Pablo Fanjul-Bolado

Manufacture and evaluation of carbon nanotube modified screen-printed electrodes as electrochemical tools

Carboxylated multiwalled carbon nanotubes (MWCNT-COOH) dissolved in a mixture of DMF:water were used to modify the surfaces of commercially available screen-printed electrodes (SPEs). The morphology of the MWCNT-COOH and the modified SPEs was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. SEM analysis showed a porous structure formed by a film of disordered nanotubes on the surface of the working electrode. The modification procedure with MWCNT-COOH was optimised and it was applied to unify the electrochemical behaviour of different gold and carbon SPEs by using p-aminophenol as the benchmark redox system. The analytical advantages of the MWCNT-COOH-modified SPEs as voltammetric and amperometric detectors as well as their catalytic properties were discussed through the analysis, for instance, of dopamine and hydrogen peroxide. Experimental results show that the electrochemical active area of the nanotube-modified electrode increased around 50%. The repeatability of the modification methodology is around 6% (R.S.D.) and the stability of MWCNT-COOH-modified SPEs is ensured for, at least, 2 months.

Electrochemical study and flow injection analysis of paracetamol in pharmaceutical formulations based on screen-printed electrodes and carbon nanotubes

Acetaminophenol or paracetamol is one of the most commonly used analgesics in pharmaceutical formulations. Acetaminophen is electroactive and voltammetric mechanistic studies for the electrode processes of the acetaminophenol/N-acetyl-p-quinoneimine redox system are presented. Carbon nanotubes modified screen-printed electrodes with enhanced electron transfer properties are used for the study of the electrochemical-chemical oxidation mechanism of paracetamol at pH 2.0. Quantitative analysis of paracetamol by using its oxidation process (in a Britton-Robinson buffer solution pH 10.0) at +0.20 V (vs. an Ag pseudoreference electrode) on an untreated screen-printed carbon electrode (SPCE) was carried out. Thus, a cyclic voltammetric based reproducible determination of acetaminophen (R.S.D., 2.2%) in the range 2.5x10(-6) M to 1x10(-3) M, was obtained. However, when SPCEs are used as amperometric detectors coupled to a flow injection analysis (FIA) system, the detection limit achieved for paracetamol was 1x10(-7) M, one order of magnitude lower than that obtained by voltammetric analysis. The repeatability of the amperometric detection with the same SPCE is 2% for 15 successive injections of 10(-5) M acetaminophen and do not present any memory effect. Finally, the applicability of using screen-printed carbon electrodes for the electrochemical detection of paracetamol (i.e. for quality control analysis) was demonstrated by using two commercial pharmaceutical products.

Screen-printed electrodes for environmental monitoring of heavy metal ions: a review

AbstractHeavy metals such as lead, mercury, cadmium, zinc and copper are among the most important pollutants because of their non-biodegradability and toxicity above certain thresholds. Here, we review methods for sensing heavy metal ions (HMI) in water samples using screen-printed electrodes (SPEs) as transducers. The review (with 107 refs.) starts with an introduction into the topic, and this is followed by sections on (a) mercury-coated SPEs, (b) bismuth-coated SPEs, (c) gold-coated SPEs (d) chemically modified and non-modified carbon SPEs, (e) enzyme inhibition-based SPEs, and (f) an overview of commercially available electrochemical portable heavy metal analyzers. The review reveals the significance of SPEs in terms of decentralized and of in situ analysis of heavy metal ions in environmental monitoring. Graphical AbstractThis review summarises recent advances in the use of screen-printed electrodes (SPEs) for the electrochemical detection of heavy metal ions in water samples. Research proofs of concept and commercially available portable equipments for ‘in situ analysis’ are discussed.

Multiwalled carbon nanotube modified screen-printed electrodes for the detection of p-aminophenol: Optimisation and application in alkaline phosphatase-based assays

Carboxylated multiwalled carbon nanotubes (MWCNT-COOH) were used to modify the working electrode surface of different screen-printed electrodes. The effect of this modification on the electrodic characteristics (double layer capacitance, electroactive area and heterogeneous rate constants for the electron transfer) was evaluated and optimized for the cyclic voltammetric determination of p-aminophenol. The enzymatic hydrolysis of p-aminophenylphosphate was employed for the quantification of alkaline phosphatase, one of the most important label enzymes in immunoassays. Finally, ELISA assays were carried out to quantify pneumolysin using this enzymatic system. Results obtained indicated that low superficial densities of MWCNT-COOH (0.03-0.06 microg mm(-2)) yielded the same electrodic improvements but with better analytical properties.

Miniaturized analytical instrumentation for electrochemiluminescence assays: a spectrometer and a photodiode-based device

AbstractHerein, a new miniaturized analytical instrumentation for electrochemiluminescence (ECL) assays is presented. A photodiode integrated in an ECL cell combined with a potentiostat/galvanostat, all integrated in a one-piece instrument (μSTAT ECL), was developed. In addition, a complementary micro-spectrometer integrated in a similar ECL cell for luminescence spectra recording is also proposed. Both cells are intended to be used with screen-printed electrodes and all the devices are portable and small sized. Their performance was corroborated with two innovative proofs-of-concept that centered on the luminol transduction chemistry: a first time reported ECL assay based on the enzymatic reaction between an indoxyl substrate and the enzyme alkaline phosphatase, and the electrochemiluminescence resonance energy transfer (ECL-RET) process triggered by the electro-oxidized luminol to the acceptor fluorescein. The photodiode system revealed to be more sensitive than the spectrometer device in collecting the light; however, with the latter, it is possible to discriminate different luminescent species according to their maximum wavelength emission, which is extremely useful for carrying out simple and simultaneous ECL multiplex analyzes. The spectrometer device works as an excellent accessory to couple with the μSTAT ECL instrument, complementing the experiments. Graphical abstractSchematic representation of the ECL-RET: from luminol–H2O2 system to fluorescein, the micro-spectrometer for the light collection and the 3D representation of the ECL-RET reaction.

Time-Resolved Luminescence Spectroelectrochemistry at Screen-Printed Electrodes: Following the Redox-Dependent Fluorescence of [Ru(bpy)3]2+

In this work, a compact instrument for time-resolved luminescence spectroelectrochemistry using low-cost disposable electrodes is reported. This instrument can be coupled with screen-printed electrodes via a specific cell and a reflection probe, which allows one to observe changes occurring at the electrode/solution interface. This approach allowed one to follow the fluorescence variation of electrofluorochromic species such as [Ru(bpy)3]2+ at screen-printed carbon electrodes. A strong correlation between the electrochemical processes and the fluorescence was found during potentiostatic or multipulsed amperometric measurements. A decrease of the fluorescence was observed when the [Ru(bpy)3]2+ was oxidized to [Ru(bpy)3]3+ and part of this fluorescence is recovered when [Ru(bpy)3]3+ was reduced to the initial species. Moreover, a significant increment of the fluorescence was found when the oxygen reduction reaction takes place, which also confirms its quenching effect. Finally, multipulsed amperometric detection was employed in order to obtain more information about the redox-dependent luminescence of [Ru(bpy)3]2+ finding a continuous quenching over time attributed to bleaching chlorine-based species.

Evaluation of electrochemical, UV/VIS and Raman spectroelectrochemical detection of Naratriptan with screen-printed electrodes

Naratriptan, active pharmaceutical ingredient with antimigraine activity was electrochemically detected in untreated screen-printed carbon electrodes (SPCEs). Cyclic voltammetry and differential pulse voltammetry were used to carry out quantitative analysis of this molecule (in a Britton-Robinson buffer solution at pH 3.0) through its irreversible oxidation (diffusion controlled) at a potential of +0.75V (vs. Ag pseudoreference electrode). Naratriptan oxidation product is an indole based dimer with a yellowish colour (maximum absorption at 320nm) so UV-VIS spectroelectrochemistry technique was used for the very first time as an in situ characterization and quantification technique for this molecule. A reflection configuration approach allowed its measurement over the untreated carbon based electrode. Finally, time resolved Raman Spectroelectrochemistry is used as a powerful technique to carry out qualitative and quantitative analysis of Naratriptan. Electrochemically treated silver screen-printed electrodes are shown as easy to use and cost-effective SERS substrates for the analysis of Naratriptan.

Streptavidin functionalized nickel nanowires: A new ferromagnetic platform for biotinylated-based assays

Herein we present highly stable ferromagnetic nickel nanowires modified with streptavidin (NiNW-STR). This versatile functionalized nanomaterial works as an excellent biosensing platform for the immobilization of a wide range of biotinylated molecules. Moreover, these NWs can be employed in magnetic-based assays. Different proofs-of-concept such as streptavidin-biotin assays and capture of single and double stranded DNA were successfully carried out, corroborating NiNW-STR usefulness. Moreover, repeatability and stability studies were also effectively performed.

A non-enzymatic ethanol sensor based on a nanostructured catalytic disposable electrode

Herein, a simple and fast method for the electrocatalytic detection of ethanol using disposable nanostructured screen-printed carbon electrodes (SPCEs) is presented for the first time. Platinum nanoparticles (PtNPs), prepared in the presence of citrate and later purified and dispersed in ultrapure water, were employed in the modification of the SPCEs (SPCE-PtNPs). The synthetized nanoparticles and the catalytic nanostructured solid surface were characterized with transmission electron microscopy (TEM) and with scanning electron microscopy (SEM), respectively. Both systems were also characterized using voltammetric techniques. Finally, the PtNPs modified SPCEs were employed for the electro-oxidation of ethanol in an alkaline medium using portable instrumentation. The electrochemical results revealed that PtNPs can effectively enhance the electron transfer between the analyte of interest and the electrode. The content of ethanol was assayed in real samples (alcoholic beverages) revealing an accurate performance. Additionally, a stability study of the nanostructured surface was carried out. The results obtained corroborate the promising catalytic activity of PtNPs in ethanol detection using disposable, cost-effective and miniaturized sensing devices.

In Situ Spectroelectrochemical Monitoring of Dye Bleaching after Electrogeneration of Chlorine-Based Species: Application to Chloride Detection

Spectroelectrochemical techniques are becoming increasingly versatile tools to solve a diverse range of analytical problems. Herein, the use of in situ real-time luminescence spectroelectrochemistry to quantify chloride ions is demonstrated. Utilizing the bleaching effect of chlorine-based electrogenerated products after chloride oxidation, it is shown that the fluorescence of the rhodamine 6G dye decreases proportionally to the initial chloride concentration in solution. A strong decrease of fluorescence is observed in acidic media compared to a lower decrease in alkaline media, which suggests that Cl2, favorably generated at low pH, could be the main species responsible for the fluorescence loss. This fact is corroborated with chronoamperometric measurements where the complete loss of fluorescence for the bulk solution is achieved. A fast mass transfer is needed to explain this behavior, in agreement with the generation of gaseous species such as Cl2. Chloride detection was performed in artificial sweat samples in less than 30 s with great accuracy. This electrochemical/optical combined approach allows us to quantify species that are difficult to measure by electrochemistry due to the inadequate resolution of their redox processes or being without significant optical properties.