Microchemical single droplet reaction analysis by online cavity ring-down spectroscopy

Microfluidics provides an exceptional environment for the generation of controlled droplet dispersions and their manipulation in prescribed flow fields. The spatio-temporal correspondence between microchannel position and reaction 'time' permits the study of kinetics of (chemical and physical) processes with unprecedented time resolution and dynamic range. Further, the combination of the small volumes of droplet 'reactors' and the precise formulation of their composition opens vast possibilities in chemical synthesis, including screening, discovery and optimisation. Monitoring reactions in real-time with non-invasive probes remains, hitherto, a major shortcoming of microchemical reactors due to the minute sample volumes (pL-nL) and fast travel speeds (1-1000 mm/s). This proposal seeks to develop, implement and validate a novel experimental approach to monitor microchemical reactions in real-time by coupling, for the first time, cavity ring-down spectroscopy and solvent-resistant microfabrication. This approach will permit the online study of model catalytic reactions, with unprecedented reproducibility and flow control. Cavity ring-down spectroscopy will permit the analysis of pL volumes, effectively eliminating the restriction of path length in microchannels, with nanosecond to microsecond time resolution, compatible with microreaction drops. In particular, we will elucidate individual and global reaction population outcomes and the effect of mixing and flow, with spatiotemporal resolution. This approach is applicable to a range of organic chemical reactions and, for this work, we will focus on selected model systems (detailed below) of fundamental and industrial relevance.