Prooxidant effects of inorganic chromium compounds in the autoxidation of methyl linoleate

The prooxidant property of inorganic chromium compounds was determined in methyl linoleate free from natural antioxidants and metals. Prooxidant properties of inorganic chromium compounds appeared in order of sodium chromate > chromium (VI)-oxide > chromium chloride > potassium chromate > chromium (III)-oxide > potassium dichomate. In comparison with the control, additions of chromium compounds induced different amounts of autoxidation products derived from methyl linoleate, such as small amounts of hydroperoxides and conjugated dienes and large amounts of hydroxy groups,α,β,γ,δ-unsaturated carbonyls, isolatedtrans double bonds, polymers, and free radicals. From these analytical data, the catalysis of chromium compounds in the autoxidation of methyl linoleate seemed to be based on their abilities of abstracting a hydrogen from methyl linoleate and decomposing hydroperoxides derived from the autoxidation of methyl linoleate.     

Further observations on the dicarbonyl compounds formed via autoxidation of methyl linoleate

a-Dicarbonyls isolated from oxidized methyl linoleate and conclusively identified as DNP-osazones³ were glyoxal, methyl glyoxal,a-keto hexanal,a-keto heptanal, anda-keto octanal. Technical Paper No. 2012, Oregon Agricultural Experiment Station.     

Kinetic investigation into glucose-, fructose-, and sucrose-activated autoxidation of methyl linoleate emulsion

Autoxidation of methyl linoleate emulsions in aqueous phosphate buffer solutions in the presence of glucose, fructose, and sucrose has been studied by the rate of oxygen uptake. Oxidation rates increased with increasing concentration of sugars in the system. At comparable molar ratios of sugar to methyl linoleate the rate of oxidation in the presence of fructose was greater than with glucose which, in turn, was greater than with sucrose. Oxidation rates increased with pH until a maximum rate was reached at pH 8.00. There was less conjugation and more CO₂ with fructose than with glucose at a comparable level of oxygen uptake and pH value. This suggested concurrent oxidation of methyl linoleate and sugars; fructose is the most readily oxidized of those studied. Sugars seemed to be effective only in combination with the resulting methyl linoleate hydroperoxide. The effect of sugars rests in an activation of the decomposition of the linoleate hydroperoxide, and on the acceleration of the autocatalysis. The activation energy values for the autoxidation of methyl linoleate emulsions in the presence of sucrose, glucose, and fructose are 14.9, 10.6, and 10.6 K. Cal./mol. at pH 5.50; 16.0, 10.8, and 10.4 K. Cal./mol. at pH 7.00; and 14.4, 10.2, and 8.8 K. Cal. at pH 8.00, respectively. Addition of ascorbic acid to the system at zero time or after 2 hrs. increased oxygen absorption. It appeared that oxidized methyl linoleate caused co-oxidation of the ascorbic acid. Additions of nordihydroguaiaretic acid, propyl gallate, and hydroquinone to the system were ineffective in stopping oxidation when they were added after oxidation had commenced. They reduced effectively the rate of oxidation when added at zero time. Presented at the 52nd annual meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. American Meat Institute Foundation Journal Paper No. 215.     

Autoxidation of fatty materials in emulsion. II. Factors affecting the histidine-catalyzed autoxidation of emulsified methyl linoleate

Several factors which affect autoxidation of methyl linoleate in emulsion have been examined. Data are presented which indicate: 1) In the presence of histidine, the ionic (anionic) emulsifiers examined promote autoxidation of emulsified methyl linoleate, but nonionic emulsifiers do not. 2) The concentration of an emulsifier affects the rate of oxygen absorption. 3) Inorganic salts (0.1 M or less) such as sodium chloride, sodium acetate and sodium sulfate affect oxygen absorption of emulsified methyl linoleate prepared with either ionic or nonionic emulsifiers. In histidine-catalyzed autoxidation there is a suppressing effect in the case of the ionic and a promotional effect in the case of the nonionic. In uncatalyzed autoxidation, these salts have a promotional effect in ionic emulsions and none in nonionic emulsions. 4) Sodium phosphate buffers completely suppress autoxidation due to histidine catalysis, but do not suppress the normal uncatalyzed autoxidation of emulsified methyl linoleate. 5) The pro-oxidative effects of histidine and histidine-metal ion complexes on emulsified unsaturated materials is not limited to polyolefins but also includes mono-olefinic compounds. Presented at the AOCS meeting in Toronto, October, 1962. E. Utiliz. Res. and Dev. Div., ARS, USDA.     

Concurrent oxidation of accumulated hydroperoxides in the autoxidation of methyl linoleate

Summary 1. Kinetic studies showed that concurrent oxidation of preformed hydroperoxides may be expected to take place at all stages of the autoxidation of methyl linoleate. The rate of oxidation relative to the rate of autoxidation of unoxidized ester is determined chiefly by the extent of the accumulation of hydroperoxides. 2. Infrared spectral analysis of hydroperoxides oxidized to various degrees indicated thattrans, trans diene conjugation and isolatedtrans double bonds produced in the autoxidation of methyl linoleate are related to the concurrent oxidation of the accumulated hydroperoxides. 3. The low absorptivity observed for diene conjugation, compared to that which may be expected for the exclusive production ofcis, trans diene conjugated hydroperoxide isomers during the autoxidation of methyl linoleate is attributed to the concurrent oxidation of accumulated hydroperoxides. 4. The effect of antioxidants in giving a well-defined induction period in the oxidation of hydroperoxides isolated from autoxidized methyl linoleate indicated that the oxidation proceeds by a chain reaction. 5. The primary reaction products of the oxidation of hydroperoxides isolated from autoxidized methyl linoleate were found to be polymers formed in a sequence of reaction involving the diene conjugation. 6. Studies on the autoxidation of methylcis-9,trans-11-linoleate showed thatcis, trans isomerization of the conjugated diene took place with the concurrent production of isolatedtrans double bonds and loss of diene conjugation. Hormel Institute publication no. 138. Presented before the American Oil Chemists’ Society, Philadelphia, Pa., Oct. 10–12, 1955. This work was supported by a grant from the Hormel Foundation.     

Identification of some acids from autoxidation of methyl linoleate

The acids from autoxidation of methyl linoleate have been analyzed as their methyl esters by combined capillary gas chromatography-mass spectrometry (GC-MS). The principal components were hexanoic, trans-2-octenoic, suberic and azelaic acid. Minor components included formic, pentanoic, heptanoic, trans-2-heptenoic, octanoic and nonanoic acid. In addition,trans-2,3-epoxy-octanoic acid was isolated as its methyl ester by preparative GLC and was identified by means of NMR, high resolution MS, IR and by conversion to a known derivative. W. Utiliz. Res. Dev. Div., ARS, USDA.     

The chemistry of polymerized oils. V. The autoxidation of methyl linoleate

1. The geometrical forms obtained during autoxidation of methyl linoleate at ordinary temperatures are largely conjugatedcis-trans andtrans-trans as shown by previous workers; there is a possibility that conjugatedcis-cis forms are also produced. 2. Thetrans-trans molecules arise partly, at least, by thermal rearrangement of already formedcis-trans peroxide. 3. Some proportion, at least, of thecis-trans molecules have theirtrans double bonds nearest to the hydroperoxide group. 4. A partial separation of the geometrical forms can be accomplished by reversed phase partition chromatography both on methyl linoleate hydroperoxides and on the corresponding mixed hydroxy compounds; isolation of thetrans-trans forms can be accomplished in the latter case by urea complex fractionation. 5. No position isomers except the known 9- and 13-isomers have been positively identified; there is a possibility that very minor amounts of the 2-isomer are formed; the 9- and 13-isomers are present in about equal amounts; the 11-isomer was not detected by the methods applied. 6. Various ways in which the linoleate autoxidation problem might be advanced further are suggested.     

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.     

Metal-requiring and non-metal - requiring catalysts in the autoxidation of methyl linoleate

During the autoxidation of methyl linoleate, peroxide-containing substances are formed which, when added to unoxidized methyl linoleate, will catalyze oxygen uptake. Materials active only in the presence of added metal ions (MCs) were not inactivated during aerobic thin-layer chromatography on silicic acid or alumina but were selectively inactivated by treatment with triphenylphosphine. Catalysts not requiring added metal ions for activity (NCs) are not affected by triphenylphosphine, but the catalytic activity is lost during aerobic thin-layer chromatography. Autoxidized methyl linoleate was separated into four peroxide-containing fractions by elution from a silicic acid column with hexane-diethyl ether mixtures. Each fraction was found to contain both MCs and NCs. Presented at the 4th International Symposium on Metal Catalyzed Lipid Oxidation, London, April 1975.     

The kinetics of autoxidation of methyl linoleate. The effect of added antioxidants and a new method for the evaluation of antioxidants

A new method is described for the evaluation of antioxidants. Oxygen uptake by autoxidizing methyl linoleate both with and without antioxidants is measured in the Warburg apparatus and reaction orders, reaction rate constants, and length of induction periods determined. Tenox's BHT and BHA and Griffith's G-16 are evaluated and compared.     

Oxidation of methyl linoleate in the presence of lignin

The overall aim of this study is to develop new wood modifications using vegetable oils to obtain improved durability of wood materials in an environmentally friendly way. Nuclear magnetic resonance (NMR) and Fourier-transform infrared (FT-IR) spectroscopies were used to study oxidation and possible chemical coupling reactions between polyunsaturated fatty acids and model lignin compounds in order to better understand the interactions between oxidatively drying systems such as vegetable oils or alkyds with the lignin part in wood. This was done by studying mixtures of different model lignin compounds and methyl linoleate. The oxidation process was analyzed at 70 °C both in methyl linoleate alone and in combination with 20 wt% of lignin model compounds. The effects of those compounds on the oil polymerization processes were monitored by NMR (both ¹³C and ¹H experiments) and the domain specific reactivity and patterning were then combined with FT-IR data. No covalent bonds having formed between the oil and the model compounds were detected by combination of several ¹³C/¹H 2D NMR methods. From the spectra, the oxidation degrees of model compounds were calculated, and for some lignin model compounds alcohols were oxidized to carbonyls during the process. Those results were in excellent agreement with FT-IR data and oxidation mechanisms were proposed. The combination of both analytical techniques was necessary to have a better understanding of these systems: NMR demonstrated the absence of chemical bond and quantified oxidation degree of model lignin molecules while FT-IR focused on oil oxidation.     

The peroxidizing effect of α-tocopherol on autoxidation of methyl linoleate in bulk phase

In order to understand the effect of α-tocopherol on the autoxidation mechanism of edible oil under storage conditions, methyl linoleate was allowed to autoxidize at 50 C in bulk phase without any radical initiator. The reaction was monitored by determining the production of four isomeric hydroperoxides (13-cis,trans; 13-trans,trans; 9-cis,trans; 9-trans,trans) by high performance liquid chromatographic analysis after reduction. In the absence of α-tocopherol, the rate of autoxidation depended on the sample size, and the duration of the induction period was affected by the initial level of hydroperoxides. However, the distribution of c-t and t-t hydroperoxide isomers remained constant during the propagation period regardless of the sample size. The addition of α-tocopherol at 0.1 and 1.0% caused a linear increase in the amount of hydroperoxides and elevated the distribution of the c-t isomers. The rate of hydroperoxidation appeared to be governed by the initial concentration of α-tocopherol rather than the sample size or the initial hydroperoxide level. This peroxidizing effect of α-tocopherol was suppressed by the presence of ascorbyl palmitate. A mechanism in which chromanoxy radical participates is proposed for the effect of α-tocopherol on lipid autoxidation in bulk phase. It is therefore suggested that α-tocopherol at high concentrations influences the mechanism of autoxidation of edible oil.     

The effect of sensitizing dyes for photo as antioxidants on the autoxidation of methyl linoleate

The sensitizing dyes for photo which are cyanine homologues have been used as medicine and cosmetics. Their uses are widespread. The authors expected that these dyes might serve as antioxidants by a radical termination mechanism such as hydroperoxy radicals added to the many conjugated double bonds which exist in the dyes. Determination of the induction period by the weighing method confirmed that some sensitizing dyes for photo are available as antioxidants in the autoxidation of methyl linoleate. Therefore, these dyes may serve as new types of antioxidants.     

Effect of browning reaction products of phospholipids on autoxidation of methyl linoleate

Methyl linoleate was allowed to autoxidize in bulk phase at 50 C in the presence of either synthetic phospholipids consisting of saturated fatty acids or egg yolk phospholipids to estimate the effect of base group and fatty acid moiety of phospholipids on oil autoxidation. Dipalmitoyl phosphatidylcholine (DPPC) and dipalmitoyl phosphatidylethanolamine (DPPE) exhibited poor antioxidant activity at 50 C and showed no synergistic effect with α-tocopherol. The addition of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) of egg yolk accelerated the oxidation of methyl linoleate. However, egg yolk PC and PE collected at various stages of heating at 180 C inhibited hydroperoxide formation at the initial stage of oxidation. This effect could be attributed to the browning products formed during heating reaction. Thus, browning color products formed from unsaturated phospholipids at high temperatures may influence oil stability, although the base group of phospholipids did not exert any significant effect.     

Role of the bases and phosphoryl bases of phospholipids in the autoxidation of methyl linoleate emulsions

Methyl linoleate, emulsified in borate buffer with sodium lauryl sulfate, was used to study the pro- or antioxidant effect of 0-phosphocholine, 0-phosphoethanolamine, 0-phosphoserine, as well as the corresponding nonphosphoryl compounds. Oxygen uptake was calculated from rate data obtained at 37 C with an oxygen electrode. The results were similar for the corresponding phosphoryl and nonphosphoryl bases. 0-Phosphocholine and choline had little effect at either pH 7.9 or 10.2. 0-Phosphoethanolamine and ethanolamine significantly increased oxygen uptake at pH 7.9, but significantly decreased uptake at pH 10.2. 0-Phosphoserine and serine decreased oxygen uptake at both pH values. The catalytic activities of the bases investigated may be attributed to their functional groups. The phosphoryl and β-hydroxy groups exhibited no catalytic activity in the autoxidation of methyl linoleate emulsions at either pH 7.9 or 10.2. The α-carboxyl amino group of 0-phosphoserine and serine decelerated autoxidation at both pH values. The amino group H₃N⁺ of the primary amine accelerated autoxidation, but the H₂N: group and the reverse effect. Since the quaternary amino group (CH₃)₃N⁺ did not affect autoxidation at either pH 7.9 or 10.2, we concluded that the presence of the N−H bond may be necessary for the prooxidant activity of an amine, and that the presence of a pair of free electrons on the nitrogen of an amine is necessary for its antioxidant activity. Kinetically, the autoxidation of methyl linoleate emulsion without added base was in agreement with Farmer’s proposed mechanism involving a bimolecular dissociation of hydroperoxides. However, methyl linoleate emulsion at pH 7.9 and 37 C in the presence of ethanolamine or 0-phosphoethanolamine was autoxidized by a mechanism involving a combined mono- and bimolecular dissociation of hydroperoxides. Submitted as partial requirement for a Ph.D. degree in Agricultural Chemistry. Presented in part at the AOCS Meeting, San Francisco, April 1969.     

Isolation and identification of carbonyl compounds formed by autoxidation of ammonium linoleate

1. The isolation and identification of carbonyl compounds formed by autoxidation of pure ammonium linoleate (0.02 M. in water) has been carried out.
2. The autoxidation has been performed according to a method described by Tappel (23). A solution of 0.02 M. ammonium linoleate in 0.1 M. phosphate buffer of pH 6.9, containing 10⁻⁴ M. CuSO₄, was subjected to autoxidation at 37.2°C.
3. The isolation and identification of the D.N.P.-ones of the carbonyl compounds have been carried out, using a method of partition and adsorption chromatography published by van Duin (10, 11).
4. It was demonstrated that the principal compounds formed were n-hexanal, 2-octenal, and 2,4-decadienal.
5. The formation of these aldehydes is fully in line with the theories of autoxidation of unsaturated fatty acids (1, 3, 13) and of the dismutation of the hydroperoxides formed (2).

     

Studies on kinetics of catalytic isomerization of methyl linoleate

Kinetics of isomerization of methyl linoleate are studied on ruthenium (5%) on carbon in the temperature range 200–270 C with different solvents. Some equilibrium experiments also are carried out with rhodium and ruthenium catalysts. The reactions taking place are isomerization, hydrogenation and polymerization. The activities and the selectivities are dependent on the nature of the solvent used. Highly protic solvents like methanol or isopropyl alcohol exhibited very high activity and selectivity for hydrogenation, whereas aprotic solvents like hexane or cyclohexane showed very high selectivities for isomerization reaction. The reaction kinetics were found to be further complicated by polymer formation at low solvent concentrations. The effects of temperature, solvent concentration, catalyst quantity and time of reaction also were investigated.     

Phenothiazine derivatives as new antioxidants for the autoxidation of methyl linoleate and their reaction mechanisms

The effect of new antioxidants, such as phenothiazine derivatives, on the autoxidation of methyl linoleate was evaluated by estimating the induction period using the weighing method. Peroxide values (iodometry and IR), refractive indices, mol wts, and UV and IR spectra were measured to investigate the extent of the autoxidation. The induction period evaluated from the weighing method gives almost the same value as that from the peroxide values. It was shown that some new phenothiazine derivatives are remarkably effective antioxidants, and, besides, the mechanism for the autoxidation of methyl linoleate containing phenothiazine derivatives as antioxidants is probably of the same type as that for the substrate alone. This study also investigated the reaction mechanism of phenothiazine derivative antioxidants by determining the electron spin resonance spectra for the antioxidants in the autoxidation of methyl linoleate. Then, the following mechanism was proposed. That is, within the induction period, these inhibitors hold stable nitroxide radicals (>NO*) in the reaction between the antioxidant amino radical (>N*), produced by the reaction of the antioxidant with ROO* or O₂, and the peroxy radical (ROO*). Besides, the more superior the phenothiazine derivative antioxidant, the more inactive the antioxidant makes oxygen and the peroxy radical for the methyl linoleate autoxidation and also for the antioxidant oxidation. Presented at the 12th World Congress of ISF, Milan, 1974.     

Vapor-Phase hydrogenation of methyl linoleate in the presence of a supported copper catalyst

Methyl linoleate was hydrogenated in the vapor phase in the presence of a copper-on-alpha alumina catalyst. The kinetics of the reaction could be formulated with a Eley-Rideal mechanism including the reaction between chemisorbed methyl ester and hydrogen in the gas phase. The absorption coefficients in the rate equation were based on separately performed adsorption studies recently reported.