Lignans and tocopherols in Indian sesame cultivars

Lignan (sesamol, sesamin, and sesamolin) profile was determined in different cultivars (botanically identified or market samples) of sesame seeds and commercial oils procured from different parts of India. The wide variation observed in total lignans from 21 sesame seed and 9 commercial oils was attributed to variations in sesamin and sesamolin contents. Lignan content was high (18 g sesamin/kg, 10 g sesamolin/kg) in seasame cultivars obtained from the northeastern states of India. In two of the commercial oils having the Agmark label, the total lignan content was ∼12 g/kg (7.3 g sesamin, 4.7 g sesamolin), 50% of the maximum permissible levels of unsaponifiable matter. In both the seeds and commercial oils, γ-tocopherol was the only representative of tocopherol isomers identified. Sesamin and sesamolin were isolated and crystallized from high-lignan cultivars, and their purity was confirmed by HPLC and spectral (UV and fluorescence) analysis.     

Endogenous antioxidants and stability of sesame oil as affected by processing and storage

The effect of processing of coated and dehulled sesame seeds on the content of endogenous antioxidants, namely sesamin, sesamolin, and γ-tocopherol in hexane-extracted oils, was studied over 35 d of storage under Schaal oven test conditions at 65°C. Seeds examined were Egyptian coated (EC) and dehulled (ED) and Sudanese coated (SC) varieties. Processing conditions of raw (RW) seeds included roasting at 200°C for 20 min (R), steaming at 100°C for 20 min (S), roasting at 200°C for 15 min plus steaming for 7 min (RS) and microwaving at 2450 MHz for 15 min (M). The sesamin content in fresh oils from EC, ED, and SC raw seeds was 649, 610, and 580 mg/100 g oil, respectively. Corresponding values for the content of sesamolin in oils tested were 183, 168 and 349 mg/100 g oil, respectively. Meanwhile, the content of γ-tocopherol, the only tocopherol present in the oils, ranged from 330 to 387 mg/kg sample. The effect of processing on changes in the sesamin content in oils from coated seeds was low and generally did not exceed 20% of the original values. On the other hand, oils from dehulled seeds underwent a more pronounced decrease in their sesamin content than the oil from coated seeds after 35 d of storage at 65°C. The corresponding changes in sesamolin and γ-tocopherol contents were more drastic. The RS treatment, which would be the optimal to prepare sesame oil with better quality, was found to retain 86, 80 and 60% of the sesamin, sesamolin and γ-tocopherol, respectively, originally present in the seeds after the storage period. The loss in the content of endogenous antioxidants present in the oils paralleled an increase in their hexanal content.     

Detection of hydrocarbons in irradiated and roasted sesame seeds

Hydrocarbons produced by γ-radiation of sesame seed were analyzed to determine the relation of irradiation dose to the production of hydrocarbons and to eventually use them as markers for identifying post-irradiated sesame seed. Hydrocarbons in sesame seed were determined by a sequential procedure of lipid extraction by hexane, Florisil column chromatography, and gas chromatography. 16:2, 16:3, 17:1, and 17:2 were prominently detected in irradiated sesame seed, 17:2 was detected in seed irradiated at 0.1 kGy or higher, and the others were detected at 0.5 kGy or higher. These hydrocarbons were not detected in unirradiated sesame seeds that were raw, roasted, whole, ground, or stored.     

Sesame seed is a rich source of dietary lignans

The variation in the contents of sesamin and sesamolin was studied in oils extracted from 65 samples of sesame seeds (Sesamum indicum L.) from plants with shattering (n=29), semishattering (n=7), and nondehiscent (n=29) capsules. The oil content ranged from 32.5 to 50.6% and was greater in white than black seeds (P<0.001). The sesamin and sesamolin contents in seeds ranged from 7 to 712 mg/100 g (mean±SD, 163±141 mg/100 g) and from 21 to 297 mg/100 g (101±58 mg/100 g), respectively, with no difference between black and white seeds. Thus, there was a wide variation in the contents of sesamin and sesamolin, which were positively correlated (R ²=0.66, P<0.001). There were negative correlations between the contents of sesamin and the contents of sesaminol (R ²=0.37) and sesamolinol (R ²=0.36) and between the content of sesamolin and those of sesaminol (R ²=0.35) and sesamolinol (R ²=0.46) (P<0.001). Sesame seeds had an average of 0.63% lignans, making them a rich source of dietary lignans.     

Oil and minor components of sesame (Sesamum indicum L.) strains

Oil and mior components of sesamin and sesamolin were studied in 42 strains ofSesamum indicum L. The oil contents of the seed ranged from 43.4 to 58.8% and varied inversely with the percentage of hull (r=−0.804, significant at the 1% level). The hull percentage was used as a criterion to predict oil content. The percentage of sesamin in the oil ranged from 0.07 to 0.61% and that of sesamolin from 0.02 to 0.48%. There was a significant positive correlation between the oil content of the seed and the sesamin content of the oil (r=0.608, significant at the 1% level); no correlation was found between the oil and sesamolin contents. The average oil content found for the white-seeded strains was 55.0% and for the black-seeded strains 47.8%, the difference of 7.2% being significant at the 1% level. The white- and black-seed strains also differed significantly in sesamin content, but not in sesamolin content.     

Effects of processing on oxidative stability of sesame oil extracted from intact and dehulled seeds

Oxidative stability of oils extracted from intact and dehulled sesame seeds was determined by monitoring changes in fatty acid composition, iodine value (IV), peroxide value (PV), conjugated diene (CD), para-anisidine value (p-AV), and 2-thiobarbituric acid (TBA) value and by nuclear magnetic resonance spectroscopy after storage under Schaal oven conditions at 65°C for up to 35 d. The oils from coated seeds were more stable, as reflected in PV, CD, p-AV and TBA values, than those extracted from dehulled seeds after roasting at 200°C, steaming at 100°C, roasting at 200°C plus steaming, or microwaving at 2450 MHz, except for TBA values of oil from microwaved seeds. After 35 d of storage at 65°C, the CD, p-AV, and TBA values of extracted oil from dehulled microwaved seeds were 17.72, 10.20, and 1.22, respectively, while those of their coated counterparts were significantly (P<0.05) different at 14.20, 16.47, and 1.26, respectively. Few significant changes were evident in the fatty acid composition of oil obtained from either coated and dehulled seeds subjected to different treatments. Nuclear magnetic resonance analyses found that R_ao (aliphatic to olefinic protons) and R_ad (aliphatic to diallylmethylene protons) ratios increased steadily over the entire storage period, which indicated progressive oxidation of unsaturated fatty acids.     

Lignan analysis in seed oils from fourSesamum species: Comparison of different chromatographic methods

Different chromatographic methods, thin-layer chromatography (TLC), gas chromatography (GC), gas chromatography/mass spectrometry (GC/MS) and normal- and reversed-phase high-performance liquid chromatography (HPLC), were compared for their ability to separate the different lignans present in fourSesamum species,viz., S. indicum Linn.,S. alatum Thonn., S. radiatum Schum & Thonn. andS. angustifolium (Oliv.) Engl. The advantages and limitations of each method are discussed, and a combination of methods is suggested for qualitative analyses. Two-dimensional TLC was found to be a valuable qualitative technique and one-dimensional TLC is useful for preparative purposes. GC is a good supplement for qualitative analysis, but it had many limitations as a quantitative tool—it involves many preparative steps, no suitable internal standard was found to be commercially available and the various lignans had markedly different response factors. GC/MS is a necessary techniqee to confirm the identity of the lignans present. HPLC is a one-step technique suitable for quantitative analyses, and is fast and simple because it involves direct injection of oil solutions. Reversed-phase HPLC was unable to separate sesamolin and sesangolin, but a normal-phase silica column provided satisfactory separation for these two lignans. 2-Episesalation ofS. alatum, however, did not elute from the normalphase column. Once lignans are identified, a relevant HPLC method can be used for quantitative analyses. Sesamin was present in large amounts inS. radiatum, in considerable amounts inS. indicum andS. angustifolium, and in small amounts inS. alatum. Sesamolin occurred in considerable amounts inS. indicum andS. angustifolium, but only in small amounts in the other two wild species studied.Sesamum alatum was characterized by high amounts of 2-episesalatin, andS. angustifolium was characterized by high levels of sesangolin.     

Thin-layer chromatographic separations of seed oil unsaponifiables from fourSesamum species

A new, two-dimensional thin-layer chromatographic system was established to provide good separation of the unsaponifiable fractions from the seed oils of three wildSesamum species, [S. alatum, Thonn.;S. radiatum, Schum and Thonn.; andS. angustifolium, (Oliv.) Engl.] and of the cultivatedS. indicum, L. The system utilizes silica gel plates and n-hexane/diethyl ether (7:3, v/v) and chloroform/diethyl ether (9:1, v/v) as mobile phases in the first and second directions, respectively. The system could be used for qualitative studies and as a preparative technique for subsequent quantitative gas chromatographic separations in chemotaxonomic and related studies onSesamum spp.     

Detection of adulteration in camellia seed oil and sesame oil using an electronic nose

An electronic nose was used for the detection of maize oil adulteration in camellia seed oil and sesame oil. The results of multivariate analysis of variance showed that the sensor signals of different kinds of oil are significantly different from each other. Principal component analysis (PCA) cannot be used to discriminate the adulteration of camellia seed oil, but can be used in the discrimination of adulteration in sesame oil. Linear discriminant analysis (LDA) is more effective than PCA and can be used in adulteration discrimination for both camellia seed oil and sesame oil. In order to check the discriminative power of LDA, canonical discriminant analysis was performed as well. Acceptable results were also obtained: The accuracy of prediction was 83.6% for camellia seed oil and 94.5% for sesame oil. The artificial neural network (ANN) model was used to detect the percentage of adulteration in camellia seed oil and sesame oil. The results showed that, based on ANN as its pattern recognition technique, the electronic nose cannot predict the percentage of adulteration in camellia seed oil, but can be used in the quantitative determination of adulteration in sesame oil.     

Effect of the extraction solvent polarity on the sesame seeds oil composition

This study highlights the effect of solvent polarity on the yield (Y%) and properties of oil extracted from Algerian sesame seeds. Extractions were carried out under Soxhlet conditions with the following solvents: hexane (Hx), ethanol (Eth), acetone (Ac), dichloromethane (Di), isopropanol (Iso), hexane:isopropanol (Hx:Iso), and chloroform:methanol (Chf:Me). The sesame oil yield obtained using different solvents ranged from 28.86 to 52.83%. Fatty acids and sterols analyses were performed by GC on capillary column. γ‐Tocopherol was the major tocochromanol compound detected by HPLC‐fluorescence. Fourteen fatty acids were identified, with the predominance of oleic and linoleic acids. The main sterol in sesame oil was β‐sitosterol, followed by stigmasterol, campesterol, and Δ⁵‐avenasterol which were present in lower concentrations. High correlations were found between arachidic, gadoleic, behenic, and lignoceric acids concentrations; these results were explained by the metabolic biosynthesis pathway of the biologically active long‐chain PUFA by successive elongation and desaturation. Principal component analysis (PCA) of the data obtained from sesame oil composition enabled an easy comparison of the different extraction solvents, and correlated their properties with the most characteristic components of the extracted oils with a view to understand solvent–oil interaction, and to establish the effects of extracting solvent on such oil composition. Practical applications: This study showed that the choice of solvent depends largely on the desired fraction to be extracted. Sesame oil was better extracted with less‐polar solvents but membrane‐associated lipids are more polar and require polar solvents capable of breaking hydrogen bonds or electrostatic forces. Owing to the differences in solvent capacity, the fatty acids, sterols, and tocopherols extracted along with the oil vary, leading to differences in the quality of the extracted oil. The results obtained in this study could be applied in industrial extraction to encourage the use of alternative extraction solvents.     

Isothermal crystallization of tripalmitin in sesame oil

Crystallization of tripalmitin (TP) in sesame oil was investigated under isothermal conditions at a cooling rate similar to the one achieved in industrial crystallizers (1 K/min). The results obtained indicated that, at TP concentrations <0.98%, triacylglycerides of sesame oil developed mixed crystals with TP. However, at concentrations within the interval of 0.98 to 3.44%, tripalmitin crystallized independently from sesame oil. Within this concentration interval, discontinuities were observed in the behavior of the induction time of TP crystallization (T _i) in sesame oil as evidenced by differential scanning calorimetry, polarized microscopy studies, and determination of the Avrami index (n). In general, the discontinuities in T _i were associated with different polymorph states developed by TP in sesame oil as a function of its concentration and crystallization temperature. Thus, TP crystals obtained at temperatures above 296 K with 1.80 and 2.62% TP solutions had n values close to 3 and developed lamellar-shaped crystals that are characteristic of β tripalmitin. In contrast, the crystals obtained at temperatures of 296 K and below with 1.80% and 2.62% TP solutions provided n values close to 3. Axialite-shaped β′ TP crystals were obtained under these conditions. For the 0.98% TP solution, simultaneous production of α and β′ crystals occurred below 291 K. However, at temperatures above 291 K, a crystallization process with n=3 was obtained, and it developed a different polymorph state, i.e., β, with lamellar-shaped TP crystals.     

Palm oil analysis in adulterated sesame oil using chromatography and FTIR spectroscopy

This study highlights the application of two analytical techniques, namely GC‐FID and FTIR spectroscopy, for analysis of refined‐bleached‐deodorized palm oil (RBD‐PO) in adulterated sesame oil (SeO). Using GC‐FID, the profiles of fatty acids were used for the evaluation of SeO adulteration. The increased concentrations of palmitic and oleic acids together with the decreased levels of stearic, linoleic, and linolenic acids with the increasing contents of RBD‐PO in SeO can be used for monitoring the presence of RBD‐PO in SeO. Meanwhile, FTIR spectroscopy combined with multivariate calibration of partial least square (PLS) has been successfully developed for the detection and quantification of RBD‐PO in SeO using the combined frequencies of 3040–2995, 1660–1654, and 1150–1050 cm^?1. The values of coefficient of determination (R²) for the relationship between actual versus FTIR‐calculated values of RBD‐PO in SeO and root mean square error of calibration (RMSEC) obtained are 0.997 and 1.32% v/v, respectively. In addition, using three factors, the root mean square error of prediction (RMSEP) value obtained using the developed PLS calibration model is relatively low, i.e., 1.83% v/v. Practical Application: The adulteration practice is commonly encountered in fats and oils industry. It involves the replacement of high value edible oils such as sesame oil with the lower ones like palm oil. Gas chromatography and FTIR spectroscopy can be used as reliable and accurate analytical techniques for detection and quantification of palm oil in sesame oil.     

Functional properties of dehulled sesame (sesamum indicum L.) seed flour

Certain functional properties of sesame seed flour were obtained after oil extraction from dehulled seed meal was investigated. The protein content in the flour was 69.7% and the least gelation concentration was 6.0%. Water and oil absorption capacities at room temperature (31 ± 2°C) were 2.3 g H₂O/g sample and 3.0 g oil/g sample, respectively. The values were higher at 100°C. The emulsification capacity, which was more stable at alkaline conditions, ranged from 25.0 mL oil/g sample at pH 4 to 66.0 mL oil/g sample at pH 10. The foaming capacity was more stable at pH 4 but lower (205.0%). The highest foaming capacity (315.0%) was at pH 2 whereas at pH 10 it was 310.0%. Protein solubility, which was least at pH 4, ranged from 7.9% at pH 2 to 14.2% at pH 10. The viscosity of the flour dispersion ranged from 2.5 cps at 1% concentration to 7.0 cps at 10% concentration. The findings show that sesame flour could impart desirable characteristics when incorporated into products such as ice cream, frozen dessert, sausages, baked food and confections.     

The Contents of Lignans in Sesame Seeds and Commercial Sesame Oils of China

In this study, the concentrations of three lignans in 100 sesame seeds and 56 sesame oils were determined using a newly developed method based on high‐performance liquid chromatography coupled with a UV/Vis detector. Total lignan contents in sesame seed and oil samples ranged from 2.52 to 12.76 and 3.38 to 11.53 mg/g, respectively. Black sesame seeds showed higher sesamin content (range 1.98–9.41 mg/g, mean 4.34 mg/g) and sesamolin content (range 1.06–3.35 mg/g, mean 1.92 mg/g) than the other three varieties of sesame seeds. Black sesame oils had higher contents of lignans than the white sesame oils, although remarkable differences were not observed. Hot pressed and small mill sesame oils expressed higher contents of sesamol, sesamin, and total lignans than the cold pressed and refined sesame oils. The results revealed that there is extensive variability in lignan concentration in sesame oils and seeds.     

Antioxidant activity of sesame,rice bran and bene hull oils and their unsaponifiable matters

Chemical composition of sesame (SEO), rice bran (RBO) and bene hull (BHO) oils was determined. During oven test, peroxide value on day 8 (PV₈, meq/kg) and carbonyl value on day 6 (CV₆, µmol/g) were considered as measures of resistance to the formation of primary and secondary oxidation products, respectively. The SEO and BHO showed statistically the same PV₈ (381.4 and 359.8, respectively) and CV₆ (25.2 and 25.8, respectively), and their stabilizing effect was significantly better than that of the RBO (455.5 and 32.7, respectively). The unsaponifiable matters (USM) fraction of the BHO (443.7 and 26.8, respectively) had an antioxidative effect higher than those of the SEO (478.0 and 38.6, respectively) and RBO (482.4 and 37.4, respectively). There was a good correlation (R² = 0.972) between the PV₈ and CV₆ throughout oxidation period. On the basis of the oxidative stability index (OSI, h) of Rancimat test, the best carry‐through properties belonged to the SEO (6.92 h), followed by the RBO (6.12 h) and BHO (5.0 h), and also a similar order was observed for the USM fractions (5.89, 5.28 and 4.50 h, respectively). There was no correlation between the results of Rancimat and oven tests, showing that the powerful antioxidative agents under oven test conditions were lack of appropriate carry‐through properties. The highest significant reducing power (mmol/L) belonged to the SEO (258.1), followed by the RBO (218.7) and BHO (152.4), whereas the USM fraction of the SEO indicated the least significant quantity among the USM fractions (89.3 vs. 216.6 and 158.0 for the RBO and BHO, respectively).     

Evaluation of tripalmitin crystallization in sesame oil through a modified avrami equation

Tripalmitin (TP) crystallization in sesame oil solutions (0.98, 1.80, and 2.62%, wt/vol) was investigated by utilizing a modification of the Avrami equation. The modified equation retains the original correspondence to the nucleation process (i.e., n) and crystal growth and simply corrects the value of the crystallization rate constant (z) by eliminating the influence of n. The energy of activation (E _a ) values for TP crystallization in sesame oil solution, calculated with the modified z, were quite similar to those calculated with the reciprocal of time required to achieve 50% of TP crystallization (t _F =0.50⁻¹). However, E _a values calculated with z from Avrami’s original equation were quite different from those obtained with t _F =0.50⁻¹. Thus, z and E _a values calculated through the Avrami equation yield erroneous results, especially when comparing crystallization processes having different magnitudes of n, as in this study. Additional analysis that considered the viscosity of the TP oil solutions concluded that, at equal supercooling conditions (e.g., 22.0–22.5), the magnitude of z and E _a became more dependent upon the crystal growth process as oil viscosity decreased. In contrast, as viscosity of the oil phase increased, the main crystallization process, evaluated through z and E _a′ was nucleation. Furthermore, within the supercooling interval achieved at the temperatures utilized, the increase in supercooling at constant viscosity conditions (e.g., 5.25–5.5 dynes/cm²) would produce a higher degree of nucleation without an appreciable effect on TP crystal size. The results obtained indicate that investigating the effects of supercooling, molecular diffusion (i.e., viscosity) and TP concentration on the magnitude of z and E _a during TP crystallization in sesame oil requires a multiple variable statistical approach.     

Competitive adsorption among sesame oil components in a concentrated miscella system

Competitive adsorption of free fatty acids and carotenoids adsorption from sesame oil miscellas on vegetable carbon was studied by regression analysis. The equations obtained indicated that unsaturated carbonyls, free fatty acids (FFA₀), and carotenoids interacted to determine fatty acid and carotenoid adsorption. The driving force for carotenoid adsorption, the carotenoid concentration (C₀), was affected by a quadratic function of free fatty acid concentration [i.e., (FFA₀/C₀)²]. As FFA₀/C₀ increased, carotenoid adsorption efficiency was reduced, possibly because the accessible adsorption sites for carotenoids were occupied by fatty acids. Unsaturated carbonyls promoted free fatty acid adsorption, probably in the pores that were readily accessible for fatty acids. However, when the carbonyl concentration increased in the oil miscella, carbonyls were adsorbed instead of fatty acids. The results indicated how different oil molecules interact and affect adsorption (i.e., free fatty acids and carotenoids). Therefore, the adsorption process of vegetable oils (i.e., bleaching) has to be considered a multicomponent adsorption system.     

Viscosity and its relationship to crystallization in a binary system of saturated triacylglycerides and sesame seed oil

This paper describes the relationship of viscosity with the crystallization process in a binary system formed by sasame oil and different concentrations of tripalmitin (TP) and tristerian (TS) (0.0, 0.032, 0.098, 0.18, 0.26, 0.344 g/dL). The behavior of the reduced viscosity (η_red) indicated that TP and TS affected the native bilayer lamellar organization of sesame oil triacylglycerides. The behaviour of η_red at TP or TS concentrations ≤0.098 g/dL suggested that, as a result of intermolecular interactions between the saturated triacylglyceride and the unsaturated triacylglycerides of sesame oil, the oil solution developed lamellar structures with a smaller size than the native structures in sesame oil. At TP or TS concentrations >0.098 g/dL, the behavior of η_red indicated that TP or TS segregated out of the lamellar structure as the temperature was decreased. The kinetics of the segregation phenomenon was a function of the concentration of saturated triacylglyceride and the type of triacylglyceride (i.e., TP or TS), and was favored by an increase in the shear rate. In all situations, the temperature of nucleation was achieved when η_red=0, which may represent the point at which the interfacial energy between sesame oil and the developing nuclei achieved its maximum value. The higher the intermolecular interaction between the TP or TS and the triacylglyceride structure of the sesame oil, the lower the temperature at which η_red=0 in the oil solutions. As a result, the diffusion term (i.e., viscosity of the liquid phase) became a limiting factor for crystal growth rate, especially at TP and TS concentrations ≤0.18 g/dL.     

The impact of processing on the profile of volatile compounds in sesame oil

The flavor of sesame oil significantly depends on the roasting conditions and the relative concentrations of volatiles. In the present study, volatile components from three varieties of sesame oil produced by roasting the seeds under different conditions were analyzed and profiled using GC–mass chromatography. The results showed that the roasting temperature had an obvious effect on the aroma of the oils since there was an increase in the concentration of the volatiles responsible for aroma such as pyrazines, furans, and sesamol as the temperature at which the seeds were roasted was increased. However, the concentration of some components such as alcohols and aldehydes, decreased with an increase in the roasting temperature. The roasting conditions have an important effect on the characteristic aroma of sesame oil. Other methods used to process sesame oil, such as solvent extraction, mechanical pressing and hot water flotation, were also investigated. Sesame oil produced using the Chinese traditional hot water flotation method had the most preferred flavor. There was good consistency between the principal components analysis (PCA) and sensory evaluation. The results of the present study suggested that production of sesame oil with the most acceptable aroma was dependent on the appropriate processing method.     

Extraction of sesame seed (Sesamun indicum L.) oil using compressed propane and supercritical carbon dioxide

This work is aimed to investigate the extraction of sesame seed (Sesamun indicum L.) oil using supercritical carbon dioxide and compressed propane as solvents. The extractions were performed in a laboratory scale unit in a temperature and pressure range of 313-333 K and 19-25 MPa for carbon dioxide and 303-333 K and 8-12 MPa for propane extractions, respectively. A 2² factorial experimental design with three replicates of the central point was adopted to organize the data collection for both solvents. The results indicated that solvent and density were important variables for the CO₂ extraction, while temperature is the most important variable for the extraction yield with propane. The extraction with propane was much faster than that with carbon dioxide due to the fact that propane is a better solvent for vegetable oils compared to carbon dioxide. On the other hand, characteristics of extracted oil, its oxidative stability determined by DSC and chemical profile of constituent fatty acids determined by gas chromatography, were similar to both solvents. The mathematical modeling of the extraction kinetics using a second order kinetic presented good results for the extraction with both solvents.