Abstract: We present the state-of-the-art in miniaturized sample preparation, immunoassays, one-dimensional and multidimensional analyte separations, and coupling of microdevices with electrospray ionization-mass spectrometry. Hyphenation of these different techniques and their relevance to proteomics will be discussed. In particular, we will show that analytical performances of microfluidic analytical systems are already close to fulfill the requirements for proteomics, and that miniaturization results at the same time in a dramatic increase in analysis throughput. Throughout this review, some examples of analytical operations that cannot be achieved without microfluidics will be emphasized. Finally, conditions for the spreading of microanalytical systems in routine proteomic labs will be discussed.

Abstract: A pinched pressure-driven flow injection on a microchip is numerically simulated in order to optimize the relative values of the operational parameters. The geometry studied is a two-dimensional rectangular channel featuring a cross-junction with a large depth-over-width ratio. The hydrodynamic and convection-diffusion equations are solved for the two steps of the process: first, the sample solution is pinched into the transversal channel (injection channel), and then it is injected into the longitudinal one (separation channel), where the time evolution of the concentration is analyzed for different types of the detectors. Electroosmotic flow calculations have also been performed and have shown a good agreement with literature. The results for pressure-driven flow point out that the shape of the detection signal is strongly dependent on the velocity in the separation channel and on the position of the detection probes. The so-called double-humped peak, caused by the parabolic flow profile at high driving flow rate is analyzed. A tight pinch greatly decreases the amount of injected sample and, consequently, the signal sensitivity without increasing its quality. A proper pullback of the sample during the separation process can decrease the tailing due to the sample leakage from the injection channel. Although a high sample pullback causes a considerable decrease in the signal sensitivity, it also greatly enhances the peak resolution. Finally, it is shown that a wider injection channel with high sample pullback ensures an improved signal sensitivity with good resolution.

Abstract: The electroosmotic flow in laminated excimer laser-ablated microchannels has been studied as a function of the depth of the rectangular channels, and particular emphasis has been given to the difference in the g-potentials between the lamination layer and the ablated substrate. Experimental electroosmotic flow follows the tendency predicted by a recently published model. The g-potentials of lamination and ablated surfaces were determined for poly(ethylene terephthalate) and poly(carbonate) substrates by fitting the experimental data with a numerical implementation of this model. In the experimentally investigated range of channel cross sections, a linear fit to the data gives a good approximation of the zeta -potentials for both materials. Moreover, a flow injection analysis of fluorescein dye has been performed to show the severe loss in numbers of theoretical plates, caused by Taylor dispersion, when such microchannels, dedicated to microcapillary electrophoresis, are used.

Abstract: A sensitive novel approach of using an amperometric ion detector for the now injection analysis of salts has been developed. The detection methodology is based on measuring the-current associated with the transfer of ions across polarized microinterfaces between the aqueous sample solution and a 2-nitrophenyloctyl ether-poly(vinyl chloride) gel phase, referred to as ionodes, Different sodium salts of fluoride, chloride, bromide, nitrate, and sulfate were investigated. It was found that by employing an amperometric pulse detection mode and pure water as eluent; the detection limit of the ionode detector could be lowered to ppt level of salt concentrations under flowing conditions.