The interactions of several water-soluble ionic porphyrins with different ionic or neutral surfactants in aqueous solutions were studied as a function of surfactant concentration. The interaction leads to the formation of porphyrin aggregates and/or micelle-encapsulated monomers with the exception of those porphyrin−surfactant pairs for which the interaction is Coulombically repulsive. The premicellar surfactant−porphyrin aggregate is identified by absorption and fluorescence spectroscopy, fluorescence lifetime and anisotropy, and resonance light scattering. The spectroscopic results are used to characterize the premicellar aggregates as J-type, H-type, or nonspecific aggregates. All premicellar surfactant−porphyrin aggregates dissociate to form micelle-encapsulated monomers when the surfactant concentration approaches cmc (critical micellar concentration). The interaction of tetrakis-(4-sulfanatophenyl)porphine dianion (H4TPPS2-) at pH <3.5 with cetyltrimethylammonium cation (CTAB) is described by the following sequential equlibria controlled by the surfactant concentration:  M ⇌ J ⇌ H ⇌ Mm. The stoichiometric ratio of porphyrin/surfactant is 1:2 for the J-aggregate and ∼1:4 for the H-aggregate. Kinetic intermediates were also observed prior to the formation of the J-aggregate. The J-aggregate exhibits circular dichroism (spontaneous chirality, not seen in H-type or micellar aggregates), intense resonance light scattering, low fluorescence quantum yield and lifetime, and unusually high fluorescence anisotropy.

The fluorescence depolarization dynamics of organic fluorescent dye probes (nile red, cresyl violet, DODCI, rhodamine B, and rhodamine DPPE) were studied in cationic, anionic, and neutral micelles by picosecond time-resolved single-photon-counting technique. The fluorescence anisotropy decay of the dye intercalated inside the micelle is a two-exponential function. The anisotropy decay was interpreted by using a model of rotational (wobbling) and translational diffusion of the dye in the micelle coupled with the rotational motion of the micelle as a whole. The rotational and translational diffusion coefficients of the dye, the order parameter, and the semicone angle for the wobbling diffusion in the micelle were determined. The concept of “microviscosity” in the micelle was critically discussed in the light of the rotational and translational diffusion coefficients and their temperature dependence.

A model-free method is described for constructing time-resolved area-normalized emission spectra (TRANES) using luminescence decays at all emission wavelengths. An isoemissive point in TRANES indicates that the observed emission from the sample is due to two species only, irrespective of the origin of the two species or the excited-state kinetics. Proof for the existence of an isoemissive point in TRANES is given for various cases involving two emissive species. The isoemissive point in TRANES is qualitatively similar to the isosbestic point in time-resolved absorption spectra (TRAS) in kinetic spectrophotometry involving two species.

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Fluorescence correlation spectroscopy (FCS) is a sensitive and widely used technique for measuring diffusion. FCS data are conventionally modeled with a finite number of diffusing components and fit with a least-square fitting algorithm. This approach is inadequate for analyzing data obtained from highly heterogeneous systems. We introduce a Maximum Entropy Method based fitting routine (MEMFCS) that analyzes FCS data in terms of a quasicontinuous distribution of diffusing components, and also guarantees a maximally wide distribution that is consistent with the data. We verify that for a homogeneous specimen (green fluorescent protein in dilute aqueous solution), both MEMFCS and conventional fitting yield similar results. Further, we incorporate an appropriate goodness of fit criterion in MEMFCS. We show that for errors estimated from a large number of repeated measurements, the reduced chi(2) value in MEMFCS analysis does approach unity. We find that the theoretical prediction for errors in FCS experiments overestimates the actual error, but can be empirically modified to serve as a guide for estimating the goodness of the fit where reliable error estimates are unavailable. Finally, we compare the performance of MEMFCS with that of a conventional fitting routine for analyzing simulated data describing a highly heterogeneous distribution containing 41 diffusing species. Both methods fit the data well. However, the conventional fit fails to reproduce the essential features of the input distribution, whereas MEMFCS yields a distribution close to the actual input.

Time resolved emission spectroscopy (TRES) provides information on the excited state kinetics and heterogeneity of emissive species in a system. Time resolved area normalized emission spectroscopy (TRANES), an extension to TRES, is a novel, model-free method for the analysis of intrinsic or extrinsic fluorescence probes in complex chemical and biophysical systems [Koti, Krishna, and Periasamy, J. Phys. Chem. A 105, 1767 (2001)]. Observation of a single isoemissive point in TRANES analysis of fluorescence is an unambiguous indication of the presence of two emissive species in the system. The presence of multiple isoemissive points in TRANES spectra is confirmed using simulation and experimental data of multicomponent systems.

We have performed steady-state and time-resolved fluorescence studies on undoped and Mn-doped ZnS nanocrystals with approximately 16 A diameter. While there is no band-edge emission, the intensity of the steady-state blue fluorescence from ZnS surface states decreases upon Mn incorporation, which gives rise to an orange emission. These results show that Mn incorporation competes very effectively with the donor-acceptor surface states for the energy transfer from the electron-hole pair excited across the band gap. In both undoped and doped samples, the time-resolved fluorescence studies establish the presence of a distribution of decay lifetimes possibly due to a number of emission centers in the nanocrystals. A faster short-time decay of the blue emission in the Mn-doped samples compared to that in the undoped sample suggests an additional decay channel for the surface states via an energy transfer from these states to the dopant levels.

Fluorescence lifetimes and rotational reorientation times for four structurally similar dye molecules—three monocations: cresyl violet, nile blue, and oxazine 720 and one neutral but polar: nile red—have been measured by picosecond time-resolved fluorescence depolarization spectroscopy using the single-photon counting technique, in a number of solvents, which included a wide range of alcohols, other hydrogen-bonding liquids, and a few aprotic liquids. The rotational reorientation of the dye probes (assumed to be oblate ellipsoids) are sought to be explained in terms of the Stokes–Einstein–Debye theory and dielectric friction. The individual contributions to the rotational friction due to the above two factors were calculated using reasonable values for the molecular volume and dipole moment of the solute. The rotational behavior of all the four dyes in amides and aprotic solvents is reasonably well explained in terms of the simple stick hydrodynamic model with the ‘‘molecular volume’’ obtained by using the measured rotational reorientation time in water. On the other hand, in order to describe the rotational reorientation dynamics of all the dye molecules in n-alcohols, it is necessary to include the friction contribution due to the dielectric properties of the solvent. It appears that a change in boundary condition, something intermediate between stick and slip or close to slip, is required to satisfactorily explain the rotational reorientation times of the dye molecules in polyalcohols like ethylene glycol and glycerol. Investigation of the rotational behavior of all the four dyes as a function of viscosity by varying the temperature has been carried out in three solvents: 1-heptanol, 1-undecanol, and ethylene glycol. While the rotational reorientation times had a good linear η/T dependence, it was found that at a particular macroscopic viscosity value the rotational reorientation times obtained by the solvent variation and temperature variation are different. From the temperature variation study it was found that there is a satisfactory agreement between the solvent viscosity activation energy and the activation energy obtained for the reorientation rate of the dye probe molecules.