Fullerene-linked particles as LC chromatographic media and modification of their electron donor/acceptor properties by secondary chemical reactions

Fullerenes (C60 and C70) linked to small silica or polymer particles provide novel chromatographic stationary phases with electron donor/acceptor surface interactions that may parallel those of aromatic carbons. Separations of fullerenes and aromatic compounds frequently encountered as environmental contaminants were investigated using LC microcolumns containing either particles prepared from BrHC60 linked to amino-silica (Spherisorb-NH2, Phenomenex) or porous polymers containing ca. 12% fullerene by weight. The polystyrene divinylbenzene (PSDVB)-C60/70H column had greater capacity (k') than the SiNHC60/70H column. Toluene and polycyclic aromatic hydrocarbons (PAHs), naphthalene, anthracene, pyrene, and perylene, were retained in the order of increasing ring number; nitro-substituents increased retention; and chlorinated-dibenzo-p-dioxins and -dibenzofurans were more strongly retained than their parent compounds. PCB congeners with no chlorine in the ortho, ortho'-positions are co-planar and are strongly retained; for these isomers, retention increased with higher chlorination. We demonstrate that surface-linked fullerenes can also accommodate further chemical modification through the addition of 2-(4-nitrophenyl)ethyl or -NHCH2CH2NH2 moieties to yield altered electron donor/acceptor affinity. Separations appear to be derived primarily from aromatic electron induced dipole-dipole or electron-pair donor or acceptor interactions (charge transfer complexes). Except for the fullerenes, surface interactions with compounds are largely suppressed with methylene chloride as the mobile phase.