Spectral and chemical evidence for the direct formation of carboxylic groups in aerobically oxidised water-soluble fullerenes

The synthesis of oxidised water-soluble fullerenes, prepared by chemically-induced aerobic oxidation, yields functionalised carbon cluster structures, which are oxidised by the covalent insertion of different oxygen units. Their strictly pH-dependent behaviour in aqueous solutions appears to be properly ascribed to the existence of directly attached carboxylic moieties. The presence of these groups, which are usually neglected and underestimated, has been thoroughly investigated. Several concurrent spectral (UV–VIS, XPS, solid-state 13C CPMAS NMR, FT-IR, Raman, EDAX, TGA-MS, ESI-MS) and chemical (acid–base behaviour, salt precipitation by metal-complexation, carboxylic functionalisation) methods have provided a definitive set of consistent evidence, indicating for the first time the direct linkage of carboxylic groups on water-soluble fullerenes prepared in this manner.