REZNIK RENA (IL)
| WO2005011390A1 | 2005-02-10 | |||
| WO2005019397A1 | 2005-03-03 | |||
| WO2000039248A1 | 2000-07-06 |
| US20030026887A1 | 2003-02-06 | |||
| US5084289A | 1992-01-28 |
DATABASE WPI Week 200761, Derwent World Patents Index; AN 2007-644267, XP002504395
P.D. DUH: "Antioxidant Activity of Water Extract of Four Harng Jyur (Chrysanthemum Morifolium Ramat) Varieties in Soybean Oil Emulsion", FOOD CHEMISTRY, vol. 66, 1999, pages 471 - 476, XP002504391
K. SCHWARZ, S.W. HUANG, J.B. GERMAN, B. TIERSCH, J. HARTMANN, E.N. FRANKEL: "Activities of Antioxidants are Affected by Colloidal Properties of Oil-in-Water and Water-in-Oil Emulsions and Bulk Oils", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 48, 2000, pages 4874 - 4882, XP002504392
HERSCHOWITZ B., REZNIK R., IOUDKEVITCH C., SEGAL R.: "Synergetic Action of Herbal Extracts on Antioxidative Capacity of Lupine Protein Derivates", THE ANNALS OF THE UNIVERSITY DUNAREA DE JOS OF GALATI, 2003, Romania, pages 28 - 32, XP002504393, Retrieved from the Internet
CLAIMS
1. A water-in-oil antioxidant composition comprising (i) water; (ii) at least one water-soluble antioxidant; (iii) at least one oil soluble and water insoluble emulsifier; and
(iv) oil.
2. A water-in-oil antioxidant composition according to claim 1 wherein said composition comprises at least 20% w/w water.
3. A water-in-oil antioxidant composition according to claim 2 wherein said composition comprises from about 20% to about 30% (w/w) water.
4. A water-in-oil antioxidant composition according to claim 1 wherein said at least one water soluble antioxidant is selected from the group consisting of ascorbic acid, citric acid, L-ascorbate (Vitamin C), erythrobic acid, lactic acid, ellagitannin, chlorogenic acid, anthocyanin, water soluble antioxidant herb or plant extract and combinations thereof. 5. A water-in-oil antioxidant composition according to claim 1 wherein said water- in-oil antioxidant composition comprises from about 5% to about 40% w/w water-soluble antioxidant.
6. A water-in-oil antioxidant composition according to claim 5 wherein said water- in-oil antioxidant composition comprises from about 5% to about 40% w/w water-soluble antioxidant.
7. A water-in-oil antioxidant composition according to claim 4 wherein said water soluble antioxidant is ascorbic acid.
8. A water-in-oil antioxidant composition according to claim 7 wherein said composition comprises from about 10% to about 30% w/w ascorbic acid. 9. A water-in-oil antioxidant composition according to claim 4 wherein said composition comprises a combination of ascorbic acid and a water soluble antioxidant herb extract.
10. A water-in-oil antioxidant composition according to claim 9 wherein said herb extract is selected from the group consisting of basil, lemon balm {Melissa officinalis), mint, rosemary, sage, savory, marjoram, oregano, thyme, lavender, and perilla extracts, and combinations thereof.
11. A water-in-oil antioxidant composition according to claim 10 wherein said water soluble antioxidant extract is a lemon balm (Melissa officinalis) extract.
12. A water-in-oil antioxidant composition according to any of claims 9-11 wherein said water soluble antioxidant herb extract is present at a concentration of from about 0.1 % to about 10% w/w.
13. A water-in-oil antioxidant composition according to claim 12 wherein said water soluble antioxidant herb extract is present at a concentration of from about 0.5% to about 5% w/w.
14. A water-in-oil antioxidant composition according to claim 13 wherein said water soluble antioxidant herb extract is present at a concentration of about 0.5% w/w.
15. A water-in-oil antioxidant composition according to claim 13 wherein said water soluble antioxidant herb extract is present at a concentration of about 5% w/w.
16. A water-in-oil antioxidant composition according to claim 1 wherein said composition comprises from about 0.5% to about 30% w/w oil soluble and water insoluble emulsifier.
17. A water-in-oil antioxidant composition according to claim 16 wherein said composition comprises from about 2% to about 20% w/w oil soluble and water insoluble emulsifier.
18. A water-in-oil antioxidant composition according to claim 1 wherein said at least one oil soluble and water insoluble emulsifier is selected from the group consisting of mono and di glycerides, glycerol, Tween® 40, Tween® 80, Span 80, Polyglycerol Polyricinoleate (PGPR), lecithin, propylene glycol, linoleic acid and combinations thereof.
19. A water-in-oil antioxidant composition according to claim 18 wherein said at least one oil soluble and water insoluble emulsifier is a mono or diglycerid.
20. A water-in-oil antioxidant composition according to claim 18 wherein said at least one oil soluble and water insoluble emulsifier is Polyglycerol Polyricinoleate (PGPR).
21. A water-in-oil antioxidant composition according to claim 20 wherein said composition comprises from about 2% to about 15% w/w PGPR.
22. A water-in-oil antioxidant composition according to claim 18 wherein said at least one oil soluble and water insoluble emulsifier is a combination of Polyglycerol Polyricinoleate (PGPR) and Span 80.
23. A water-in-oil antioxidant composition according to claim 22 wherein said composition comprises about 2% w/w PGPR and from about 0.1% to about 2% w/w Span
80.
24. A water-in-oil antioxidant composition according to claim 1 wherein said oil is selected from animal fat and plant oil.
25. A water-in-oil antioxidant composition according to claim 24 wherein said plant oil is selected from the group consisting of palm oil, olive oil, soybean oil, canola oil, pumpkin seed oil, corn oil, sunflower oil, safflower oil, peanut oil, grape seed oil, sesame oil, argan oil, rice bran oil, and combinations thereof.
26. A water-in-oil antioxidant composition according to any of claims 24 or 25 wherein said composition comprises from about 10% to about 60% (w/w) oil. 27. A water-in-oil antioxidant composition according to claim 25 wherein said oil is canola oil.
28. A water-in-oil antioxidant composition according to claim 27 wherein said composition comprises from about 15% to about 41% (w/w) canola oil.
29. A water-in-oil antioxidant composition according to any of claims 1-28 additionally comprising at least one fat soluble antioxidant.
30. A water-in-oil antioxidant composition according to claim 29 wherein said fat soluble antioxidant is selected from the group consisting of tocopherols, tocotrienols, retinol, rosemary oil, ascorbyl-palmitate and combinations thereof.
31. A water-in-oil antioxidant composition according to claim 29 wherein said composition comprises from about 5% to about 35% w/w fat-soluble antioxidant.
32. A water-in-oil antioxidant composition according to claim 30 wherein said fat soluble antioxidant are tocopherols.
33. A water-in-oil antioxidant composition according to claim 32 wherein said tocopherols are Natural Mixed Tocopherols 50% or 70%.
34. A water-in-oil antioxidant composition according to claim 33 wherein said composition comprises Natural Mixed Tocopherols 50% at a concentration of about 20% to about 30 % w/w.
35. A method of inhibiting oxidation of fats and oils comprising adding to said fats and oils an antioxidant effective amount of a water-in-oil antioxidant composition according to any of claims 1- 34.
36. Use of the water-in-oil antioxidant composition according to any of claims 1- 34 as an additive to fats and oils, for inhibiting oxidation thereof.
37. The method of claim 35 or use of claim 36 wherein the fats and oils are of plant or animal origin.
38. The method of claim 35 or use of claim 36 wherein the oils are essential oils.
39. The method of claim 35 or use of claim 36 wherein the fats and oils are cooking and frying oils.
40. Fried products, wherein said fried products were fried in oil comprising the water- in-oil antioxidant composition of claims 1-34.
41. Baked products, wherein said baked products were baked using oil comprising the water-in-oil antioxidant composition of claims 1-34. |
COMPOSITION FOR PROTECTING OILS AND FATS
FIELD OF THE INVENTION
The present invention relates to the field of protecting oils and fatty substances. In particular, the invention relates to compositions and methods for improving the stability and quality of cooking oils, specifically oils for frying and baking foods.
BACKGROUND
Cooking or frying at elevated temperatures (normally carried out at 100-250 0 C) is a complex process during which simultaneous heat and mass transfer take place.
During the frying process a variety of chemical reactions occur that cause progressive deterioration of the frying medium (i.e. oxidation, hydrolysis and/or polymerization) and the quality, nutritional profile and cooking performance of the oil quickly diminishes.
Certain compositions and methods for protecting oils and fatty substances have been previously described, for example:
US Published Application No. 20030026887 discloses water-in-oil emulsions as additive for frying or boiling fat, wherein the water-in-oil emulsion includes antioxidants in combination with water soluble carboxylic acids. The amount of oil (fat) in the emulsion is in the range of 70-90% weight. The emulsion preferably comprises one or more water soluble carboxylic acids (for example citric acid) in an amount of approximately 0.5-4% weight, and one or more antioxidation agents (antioxidants), for example tocopherol extract and/or ascorbyl palmitate, in an amount of about 0.1-1% weight.
PCT Publication No WO 03/082021 discloses a process for stabilizing hot cooking oil, comprising periodically introducing into hot cooking oil an aqueous composition comprising at least one antioxidant. Typically, the composition can be prepared by mixing an antioxidant and water-soluble or water-dispersible emulsifϊer in water. The aqueous composition does not comprise oil as one of its components.
US Patent No. 5,084,289 discloses a method for inhibiting the oxidation of edible oils and fats by admixing an aqueous solution containing a water-soluble antioxidant and
a surfactant with the oils or fats. The aqueous composition does not comprise oil as one of its components.
SUMMARY OF THE INVENTION The present invention provides compositions and methods for improving the stability and quality of oils, fat and fatty substances.
The composition of the invention comprises an antioxidant water-in-oil emulsion having exceptionally high water content.
Accordingly, in a first of its aspects the present invention provides a water-in-oil antioxidant composition comprising: (i) water; (ii) at least one water-soluble antioxidant; (iii) at least one oil-soluble and water insoluble emulsifier; and (iv) oil.
According to one embodiment, said water-in-oil antioxidant composition comprises at least 20% weight per weight (w/w) water. In another embodiment said water-in-oil antioxidant composition comprises from about 20% to about 30% (w/w) water. In another embodiment said water-in-oil antioxidant composition comprises from about 24% to about 28% (w/w) water.
The water-in-oil antioxidant composition may further include glycerol and/or propylene glycol.
According to one embodiment, said at least one water soluble antioxidant in the water-in-oil antioxidant composition of the invention is selected from the group consisting of ascorbic acid, citric acid, L-ascorbate (Vitamin C), erythrobic acid, lactic acid, ellagitannin, chlorogenic acid, anthocyanin, water soluble antioxidant herb or plant extract and combinations thereof.
According to one embodiment, said water-in-oil antioxidant composition comprises from about 5% to about 40% w/w water-soluble antioxidant. According to another embodiment said water-in-oil antioxidant composition comprises from about 10% to about 30% w/w water-soluble antioxidant.
According to one specific embodiment, said at least one water-soluble antioxidant is ascorbic acid.
According to another specific embodiment, said water-in-oil antioxidant composition comprises as water-soluble antioxidants a combination of ascorbic acid and a water soluble antioxidant herb extract.
In one embodiment, said herb is selected from the group consisting of basil, lemon balm (Melissa officinalis), mint, rosemary, sage, savory, marjoram, oregano, thyme, lavender, perilla extracts, and combinations thereof.
In one embodiment, said water soluble antioxidant herb extract is present at a concentration of from about 0.1% to about 10% w/w, more preferably from about 0.5% to about 5%. In one specific embodiment, said water-soluble antioxidant herb extract is a lemon balm (Melissa officinalis) extract. In one embodiment, said lemon balm extract is present at a concentration of about 0.5% w/w, or about 1% w/w or about 5% w/w.
According to one embodiment, the water-in-oil antioxidant composition of the invention comprises from about 10% to about 30% w/w ascorbic acid. In another embodiment the water-in-oil antioxidant composition of the invention comprises from about 15% to about 28% w/w ascorbic acid.
According to one embodiment, said at least one oil soluble and water insoluble emulsifier in the water-in-oil antioxidant composition of the invention is selected from the group consisting of mono and di glycerides, glycerol, Tween® 40, Tween® 80, Span 80, Polyglycerol Polyricinoleate (PGPR), lecithin, propylene glycol, linoleic acid and combinations thereof.
According to one embodiment, the water-in-oil antioxidant composition of the invention comprises from about 0.5% to about 30% w/w emulsifier. In another specific embodiment, the water-in-oil antioxidant composition of the invention comprises from about 2% to about 20% w/w emulsifier.
According to one specific embodiment, said at least one oil-soluble and water insoluble emulsifier is a mono or di-glycerid.
According to another specific embodiment, said at least one oil-soluble and water insoluble emulsifier is Polyglycerol Polyricinoleate (PGPR). According to one embodiment, the water-in-oil antioxidant composition of the invention comprises from about 2% to about 15% w/w PGPR. In another embodiment,
the water-in-oil antioxidant composition comprises a combination of PGPR and Span 80. In one embodiment, the water-in-oil antioxidant composition comprises about 2% w/w PGPR and from about 0.1% to about 2% w/w Span 80.
According to one embodiment, said oil in the water-in-oil antioxidant composition of the invention is animal fat or plant oil. hi one embodiment, said plant oil is selected from the group consisting of palm oil, olive oil, soybean oil, canola oil, pumpkin seed oil, corn oil, sunflower oil, peanut oil, grape seed oil, sesame oil, argan oil, rice bran oil, and combinations thereof.
In another embodiment said water-in-oil antioxidant composition comprises from about 10% to about 60% (w/w) oil. In another embodiment said water-in-oil antioxidant composition comprises from about 15% to about 50% (w/w) oil.
In one embodiment, said water-in-oil antioxidant composition comprises canola oil. hi one specific embodiment, said water-in-oil antioxidant composition comprises from about 15% to about 41% (w/w) canola oil. According to another embodiment the composition of the invention additionally comprises at least one fat-soluble antioxidant.
According to certain embodiments said fat-soluble antioxidant is selected from the group consisting of tocopherols, tocotrienols, retinol, rosemary oil, ascorbyl-palmitate and combinations thereof. According to one embodiment, said water-in-oil antioxidant composition comprises from about 5% to about 35% w/w fat-soluble antioxidant.
In one specific embodiment, said fat-soluble antioxidants are tocopherols. Non- limiting examples of such tocopherols are Natural Mixed Tocopherols 50% or Natural Mixed Tocopherols 70%. hi one embodiment, said water-in-oil antioxidant composition comprises Natural
Mixed Tocopherols 50% at a concentration of about 20% to about 30 % w/w.
By another of its aspects the present invention provides a method of inhibiting oxidation and enhancing the stability and quality of fats and oils that comprises adding to said fats or oils an antioxidant effective amount of the water-in-oil antioxidant composition of the invention.
By yet another of its aspects the present invention provides use of the water-in-oil antioxidant composition of the invention as an additive to fats and oils, in order to inhibit oxidation and enhance the stability and quality of fats and oils.
In accordance with the invention, said fats and oils may be of plant or animal origin.
In accordance with one specific embodiment, said oils are cooking or frying oils.
In accordance with another specific embodiment, said oils are essential oils.
In yet another aspect, the present invention provides fried products, wherein said fried products were fried in oil comprising the water-in-oil antioxidant composition of the invention. Said fried products include, for example fried potato chips and fried peanuts.
In yet another aspect, the present invention provides baked products, wherein said baked products were baked using oil comprising the water-in-oil antioxidant composition of the invention. Said baked products include, include for example crackers and waffles.
BRIRF DESCRIPTION OF THE FIGURES
Figure IA is a graph showing the amount of hexanal generated in Crown Waffles over time. The Crown Waffles were baked with oil containing either 0.03% OS-MX or 0.03% Rosemary oil (Herbalox™). Time is indicated as days after production in closed packaging. Figure IB is a graph showing the amount of aldehydes generated in Crackers over time. The Crackers were baked with oil containing either 150ppm (parts per million) OS-MX, 150ppm Rosemary oil (Herbalox™), or with no anti-oxidant (Control). Figure 2 is a graph showing the amount of hexanal generated in fried potato chips. The potato chips were fried in oil containing either 0.1% OS-A, 0.2% OS-A, or with no anti- oxidant (Control).
Figure 3 is a graph showing the amount of hexanal generated in fried peanuts after 15 and 30 days of accelerated conditions (storage at 60°C), as measured by HS-GC. 0.07% Origanox™ OS (OS-A) was dissolved in the frying oil. Control - no anti-oxidant added.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a water-in-oil antioxidant composition intended for use in protecting oils, fats and fatty substances. Within the context of the present invention, the terms "oils", "fats" and "fatty substances" are used interchangeably to denote any oil or fat which is liquid, solid or pasty at room temperature, whether it is of plant, animal, mineral or synthetic origin or whether it is used as it is or chemically modified, as well as any extract resulting from one of these fatty substances such as, for example, phytosterols, cholesterol, undecylenic acid or alternatively a mixture of a number of these compounds. The terms include edible fatty substances in a general sense, including but not limited to digestible and non- digestible fats, oils, and fat substitutes.
The essence of this novel water-in-oil antioxidant composition of the subject invention lies in the provision of water-in oil composition containing a relatively high load of water-soluble antioxidants and water.
The term "relatively high load" as used herein denotes that the load of the water soluble antioxidants in the composition is at least about 5% by weight and the load of water in the compositions is at least about 20% by weight.
As used herein the term "about" refers to a value of +/- 10% of the indicated number.
Without wishing to be bound by theory, it is believed that the efficiency of the water-in-oil antioxidant composition of the invention can be attributed to the high content of water soluble antioxidants and water, since most of the deteriorative / oxidative reactions that lead to progressive deterioration of fats and oils occur at the oil-water interface.
The water-in-oil antioxidant composition of the present invention can be used in protecting any oils, fats and fatty substances of plant, animal, mineral or synthetic origin. In one specific embodiment the oils are cooking and frying oils, including oils used in deep-frying. The terms "cooking oil" and "frying oil" are used interchangebly throughout this specification and should be understood to encompass any organic cooking media which is
liquid at cooking temperature (normally around 100-250 0 C) but may not be liquid at lower temperatures.
Frying oils decompose over time and use, due to the formation and acquisition of various contaminants during the cooking process. Soaps, polar compounds, polymers, free fatty acids (FFA), color bodies and trace metals are the major contaminants which contribute to oil degradation through increased instability. The cooking process and the accumulation of these contaminants also result in a visibly darker color of the oil that can be displeasing in appearance.
The exact formulation of the composition of the invention will vary depending on the type of oil, the use of the specific oil and the conditions (e.g. temperature, pattern of use, exposure pattern, duration of use) to which the specific oil is subjected.
The provision of a water-in-oil antioxidant composition of the subject invention is accomplished by combining (i) water; (ii) at least one water-soluble antioxidant; (iii) at least one oil-soluble and water insoluble emulsifϊer; and (iv) oil. Optionally, the water-in- oil antioxidant composition of the invention may further comprise at least one oil soluble antioxidant.
The water-in-oil antioxidant composition of the invention comprises water as one of the components of the novel composition. The water content is relatively high and the composition preferably comprises above 20% water. In one embodiment said water-in-oil antioxidant composition comprises from about 20% to about 30% (w/w) water. In another embodiment said water-in-oil antioxidant composition comprises from about 24% to about 28% (w/w) water.
The water-in-oil antioxidant composition of the invention also comprises at least one water-soluble antioxidant. The water-soluble antioxidant of the present invention can be any suitable antioxidant having a relatively good solubility in water. Examples of such water soluble antioxidants include, but are not limited to, ascorbic acid, citric acid, L- ascorbate (Vitamin C), erythrobic acid, lactic acid, ellagitannin, chlorogenic acid, anthocyanin, water soluble extract of plant origin (e.g. Labiate herb extracts), and combinations thereof. The term "relatively good solubility in water" should be understood to encompass solubility that is sufficiently high to load the desired amount of the antioxidant in the
water-in-oil antioxidant composition. The desired amount of the water soluble antioxidant follows from the required/desired load that needs to be present in order to obtain the desired antioxidant effect and is dependant on the type of the oil to be protected, the use of the specific oil and the conditions (e.g. temperature, pattern of use, exposure pattern, duration of use) to which the specific oil is subjected.
According to one embodiment, said water-in-oil antioxidant composition comprises from about 5% to about 40% w/w water-soluble antioxidant. According to another embodiment said water-in-oil antioxidant composition comprises from about 10% to about 30% w/w water-soluble antioxidant. In one specific embodiment of the present invention, the water-soluble antioxidant is ascorbic acid. In another specific embodiment of the present invention, the water soluble antioxidant is a combination of ascorbic acid and citric acid.
According to another specific embodiment, said water-in-oil antioxidant composition comprises as water-soluble antioxidants a combination of ascorbic acid and a water soluble antioxidant extract of plant origin.
The natural water soluble antioxidant extract of plant origin (also termed "herb extract"), may be, but is not limited to a Lamiaceae family or Labiatae family herb. An example of a water soluble extract of a Lamiaceae family or a Labiatae family of herbs as contemplated to be incorporated into the water-in-oil antioxidant composition of the present invention is described in WO 0039066 and the corresponding US patent No. 6,383,543 and in WO 0039248. Examples of herbs of a Lamiaceae family or a Labiatae family include, but are not limited to basil, lemon balm {Melissa officinalis), mint, rosemary, sage, savory, marjoram, oregano, thyme, lavender, perilla. Other plant origins include tea and grape seeds. In one embodiment of the subject invention, the natural water soluble antioxidant extract oϊ Ά Lamiaceae family or a Labiatae family of herbs is present in the novel water- in-oil antioxidant composition at about 0.1-10% by weight. In a specific embodiment of the subject invention, the natural water soluble antioxidant composition comprises a lemon balm {Melissa officinalis) extract. In one specific embodiment of the subject invention, natural water soluble antioxidant lemon balm {Melissa officinalis) extract is present in the water-in-oil antioxidant composition of the invention at about 0.1-10% by
weight. In another specific embodiment of the subject invention, natural water soluble antioxidant lemon balm {Melissa officinalis) extract is present in the water-in-oil antioxidant composition of the invention at about 0.5% by weight. In yet another specific embodiment of the subject invention, natural water soluble antioxidant lemon balm {Melissa officinalis) extract is present in the water-in-oil antioxidant composition of the invention at about 1% or about 5% by weight.
The water-in-oil antioxidant composition of the invention also comprises at least one oil-soluble and water insoluble emulsifier as one of the components of the novel composition. The at least one oil-soluble and water insoluble emulsifier of the subject invention can be any suitable emulsifier having a relatively good solubility in oil and relatively poor solubility in water. Examples of such emulsifiers include, but are not limited to mono and di glycerides, glycerol, Tween® 40 (Polyoxyethylene sorbitan mono-palmitate), Tween® 80 (Polyoxyethylene sorbitan monooleate), Span 80 (Sorbitan monooleate), Polyglycerol Polyricinoleate (PGPR), lecithin, propylene glycol, linoleic acid and combinations thereof.
The term "relatively good solubility in oil" should be understood to encompass solubility of the emulsifier between 0.5%-30% by weight.
The term "relatively poor solubility in water" should be understood to encompass solubility of the emulsifier that is lower than 1% by weight. In one embodiment of the subject invention, the emulsifier is present in the novel water-in-oil antioxidant composition at about 0.5% to about 30% but preferable at about 2 - 20 % by weight. In a specific embodiment of the subject invention, the emulsifier is Polyglycerol Polyricinoleate (PGPR). In one specific embodiment of the subject invention, PGPR is present in the water-in-oil antioxidant composition of the invention at about 2 - 15 % by weight, hi another specific embodiment of the subject invention, the emulsifier is a combination of Polyglycerol Polyricinoleate (PGPR) and Span 80.
In one specific embodiment of the subject invention, PGPR is present in the water-in-oil antioxidant composition of the invention at about 2 % by weight and Span 80 is present in the water-in-oil antioxidant composition of the invention at about 0.1 - 2 % by weight. In one specific embodiment of the present invention, PGPR is present in the
water-in-oil antioxidant composition of the invention at about 1-3% by weight and mono and diglycerids are present in about 0.5-2% by weight.
The water-in-oil antioxidant composition of the invention also comprises oil as one of the components of the novel composition. The oil can be any suitable animal fat or plant oil. Examples of such plant oils include, but are not limited to palm oil, olive oil, soybean oil, canola oil, pumpkin seed oil, corn oil, sunflower oil, safflower oil, peanut oil, grape seed oil, sesame oil, argan oil, rice bran oil and combinations thereof.
The term "suitable oil" should be understood as any oil that can be utilized successfully in the preparation of an emulsion. In one embodiment of the subject invention, oil is present in the novel water-in-oil antioxidant composition at about 10-60% by weight and preferably at about 15-50% by weight. In a specific embodiment of the subject invention, the oil is Canola oil. In one specific embodiment of the subject invention, Canola oil is present in the water-in-oil antioxidant composition of the invention at about 15 -41 % by weight. The water-in-oil antioxidant composition of the invention may also additionally contain as one of its components at least one fat soluble antioxidant. The at least one fat soluble antioxidant of the subject invention can be any suitable antioxidant having a relatively good solubility in oil and relatively poor solubility in water. Examples of such antioxidants include, but are not limited to tocopherols, tocotrienols, retinol, rosemary oil, ascorbyl-palmitate, and combinations thereof.
The term "Tocopherols " refers to a class of chemical compounds of which many have vitamin E activity, tocopherols are a series of organic compounds consisting of various methylated phenols. Tocopherols are fat-soluble antioxidants.
The term "relatively good solubility in oil" should be understood to encompass solubility of the antioxidant that is higher than 0.1% by weight.
The term "relatively poor solubility in water" should be understood to encompass solubility of the antioxidant that is lower than 0.1% by weight.
In one embodiment of the subject invention, the at least one fat soluble antioxidant is present in the novel water-in-oil antioxidant composition at about 5-35% by weight. In a specific embodiment of the subject invention, the fat soluble antioxidants are tocopherols. In one specific embodiment of the subject invention, the tocopherols are
Natural Mixed Tocopherols 50%. In a specific embodiment of the subject invention, Mixed Tocopherols 50% are present in the water-in-oil antioxidant composition of the invention at about 20 - 30 % by weight.
Another object of present invention is to provide a method of inhibiting oxidation of fats and oils, which comprises adding to said fats and oils an antioxidant effective amount of the water-in-oil antioxidant composition of the invention.
As used herein "inhibiting oxidation " also encompasses the consequences of such inhibition namely enhancement of the stability and quality of said fats and oils.
The water-in-oil antioxidant composition of the subject invention can be used in protecting any oils, fats, and fatty substances of plant, animal, mineral or synthetic origin. In one specific embodiment the oils are essential oils. In another specific embodiment the oils are cooking and frying oils.
By employment of the water-in-oil antioxidant composition the stability (usability) of a frying fat can be increased by a multiple (for example, extended at least by 1.5-fold as compared to the frying medium in the absence of the composition of the invention).
The term "antioxidant effective amount" refers to the amount of the composition which is sufficient to reduce the oxidation of a frying medium. The antioxidant effective amount may be determined using procedures well described in the art, for example, by the Oil Stability Index (OSI), an American Oil Chemists Society (AOCS) approved method Cd 12B-92. The OSI method determines the relative resistance of fat and oil samples to oxidation.
In practice, for stabilization of a frying medium, the quantity by weight of the water-in-oil antioxidant composition of the invention is added in amounts of 0.02% to 0.5% by weight of the frying medium.
The invention further provides a method of improving the quality of a fried product which comprises cooking the product in a frying medium that contains an antioxidant effective amount of the water-in-oil antioxidant composition of the invention.
The term "fried product" refers to fried food products such as for example fabricated crisps, tortillas, wheat thins, crackers, rice cakes, cereals, extruded snacks, potato chips, granola bars, etc. The fried food products may be sweet, salty, or savory.
The invention further provides a method of improving the quality of a baked product which comprises baking the product using oil that contains an antioxidant effective amount of the water-in-oil antioxidant composition of the invention.
The term "baked product" refers to baked food products such as for example, crackers, waffles, pretzels, biscuits, cookies, Bars.
In another embodiment, the water-in-oil antioxidant composition of the invention can be used as an additive to fats, oils and fatty substances, to inhibit oxidation and enhance the stability and quality thereof.
The subject invention encompasses a use of a water-in-oil antioxidant composition of the invention as an additive to essential oils.
The subject invention also provides a use of a water-in-oil antioxidant composition of the invention as an additive to cooking and frying oils, such as for example deep-frying oils.
The water-in-oil antioxidant compositions of the invention are characterized by being an emulsion, having a shelf life of about one year, having an off white/beige to yellow/brown color, and a tea like oily taste.
EXAMPLES
EXAMPLE 1 - Preparation of water-in-oil antioxidant compositions of the invention
Origanox ™ WS-LB is a water-soluble powder of natural extract from lemon balm, an edible herb species belonging to the Labiatae family, available from RAD Natural Technologies Ltd. (Israel), and having the following specifications:
Appearance: Golden powder, Agglomerated
Aroma and flavor: Extra mild, tea like flavor
Antioxidant activity: > 90 units (Standardized by an in-house method)
Total Plate Count: < 5000 CFU/g
E. CoIi Absent / Ig
Salmonella Absent / 25g Yeast and molds < 100 CFU/g
Solubility: Soluble in cold water Toxicity: Non toxic Shelf life 3 years when stored unopened according to specified conditions in original sealed packaging
The following formulations were prepared by mixing the aqueous phase (including water and water soluble components) with the oil phase, followed by homogenizing the mixture using a piston type homogenizer.
Formulation I:
Formulation II
Formulation III:
Formulation IV:
Formulation V:
Formulation VI:
In Formulations IV-VI, which include Tocopherols the Tocopherols were mixed with the Canola oil prior to mixing the oil component with the water and emulsifier.
EXAMPLE 2 - Antioxidant Activity of the Water-in-oil Compositions of the Invention
Antioxidant activity of Formulations I to VI was determined according to the Oil Stability Index (OSI), an American Oil Chemists Society (AOCS) approved method Cd 12B-92. The OSI method determines the relative resistance of fat and oil samples to oxidation.
OSI determinations were made in canola oil with Rancimat instrument at 12O 0 C and 20 liters/hours of air. The results are provided in Table 1.
Table 1
The results in Table 1 show that Formulations I- VI are effective in delaying oxidation. Natural antioxidants were employed for comparative purposes, i.e. Rosemary oil (4% carnosic acid) available from Kalsec (USA), under the trade name Herbalox™, and mixed Tocopherols.
The effect of Tocopherols was further investigated by adding Tocopherols to
Formulation I. As shown in Table 2 Formulation IV that contains tocopherols (in the oil before mixing with water and emulsifier) has a superior effect as compared to
Formulation I. Tocopherols has no effect when it is added separately to the Formulation
(Formulation I + tocopherols). Tocopherols alone (as well as Rosemary oil) have a lower activity than Formulation IV. These results suggest that mixing tocopherols in the oil component of the Formulation prior to mixing with the aqueous component affects the activity of the Formulation.
Table 2
EXAMPLE 3 - Inhibition of oxidation by Origanox™ OS-MX in a baked product
Origanox™ OS-MX is an anti-oxidant composition comprising the following components: 15% Ascorbic acid 1% Origanox WS-LB
10% Mix tocopherols (soy oil)
24% Water
10% PGPR
40% oil (vegetable oil)
Origanox™ OS-MX was added to the oil prior to mixing of the oil with water and flour. Two types of products, Crown waffles and crackers were then prepared according to conventional baking procedures.
The degree of oxidation in the baked products was determined by measuring the level of aldehydes that are generated upon decomposition of the oil and are thus used as an indication of the degree of the oxidation. Hexanal (an alkyl aldehyde) level was measured as shown in St. Angelo, et al (1980) Lipids 15, 45-49 using Headspace Gas chromatography (HS-GC). HS-GC is used for the analysis of volatiles and semi-volatile organics in solid, liquid, and gas samples. As shown in Figure 1, in both products Origanox™ OS-MX inhibits the formation of hexanal (Figure IA) and other aldehydes (off flavor, Figure IB) and therefore maintains the freshness longer.
EXAMPLE 4 - Use of Origanox™ OS-A in frying oil
Fried potato chips
Origanox™ OS-A is an anti-oxidant composition comprising the following components: 10% Ascorbic acid 5% Origanox WS- LB (Lemon balm extract) 20% water 15% PGPR 50% oil (Vegetable oil)
Origanox™ OS-A was added to oil used for frying potato chips. Origanox™ OS- A was used in the frying oil in order to increase shelf life and reduce rancidity of the fried potato chips.
Fried products may absorb around 30% of the frying oil, which is the main cause for rancidity development of the fried product.
As shown in Figure 2, addition of 0.1% or 0.2% of Origanox™ OS-A to the frying oil delayed oxidation of the potato chips (as measured by the Hexanal method) by 32% and 67% respectively.
Fried peanuts
0.07% Origanox™ OS-A was dissolved in the frying oil used for flying peanuts.
The level of oxidation of the peanuts was measured by the Hexanal method using HS- GC. The test was carried out at accelerated conditions, namely the peanuts were stored at 6O 0 C for 30 days.
As shown in Figure 3, after 15 days, the oxidation level (as measured by the
Hexanal method) of a Control set (control=no anti oxidant added to the oil) and of the peanuts fried with 0.07% Origanox™ OS-A was similar. However, after 30 days the oxidation level of the peanuts fried with Origanox™ OS-A was about 40% that of the control.