ABSTRACT
The electrooxidation of thymine on screen-printed carbon electrodes was investigated utilizing different complementary instrumental approaches. The potential-dependent product profile was obtained by recording real-time mass voltammograms. Electrochemical flow cells with integrated disposable electrodes were directly coupled with mass spectrometry to facilitate a very fast detection of electrogenerated species. Thymine dimers were found at a potential of about 1.1 V in ammonium acetate (pH 7.0) and 1.25 V in ammonium hydrogen carbonate electrolyte (pH 8.0). Electrochemistry-capillary electrophoresis-mass spectrometry measurements revealed that two isobaric isomers of a dimeric oxidation product were formed. Separations at different time intervals between end of oxidation and start of separation showed that these were hydrated over time. An investigation of the pKa values by changing the separation conditions in electrochemistry-capillary electrophoresis-ultraviolet-visible spectroscopy measurements allowed for further characterization of the primary oxidation products. The results showed that both isomers exhibited two deprotonation steps. The oxidation products were further characterized by high-performance liquid chromatography-tandem mass spectrometry. Based on the obtained data, the main oxidation products of thymine in aqueous solution could most likely be identified as N(1)-C(5') and N(1)-C(6') linked dimer species evolving into the corresponding dimer hydrates over time. The presented methods for online characterization of electrochemically pretreated samples showed that not only mass spectrometric data can be obtained by electrochemistry-mass spectrometry but also further characterizations such as the investigation of product stability and the pH-dependent protonation or deprotonation behavior are possible. This is valid not only for stable oxidation products but also for intermediates, as analysis can be carried out within a short time scale. Thus, a vast amount of valuable experimental data can be acquired, which can help in understanding electrooxidation processes.
ABSTRACT
For the identification and quantification of analytes in complex samples, highly selective analytical strategies are required. The selectivity of single separation techniques such as gas chromatography (GC), liquid chromatography (LC), or capillary electrophoresis (CE) with common detection principles can be enhanced by hyphenating orthogonal separation techniques but also by using complementary detection systems. In this review, two-dimensional systems containing CE in at least one dimension are reviewed, namely LC-CE or 2D CE systems. Particular attention is paid to the aspect of selectivity enhancement due to the orthogonality of the different separation mechanisms. As an alternative concept, dual detection approaches are reviewed using the common detectors of CE such as UV/VIS, laser-induced fluorescence, capacitively coupled contactless conductivity (C4D), electrochemical detection, and mass spectrometry. Special emphasis is given to dual detection systems implementing the highly flexible C4D as one detection component. Selectivity enhancement can be achieved in case of complementarity of the different detection techniques.
ABSTRACT
A newly configured electrochemical flow cell to be used for (end-channel) amperometric detection in a microfluidic device is presented. The design was assembled to place the reference electrode in a separated compartment, isolated from the flow in the microchannel, while the working and counter electrodes remain in direct contact with both compartments. Moreover, a three-dimensional coil-shaped microfluidic device was fabricated using a nonconventional protocol. Both devices working in association enabled us to solve the drawback caused by the discrete injection when the automatic micropipette was used. The high performance of the proposed electrochemical flow cell was demonstrated after in situ modifying the surface of the platinum working electrode with surfactant (e.g., using Tween 20 at 0.10%). As the reference electrode remained out of contact with the flowing solution, there was no trouble by air bubble formation (generated by accidental insertion or by presence of surfactants) throughout the measurements. This device was characterized regarding its analytical performance by evaluating the amperometric detection of acetaminophen, enabling determination from 6.60 to 66.0 µmol L-1. This issue is important since at high concentration (e.g., as assessed in clinical analysis) the acetaminophen is known to passivate the working electrode surfaces by electrogenerated products, impairing the accuracy of the electrochemical measurements.
