Mobility, alkyl chains

Extensive discussions have focused on the conformation of the alkyl chains in the interior ". It has been has demonstrated that the alkyl chains of micellised surfactant are not fully extended. Starting from the headgroup, the first two or three carbon-carbon bonds are usually trans, whereas gauche conformations are likely to be encountered near the centre of tlie chain ". As a result, the methyl termini of the surfactant molecules can be located near the surface of the micelle, and have even been suggested to be able to protrude into the aqueous phase "". They are definitely not all gathered in the centre of tire micelle as is often suggested in pictorial representations. NMR studies have indicated that the hydrocarbon chains in a micelle are highly mobile, comparable to the mobility of a liquid alkane ... 

Also, the segmental mobility and preferential conformation of surfactant alkyl chains is perturbed by water addition [92,99]. 

Phospholipids, which are one of the main structural components of the membrane, are present primarily as bilayers, as shown by molecular spectroscopy, electron microscopy and membrane transport studies (see Section 6.4.4). Phospholipid mobility in the membrane is limited. Rotational and vibrational motion is very rapid (the amplitude of the vibration of the alkyl chains increases with increasing distance from the polar head). Lateral diffusion is also fast (in the direction parallel to the membrane surface). In contrast, transport of the phospholipid from one side of the membrane to the other (flip-flop) is very slow. These properties are typical for the liquid-crystal type of membranes, characterized chiefly by ordering along a single coordinate. When decreasing the temperature (passing the transition or Kraft point, characteristic for various phospholipids), the liquid-crystalline bilayer is converted into the crystalline (gel) structure, where movement in the plane is impossible. 

It has been experimentally and theoretically verified that the organic component of the mobile phase adsorbs on the surface of the stationary phase forming a mono- or multi-molecular layer. The volume of the adsorbed layer is not dependent on the length of the alkyl chain [89],... 

NMR relaxation measurements such as cross-polarization time constants (7ch) can also yield useful information regarding alkyl-chain mobility. Sindorf and Maciel [159] have characterized the relative mobility of low-density Cg and Cig stationary phases ( 2.6 and 1.7 p,mol/m, respectively) as a function of carbon position from the... 

Several workers have concluded that under conditions used in their study ion-pairing in the mobile phase between amphiphilic hetaeron ions and oppositely charged sample components governed retention. Horvath et al. (34) examined the effect of alkyl sulfates and other alkyl anions on the retention of catecholamines in which both the concentration and the length of the alkyl chains of the hetaerons were varied. The hyperbolic concentration dependence of the retention factor shown in Fig. 48, was found to be similar to that reported by others. 

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