Watching Molecular Nanotubes Self-Assemble in Real Time
Maríck Manrho, Sundar Raj Krishnaswamy, Björn Kriete, Ilias Patmanidis, Alex H. de Vries, Siewert J. Marrink, Thomas L. C. Jansen, Jasper Knoester, Maxim S. Pshenichnikov
Journal of the American Chemical Society
145
22494-22503
2023
abstract
Molecular self-assembly is a fundamental process in nature that can be used to develop novel functional materials for medical and engineering applications. However, their complex mechanisms make the short-lived stages of self-assembly processes extremely hard to reveal. In this article, we track the self-assembly process of a benchmark system, double-walled molecular nanotubes, whose structure is similar to that found in biological and synthetic systems. We selectively dissolved the outer wall of the double-walled system and used the inner wall as a template for the self-reassembly of the outer wall. The reassembly kinetics were followed in real time using a combination of microfluidics, spectroscopy, cryogenic transmission electron microscopy, molecular dynamics simulations, and exciton modeling. We found that the outer wall self-assembles through a transient disordered patchwork structure: first, several patches of different orientations are formed, and only on a longer time scale will the patches interact with each other and assume their final preferred global orientation. The understanding of patch formation and patch reorientation marks a crucial step toward steering self-assembly processes and subsequent material engineering.