Head group surface

A theoretical model predicting the shape-structure relationship between the monomeric units and their aggregates was developed by Israelachvili and was based on statistical mechanics of phospholipids.23 This model predicts the type of the aggregate formed on the basis of the packing parameter (P), which relates the volume of the molecule (V) to its length (1) and to the mean cross-sectional (effective) head group surface area (a) ... 

Here, v is the hydrocarbon chain volume, a<> is the optimal head group surface area, and is the critical chain length. For packing parameters between and 1, amphiphiles should form flexible bilayers (vesicles), or planar bilayers as the packing parameter approaches 1. On the contrary, a packing paramter less than j should hinder the formation of bilayers in particular, the theory predicts micelle formation. 

The formation of ME systems can be explained with reference to the self-assembly theory of micelle and bilayer forming surfactant molecules where the volume of the surfactant is denoted v, its head group surface area a, and its... 

The acid monolayers adsorb via physical forces [30] however, the interactions between the head group and the surface are very strong [29]. While chemisorption controls the SAMs created from alkylthiols or silanes, it is often preceded by a physical adsorption step [42]. This has been shown quantitatively by FTIR for siloxane polymers chemisorbing to alumina illustrated in Fig. XI-2. The fact that irreversible chemisorption is preceded by physical adsorption explains the utility of equilibrium adsorption models for these processes. 

Fig. 7.23 In simulations of stearic add on a hydrophobic surface hydrogen bonding between the head groups is important in controlling the orientation of the molecules [Kim et al, 1994b],...

Soap is one example of a broader class of materials known as surface-active agents, or surfactants (qv). Surfactant molecules contain both a hydrophilic or water-liking portion and a separate hydrophobic or water-repelling portion. The hydrophilic portion of a soap molecule is the carboxylate head group and the hydrophobic portion is the aUphatic chain. This class of materials is simultaneously soluble in both aqueous and organic phases or preferential aggregate at air—water interfaces. It is this special chemical stmcture that leads to the abiUty of surfactants to clean dirt and oil from surfaces and produce lather. 

Within a series with a fixed hydrophilic head group, detergency increases with increasing carbon chain length, reaches a maximum, and then decreases. This behavior frequentiy reflects a balance between increased surface activity of the monomer and decreased monomer concentration with increased surface activity. Similar effects are seen in surfactants in biological systems. 

Bead-spring models without explicit solvent have also been used to simulate bilayers [40,145,146] and Langmuir monolayers [148-152]. The amphi-philes are then forced into sheets by tethering the head groups to two-dimensional surfaces, either via a harmonic potential or via a rigid constraint. 

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