Unlocking the Catalytic Potential of Anionic Micelles: Insights into the Ce(IV)-Directed Phenylalanine Oxidation Kinetics in Asymmetric Hydrophobic Environments.

The oxidation kinetics of phenylalanine (Phe) by Ce(IV) have been examined in both the absence and presence of aqueous micellar media with asymmetric tails, specifically using sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS) surfactants. The reaction progress was monitored by observing a decrease in absorbance using UV-vis spectroscopy. Interestingly, the kinetic profile revealed a consistent increase in the observed rate constant values as the concentration of the surfactant increased. The kinetic results have been analyzed by using numerous experimental studies, such as dynamic light scattering (DLS), zeta potential, ¹H NMR analysis, FT-IR spectroscopy, conductometry, scanning electron microscopy (SEM), fluorometry, time-correlated single-photon counting (TCSPC), and transmission electron microscopy (TEM). Micellar aggregates maintain their spherical shape in the presence of the substrate, even at higher surfactant concentrations, as revealed by microstructural analysis. The substrate molecules are encapsulated to a greater extent in the inner micellar core of STS micelles on account of the more hydrophobic nature of STS surfactants. Therefore, in STS micellar media, fewer substrate molecules diffuse to the Stern layer compared to the SDS micellar medium, resulting in fewer molecules participating in the oxidative transformation reaction. As a result, the rate enhancement of oxidation kinetics is less pronounced in STS micelles than in SDS micelles. A plausible mechanism that aligns with the kinetic results has been highlighted, along with the interpretation of the Piszkiewicz model, to explain the observed catalytic effect of both micellar mediums.