As novel magnetic resonance imaging (MRI) contrast agent, gadofullerene encapsulated redox nanoparticles (Gd3NPs) were prepared by encapsulation of Gd3N@C80 in the core of core-shell-type polymer micelles composed of original polyamine with a reactive oxygen species (ROS)-scavenging ability. Because Gd3NPs possess biocompatible PEG shell with a smaller size (ca. 50 nm), they had high colloidal stability in a physiological environment, and showed low cytotoxicity. Specific accumulation of Gd3NPs in a tumor was confirmed in tumor-bearing mice after systemic administration. The tumor/muscle (T/M) ratio of the Gd ion reached five at 7.5 h after the administration. T1-weighted MRI signal enhancement of the T/M ratio increased by 8% at 6 h postinjection of Gd3NPs (Gd dose:14.35 μmol/kg). Although Gd3NPs showed a tendency for extended blood circulation, they did not have severe adverse effects, probably due to the confinement of Gd in a hydrophobic fullerene in addition to the ROS-scavenging capacity of these nanoparticles. In sharp contrast, systemic administration of Gd-chelate nanoparticles (GdCNPs) to mice disrupts liver function, increases leukocyte counts, and destroys spleen and skin tissues. Leaking of Gd ions from GdCNPs may cause such adverse effects. Based on these results, we expect that Gd3NPs is high-performance MRI contrast agents for tumor diagnosis.
The photoluminescence of lanthanide ions inside fullerenes is usually very weak due to the quenching effect of the fullerene cage. In the case of Er@C82, the near-infrared emission from the Er3+ ion is completely quenched by the C82 fullerene cage. It remains challenging to turn on the photoluminescence of Er@C82 and other monometallofullerenes. In this work, we adopt a covalent modification strategy to alter the electronic structure of the fullerene cage for sensitizing the near-infrared emission of Er3+ ions in metallofullerenes Er@C2n (2n = 72, 76, and 82). After covalent modification with trifluoromethyl, phenyl, or dichlorophenyl groups, the erbium metallofullerenes exhibit photoluminescence at 1.5 μm, which is the characteristic emission of the Er3+ ion. Particularly, the otherwise nonfluorescent metallofullerene Er@C82 is transformed into fluorescent derivatives by using this strategy. The photoluminescence from the Er3+ ion is ascribed to energy transfer from the fullerene cage to the Er3+ ion. According to theoretical calculations, the sensitization of the Er3+ ion by the fullerene cage is associated with the large HOMO-LUMO gap and the closed-shell electronic structure of the metallofullerene derivatives. This work provides useful guidance for the design and synthesis of new fluorescent metallofullerenes.
Abstract D 5 h ‐symmetric fullerene C 70 ( D 5 h ‐C 70 ) is one of the most abundant members of the fullerene family. One longstanding mystery in the field of fullerene chemistry is whether D 5 h ‐C 70 is capable of accommodating a rare‐earth metal atom to form an endohedral metallofullerene M@ D 5 h ‐C 70 , which would be expected to show novel electronic properties. The molecular structure of La@C 70 remains unresolved since its discovery three decades ago because of its extremely high instability under ambient conditions and insolubility in organic solvents. Herein, we report the single‐crystal X‐ray structure of La@C 70 (CF 3 ) 3 , which was obtained through in situ exohedral functionalization by means of trifluoromethylation. The X‐ray crystallographic study reveals that La@C 70 (CF 3 ) 3 is the first example of an endohedral rare‐earth fullerene based on D 5 h ‐C 70 . The dramatically enhanced stability of La@C 70 (CF 3 ) 3 compared to La@C 70 can be ascribed to trifluoromethylation‐induced bandgap enlargement.
Owing to their remarkable properties, single-walled carbon nanotube thin-film transistors (SWCNT-TFTs) are expected to be used in various flexible electronics applications. To fabricate SWCNT channel layers for TFTs, solution-based film formation on a self-assembled monolayer (SAM) covered with amino groups is commonly used. However, this method uses highly oxidized surfaces, which is not suitable for flexible polymeric substrates. In this work, a solution-based SWCNT film fabrication using methoxycarbonyl polyallylamine (Moc-PAA) is reported. The NH2 -terminated surface of the cross-linked Moc-PAA layer enables the formation of highly dense and uniform SWCNT networks on both rigid and flexible substrates. TFTs that use the fabricated SWCNT thin film exhibited excellent performance with small variations. The presented simple method to access SWCNT thin film accelerates the realization of flexible nanoelectronics.
Carbon nanotubes (CNTs) are promising materials for gas sensing because of their large specific area and high sensitivity to charge differentiation. In CNT-based field-effect transistors (FETs) for gas sensing, both CNT potential modulation in the channels and Schottky barrier height modulation at the CNT/metal electrode contact influence the current properties. However, researchers have not used Schottky barrier height modulation for gas detection. To investigate and compare the effects of Schottky barrier height modulation and CNT channel potential modulation on NO2 gas exposure, we fabricated ambipolar CNT FETs by the dielectrophoretic assembly. We exposed CNT FET gas sensors to N2 gas containing 100-ppb NO2 and observed two different responses in the electric properties: a steady current shift in the positive direction in the hole-conduction region because of the channel potential modulation, and an abrupt decrease in transconductance in the electron-conduction region because of the Schottky barrier modulation. The CNT channels and CNT/metal contact both contributed to the sensor response, and the modulation rate of the Schottky barrier was higher than that of the CNT potential shift in the channel.
Nanotemplated growth of graphene nanoribbons (GNRs) inside carbon nanotubes is a promising mean to fabricate ultrathin ribbons with desired side edge configuration. We report the optical properties of the GNRs formed in single-wall carbon nanotubes. When coronene is used as the precursor, extended GNRs are grown via a high-temperature annealing at 700 °C. Their optical responses are probed through the diazonium-based side-wall functionalization, which effectively suppresses the excitonic absorption peaks of the nanotubes without damaging the inner GNRs. Differential absorption spectra clearly show two distinct peaks around 1.5 and 3.4 eV. These peaks are assigned to the optical transitions between the van Hove singularities in the density of state of the GNRs in qualitative agreement with the first-principles calculations. Resonance Raman spectra and transmission electron microscope observations also support the formation of long GNRs.
Eine neue Strategie zur nichtchromatographischen Extraktion von Metallofullerenen aus Lösungen von Lichtbogenruß wird von K. Itami, H. Shinohara et al. in ihrer Zuschrift auf S. 3166 ff. beschrieben. Diese Methode beruht auf der größenselektiven Komplexierung mit kommerziell erhältlichem Cycloparaphenylen (CPP). Beispielsweise kann Gd@C82 durch die Addition von [11]CPP selektiv aus einer Fullerenmischung extrahiert werden.
