RESUMO
Caffeine is widely present in food and drinks, such as teas and coffees, being also part of some currently commercialized medicines, but despite its enhancement on several functions of human body, its exceeding use can promote many health problems. In order to develop new fast approaches for the caffeine sensing, graphite-epoxy composite electrodes (GECE) were used as substrate, being modified by different diazonium salts, synthetized as their tetraflouroborate salts. An analytical method for caffeine quantification was developed, using sware wave voltammetry (SWV) in Britton-Robinson buffer pH 2.0. Detection limits for bare electrode and 4-benzenesulfonic modified electrode were observed circa 145 µmol·L-1 and 1.3 µmol·L-1, respectively. The results have shown that the modification shifts the oxidation peaks to lower potential. Kinetics of the reaction limited by diffusion was more expressive when caffeine was added to the solution, resulting in decreases of impedance, characterized by lower R ct. All results for caffeine determination were compared to a reference chromatographic procedure (HPLC), showing no statistical difference. Analytical parameters for validation were suitably determined according to local legislation, leading to a linear behaviour from 5 to 150 µmol·L-1; precision of 4.09% was evaluated based on the RDC 166/17, and accuracy was evaluated in comparison with the reference method, with recovery of 98.37 ± 2.58%.
RESUMO
The phenazine monomers neutral red (NR) and methylene blue (MB) have been electropolymerised on different quartz crystal microbalance (QCM) substrates: MB at AuQCM and nanostructured ultrathin sputtered carbon AuQCM (AuQCM/C), and NR on AuQCM and on layer-by-layer films of hyaluronic acid with myoglobin deposited on AuQCM (AuQCM-{HA/Mb}(6)). The surface of the electrode substrates was characterised by atomic force microscopy (AFM), and the frequency changes during potential cycling electropolymerisation of the monomer were monitored by the QCM. The study investigates how the monomer chemical structure together with the electrode morphology and surface structure can influence the electropolymerisation process and the electrochemical properties of the phenazine-modified electrodes. Differences between MB and NR polymerisation, as well as between the different substrates were found. The electrochemical properties of the PNR-modified electrodes were analysed by cyclic voltammetry and electrochemical impedance spectroscopy and compared with the unmodified AuQCM. The results are valuable for future applications of modified AuQCM as substrates for electroactive polymer film deposition and applications in redox-mediated electrochemical sensors and biosensors.
RESUMO
A new conducting composite flexible material prepared from cellulose acetate (CA) polymer and graphite has been developed and used for the fabrication of electrodes, which were then characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy (SEM) was used to provide information concerning the morphology of the composite electrode surface. The potential window, background currents and capacitance were evaluated by cyclic voltammetry in the pH range from 4.6 to 8.2. The voltammetry of model electroactive species demonstrates a close to reversible electrochemical behaviour, under linear diffusion control. The electroactive area of the composite electrodes increases after appropriate electrode polishing and electrochemical pre-treatment. The electrodes were used as substrate for the electropolymerisation of the phenazine dye neutral red, for future use as redox mediator in electrochemical biosensors. The composite electrodes were also successfully used for the amperometric detection of ascorbate at 0.0 V vs. SCE, and applied to the measurement of ascorbate in Vitamin C tablets; the sensor exhibits high sensitivity and a low detection limit of 7.7 microM. Perspectives for use as a versatile, mechanically flexible and robust composite electrode of easily adaptable dimensions are indicated.
