In order to improve the life and stability of food, pharmaceuticals, cosmetics, and personal care products reduction agents are added to these products, which prevent their non-enzymatic oxidation as well as any undesired formation of aromas resulting therefrom. Ascorbic acid is widely used as a reduction agent, with its use being aggravated in that it is insufficiently stable in aqueous solutions. For example, in an aqueous ascorbic acid solution only approximately 70% of the added ascorbic acid is present after 30 days.
An increased stability of the reduction agent in aqueous solutions is achieved by derivation of the antioxidants. Here, for example, sodium ascorbic phosphate or ascorbylpalmitate are frequently used. Although the content of these agents remains constant in an aqueous solution over an extended period of time, however, the ascorbic acid derivatives are several times more expenses than pure ascorbic acid. Furthermore, in higher concentrations the ascorbic acid derivatives tend to crystallize and lead to a discoloration of the final product.
Additionally, the above-mentioned reduction agents show an insufficient effectiveness for preserving fatty substances due to their solubility in the fats and oils used in the above-mentioned products being too low. The reduction agent adheres to the exterior of the fat droplets and cannot develop its antioxidative effect on the interior of the fatty mixtures.
The document EP 1338271 A1 describes a fat and water soluble solubilisate with ascorbic acid, comprising polysorbate 80, which renders ascorbic acid fat-soluble. By adding a triglyceride the stability of the solubilisate is increased. Additionally, in this document the combined use of ascorbic acid and tocopherol-solubilisates is discussed, in which the mixed solubilisate is included in a portion of 3% ascorbic acid and 7% tocopherol. In the patent DE 19647352 C2 a water-soluble solubilisate of the fat-soluble reducer ubichinon Q10 is described with the help of the solving agent polyoxyethylene-sorbitane monooleate (polysorbate 80), which can be vitaminized by the addition of vitamin E, which is also fat-soluble.
The invention is based on the object to provide a reduction agent in an easily mixable liquid, aqueous or fat-soluble form, which is suitable for preserving fatty foods. It shall be very stable over many months in high concentrations.
This object is attained according to the invention in a solubilisate, comprising an aqueous solution of alkali and/or earth-alkali salts of the ascorbic acid for foods, cosmetics, and the like and an emulsifier with an HLB-value from 9 to 18, for example polysorbate or cremophore. The alkali and/or earth alkali salts of ascorbic acid are particularly well suitable based on non-acidic features in an aqueous environment for attaining the above-mentioned object, particularly for such uses (e.g., ointments) in which a slightly acrid effect of the ascorbic acid is undesired. The solubilisate is clear and almost gelatinous at room temperature, can be thinned with water without becoming turbid and can easily be mixed, when heated to approximately 35° C. in aqueous as well as fatty end products of the cosmetics or food sector, primarily sausage or meat products of all sorts, without any additional processing steps. From professional literature the use of sodium-L-ascorbate in a crystalline form is known as an additive for the production of sausage and ham.
Therefore, preferably alkali and/or earth alkali salts of sodium-L-ascorbate are used, which are contained in the solubilisate, beneficially at a concentration from approximately 9% by weight to approximately 11% by weight. It is further beneficial to add one or more mid-chain triglycerides to the solubilisate at a concentration of preferably approximately 8% by weight to approximately 11% by weight, with the triglycerides beneficially containing octanoic acid and/or decanoic acid. The solubilisate may contain, instead of triglycerides, one or more vegetable oils, such as for example safflower oil, rape-seed oil, soy bean oil, or sunflower-seed oil in essentially identical percentages. Further, it has shown advantageous when the solubilisate contains one or more tocopherols or a tocopherol-mixture and/or derivatives therefrom, such as for example the acetate of the tocopherol, beneficially as a vitamin-E-acetate at a concentration from approximately 9% by weight to approximately 11% by weight.
The solubilisate according to the invention may contain a non-ionic emulsifier, properly licensed in the respective country for the food purpose according to the invention. Particularly beneficial are those with a HLB-value ranging from 9 to 18, because they lead to optically clear end products. Therefore, in many European countries a polysorbate may be used, preferably polysorbate 80 or polysorbate 20, having a HLB-value of 15, and a sufficient amount of hydrophilic and hydrophobic groups. The percentage of polysorbate in the solubilisate according to the invention ranges beneficially from approximately 50% by weight to approximately 70% by weight.
The production method according to the invention for the solubilisate mentioned is characterized in that the alkali and/or earth alkali salt of the ascorbic acid, beneficially sodium-L-ascorbate, is dissolved in warm water, preferably at a temperature from approximately 60° C. to approximately 85° C., with an emulsifier having a HLB-value ranging from 9 to 18 being added to the solution when warm and agitated until clear. It is beneficial to dissolve one or more mid-chain triglycerides in the warm solution, containing for example octanoic acid and/or decanoic acid, and then to add and agitate the emulsifier, beneficially a polysorbate such as, for example, polysorbate 80 or polysorbate 20. Instead of triglycerides tocopherols or derivatives therefrom, such as for example tocopherol acetate, may also be added to and agitated in the solution. Further, one or more vegetable oils may also be used instead of the mid-chain triglycerides, such as for example safflower oil, rape-seed oil, soy bean oil, or sunflower-seed oil.
The solubilisate according to the invention may also be used as an additive to foods, primarily meat and sausage products of all types, for preserving oils, fats, emulsions, as well as drugs.
It is well known that ascorbate oxidize relatively easily. Based on this characteristic, a further development of the invention improves the life of alkali and/or earth alkali salts by the solubilisate micelles each being additionally provided with one or more tocopherols or a tocopherol mixture. Each solubilisate micelle then contains both the ascorbate as well as the tocopherol and/or a mixture of individual ascorbate and tocopherol micelles.
For the above-mentioned solubilisates, for example, the alkali salt sodium-L-ascorbate can be used as the base, which primarily ensures the color stability of meat and sausage products. In the solubilisate α-tocopherol, tocopherol derivatives, and/or tocopherol-mixtures can be used as tocopherols.
The sodium-L-ascorbate content of the formulation according to the invention, which may amount up to 11% by weight, remains practically free from loss over months. The vitamin E-acetate content in the solubilisate amounts to approximately 10% by weight. The polysorbate content beneficially amounts to approximately 69% by weight.
The sodium-L-ascorbate/vitamin E-acetate-solubilisate according to the invention can easily be added to foods, drugs, cosmetics (skin and hair care products) with the consequence that the integrity of these products is considerably increased. The polysorbate content of the solution according to the invention develops a type of retard function for the anti-oxidative features of ascorbic acid as well as the tocopherol, if applicable, for the easily oxidating contents of pharmaceutical formulations and foods. This way the desired protective function is maintained over a considerably longer period of time.
A method for producing the solubilisate according to the invention provides that alkali and/or earth alkali salts of the ascorbic acid are dissolved in warm water and an emulsifier with a HLB-value ranging from 9 to 18 is added while heated, preferably a polysorbate, and agitated until clear. It is useful to add the emulsifier polysorbate 20 and/or polysorbate 80 at a temperature of approximately 70 to 75° C., and to heat the mixture under agitation for some minutes until clear and homogenous. Spherical micelles develop when the emulsifier is added.
In a further development of the invention tocopherol oil is added to the aqueous solution of alkali and/or earth alkali salts of the ascorbic acid at a temperature of approximately 85° C., which leads to the formation of an emulsion. Subsequently the emulsifier polysorbate 20 is added at a temperature of approximately 85° C. The mixture is held for some minutes under agitation at the temperature listed until clear and homogenous. Spherical micelles develop when the emulsifier is added, in which both the ascorbate as well as vitamin E molecules are enclosed. Instead of tocopherol or additionally thereto an addition of mid-chain triglycerides may also be considered, such as liquid vegetable oil.
While the polysorbate molecules, at the beginning of the micelle formation, attach at the surface, the vitamin E-molecules associate to the hydrophobic areas of the emulsifier molecules. After exceeding the critical concentration of the micelle formation spherical micelles begin to form from the aggregate surfaces, with an aqueous compartment with dissolved alkali and/or earth alkali salts of the ascorbic acid being enclosed in their interior. In an aqueous environment the micelles are structurally provided with a double-walled shell of radially arranged polysorbate molecules. Here, the polysorbate molecules of the interior shell enclose with their hydrophilic section the polysorbate molecules the interior compartment with the enclosed alkali and/or earth alkali salt solution of the ascorbic acid and the hydrophilic sections of the polysorbate molecules of the exterior shell align towards the exterior. The vitamin E is associated to the hydrophobic section of the polysorbate molecule. The anti-oxidants are therefore micelles together in the solubilisate. Due to the fact that the reduction agents enclosed in the micelles are released only with a delay the anti-oxidative effect of the solubilisate remains effective in the agents mentioned for a longer period of time than, for example, when added alone to the ascorbylpalmitate, thus one of the ascorbic acid derivatives mentioned at the outset. Furthermore, the inclusion of the vitamin E, insoluble in water, in the micelle causes a distinct stabilization of the ascorbic acid, very easily decomposable as an enediol. By the joint implementation of the two reducers in the micelle the ascorbic acid is additionally protected from disintegration, leading to an increased stability thereof.
With regard to the use of the solubilisate according to the invention it is very advantageous that the water-soluble sodium ascorbate and the fat-soluble vitamin E are provided in the mixed micelles both in a water as well as a fat soluble form.
In order to allow a longer shelf life of the formulation the addition of one or more mid-chain triglycerides or vegetable oils to the solubilisate is advantageous, such as for example safflower oil, its concentration should approximately amount from 10 to 11% by weight, which reliably prevents the precipitation of parts of the reduction agent.
In food the inclusion of anti-oxidative effective substances in micelles prevents by the emulsifier that in oral application of the solubilisate according to the invention the ascorbic acid and/or the vitamin E already develops its effect already in the middle of the intestinal tract, i.e. in the stomach and the duodenum, and is hereby consumed. Rather, the above-mentioned micelled effective agents are rather not absorbed until they reach the small intestines (without the participation of bile acid, bile salts, and enzymes several times better in quality.)
The following examples illustrate the invention.
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For the above-listed exemplary applications of the invention the qualitative statements concerning the material used are irrelevant, only the ratios of this data. For example, 5750 g water can be used as the original material and accordingly the 50-fold higher values of the materials mentioned can be added in order to yield the same result. Instead of polysorbates, within the scope of the invention, cremophores of the series RH 40, A 6, A 25, EL may also be used, with their HLB-values ranging from 10 to 17.
Number | Date | Country | Kind |
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10 2004 051 245.0 | Oct 2004 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP05/04993 | 5/9/2005 | WO | 00 | 4/17/2007 |