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.