Creation of self-assembled mesoscale chainmail and application

在上个财政年度，我们努力控制纳米环的连结，这对中尺度链状邮件的产生至关重要。这种链化依赖于纳米环的空隙的大小和其表面的二次成核。我们很难使用所提出的极性分子来控制这些因素。因此，我们在实验室进行了基于巴比妥酸的非极性分子设计，用于制备聚戊二烯。由于相应的纳米环被巴比妥酸盐单体的烷基链覆盖，我们增加了分子的烷基链长，以制备具有更大的空隙和更高的表面二次成核频率的纳米环。引人注目的是，原子力显微镜和小角X射线散射实验表明，纳米环的内部空隙减少。光谱研究表明，这些纳米环表面的二次成核效率提高了。有趣的是，这两种效应的结合导致了更高的纳米[2]链烷的产率，并抑制了低辛烷的形成。这些初步的结果已经发表在最近的一篇论文中。受上述令人惊讶的观察结果的启发，我们计划在不久的将来研究纳米环状结构尺寸调制的详细机制及其对连锁的影响。

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.