KR100792615B1 - Selenium containing germinated unpolished rice and its preparation method - Google Patents

Abstract

Selenium or germanium or mixtures thereof by immersing and sprinkling crops such as cereals, root vegetables and bulbs in an aqueous solution in which a water-soluble selenium compound or a water-soluble germanium compound or a mixture thereof is dissolved, or by spraying an aqueous solution on the crop. There is provided a method of producing a germinated crop containing organic selenium or organic germanium, characterized in that the crop is absorbed into the crop as an organic form, and a selenium or germanium containing germinated crop produced by the method, in particular germinated brown rice. The germinated brown rice of the present invention thus prepared can be used as processed food or feed because it can elute selenium or germanium therefrom.

Germination, Grains, Brown Rice, Selenium, Germanium

Description

Selenium-containing germinated brown rice and its manufacturing method {SELENIUM CONTAINING GERMINATED UNPOLISHED RICE AND ITS PREPARATION METHOD}

The present invention relates to germinated grains including germinated brown rice to which selenium and / or germanium are added, and a method for producing the same. More specifically, the present invention is selenium and / or germanium is a water-soluble basic salt (K ₂ SeO ₃ , K ₂ SeO ₄ , K ₂ GeO ₃ , K ₂ GeO ₄ , Na ₂ SeO ₃ , Na ₂ SeO ₄ , Na ₂ GeO ₃ , Na ₂ GeO ₄ , (NH ₄ ) ₂ SeO ₃ , (NH ₄ ) ₂ SeO ₄ , (NH ₄ ) ₂ GeO ₃ , (NH ₄ ) ₂ GeO ₄ , CaSeO ₃ , CaSeO ₄ , CaGeO ₃ , Organic selenium and / or organic, which is formed in the form of CaGeO ₄ ) and inoculated into water in which these basic salt forms of selenium and / or germanium are dissolved or sprinkled by absorbing such water when germinating brown rice. The present invention relates to germinated brown rice containing germanium, or cereals or sprouted bulbs, root vegetables, and methods for producing the same, which have been sprinkled or immersed in a solution containing selenium and / or germanium.

Selenium (Se) and germanium (Ge) are elements that have attracted much attention recently in academia and industry due to their various functions and effects such as antioxidant activity, anti-aging, and anticancer properties. Overuse is well known in many studies and is not specifically described in the present invention.

Background Art Conventionally, various attempts have been made to link useful functions of selenium or germanium to food, and as an example, research on grains containing selenium or germanium is steadily being conducted. For example, selenium has been used to spray soil or mix with fertilizer alone or mixed with fertilizers, and germanium has been used to spray germanium ore as a powder, but germanium ore is insoluble in water. Because of this, only a very small amount of absorption was difficult to expect the effect in this way.

In addition, Ge-132, developed by the Asahi Research Institute in Japan, is a water-soluble organic germanium, which can be absorbed by crops, but is too expensive to use as a fertilizer.

When the seeds of plants such as germinated brown rice germinate, the nutritional value is maximized by increasing the amino acids and vitamins, which are various nutrients contained in the seeds, by 5 to 10 times.

On the other hand, when selenium is absorbed by a plant, it binds to the protein of the plant and turns into organic selenium. Mostly, selenium exists in the form of selenomethionin, selenocysteine, or methylselenocysteine (Tinggi U, Toxicology Letters 137 : 103-110, 2003 "Essentiality and toxicity of selenium and its status in Australia").

Among plants, selenium absorbed by cereals is 100% organic (Tapiero HDM Townsend and KD Tew, Biomedicine & Pharmacotherapy 57 : 134-144, 2003 "The antioxidant role of selenium and seleno-compounds").

Germination of brown rice is performed by spraying 24 to 36 hours after immersion in water for 24 to 36 hours, or by spraying for 48 to 72 hours immediately without immersion step.

As the water used to soak brown rice, oxygen-rich clean water of about 10 ° C to 30 ° C is suitable.

In the prior art, in order to produce selenium or germanium-containing rice, two or three times the spraying work in the rice paddy is required a lot of manpower required for the spreading work carried out in a large area and costs a lot. In addition, the amount of selenium or germanium that is lost in soil or paddy fields, or wasted in straw or rice husk is enormous, so that the amount of selenium or germanium consumed by the rice is insignificant compared to the amount of selenium or germanium that is consumed.

One object of the present invention is to provide a method for absorbing selenium and / or germanium in cereals.

A particularly important object of the present invention is to provide a method for absorbing high concentrations of selenium and / or germanium in germinated brown rice and the germinated brown rice thus produced.

Another object of the present invention is to provide a method for economically absorbing grains including brown rice without wasting selenium or germanium.

Another object of the present invention is to provide selenium and / or germanium in the form of organic selenium and / or organic germanium in germinated brown rice.

Still another object of the present invention, in addition to brown rice, barley, wheat, soybeans, green beans, corn, oats, buckwheat, crude, sorghum, yulmu and other cereals and garlic, onions, leeks, ginger, hemp, carrots, taro, lotus root, bellflower, When the germination or sprouting of vegetables, papers, herbs, etc., such as deodeok, ginseng to provide a method for absorbing a large amount of selenium and / or germanium to contain a high concentration of organic selenium and / or germanium.

Another object of the present invention is to provide a functional processed food or feed using germinated grains such as germinated brown rice and germinated bulbs or root vegetables prepared according to the present invention.

As a result of intensive research to achieve the above object, the present inventors have absorbed a lot of water when brown rice germinates and absorbs nutrients to produce energy necessary for germination. It has been found that the absorption of inorganic soluble selenium or germanium binds to plant proteins and transforms them into organic form.

In other words, a mechanism similar to crops absorbing selenium and germanium from leaves and converting them into organic selenium and organic germanium.

The selenium compounds used for the germinated brown rice containing selenium include K ₂ SeO ₃ , K ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ SeO ₄ , (NH ₄ ) ₂ SeO ₃ , (NH ₄ ) ₂ SeO ₄ , CaSeO ₃ , And any water-soluble selenium compound such as CaSeO ₄ , and the germanium compound may be Na ₂ GeO ₃ , Na ₂ GeO ₄ , K ₂ GeO ₃ , K ₂ GeO ₄ , (NH ₄ ) ₂ GeO ₃ , (NH ₄ A water-soluble germanium compound such as ₂ GeO ₄ , CaGeO ₃ , or CaGeO ₄ can be used.

The above-described water-soluble germanium compound may be prepared by first preparing a saturated solution of alkali metal hydroxide, and adding germanium dioxide to the saturated solution of alkali metal hydroxide and stirring and reacting with strong stirring. In this process, hydrogen peroxide can be added to form a water-soluble powder. Examples of the alkali metal hydroxides include ferrous hydroxide and sodium hydroxide, but it is preferable to use ferric hydroxide. The method for preparing the water-soluble germanium compound described above is described in detail in Korean Patent Application No. 2004-29181, and the method for preparing a water-soluble selenium compound is also described in the above-mentioned Korean patent application, and the method for preparing the water-soluble germanium compound described above Substituting selenium dioxide instead of germanium gives a water soluble selenium compound. All the contents of this patent application are incorporated by reference in their entirety.

The use concentration of the water-soluble selenium compound is suitably within the range of 0.01 ppm to 200 ppm, more preferably 1 ppm to 50 ppm, based on the element selenium. If it is less than 0.01 ppm, selenium absorption effect is not obtained, and if it exceeds 200 ppm, it will not germinate.

The use concentration of the water-soluble germanium compound is used within the range of 0.01 ppm to 500 ppm based on the germanium element, and more preferably 1 ppm to 50 ppm. If it is less than 0.01 ppm, selenium absorption effect is not obtained, and if it exceeds 500 ppm, it will not germinate.

Germination can be carried out according to the general seed germination method, but inoculated with 5 ppm solution of Se (K ₂ SeO ₃ ) at 10 to 30 ° C., preferably 25 ° C., for 24 to 36 hours, and then sprinkled for 24 to 36 hours to be sprayed. ) If you grow rice snow 0.5 ~ 1.5mm, at this time, wash it with water and dry it. In addition to the above-mentioned immersion method, it may be germinated by only performing watering treatment for 48 hours to 72 hours. The watering can be carried out using an automatic circulation watering machine.

When white rice is needed depending on the processing purpose, dried selenium or germanium-containing germinated brown rice may be milled and processed into germinated rice.

Brown rice for rice should be germinated within 0.5 ~ 1 mm, and brown rice for green tea, sikhye, brew, rice cake, meat powder, baby food, etc., germinated at 1 ~ 1.5 mm has high absorption rate of selenium or germanium. It is advantageous. That is, the degree of germination can be properly adjusted according to the end use.

For grains other than brown rice, barley, wheat, soybeans, green beans, corn, oats, buckwheat, crude, sorghum and yulmu are inoculated and immersed in a solution of selenium or germanium compounds in the same way as brown rice. It is used for food, processing and feed. For edible or processed foods, it is appropriate to minimize it at about 0.5 to 1.5 mm, and for feed, you can further minimize it. Garlic, onions, leeks, ginger, hemp, carrots, taro, potatoes, sweet potatoes, etc., immerse or sprinkle roots in a solution of selenium or germanium compounds to promote germination until new shoots emerge 1-2 mm. .

The following examples are intended to illustrate the present invention in more detail, and therefore the present invention is not limited to these examples.

Example 1

14.05 g of SeO ₂ (manufactured by Duksan Pure Chemicals Co., Ltd.) was added to a saturated KOH solution, reacted with vigorous shaking to form a water-soluble selenium compound K ₂ SeO ₃ . made.

Example 2

14.4 g of GeO ₂ (from Shinwha Chemical Co., Ltd.) was added to a saturated KOH solution and reacted with vigorous shaking to form K ₂ GeO ₄ , a water-soluble germanium, which was washed with water in a 1 L container and used to make a 10,000 ppm solution based on elemental germanium. .

Example 3

14.05 g of SeO ₂ (manufactured by Duksan Pure Chemicals Co., Ltd.) was added to a saturated solution of NaOH and reacted with vigorous shaking to form Na ₂ SeO ₃ , a water-soluble selenium. .

Example 4

25 g of Ge-132 (Nanjing Direction Health Technic Cevelop Co., Ltd., China) was dissolved in 1 L to make a 10,000 ppm solution based on elemental germanium.

Example 5

1 ml of the solution of Example 1 was diluted in 5 L of water to form a 2 ppm solution (hereinafter referred to as "Se 2 ppm solution") on the basis of elemental selenium, and 2 ml of the solution was diluted in 5 L of water and 4 ppm on the basis of elemental selenium A solution (hereinafter referred to as "Se 4 ppm solution") was prepared, and 5 Kg of brown rice was added to each of these aqueous solutions at 25 ° C, soaked for 36 hours, completely soaked, and then washed and transferred to the sprinkler pancreas, respectively. The ppm and Se 4 ppm solutions were sprinkled with an automatic circulation sprinkler for about 1 mm, washed, and dried with hot air (45 ° C.) at 15% moisture.

Example 6

2 mL of the solution of Example 2 was dissolved in 5 L of water to form a 4 ppm solution (hereinafter referred to as a "Ge 4 ppm solution") on an elemental germanium basis, and 4 mL of the solution was diluted in 5 L of water on an elemental germanium basis. A 8 ppm solution (hereinafter referred to as a "Ge 8 ppm solution") was prepared and each of these aqueous solutions was kept at 25 ° C. with 5 Kg of brown rice, soaked completely for 36 hours and dried without washing to remove Ge 4 ppm solution and Ge 8, respectively. The solution of ppm was minimized by about 1 mm while being sprayed with an automatic circulation sprinkler, washed, and dried with hot air (45 ° C.) with a water content of 15%.

Example 7

1 mL of the solution of Example 3 was diluted in 5 L of water to make a solution of 2 ppm on the basis of elemental selenium, and 2 mL of the solution was diluted to 5 L of water to make a 4 ppm solution on the basis of elemental selenium to prepare selenium germinated brown rice as in Example 5. .

Example 8

Germanium germinated brown rice was prepared in the same manner as in Example 6 by diluting 2 mL of the solution of Example 4 in 5 L of water to make a 4 ppm solution on the basis of elemental germanium, and 4 mL of the solution in 5 L of water to make an 8 ppm solution on the basis of elemental germanium. .

Example 9

2 mL of the solutions of Examples 1 and 3 were diluted in 5 L of water, respectively, to make a solution of 4 ppm on the basis of elemental selenium, and 4 mL of the solutions of Examples 2 and 4 were diluted in 5 L of water, respectively, on the basis of elemental germanium. 8 ppm solution of Se and 4 ppm solution of Se and 8 ppm solution of Ge were continuously sprinkled with garlic at 19 ° C. for 48 hours using an automatic circulating sprinkler, and stopped when sprouted germs grew about 0.5 to 1 cm and washed with garlic. Freeze-dried.

Experimental Example 1

Example 5, 6, 7, and 8 of the brown rice and garlic of Example 9 were pulverized, wetted using microwaves, and cooled after cooling to Atom Absorbtion Spectrometer (AAkinyst 800: Permanent Absorption Spectrophotometer of Perkin Elmer). The amount of selenium and germanium was measured using a device equipped with a graphite tube) and the results are shown in Table 1 and Table 2, respectively. The untreated groups in Table 1 and Table 2 are common germinated brown rice and germinated garlic without addition of selenium and germanium.

Contents of Selenium (Se) and Germanium (Ge) in Germinated Brown Rice  division Se Ge 2 ppm 4 ppm 4 ppm 8 ppm Example 5 Example 6 Example 7 Example 8 No treatment group 1,983 ppb-1,826 ppb-0 3,121 ppb-2,738 ppb- -2,930 ppb-2,813 ppb 30 ppb -5.692 ppb-5.315 ppb

According to the conventional technique of spraying selenium in rice cultivation, only about 300 ppb of brown rice is contained in two sprays of Se 2ppm. Therefore, the results of Table 1 confirm that the absorption effect of selenium or germanium by the method of the present invention is superior to the brown rice absorption rate by the prior art spraying operation.

Content of Selenium (Se) and Germanium (Ge) in Sprouted Garlic division Se 4 ppm Ge 8 ppm Example 1 Example 2 Example 3 Example 4 No treatment group 2,076 ppb-1,960 ppb-20 ppb -2,230 ppb-2,189 ppb 12 ppb

From the results of Table 2, it was confirmed that the sprouted garlic to which selenium and germanium were added according to the present invention had significantly higher selenium and germanium contents than the untreated group.

Experimental Example 2

Example 4, 6, 7, and 8 Se 4 ppm and Ge 8 ppm brown rice was pulverized and quantified in 5 g each, put in 100 mL of water, and the result of shaking extraction for 24 hours was compared with the results of experiments on the untreated group. 3 is shown.

Content of Selenium (Se) and Germanium (Ge) in Germinated Brown Rice Extract division Se 4 ppm Ge 8 ppm Example 5 Example 6 Example 7 Example 8 No treatment group 1,760 ppb-1,742 ppb-0 -1,526 ppb-1,411 ppb 12 ppb

In Table 3, the untreated group is a general germinated brown rice and germinated garlic without added selenium and germanium. As can be seen from Table 3, the germinated brown rice of Examples 5 to 8 according to the present invention eluted selenium and germanium therefrom when extracted with water. This is a test result confirming that the selenium and germanium components are eluted in water from the selenium or germanium-containing germinated brown rice according to the present invention, indicating that the selenium or germanium-containing germinated brown rice of the present invention can be used in processed foods such as green tea and Sikhye. Very significant result.

According to the present invention, it is possible to effectively absorb selenium or germanium in crops by invading and minimizing crops, such as brown rice, various root vegetables, bulbs, and the like, in the water-soluble selenium or water-soluble germanium aqueous solution at the germination or germination stages. Since the method of the present invention absorbs selenium or germanium compounds during germination or germination, they can be transformed into organic selenium or germanium in crops, and compared with conventional techniques such as spraying on a wide area of packaging or releasing foliar surfaces. Selenium or germanium can be absorbed into crops economically without waste. In addition, since selenium or germanium can be eluted from crops including selenium or germanium-containing grains thus obtained, it can be used as processed food or feed.

Claims (13)

The aqueous solution of water-soluble selenium compound in which the concentration of the water-soluble selenium compound in the aqueous solution is 0.01 ppm to 200 ppm based on the element of selenium is germinated by spraying the grain with an automatic sprayer for 48 to 72 hours to absorb the selenium into the grain. Characterized in that, the method for producing a germinated grains containing organic selenium. The method of claim 1 further comprising immersing the cereal in a water soluble selenium compound. The aqueous solution of the water-soluble selenium compound in which the concentration of the water-soluble selenium compound in the aqueous solution is 0.01 ppm to 200 ppm based on the element selenium is used as a bulb selected from garlic, onion, green onion, ginger, hemp, carrot, taro, lotus root, potato, and sweet potato. Organic selenium-containing ocular bulbs, characterized by absorbing selenium into the bulbs or root vegetables by sprinkling with an automatic sprinkling agent for 48 to 72 hours in the root vegetables, or herb selected from bellflower, deodeok and ginseng. How to prepare sprouted vegetables. 4. The method of claim 3, further comprising dipping bulbs, root vegetables or herbs in the water soluble selenium compound. The method according to claim 1 or 3, wherein the water-soluble selenium is selected from K ₂ SeO ₃ , K ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ SeO ₄ , (NH ₄ ) ₂ SeO ₃ , (NH ₄ ) ₂ SeO ₄ , CaSeO ₃ , and CaSeO ₄ . The method of claim 1, wherein the grains are brown rice and the germination temperature is 10 to 30 ° C. 3. Germinated brown rice containing organic selenium prepared according to the method of claim 1. Processed food or feed using germinated grains, sprouts, herbs, or sprouted vegetables obtained according to the method of claim 1. delete delete delete delete delete