Instrument miniaturization is one way of addressing the issues of sensitivity, speed, throughput, and cost of analysis in DNA diagnostics, proteomics, and related biotechnology areas. Microfluidics is of special interest for handling very small sample amounts, with minimal concerns related to sample loss and cross‐contamination, problems typical for standard fluidic manipulations. Furthermore, the small footprint of these microfabricated structures leads to instrument designs suitable for high‐density, parallel sample processing, and high‐throughput analyses. In addition to miniaturized systems designed with optical or electrochemical detection, microfluidic devices interfaced to mass spectrometry have also been demonstrated. Instruments for automated sample infusion analysis are now commercially available, and microdevices utilizing chromatographic or capillary electrophoresis separation techniques are under development. This review aims at documenting the technologies and applications of microfluidic mass spectrometry for the analysis of proteomic samples. © 2006 Wiley Periodicals, Inc., Mass Spec Rev 25:573–594, 2006

We report a construction of a self-aligning subatmospheric hybrid liquid junction electrospray interface for CE eliminating the need for manual adjustment by guiding the capillaries in a microfabricated liquid junction glass chip at a defined angle. Both the ESI and separation capillaries are inserted into the microfabricated part until their ends touch. The distance between the capillary openings is defined by the angle between the capillaries. The microfabricated part contains channels for placement of the capillaries and connection of the external electrode reservoirs. It was fabricated using standard photolithographic/wet chemical etching techniques followed by thermal bonding. The liquid junction is connected to a subatmospheric electrospray chamber inducing the flow inside the ESI needle and helping the ion transport via aerodynamic focusing.

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A new concept for electrospray coupling of microfluidic devices with mass spectrometry was developed. The sampling orifice of the time-of-flight mass spectrometer was modified with an external adapter assisting in formation and transport of the electrosprayed plume from the multichannel polycarbonate microdevice. The compact disk sized microdevice was designed with radial channels extending to the circumference of the disk. The electrospray exit ports were formed by the channel openings on the surface of the disk rim. No additional tips at the channel exits were used. Electrospray was initiated directly from the channel openings by applying high voltage between sample wells and the entrance of the external adapter. The formation of the spatially unstable droplet at the electrospray openings was eliminated by air suction provided by a pump connected to the external adapter. Compared with the air intake through the original mass spectrometer sampling orifice, more than an order of magnitude higher flow rate was achieved for efficient transport of the electrospray plume into the mass spectrometer. Additional experiments with electric potentials applied between the entrance sections of the external adapter and the mass spectrometer indicated that the air flow was the dominant transport mechanism. Basic properties of the system were tested using mathematical modeling and characterized using ESI/TOF-MS measurements of peptide and protein samples.

A novel method of etching channels in glass microchips with the most tunable solvent, water, was tested as an alternative to common hydrogen fluoride-containing etchants. The etching properties of water strongly depend on temperature and pressure, especially in the vicinity of the water critical point. The chips were etched at the subcritical, supercritical and critical temperature of water, and the resulting channel shape, width, depth and surface morphology were studied by scanning electron microscopy and 3D laser profilometry. Channels etched with the hot water were compared with the chips etched with standard hydrogen fluoride-containing solution. Depending on the water pressure and temperature, the silicate dissolved from the glass could be re-deposited on the channel surface. This interesting phenomenon is described together with the conditions necessary for its utilization. The results illustrate the versatility of pure water as a glass etching and surface morphing agent.