Study of effectiveness of pyrene concentration dependence on the kinetics of electron transfer process with N,N-dimethylaniline in condensed phase.

The role of another excited pyrene molecule in the vicinity of an excited pyrene molecule undergoing electron transfer (ET) process with a N,N,-dimethylaniline molecule has been explored in non-polar and polar solvents where specifically solvent mediated nature of ET is prominent. Analytic expression has been derived for the dependence of ET kinetics on pyrene concentration in the experimental conditions normally encountered in sub-nanosecond time correlated single photon counting (TCSPC) apparatus which is mostly used. The life time data has been explained on the basis of present day understanding.

Photoreaction of thioxanthone with indolic and phenolic derivatives of biological relevance: magnetic field effect study.

The photoinduced reaction of thioxanthone (TX) with various indolic and phenolic derivatives and amino acids like tryptophan and tyrosine has been monitored in sodium dodecyl sulfate micellar medium. Laser flash photolysis and magnetic field effect (MFE) experiments have been used to study the dynamics of the radical pairs. The quenching rate constant with different quenchers in SDS micellar solution has been measured. For indoles the electron-transfer reaction has been found to be followed by proton transfer from the donor molecule, which gives rise to the TX ketyl radical. On the other hand, the electron-transfer reaction in the case of phenols is preceded with formation of a hydrogen-bonded exciplex. The extent of the MFE and magnitude of the magnetic field corresponding to one-half of the saturation value of MFE ( B 1/2) support the fact that hyperfine mechanism plays the primary role. Quenching of MFE in the presence of gadolinium ions confirms that the radical pair is located near the micellar interface. MFE study has been further extended to protein-like bovine serum albumin in micellar solution. The results indicate loss in mobililty of radical pairs in the protein surfactant complex.

Temperature-dependent magnetic field effect study on exciplex luminescence: probing the triton X-100 reverse micelle in cyclohexane.

The microenvironment within the reverse micelle of the nonionic surfactant Triton X-100 (TX-100) in cyclohexane has been investigated by studying the magnetic field effect (MFE) on pyrene-dimethylaniline exciplex luminescence. The nature of exciplex fluorescence and its behavior in the presence of a magnetic field have been found to vary significantly with the water content of the medium. Results are discussed in light of multiple exciplex formation within the micelle which is further supported by the fluorescence lifetime measurements. Those exciplexes emitting at longer wavelength are found to be magnetic field sensitive while those emitting toward the blue region of the spectrum are insensitive toward magnetic field. Since the exciplex's emission characteristics and magnetic field sensitivity depend on its immediate surrounding, it has been concluded that the environment within the micelle is nonuniform. With an increase in hydration level, different zones of varying polarity are created within the reverse micelle. It has been pointed out that the magnetic field sensitive components reside inside the polar core of the micelle while those located near the hydrocarbon tail are field insensitive. However it has been presumed that an interconversion between the different types of exciplexes is possible. The environment within the reverse micelle is found to be largely affected by the change in temperature, and this is reflected in the exciplex emission property and the extent of magnetic field effect. Interestingly, the variation of MFE with temperature follows different trends in the dry and the wet reverse micelle. A comparison has been drawn with the reverse micelle of the ionic surfactant to get an insight into the difference between the various types of micellar environment.