Singlet oxygen, O(2)(a(1)Δ(g)), was produced upon pulsed-laser irradiation of an intracellular photosensitizer and detected by its 1275 nm O(2)(a(1)Δ(g)) → O(2)(X(3)Σ(g)(-)) phosphorescence in time-resolved experiments using (1) individual mammalian cells on the stage of a microscope and (2) suspensions of mammalian cells in a 1 cm cuvette. Data were recorded using hydrophilic and, independently, hydrophobic sensitizers. The microscope-based single cell results are consistent with a model in which the behavior of singlet oxygen reflects the environment in which it is produced; nevertheless, the data also indicate that a significant fraction of a given singlet oxygen population readily crosses barriers between phase-separated intracellular domains. The singlet oxygen phosphorescence signals reflect the effects of singlet-oxygen-mediated damage on cell components which, at the limit, mean that data were collected from dead cells and, in some cases, reflect contributions from both intracellular and extracellular populations of singlet oxygen. Despite the irradiation-induced changes in the environment to which singlet oxygen is exposed, the "inherent" intracellular lifetime of singlet oxygen does not appear to change appreciably as the cell progresses toward death. The results obtained from cell suspensions reflect key features that differentiate cell ensemble from single cell experiments (e.g., the ensemble experiment is more susceptible to the effects of sensitizer that has leaked out of the cell). Overall, the data clearly indicate that measuring the intracellular lifetime of singlet oxygen in a O(2)(a(1)Δ(g)) → O(2)(X(3)Σ(g)(-)) phosphorescence experiment is a challenging endeavor that involves working with a dynamic system that is perturbed during the measurement. The most important aspect of this study is that it establishes a useful framework through which future singlet oxygen data from cells can be interpreted.

The unique optical properties of squaraines render these molecules useful for applications that range from xerography to photodynamic therapy. In this regard, squaraines derived from the condensation of nitrogen-based heterocycles and squaric acid have many promising attributes. Key solution-phase photophysical properties of six such squaraines have been characterized in this study. One feature of these molecules is a pronounced absorption band in the region approximately 600-720 nm that has significant spectral overlap with the fluorescence band (i.e., the Stokes shift is small). As such, effects of emission/reabsorption yield unique excitation wavelength dependent phenomena that are manifested in quantum yields of both fluorescence and sensitized singlet oxygen production. Comparatively small squaraine-sensitized yields of singlet oxygen production and, independently, large rate constants for squaraine-induced deactivation of singlet oxygen are consistent with a model in which there is appreciable intra- and intermolecular charge-transfer in the squaraine and squaraine-oxygen encounter complex, respectively. The results reported herein should be useful in the further development of these compounds for a range of oxygen-dependent applications.

The extent to which an intermolecular charge-transfer (CT) state can influence excited-state relaxation dynamics is examined for the system wherein 1-methylnaphthalene (MN) interacts with molecular oxygen. The MN-O2 system is ideally suited for such a study because excited states can be independently accessed by (i) irradiation into the discrete MN-O2 CT absorption band, (ii) direct irradiation of MN, and (iii) the photosensitized production of triplet state MN. Changing the solvent in which the MN-O2 system is dissolved influences the MN-dependent photoinduced production of singlet oxygen, O2(a1Delta(g)), which, in turn, yields information about fundamental concepts of state mixing. Results of experiments conducted in the polar solvent acetonitrile differ substantially from those obtained from the nonpolar solvent cyclohexane. The data reflect differences in the energy and behavior of the solvent-equilibrated MN-O2 CT state, CT(SE), and the extent to which this state couples to other states of the MN-O2 system. In particular, the data are consistent with a model where both the MN triplet state and the MN-O2 CT(SE) state are immediate precursors of O2(a1Delta(g)). Although the work reported herein is of direct and practical significance for the wide variety of systems in which O2(a1Delta(g)) can be produced upon irradiation, it also serves as an accessible model for a study of general issues pertinent to state mixing and the solvent-dependent dynamics of CT-mediated excited-state relaxation.