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In this chapter, we highlight recent developments using laser irradiation to probe ions in mass spectrometers. We will primarily cover the structural characterisation of biomolecules. This chapter will introduce the principles behind laser irradiation and describe some of the common instrument configurations, with an emphasis on benchtop laser systems coupled to instruments in laboratories. We have ordered the narrative in this chapter according to what has been achieved with three different irradiation wavelengths namely UV, visible and infrared. Instrumentation developed to permit laser irradiation along with mass spectrometry is described in each section along with some examples of recent applications primarily focused on the analysis of peptides and proteins.

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