From free to effective diffusion coefficients in fluorescence correlation spectroscopy experiments.

Diffusion is one of the main transport processes that occur inside cells determining the spatial and time distribution of relevant action molecules. In most cases these molecules not only diffuse but also interact with others as they get transported. When these interactions occur faster than diffusion the resulting transport can be characterized by "effective diffusion coefficients" that depend on both the reaction rates and the "free" diffusion coefficients. Fluorescence correlation spectroscopy (FCS) gives information on effective rather than free diffusion coefficients under this condition. In the present paper we investigate what coefficients can be drawn from FCS experiments for a wide range of values of the ratio of reaction to diffusion time scales, using different fitting functions. We find that the effective coefficients can be inferred with relatively small errors even when the condition of fast reactions does not exactly hold. Since the diffusion time scale depends on the size of the observation volume and the reaction time scale depends on concentrations, we also discuss how by changing either one or the other property one can switch between the two limits and extract more information on the system under study.