Monolayers of amino acid-type amphiphiles

Abstract

The monolayer characteristics of selected N-alkanoyl substituted α-amino acid are studied with the objective to demonstrate the specific effect of the chemical structure of the polar head group which is highlighted with the D- and L-enantiomers of the following selected examples: R-alanine, R-serine, R-threonine, R-allo-threonine, and R-aspartic acid (R = C₁₆, C₁₈). The thermodynamic effect of the head group variation is studied. Experimental π-A isotherms of the N-tetradecyl-L-alanine monolayers show similar behavior as those of usual amphiphiles. The -CH₃-group in R-alanine with the simplest head group structure is substituted by a -CH₂-OH group in R-serine and serine methylester and by a -CH- CH₃-OH group in R-threonine (or allo-threonine) and threonine methylester. The introduction of the methyl group in 3-position of serine (serine to 3-methyl-serine = threonine) shifts the characteristic temperatures by >20 K to lower values determined for N-C16-Dl-serine. The formation of the corresponding methylester decreases these temperatures by 15 K for serine with the shorter (C16) alkyl chain and only by ∼5 K for threonine with the longer chain (C18). The π-A curves of the enantiomeric and racemic allo-forms show similar features to those of N-stearoyl-threonine. The absolute T₀-values (disappearance of the LE/LC-transition) are 4-5 K larger compared with the corresponding N-stearoyl-threonines, but the ΔT₀ between the enantiomeric (D) and the racemic (DL) forms is only slightly larger than that of N-stearoyl-threonine. Monolayers of different N-alkanoyl substituted α-amino acid amphiphiles have been mesoscopically characterized. Substantial topological differences are observable at the condensed phase domains of several amino acid amphiphiles, such as, N-palmitoyl aspartic acid, N-palmitoyl- or N-stearoyl serine methyl ester, N-stearoyltyrosine, N-palmitoyl or N-myristoyl alanine. Many fascinating domain shapes are found, but always the curvatures of the two enantiomeric forms are directed in an opposite sense. The domain shape of the 1:1 racemic mixtures is usually different, but very often oppositely curved texture elements are observable. GIXD is used to study the characteristic features of the lattice structure of condensed monolayer phases on the Angstrom scale. Specific for all structures is the large tilt angle with respect to the surface normal, which decreases only marginally by compression. The large size of the head groups and strong interactions between them dominate the monolayer structure. As presented for NC16 and N-C18-threonine, N-C16-DL -serine, N-C16-L -serine, NC16 DL -serine-ME, NC16 L -serine-ME, NC18 DL -threonine-ME, and NC18 L -threonine-ME the enantiomers form an oblique lattice structure (3 diffraction peaks), whereas two peaks are observed for the racemates forming NNN tilted orthorhombic structures. A complete phase diagram of mixed monolayers of the D- and L-enantiomers of N-stearoyl-threonine with two eutectic points at x_D ≈ 0.25 and x_D ≈ 0.75 is proposed. The quantum chemical semiempirical PM3 method is applied to calculate the thermodynamic and structural parameters of clusterization in finite and infinite clusters for N-alkanoyl-substituted alanine with n = 8-17 carbon atoms in the chain at the air/water interface with the aim to obtain a new theoretical verification of the experimental results.

Keywords: Amino acids; GIXD; Monolayers; Quantum chemical simulations; Structure parameters; Thermodynamics of clusterization.