Sheathless coupling of microchip electrophoresis to ESI-MS utilising an integrated photo polymerised membrane for electric contacting.

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 droplet-chip/mass spectrometry approach to study organic synthesis at nanoliter scale.

A droplet-based microfluidic device with seamless hyphenation to electrospray mass spectrometry was developed to rapidly investigate organic reactions in segmented flow providing a versatile tool for drug development. A chip-MS interface with an integrated counterelectrode allowed for a flexible positioning of the chip-emitter in front of the MS orifice as well as an independent adjustment of the electrospray potentials. This was necessary to avoid contamination of the mass spectrometer as well as sample overloading due to the high analyte concentrations. The device was exemplarily applied to study the scope of an amino-catalyzed domino reaction with low picomole amount of catalyst in individual nanoliter sized droplets.

Integrated on-chip mass spectrometry reaction monitoring in microfluidic devices containing porous polymer monolithic columns.

Chip-based microfluidics enable the seamless integration of different functions into single devices. Here, we present microfluidic chips containing porous polymer monolithic columns as a means to facilitate chemical transformations as well as both downstream chromatographic separation and mass spectrometric analysis. Rapid liquid phase lithography prototyping creates the multifunctional device economically.

On-chip monitoring of chemical syntheses in microdroplets via surface-enhanced Raman spectroscopy.

Conducting organic syntheses in microfluidic chips allows studying and optimising chemical reactions at minimal time-scales and resource consumption. Herein, we describe a multi-channel microdroplet chip, which allows fast and directed dispensing of reactants into individual droplets in a segmented flow. This gives access to study the reaction progress in situ via surface-enhanced Raman spectroscopic monitoring of fast moving individual droplets. This opens up new avenues for high-throughput screening of organic reactions at the micro- and nano-scale.