Head group control

Although the formalism of cationation by alkyl halides was in principle correct, the significance of this mechanism for head group control could not be exploited because the conventional Friedel-Crafts acids... 

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],...

There are a few exceptions to this general rule. One of the few examples of an effect on polymer stereochemistry was provided by Dais et al.m who found that polymerization of 31 above the cmc initiated by y-irradiation at 25 °C yields polymer composed entirely of syndiolaclic dyads P(m) =0. When the double bond was distant from the polar head group in 32, the tacticity observed was similar to that observed in solution polymerization / ( )-0,18. Polymerization of 31 at higher temperatures (50 °C) initiated by AIBN also showed no sign of tacticity control. The stcrcospccific polymerization of 31 was attributed to organization of the methacrylate moiety on the surface of the micelle. 

Some investigations have emphasized the importance of micellar size as a control parameter of nanoparticle size [224]. It has been suggested that other factors also influence the nanoparticle size, such as the concentration of the reagents, hydration of the surfactant head group, intermicellar interactions, and the intermicellar exchange rate [198,225-228],... 

The incorporation of dendritic moieties into amphiphilic structures is attractive as the dendritic component provides a unique opportunity to vary, in a controlled fashion, head group properties such as size and polarity, by simply changing the generation or the nature of its surface groups. Similarly, the length of the linear fragment can easily be modified to adjust properties. 

Meijer and co-workers have also explored hybrids based on polystyrene and polypropylene imine) dendrons with carboxylic acid functionalities on the surface of the dendrons [48], In these materials the polarity of the head group can easily be modified in a controlled manner leading to both pH and gener-... 

Traditionally, the sol-gel process has been used for the preparation of silica nanoparticles via the hydrolysis of alkoxides in organic solvents [52,53]. Similar hydrolysis and condensation carried out in w/o microemulsion offers robust control over the synthesis process. W/o emiflsion-mediated sol-gel synthesis is currently used for the fabrication of pure sihca, as well as inorganic and organic dye-doped silica nanoparticles. The synthesis of sihca and dye-doped nanoparticles is classified in the following sections on the basis of the classification of the head group fimctionahty of the major surfactant used. 

According to this method, Fyles analyzed the transport rate of alkali metal cations for a series of 21 synthetic transporters (Figure 14). The whole molecules were designed to elucidate the structure-function relationship. They are composed of three parts core, wall, and head units. The core units were derived from tartaric acids so that the wall units may be fixed to provide structural control by incorporating both the polar and nonpolar functionality (Y and Z in Figure 14). The head groups (X) are attached to provide an overall amphiphilic nature. 

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