Fabrication of nanowalled catalytically self-threaded supramolecular polyrotaxane microcapsules using droplet microfluidics

Micrometer-scale monodisperse droplets are produced to generate nanowalled supramolecular microcapsules using microfluidics for high reproducibility and high-throughput manipulation, efficient material consumption, and control over hierarchical structure, shape, and size. In this study, an optimized microfluidic droplet generation technique and a unique liquid-liquid interfacial polymerization method were applied to fabricate the monodisperse polyrotaxane-based supramolecular microcapsules in a fast and simple way. To minimize the uncertainty due to droplet volume variation, the inlet pressures were supplied from the same source while lowering the interfacial tension and the main channel hydrodynamic resistance, which are critical for high monodispersity. The target polyrotaxane network (PN) was simply formed at the interface of the water and oil phases in ultra-monodisperse microdroplets via the cucurbit[6]uril (CB6)-catalyzed azide-alkyne cycloaddition (CB6-AAC) reaction between azido- and alkyne-functionalized tetraphenylporphyrin monomers (TPP-4AZ and TPP-4AL). The thickness of the interfacially assembled PN microcapsules was 20 nm as analyzed by cross-sectional TEM and TEM-EDX techniques. The resultant water-in-oil PN microcapsules were highly monodisperse in size and able to retain target molecules. Here, rhodamine 6G (Rh6G)-loaded PN microcapsules were fabricated, and the release rate of the Rh6G cargo was investigated over time for controlled drug release applications.