Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof ...are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current-voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor-acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure.
Mesoporous materials with carbon framework structure can offer distinctive functionalities with tunable electronic or catalytic properties. Many synthetic routes including hard or soft templating ...approaches are developed for the fabrication of various ordered mesoporous carbon based materials which have demonstrated unique catalytic and energy storage properties. So far, most of these techniques deliver only mesoporous carbon with amorphous wall structures which limit their performance in many applications. Fullerenes exhibit unique structure and significant properties including superconductivity, electrochemical stability, and heat resistance. Herein, for the first time, the preparation of highly ordered mesoporous fullerene C70 materials with tunable porous structure and controlled rod‐shaped morphology through the thermal oligomerization of fullerene C70 molecules inside the mesopore channels of SBA‐15 silica as a hard template with the help of chlorinated aromatics, wherein the solubility of fullerenes is high, is reported. It is demonstrated that these metal‐free mesoporous fullerene C70 framework with a high surface area and bimodal pores with multifunctionality exhibit excellent performance in the oxygen reduction reaction for fuel cells and supercapacitors. This simple strategy can also be extended to other fullerene nanostructures with different carbon atoms which can exhibit interesting physicochemical properties and find applications in catalysis and energy storage.
Highly crystalline metal‐free mesoporous fullerene C70 is prepared through combined strategy of nanotemplating and polymerization approaches. Their excellent performance in the oxygen reduction reaction with prominent four‐electron transport and high current density, comparable to that of Pt catalysts, is demonstrated and their excellent energy storage performance is also presented.
Stem cell implantation strategy has exhibited potential to treat the myocardial infarction (MI), however, the low retention and survival limit their applications due to the reactive oxygen species ...(ROS) microenvironment after MI. In this study, the fullerenol nanoparticles are introduced into alginate hydrogel to create an injectable cell delivery vehicle with antioxidant activity. Results suggest that the prepared hydrogels exhibit excellent injectable and mechanical strength. In addition, the fullerenol/alginate hydrogel can effectively scavenge the superoxide anion and hydroxyl radicals. Based on these results, the biological behaviors of brown adipose-derived stem cells (BADSCs) seeded in fullerenol/alginate hydrogel were investigated in the presence of H2O2. Results suggest that the fullerenol/alginate hydrogels have no cytotoxicity effects on BADSCs. Moreover, they can suppress the oxidative stress damage of BADSCs and improve their survival capacity under ROS microenvironment via activating the ERK and p38 pathways while inhibiting JNK pathway. Further, the addition of fullerenol can improve the cardiomyogenic differentiation of BADSCs even under ROS microenvironment. To assess its therapeutic effects in vivo, the fullerenol/alginate hydrogel loaded with BADSCs were implanted in the MI area in rats. Results suggest that the fullerenol/alginate hydrogel can effectively decrease ROS level in MI zone, improve the retention and survival of implanted BADSCs, and induce angiogenesis, which in turn promote cardiac functional recovery. Therefore, the fullerenol/alginate hydrogel can act as injectable cell delivery vehicles for cardiac repair.
Synopsis We report the first observation of the endohedral defect fullerene complex He@C59− and the first measurement of the threshold displacement energy of a fullerene.
Halogenation of terminal of acceptors has been shown to give dramatic improvements in power conversion efficiencies (PCEs) of organic solar cells (OSCs). Similar significant results could be expected ...from the halogenation of the central units of state‐of‐the‐art Y‐series acceptors. Herein, a pair of acceptors, termed CH6 and CH4, featuring a conjugation‐extended phenazine central unit with and without fluorination, have been synthesized. The fluorinated CH6 has enhanced molecular interactions and crystallinity, superior fibrillar network morphology and improved charge generation and transport in blend films, thus affording a higher PCE of 18.33 % for CH6‐based binary OSCs compared to 16.49 % for the non‐fluorinated CH4. The new central site offers further opportunities for structural optimization of Y‐series molecules to afford better‐performed OSCs and reveals the effectiveness of fluorination on central units.
A series of CH molecules with a new modification site on the central unit of Y‐series electron acceptors has been designed and synthesized to afford better‐performing organic solar cells (OSCs). Further fluorination on the largely unexplored central unit enabled significantly improved photovoltaic performance with over 18% efficiency for CH6‐based binary OSCs.
Buckminsterfullerene (C60) was recently confirmed as the largest molecule identified in space. However, it remains unclear how and where this molecule is formed. It is generally believed that C60 is ...formed from the buildup of small carbonaceous compounds in the hot and dense envelopes of evolved stars. Analyzing infrared observations, obtained by Spitzer and Herschel, we found that C60 is efficiently formed in the tenuous and cold environment of an interstellar cloud illuminated by strong ultraviolet (UV) radiation fields. This implies that another formation pathway, efficient at low densities, must exist. Based on recent laboratory and theoretical studies, we argue that polycyclic aromatic hydrocarbons are converted into graphene, and subsequently C60, under UV irradiation from massive stars. This shows that alternative—top-down—routes are key to understanding the organic inventory in space.
Highly fluorinated fullerenes with a chemical composition of C60F48 have been prepared and characterized. Their solubility of the new nanomaterials in the ionic liquid (IL) has been compared with raw ...fullerenes C60. Fluorination may appear as a convenient method to enhance the solubility of carbonaceous nanomaterials in a fluorinated based anion IL. Indeed, the ability of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmImNTf2), to solubilize C60 and C60F48 was investigated using optical microscopy and UV–vis spectroscopy. While C60 has very poor solubility in this IL (below 0.07 mmol/L), the solubility increases at least eightfold, i.e. more than 1.0 mg/mL (or 0.61 mmol/L) for C60F48 samples. The presence of fluorine atoms on fullerene seems to enhance the stability of the solvated molecules in IL thanks to the limitation of the aggregation of C60F48 in BmImNTf2. This improvement of the solubility could be explained by the beneficial effect of the fluorination that induces a decrease of the π-π interaction between carbonaceous solutes as the carbon hybridization changes from sp2 to sp3 through the formation of C-F covalent bonds and thus enhances the interaction between the solvent and the solute. Fluorination appears as an efficient approach to limit the use of volatile organic compounds usually used as co-solvent to enhance the dispersion mechanism.
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The water-soluble glycofullerenes GF1 and GF2 were synthesized using two-step modified Bingel-Hirsch methodology. Interestingly, we identified buckyballs as a novel class of non-receptor Src kinases ...inhibitors. The evaluated compounds were found to inhibit Fyn A and BTK proteins with IC
values in the low micromolar range, with the most active compound at 39 µM. Moreover, we have demonstrated that formation of protein corona on the surface of 60fullerene derivatives is changing the landscape of their activity, tuning the selectivity of obtained carbon nanomaterials towards Fyn A and BTK kinases. The performed molecular biology studies revealed no cytotoxicity and no influence of engineered carbon nanomaterials on the cell cycle of PANC-1 and AsPC-1 cancer cell lines. Incubation with the tested compounds resulted in the cellular redox imbalance triggering the repair systems and influenced the changing of protein levels.
We report the construction of blood cell membrane cloaked mesoporous silica nanoparticles for delivery of nanoparticles fullerenols (Fols) with fibrinolysis activity which endows the active Fol with ...successful thrombolysis effect in vivo. In vitro, Fols present excellent fibrinolysis activity, and the Fol with the best fibrinolysis activity is screened based on the correlation between Fols’ structure and their fibrinolysis activity. However, the thrombolytic effect in vivo is not satisfactory. To rectify the unsatisfactory situation and avoid the exogenous stimuli, a natural blood cell membrane cloaking strategy with loading the active Fol is chosen to explore as a novel thrombolysis drug. After cloaking, the therapeutic platform prolongs blood circulation time and enhances the targeting effect. Interestingly, compared with platelet membrane cloaking, red blood cell (RBC) membrane cloaking demonstrates stronger affinity with fibrin and more enrichment at the thrombus site. The Fol with RBC cloaking shows quick and efficient thrombolysis efficacy in vivo with less bleeding risk, more excellent blood compatibility, and better biosafety when compared with the clinical drug urokinase (UK). These findings not only validate the blood cell membrane cloaking strategy as an effective platform for Fol delivery on thrombolysis treatment, but also hold a great promising solution for other active nanoparticle deliveries in vivo.
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