Hydroxy oleic acid

Finally, the yeast Yarrowia lipolytica is able to transform ricinoleic acid (12-hydroxy oleic acid) into y-decalactone, a desirable fruity and creamy aroma compound however, the biotransformation pathway involves fi-oxidation and requires the lactonisation at the CIO level. The first step of fi-oxidation in Y. lipolytica is catalysed by five acyl-CoA oxidases (Aox), some of which are long-chain-specific, whereas the short-chain-specific enzymes are also involved in the degradation of the lactone. Genetic constructions have been made to remove these lactone-degrading activities from the yeast strain [49, 50]. A strain displaying only Aox2p activity produced 10 times more lactone than the wild type in 48 h but still showed the same growth behaviour as the wild type. 

Zerkowski, J. A., and Solaiman, D. K. Y. 2006. Synthesis of polyfunctional fatty amines from sophorolipid-derived 17-hydroxy oleic acid. J. Amer. Oil. Chem. Soc., 83, 621-628. 

Ricinoleic acid (dl 12-hydroxy oleic acid) [141-22-0] M 298.5, m 7-8 (a-form), 5.0 (y-form), n 1.4717, pKgst 4.5. Purified as methyl acetylricinoleate [Rider J Am Chem 5oc 53 4130 1931], fractionally distilling at 180-185 /0.3mm, then 87g of this ester was refluxed with KOH (56g), water (25mL), and MeOH (250mL) for lOmin. The free acid was separated, crystd from acetone at -50°, and distd in small batches, b 180°/0.005mm. [Bailey et al. 7 C/jem Soc 3027 7957.]... 

Starting from the carboxylic carbon (A-designation 12-hydroxy-oleic acid or ricinoleic acid). It is used to characterize the origin of the fatty acids in nutrition circle. 

CAS 141-22-0 EINECS/ELINCS 205-470-2 Synoryms Castor oil acid 12-Hydroxy-9-octadecenoic acid 12-Hydroxy-cis-9-octadecenoic acid cis-12-Hydroxyoctadec-9-enoic acid 12-Hydroxyoleic acid d-12-Hydroxyoleic acid 9-Octadecenoic acid, 12-hydroxy- Oleic acid, 12-hydroxy- Ricinic acid Ricinolic acid Classification Unsaturated fatty acid Empirical CisHsjOs... 

Croteau R, Kolattukudy P E 1975 Biosynthesis of hydroxy fatty acid polymers. Enzymatic epox-idation of 18-hydroxy oleic acid to 18-hydroxy-cis-9,10-epoxystearic acid by a particulate preparation from spinach Spinacia oleracea). Arch Biochem Biophys 170 61-72... 

Soybean oil derivatives epoxidized using 2-hydroxylethyl acrylate in the presence of an acid catalyst result in oligomers applicable in ultraviolet radiation cures. Castor oil consists of ricinoleic acid (12-hydroxy oleic acid) as a major fatty acid, which can be used for the production of polyamide building blocks. 

The enantiomers of DL-a-hydroxypalmitic acid, DL-12-hydroxystearic acid, and DL-12-hydroxy oleic acid were resolved by TLC [57]. 

Enantiomers of dl-12-hydroxy oleic acid were separated on Chiralplate (Macherey-Nagel) with acetone/water (6 4, v/v) as the mobile phase development distance 6 cm a = 1.50 detection iodine vapor. 

Sulfated Natural Oils and Fats. Sulfated natural triglycerides were the first nonsoap commercial surfactants introduced in the middle of the nineteenth century. Since then sulfates of many vegetable, animal, and fish oils have been investigated (see also Fats AND FATTY oils). With its hydroxyl group and a double bond, ricinoleic acid (12-hydroxy-9,10-octadecenoic acid) is an oil constituent particularly suited for sulfation. Its sulfate is known as turkey-red oil. Oleic acid is also suited for sulfation. Esters of these acids can be sulfated with a minimum of hydrolysis of the glyceride group. Polyunsaturated acids, with several double bonds, lead to dark-colored sulfation products. The reaction with sulfuric acid proceeds through either the hydroxyl or the double bond. The sulfuric acid half ester thus formed is neutralized with caustic soda ... 

Based on the composition of the C18 family of cutin monomers we postulated that oleic acid would be > hydroxy la ted first, followed by epoxidation of the double bond at C-9 followed by the hydrolytic cleavage of the oxirane to yield 9,10,18-trihydroxy acid. This postulate was experimentally verified by the demonstration of specific incorporation of exogenous 18-hydroxyoleic acid into 18-hydroxy-9,10-epoxy C18 acid in grape berry skin slices and apple fruit skin disks, and incorporation of exogenous labeled 18-hydroxy-9,10-epoxy C18 acid into 9,10,18-trihydroxy C18 acid of cutin in apple fruit skin slices [61]. 

As mentioned in the introduction, 3-hydroxy fatty acids with functional groups can also be incorporated in poly(3HAMCL). Table 2 illustrates this with many examples of alkenes, 3-hydroxyalkenoic acids, and substituted 3-hy-droxyalkanoic acids that are readily integrated in poly(3HAMCL). Long chain fatty acids have also been used successfully as substrates for poly(3HAMCL) production. De Waard et al. [44] used oleic acid and linoleic acid to produce... 

Figure 12.12 THM GC/MS curves of a Winsor Newton lemon alkyd paint (a) and of an alkyd sample taken from Fontana s work Concetto spaziale (1961) (b). Peak assignments 1, 1,3 dimethoxy 2 propanol 2, 1,2,3 trimethoxy propane 3, 3 methoxy 1,2 propandiol 4, 4 chloro benzenamine 5, 3 methoxy 2,2 bis(methoxymethyl) 1 propanol 6, 3 chloro N methyl benzenamine 7, 3 methoxy 2 methoxymethyl 1 propanol 8, 4 chloro N methyl benzenamine 9, phthalic anhydride 10, 3 chloro 4 methoxy benzenamine 11, suberic acid dimethyl ester 12, dimethyl phthalate 13, azelaic acid dimethyl ester 14, sebacic acid dimethyl ester 15, palmitic acid methyl ester 16, oleic acid methyl ester 17, stearic acid methyl ester 18, 12 hydroxy stearic acid methyl ester 19, 12 methoxy stearic acid methyl ester 20, styrene 21, 2 (2 methoxyethoxy) ethanol 22, 1,1 oxybis(2 methoxy ethane) 23, benzoic acid methyl ester 24, adipic acid dimethyl ester 25, hexadecenoic acid methyl ester 26, dihydroisopimaric acid methyl ester 27, dehydroabietic acid methyl ester 28, 4 epidehydroabietol...

In another investigation, the volatile compounds were isolated [19] using a Porapack Q trap by vacuum for 2 h and were then eluted with hexane. The esters were the chemical class of compounds that predominated in the samples among 21 volatile compounds detected. Ethyl butanoate, ethyl 2-methylbutano-ate, 1-butanol, ethyl hexanoate, 3-hydroxy-2-butanone, ethyl octanoate, acetic acid, linalool, palmitic acid, and oleic acid were identified in cupuacu pulp by solid-phase extracton [15]. 

Oxidation of oleic acid to 10-hydroxyoctadecanoic acid by a gram-positive bacterium was described with a transformation yield of 65% at a concentration of 50 g oleic acid after 72 h in a medium containing Tween 80 [232]. The hydroxy fatty acid can be converted to 4-dodecanolide, an important coconut-fruity like lactone, by -oxidation with yeasts, affording a total lactone yield of about 20% from oleic acid [222, 232]. 

After about 3 hours or after analysis has indicated that the peroxide has been consumed (Note 5), the formic acid is removed by distillation under reduced pressure (b.p. 50°/125 mm.) in a stream of gas (carbon dioxide or nitrogen) to prevent bumping (Note 6). The residue in the flask, which consists of hydroxy-formoxystearic acids, is heated for 1 hour at 100° with an excess of 3N aqueous sodium hydroxide, and the hot, amber-colored soap solution is cautiously poured into an excess of 3N hydrochloric acid with stirring. The oil which separates is allowed to solidify, and the aqueous layer is discarded. The tan-colored solid is remelted on the steam bath by addition of hot water and stirred well to remove residual salts and water-soluble acids (Note 7). When the oil has solidified, the aqueous layer is discarded, and the solid is broken into small pieces and dissolved in 400 ml. of 95% ethanol by heating on the steam bath. After crystallization at 0° for several hours, the product is collected on a filter and dried under vacuum. The yield of crude 9,10-dihy-droxystearic acid is 75-80 g., m.p. 85-90°. After a second recrystallization from 250 ml. of 95% ethanol, the product weighs about 60-65 g. and melts at about 90-92°. A third recrystallization may be necessary to produce a pure product melting at 94-95°. The over-all yield is 55-60 g. (50-55%, based on the available oleic acid) (Note 8). 

There is a seemingly endless variety of fatty acids, but only a few of them predominate in any single organism. Most fatty acid chains contain an even number of carbon atoms. In higher plants the C16 palmitic acid and the C18 unsaturated oleic and linoleic acids predominate. The C18 saturated stearic acid is almost absent from plants and C20 to C24 acids are rarely present except in the outer cuticle of leaves. Certain plants contain unusual fatty acids which may be characteristic of a taxonomic group. For example, the Compositae (daisy family) contain acetylenic fatty acids and the castor bean contains the hydroxy fatty acid ricinoleic acid. 

Alpha oxidation and omega oxidation. Animal tissues degrade such straight-chain fatty acids as palmitic acid, stearic acid, and oleic acid almost entirely by (3 oxidation, but plant cells often oxidize fatty acids one carbon at a time. The initial attack may involve hydroxylation on the a-carbon atom (Eq. 17-3) to form either the d- or the L-2-hydroxy add.17 18-32 323 The L-hydroxy acids are oxidized rapidly, perhaps by dehydrogenation to the oxo acids (Eq. 17-3, step b) and oxidative decarboxylation, possibly utilizing H202 (see Eq. 15-36). The D-hydroxy acids tend to accumulate... 

Ricinoleic acid (Figure 3.8) is the major fatty acid found in castor oil from seeds of the castor oil plant (Ricinus communis Euphorbiaceae), and is the 12-hydroxy derivative of oleic acid. It is formed by direct hydroxylation of oleic acid (usually esterified as part of a phospholipid) by the action of an 02- and NADPH-dependent mixed function oxidase, but this is not of the cytochrome P-450 type. Castor oil has a long history of use as a domestic purgative, but it is now mainly employed as a cream base. Undecenoic acid (A9-undecenoic acid) can be obtained from ricinoleic acid by thermal degradation, and as the zinc salt or in ester form is used in fungistatic preparations. 

A hydroxy acyloxy derivative of tall oil fatty acid (TOFA) was prepared by mixing 200 g of TOFA (63% oleic acid, 31% linoleic acid) with 500 mL of... 

Magnesium stearate, stearic acid, sodium stearyl fumarate Hypromellose, hydroxypropyl cellulose, methylcellolose Ethylenediamine tetraacetic acid, butylated hydroxy toluene Sodium lauryl sulfate, Polysorbate 80 (Tween 80) Cyclodextrins, ethyl alcohol, propylene glycol D-a-Tocopheryl polyethylene glycol 1000 succinate, oleic acid... 

Figure 9.16 Chemical structure of cutin, a biopolyester mainly composed of interester-ified hydroxy and epoxy-hydroxy fatty acids with a chain length of 16 and/or 18 carbons (Ci6 and C[s class). Also, the chemical strcuture of the aliphatic monomers of suberin, derived from the general fatty acid biosynthetic pathway, namely from palmitic (16 0), stearic (18 0), and oleic acids.

Chemistry and general properties. The product is prepared by reacting a fatty acid, typically oleic acid (a 08 1 acid), with oleum, or preferably sulphur trioxide. If a saturated fatty acid is used, the product is an a-sulphofatty acid, R(S03H)C00H and the reaction mechanism is thought to be similar to that previously suggested for the sulphonation of methyl esters. With the use of an unsaturated acid, such as oleic, the picture becomes more complex. The reaction chemistry is not fully understood, but the product is a mixture of y-hydroxy sulpho fatty acid and o -sulphonated oleic acid. 

It has been reported that a microbial isolate, Flavobacterium sp. strain DS5, produced 10-ketostearic acid (10-KSA) from oleic acid in 85% yield (Hou, 1994a). The purified product was white, plate-like crystals melting at 79.2°C. A small amount of 10-hydroxystearic acid (10-HSA) was also produced during the bioconversion, suggesting that oleic acid is converted to 10-KSA via 10-HSA, and the enzyme catalyzing the hydration is C-10 positional specific (Hou, 1994b, 1995). The DS5 bioconversion products from oleic, linoleic, a-linolenic, and y-linolenic acid are all 10-hydroxy fatty acids. The optimum time, pH, and temperature for the production of 10-KSA have been reported in flask... 

Since Wallen et al. (1962) reported the first bioconversion of oleic acid to 10-hydroxystearic acid by a Pseudomonad, microbial conversions of unsaturated fatty acids from different substrates by various microbial strains have been widely exploited to produce new, value-added products. Among the unsaturated fatty acids used for microbial production of hydroxy fatty acids, three (oleic, linoleic, and linolenic acids) were well studied as substrates to produce mono-, di-, and trihydroxy fatty acids. Recently, a bacterial strain Pseudomonas aeruginosa NRRL B-18602 (PR3) has been studied to produce hydroxy fatty acids from several fatty acid substrates. In this review, we introduce the production of hydroxy fatty acids from their corresponding fatty acid substrates by P. aeruginosa PR3 and their industrially valuable biological activities. 

Figure 31.1. Schematic diagram of the production of 7,10-dihydroxy-8( T)-octadece-noic acid (DOD) from oleic acid by P. aeruginosa PR3. HOD represents 10(S)-hydroxy-8(E)-octadecenoic acid.

Based on the postulated common metabolic pathway involved in DOD and TOD formation by PR3, it was assumed that palmitoleic acid containing a singular C9 cis double bond (a common structural property shared by oleic and ricinoleic acids), could be utilized by PR3 to produce hydroxy fatty acid. Bae et al. (2007) reported that palmitoleic acid could be utilized as a substrate for the production of hydroxy fatty acid by PR3. Structural analysis of the major product produced from palmitoleic acid by PR3 confirmed that strain PR3 could introduce two hydroxyl groups on carbon 7 and 9 with shifted migration of 9-cis double bond into 8-tram configuration, resulting in the formation of 7,10-dihydroxy-8( )-hexadecenoic acid (DHD) (Fig. 31.3).The time course study of DHD production showed that DHD formation was time-dependently increased, and peaked at 72 h after the addition of palmitoleic acid as substrate. However, production yield of DHD (23%) from palmitoleic acid was relatively low when compared to that of DOD (70%) from oleic acid (Hou and Bagby, 1991). 

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