This review presents a thorough overview covering the period 1997-2006 of microfluidic chips coupled to mass spectrometry through an electrospray interface. The different types of fabrication processes and materials used to fabricate these chips throughout this period are discussed. Three 'eras' of interfaces are clearly distinguished. The earliest approach involves spraying from the edge of a chip, while later devices either incorporate a standard fused-silica emitter inserted into the device or fully integrated emitters formed during chip fabrication. A summary of microfluidic-electrospray devices for performing separations and sample pretreatment steps before sample introduction into the mass spectrometer is also presented.
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