concerning the electrochemical energy storage mechanism of copper hexacyanoferrate (CuHCF) for supercapacitors is that CuHCF stores charge by the reversible redox processes of Fe3+/Fe2+ couple and Cu cations are electrochemically inactive. In this work, CuHCF nanocubes (CuHCF-NC) were synthesized in the presence of potassium citrate and its electrochemical properties were tentatively studied in 1 mol/L Na2SO4 aqueous electrolyte. Good supercapacitive performance was exhibited. The combined analyses of cyclic voltammogram (CV) and X-ray photoelectron spectroscopy (XPS) disclosed that the CuHCF nanocubes underwent the redox reactions of Fe3+/Fe2+ and Cu2+/Cu+ couples to store charges. The Cu2+/Cu+ redox couple was activated due to the strong coordination interaction between the carboxylate groups of citrate ions and surface Cu cations. 相似文献
The reactivity of Cu+ with OCS on both singlet and triplet potential energy surfaces (PES) has been investigated at the UB3LYP/6-311+G(d) level. The object of this investigation was the elucidation of the reaction mechanism. The calculated results indicated that both the C–S and C–O bond activations proceed via an insertion–elimination mechanism. Intersystem crossing between the singlet and triplet surfaces may occur along both the C–S and C–O bond activation branches. The ground states of CuS+ and CuO+ were found to be triplets, whereas CuCO+ and CuCS+ have singlet ground states. The C–S bond activation is energetically much more favorable than the C–O bond activation. All theoretical results are in line with early experiments. 相似文献
A set of coupled equations is given which determines the distributions of the electric potential and counterions in a system of two interacting identical ion-penetrable membranes of thickness d at separation h immersed in a salt-free medium containing only counterions. The solution to these coupled equations also gives the electrostatic repulsive force between the membranes. It is shown that the interaction force remains finite at h-->0, unlike the case of the interaction between two planar charged surfaces (d-->0), and that the interaction force becomes independent of the membrane fixed charge and membrane thickness d at very large h. Finally, an approximate single transcendental equation giving the solution to the coupled equations is derived. 相似文献
Summary The conditional protonation constants (=0.1) for 2,2:6,2-terpyridine, logK1=4.93, logK2=3.69, were determined by thepH-metric method. The compositions of complexes of Ag2+ and Ag+ ions with 2,2:6,2-terpyridine (tp) were studied and equilibria of the complex formation process were described. The values of conditional complex formation constants are as follows: for Ag(tp)
2+
:log01=5.79, log02=9.68, for Ag(tp)
22+
:log02=25.31, while the conditional constant of the Ag(tp)NO3 precipitate formation is:KSO=2.45·104. Using coulometric and chronovoltamperometric measurements, the redox systems being formed in the complex solutions of Ag(II) and Ag(I) were determined and described including their formal potentials.
Komplexibildungsgleichgewichte und Redoxpotentiale des Systems Ag(II)/Ag(I) in Gegenwart von 2,2:6,2-Terpyridin in Wasser
Zusammenfassung Mit Hilfe derpH-metrischen Methode wurden die konditionalen Protonationskonstanten (=0.1) von 2,2:6,2-Terpyridin bestimmt: logK1=4.93, logK2=3.69. Es wurde auch die Zusammensetzung der Komplexe von Ag(II) und Ag(I) mit 2,2:6,2-Terpyridin(tp) bestimmt sowie die Gleichgewichte der komplexbildung beschrieben. Die Werte der Konditionalkomplexbildungskonstanten sind: für Ag(tp)
2+
:log01=5.79, log02=9.68, für Ag(tp)
22+
:log02=25.31 und für das Löslichkeitsprodukt Ag(tp)NO3:KSO–1
=4.08·10–5. Die in Komplexlösungen von Ag(II) und Ag(I) vorliegenden Redoxsysteme wurden mittels cyclischer Voltametrie und Coulometrie untersucht und die Formalpotentialwerte dieser Systeme in Wasser bestimmt.
Ab initio Hartree-Fock calculations utilising STO-3G, 3-21G* and 6-31G* basis sets have been performed on three neutral and highly polar molecules, (diformylmethine)borondifluoride, (acetylacetonato)borondifluoride and (dibenzylmethine) borondifluoride. The calculated and experimental structures are well correlated when using the HF/3-21G* basis set, except for the structure parameters involving the boron atom. The HF/6-31G* basis set does not improve the accuracy in structure calculations. The conformational analysis is in agreement with the experimentally observed C2v symmetrical structures, where the boron atom is tetrahedrally coordinated. The calculations support a one-dimensional ground state barrier crossing reaction for (dibenzylmethine)borondifluoride, where the phenyl torsion is the most likely reaction coordinate. Both HF/6-31G* calculations and the second-order Møller-Plesset correction with the 3-21G* basis set suggest an activation energy of the ground state reaction of about 30 kJ mol−1. The ground state barrier crossing reaction kinetics is evaluated by the Kramers theory. The calculated ground state parameters relevant to the barrier crossing reaction are compared with the experimentally observed excited state values. 相似文献