Graphite vaporization provides an uncontrolled yet efficient means of producing fullerene molecules. However, some fullerene derivatives or unusual fullerene species might only be accessible through rational and controlled synthesis methods. Recently, such an approach has been used to produce isolable amounts of the fullerene C(60) from commercially available starting materials. But the overall process required 11 steps to generate a suitable polycyclic aromatic precursor molecule, which was then dehydrogenated in the gas phase with a yield of only about one per cent. Here we report the formation of C(60) and the triazafullerene C(57)N(3) from aromatic precursors using a highly efficient surface-catalysed cyclodehydrogenation process. We find that after deposition onto a platinum (111) surface and heating to 750 K, the precursors are transformed into the corresponding fullerene and triazafullerene molecules with about 100 per cent yield. We expect that this approach will allow the production of a range of other fullerenes and heterofullerenes, once suitable precursors are available. Also, if the process is carried out in an atmosphere containing guest species, it might even allow the encapsulation of atoms or small molecules to form endohedral fullerenes.
Contributing to the need for new graphene nanoribbon (GNR) structures that can be synthesized with atomic precision, we have designed a reactant that renders chiral (3,1)-GNRs after a multistep reaction including Ullmann coupling and cyclodehydrogenation. The nanoribbon synthesis has been successfully proven on different coinage metals, and the formation process, together with the fingerprints associated with each reaction step, has been studied by combining scanning tunneling microscopy, core-level spectroscopy, and density functional calculations. In addition to the GNR’s chiral edge structure, the substantial GNR lengths achieved and the low processing temperature required to complete the reaction grant this reactant extremely interesting properties for potential applications.
The properties of water at the nanoscale are crucial in many areas of biology, but the confinement of water molecules in sub-nanometre channels in biological systems has received relatively little attention. Advances in nanotechnology make it possible to explore the role played by water molecules in living systems, potentially leading to the development of ultrasensitive biosensors. Here we show that the adsorption of water by a self-assembled monolayer of single-stranded DNA on a silicon microcantilever can be detected by measuring how the tension in the monolayer changes as a result of hydration. Our approach relies on the microcantilever bending by an amount that depends on the tension in the monolayer. In particular, we find that the tension changes dramatically when the monolayer interacts with either complementary or single mismatched single-stranded DNA targets. Our results suggest that the tension is mainly governed by hydration forces in the channels between the DNA molecules and could lead to the development of a label-free DNA biosensor that can detect single mutations. The technique provides sensitivity in the femtomolar range that is at least two orders of magnitude better than that obtained previously with label-free nanomechanical biosensors and with label-dependent microarrays.
The frontier orbitals of a push-pull azobenzene adsorbed on a metal surface in different bonding geometries investigated by scanning tunneling spectroscopy and spectroscopy mappingWe have performed a careful study of the adsorption of C 60 molecules on a Au͑111͒ surface by using scanning tunneling microscopy and spectroscopy at room temperature. In coincidence with results from other techniques, differential conductance spectra give a value of 2.3 eV for the HOMO-LUMO gap of a monomolecular layer, with the LUMO level located at 0.6 eV above the Fermi level as a consequence of electronic charge transfer from the substrate into the molecule. Small differences in position ͑and shape͒ of the LUMO-derived resonance, in the order of 0.1 eV, are found on molecules adsorbed at step edges. We consider the Smoluchowski effect, i.e., the interaction of the molecules with a charge-depleted region, to explain the observed differences in their bonding nature. On some molecules forming part of bidimensional fullerene islands, similar differences were also detected with spatially resolved scanning tunneling spectroscopy, giving rise to a 2ϫ2 commensurate structure of the molecular adlayer with respect to the substrate. This finding is attributed to different electronic properties of the adsorption site, indicating that molecules adsorbed on the top position are less charged than those on bridge sites.
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