High stable vegetable oils

Description

The invention relates to a new vegetable oil, in particular sunflower oil, which is particularly advantageous for applications at high temperatures. The application concerns the use of the oil, the seed containing the oil, and the by-products resulting from the extraction of the oil. In the food industry, vegetable fats and oils used for frying, baking and other applications require high thermostability. These requirements are generally met by partially hydrogenated oils, palm oil and high-oleic vegetable oils. However, partially hydrogenated fats contain trans-isomers of fatty acids, which are not nutritionally beneficial. Fats and oils are triesters of fatty acids and are called triglycerides or triacylglycerols (abbreviated as TAG). The fatty acids in a fatty glycerol may be the same or different, and may be saturated or unsaturated. The physical properties of a fatty glycerol depend on the fatty acid composition. Palmitate and partially hydrogenated fats contain a high amount of saturated fatty acids in the sn-2 position of the glycerol in comparison with vegetable oils such as soybean, sunflower and rapeseed oils. The localization of saturated fatty acids in the sn-2 position is responsible for the alerogenic effect of such acids, according to research (Renaud et al.: J, Kotr,. / 25. 229-237 (1995)). Their use as food should therefore be avoided. Considering the above, there is a need to develop new natural oils that have higher tenostat and also avoid the excess of saturated fatty acids in the sn-2 position of TAG. The invention therefore relates to sunflower oil, which is extracted from sunflower seeds, and: in which at least 12% of the fatty-glycerol species constituting the oil can be represented by the general formula SMS and at least 25% of the tri-glycerol species can be represented by the general formula SMM, and the formula, from left to right, gives the first, second and third fatty acids of the tri-glycerol, where S is a monounsaturated fatty acid and M is a monounsaturated fatty acid. Surprisingly, we found that the begonia type oil shows special thermostability and has a saturated fatty acid content of up to 8% at the TAG srt-2 position. The thermal stability of the oil according to the invention can be expressed in the amount of changed types of triglycerides (oxidized TAG monomer and polymerized TAG) after heat treatment at room temperature, in air, through a furnace. In the case of sunflower oil (IShEEÖ sunflower oil, Vanderhave), this value is 24.6%, in the case of high oleic sunflower oil (OLE, Cargill), this value is 21.2%, and in the oil according to the invention; In the case of 93563-3615 / SL _ ο „ this value varies between 1 1-17%. It follows that the thermostability of the oil according to the invention is significantly higher than that of oils known from the state of the art. EfoA-0 797 921 discloses a frying fat and oil derived from palm oil or a mixture of palm oils and: liquid vegetable oil. The triadiglycerin composition of the oil according to the invention differs significantly from the composition of oils known from the prior art, as can be seen from the examples. One type of oil according to the invention is extracted from the seeds of the mutant sunflower line KS-1297M, which seeds were deposited in the American Type Culture Collection (ATCC) on January 20, 1998 under the deposit number ATCC 209501, The invention is based on the recognition that in the case of oil containing a relatively high amount of SMS and SMM triacylglycerols, preferably at least 12% SMS and at least 25% SMM triacylglycerols, the advantageous low content of saturated fatty acids in the S-S position is accompanied by a high thermal stability. Such oil can be produced from other mutant sunflower lines, for example by irradiating dry seeds with a radiation dose of 300 cGy / cm (beam 200 kV, 18 mA'\ dose rate). A person skilled in the art can easily select an oil satisfying the characteristics of the invention by simply examining the LAG content, as described in the examples. The natural oil of the invention, which is extracted from sunflower seeds and can be used directly without further methods aimed at modifying the TAG content of the invention. Examples of such modification processes include the so-called "hardening" of the oil, which means hydrogenation of the double bonds in the oil. The oil of the invention can be produced without performing such artificial modification processes. The sunflower oil according to the invention also contains at least § % of triacylglycerols, which can be represented by the general formula MMM: It is further preferred that the oil according to the invention contains at most 8 % of saturated fatty acids in the sn-2 position of the triacylglycerols constituting the oil. The amount of saturated fatty acids is preferably at most 5 %, particularly preferably at most 3 %. The saturated fatty acids are generally stearic acid and palmitic acid. It is preferred that the oil of the invention contains a relatively high amount of palmitic acid relative to stearic acid, since in this case the oil is liquid at room temperature. In order to ensure optimal thermal stability, it is advantageous if the total amount of saturated fatty acids is at least 25%, particularly preferably at least 35%, especially 45% or more. It is also beneficial if the oil contains a high amount of oleic acid, as oleic acid is more stable than linoleic acid and has very good nutritional properties. - 3 furthermore, the oil additionally contains at most 15%, particularly preferably at most 10%, in particular at most 5% or less of Bftgísaw. Particularly preferred is a tntpraibrgóabj» whose pabnlitic acid content is at least 23% and oleic acid content is at least 52%. .A preferred embodiment of the invention is a sunflower oil:, where 20-2* % of the trsacli gbcenn. do-goson 2% 50«-3 can be represented by the general formula SMS nhahno», 45-55 preferably 51.9 % can be represented by the general formula SMM, and 20-25 %, •preferably® 22»? % can be represented by the general formula MhM. The market l-glycerol composition of oil extracted from the seeds of the lö-129?y sunflower line is 20 M POP, 11.1 % POPo, 0 % PoOPo, 2.7 % 'FOS, 37.9 % POO, <M % PoOÖ, 2,f % SOÖ, 11,8 % ÖÖO és 0,9 % ettől eltérő, ahol P jelentése palmitiosav, Po jelentése palmitöleinsav, O-jelentése oleiosav és S jelentése sztearinsav. The minimum and maximum amounts of different types of TAG species in oil according to the soil type are shown in Table I. S ~ saturated fatty acids (palmitic acid and stearic acid), M ~ monoenoic fatty acid (palm oleic acid and oleic acid) D ™ allene fatty acid (linoleic acid) In addition to the oil, the application also relates to sunflower seeds, such as IG-I297M seeds, which contain the oil according to the invention. The application also relates to the use of such seeds in the extraction of sunflower oil. The oil according to the invention: includes the extracted oil, The oil according to the invention is thermostable in the sense that it is more resistant to oxidation and polymerization of the types of fatty acids constituting the oil than the known sunflower oils. Consequently, the oil according to the invention is particularly suitable for use in frying at temperatures of at least 100°C, preferably 160-180°C. In the oil, frying is understood as the frying of foods such as meat, poultry, fish, fruits, vegetables and the like in oil and the frying of foods in oil while stirring, as well as the deep frying of doughs, fried foods and snacks. The oil according to the invention can be used for frying, toasting and cooking. In a more general sense, the invention relates to the use of an oil at high temperatures which contains up to 15% saturated fatty acids and up to 10%, preferably up to 5%, of linoleic acid. Examples of high temperature applications include frying and frying. The oil is preferably of vegetable origin, such as sunflower oil. The invention is not limited to the oil alone. The invention extends to the use of the oil in mixtures with other oils. The combined properties of the mixture may differ from the properties of the oil according to the invention. The oil is produced by extracting the oil-containing sunflower seeds. During the extraction of the seeds, flour is formed as a by-product. The application covers such flour. In addition, the application covers pressed sunflower seeds, which seeds contain the oil according to the invention before pressing. The invention is further illustrated by the following examples. In the examples: reference is made to Figure I, which compares the dimensional stability of different oils, Example 1; X&lálmánxsze^ The oil of the invention can be prepared from seeds of the deposited strain 1G-1297M' or from seeds prepared in other ways. One variant of the preparation of such seeds is illustrated in the following example. 5.degree.) dry seed is irradiated with 300 c / min of X-rays (radiation 20 kV, 18 mA'!, dose 161 Gy) using a Siemens Slabihpau (Bnlargeo, Germany), then the seeds are planted in spring: in dry soil. After self-pollination: the plants are collected individually, and the seeds are analyzed for fatty acid content according to Garcés and Manóba, Anah Bioehem,, 3 / / , 139--143 (1.993). Those seeds that show a saturated fatty acid content of at least three times the standard deviation of the given fatty acid are selected, and they are grown in series until the new characteristic stabilizes:, in this way several new mutant lines can be selected, The TAG-assembly can be further selected to produce the. 10-1297.M strain. 2, example: Otapez's robbery 1. Plant material ~ $ For the control of olm cRm!, mature seeds of the 1G-Í207M line (BPHÖ) according to the invention are used, which have a high palmitic acid content in a high oleic acid background. As control material, mature seeds of a normal sunflower line (normal), a high oleic acid sunflower line (Flö) (both Adv&nta, Marehena, Spain), and a high palmitic acid sunflower line (HA) (CAS-5, own breeding) are used, 2, Peptide extraction The seeds are ground, mixed with anhydrous sodium sulfate, and extracted with Soxhis extractant and petroleum jelly for 5-7 hours. Example 3; syllabus 1. TAG distribution in oil Purified TAG species from sunflower seeds according to the invention are prepared by passing a solution of 3 g of oil in 3 ml of petroleum ether over activated alumina at 20°C for 3 hours. 2 x 1.5 g of alumina are loaded into small columns, connected with a piece of silicone tubing, and the lipid solution is transferred to the packing and allowed to settle on the packing. The columns are washed with a further 6 ml of petroleum ether. The solvent is removed and the purified TAG content is stored under nitrogen at -20°C. The fatty acid components are extracted from the TAG sample by MPLC according to UFAC Standard Method 2432; (UFAC Standard Methods for the Analysis of Oils, Fats and Derivatives, Biaekweili;, Oxford, 7th edition (1987)). The total number of TAG files (Table 2) was determined by gas chromatography on the purified TAG sample, on a 4öö-é5HT-i5-0.iF capillary column (15 mm x 0.25 mm (Qnadrex, CH USA) with a film thickness of 0.1 µm, using hydrogen gas as the carrier, with FID detection. The fatty acid methyl ester derivatives of TAG are prepared by eluting 10 2 Figure 2A shows the TAG distribution of the HPFIO oil according to the invention, which shows significant differences from the control oils. Table 2B gives an overview of the different TAG types. The SMS and SMM content is significantly higher in the HPFIO oil according to the invention. ... 6 .. 2Α, table 1 \G Solar oil Standard HO HP HPHO PPoP 1.4 POP 3.2 21.8 POPo 11.1 PoOPo 1.5 PLP LO 27.5 PLPo 9.1 POS LO 2.7 POO 3.1 10.0 37.9 Pü u 3.7 PeOO 9.4 PÖt 7.6 1.0 12.3 PLL 6.4 $0 ·*? PoLL 3.5 soo 2.4 10.6 2.9 ooo 6.8 71.7 11.8 SOI'.. 5.4 OOL. 19.2 4.3 SLL 4.9 2.4 OLE 26.5 L0 4.0 Ili 15.1 5.1 Other 0.5 0.4 2.6 0.9 P ~ pabnitic acid 16:0 Pr> - paimítoHnacid shoot:: S = sialic acid 18:ö O-Otoic acid 18:1 L - Ht-tocopherol :8:2. In the table, only TAG types present in quantities greater than 1% are listed, the remainder are converted to other types. Table 2IL TAG Sunflower oil Normal HO HP HPHO SMS 1.9 4.6 24.5 S'MM 5.5 29.6 51.9 SAS 2.1 31.2 MMM ÓJ 71.7 22.7 SOM 13 1.0 21.4 MD.M 19.2: 4.3 SDD 11.3 27.6 MDD 26.5 KÖ 7.5 DDD 15.1 5.1 S::::saturated fatty acids (palmitic acid and stearic acid) M ” a»» fatty acid (palmitolenic acid and oleic acid) D ~ dionic fatty acid {Imolic acid) 2. Temperature stability The quality of the oil deteriorates upon heating, as the TAG content oxidizes and / or polymerizes. To test the thermostability, heat treatment is performed at 180-C and 1 hour as follows, The thermal oxidation treatment of the samples was carried out under strictly controlled conditions in a Katótol reactor (Metrohm tfd.., Herisan, Switzerland) according to Barrcra-Arelinö et al. Grasss Áceites 4Ö, 231-235 (1997). Briefly, 2 ± Ö.Ál g of purified TAG .mitot. was weighed into a standard glass tube (13 cm χ 1 cm) containing glycerol to accelerate heat transfer and placed in a cooling block previously heated to 1:80 ± 1T. At 2-hour intervals: 59 mg of the mixture was taken for analysis of polymerized TAG. In total: After 1 ö hour of treatment, the liquid sample was taken and the polar compounds (Table 3) and the distribution of oxidized TAG monomers and TAG polymers (Table 4) were examined. We strictly follow the Katómat regulations for cleaning the vessels and regulating the temperature. We do not introduce air during heating, and the vessels are left open. The polymerized TAG species in the various oils were analyzed by high-performance size exclusion chromatography (HPSPC) according to the above-cited I.UPAC Standard Method 2508: srlm. The total polar compounds and their distribution in the oxidized TAG monomers and TAG polymers were determined by a combination of absorption chromatography and GFSIsC (Dobarganes et al.: Fat Se!. Technol M 3®S-311 (1988) (Table 3)). . g . The conditions used in the HFSEC procedure are as follows; a Rebeodyne 77251 injector with a sample loop and a Waters 510 HPLC pump (Waters Associates, Milliord, MA, USA), two 100 A and 500 A bltrastymgel columns (Waters Associates, Milliord, MA, USA), connected in series and operating at 35°C, and a refractive index detector (Hewlett-Packard, CA, USA). The columns (25 cm x 0.77 cm) were loaded with porous, highly cross-linked silane / dichlorobenzene copolymers (< 10 g). HPLC-grade ethylenediaminetetraacetic acid was used as the mobile phase at a flow rate of 1 ml / min. The method used to analyze the distribution of polymerized IAG and polar compounds. solution. 1 ml of tetrahydrofuran contains 50 mg of oil and 15 mg of polar compound. Oil Polar compounds Total oxidized TAG Oxidized TAG monomer Oxidized TAG polymer Norms 24.6 9.7 14.9 HO 21.2 10.6 10.6 HP 21.1 O .12.2 HPHO 12.8 6.7 6.1 Table 4 shows the TAG composition of the 4 different oil types. The data were determined for the original oil (0 h) and for the oil heat-treated for 10 hours at 180°C (10 h). The oxide % data is the percentage of TAG changed during the 1:0 hour heat treatment, Table 4 Normal HO Oh 10 h ovid <%lj 0 h 10 h OXÍd (%) SMS ί SMM 5.5 5.1 : 7.4 20.ö 16.9 18.2 SDS MMM 63 6.1 9.8 71.7 56.9 2Ö.7 SOM 12.9 10.5 : 18.9 MŰM 19.2 14.7 i 23.3 4.3 2.5 42.7 SDÜ : 113 8.4 25.7 MDD : 26.5 18.1 31.6 DDD 15.1 9.0 40.3 Total 97.3 72.0 26.0* 96.7 76.3 ί 21.1* • 9 .· HP HFHO Oh 50 h oxsd iW 0 b 10 h oxide (%) SMS 4.6 1.3 8.9 25.4 22.3 12.1 : SM.M 51.8 45.7 Π .8 SDS 31.2 27.2 12.6 MMM 21.2 18.1 á ) SDM 12.3 10.. 2 17.0 MDM 9.1 7.7 15.0 SDD 27.5 19.4 i 29.4 MDD .......7.5....... 5.2 30.7 DDD SJ 2.9 i 43.6 Total 97.3 76.9 : 20.9* M 86.1 12.5* *: percentage of total oxidized and polymerized TAG. Table 5 shows the percentage of saturated fatty acids in the stt-2 composition of TAG oils. 5, table Oil Panthic acid Stearic acid Total Normal 0.8 0.6 ÍJ HO 0.8 0.5 U HP 1.3 0.5 1.8 HPHO r,4 0.8 0 0 Example 4: Comparison of thermal stability Our watches: The general method for determining the oxidation resistance is the Kaneimaí (Metrnhm, Hertsau, Switzerland). In this method, the results are expressed in terms of oxidation resistance at a given temperature: time (hours). In this example, two natural vegetable oils are compared, which are used for industrial frying, one is sunflower oil with a high oleic acid content (Figure 1, samples 1 and 2), the other is oil with a high palmitic acid content (Figure 1, samples 3 and 4), and these are compared with the HPRO oil according to the invention (Figure 1, samples 5 and 6). The heat treatment is carried out at a temperature of 100°C, the conductivity value is 288 pSfonn delta K. ~ 25 nS / ont. The results show that the HFRO oil according to the invention has the highest thermal conductivity. In the experiment: the point of reaching the delta K ~ 25 ttSfem is determined in two parallels (Figure 1). The average value of the high oil * - 8.6 hours for oil containing 10, 19.9 hours for oil containing high palmitic acid, and 30.4 hours for the HP.HO oil according to the invention.

Claims

1. Sunflower oil, which is extracted from sunflower seeds and in which the oil, at least 12% of the triacylglycerol varieties can be represented by the general formula SMS, and at least 25% of the triacylglycerol varieties can be represented by the general formula SMM, and at least 8% of the triacylglycerol varieties can be represented by the general formula MMM, where the formula from left to right gives the first, second and third fatty acids of the triacylglycerol, where S means saturated fatty acid and M means monounsaturated fatty acid, the seed can be obtained from the 1GO297M mutant sunflower line, which was deposited in the Ánveriosn Type Culture Celletion collection under the number ÁTCC 209591 on January 25, 1998, 2. Oil according to claim Ι, which contains up to 8% saturated fatty acids in the sn-2 position of the glycerol species constituting the oil, 3. Oil according to claim 1 or 2, which contains not more than 5% saturated fatty acids in the sn-2 position of the triglycerides constituting the oil, 4. An oil according to any one of claims 1-3, which contains up to 3% saturated fatty acids in the sn-2 position of the triacylglycerols constituting the oil.

5. The oil of claim 1 or 2, wherein the total saturated fatty acid content is at least 25%. The oil of claim 5, wherein the total saturated fatty acid content is at least 35%. 7, Ar 5. or 8. Oil according to claim 1, wherein the total fatty acid content is at least 45%.

8. Oil according to any one of claims 1-7, wherein the gallic acid content is at least 23-35% and the ©Time Band content is at least 52%.

9. Oil according to any one of claims 1-8, wherein 20-25%, preferably 24.5% of the triacylglycerol species are represented by the general formula SMS, 45-55%, preferably 51.9% are represented by the general formula SMM, and 20-25%, preferably 22.7% are represented by the general formula MMM.

19. Oil according to claim 9, wherein 21.8% of the triacylglycerol species are represented by the general formula MMM. POF, 11.1% POPo, 1.5% PoOPo, 2.7% FOS, 37.9% POÖ, 9.4% PoOO, 2.9800, 1.8% OOO and 0.9% other, where P is palmitic acid, P© is palmitic acid, O is oleic acid and S is stearic acid.

11. The oil according to any one of claims 1-1.0, which is extracted and can be used at high temperatures.

12. The oil of claim 11, wherein the high temperature application is frying in oil at a temperature of at least 190°C.

13. The oil of claim 11, wherein the high temperature application is frying.

14. The oil of claim 11, wherein the high temperature application is frying.

15. The oil of claim 11, wherein the high temperature application is frying.

11. The sunflower oil of claim 11, wherein the high temperature application is heating at a temperature of at least 100°C.

12. A mixture comprising at least in part an oil according to any one of claims 1-15. It. Plants from mutant sunflower line strains, wherein the mutant sunflower line is 1G-1297M, which was deposited in the American Type Culture Collection on January 29, 1998 under the number ATCC 299591, which plants contain the oil-containing seeds according to any one of claims 11 to 19. 19.Use of an oil according to any one of claims 1 to 10, which contains at least 15% saturated fatty acids and at most 19%, preferably at most 5%, of monounsaturated fatty acids, at high temperatures.

29. Use according to claim 19, wherein the high temperature is frying, sautéing, browning or cooking in oil.