Regiochemically Controlled Synthesis of a ß-4-ß' [70]Fullerene Bis-Adduct.

A ß-4-ß' C70 bis-adduct regioisomer and an uncommon mono-adduct ß-malonate C70 derivative were synthesized by using a Diels-Alder cycloaddition followed by an addition-elimination of bromo-ethylmalonate and a retro-Diels-Alder cycloaddition reaction. We also report the regioselective synthesis and spectroscopic characterization of Cs-symmetric tris- and C2v-symmetric tetra-adducts of C70, which are the precursors of the mono- and bis-adduct final products.

Functionalization of carbon nanoparticles modulates inflammatory cell recruitment and NLRP3 inflammasome activation.

The inflammatory effects of carbon nanoparticles (NPs) are highly disputed. Here it is demonstrated that endotoxin-free preparations of raw carbon nanotubes (CNTs) are very limited in their capacity to promote inflammatory responses in vitro, as well as in vivo. Upon purification and selective oxidation of raw CNTs, a higher dispersibility is achieved in physiological solutions, but this process also enhances their inflammatory activity. In synergy with toll-like receptor (TLR) ligands, CNTs promote NLRP3 inflammasome activation and it is shown for the first time that this property extends to spherical carbon nano-onions (CNOs) of 6 nm in size. In contrast, the benzoic acid functionalization of purified CNTs and CNOs leads to significantly attenuated inflammatory properties. This is evidenced by a reduced secretion of the inflammatory cytokine IL-1ß, and a pronounced decrease in the recruitment of neutrophils and monocytes following injection into mice. Collectively, these results reveal that the inflammatory properties of carbon NPs are highly dependent on their physicochemical characteristics and crucially, that chemical surface functionalization allows significant moderation of these properties.

Redox-active scandium oxide cluster inside a fullerene cage: spectroscopic, voltammetric, electron spin resonance spectroelectrochemical, and extended density functional theory study of Sc4O2@C80 and its ion radicals.

The clusterfullerene Sc(4)O(2)@C(80) with a mixed redox state of scandium was found to be an exciting molecule for endohedral electrochemistry as demonstrated by means of an in situ electron spin resonance (ESR) spectroelectrochemical study of the spin density distribution in its electrochemically generated cation and anion radicals. The compound exhibits two reversible reduction and oxidation steps with a relatively small electrochemical gap of 1.10 V. The ESR spectra of the ion radicals have a rich hyperfine structure caused by two pairs of equivalent Sc atoms. The Sc-based hyperfine structure with large hyperfine coupling constants shows that both oxidation and reduction of Sc(4)O(2)@C(80) are in cavea redox processes, which is the subject of endohedral electrochemistry. The assignment of the experimentally determined a((45)Sc) values to the two types of Sc atoms in the Sc(4)O(2) cluster was accomplished by extended density functional theory and molecular dynamics simulations. Sc atoms adopting a divalent state in the neutral Sc(4)O(2)@C(80) exhibited an especially large coupling constant of 150.4 G in the cation radical, which is the record high a((45)Sc) value for Sc-based endohedral metallofullerenes. Such a high value is explained by the nature of the highest occupied molecular orbital (HOMO) localized on the six-atom Sc(4)O(2) cluster. This HOMO is a Sc-Sc bonding MO and hence has large contributions from the 4s atomic orbitals of Sc(II). We claim that ESR spectroelectrochemistry is an invaluable experimental tool in the studies of metal-metal bonding in endohedral metallofullerenes and in endohedral electrochemistry.

Self-assembled monolayers of C60-triphenylamine dyads as photo-switched interfacial layers for potential application in photovoltaic cells.

C60-Triphenylamine dyads were synthesized for incorporation as photoswitched interfacial layers in organic photovoltaic (OPV) cells. Self-assembled monolayers (SAMs) of these dyads on gold (through S-Au and C60-Au interactions) were prepared through one or two adsorption processes, and their packing densities were fully characterized. Analysis using quartz crystal microbalance (QCM) and electrochemical impedance spectroscopy (EIS) measurements indicated that all SAMs exhibit dense coverage on the gold surfaces. Electrochemical desorption in KOH confirmed that the cis-1 dyad is anchored to the gold surface through its thiol group. Impedance measurements in the absence and presence of UV irradiation were performed to observe the photoswitched properties of these surface confined dyads. Upon UV light exposure of the SAMs, the charge-transfer resistance decreased when Fe(CN)6(3-/4-) was used as the probe redox couple and increased with Ru(NH3)6(3+/2+), confirming the generation of positive charges on the surface upon UV irradiation.