HU203467B - Process for producing stabilized powders of vitamins a, b, c, d or e - Google Patents

Abstract

A stabilised vitamin powder contains at least one of gliadin (I; a protein in gluten contg. mainly Glu and Pro, with mol. wt. 35000-45000) and glutenin (II; a protein in gluten of mol. wt. several millions). - The prod. contains 1-51wt. pts.: one or more vitamins per 100 wt. pts. (I) and/or (II). The vitamins can be (partly) clathrated and/or coated with (I) and/or (II).

Description

The present invention relates to a process for the preparation of stabilized vitamin P, B, C, Dv or E powders.

In recent years, vitamins have been widely used in food and animal nutrition. To facilitate handling in food and nutrition applications, fat soluble vitamins are emulsified with emulsifiers or dextrin and then dried by a suitable process for powdering. However, fat soluble vitamins tend to be degraded or altered by heat, light, oxygen and the like. Vitamin A, for example, is relatively stable to heat but very unstable to oxygen or light, so decomposes in the powdering step, making powdering very difficult. Other fat-soluble vitamins also tend to decompose or change their quality when exposed to heat during the pulverization process or when their air-contact surface is enlarged due to the larger surface area of the fine particles obtained during pulverization. It is therefore difficult to produce stable vitamin powders. On the other hand, water-soluble vitamins are generally used as crystalline powders and in most cases are more stable than fat-soluble vitamins in powder form. However, water-soluble vitamins undergo a quality change when they absorb moisture. thus, the problem arises when these vitamins are added to food or nutrition containing absorbed moisture; due to light, oxygen, heat and other effects, vitamins are prone to degradation or other degradation

To avoid this, stable vitamin powders are generally prepared by encapsulating the powdered vitamins in microcapsules (microcapsulation process) or by enclosing and pulverizing the vitamins in cyclodextrin (cyclodextrin process). Disadvantages of the microencapsulation process are the low productivity of the production process, the high production costs, other problems during storage, capsule breakage and the limited range of capsules suitable for use in food or nutrition. When using the cyclodextrin process, the ratio of the substance (s) to be closed and the cyclodextrin is so low that the resulting product has a low vitamin content. A further disadvantage is that the product has low water solubility and that the vitamins encapsulated in the cyclodextrin can be released from the cyclodextrin ring by heat or by the addition of water-containing substances.

Vitamin Bj is sometimes used to enrich the diet of fish. In this case, vitamin Bj is degraded by enzymes in the diet. Vitamin Bj is coated with hardened oil or fat to prevent enzymatic degradation. This solution is problematic because the hardened oil or fat coating impairs the effectiveness of vitamin absorption in fish.

Intensive studies of this state of the art have found that when gluten or gliadin and vitamins are added to a solvent, the mixture is stirred and then the solvent is removed from the mixture and the residue is pulverized to give a stable vitamin powder in which , and whose deterioration decreases.

The use of Gliadin is described in U.S. Patent 3,159,512. The described procedure consists of mixing flour and protein, then kneading the milk with milk to obtain a superfine dietary dough. Proteins that can be mixed with flour include gliadin. However, gliadin was not used in the preparation of vitamin products in any of the above patents or other processes.

The present invention relates to a process for the preparation of a stabilized vitamin powder comprising gliadin and vitamins.

The vitamin content of the vitamin products of the present invention is stabilized in the inclusion sites of gliadin structures or as a gliadin-coated form.

The vitamin powder contains 100 parts by weight of gliadin and 1 to 51 parts by weight of vitamin A. According to the invention, the vitamins may be enclosed in gliadin and / or coated with gliadin.

The stabilized vitamin powders according to the invention contain gliadin and vitamins, which are dissolved in gluten in a solvent to dissolve gliadin in gluten, the vitamins are added to the solution and the powder is removed to remove the solvent.

Alternatively, gliadin may be added to the solvent followed by the addition of vitamins to the solution and the solvent removed from the solution to form a powder.

According to the present invention, (1) a stabilized vitamin powder is prepared from glidain and vitamins;

(2) providing a composition in which the vitamins are incorporated in gliadin;

(3) providing a composition wherein at least a portion of the vitamins is covered by gliadin;

(4) adding vitamins to the solvent solution of gliadin with stirring and then removing the solvent by powdering the residue;

(5) adding gluten to the solvent with stirring, dissolving the gliadin from the gluten, adding vitamins to the solvent with stirring, removing the solvent, and powdering the residue;

(6) preparing the stabilized vitamin powder according to (4) to (5) above by dissolving or orally dispersing the vitamins in an oil or fat and adding it to the solvent;

(7) Figures 4-6. The preparation of stabilized vitamin powder formulations according to any one of claims 1 to 5 is carried out by using an aqueous alcohol containing 20-80% by volume of alcohol as the solvent.

The stabilized vitamin powders according to the invention contain gliadin and vitamins. It is believed that gliadin brings the vitamins into the hydrophobic region of the molecule and thus prevents the vitamins from contacting with oxygen, thereby preventing the degradation of the vitamins. Vitamins can be incorporated into or coated with gliadin, or the two conditions can coexist, that is, the vitamins are incorporated into gliadin and can also be coated. If the

As a gliadin coating, vitamins may be partially coated (for example, in reaction sites exposed to degradation reactions). Alternatively, not only may the vitamin particles be coated with a uniform film coating, but at least 5 of the particle surface may be coated with gliadin particles.

The vitamin powder of the present invention contains from 1 to 51 parts by weight of gliadin per 100 parts by weight of gliadin.

Gliadin is a protein composed mainly of glutamic acid and proline with an average molecular weight of 45,000 to 35,000. In the practice of the invention, gluten containing gliadin and glutenin is used in its original state. Gluten contains about 40% gliadin and 40% glutenin and about 20% starch. When water is added to gluten, it has a very high viscoelasticity, which is why gluten is used as a thickener, binder or water-binding agent in foods. Viscosity is generally attributed to gliadin and elasticity to glutenin.

According to the invention, the vitamin powders are prepared by adding gliadin and vitamins to a solvent and dissolving or dispersing therein with stirring, and then removing the solvent by powdering the residue; The gliadin is extracted with gluten or solvent, the insolubles are removed and the vitamins are added to the resulting solution with stirring, then the solvent is removed from the mixture and the residue is powdered. 30

Gluten is soluble in dilute acetic acid, in ammonia, in a mixture of acetic acid and in ethanol, and is soluble in, inter alia, aqueous alcohol, dilute acids and dilute alkalis. In view of this, when the gliadin in gluten is to be solubilized, aqueous alcohol is preferably used as the solvent, since the alcohol prevents the glutenin from swelling with water, thereby inhibiting the increase in viscosity and thus providing a better process efficiency.

The gluten may be wet gluten isolated from wheat flour or activated gluten obtained after drying. Activated gluten in the form of a dried powder is preferred for use.

The aqueous alcohol may be a mixture of from 20 to 80% by volume, preferably 6575% by volume of alcohol. The aqueous alcohol is used in a proportion of 3-6 parts by weight, preferably 4-5 45 parts by weight, based on 1 part by weight of gluten. Preferred alcohols are monohydric alcohols such as methanol, ethyl alcohol or isopropyl alcohol. When gluten is added to aqueous alcohol, the gliadin is extracted from gluten into aqueous alcohol 50. The mixing is preferably carried out using a high speed mixer for at least 30 minutes, during which time substantially all gliadin is extracted from the gluten into the aqueous alcohol.

After the addition of the vitamins to the gliadin solubilizing or dispersing solvent, the mixture is stirred. Stirring is carried out for 10 to 30 minutes or more, preferably 15 to 45 minutes, with stirring, for example, high speed homogenizing stirrer. The amount of vitamins used is preferably 0.05, 0.1-0.51 parts by weight per part by weight gliadin.

Fat soluble or water soluble vitamins may also be used in the practice of the invention. Vitamins A, B, C, D, and E, in free or ester form, may be used. These vitamins may be used singly or in combination of two or more vitamins.

Vitamins can be added in animal or vegetable oils or fats dissolved or dispersed form, thereby significantly reducing the contact between the vitamins and the water-soluble enzymes, thereby reducing the degradation action of the enzymes. In particular, the Bj vitamins should be added after dissolution or dispersion in animal or vegetable oils or fats. Suitable animal or vegetable oils or fats include, for example, liquid oils such as soybean oil, rapeseed oil and solid fats such as lard or palm fat.

When the vitamins are added to feeds, the digestible and absorbable fish oil is preferably used as a liquid oil. f.

If desired, an antioxidant may be added to the solvent of the present invention. The antioxidant.

its application further improves resistance to oxygen. In addition, if desired, the solution may be supplemented with milk?

such as citric acid or ethylenediaminetetraacetic acid; or other additives such as lecithin. it y

According to the process of the invention, after the addition and mixing of the vitamins, the solvent is removed and the residue is pulverized. Powdering is done->

weekly spray drying, vacuum drying, freeze drying, tumble dryer &

or other known drying methods. If &

with dilute acid, the pH is preferably adjusted to between 3 and 4. When dilute ammonia is used, the pH is preferably adjusted to 10-11. The vitamin is then added.

The vitamin powder produced by the process of the present invention is stable when stored in air or when added to water-containing foods, it does not change its quality, is not degraded by oxygen, by light or heat, by moisture absorption or by enzymes in food or nutrition. It is also advantageous for the powder to be added to food or nutrition in that it has a thickening and binding effect and retains water therein.

As shown above, the vitamin powder of the present invention rarely decomposes or changes its quality by absorbing moisture when added to food, by oxygen, heat, light or enzymes, and has good stability at high vitamin contents.

The vitamin powders of the present invention, when added to food, not only retain their good properties but also exhibit other properties such as thickening, binding and water-binding properties,

The process of the present invention provides a reliable preparation of vitamin powder with good properties. Gluten

It is relatively inexpensive to obtain gliadin from gluten, making it very cheap to obtain very stable vitamin powder.

Figure 1 shows the thermal stability of vitamin A powder prepared according to Example 1 and Comparative Example 1; Figure 2 shows the thermal stability of vitamin D powder prepared according to Example 2 and Comparative Example 2; Figure 3 shows the thermal stability of vitamin A powder prepared according to Example 6 and Comparative Example 6; the thermal stability of the vitamin A powder prepared according to Example 7 and Comparative Example 7 is shown.

The invention will now be illustrated by the following examples.

Example 1, Comparative Example 1 To a volume of 70% v / v aqueous ethanol was added 1 kg of activated gluten powder and the mixture was stirred for 30 minutes using a stirrer.

The aqueous alcohol mixed with activated gluten for 30 minutes is separated by precipitation (glutenin, starch, etc.) and solution by centrifugation for 20 minutes at 3000 rpm. The gliadin-containing solution is then evaporated to a concentration of 20% w / v gliadin in aqueous alcohol, followed by the addition of 45 g of vitamin A palmitate (150000 IU / g) per liter of aqueous alcohol, and stirred for 15 minutes with a homogenizer mixer, then dried and powdered in a vacuum dryer. Vitamin A powder (2) is thus obtained.

Vitamin A powder (Comparative sample) (5) is prepared by emulsifying vitamin A palmitate in dextrin followed by dehydration and powdering. Samples (2) and (5) are heated in a 50 ° C oven in an open system to test for vitamin A degradation over time. Our results are shown in Figure 1. The results show that the vitamin A sample produced by the process of the invention is significantly more stable than the vitamin A sample produced by the known process, i.e., only emulsified and then powdered.

Example 2, Comparative Example 2

0.6 g of crystalline vitamin D ₃ (40,000,000 IU / g) is dissolved in 45 g of soybean oil and added to 1 liter of gliadin aqueous ethanol obtained by removal of the aqueous ethanol insoluble material as described in Example 1 and having a gliadin concentration. 20% w / v. The mixture was then stirred under the same conditions as in Example 1 and the solvent was removed by spray drying to give the powder as vitamin D powder (1) prepared using gliadin-containing solution.

A reference sample is prepared by emulsifying vitamin Dj in soybean oil and then spray-drying to a concentration of Dyvitamin corresponding to that previously given in aqueous ethanol. The powder thus obtained is vitamin D powder. Vitamin D powders (1) and (3) are subjected to the heat treatment described in Example 1. Our results are shown in Figure 2. The results show that the D ₃ -vitaminpor produced according to the present invention produced stable than just the known emulsification and subsequent pulverization manner -vitaminpor D _3.

Example 3, Comparative Example 3 To an aqueous ethanol solution containing a volume of alcohol is added 1 kg of activated gluten powder and the mixture is stirred as described in Example 1. This dissolves gliadin from gluten. 20 g of ascorbic acid per liter of aqueous ethanol are added and stirring is continued and the solution is spray dried. Vitamin C powder (1) is thus obtained. This vitamin C powder (1) and the ascorbic acid crystal powder as a reference sample are used to make sausage (in which the concentration of ascorbic acid is 0.1% by weight based on the total weight).

Immediately after the preparation of the sausage, and after 3 weeks, the residual ascorbic acid content, yield, color development and elasticity of the product are examined.

Table I

It's done right away 3 weeks: after feeding Sample of the invention Residual ascorbic acid content (% by weight) 70 30 Yield (%) * 1 104 101 The color development of the products ♦ 2 good moderate Flexibility * 3 good moderate Comparative sample: Residual ascorbic acid content (% by weight) 10 0 Yield (% by weight) * 1 The color of the products 100 98 development * 2 moderate weak Flexibility * 3 moderate weak

* 1 Yield value indicates good or weak water retention of the product compared to freshly prepared comparative sausage.

* 2 The color development is also given in relation to the standard color of a freshly prepared sausage used as a reference sample.

The term "good" means a purer pink than the color of the reference sample, corresponding to the color of the meat.

The moderate mark indicates the level corresponding to the color of the reference sample.

A weak mark is a product that is discolored or stared at the comparison sample.

* 3 The definition of elasticity is as follows: the elasticity of the product prepared immediately after the preparation of the comparative example is denoted as moderate, the product with the higher elasticity is designated as good, and the weaker elasticity as weak.

HU 203 467 Β

As can be seen from the foregoing results, the vitamin C powder produced according to the invention exhibits only minor degradation of the vitamin C product and good color development due to the presence of vitamin C. In addition, such articles also have good water retention capacity and flexibility.

Example 4, Comparative Example 4

To the gluten-containing aqueous ethanol, prepared as in Example 1, was mixed with 10 g of thiamine cetyl sulfate dissolved and dispersed in 190 g of soy oil, and the mixture was stirred and dried in a vacuum dryer. The powder thus obtained (1) is designated as vitamin Bj. To 1 kg of melted shredded sardines is added 10 g of the above powder, and another sample is prepared from 1 kg of similar sardines by addition of 0.1 g of vitamin Bj. Each sample is stored for 5 hours at 15 ° C and the residual vitamin Bj content of the two samples is compared. Similar sardine samples with the same vitamin Bj content are heat treated with vitamin Bj digestive enzymes present in the sardine additive. and then cover the flour with 2 ° C saline corresponding to the seawater salt concentration. After 5 hours, the brine is filtered and the residual vitamin B1 is weighed in the remaining sardines. Our results are shown in Π. See Table 1.

II. Spreadsheet

Residual vitamin B1 content (% w / w) 5 hours 5 hours 15 'C-on saline Example 4 70 80 Comparative Example 4 0 5

Similar results are obtained when the gliadin solution dissolved from gluten is used separately to prepare a vitamin powder.

Example 5, Comparative Example 5 To 1 liter of aqueous ethanol containing 70% by volume of alcohol is added 1 kg of activated gluten powder and mixed as in Example 1. Subsequently, 45 g of vitamin E (total tocopherol content 80% by weight) are added and the mixture is stirred and then spray-dried. The powder thus obtained is vitamin E powder (1). The total tocopherol content of the vitamin E powder (1) is 16% by weight. This Evitamin powder (1) is mixed with 1% by weight of wheat flour and the flour is used to make dough. As a reference sample, a total emulsion of vitamin E emulsion containing 16% by weight of tocopherol was also mixed with 1% by weight of wheat flour and a dough made of flour. Cook both doughs and determine the amount of vitamin E remaining and the dough quality. Our results are shown in ΙΠ. See Table 1.

ΠΙ. Spreadsheet

Amount of residual vitamin E (% by weight) The quality of the pasta Example 5 90 solid, boiling stifled by boiling Comparative Example 5 60 moderate

As can be seen from the results in the table, the loss of vitamin E in pasta made with (1) Vitamin E powder is low during spinning. After cooking in this dough, the vitamin E content is high and the dough has good strength. In addition, the vitamin powder of the present invention is used to prevent puffiness of the dough during cooking.

A similar result is obtained when the gliadin solution dissolved from gluten is used separately to prepare a vitamin powder.

Example 6, Comparative Example 6 * To 1 liter of aqueous ethanol containing 70% by volume of alcohol is added 1 kg of activated gluten powder and the mixture is stirred for 30 minutes. The mixture is then centrifuged at 3000 rpm for 20 minutes to isolate the crude glutenin as an insoluble material and separate the aqueous alcohol supernatant containing the dissolved gliadin. The supernatant was concentrated to a concentration of 20% w / v gliadin. The resultant crude glutenin was washed three times with 70% v / v aqueous ethanol and then 70% v / v aqueous ethanol was added to the precipitate to reach a dry weight concentration of 20% v / v. Vitamin A acetate (170000 IU / g) was added to each aqueous ethanol solution to an amount of 20% w / v on a dry basis, and the mixture was stirred in a homogenizer for 10 minutes, then dried in a vacuum dryer, powder and sift the powder not exceeding 0.287 mm. This powder is subjected to a thermal stability test as described in Example 1. Our results are shown in Figure 3. The powder (6) was prepared using aqueous ethanol containing dissolved gliadin.

A comparative sample is prepared using 2% w / w emulsifier, emulsifying vitamin A with emulsifier such as glycerol fatty acid ester at a concentration corresponding to the above samples, and pulverizing as above to give vitamin powder (8). The thermal stability of this powder is also shown in Figure 3.

Example 7, Comparative Example 7

20 g of vitamin A palmitate (170000 IU / g) were added to aqueous ethanol containing the dissolved gliadin prepared as in Example 6 and then prepared according to the procedure described in the example using the gliadin-containing solution.

HU 203 467 Β

As a comparative sample, an emulsion containing the same concentration of Avamin was prepared, emulsifying (glycerol fatty acid ester), dextrin and casein, emulsifying at 2%, dextrin at 16.8%, casein at 11.2%, material is pulverized as described above. Vitamin A powder (12) is thus obtained. The powders are sieved and powders less than 0.287 mm in size are subjected to a thermal stability test as described in Example 1. Our results are shown in Figure 4.

PATENT CLAIMS

Claims (5)

PATENT CLAIMS A process for the production of stabilized vitamin P, B, C, D and / or vitamin E, characterized in that: a) Dissolve gliadin in gluten in a suitable solvent, add Α-, B-, C-, D- and / or vitamin E to 1-5 parts by weight per 100 parts by weight of gliadin, to the solution containing the dissolved gliadin and mix the solvent removing from the solution and then converting the resulting material to a powder, or (b) dissolve gliadin in a suitable solvent, add to the solution 1 to 51 parts by weight of vitamin E, B, C, D and onions E, add 100 parts by weight of gliadin, remove the solvent and remove the the resulting material is powdered. Process according to claim 1, characterized in that the solvent is aqueous alcohols. Process according to claim 1 or 2, characterized in that the product is partially or completely gliadin-encapsulated and / or gliadin-coated. 4. Process according to any one of claims 1 to 3, characterized in that the aqueous alcohol is 65-75% by volume aqueous ethanol. 5. A process according to any one of claims 1 to 6, wherein the vitamin is added to the gliadin solution in a solution or dispersion in animal or vegetable fat or oil.