Ferrocene-functionalized carbon nanoparticles †

Carbon nanoparticles were synthesized from natural gas soot and functionalized with ferrocenyl moieties by using 4-ferrocenylphenyldiazonium as the reactive precursor. The incorporation of the ferrocenyl units onto the carbon nanoparticle surface was confirmed by varied spectroscopic measurements. For instance, in FTIR measurements the characteristic vibrational bands of the ferrocenyl and phenyl moieties could be clearly identified. XPS measurements showed that there were approximately 31.9 ferrocenyl units per nanoparticle. UV-vis spectroscopic measurements displayed an absorption band at ca. 465 nm which was consistent with the optical characteristics of ferrocenyl derivatives. Furthermore, with surface functionalization by the ferrocenyl moieties, the photoluminescence of the carbon nanoparticles was found to diminish in intensity and red-shift in energy with the addition of NOBF 4 . This was accounted for by the formation of varied electronaccepting moieties on the particle surface, such as positively charged ferrocenium, quinone-like derivatives, and nitrosation of the aromatic rings of the graphitic cores. Interestingly, in electrochemical studies the nanoparticle-bound ferrocenyl moieties were found to exhibit two pairs of voltammetric waves with a difference of their formal potentials at about 78 mV, suggesting nanoparticle-mediated intraparticle charge delocalization at mixed valence as a result of the strong core-ligand covalent bonds and the conductive sp 2 carbon matrix of the graphitic cores. Consistent behaviors were observed in near-infrared measurements, indicating that the particles behaved analogously to a Class I/II mixedvalence compound

Total synthesis of nominal cyclocinamide B and investigation into the identity of the cyclocinamides

The total synthesis of nominal cyclocinamide B, a cyclic peptide marine natural product, is reported together with an isomer of nominal cyclocinamide A. Initial attempts at the synthesis of the title compounds by inclusion of a turn inducer failed. However, direct synthesis succeeded in formation of the 14-membered cyclic peptide structure. Comparison of the data from all synthetic cyclocinamide A and B compounds with those of the natural products leads to the conclusion that the two natural products possess the same relative stereochemistry and that the true structures have not been defined