Creation of self-assembled mesoscale chainmail and application

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In the last fiscal year, we made our effort toward controlling of catenation of nanotoroids, which is crucial for the creation of mesoscale chainmail. The catenation relies on the size of the void of the nanotoroids and the secondary nucleation on their surface. We faced difficulty to control these factors using the proposed polar molecule. So, we worked on the barbituric acid-based nonpolar molecular design used in the preparation of polycatenanes in our laboratory. Since the corresponding nanotoroids are covered with alkyl chains of the barbiturate monomer, we increased the alkyl chain length of the molecule to prepare nanotoroids with a larger void space and with a higher frequency of secondary nucleation on their surface. Strikingly, atomic force microscopy and small-angle X-ray scattering experiments revealed a decrease in the inner void space of nanotoroids. Spectroscopic studies revealed increased efficiency of secondary nucleation on the surface of these nanotoroids. Interestingly, a combination of these two effects resulted in a higher yield of nano-[2]catenane and suppressed the formation of oligocatenanes. These preliminary results have been published in a paper recently.Stimulated by the aforementioned surprising observation, we plan to investigate the detailed mechanism of the size modulation of the nanotoroids and its effect on the catenation in the near future.