Fatty acids, long chain

Peroxisomal disorders are characterized by impaired, reduced, or total absence of peroxisomes in cells. These disorders imply an accumulation of very long chain fatty acids (VLCFA) such as tetracosanoic and hexacosanoic acids in plasma and red blood cells. Some variants of these disorders are characterized by an accumulation of phytanic acid. 

Up to now quantification of VLCFAhas been done by GC or GC-MS. So far these methods are time-consuming and quite demanding in terms of sample preparation. 

VLFAC measurements are accompanied by the calculation of some significant ratios like C26 0/C22 0 and C24 0/C22 0. 

Some authors are pursuing the VLCFA characterization through their AC profile [17]. Only 5% of the VLCFA are incorporated within AC, and therefore the resulting detectability is questionable. 

Recently Johnson [18] has proposed an interesting procedure employing LC-MS/MS for a rapid screening. 

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The first work published in this area was that of Bigelow mentioned above [116], In 1957, monolayers of long-chain fatty acids were fonned on thin films of silver, copper, iron and cadmium deposited on glass microscope slides [43],... 

Animal fats and vegetable oils are triacylglycerols, or triesters, formed from the reaction of glycerol (1,2, 3-propanetriol) with three long-chain fatty acids. One of the methods used to characterize a fat or an oil is a determination of its saponification number. When treated with boiling aqueous KOH, an ester is saponified into the parent alcohol and fatty acids (as carboxylate ions). The saponification number is the number of milligrams of KOH required to saponify 1.000 g of the fat or oil. In a typical analysis, a 2.085-g sample of butter is added to 25.00 ml of 0.5131 M KOH. After saponification is complete, the excess KOH is back titrated with 10.26 ml of0.5000 M HCl. What is the saponification number for this sample of butter ... 

Sucrose polyesters, which are made by esterilying sucrose with long-chain fatty acids, have the physical properties of fat, but are resistant to digestive enzymes (40). Olestra, a sucrose polyester developed by Procter Gamble, was submitted for regulatory approval in May 1987. In order to faciUtate the approval process, Procter Gamble has since narrowed the scope of its food additive petition to include olestra s use only in savory and extmded snacks. 

Inversion ofMon cjueous Polymers. Many polymers such as polyurethanes, polyesters, polypropylene, epoxy resins (qv), and siHcones that cannot be made via emulsion polymerization are converted into latices. Such polymers are dissolved in solvent and inverted via emulsification, foUowed by solvent stripping (80). SoHd polymers are milled with long-chain fatty acids and diluted in weak alkaH solutions until dispersion occurs (81). Such latices usually have lower polymer concentrations after the solvent has been removed. For commercial uses the latex soHds are increased by techniques such as creaming. 

Reaction with Fatty Acids and Esters. Alkanolamines and long-chain fatty acids react at room temperature to give neutral alkanolamine soaps, which are waxy, noncrystaUine materials with widespread commercial appHcations as emulsifiers. At elevated temperatures, 140 —160°C, A/-aIkanolamides are the main products, at a 1 1 reaction ratio (7,8). 

Monobasic Acids. The overwhelming majority of moaobasic acids used ia alkyd resias are long-chain fatty acids of aatural occurreace. They may be used ia the form of oil or free fatty acids (see Fats and fatty oils). Free fatty acids are usually available and classified by their origin, viz, soya fatty acids, linseed fatty acids, coconut fatty acids, etc. Fats and oils commonly used ia alkyd resias are givea ia Table 4. 

Sodium Dispersions. Sodium is easily dispersed in inert hydrocarbons (qv), eg, white oil or kerosene, by agitation, or using a homogenizing device. Addition of oleic acid and other long-chain fatty acids, higher alcohols and esters, and some finely divided soHds, eg, carbon or bentonite, accelerate dispersion and produce finer (1—20 -lm) particles. Above 98°C the sodium is present as Hquid spheres. On cooling to lower temperatures, soHd spheres of sodium remain dispersed in the hydrocarbon and present an extended surface for reaction. Dispersions may contain as much as 50 wt % sodium. Sodium in this form is easily handled and reacts rapidly. For some purposes the presence of the inert hydrocarbon is a disadvantage. 

LB Films of Long-Chain Fatty Acids. LB films of saturated long-chain fatty acids have been studied since the inception of the LB technique. The most stable films of long-chain fatty acids are formed by cadmium arachidate deposited from a buffered CdCl2 subphase. These films, considered to be standards, have been widely used as spacer layers (23) and for examining new analytical techniques. Whereas the chains are tilted - 25° from the surface normal in the arachidic acid, CH2(CH2) gCOOH, films (24), it is nearly perpendicular to the surface in the cadmium arachidate films (25). 

Chromium complexes of long-chain fatty acids are exceUent water repeUents which are also used for their food-release properties in certain packaging appHcations. The presence of chromium has raised environmental concerns, despite the fact that the metal is in the trivalent rather than in the highly toxic hexavalent state. This material is available as Qudon (DuPont). 

Although vegetable oils and animals fats were commonly used in ancient times, most higher acids were not known until the beginning of the nineteenth century. Then the nature of the naturally occurring 18-carbon fatty acids was estabHshed, and hundreds of long-chain fatty acids have been isolated from natural sources and characterized. 

The hydrophilic nature of the carboxyl group balanced against the hydrophobic nature of the hydrocarbon chain allows long-chain fatty acids to form monomolecular films at aqueous Hquid-gas, Hquid—Hquid, or Hquid—soHd interfaces (18). 

QuaterniZation. Choline chloride [67-48-1] was prepared ia nearly quantitative yield by the reaction of trimethylamine [121-44-8] with ethylene chlorohydrin at 90—105°C and 981—1471 kPa (10—15 kg/cm ) pressure (44). Precursors to quaternary ammonium amphoteric surfactants have been made by reaction of ethylene chlorohydrin with tertiary amines containing a long chain fatty acid group (45). 

Surface-Active Agents. Polyol (eg, glycerol, sorbitol, sucrose, and propylene glycol) or poly(ethylene oxide) esters of long-chain fatty acids are nonionic surfactants (qv) used in foods, pharmaceuticals, cosmetics, textiles, cleaning compounds, and many other appHcations (103,104). Those that are most widely used are included in Table 3. 

Another interesting class of phase transitions is that of internal transitions within amphiphilic monolayers or bilayers. In particular, monolayers of amphiphiles at the air/water interface (Langmuir monolayers) have been intensively studied in the past as experimentally fairly accessible model systems [16,17]. A schematic phase diagram for long chain fatty acids, alcohols, or lipids is shown in Fig. 4. On increasing the area per molecule, one observes two distinct coexistence regions between fluid phases a transition from a highly diluted, gas -like phase into a more condensed liquid expanded phase, and a second transition into an even denser... 

The preparation of long-chain fatty acids has been carried out in this way because cleavage of 115 with strong sodium hydroxide gives the ketoacid (116), which is easily reduced by the Wolf-Kishner method to the saturated acid. A similar sequence of reactions can be carried out starting with the cyclopentanone enamine, and this method allows lengthening the chain... 

Pollitt, R. J., 1995. Disorders of mitochondrial long-chain fatty acid oxidation. Journal of Inherited Metabolic Disease 18 473—490. 

Kim, K-H., et al., 1989. Role of rever.sible pho.sphorylation of acetyl-CoA carboxyla.se in long-chain fatty acid. syndie.sis. The EASEB Journal 3 22 0-2256. 

Although both estrone and estradiol are available for replacement therapy, they suffer the disadvantage of poor activity on oral administration and short duration of action even when administered parenterally, because of ready metabolic disposition. In order to overcome these deficiencies, there was developed a series of esters of estradiol with long-chain fatty acids. These esters are oil-soluble and correspondingly water-insoluble compounds. 

In the case of androgens as with estrogens there is occasionally need for treatment of patients with chronic sustained doses of these drugs. Resort is made to esters of the androgen with long-chain fatty acids in order to provide oil-soluble agents ... 

Similarly, esters of fatty acids and polyethylene glycols are produced by the reaction of long-chain fatty acids and ethylene oxide ... 

The mechanism of inhibition by the salts of the long chain fatty acids has been examined . It was concluded that, in the case of the lead salts, metallic lead was first deposited at certain points and that at these points oxygen reduction proceeded more easily, consequently the current density was kept sufficiently high to maintain ferric film formation in addition, any hydrogen peroxide present may assist in keeping the iron ions in the oxide film in the ferric condition, consequently the air-formed film is thickened until it becomes impervious to iron ions. The zinc, calcium and sodium salts are not as efficient inhibitors as the lead salts and recent work has indicated that inhibition is due to the formation of ferric azelate, which repairs weak spots in the air-formed film. This conclusion has been confirmed by the use of C labelled azelaic acid, which was found to be distributed over the surface of the mild steel in a very heterogeneous manner. ... 

The chloride ion is the most frequent cause of contact corrosion, since chlorine is present in the many chlorinated plastics, and is also frequently retained in residual amounts from reactive intermediates used in manufacture. Thus epoxides usually contain chloride derived from the epichlor-hydin used as the precursor of the epoxide. In addition to the contaminants referred to in Table 18.18, various metal and ammonium cations, inorganic anions and long-chain fatty acids (present as stabilisers, release agents or derived from plasticisers) may corrode metals on contact. 

Copper alloys are particularly prone to attack by long-chain fatty acids which are often present in sealing compositions, temporary protectives and as trace additives in many plastics under acid conditions ester plasticisers may saponify in the presence of copper giving rapid corrosion of the copper and accelerating degradation of the polymer. 

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