alexa IRRAS studies on chain orientation in the monolayers of amino acid amphiphiles at the air-water interface depending on metal complex and hydrogen bond formation with the headgroups.


Journal of Physical Chemistry & Biophysics

Author(s): Du X, Miao W, Liang Y, Du X, Miao W, Liang Y, Du X, Miao W, Liang Y, Du X, Miao W, Liang Y

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Abstract Monolayers of N-octadecanoyl-L-alanine at the air-water interface on pure water and metal ion containing subphases have been studied using polarized infrared reflection-absorption spectroscopy (IRRAS). The metal complex and hydrogen bond formation with the headgroups give rise to a change in chain order depending on metal ion in the subphase. On pure water and Ag(+)-/Pb(2+)-containing subphase, the antisymmetric CH(2) stretching band intensity [nu(a)(CH(2))] undergoes a slower increase than the symmetric one [nu(s)(CH(2))] below the Brewster angle, so the intensity ratios of nu(a)(CH(2))/nu(s)(CH(2)) are less than 1 in the cases of Ag(+) and Pb(2+). Beyond the Brewster angle, the nu(a)(CH(2)) band intensities are substantially reduced in comparison with the nu(s)(CH(2)) ones in the cases of pure water and Ag(+), but the nu(a)(CH(2)) bands still remain negative-oriented in the presence of Pb(2+). These unusual spectral features indicate that the alkyl chains take a preferential orientation with their C-C-C planes parallel to the water surface. The parallel packing of the alkyl chains results from the intermolecular hydrogen bonds C=O...H-N between the neighboring amide groups, strengthened by the metal complex of covalent interaction. On the Ca(2+)-/Cu(2+)-containing subphase, the corresponding polarized spectra display a usual behavior. The alkyl chains are roughly estimated to be inclined around 35-40 degrees from the surface normal on the assumption of chain segment orientation for the monolayers in the liquid-expanded phase. The chain conformation and tilt are closely related to the formation of intramolecular hydrogen bonds and the ionic interaction of the metal complex in the cases of Ca(2+) and Cu(2+). This article was published in J Phys Chem B and referenced in Journal of Physical Chemistry & Biophysics

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