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Droplet microfluidics has emerged as a powerful platform allowing a largenumber of individual reactions to be carried out in spatially distinctmicrocompartments. Due to their small size, however, the spectroscopiccharacterisation of species encapsulated in such systems remains challenging.In this paper, we demonstrate the acquisition of infrared spectra from singlemicrodroplets containing aggregation-prone proteins. To this effect, dropletsare generated in a microfluidic flow-focussing device and subsequentlydeposited in a square array onto a ZnSe prism using a micro stamp. Afterdrying, the solutes present in the droplets are illuminated locally by aninfrared laser through the prism, and their thermal expansion upon absorptionof infrared radiation is measured with an atomic force microscopy tip, grantingnanoscale resolution. Using this approach, we resolve structural differences inthe amide bands of the spectra of monomeric and aggregated lysozyme from singlemicrodroplets with picolitre volume.

Nanoscale spatially resolved infrared spectra from single microdroplets