RESUMO
Laser trapping in chemistry covers various studies ranging from single molecules, nanoparticles, and quantum dots to crystallization and liquid-liquid phase separation of amino acids. In this work, a supramolecular assembly of azobenzene-based biscalix[4]arene is generated in ethyl acetate using laser trapping; its nucleation and growth are elucidated. No trapping behavior was observed when a 1064 nm laser beam was focused inside of the solution; however, interesting assembling phenomena were induced when it was shined at the air/solution interface. A single disk having two layers was first prepared at the focal point of â¼1 µm and then expanded to the size of a few tens of micrometers, although no optical force was exerted outside of the focal volume. Upon switching the trapping laser off, needles were generated at the outer layer of the assembly, giving a stable sea urchin-like morphology to the generated assembly. At a 30-50% dilution of the initial solution in ethyl acetate, a mushroom-like morphology was also observed. Laser trapping-induced assembly of azobenzene-based biscalix[4]arene was quite different from the sharp-ellipsoidal aggregates obtained by the spontaneous evaporation of the solution. These trapping phenomena were specifically observed for biscalix[4]arene in the trans conformation of azo-benzene moiety but not for the cis-form, suggesting that the laser trapping of this azobenzene-based biscalix[4]arene is photocontrollable. Dynamics and mechanism of the supramolecular assembling are considered, referring to laser trapping-induced nucleation and liquid-liquid phase separation of amino acids.
RESUMO
The morphologies of an azobenzene-bridged biscalix[4]arene organogel in different organic solvents can be photo-reversibly switched between nanofibers and nanorings as well as between closed and open-form vesicles.