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Ultrafast bimolecular photoinduced electron transfer (PET) between six coumarin dyes and four viologen molecules in the stern layer of sodium dodecyl sulfate micelle have been studied using femtosecond broadband transient absorption spectroscopy and femtosecond fluorescence up-conversion spectroscopy over a broad reaction exergonicity (ΔG). Emanating the formation of radical cation intermediates of viologen molecules using the transient absorption and the fast decay component of coumarins using the fluorescence up-conversion studies the forward bimolecular electron transfer rate (k) have been measured with high accuracy. The relationship of k with ΔG found to follow a Marcus type bell-shaped dependence with an inversion at -1.10 eV. In this report, we have studied PET reaction using ultrafast spectroscopy at the quencher concentration where static quenching regime prevails. Moreover, the incompetency of Stern-Volmer experiments in studying ultrafast PET has been revealed. In contrary to previous claims, here we found that the k is lower for lower lifetime coumarins, indicating that static, nonstationary and stationary regime of quenching have the minimal role to play to in the bimolecular electron transfer process. By far, this report is believed to be the most efficient and immaculate way of approaching Marcus inverted region problem in the case of bimolecular PET and settles the long-lasting debate of whether the same can be observed in micellar systems.

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

The present investigation reports new results on optical properties of graphene-metal nanocomposites. These composites were prepared by a solution-based chemical approach. Graphene has been prepared by thermal reduction of graphene oxide (GO) at 90°C by hydrazine hydrate in an ammoniacal medium. This ammoniacal solution acts as a solvent as well as a basic medium where agglomeration of graphene can be prevented. This graphene solution has further been used for functionalization with Ag, Au, and Cu nanoparticles (NPs). The samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, UV-Vis spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) to reveal the nature and type of interaction of metal nanoparticles with graphene. The results indicate distinct shift of graphene bands both in Raman and UV-Vis spectroscopies due to the presence of the metal nanoparticles. Raman spectroscopic analysis indicates blue shift of D and G bands in Raman spectra of graphene due to the presence of metal nanoparticles except for the G band of Cu-G, which undergoes red shift, reflecting the charge transfer interaction between graphene sheets and metal nanoparticles. UV-Vis spectroscopic analysis also indicates blue shift of graphene absorption peak in the hybrids. The plasmon peak position undergoes blue shift in Ag-G, whereas red shift is observed in Au-G and Cu-G.

In this work, we have addressed the problem of "acidity" of the water-pool of a reverse micelle (RM) through the well-known inversion of sucrose reaction as a tool of investigation. This reaction has been performed inside positively and negatively charged RM and the rates are compared with that in bulk water. We propose that the buffer-like action in a water-pool is much stronger than expected earlier. The rate of sucrose hydrolysis slowed down in the negatively charged AOT reverse micelle while it sped up for the positively charged CTAB reverse micelle. However, temperature-dependent measurements showed that the activation energy remained the same for all the cases. It has been concluded that a proton gradient exists inside the water-pool of the reverse micelle and it determines the buffer-like action of the water-pool that persists until about 2 N of HCl in AOT RM of w(0) = 10.5.