Surfactant Micellar and Vesicle Microenvironments and Structures under Synthetic Organic Conditions

Fluorescence lifetime imaging microscopy (FLIM) reveals vesicle sizes, structures, microenvironments, reagent partitioning, and system evolution with two chemical reactions for widely used surfactant-water systems under conditions relevant to organic synthesis, including during steps of Negishi cross-coupling reactions. In contrast to previous investigations, the present experiments characterize surfactant systems with representative organohalide substrates at high concentrations (0.5 M) that are reflective of the preparative-scale organic reactions performed and reported in water. In the presence of representative organic substrates, 2-iodoethylbenzene and 2-bromo-6-methoxypyridine, micelles swell into emulsion droplets that are up to 20 μm in diameter, which is 3-4 orders of magnitude larger than previously measured in the absence of an organic substrate (5-200 nm). The partitioning of reagents in these systems is imaged through FLIM─demonstrated here with nonpolar, amphiphilic, organic, basic, and oxidative-addition reactive compounds, a reactive zinc metal powder, and a palladium catalyst. FLIM characterizes the chemical species and/or provides microenvironment information inside micelles and vesicles. These data show that surfactants cause surfactant-dictated microenvironments inside smaller micelles (<200 nm) but that addition of a representative organic substrate produces internal microenvironments dictated primarily by the substrate rather than by the surfactant, concurrent with swelling. Addition of a palladium catalyst causes the internal environments to differ between vesicles─information that is not available through nor predicted from prior analytical techniques. Together, these data provide immediately actionable information for revising reaction models of surfactant-water systems that underpin the development of sustainable organic chemistry in water.