Fatty acids conformation

Kaneko, F., J. Yano, and K. Sato, Diversity in Fatty Acid Conformation and Chain Packing in cw-Unsaturated Lipids, Curr. Opin. Struct. Biol. 8 417-425 (1998). 

DeJong, S. (1980). Triacylglycerol Crystal Structures and Fatty Acid Conformations, A Theoretical Approach, Dissertation, Amsterdam. 

Arachidonic Acid and Related Fatty Acids Conformational Analysis... 

De Jong, S. 1980. Diacylglycerol structures and fatty acid conformations. A theoretical approach. Ph.D. thesis University of Ulrecht. The Netherlands 171... 

Grease Refining and Fractionation. Lanolin to be used in pharmaceuticals and cosmetics must conform to strict requirements of purity, such as those in the U.S. and British Pharmacopoeias (181,182). These include specifications for the maximum allowable content of free fatty acids, moisture, ash, and free chloride. Lanolin intended for certain dermatological appHcations may have to meet further specifications in relation to free-alcohol and detergent contents (183,184). 

Free rotation around each of the carbon-carbon bonds makes saturated fatty acids extremely flexible molecules. Owing to steric constraints, however, the fully extended conformation (Figure 8.1) is the most stable for saturated fatty acids. Nonetheless, the degree of stabilization is slight, and (as will be seen) saturated fatty acid chains adopt a variety of conformations. 

Acyl groups are common in bacterial polysaccharides. The parent acids are fatty acids, hydroxy acids, and amino acids. The simplest acid, formic acid, has only been found as the amide. The occurrence of O-formyl groups had been reported, but proved to be incorrect. A-Formyl groups have been found in different polysaccharides for example, in the 0-specific side-chains of the LPS from Yersinia enlerocolitica 0 9, which are composed of 4,6-dideoxy-4-formamido-D-mannopyranosyl residues. The formyl group can assume two main conformations, s-cis (41) and s-trans (42), which are... 

In general for the C20 series, maximal activity is achieved with amides of arachidonic acid (1) [81], mead acid (199) [149], and dihomo-y-linoleic acid (200) [150] (see Table 6.18). Decreasing the unsaturation (201), (202), or abolishment of the n-pentyl chain (203) [150] led to less active or inactive compounds. Variable results were seen with longer chains. The C22 4 n-6 analogue (204) is as active as AEA (1) whereas the C22 6 n-3 analogue (205) is less active than the C20 5 n-3 analogue (203) [150]. Replacement of the double bonds with triple bonds (206) resulted in loss of activity [150] (see Table 6.18). Forcing the fatty acid chain into a hairpin conformation by cyclisation (207) also resulted in inactive compounds [151]. 

These results are quite compatible with the preferred conformations of the two-chain carbonyl diacids in aqueous media mentioned above (Porter et al, 1986b, 1988). The meso-compounds preferred collinear conformation, which places the hydrogens at the asymmetric carbons in a nearly eclipsed position relative to each other (Fig. 44), is more stable than that of the ( )-diastereomer by about 1.2kcalmol 1. In this conformation, the two carboxylic acid groups at the ends of the chain can be attached to the water surface side-by-side. The entire molecule can then behave as a good-amphiphile whose structure is similar to a pair of single-chain fatty acid molecules bound side-by-side, each chain mirroring the other about the molecules plane of symmetry. 

The close packing of the acyl groups associated with the inclination of the lipid A backbone with respect to the fatty acid orientation seems to constitute a common and characteristic feature of the lipid A conformation. This specific (endotoxic) conformation is very likely to influence greatly the tendency of the amphiphilic lipid A to adopt peculiar supramolecular structures. 

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