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Amphiphilic Lauryl Ester Derivatives from Aromatic Amino Acids: Significance of Chemical Architecture in Aqueous Aggregation Properties

Lauryl esters of L-tyrosine (LET) and L-phenylalanine (LEP) were, in a previous interface adsorption study, found to adopt very different interfacial conformations. The present study is an investigation of their aqueous aggregation properties with the goal of elucidating the effects of the presence in LET and absence in LEP of the phenolic OH group on their aqueous aggregate structures and micellar conformations of the surfactant monomers. The measured properties included aggregation numbers from time-resolved fluorescence quenching (TRFQ), interface hydration index and microviscosity by electron spin resonance (ESR), chemical shifts of 1H resonance lines by NMR, and Krafft temperatures and enthalpies of structural transitions by differential scanning calorimetry (DSC). The TRFQ, ESR, and NMR experiments were conducted at various temperatures from 23 to 70 °C for various surfactant concentrations from 0.050 to 0.200 M. Markedly different temperature dependences of aggregation number and 1H NMR chemical shifts are exhibited by LET and LEP micelles. LET and LEP form ionic micelles. The aggregation number of LEP decreases as is characteristic of ionic micelles, but that of LET increases slightly with temperature. The changes with temperature in the NMR chemical shifts and width of the resonance lines are significantly greater for the various LEP protons than for those of LET. The differences in these properties and other fluorescence decay characteristics of fluorophores incorporated into the micelles could be attributed to the difference in the micellar conformations of LET and LEP which are postulated to be similar to that at oil−water interfaces. The phenolic group is hypothesized to be in the micelle−water interface as part of the headgroup in LET micelles, and its location does not change with temperature. On the other hand, in LEP micelles, the phenyl ring is folded into the core overlapping with the flexible hydrophobic chains. The resulting closer proximity between the phenyl ring and the flexible hydrocarbon chain causes interdependence of the phenyl ring and chain proton resonances, leading to the observed temperature dependence of the chemical shifts in LEP. The TRFQ and ESR data are combined together in a molecular space-filling model, referred to as the polar shell model, to derive the geometrical properties of the micelle. The DSC scans in the temperature range 10−55 °C showed the presence of distinctly different endotherms for LET and LEP. The Krafft temperatures, KT, and the enthalpies were determined. The higher KT and broader peak of the DSC endotherm of LET as compared to LEP are attributed to the stabilization of fiberlike structures below the Krafft temperature due to its chirality and the hydrogen bonding capability of the phenolic OH and also to the ion−dipole interactions. Thus, all of the observed differences between LET and LEP could be attributed to the difference in their chemical architecture.

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