The development of new photoactivated anticancer complexes is of major importance for the effective treatment of cancer. Such complexes are inert, nontoxic and are activated only locally in cancer cells by light. In collaboration with co-workers from the University of Warwick in the UK, we have developed a new method that allows rapid testing and optimization of photochemical compounds [Chen (2010); Unterkofler (2012)]. It makes use of the unique waveguiding properties of liquid-filled hollow-core photonic crystal fibres to bring together for the first time the fields of microfluidics, chemistry, and optics. The hollow core is loaded with chemicals and acts as a miniature photochemical reactor. Both the chemicals and the excitation light are confined to the core. Consequently, the entire sample volume interacts strongly with the light, resulting in much shorter reaction times than in conventional cuvettes. Importantly, the required sample volume is reduced by four orders of magnitude. The reaction is monitored in real-time by in-fibre broadband absorption spectroscopy, offering insight in the dynamics of the chemistry. As a proof-of-principle study, the photochemical conversion of Vitamin B12a to vitamin B12b upon excitation with blue laser light was investigated. In a continuous-flow configuration, the method enables a rapid optimization of the excitation wavelength and light dosage of photoactivated anticancer complexes.

PCF nanoreactors can also be used to study fast, reversible photoswitching processes in real-time [Chen (2010a)]. The figure shows photoisomerization of an azobenzene derivative: upon irradiation with blue light, the thermally stable trans molecules are converted to the cis form at a rate that is proportional to the irradiance. The cis molecules are subsequently converted back to the trans form by both photochemical and (slow) thermal processes. After a certain exposure time, a photostationary state (PSS) is reached. In typical photoswitching experiments, high laser intensities are required to obtain a large fraction of cis molecules in the PSS. The strong confinement of both light and sample in hollow core PCF results in a high intensity throughout the entire sample volume. Consequently, the laser power required is reduced by at least five orders of magnitude compared to that in a standard cuvette.

To date, the use of liquid-filled HC-PCF in photochemical experiments have only been performed in fused silica HC-PCFs, which limits the choice of solvent to liquids with refractive index less than that of silica (nG = 1.45 at 600 nm), if the benefits of single-mode guidance are to be preserved. This is because the guidance mechanism switches to total internal reflection (TIR) for nL > nG, resulting in increasingly multi-mode operation as nL rises and making accurate spectroscopic measurements very difficult. We have overcome this limitation by employing single-ring HC-PCF made from a lead-silicate glass (Schott SF6) with index nG = 1.80 at 600 nm. The fibre was fabricated using an improved "stack-and-draw" technique. In a proof-of-principle experiment, this fibre was used to demonstrate photochemical conversion of an organometallic complex in toluene [Cubillas (2017)].