Despite the importance of spatially resolved self‐assembly for molecular machines, the spatial control of supramolecular polymerization with synthetic monomers had not been experimentally established. Now, a microfluidic‐regulated tandem process of supramolecular polymerization and droplet encapsulation is used to control the position of self‐assembled microfibrillar bundles of cyclic peptide nanotubes in water droplets. This method allows the precise preferential localization of fibers either at the interface or into the core of the droplets. UV absorbance, circular dichroism and fluorescence microscopy indicated that the microfluidic control of the stimuli (changes in pH or ionic strength) can be employed to adjust the packing degree and the spatial position of microfibrillar bundles of cyclic peptide nanotubes. Additionally, this spatially organized supramolecular polymerization of peptide nanotubes was applied in the assembly of highly ordered two‐dimensional droplet networks.

Despite the importance of spatially resolved selfassembly for molecular machines,t he spatial control of supramolecular polymerization with synthetic monomers had not been experimentally established. Now,amicrofluidicregulated tandem process of supramolecular polymerization and droplet encapsulation is used to control the position of selfassembled microfibrillar bundles of cyclic peptide nanotubes in water droplets.T his method allows the precise preferential localization of fibers either at the interface or into the core of the droplets.U Vabsorbance,c ircular dichroism and fluorescence microscopyindicated that the microfluidic control of the stimuli (changes in pH or ionic strength) can be employed to adjust the packingd egree and the spatial position of microfibrillar bundles of cyclic peptide nanotubes.Additionally,this spatially organized supramolecular polymerization of peptide nanotubes was applied in the assembly of highly ordered twodimensional droplet networks.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Hydrogels are soft materials of great interest in different areas such as chemistry, biology and therapy. Those made by the self-assembly of small molecules are known as supramolecular gels. The...