Phosphatidylethanolamin

The identity of the moiety (other than glycerol) esterified to the phosphoric group determines the specific phosphoHpid compound. The three most common phosphoHpids in commercial oils are phosphatidylcholine or lecithin [8002-45-5] (3a), phosphatidylethanolamine or cephalin [4537-76-2] (3b), and phosphatidjlinositol [28154-49-7] (3c). These materials are important constituents of plant and animal membranes. The phosphoHpid content of oils varies widely. Laurie oils, such as coconut and palm kernel, contain a few hundredths of a percent. Most oils contain 0.1 to 0.5%. Com and cottonseed oils contain almost 1% whereas soybean oil can vary from 1 to 3% phosphoHpid. Some phosphoHpids, such as dipaLmitoylphosphatidylcholine (R = R = palmitic R" = choline), form bilayer stmetures known as vesicles or Hposomes. The bdayer stmeture can microencapsulate solutes and transport them through systems where they would normally be degraded. This property allows their use in dmg deHvery systems (qv) (8). 

Fig. 1. Chemical stmcture of phosphatidylcholine (PC) (1) and other related phosphohpids. R C O represents fatty acid residues. The choline fragment may be replaced by other moieties such as ethanolamine (2) to give phosphatidylethanolamine (PE), inositol (3) to give phosphatidylinositol (PI), serine (4), or glycerol (5). IfH replaces choline, the compound is phosphatidic acid (6). The corresponding lUPAC-lUB names ate (1), l,2-diacyl-t -glyceto(3)phosphocholine (2), l,2-diacyl-t -glyceto(3)phosphoethanolamine (3), 1,2-diacyl-t -glyceto(3)phosphoinositol (4), 1,2-diacyl-t -glyceto(3)phospho-L-serine and (5), l,2-diacyl-t -glyceto(3)phospho(3)-t -glycetol.

Browning Reactions. The fluorescent components formed in the browning reaction (8) of peroxidized phosphatidylethanolamine are produced mainly by interaction of the amine group of PE and saturated aldehydes produced through the decomposition of fatty acid hydroperoxides. 

Other Reactions of Phospholipids. The unsaturated fatty acid groups in soybean lecithin can be halogenated. Acetic anhydride combined with the amino group of phosphatidylethanolamine forms acetylated compounds. PhosphoHpids form addition compounds with salts of heavy metals. Phosphatidylethanolamine and phosphatidjhnositol have affinities for calcium and magnesium ions that are related to interaction with their polar groups. 

Alcohol fractionation redistributes the phosphoHpids according to their respective hydrophilic and lipophilic properties (13). A process to produce fractionated phosphoHpids with a phosphatidylcholine (PC) content of more than 30% and a PC/PE (phosphatidylethanolamine) quotient of ca 4 has been developed. With this process it is possible to produce 1000 t per year. 

Food. Lecithin is a widely used nutritional supplement rich ia polyunsaturated fatty acids, phosphatidylcholine, phosphatidylethanolamine, phosphatidjhnositol, and organically combiaed phosphoms, with emulsifying and antioxidant properties (38). 

Amphiphilic Molecules. In just about all cases of lyotropic Hquid crystals, the important component of the system is a molecule with two very different parts, one that is hydrophobic and one that is hydrophilic. These molecules are called amphiphilic because when possible they migrate to the iaterface between a polar and nonpolar Hquid. Soaps such as sodium laurate and phosphoHpids such as a-cephalin [5681-36-7] (phosphatidylethanolamine) (2) are important examples of amphiphilic molecules which form Hquid crystal phases (see Lecithin Soap). 

Muramyl tripeptide phosphatidylethanolamine (MTP-PE), a synthetic analogue of muramyl dipeptide and an effective systemic macrophage activator, induces a variety of cytokines such as IL-1, IL-6, and TNE, as well as PGE2 (205). Preirradiation treatment of mice using MTP-PE encapsulated in Hposomes, which can intensify radioprotective abiHty, stimulates the monocyte/macrophage system and accelerates the recovery of hemopoietic cells. 

In addition to the triglycerides, the four oilseeds also contain phosphatides. For example, soybean oil containing 1.47% phosphatides consists of 48.9% phosphatidylcholine, 27.0% phosphatidylethanolamine, 21.9% phosphatidjlinositol and 2.2% phosphatidic acid (24). Total phosphatides of cottonseed and peanut kernels are estimated to be 1.5—1.9 and 0.8%, respectively (25). 

In a typical experiment, Israelachvili deposited monolayers of surfactants onto cleaved mica sheets, and evaluated the surface energies using the JKR equation. Fig. 11 contrasts results for mica coated with monolayers of (a) L-a-dipalmitoyl-phosphatidylethanolamine (DMPE) where j/a = = 27 mJ/m and (b) hexa-decyltrimethylammonium bromide (CTAB) where = 20 mJ/m and = 50 mJ/m. ... 

Phosphatidylethanolamine synthesis begins with phosphorylation of ethanol-amine to form phosphoethanolamine (Figure 25.19). The next reaction involves transfer of a cytidylyl group from CTP to form CDP-ethanolamine and pyrophosphate. As always, PP, hydrolysis drives this reaction forward. A specific phosphoethanolamine transferase then links phosphoethanolamine to the diacylglycerol backbone. Biosynthesis of phosphatidylcholine is entirely analogous because animals synthesize it directly. All of the choline utilized in this pathway must be acquired from the diet. Yeast, certain bacteria, and animal livers, however, can convert phosphatidylethanolamine to phosphatidylcholine by methylation reactions involving S-adenosylmethionine (see Chapter 26). 

Exchange of Ethanolamine for Serine Converts Phosphatidylethanolamine to Phosphatidylserine... 

Mammals synthesize phosphatidylserine (PS) in a calcium ion-dependent reaction involving aminoalcohol exchange (Figure 25.21). The enzyme catalyzing this reaction is associated with the endoplasmic reticulum and will accept phosphatidylethanolamine (PE) and other phospholipid substrates. A mitochondrial PS decarboxylase can subsequently convert PS to PE. No other pathway converting serine to ethanolamine has been found. 

FIGURE 25.19 Diacylglycerol and CDP-diacylglycerol are the principal precursors of glycerolipids in eukaryotes. Phosphatidylethanolamine and phosphatidylcholine are formed by reaction of diacylglycerol with CDP-ethanolamine or CDP-choline, respectively. 

Write a balanced, stoichiometric reaction for the synthesis of phosphatidylethanolamine from glycerol, fatty acyl-CoA, and ethanolamine. Make an estimate of the AG° for the overall process. 

Phosphatidylethanolamine (cephalin) and ph os-phatidylserine (found in most tissues) differ from phosphatidylcholine only in that ethanolamine or serine, respectively, replaces choline (Figure 14-8). 

Figure 14-8. Phosphatidic acid and its derivatives. The 0 shown shaded in phosphatidic acid is substituted by the substituents shown to form in (A) 3-phosphatidylcholine, (B) 3-phosphatidylethanolamine,...

These compounds constimte as much as 10% of the phospholipids of brain and muscle. StmcmraUy, the plasmalogens resemble phosphatidylethanolamine but possess an ether link on the sn- carbon instead of the ester link found in acylglycerols. Typically, the alkyl radical is an unsamrated alcohol (Figure 14-10). In some instances, choline, serine, or inositol may be sub-stimted for ethanolamine. 

Figure 24-2. Biosynthesis of triaq/lglycerol and phospholipids. ( , Monoacylglycerol pathway (D, glycerol phosphate pathway.) Phosphatidylethanolamine may be formed from ethanolamine by a pathway similar to that shown for the formation of phosphatidylcholine from choline.

The regulation of triacylglycerol, phosphatidylcholine, and phosphatidylethanolamine biosynthesis is driven by the availability of free fatty acids. Those that escape oxidation are preferentiaUy converted to phos-phohpids, and when this requirement is satisfied they are used for triacylglycerol synthesis. 

The major lipid classes are phospholipids and cholesterol the major phospholipids are phosphatidylcholine (PC), phosphatidylethanolamine (PE), and phosphatidylserine (PS) along with sphingomyelin (Sph). 

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