Electrochemical DNA Analysis with a Supramolecular Assembly of Naphthalene Diimide, Ferrocene, and β-Cyclodextrin

Naphthalene diimide 1 bearing ferrocene and β-cyclodextrin (β-CD) was prepared. Its half-wave potential at 420 mV shifted 40-50 mV upon addition of an excess of adamantylamine, suggesting that the ferrocene of 1 is included in the cavity of β-CD intramolecularly to form a pseudocyclic structure. This unique architecture is retained even where 1 is bound to calf thymus DNA to give rise to a catenane-like structure. Morphology of the DNA complex with 1 was further explored by atomic force microscopy to reveal that the DNA strand tends to bend as the amount of 1 on it increases. Presumably, intermolecular, yet intrastrand, inclusion of ferrocene into β-CD is responsible for this phenomenon. The resulting globular structure reverted partially by the addition of adamantylamine. At a low ratio of 1 to DNA, a novel reduction peak appeared at 320 mV in the differential pulse voltammograms of 1 at the expense of the 420 mV peak. The peak current of the former was proportional to the DNA concentration, thereby enabling quantitation of DNA in a signal-on way. Likewise, a polymerase chain reaction (PCR) product of 754 bp was analyzed successfully with a detection limit of 13 nM.