Convenient syntheses of fullerynes for ‘clicking’ into fullerene polymers

Abstract

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition ‘click’ chemistry to form two fullerene polymers: one with C60 tethered to the end of a PS chain (C60-1PS) and the other with C60 tethered at the junction point of two PS chains of identical molecular weight (C60-2PS). The fullerene polymers were characterized by 1H NMR, 13C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C60 in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV–Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C60. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C60 content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.

In Situ Cellular Localization of Nonfluorescent [60]Fullerene Nanomaterial in MCF-7 Breast Cancer Cells

“…A lightly brownish solid was obtained (102 mg, 22% yield), which was further characterized by NMR and FT-IR spectroscopies and MALDI-TOF spectrometry. The [60]­fullerene monoadduct ( 2 ) spectral characterization was in accordance with literature describing triple-bonded [60]­fullerene derivatives (with 3-butynyl fragments) . The spectral characterization and MALDI-TOF mass spectrometry of compound ( 2 ) can be found in the Supporting Information (Figures S8 and S9).…”

“…The [60]fullerene monoadduct (2) spectral characterization was in accordance with literature describing triple-bonded [60]fullerene derivatives (with 3-butynyl fragments). 36 The spectral characterization and MALDI-TOF mass spectrometry of compound (2) can be found in the Supporting Information (Figures S8 and S9).…”

Divergent Synthesis of Molecular Winch Prototypes

“…Compounds 5 a, [26] 5 b, [20] 4 a, [5] 4 b, [22] 10 [24] and [(3-cyanopropyl) dimethylsilyl]acetylene [23] were synthesized according to previously reported procedures. Compounds 3, 4 c, 4 d, 6, 7, 8, 9, 11, 12 and 13 are described in the Supporting Information.…”

“…9-Ethynyltriptycene 4 a was prepared according to a standard synthetic route exploited for the synthesis of other molecular machines. [5] The C 60 -appended malonate derivative 4 b was obtained in two steps from ethylmalonate as recently reported, [22] with a Steglich esterification in the presence of but-3-yn-1-ol followed by a Bingel reaction.…”

High shear spheroidal topological fluid flow induced coating of polystyrene beads with C60 spicules

“…This is consistent with the coating of the polystyrene beads with C 60 'shielding' the polystyrene beads from the heat generated during the TGA. 24,25 To ascertain the effect of the choice of operating parameters of the VFD for coating the polystyrene beads, and the importance of the associated topological fluid flows, we altered the tilt angle from +451 to +40 and +501 for beads 2 to 6 mm in diameter. For the lower tilt angle, there is more agglomeration of the beads but nevertheless they are coated with spicules, Fig.…”