A dimerization model for the concentration dependent photophysical properties of diphenylhexatriene and its...

We have investigated the reason for the sensitivity of the fluorescence excited-state lifetime of 1,6-diphenyl-1,3,5-hexatriene (DPH) and its phospholipid derivatives, 1-palmitoyl-2-[2-[4-(6-phenyl-trans-1,3,5- hexatrienyl)phenyl]ethyl)carbonyl)-3-sn-phosphatidylcholine (DPHpPC) and 1-palmitoyl-2-[2-[4-(6-phenyl-trans-1,3,5- hexatrienyl)phenyl]ethyl)carbonyl)-3-sn-phosphatidic acid (DPHpPA), to the concentration of these probes in dipalmitoylphosphatidylcholine (DPPC) multilamellar membranes (Barrow, D. A., and B. R. Lentz, 1985. Biophys. J. 48:221-234; Parente, R. A., and B. R. Lentz. 1985. Biochemistry. 24:6178-6185). We have interpreted self-quenching data, excitation and emission spectra, and phase and modulation lifetime data in terms of a model that envisions dimerization of these probes in a membrane bilayer. It is proposed that dimerization alters the symmetry of the DPH excited state so as to allow more rapid decay via the normally symmetry-disallowed route from the 1Ag* state. Global analysis of fluorescence phase shift and modulation ratio data for DPHpPC in terms of the dimerization model provided a good fit of these data as a function of both modulation frequency and probe concentration. Global analysis of a similar set of data for the charged phosphatide DPHpPA predicted that this probe was much less prone to dimerize than was the uncharged DPHpPC. This physically reasonable result provides support for the assumptions made in the development of our model. We conclude that the dimerization model allows rationalization of many of the anomalous photophysical properties of DPH and its derivatives in membranes.