Photophysical properties of methylene blue in water and in aqueous solutions of dimethylsulfoxide.

A detailed study of the effect of aprotic polar solvents such as dimethylsulfoxide on methylene blue (MB) was carried out through a combination of UV-vis absorption and steady-state fluorescence spectroscopy techniques at 293.15 K. In aqueous solutions MB tends to exhibit strong tendency to aggregate. The dimerization behavior of MB in water was analyzed in terms of monomer-dimer equilibrium. The addition of dimethylsulfoxide prevents dimerization of dye molecules. From absorption spectra the dimerization constants and changes of standard Gibbs energy were calculated. From the steady-state fluorescence spectra the quantum yields and Stokes shifts were determined. To explain the effect of dimethylsulfoxide properly the other polar aprotic solvents such as N, N-dimethylformamide, acetonitrile and acetone were used. It is suggested that water structural effect is the major factor in aggregation phenomenon. Moreover the quantum yield increases drastically in dimethylsulfoxide compared with water assuming that MB may be characterized as viscosity probe.