(360g) Influence of Order within Non-Polar Monolayers on Hydrophobic Interactions

This presentation will describe the results of an experimental investigation of the influence of molecular-level order (crystallinity) within non-polar 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, we measured pull-off forces arising from hydrophobic adhesion to increase in a non-linear manner with chain-length (abrupt increase between n = 5 and 6 from 2.1±0.3 nN to 14.1±0.7 nN) and to correlate closely with a transition from a liquid-like to crystalline-like monolayer phase. In contrast, adhesion in methanol increased gradually with chain-length from 0.3±0.1 nN to 3.2±0.3 nN for n=3 to 7, and then did not change further with an increase in chain-length. These results lead to the hypothesis that order within non-polar monolayers influences hydrophobic interactions. Additional support for this hypothesis was obtained from measurements reported in this paper using long-chain alkanethiols (ordered) and alkenethiols (disordered). The results are placed into the context of recent spectroscopic studies of hydrogen bonding of water at non-polar monolayers. Overall, our study provides new insight into factors that influence hydrophobic interactions at non-polar monolayers.