The extent of intra- and interchain associations of (un)charged water-soluble monomers in the homogeneous and micellar solutions was studied with steady-state fluorescence spectroscopy. Fluorescence spectroscopic experiments were performed on uncharged (acryl amide) and charged hydrophilic monomers [zwitterionic 3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate (I)MAPS), etc.] with pyrene as a probe. In both the homogeneous and micellar solutions, linear Stern-Volmer plots were obtained that implied that the quenching process can be considered as totally dynamic. The Stern-Volmer constant (K-sv) for DMAPS decreased with an increasing dielectric constant of solvent and the concentration of simple electrolyte. An abrupt decrease in K-sv was observed in the presence of a small amount of anionic emulsifier [below the critical micelle concentration (cmc)]. The dependence of K-SV on pH for DMAPS was described by a curve with a maximum at about pH = 7. This was interpreted in terms of segregation of DMAPS and the variation of a optimal microenvironment for the probe and quencher with pH. The quenching rate in the micellar solutions strongly increased above the cmc but was lower than that in the homogeneous solutions. In the micellar solutions (above the cmc), the microenvironment for an interaction between the probe and quencher was suggested to be the whole microdroplet. The dependence of K-SV on pH for DMAPS is described by a curve with a maximum at about pH = 9.3. The synergistic effect arises from the segregation of charged quencher molecules within the microdroplets. The complex (or strong interaction) between quencher and additive(s) is supposed to increase the dynamic nature of microdroplets that provides an optimal microenvironment for probe and quencher. A good coemulsifier, however, removes quencher from the interface and creates a barrier for entering monomer (quencher) into the core of micelles; therefore, quenching is depressed. (C) 2003 Wiley Periodicals, Inc.