The interaction of a tetracationic porphyrin is[4[(3-trimethylaminopro
pyl)oxy]-phenyl]porphine, TTHETAOPP, and Calf Thymus DNA can lead to t
he formation of a DNA-bound protonated porphyrin species. Protonation
of the bound TTHETAOPP is promoted both by lower pH and larger DNA exc
ess. This species can be formed even at pH 7 under optimal conditions.
At pH 6, in large nucleic acid excess, this protonated species is dom
inant and exhibits a single positive CD signal. The formation of the g
reen colored protonated species is unfavored in solution at low DNA ex
cess both at pH 7 and pH 6; the CD shows exciton curves. The presence
of PIPES (pH 7) favors porphyrin stacking and prevents porphyrin proto
nation.