Influence of Order within Nonpolar Monolayers on Hydrophobic Interactions

We report an experimental investigation of the influence of molecular-level order (crystallinity) within nonpolar monolayers on hydrophobic interactions. The measurements were performed using gold film-supported monolayers formed from alkanethiols (CH3(CH2)nSH, with n ranging from 3 to 17), which we confirmed by using polarization–modulation infrared reflection–adsorption spectroscopy to exhibit chain-length-dependent order (methylene peak moves from 2926 to 2919 cm–1, corresponding to a transition from liquid- to quasi-crystalline-like order) in the absence of substantial changes in chain density (constant methyl peak intensity). By using monolayer-covered surfaces immersed in either aqueous triethanolamine (TEA, 10 mM, pH 7.0) or pure methanol, we quantified hydrophobic and van der Waals contributions to adhesive interactions between identical pairs of surfaces (measured using an atomic force microscope) as a function of the length and order of the aliphatic chains within the monolayers. In particular, ...