One-Pot in Situ Fabrication of Stable Nanocaterpillars Directly from Polyacetylene Diblock Copolymers Synthesized by Mild Ring-Opening Metathesis Polymerization

Abstract

We report a direct one-pot route for the preparation of supramolecules from simple polyacetylene diblock copolymers synthesized by mild ring-opening metathesis polymerization of cyclooctatetraene. This in situ nanoparticlization of conjugated polymer (INCP) approach is advantageous over conventional self-assembly processes because this method does not require any tedious postsynthetic treatments. Also, this direct approach provides intriguing supramolecules with a unique nanostructure resembling a caterpillar. Furthermore, the new supramolecules are highly stable adducts because the polyacetylene core block provides an exceptionally strong driving force for the self-assembly. Even though pristine polyacetylene is unstable in air, the polyacetylene segment in the nanocaterpillar is very stable because it is protected within the shell of the supramolecule.

Computer simulation study on the self-assembly of tethered nanoparticles with tunable shapes

“…Similar structures have been observed in experiments. [39][40][41] This type of structure obtained in our simulations is related to the stable interface formed by rigid nanocubes. The packing of the nanocubes on the surface of micelles slows down the surfactant exchange between micelles and the corresponding structure rearrangement; therefore the pearl-necklace-like structure can be stably formed as shown the movie in ESI.…”

Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene

“…A broad absorption peak with a maximum over 600 nm and an onset at 850 nm were clearly and consistently observed throughout the course of sonication. These observed wavelengths are among the highest reported for solution-synthesized PAs (26)(27)(28)(29), suggesting the formation of PA blocks with long conjugation lengths. The absorption peak continuously grew in intensity during the sonication process, indicating continuous formation of PA. After 120 min of sonication, the absorption maximum slightly shifted hypsochromically to 605 nm with a concomitant decrease in solubility and formation of particulates due to the relatively high content of insoluble PA. Long-wavelength absorption was observed even at the beginning of sonication, when the absorbance was still low ( fig.…”

50th Anniversary Perspective: Functional Nanoparticles from the Solution Self-Assembly of Block Copolymers

“…102 Moreover, studies of PFDMS BCPs with short corona -forming blocks showed that these materials yielded platelet micelles. 103 A wide range of crystallizable core-forming blocks other than PFDMS have now been employed to enable the formation of cylindrical/fiber-like micelles with crystalline cores and these include poly(3-hexylthiophene)), [104][105][106][107][108][109] poly(L-lactic acid) (PLLA), [110][111][112][113] polycaprolactone (PCL), 114,115 PEO, 116 PE, [117][118][119][120] poly(acrylonitrile), 121 poly(ferrocenyldimethylgermane) (PFDMG), 122 poly(ferrocenyldiethylsilane) (PFDES), 123 poly(ferrocenylmethylsilane)(PFMS), 124 PCL/PLLA, 125 poly(perfluoroethyloctylmethacrylate), 126,127 cholestorol-based polymers, 128 polyacetylene, 129,130 poly(pphenylene), 131 poly(3-heptylselenophene), 132 polyfluorene, [133][134][135] poly(pphenyleneethynylene), 136,137 poly(p-phenylenevinylene), [138][139][140][141][142] cyclic polypeptoids, 143 and poly(2-isopropyl-2-oxazoline).…”