As. Fabiano et al., SYNTHESIS OF A NEW CATIONIC PYROPHEOPHORBIDE DERIVATIVE AND STUDIES OF ITS AGGREGATION PROCESS IN AQUEOUS-SOLUTION, Photochemistry and photobiology, 66(3), 1997, pp. 336-345
A new water-soluble cationic pyropheophorbide vas prepared from pyroph
eophorbide a by a Curtius rearrangement, The self-aggregation process
of this chlorhydrate of aminopyropheophorbide was investigated from th
e changes observed in its spectroscopic properties when passing from e
thanol to aqueous solutions The formation of aggregates was characteri
zed in tile absorption spectrum by a broadening of the Qy band, which
is slightly shifted to the red, a significant increase in signals of c
ircular dichroism and a drastic quenching of the fluorescence intensit
y at 674 nm, Analysis of the nonlinear variation of the fluorescence i
ntensity with the dye concentration in Tris-buffered solutions shows t
hat dimerization is the dominant aggregation process, The dimerization
equilibrium constant (at 25 degrees C, pH 7.5 in 5 mM Tris buffer, 10
mM NaCl) was determined to be 3.10(6) M-1. NMR measurements performed
in DMSO at various dye concentrations showed that only the chemical s
hifts of some atoms are affected by these changes, indicating the part
of the ring involved in the overlap of the two molecules in the dimer
. A molecular modeling study of the packing arrangement of the aminopy
ropheophorbide molecules in aggregates performed by both semi-empirica
l quantum chemical PM3 and force field MM2 methods provided a structur
e consistent with these spectroscopic data.