Novel long alkyl side chain benzo[a]phenoxazinium chlorides: synthesis, photophysical behaviour and DNA interaction

Several fluorescent benzo[a]phenoxazinium chlorides possessing a propyl-, octyl-, decyl-, dodecyl- or tetradecylamino at the 5-position of the heterocyclic moiety were efficiently synthesised. The absorption and emission maxima of all compounds lie in the range 627-638 nm and 654-678 nm, respectively, with good fluorescence quantum yields. Studies of their photophysical properties in ethanol allowed for the estimation of the acid-base dissociation constant, Ka, revealing an enhancement with the increase in the alkyl side-chain length. It is in the aqueous medium only that the acid form is observed as coexisting with H-aggregates. The solubility markedly decreased when the chain length increased. The residual ethanol (0.2% v/v) used to facilitate the solubilisation of the benzo[a]phenoxazinium dyes allow for the existence of the basic form in an aqueous solution, possibly through preferential solvation. Photophysical studies in the presence of DNA revealed that the compounds with an alkyl side chain of up to eight carbon atoms could intercalate between DNA nucleotides. Moreover, other forms of DNA binding were found to be operative, involving also the basic form of benzo[a]phenoxazinium dyes.

Graphical abstractDownload full-size image A series of benzo[a]phenoxazinium chlorides possessing long alkyl side chains at the 5-amino position of the heterocycle were efficiently synthesised and photophysical studies revealed that the compounds with an alkyl side chain of up to eight carbon atoms have the ability to act as new long-wavelength fluorescent probes for DNA.