Suppressive effect of alkyl ferulate on the oxidation of microencapsulated linoleic acid

The oxidation processes of linoleic acid mixed with ferulic acid or the 1‐pentyl, 1‐hexyl and 1‐heptyl ferulates, encapsulated with gum arabic or maltodextrin, were studied. The alkyl ferulates had a higher antioxidative effect than ferulic acid, but there was no significant difference among the three alkyl ferulates. Suppression of the oxidation by 1‐hexyl ferulate or ferulic acid was more effective at the higher molar ratios of the additive to linoleic acid. The processes were analyzed using the Weibull equation to evaluate the rate constant, k, and the shape constant, n. Although the k values for linoleic acid encapsulated with gum arabic were lower than that with maltodextrin, the suppressive effect of the alkyl ferulates was more remarkable for linoleic acid encapsulated with maltodextrin than with gum arabic because of the non‐antioxidative ability of maltodextrin. Because the partition coefficient of the alkyl ferulates was much greater than that of ferulic acid, most of the alkyl ferulates would be located in the linoleic acid phase of the microcapsules and effectively suppress the oxidation of linoleic acid.     

A rapid method for determining the oxidation of n-3 fatty acids

The stability of unsaturated fatty acids to oxidation was monitored by following gas chromatographic (GC) analyses of headspace volatiles in comparison to changes in polyunsaturated fatty acids (PUFA) and increases in malonaldehydevia the 2-thiobarbituric (TBA) assay. Pure standards of linoleic acid (Lo) and n-3 fatty acids [eicosapentaenoic (EPA) and docosahexaenoic acid (DHA)] were added to headspace vials, equilibrated in air for 10 min, followed by heating at 80°C in teflon-capped vials for different time intervals. Headspace analysis showed increases in acetaldehyde, propenal, and propanal, corresponding to the oxidation of n-3 fatty acids, whereas hexanal production corresponded to losses of linoleic acid. The analysis of propanal by GC-headspace after only five minutes of heating appeared to be the most effective method of monitoring the oxidation of n-3 fatty acids, as indicated by correlations between TBA values and loss of PUFA. The oxidation of Lo, EPA and DHA appeared to be a function of the number of double bonds. Correlations between PUFA depletion, TBA values and volatile formation indicate that under the prescribed conditions of this experiment, GC-headspace analysis of propanal and pentane/hexanal is an excellent method for following the oxidation of selected n-3 fatty acids and linoleic acid.     

Antioxidant activity of some spice essential oils on linoleic acid oxidation in aqueous media

Some spice essential oils (caraway, clove, cumin, rosemary, sage and thyme) and their major constituents were added to emulsified linoleic acid in aqueous media to examine their antioxidant activity. The methods used for measuring linoleic acid oxidation were coupled oxidation ofβ-carotene, conjugated diene formation and thiobarbituric acid test. The essential oils under study possess an antioxidant effect and this phenomenon was increased by increasing their concentration. Generally, the effectiveness of the various essential oils on linoleic acid oxidation was in the following descending order: caraway >sage>cumin>rosemary>thyme>clove. It appears that there was a relationship between the antioxidant effect and the chemical composition of the oils.     

A soy extract catalyzes formation of 9-oxo-trans-12,13-epoxy-trans-10-octadecenoic acid from 13-hydroperoxy-cis-9,trans-11-octadecadienoic acid

In the presence of oxygen, a crude soy extract converted 13-hydroperoxy-cis-9,trans-11-octadecadienoic acid into numerous products, from which 9-oxo-trans-12,13-epoxy-trans-10-octadecenoic acid was isolated. Additionally, the soy extract oxidized linoleic acid to the oxo-epoxyoctadecenoic acid, presumably via a sequential reaction involving lipoxygenase oxidation of linoleic acid followed by degradation of the resultant linoleic acid hydroperoxide. However, the linoleic acid substrate yielded two isomeric linoleic acid hydroperoxides and because of this, two isomeric oxoepoxyoctadecenoic acids. Presented in part at the 13th Congress, International Society for Fat Research, Marseilles, France, August 30–September 4, 1976.     

Evaluation of antioxidant activity: II. application of a heme- Catalyzed system

A study was made of the inhibitory effect of the antioxidants propyl gallate,tert-butylated hydroxyanisol, α-tocopherol and ethoxyquin on the hemoglobin-catalyzed oxygenation of linoleic acid. The concentration of unchanged fatty acid after varying incubation periods and at varying concentrations of antioxidant was measured by gas chromatography. The effect of the antioxidants is compared with results obtained previously from the lipoxygenase-catalyzed oxidation of a linoleic acid emulsion. It is concluded that all 4 antioxidants are good inhibitors of fatty acid oxidation cata-lyzed by hemoglobin.     

Oxidative Stability of Conjugated Linoleic Acid Rich Soy Oil

This study was conducted to determine the oxidative stability of conjugated linoleic acid rich soy oil (CLARSO) and the effects of conjugated linoleic acid (CLA) levels on volatile oxidation products formed during CLARSO oxidation. CLARSO oxidative stability was determined by gravimetric analysis, peroxide value, headspace oxygen analysis and p-anisidine value. Volatile oxidation compounds were analyzed by solid phase microextraction–gas chromatography with a flame ionization detector and a mass spectrometer. CLA oxidation results were highly dependent on analytical methods used and oxidation parameters measured. The gravimetric study showed a CLA concentration effect on oxidation, which was not seen in the headspace oxygen depletion and peroxide value. Volatile oxidation data indicate that CLARSO had significantly higher (p < 0.05) levels of pentanal and trans-2-heptenal than the other oils, but there was no significant difference between the amounts of any volatiles present in 8 and 15% CLARSO. This suggests that oxidation was greater in CLARSO and that CLA concentration did not affect oxidation.     

The performic acid oxidation of linoleic acid

The performic acid oxidation of linoleic acid has been shown to form 9,12-dihydroxy-trans-10,11-methylene-heptadecanoic acid (I) after hydrolysis of the formate ester. A sequence of reactions led to the identification of dimethyl-trans-1,2-cyclopropanedicarboxylate by gas liquid chromatography. Spectroscopic evidence is presented for thetrans geometry in I. Failure of the monoepoxide of linoleic acid to give the formate ester of I suggests the alternative that a homoallylic carbonium ion is formed directly upon attack of the peroxide reagent.     

Monooxygenase system of Bacillus megaterium ALA2: Studies on linoleic acid epoxidation products

Bacillus megaterium ALA2 produces many oxygenated FA from linoleic acid: 12,13-dihydroxy-9(Z)-octadecenoic acid; 12,13,17-trihydroxy-9(Z)-octadecenoic acid; 12,13,16-trihydroxy-9(Z)-octadecenoic acid; 12-hydroxy-13,16-epoxy-9 (Z)-octadecenoic acid; and 12,17;13,17-diepoxy-16-hydroxy-9 (Z)-octadecenoic acid. Recently, we studied the monooxygenase system of B. megaterium ALA2 by comparing its palmitic acid oxidation products with those of the well-studied catalytically self-sufficient P450 monooxygenase of B. megaterium ATCC 14581 (NRRL B-3712) and of B. subtilis strain 168 (NRRI B-4219). We found that their oxidation products are identical, indicating that their monooxygenase systems (hydroxylation) are similar. Now, we report that strain ALA2 epoxidizes linoleic acid to 12,13-epoxy-9(Z)-octadecenoic acid and 9,10-epoxy-12 (Z)-octadecenoic acid, the initial products in the linoleic acid oxidation. The epoxidation enzyme did not oxidize specific double bond of the linoleic acid. The epoxidation activity of strain ALA2 was compared with the above-mentioned two Bacillus strains. These two Bacillus strain also produced 12,13-expoxy-9 (Z)-octadecenoic acid and 9,10-epoxy-12(Z)-octadecenoic acid, indicating that their epoxidation enzyme systems might be similar. The ratios of epoxy FA production by these three strains (A1 A2, NRRI B-3712, and NRRI B-4219) were, respectively, 5.56∶0.66∶0.18 for 12,13-epoxy-9(Z)-octadecenoic acid and 2.43∶0.41∶0.57 for 9,10-epoxy-12(Z)-octadecenoic acid per 50 mL medium per 48 h.     

Solubility of linoleic acid in aqueous solutions and its reaction with water

In a study of stable emulsions of linoleic acid in 0.1M-KH₂PO₄/Na₂HPO₄ buffer solutions prepared by sonic vibrations, the influence of linoleic acid on pH was manifested in buffer solutions of pH 8.00 and decreased gradually till it became negligible in pH 4.50. This change in pH values was due to differences in solubility of linoleic acid in the buffer solutions. Ultraviolet spectra of soluble linoleic acid in buffer solutions indicated the presence of conjugated dienes, which increased with the increasing of the pH of the system. Unbuffered aqueous emulsions of linoleic acid had a pH value which ranged between 4.69 and 5.10. Saturated aqueous solutions, obtained by high-speed centrifugation, had concentrations of 15.80 to 16.00 mg. linoleic acid per 100 ml. of D.I. water. From the solubility data and conductivity values of linoleic acid the apparent classic and thermodynamic ionization constants were calculated to be 6.974±0.023×10⁻⁶ and 6.905±0.017×10⁻⁶ at 0.7°C. and 1.730±0.009×10⁻⁵ and 1.689±0.007×10⁻⁵ at 25°C., respectively. The result of the chemical interaction of linoleic acid and water is a saturated hydroxy fatty acid. This acid gave a positive test for glycol groups with periodic acid oxidation test and appeared to be a tetrahydroxy compound with the exact structure unknown. Presented at the 51st Annual Meeting, American Oil Chemists' Society at Dallas, Tex., April 4–6, 1960. American Meat Institute Foundation Journal Paper No.204.     

Hydroperoxides from oxidation of linoleic and linolenic acids by soybean lipoxygenase: Proof of thetrans-11 double bond

Hydroperoxides produced by oxidation of linoleic and linolenic acids with soybean lipoxygenase were analyzed by nuclear magnetic resonance. The isomerized double bond α,β to the hydro-peroxide group at carbon-13 was determined to betrans. The complete structures of the major products proved to be 13-hydroperoxy-cis-9,trans-11-octa-decadienoic acid from linoleic acid and 13-hydroperoxy-cis-9,trans-11,cis-15-octadecatrienoic acid from linolenic acid. The configuration of the double bonds indicates that oxidation took place through a free radical mechanism as proposed previously by others. N. Market. Nutr. Res. Div., ARS, USDA.     

Influence of native antioxidants on the formation of fatty acid hydroperoxides in model systems

The effect of alpha‐tocopherol (alpha‐T) and quercetin on the formation of hydroperoxides of linoleic and linolenic acids during autoxidation at 60 ± 1 °C was investigated. Three isomers of hydroperoxides were detected using HPLC. Of isomers of linoleic acid hydroperoxides, 13‐hydroperoxy‐octadecadienoic acid trans‐trans (13‐HPODE t‐t), 9‐HPODE cis‐trans (9‐HPODE c‐t) and 9‐HPODE trans‐trans (9‐HPODE t‐t) were identified, constituting 64, 19 and 17% of the total amount, respectively. For linolenic acid, the components 13‐hydroperoxy‐octadecatrienoic acid trans‐trans (13‐HPOTE t‐t), 9‐HPOTE c‐t and 9‐HPOTE t‐t contributed 7, 33 and 60% to the total, respectively. The different dominant hydroperoxide isomers detected in linoleic and linolenic acids during oxidation are related to their chemical structure and the microenvironment of emulsion droplets. The ratios between specific isomers for both fatty acid hydroperoxides did not change during oxidation with or without antioxidants. Alpha‐T effectively inhibited the oxidation of fatty acids and reduced the formation of hydroperoxides. The total amount of the hydroperoxides decreased along with the increase in the concentration of alpha‐T, 1–40 µM. Quercetin inhibited the oxidation of both fatty acids at similar efficiency only at 40 µM concentration. A synergistic antioxidant effect of quercetin with alpha‐T in a binary system on both fatty acids was observed.     

Anorexic contribution to increased linoleate mobilization and oxidation in lymphoma-bearing mice

To test for a regulatory defect in adipose triacylglycerol (essential) fatty acid mobilization in lymphoma-bearing mice, free [1-¹⁴C]linoleic acid/mouse serum albumin was injectediv into lymphoma-bearing and control mice, adapted to a reversed light cycle, and studied in three dietary states in the dark period. Mean daily food intake decreased in mice with small and large tumor burdens. Plasma free fatty acid (FFA) oxidation rates, which approximate FFA mobilization rates, were estimated by multicompartmental analysis (CONSAM). Oxidation of linoleate to CO₂ was reduced significantly (85%) inad libitum fed as compared to briefly fasted control mice but not in fedvs. fasted mice with large or small tumor burdens. However, plasma FFA oxidation rates to CO₂ did not differ in briefly fasted tumor-bearing and pairfed control mice. When re-fed a 250-mg test meal, briefly fasted mice with small tumors suppressed plasma free linoleic acid oxidation, as did controls. During simulated night, mildly anorexic, tumor-bearing mice with small tumor burdens mobilized essential fatty acids much faster than controls. This could explain body fat loss. The abnormally rapid rates of FFA (free linoleic acid) mobilization at night probably result from anorexia rather than from inability of food to suppress fat mobilization.     

Preferential oxidation of linolenic acid compared to linoleic acid in the liver of catfish (Heteropneustes fossilis andClarias batrachus)

The fate of [1-¹⁴C] linoleic acid and [1-¹⁴C] linolenic acid in the liver slices and also in the liver tissues of live carnivorous catfish,Heteropneustes fossilis andClarias batrachus, was studied. Incorporation of the fatty acids into different lipid classes in the live fish differed greatly from the tissue slices, indicating certain physiological control operative in vivo. The extent of desaturation and chain elongation of linoleic and linolenic acids into long-chain polyunsaturated fatty acids was low. Linolenic acid was oxidized (thus labeling the saturated fatty acid with liberated¹⁴C-acetyl-CoA) in preference to linoleic acid, and this oxidation also seemed to be under physiological control since both of the fatty acids were poorly oxidized in the tissue slices and in the killed fish. These fish can therefore recognize the difference in the acyl chain structures of linoleate and linolenate. The higher oxidation of liolenic acid and poor capacity for its conversion to longer chain, highly unsaturated derivatives indicates a higher demand for the dietary supply of these essential fatty acids in these two species.     

Soybean lipoxygenase is active on nonaqueous media at low moisture: a constraint to xerophilic fungi and aflatoxins?

Previous workers have reported that certain products of the lipoxygenase pathway are detrimental either to the development and growth of Aspergillus species or to aflatoxin production by these organisms. Since Aspergillus often thrives on “dry” stored grains, depending on the level of the relative humidity, we sought to determine if lipoxygenase could catalyze the oxidation of linoleic acid on these “dry” substrates equilibrated at various relative humidities. A desiccated model system, previously adjusted to pH 7.5, was composed of soybean extract, linoleic acid, and cellulose carrier. The model system was incubated for up to 24 h at four relative humidities ranging between 52 and 95% to determine the extent of oxidation catalyzed by lipoxygenase, compared with heat-inactivated controls. Oxidation in the active samples was much greater than in the controls at all relative humidities, and oxidation was principally enzymatic as demonstrated by chiral analysis of the linoleate hydroperoxides formed. The main product was 13S-hydroperoxy-9Z,11E-octadecadienoic acid, accompanied by a significant percentage of 9S-hydroperoxy-10E,12Z-octadecadienoic acid. Since the products became more racemic with time of incubation, autoxidation appeared to be initiated by the lipoxygenase reaction in dry media. Additionally, the biological relevance of lipoxygenase activity was tested under these xerophilic conditions. Thus, enzyme-active and heat-inactivated defatted soy flour amended either with or without 3.5% by weight linoleic acid was inoculated with fungal spores and incubated at 95% relative humidity. Although fungal growth occurred on all treatments, samples inoculated with Aspergillus parasiticus showed significantly less aflatoxin in the enzyme-active samples, compared to inactivated flour. Addition of linoleic acid had little effect, possibly because the defatted soy flour was found to contain 1.7% residual linoleic acid as glyceride lipid.     

Oxidation of acylglycerols and phosphoglycerides by soybean lipoxygenase

Lipoxygenase (EC 1.13.11.12) catalyzes the incorporation of oxygen into polyunsaturated fatty acids, resulting in the formation of their corresponding hydroperoxides. The ability of a commercial preparation of soybean (Glycine max L. Merr.) lipoxygenase to catalyze the oxidation of acylglycerols and phosphoglycerides was investigated. The oxidation rate of trilinolein increased nearly 100% when 5 mM deoxycholate was added to the reaction medium. With further increases in the concentration of deoxycholate, the oxidation rate decreased slightly. The pH profile of trilinolein oxidation was bell-shaped. The rate of oxidation was maximal at pH 8, and it decreased to near zero at pH 5 and pH 11. Even under optimal conditions, the rate of trilinolein oxidation was only 3% of that of linoleic acid, and analysis of time course data showed that, at most, 15% of available linoleate was oxidized. In contrast to the slow rate of trilinolein oxidation, tested phosphoglycerides and diacylglycerols were oxidized at moderate rates. The rate of phosphoglyceride oxidation depended upon the structure of the polar head group and varied between 7–28% of the rate of linoleic acid oxidation. Diacylglycerols reacted at a rate that was 40% of that of linoleic acid. Analysis of the time course of 1,3-dilinolein oxidation showed that as much as 67% of the available linoleate could be converted to the corresponding hydroperoxide. Analyses by high-performance liquid chromatography revealed that more than 20% of the 1,3-dilinolein was converted to unidentified products that are not hydroperoxides.     

An epoxy alcohol synthase pathway in higher plants: Biosynthesis of antifungal trihydroxy oxylipins in leaves of potato

[1-¹⁴C]Linoleic acid was incubated with a whole homogenate preparation of potato leaves (Solanum tuberosum 1., var. Bintje). The methyl-esterified product was subjected to straight-phase high-performance liquid chromatography and was found to contain four major radioactive oxidation products, i.e., the epoxy alcohols methyl 10(S), 11(S)-epoxy-9(S)-hydroxy-12(Z)-octadecenoate (14% of the recovered radioactivity) and methyl 12(R), 13(S)-epoxy-9(S)-hydroxy-10(E)-octadecenoate (14%), and the trihydroxy derivatives methyl 9(S), 10(S), 11(R)-trihydroxy-12(Z)-octadecenoate (18%) and methyl 9(S), 12(S), 13(S)-trihydroxy-10(E)-octadecenoate (30%). The structures and stereochemical configurations of these oxylipins were determined by chemical and spectral methods using the authentic compounds as references. Incubations performed in the presence of glutathione peroxidase revealed that lipoxygenase activity of potato leaves generated the 9- and 13-hydroperoxides of linoleic acid in a ratio of 95∶5. Separate incubations of these hydroperoxides showed that linoleic acid 9(S)-hydroperoxide was metabolized into epoxy alcohols by particle-bound epoxy alcohol synthase activity, whereas the 13-hydroperoxide was metabolized into α- and γ-ketols by a particle-bound allene oxide synthase. It was concluded that the main pathway of linoleic acid metabolism in potato leaves involved 9-lipoxygenase-catalyzed oxygenation into linoleic acid 9(S)-hydroperoxide followed by rapid conversion of this hydroperoxide into epoxy alcohols and a slower, epoxide hydrolase-catalyzed conversion of the epoxy alcohols into trihydroxyoctadecenoates. Trihydroxy derivatives of linoleic and linolenic acids have previously been reported to be growth-inhibitory to plant-pathogenic fungi, and a role of the new pathway of linoleic acid oxidation in defense reactions against pathogens is conceivable.     

Sulfite-induced lipid peroxidation

Sulfite initiated the peroxidation of linoleic acid and linolenic acid emulsions via a free radical mechanism. Peroxidation of these fatty acids required oxygen and sulfite and occurred with concomitant oxidation of sulfite to sulfate. In reaction mixtures containing linoleic acid, the formation of conjugated diene equaled the formation of hydroperoxide. In reaction mixtures containing linolenic acid emulsions, thiobarbituric acid reactive materials were also formed. Peroxidation was pH-dependent; peroxidation of linoleic acid proceeded between pH 4 and 7, but linolenic acid peroxidation was significant only if pH was below pH 6. The linoleic acid hydroperoxides thus formed were reduced and methylated to methyl hydroxystearate. Analysis of methyl hydroxystearate by gas chromatographymass spectrometry indicated that sulfite-induced peroxidation gave rise to the 9- and 13-hydroperoxy isomers. In addition to the hydroperoxides, sulfite adducts were detected. Hydroquinone, butylated hydroxytoluene and α-tocopherol effectively inhibited both sulfite oxidation and hydroperoxide formation. Conjugated diene formation also was inhibited by 4-thiouridine, suggesting that the reaction is mediated by the sulfite radical. No significant inhibition was observed with the addition of superoxide dismutase, catalase, or the hydroxyl radical scavengers, mannitol ort-butanol. A possible mechanism is presented to account for sulfite-induced peroxidation of linoleic acid.     

Antioxidant activities of selected oriental herb extracts

Antioxidant activities of methanol extracts of 180 Oriental herbs were studied by determining the peroxide values of linoleic acid during storage at 50°C. Among the herb extracts tested, 44 species showed strong antioxidant activities on the oxidation of linoleic acid. The antioxidative effects of these 44 selected herb extracts were studied further in a methyl linoleate system during storage for 35 d. Among the 44 species tested, 11 species had particularly high antioxidative effects. The effects of type of extraction solvent (methanol, petroleum ether and ethyl acetate) on the antioxidant activities of the 11 species were studied. Antioxidant activities of most herb extracts were greatly dependent on the extraction solvent used; however, some of the extracts showed strong antioxidant activities regardless of the solvents used for the extraction. Among the 11 herbs selected, based on the antioxidant activity of their methanol extracts, two (i.e.,Psoralea corylifolia L. andSorphora angustifolia Sieb. & Zucc.) were selected for further study in lard held at 75°C for 7 d. The methanol extracts ofP. corylifolia L. andS. angustifolia Sieb. & Zucc. greatly decreased the peroxide formation of lard during storage. Treatment with 0.20% methanolic extract ofP. corylifolia L. exhibited significantly stronger antioxidant effect on the oxidation of lard than treatment with 0.02% butylated hydroxyanisole (P<0.05).     

Reinvestigation of the antioxidant properties of conjugated linoleic acid

Despite repeated suggestions that antioxidant activity of conjugated linoleic acid (CLA), a collective of conjugated dienoic isomers of linoleic acid, underlies its reported anticarcinogenic and antiatherosclerotic effects, the antioxidant properties of CLA remain ill-defined. Therefore, this study was undertaken to gain more insight into the mechanism of potential CLA antioxidant activity. It was tested whether CLA could protect membranes composed of 1-palmitoyl-2-linoleoyl phosphatidylcholine (PLPC) from oxidative modification under conditions of metal ion-dependent or-independent oxidative stress. Progress of oxidation was determined by direct spectrophotometric measurement of conjugated diene formation and by gas chromatographic/mass spectrometric analysis of fatty acids. The oxidative susceptibility of CLA was higher than that of linoleic acid, and comparable to arachidonic acid. When oxidation of PLPC (1.0 mM) was initiated using the lipid-soluble 2,2′-azobis(2,4-dimethylvaleronitrile) or the water-soluble 2,2′-azobis(2-amidinopropane) hydrochloride, the radical scavengers vitamin E and butylated hydroxytoluene (BHT) at 0.75 μM efficiently inhibited PLPC oxidation, as evident from a clear lagphase. In contrast, 0.75 μM CLA did not have any significant effect on PLPC oxidation. Inhibition of PLPC oxidation by higher concentrations of CLA appeared due to competition, not to an antioxidant effect. When oxidation of PLPC was initiated by hydrogen peroxide/Fe²⁺ (500 μM/0.05–20 μM), both vitamin E (1 μM) and ethylene glycol-bis(aminoethyl ether) tetraacetic acid (50 μM) efficiently inhibited PLPC oxidation. However, CLA (1–50 μM) did not show a clear protective effect under any of the conditions tested. We conclude that CLA, under these test conditions, does not act as an efficient radical scavenger in any way comparable to vitamin E or BHT. CLA also does not appear to be converted into a metal chelator under metal-ion dependent oxidative stress, as had previously been suggested. On the basis of our observations, a role for CLA as an antioxidant does not seem plausible.     

A kinetic study of the autoxidation of methyl linoleate and linoleic acid emulsions in the presence of sodium chloride

Autoxidation of linoleic acid and methyl linoleate emulsions in aqueous buffer solutions was studied by the rate of oxygen uptake. The oxidation rates of methyl linoleate emulsions increased with an inerease in the pH of the buffer solution. With linoleic acid, oxidation rates rose until the increase reached its peak at pH 5.50 and then decreased gradually to a minimum at pH 8.00. Oxidation rates of methyl linolente and linoleic acid emulsious decreased with increased concentration of NaCl in the system. The effect of variation of pH of the emulsion in the range investigated was similar to that in emulsions without NaCl. There was no evidence that NaCl accelerated the oxidation rates in the system. The observed inhibitory effect of NaCl may result from the decreased solubility of oxygen in the emulsion with the increased concentration of NaCl. Consequently the availability of oxygen would be a limiting factor in oxidation rates. The activation energy for the monomolecular and bimolecular reactions of methyl linoleate and linoleic acid autoxidation was found to be independent of the pH value and sodium chloride concentration of the system. The energy of activations for the monomolecular and bimolecular reactions of methyl linoleate and of linoleic acid are 22,000, 18,200, 19,600, and 16,400 cal./mol., respectively. Spectrophotometric studies of the autoxidized emulsions of linoleic acid and its methyl ester indicate that the magnitude of the absorption at 2325 Å is the same at different pH values. On the contrary, the secondary products showing absorption at 2775 Å are to some extent dependent on the pH value of the emulsion.