A fast and straightforward method to prototype microfluidic chip systems for dead-volume-free hyphenation to electrospray-ionisation mass spectrometry is presented. The developed approach based on liquid-phase lithography provides an inexpensive and reliable access to microfluidic chips for MS coupling which can be manufactured in any laboratory with low technical demands. The rapid prototyping approach enables the seamless integration of capillaries serving as electrospray emitters with negligible dead volume. The high versatility of the presented prototyping method and the applicability of a variety of chip-based devices in different fields of lab-on-a-chip technology are established for analytical separations by means of chip-electrochromatography-MS and for continuous-flow synthesis using microreactor technology with MS detection.
In this article, we present a novel approach for the sheathless coupling of microchip electrophoresis (MCE) with electrospray mass spectrometry (ESI-MS). The key element is an ion-conductive hydrogel membrane, placed between the separation channel and an adjacent microfluidic supporting channel, contacted via platinum electrodes. This solves the persistent challenge in hyphenation of mass spectrometry to chip electrophoresis, to ensure a reliable electrical connection at the end of the electrophoresis channel without sacrificing separation performance and sensitivity. Stable electric contacting is achieved via a Y-shaped supporting channel structure, separated from the main channel by a photo polymerised, ion permeable hydrogel membrane. Thus, the potential gradient required for performing electrophoretic separations can be generated while simultaneously preventing gas formation due to electrolysis. In contrast to conventional make-up or sheathflow approaches, sample dilution is also avoided. Rapid prototyping allowed the study of different chip-based approaches, i.e. sheathless, open sheathflow and electrode support channel designs, for coupling MCE to ESI-MS. The performance was evaluated with fluorescence microscopy and mass spectrometric detection. The obtained results revealed that the detection sensitivity obtained in such Y-channel chips with integrated hydrogel membranes was superior because sample dilution or loss was prevented. Furthermore, band broadening is reduced compared to similar open structures without a membrane.
A comprehensive study for a sensitivity optimization in MCE with mass spectrometric detection is presented. As a text mixture, we chose a mixture of the cardiac drugs propranolol, bisoprolol, lidocaine, procaine and studied the effect of different chip layouts and experimental parameters with the aim of achieving both high sensitivity in MS detection and adequate chip electrophoretic separation. An important aspect was a comparison of microfluidic layouts containing various sheath-flow channels with that avoiding sheath-flow junctions on-chip. We utilized glass chips with monolithically integrated nanospray emitter tips coupled dead volume-free to an IT mass spectrometer running in fragmentation mode (MS(n) ). With this setup, detection limits down to 0.6 ng/mL for the model compound propranolol were achieved.
Rising numbers of psychoactive tryptamine derivatives have become available on the drug market over the last decade, making these naturally occurring or synthetically manufactured compounds highly relevant for forensic analysis. One of these compounds is 5-methoxy-N,N-dimethyltryptamine (5-MeO-DMT), a constituent of the dried poison of Incilius alvarius (Colorado River toad) which has a history of ritual and/or recreational use. Still, comprehensive and validated qualitative as well as quantitative analytical data on the psychoactive components of this poison are scarce. In this study samples of the poison of Incilius alvarius were collected from live toads in the Sonoran Desert, Arizona (USA) and analyzed with a set of complementary methods. Acetone/water (70/30, v/v) proved to be the solvent of choice for the extraction of tryptamine derivatives. Trace compounds were enriched and overload with 5-MeO-DMT was prevented by chromatographic separation of 5-MeO-DMT prior to qualitative analysis. The method for quantification was validated. Applying attenuated total reflection-Fourier transform infrared spectroscopy to samples of the poison, 5-MeO-DMT was identified as the main tryptamine by comparison to the reference spectrum. The combined evaluation of analytical data gained from gas chromatography-mass spectrometry (GC-MS), liquid chromatography-quadrupole time-of-flight high resolution MS (HPLC-qToF-HRMS), and HPLC-MS/MS confirmed the presence of 5-MeO-DMT, 5-MeO-N-methyltryptamine, 5-MeO-tryptamine, 5-MeO-tryptophol, 2-(5-methoxy-1H-indol-3-yl)-acetic-acid (5-MIAA), 5-HO-N-methyltryptamine, bufotenin, DMT, and tryptophan. For the first time, 5-MeO-tryptamine and two positional isomers of indole-substituted HO-MeO-DMT were detected in the poison of Incilius alvarius. The tryptamine present in the highest concentrations was 5-MeO-DMT (mean ± standard deviation: 410,000 ± 30,000 µg/g). Mean concentrations of 5-MeO-tryptamine (490 ± 260 µg/g), 5-HO-N-methyltryptamine (270 ± 120 µg/g), bufotenin (2,800 ± 1,900 µg/g), and DMT (250 ± 80 µg/g), showed a relatively high variability between individual samples. The comprehensive analytical reference data of Incilius alvarius poison presented here might prove useful for forensic chemists.
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