Adsorption of gemini surfactants with dodecyl side chains and different spacers, including partially fluorinated...

Neutron reflectometry has been used to study the adsorption of two symmetrical cationic (dimethyl ammonium bromide) gemini surfactants with two C(12)H(25) chains and different partially fluorinated spacers at three different surfaces: air/water, hydrophilic silica/water, and hydrophobic (octadecyltricholorosilane (OTS))/water. In addition, the adsorption of purely hydrocarbon geminis with the same side chains and spacers of different lengths has been studied at the same two solid surfaces. The limiting close-packed areas for the two fluorocarbon geminis, C(12)-C(3)fC(6)C(3)-C(12) and C(12)-C(4)fC(4)C(4)-C(12), are 92 and 72 ± 4 at the hydrophilic silica surface, 81 and 89 ± 4 at OTS, and 137 and 106 ± 4 Å(2) at the air/water interface with decreases of 38 and 24% from air/water to the average solid value, respectively. These changes suggest that the packing at the air/water interface is inefficient, and this allows the extra hydrophobicity of the chain environment at the two solid surfaces to promote much more efficient packing. At the air/water interface, the fluorocarbon spacers are on average the fragments furthest away from the underlying water, further out than in the nearest comparable hydrocarbon gemini, C(12)-C(12)-C(12). This is the probable explanation of the much lower value of the area per molecule at the air/water interface of C(12)-C(4)fC(4)C(4)-C(12) compared to that of C(12)-C(12)-C(12). It is also the probable cause of the inefficient packing of the hydrocarbon side chains. At the more hydrophobic OTS surface the situation is reversed and the fluorocarbon spacers are now the furthest from the hydrophobic surface, further out than the spacer in C(12)-C(12)-C(12). This is an unusually large structural change that must be associated with the greatly improved packing at the OTS surface. The efficiency of the packing is also high for the hydrophilic surface, no doubt because the hydrocarbon chains can interact favorably in the adsorbed bilayer core. The values of the area per molecule obtained for the series of hydrocarbon geminis at the air/water, OTS/water and silica/water interfaces are respectively 139, 104, and 98 ± 4 Å(2) for C(12)-C(12)-C(12), 114, 106, and 94 ± 4 Å(2) for C(12)-C(10)-C(12), 104, 84, and 85 ± 4 Å(2) for C(12)-C(6)-C(12), and 78, 66, and 70 ± 3 Å(2) for C(12)-C(3)-C(12). The area per molecule is also about 20% less on average at the two solid surfaces than at the air/water interface. This can also be attributed to more efficient packing caused by the more favorable hydrophobic interactions possible at these two surfaces than at the air/water interface, again showing that the packing at the air/water interface is inefficient and probably resulting from the competition between spacer and chains, which will be most pronounced for the C(12) spacer.