Isoprenoid fatty acids

Lipids from marine products have been studied less frequently. The detection of co-(o-alkylphenyl)alkanoic acids with 16,18 and 20 carbon atoms together with isoprenoid fatty acids (4,8,12-trimethyltetradecanoic acid and phytanic acid) and substantial quantities of bones from fish and molluscs has provided evidence for the processing of marine animal products in vessels [58 60]. C16, C18, and C20 co-(o-alkylphenyl)alkanoic acids are presumed to be formed during the heating of tri-unsaturated fatty acids (C16 3, C18 3 and C20 3), fatty acyl components of marine lipids, involving alkali isomerization, pericyclic (intermolecular Diels-Alder reaction) and aromatization reactions. 

Isoprenoid fatty acids (4,8,12 trimethyl tetradecanoic acid and phytanic acid), acids with 16, 18 and 20 carbon atoms Heated marine lipids [42,43]... 

The three major classes of biopolymers found in eukaryotic systems are nucleic acids, proteins, and polysaccharides. The latter class is the most complex with respect to structural and stereochemical diversity. Polysaccharides indeed possess a massive information content. Furthermore, polysaccharides are commonly found in nature covalently attached (conjugated) to other biomolecules such as proteins, isoprenoids, fatty acids, and lipids.1... 

Only the Green River oil shale and Scottish torbanite have so far yielded acyclic isoprenoid fatty acids (129,143,276-278). 

S. N., Correlation of Stereoisomerism in Present Day and Geologically Ancient Isoprenoid Fatty Acids, Nature (1968) 218 (5146), 1019-1024. 

Burlingame, A. L., Simoneit, B. R., Isoprenoid Fatty Acids Isolated... 

Stenhagen, S., Occurrence of Isoprenoid Fatty Acids in the Green River Shale, Science (1966) 153 (3731), 1133-1134. 

Enantiomers of carboxylic acids may sometimes be separated by GC as methyl esters, but special derivatives are mostly prepared for this purpose. Ackman et al. [188] resolved enantiomers of isoprenoid fatty acids after their conversion into L-menthyl esters. The acids under analysis were chlorinated by refluxing with distilled freshly prepared thionyl chloride and the chlorides produced were treated with L-menthol in the presence of pyridine under strictly anhydrous conditions. GC separation was carried out in a capillary column coated with butanediol succinate polyester. Annett and Stumpf [189] made use of L-menthyloxycarbonyl derivatives for the separation of enantiomers of methyl esters of hydroxy acids. The derivatization reagent, L-menthyl chloroformate, was prepared by the reaction of L-menthol with phosgene, with cooling with ice. Diastereoisomers of different hydroxy acids were thus separated on 1.5% OV-210. 

The isoprenoid fatty acid 5,9,13-trimethyltetradecanoic acid (4) is a rather intriguing fatty acid, which has been isolated from several sponges... 

Figure 10.2). Various branched-chain fatty acids exist in most animals (Nuhn et al., 1985) and others are still being discovered (Ratnayake et al., 1989a). The isoprenoid fatty acids (Ackman and Hooper, 1973a) remain of clinical interest (ten Brink et al., 1992) because of their role in a rare genetic disease called Refsum s syndrome (Yao, 1992). 

The commonest polymethyl-branched fatty acid is probably phytanic or 3,7,11,15-tetramethylhexa-decanoic acid, which is a metabolite of phytol, and can be found in trace amounts in many animal tissues. It becomes a major component of the plasma lipids in Refsum s syndrome, a rare condition in which there is a deficiency in the enzymatic fatty acid alpha-oxidation system. Lough [562] has reviewed the occurrence and biochemistry of this and other isoprenoid fatty acids. Similar fatty acids are present in the lipids of the preen gland of birds and in those of tubercle bacilli. 

Ackman, R.G. (1989) Fatty acids, in Marine Biogenic Lipids, Fats and Oils, vol. I (ed. R.G. Ackman), CRC Press, Boca Raton, FL, pp. 103-137 (Isoprenoid fatty acids are described on pp. 123-129). 

Barnathan, G. and Kornprobst, J.M. (1998) Isoprenoid fatty acids in sponge phospholipids. A review. Recent Res. Dev. Lipids Res., 2, 235-248. 

Barnathan, G., Miralles, J., and Kornprobst, J.-M. (1993a) Sponge fatty acids. 4. Co-occurrence of two isoprenoid fatty acids (4,8,12-trimethyltridecanoic and 5,9,13-trimethyltetradecanoic) in phospholipids of marine sponges from the genus Cinachyrella. Nat. Prod. Letters., 3, 113-118. 

Rhodamine 6G long-chain hydrocarbons [169] squalene, a-amyrin [170] methyl esters of fatty acids [171] glycerides [91] sterols [172, 173] isoprenoids, quinones [HI] lipoproteins [174] glycosphingolipids [175] phenolic lipids [176] phosphonolipids [177] increasing the sensitivity after exposure to iodine vapor [178,179]... 

Suzuki, K. Application of mass spectrometry to bacterial taxonomy. Cellular fatty acids and isoprenoid quinones. Iyo Masu Kenkyukai Koenshu 1987,12,45-53. 

Abstract Pheromones are utilized by many insects in a complex chemical communication system. This review will look at the biosynthesis of sex and aggregation pheromones in the model insects, moths, flies, cockroaches, and beetles. The biosynthetic pathways involve altered pathways of normal metabolism of fatty acids and isoprenoids. Endocrine regulation of the biosynthetic pathways will also be reviewed for the model insects. A neuropeptide named pheromone biosynthesis activating neuropeptide regulates sex pheromone biosynthesis in moths. Juvenile hormone regulates pheromone production in the beetles and cockroaches, while 20-hydroxyecdysone regulates pheromone production in the flies. 

Coleoptera comprise the largest order of insects and accordingly pheromone structures and biochemical pathways are diverse [98, 99]. Beetle pheromone biosynthesis involves fatty acid, amino acid, or isoprenoid types of pathways. In some cases dietary host compounds can be converted to pheromones, but it is becoming apparent that most beetle pheromones are synthesized de novo. 

It appears that, in beetles, pheromone production is regulated by JH III, despite the variations in biosynthetic pathways. JH apparently regulates pheromone production in beetles that utilize both fatty acid and isoprenoid biosynthetic pathways [8,98]. Environmental and physiological factors will in turn regulate production of JH. The endocrine regulation of pheromone production in the beetles has been best studied with regard to the bark beetles. 

Some proteins can be posttranslationally modified by the addition of prenyl groups. Prenyl groups are long-chain, unsaturated hydrocarbons that are intermediates in isoprenoid synthesis. The farnesyl group has 15 carbons, and the geranylgeranyl has 20 carbons. They are attached to a cysteine residue near the end of the protein as a thiol ether (Protein-S-R). Other proteins can have a long-chain fatty acid (C14=myristoyl, C16=palmitoyl) attached to the amino terminus as an amide. These fatty acid modifications can increase the association of proteins with the membrane. 

More than 600 different carotenoids from natural sources have been isolated and characterized. Physical properties and natural functions and actions of carotenoids are determined by their chemical properties, and these properties are defined by their molecular structures. Carotenoids consist of 40 carbon atoms (tetraterpenes) with conjugated double bonds. They consist of eight isoprenoid units j oined in such a manner that the arrangement of isoprenoid units is reversed at the center of the molecule so that the two central methyl groups are in a 1,6-position and the remaining nonterminal methyl groups are in a 1,5-position relationship. They can be acyclic or cyclic (mono- or bi-, alicyclic or aryl). Whereas green leaves contain unesterified hydroxy carotenoids, most carotenoids in ripe fruit are esterified with fatty acids. However, those of a few... 

The hydrophobic components of many lipids consist of either isoprenoids or fatty acids and their derivatives 34 Isoprenoids have the unit structure of a five-carbon branched chain 34 Brain fatty acids are long-chain carboxylic acids that may contain one or more double bonds 34... 

The second class of stable membrane anchoring motives does not rely on electrostatic interactions but supports the first (often isoprenoid) hydrophobic modification by additional thioester formation with fatty acids (eg. the H- and N-isoforms of Ras or in the a subunits of heterotrimeric G-proteins) or a second isoprenoid moiety (eg. Rab proteins).1331... 

Fatty acids and isoprenoids (precursor citrate—see below)... 

The tricarboxylic acid cycle not only takes up acetyl CoA from fatty acid degradation, but also supplies the material for the biosynthesis of fatty acids and isoprenoids. Acetyl CoA, which is formed in the matrix space of mitochondria by pyruvate dehydrogenase (see p. 134), is not capable of passing through the inner mitochondrial membrane. The acetyl residue is therefore condensed with oxaloacetate by mitochondrial citrate synthase to form citrate. This then leaves the mitochondria by antiport with malate (right see p. 212). In the cytoplasm, it is cleaved again by ATP-dependent citrate lyase [4] into acetyl-CoA and oxaloacetate. The oxaloacetate formed is reduced by a cytoplasmic malate dehydrogenase to malate [2], which then returns to the mitochondrion via the antiport already mentioned. Alternatively, the malate can be oxidized by malic enzyme" [5], with decarboxylation, to pyruvate. The NADPH+H formed in this process is also used for fatty acid biosynthesis. 

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