摘要： Optofluidic hollow-core photonic crystal fiber (HC-PCF) uniquely allows light to be guided at the centre of a microfluidic channel. The system maximizes the interaction of light with infiltrated chemicals and (nano)particles, offering unique opportunities for in-situ optical monitoring of a range of photochemical and catalytic reactions [1,2]. Our current goal is to extend this work to hybrid colloidal systems comprising a particulate light absorber and a molecular catalyst for photocatalytic fuel production [3]. Here we use HC-PCF microreactors to study novel light-absorbing particles for such systems: graphitic, N-doped, and amorphous carbon-nanodots (CNDs) that offer a unique combination of scalability, biocompatibility, water solubility, and stable optical properties [4]. To test the CNDs’ absorption- and electron-transfer properties, we combine them with the redox-active heterocycle methyl viologen dichloride (MV2+·2Cl-). Upon absorption of UV light, CNDs can transfer an electron to MV2+, whose reduction to the radical cation (MV?+) creates a strong optical absorption peak around 600 nm (Figs. 1(a,c)). An electron donor (EDTA) is added to the solution to quench the photo-induced holes in the CNDs [4]. The mixture was infiltrated into the core of a 30 cm long liquid-filled kagomé style HC-PCF (Fig. 1(b)), designed to guide in the wavelength range of the MV?+ absorption peak. To ensure a homogeneous excitation of the CNDs, a 5 cm long section of the fiber was side-illuminated by a UV lamp (λ = 365 nm). A supercontinuum source, launched into a guided mode, was used to monitor the absorption spectrum. Despite sample volumes of less than 50 nL, we obtain highly-reproducible time traces of the MV?+ absorption (Fig 1(d-e)). Unexpectedly, a significant initial time-delay of 135 s was observed in the reduction of MV2+, revealing the presence of a previously unknown activation process of the CNDs. The initial delay was found to depend on the functionalization of the CNDs, with delays for a -COOH group (81 s) being ca. three times shorter than those for NH2 (176 s) and NMe2 (204 s) groups. The subsequent reaction rate was found to be independent of the surface-group. Our unexpected results highlight the scope for urgently needed in-situ analysis of photocatalytic systems. Future experiments will include the use of surface-sensitive higher-order modes [5] to selectively probe the diffusion of reaction products within the optofluidic reactor.