T. L. Mounts

Effect of triacylglycerol composition and structures on oxidative stability of oils from selected soybean germplasm

The oxidative stability of soybean oil triacylglycerols was studied with respect to composition and structure. Crude soybean oils of various fatty acid and triacylglycerol composition, hexane-extracted from ground beans, were chromatographed to remove non-triacylglycerol components. Purified triacylglycerols were oxidized at 60°C, in air, in the dark. The oxidative stability or resistance of the substrate to reaction with oxygen was measured by determination of peroxide value and headspace analysis of volatiles of the oxidized triacylglycerols (at less than 1% oxidation). The correlation coefficients (r) for rates of peroxide formation (r=0.85) and total headspace volatiles (r=0.87) were related positively to oxidizability. Rate of peroxide formation showed a positive correlation with average number of double bonds (r=0.81), linoleic acid (r=0.63), linolenic acid (r=0.85). Rate of peroxide formation also showed a positive correlation with linoleic acid (r=0.72) at the 2-position of the glycerol moiety. A negative correlation was observed between rate of peroxide formation and oleic acid (r=−0.82). Resistance of soybean triacylglycerols to reaction with oxygen was decreased by linolenic (r=0.87) and increased by oleic acid (r=−0.76)-containing triacylglycerols. Volatile formation was increased by increased concentration of linolenic acid at exterior glycerol carbons 1,3 and by linoleic acid at the interior carbon 2. Headspace analysis of voltiles and high-performance liquid chromatography of hydroperoxides indicated that as oxidation proceeded there was a slight decrease in the linolenic acid-derived hydroperoxides and an increase in the linoleic acid-derived hydroperoxides. The oxidative stability of soybean oil triacylclycerols with respect to composition and structure is of interest to the development of soybean varieties with oils of improved odor and flavor stability.

Physical Properties of Interesterified Fat Blends

Fat blends, formulated by mixing fully hydrogenated soybean oil with nine different commonly used vegetable oils in a ratio of 1:1 (w/w), were subjected to interesterification (also commonly referred to as rearrangement or randomization) with sodium methoxide catalyst. Fatty acid composition and triacylglycerol molecular species of each fat blend and the interesterified product were determined and correlated with the following physical properties: melting, crystallization characteristics and solid fat content. The differences in the endothermic and exothermic peak temperatures, total heat of fusion and crystallization (β and β′ crystalline content) and solid fat content among the fat blends clearly showed the effect of the composition of each oil on the physical properties. Oils that contained a considerable amount of palmitic acid had a favorable influence on the crystallization and polymorphic form of interesterified fat blends.

Reversed-phase high-performance liquid chromatographic separations of tocopherols

Abstract The retention behavior and separation characteristics of five natural products α-, β−, γ-, δ-, and ξ 2 -tocopherols and their acetyl derivatives were studied by reversed-phase high-performance liquid chromatography (HPLC)-fluorescence detection. Investigated stationary phases included an octadecyl polyvinyl alcohol (ODPVA) column, several octadecylsilica (ODS) columns, and a pentafluorophenylsilica column. Mobile phases comprised methanol (or acetonitrile) and water at variable proportions. Separation factors for β- and γ-tocopherol isomers and capacity factors of the five tocopherols were determined under various conditions. The β- and γ-tocopherols were separable on ODPVA but not on ODS. However, the βγ pair was resolved with the latter column only as their ester derivatives. HPLC with mobile phases containing alkanols with carbon atoms greater than 2 favored the separation of the βγ pair on ODS and yielded results diametrically different but complementary with those obtained with the ODPVA phase. The combined effects of mobile phases, stationary phases and antioxidant structures on component separations were delineated.

Supercritical CO2 degumming and physical refining of soybean oil

A hexane-extracted crude soybean oil was degummed in a reactor by counter-currently contacting the oil with supercritical CO2 at 55 MPa at 70°C. The phosphorus content of the crude oil was reduced from 620 ppm to less than 5 ppm. Degummed feedstocks were fed (without further processing,i.e., bleaching) directly to a batch physical refining step consisting of simultaneous deacidification/deodorization (1 h @ 260°C and 1–3 mm Hg) with and without 100 ppm citric acid. Flavor and oxidative stability of the oils was evaluated on freshly deodorized oils both after accelerated storage at 60°C and after exposure to fluorescent light at 7500 lux. Supercritical CO2-processed oils were compared with a commercially refined/bleached soybean oil that was deodorized under the same conditions.Flavor evaluations made on noncitrated oils showed that uncomplexed iron lowered initial flavor scores of both the unaged commercial control and the CO2-processed oils. Oils treated with .01% (100 ppm) citric acid had an initial flavor score about 1 unit higher and were more stable in accelerated storage tests than their uncitrated counterparts. Supercritical CO2-processed oil had equivalent flavor scores, both initially and after 60°C aging and light exposure as compared to the control soybean oil. Results showed that bleaching with absorbent clays may be eliminated by the supercritical CO2 counter-current processing step because considerable heat bleaching was observed during deacidification/deodorization. Colors of salad oils produced under above conditions typically ran 3Y 0.7R.

HPLC analysis of phospholipids by evaporative laser light-scattering detection

High-performance liquid chromatography (HPLC) for analysis of phospholipids has traditionally employed ultraviolet detection of the eluted compounds. The evaporative laser light-scattering detector (ELSD) offers new opportunities for quantitative analysis of lipids. Phospholipids were isolated from crude and degummed oils prepared from soybeans subjected to storage at high moisture content. Analytical and preparative separations of phospholipids by normal-phase HPLC were accomplished. Major class fractions were analyzed by transmethylation and capillary collumn chromatography for fatty acid composition, and by reverse-phase C-18 HPLC (RP-HPLC) for molecular species composition. The RP-HPLC-ELSD system was limited to the analysis of phosphatidylcholine and phosphatidylethanolamine.

FTIR estimation of free fatty acid content in crude oils extracted from damaged soybeans

A user-interactive computer-assisted Fourier transform infrared (FTIR) method has been developed for estimation of free fatty acids (FFA) in vegetable oil samples by deconvolution of the infrared (IR) absorbances corresponding to the triglyceride ester and FFA carbonyl bonds. Peak areas were used to determine FFA as a percentage of the total carbonyl areas in weighed standards of refined, bleached, deodorized soybean oil containing from 0 to 5% added oleic acid. These data for percent FFA by FTIR were compared to corresponding FFA data obtained by two titration methods-the AOCS Official Method Ca 5a-40 and the Official Method with a slight modification. Correlation coefficients were 0.999 for the Ca 5a-40, 0.999 for the modified and 0.989 for the FTIR methods. FFA in samples of crude soybean oils extracted from damaged beans (0.5 to 2.1% FFA) were measured by FTIR and compared to data obtained by titration of the same samples (correlation coefficient, 0.869).

Photooxidation of soybean oils as affected by triacylglycerol composition and structure

The photooxidation of soybean oil was determined and correlated with triacylglycerol composition and structure. Purified triacylglycerols were photooxidized at room temperature under fluorescent light. Rates of peroxide formation and total headspace volatiles were related positively (P<0.5 significance) to oxidizability (r=0.75, r=0.76); content of linolenic acid (r=0.80, r=0.85) and linoleic acid (r=0.61, r=0.57); linoleic acid on carbon 2 (r=0.64, r=0.64); and average number of double bonds (r=0.76, r=0.76). Negative correlations were observed with respect to oleic acid (r=−0.70, r=−0.70). Soybean oil stability was decreased by linolenic acid-containing triacylglycerols and increased by oleic acid-containing triacylglycerols. Trilinoleoylglycerol and dilinoleoyl-oleoylglycerol were the most important oxidation product precursors. However, for high-linolenic acid soybean oil, dilinoleoyl-linolenoylglycerol and trilinoleoylglycerol were the most important oxidation product precursors. The most abundant volatile produced from thermal decomposition at 140°C of photooxidized triacylglycerols was 2-heptenal, except for high-linolenic acid oils, where the most abundant volatile was propanal. The photooxidative stability of soybean oil triacylglycerols with respect to composition and structure is of interest for the development of soybean varieties with oils of improved odor and flavor stability.

Factors promoting the formation of nonhydratable soybean phosphatides

Whole, cracked and flaked soybeans were stored under a variety of conditions. After extraction with hexane, the crude oils were degummed in the laboratory, and the nonhydratable phospholipid (NHP) content was estimated from the phosphorus content of the degummed oil. Results showed that four interrelated factors promote NHP formation. These include (i) moisture content of beans or flakes entering the extraction process; (ii) phospholipase D activity; (iii) heat applied to beans or flakes prior to, and during, extraction; (iv) disruption of the cellular structure by cracking and/or flaking. Results from this study suggest that NHP formation can be minimized by control of the moisture of beans and/or flakes entering the extraction process, inactivation of phospholipase D enzyme, and optimizing temperatures during the conditioning of cracked beans or flakes.

Chemical interesterification with regioselectivity for edible oils

Chemical interesterification reaction conditions that provide regioselectivity regarding fatty acid positions in triacylglycerol have been investigated. Sodium methoxide-catalyzed ester interchange between soybean oil and methyl stearate was performed in hexane at low reaction temperature,i.e., 30 to 60°C. The results showed regioselectivity was obtained at 30°C. The ester interchange at 1,3-carbons progressed 1.7 times faster than at 2-carbon of the glycerol moiety of triacylglycerol at 24 h. Preheating of the mixture of reactant and catalyst at 60°C for 15 min promoted catalyst activation to accelerate the interesterification while maintaining regioselectivity. This method is believed to be feasible for modification of edible fats and oils.

High-performance liquid chromatographic separation of molecular species of neutral phospholipids

Molecular species of neutral phospholipids, phosphatidylcholine (PC) and phosphatidylethanolamine (PE), were resolved by reversed-phase high-performance liquid chromatography (HPLC) using mobile phases of acetonitrile-methanol-water containing tetraalkylammonium phosphates (TAAPs). Competitive interactions of TAAPs and analyte solutes with a reversed-phase HPLC column resulted in reduced retention of PC or PE with concomitant increase in detection sensitivity. The chromatographic data for PC and PE were distinctly different from those for negatively charged phospholipids where ion-pair retention mechanisms prevailed. While PC (or PE) components eluted at longer retention times with a larger size of TAAP, an increase in the TAAP concentration invariably caused a decrease in phospholipid retention times. Optimization of HPLC conditions by using high concentrations (25-100 mM) of tetramethylammonium phosphate in acetonitrile-methanol-water (70:22:8) facilitated elution of components with improved peak symmetry. HPLC separations of neutral phospholipids derived from animal sources were more complex than those from soybeans.