Hydrophobic derivatives of tyrosine and tryptophan, viz. octyl and dodecyl esters of tyrosine and octyl ester of tryptophan, are synthesized, and the interfacial and bulk properties in aqueous media are investigated as models for the membrane proteins. Molecular modeling by the density functional theory method is carried out to understand the molecular conformation and geometry for the purpose of determining the packing parameters. Water-induced molecular folding of the esters of both tyrosine and tryptophan, as observed using rotating frame nuclear Overhauser effect spectroscopy, indicates that the segregation of the hydrophobic and hydrophilic blocks in water is the key to the development of fascinating interfacial property displayed by the aromatic amino acid esters. The unusually high-order morphology of the aggregates, as observed using high-resolution transmission electron microscopy, is highly uncommon for single-chain amphiphiles and points to the fact that the self-assembly behavior of the present systems resembles that of block copolymers. The study of the growth of mesosized hollow aggregates with internal bilayer structures from tyrosine and tryptophan-based model systems would add to the understanding of biochemistry and biotechnology relevant to the cell membrane. The potential of biocompatible nanostructured motifs as the drug carriers is discussed. The highly functional role played by the aromatic amino acids at the membrane-water interface will be considered with the present amphiphilic models for future perspective.

The surface property of the cationic micelles of cetyltrimethylammonium bromide (CTAB) in an aqueous medium is highly modified in the presence of tyrosineoctyl ester (TYOE) and tyrosinedodecyl ester (TYDE), the models for aromatic amino acid side chains of transmembrane proteins. While the synergistic interaction between the quaternary ammonium head group of CTAB and the π-electron cloud of aromatic amino acid ester is influenced by the relative orientation and the unusual molecular geometry of the latter, this eventually triggers a morphology transition of the spherical micelle to cylindrical/wormlike micelles and imparts a strong viscoelasticity in the medium. Physical characteristics of the elongated micelles have been investigated by high resolution transmission electron microscopy (HRTEM) and the small angle neutron scattering (SANS) technique; the complex fluidic nature of the system is investigated by a dynamic rheological measurement. The intermolecular interactions have been recognized via H NMR and 2D nuclear Overhauser effect spectroscopy (NOESY), and the unambiguous geometry of the end-caps of the rods has been ascertained for the first time. While the interplay between lipids and transmembrane proteins is thought to be crucial in controlling the membrane shape of the cells during many vital events such as cellular fission, fusion, and virus entry, the observed tuning of the micellar surface curvature via the cation-π interaction involving tyrosine analogues is thought provoking and opens up an avenue for new physical chemistry research on a vital biological phenomena.

The present report was undertaken due to the scarcity of information regarding the microstructural transition from aqueous to acetonitrile (ACN)‐based non‐aqueous reverse micelles (RMs) stabilized by cationic didodecyldimethylammonium bromide (DDAB) and anionic sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) in cyclohexane. The synergistic solubilization capacity of corresponding polar solvent at a fixed composition and the nature of conductance plots in these RMs were markedly varied along with the composition of binary solvents (water and ACN at pure or mixed states) and the surfactant charge types (DDAB and AOT). The structural alteration in these RMs through water‐ and ACN‐rich compositions were studied by FTIR, where the results were explained in terms of molecular states of water and ACN inside RMs. The differential binding affinity of both polar solvents with the two surfactants was shown using ab initio calculations. The subsequent appearance and disappearance of aqueous nano‐pool was verified from UV‐Vis technique using CoCl2. The lack of H‐bonding ability on going from aqueous to ACN‐based RMs was evidenced from the temperature‐dependent DLS study along with the absorption profiles of 7‐hydroxycoumarin. The results showed how the microstructures and H‐bonding interactions inside RMs are dramatically altered by simply changing polarity of the solvents or the surfactant charge‐types. This report could be useful to understand the formation mechanism of two class of RMs.

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