Ionic Binding of Na+ versus K+ to the Carboxylic Acid Headgroup of Palmitic Acid Monolayers Studied by Vibrational Sum Frequency Generation Spectroscopy

Abstract

Ionic binding of alkali ions Na(+) and K(+) to the carboxylic acid headgroups of fatty acid monolayers is studied as a proxy toward understanding the fundamental chemistry in cell biology. In this study, we used broad-bandwidth sum frequency generation (BBSFG) vibrational spectroscopy to investigate the ionic binding event that leads to deprotonation and complex formation of fatty acid headgroups. Palmitic acid (C(15)H(31)COOH) exists as a monolayer on aqueous surfaces. Surface vibrational stretch modes of palmitic acid from 1400 cm(-1) to 3700 cm(-1) were observed (nu(s)-COO(-), nu-C horizontal lineO, nu-C-H, nu-O-H of -COOH, free OH). Palmitic acid is mostly protonated at the aqueous surface at neutral pH (approximately 6). However, various degrees of deprotonation are initiated by the introduction of Na(+) and K(+) that results in the complexation of K(+):COO(-) and solvent separated Na(+):COO(-). Evidence in several spectral regions indicates that K(+) exhibits stronger ionic binding affinity to the carboxylate anion relative to Na(+).