Modeling Chemical Reactivity in Ionic Detergent Micelles: a Review of Fundamentals

Ionic detergent micelles have the capacity to solubilize organic substrates, interact selectively with counterions, repel coions, exhibit partial “dissociation” of the counterions, grow in size with added salt, affect the position of chemical equilibria, accelerate or inhibit the rates of chemical reactions, modulate photochemical reactivity and determine the dynamics of diffusion or neardiffusion controlled processes. Many of these phenomena can be understood and analyzed quantitatively in terms of relatively simple models for binding, selectivity and electrostatics that often require no knowledge of micellar structure or dynamics (the pseudophase limit), without compromising chemical intuition. An overview is provided of our current understanding of the interplay between micellar structure and electrostatics, selectivity, solubilization, and reactivity and their role in the development of quantitative formalisms for analyzing micellar effects on reactivity and equilibria.