KR20020086117A - Anti-oxidant containing alkali extract of non-fat rice bran and onion peel mixture - Google Patents

Abstract

PURPOSE: An antioxidant containing an alkali extract from a mixture of defatted rice bran and onion skin is provided, therefore the antioxidant has improved antioxidative activity and stability, so that it can be used as food additives. CONSTITUTION: The antioxidant containing an alkali extract from a mixture of defatted rice bran and onion skin is produced by extracting a mixture of defatted rice bran and onion skin using metal oxide or an alkali salt solution at 0 to 150 deg. C, in which the defatted rice bran and the onion skin are mixed in a weight ratio of 1:0.1 to 1:2, and used in the amount of 0.1 to 10 wt.%; the metal oxide is selected from the group consisting of magnesium oxide, calcium oxide, zinc oxide, aluminium oxide, manganese oxide and copper oxide; and the alkali salt is sodium hydroxide, kalium hydroxide, sodium carbonate, calcium hydroxide and magnesium hydroxide.

Description

ANTI-OXIDANT CONTAINING ALKALI EXTRACT OF NON-FAT RICE BRAN AND ONION PEEL MIXTURE}

The present invention relates to a method for producing an alkali extract having an antioxidant effect from a mixture of degreasing rice bran and onion skin, which is a natural material, and an antioxidant including the alkali extract extracted by the method.

Antioxidant substances are substances that have excellent scavenging ability against free radicals, which are harmful to the human body. The free radicals here oxidize various substances. Combined to make harmful substances called lipid peroxides. About 80% or more of human diseases are due to oxidation by free radicals, and aging is also known to be due to the oxidation of free radicals. Aging is mainly caused by the peroxidation of these lipids, and lipid peroxide acts on blood vessels and causes various adult diseases including atherosclerosis and thrombosis.

Recently, there is a growing interest in the development of natural antioxidants having a clear physiological action due to strict restrictions on their use due to the stability of synthetic antioxidants among antioxidants that prevent oxidation by such free radicals. In particular, due to concerns about the stability of synthetic antioxidants such as BHA, BHT, and TBHQ, which have been widely used for decades, they are legally regulated in developed countries such as the US and Japan. Tocopherol, a natural material, is widely used due to its high price and stability. This situation is not used.

Therefore, in recent years, much research is being conducted to develop natural antioxidants that are safer for humans, cheaper, and have excellent antioxidant power, and are actively being made in various spices, herbal medicines, edible plants, and plant seed extracts.

Rice bran means the powder of brown rice and rice snow, or rice bran, which is essential to rice grains used as a staple food in Korea, and contains 95% of the nutrients of rice so that it is called ginseng in rice. It contains protein, various vitamins, rich mineral salts and fats, and it is also used in various human body including tocopherol, dietary fiber, oryzanol, tocotrienol, sitotrol, unsaturated fatty acid, etc. It is known to have various physiological effects including cholesterol synergistic effect because it contains a large amount of effective trace ingredients. In the United States and Western countries, rice bran has been applied to baked products such as bread, cookies, and snacks for a long time, and health food has been stabilized.

Recently, the rice grain processing plant is being mass-produced in Korea as it is rapidly spread, but some of them are used for the manufacture of rice bran oil, and most of them are used as feed. It contains abundant amounts of dietary fiber, but fat is also present, so it is difficult to store due to rancidity caused by lipase, so it has been used mainly as a feed rather than a food. In addition, since dietary fiber is composed of strong combinations of the constituents of it, when it is added to the food in its natural state, it has a great effect on the texture of the food, and also acts on microorganisms such as lipase and deterioration during storage. Will receive.

General components of rice bran are shown in Table 1 below.

ingredient unit content Crude protein (% N × 6.25) 12.0-15.6 Crude fat % 15.0-19.7 Crude fiber % 7.0-11.4 Available Carbohydrates % 34.1-52.3 View minutes % 6.6-9.9 calcium mg / g 0.3-1.2 magnesium mg / g 5-13 sign mg / g 11-25 Phytic acid mg / g 9-22 Silica mg / g 6-11 zinc Μg / g 43-258 Thiamine (B1) Μg / g 12-24 Riboflavin (B2) Μg / g 1.8-4.3 Niacin Μg / g 267-499

Among the rice bran components, particularly antioxidants are oryzanol (Oryzanol) and phytic acid, but in the case of oryzanol is mostly lost when extracting rice bran oil as an ester compound of ferulic acid and triterpene alcohol. In addition, phytic acid is effective only when used simultaneously with other antioxidants, and its own antioxidant properties are weak.

As a technique for extracting antioxidants from degreasing rice, Japanese Patent Application Laid-Open No. 62-241985 discloses a method of extracting a water-soluble antioxidant, by extracting water as an extractant at pH 4 and 30 ° C. for 5 hours. A method of extracting antioxidants has been disclosed, and Korean Patent Application No. 1993-0001378 discloses a method of extracting antioxidants by first extracting from 40 to 60% of ethanol and second extraction from water. However, the method has a disadvantage in that the yield of the antioxidant is low when extracted at a low temperature, the efficiency is lowered due to the excessive manufacturing cost and the complexity of the process when using ethanol

Onions, on the other hand, have been used directly in cooking as an important flavor vegetable that is indispensable in the diet, and mainly masks the smell of meat, so it is suitable for cooking meat and fish, and sulfur compounds, one of the ingredients, are amino acids of meat. It reacts with and produces a unique flavor, stimulating digestion of the stomach, stimulating bile secretion function, and also has a pharmacological effect such as reducing blood sugar. It contains about 93.1% of water and about 10% of sugar, and also contains glucose, sugar, fructose, maltose and other minerals such as potassium, calcium, iron, phosphorus and sodium. In particular, it has a very unique sweetness that increases when it is cooked. This is because irritant sulfur compounds are decomposed to produce propylmercaptane, which is 50 times sweeter than sugar. In general, the ingredients contained in 100g of onion are shown in Table 2 below.

Energy (Kcal) Protein (g) Fat (g) Mineral vitamin Disposal rate (%) Ca (mg) Fe (mg) A (IU) B1 (mg) B2 (mg) Niacin equivalent (mg) C (mg) 54 1.9 0.4 20 0.2 - 0.09 0.15 - 3 7

Flavonoids, which are antioxidants in onions, have significant antioxidative and indigestion effects in addition to physiological activities such as anti-inflammatory, anti-ulcer, anti-arteriosclerosis, anti-microbial, anti-mutant, anti-cancer, and anti-tumor effects. good. In addition, onions are effective in preventing osteoporosis, and the results of experiments with mice without ovaries for the model of normal rats and postmenopausal women revealed that the onions prevent osteoporosis. More than 80% of the flavonoids in the onion are composed of quercetin diglycoside, monoglycosiden, and quercetin aglycone. The red onion, which is the cortex rather than the onion, contains a large amount. Onion is a spice that is mainly used to remove unpleasant odors and tastes when cooking meat and fish, and the above-mentioned quercetin enhances the efficacy of vitamin C and enhances capillaries, so it is used as a prevention of cerebral hemorrhage due to high blood pressure and atherosclerosis. .

Therefore, the present inventors continue to research to extract excellent antioxidants from natural materials, and mixed with a certain ratio of degreasing rice bran and onion blood, which are used for food as a safe substance, which is not toxic to humans at all, and this is a metal oxide or The present invention was completed by discovering that the alkali extract obtained by extracting with an aqueous alkali salt solution was very excellent in antioxidant power and stability as compared to a conventional antioxidant.

An object of the present invention is to provide a method for extracting an antioxidant effect from a mixture of natural degreasing rice bran and onion skin and an antioxidant containing the antioxidant material extracted therefrom.

1 is a graph showing the antioxidant power of the antioxidant and the existing antioxidant containing an alkali extract of the skim bran and onion peel mixture of the present invention,

Figure 2 is a graph comparing the antioxidant power of the antioxidant and the conventional antioxidant of the present invention over time.

In order to achieve the above object, in the present invention, the mixture of degreasing rice bran and onion peel is extracted at 0 to 150 ° C. using a metal oxide or an alkali salt aqueous solution as an extraction solvent. It provides a method of manufacturing.

In order to achieve the above another object, the present invention provides an antioxidant containing the alkali extract prepared by the above method as an active ingredient.

Alkali extract of the skim bran and onion skin mixture of the present invention can be prepared as follows. That is, the skimmed rice bran and onion skin are mixed in a weight ratio of 1: 0.1 to 1: 2, preferably 1: 0.4 to 1: 1.2, and powdered or pulverized, and then the mixture is mixed with an aqueous metal oxide or alkali salt solution as an extraction solvent. Is added to 1 to 30% by weight, preferably 5 to 10% by weight, and then the pH is adjusted to 7-12. At this time, the degreasing rice bran and onion blood may be mixed after being powdered or ground in advance. It is also preferred in the present invention to use red onion peels which are not particularly dry.

The metal oxide usable in the present invention is at least one selected from the group consisting of magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, manganese oxide and copper oxide, and usable alkali salts are sodium hydroxide, potassium hydroxide, sodium carbonate and hydroxide. At least one selected from the group consisting of calcium and magnesium hydroxide. In addition, the amount of the metal oxide or alkali salt used in the extraction solvent is 0.01 to 10% by weight, preferably 0.1 to 0.5% by weight based on the total amount of the extraction solvent.

The mixture is then extracted for 1 minute to 10 hours, preferably 2 to 6 hours at an extraction temperature of 0 to 150 ° C, preferably 60 to 121 ° C. At this time, the extraction pressure is in the range of 0 to 1.5 psi. After the extraction process, the extract is centrifuged or filtered to separate the residue and the filtrate, thereby obtaining an aqueous alkaline extract.

Antioxidant activity of the alkaline extract of the skim stew and onion skin mixture prepared in the present invention shows the inhibition ratio (IC) and the free radical scavenging ability by TBA (Thiobabitric acid) method showing the inhibition of lipid peroxidation in linoleic acid emulsion It is measured by the elimination rate (IC) by the DPPH (1,1-diphenyl-2-picrylhydrazyl) method.

Through antioxidative experiments on alkaline extracts extracted from the skim bran and onion skin mixtures of the present invention, the substance can be usefully used as an antioxidant by significantly inhibiting or eliminating free radicals that act as harmful components in combination with peroxidants. Confirmed that the

Accordingly, in the present invention, it is possible to prepare an antioxidant comprising an alkali extract of skim bran and onion peel mixture as an active ingredient and a pharmaceutically acceptable carrier. The antioxidant may further include conventionally used excipients, disintegrants, sweeteners, lubricants, flavoring agents and the like, tablets, capsules, powders, granules, suspensions, emulsifiers, syrups, It may be formulated in unit dosage forms or in multiple dosage pharmaceutical formulations, such as liquid or parenteral formulations. In addition, the alkali extract prepared above may be concentrated under reduced pressure at 60 to 70 ° C., concentrated to 20 brix (solid content) or more, and then spray dried to prepare a powder.

Antioxidants containing the alkali extract of the skim bran and onion skin mixture of the present invention can be administered parenterally or orally according to the desired method, 0.01 to 1g per 1kg body weight, preferably 0.05 as an active ingredient per day The amount of from 0.5 g to 1 to several times may be administered. Dosage levels for a particular patient may vary depending on the patient's weight, age, sex, health condition, diet, time of administration, method of administration, rate of excretion, and degree of disease.

Alkali extract of the skim bran and onion skin mixture of the present invention can be prepared by supplementing the food or beverage for the purpose of food additives and health supplements for suppressing rancidity of food. At this time, the amount of the alkali extract of the degreasing rice bran and onion skin mixture in the food or beverage may generally be added to 0.01 to 10% by weight, preferably 0.3 to 3% by weight of the total food or beverage weight.

In addition, the alkali extract of the skim bran and onion skin mixture of the present invention can be used for the purpose of suppressing rancidity of oils (cheese, mayonnaise) food. At this time, the amount of the alkaline extract of the skim bran and onion skin mixture in the fat or oil can be added to 0.01 to 10% by weight, preferably 0.1 to 1% by weight of the total food.

Hereinafter, the present invention will be described in more detail with reference to the following examples. only. The following examples are only for illustrating the present invention, but the scope of the present invention is not limited thereto.

Reference example: Method of measuring antioxidant power

In the TBA method, 50 µl of the sample was added to 3 ml of linoleic acid emulsion, and 50 µl of 0.00375M FeSO ₄ , which promotes oxidation, was added and incubated at 37 ° C. for 15 hours to induce peroxidation, and then absorbance was measured at 533 nm. .

In addition, the DPPH (1,1-diphenyl-2-picrylhydrazyl) method is measured by the hydrogen donating activity (HDA) for DPPH. That is, 50 μl of DMSO (Dimetyl sulfoxide) was added to 3.95 ml of DPPH-ethanol solvent and reacted at 37 ° C. for 30 minutes, so that the absorbance was about 1.0 at 517 nm. In the same manner, the DPPH reaction product was reacted with 50 μl of sample instead of DMSO solution. The decrease in absorbance was expressed as hydrogen donating ability to DPPH. At this time, the concentration of the sample was 50 μl.

IC (%) value was measured according to the following equation.

IC (%) = {(C-S) / C} × 100

C: absorbance of the control group

S: absorbance of the sample

In addition, the extraction rate was measured by polyphenol content and solid content (Brix) content. First, polyphenols were measured for absorbance at 700 nm for the color development of samples by a Folin reagent. A solid content was measured using a Hand Refractometer device of Atago, Japan. This value was used as is in the final extract.

Example 1

Simmered rice bran and onion skin were mixed in a weight ratio of 1: 0.8, and then added to an aqueous 0.1% MgO solution, and stirred at 100 ° C. for 1 hour. Subsequently, the extracted filtrate and residue were separated and centrifuged, and the antioxidant power and extraction rate were measured and shown in Table 3. At this time, onion skin used an undried skin.

Examples 2-4, and Comparative Examples 1 and 2

Alkali extract was extracted in the same manner as in Example 1 except for using the extraction solvent as shown in Table 3 below.

Extraction solvent Antioxidant power Extraction rate TBA (%) DPPH (%) Polyphenol Amount (mg / g) Brix Example 1 0.1% MgO aqueous solution 71.8 74.8 27.53 2.9 Example 2 0.1% NaOH aqueous solution 69.5 70.5 29.51 3.2 Example 3 0.1% CaO aqueous solution 64.2 73.4 27.25 2.6 Example 4 0.1% ZnO aqueous solution 65.5 62.4 27.93 2.6 Comparative Example 1 water 62.4 65.1 25.26 2.5 Comparative Example 2 95% ethanol 61.1 42.4 35.74 1.6

As shown in Table 3, it can be seen that the alkali extract of the present invention extracted using a metal oxide aqueous solution or an alkali salt aqueous solution has excellent antioxidant power as compared to Comparative Examples 1 and 2.

Examples 5 and 6

Alkali extract was extracted in the same manner as in Example 1 except for mixing the degreasing rice bran and onion blood in the mixing ratio as shown in Table 4 below.

Mixing ratio Antioxidant power Extraction rate TBA (%) DPPH (%) Polyphenol Amount (mg / g) Brix Example 1 Degreasing rice bran: Onion skin (1: 0.8) 71.8 74.8 27.53 2.9 Example 5 Degreasing rice bran: Onion skin (1: 1.2) 72.0 76.1 27.41 3.0 Example 6 Degreasing rice bran: Onion skin (1: 2.0) 72.8 76.0 27.78 3.0

As shown in Table 4, there was no significant difference in the antioxidant power and the extraction rate according to the mixing ratio of degreasing rice bran and onion skin, especially in Example 5 mixed at a ratio of 1: 1.2, the taste without rejection results Indicated.

Examples 7-8

An alkali extract was extracted in the same manner as in Example 5 except for using the extraction solvent as shown in Table 5 below.

Extraction solvent Antioxidant power Extraction rate TBA (%) DPPH (%) Polyphenol Amount (mg / g) Brix pH Example 5 0.1% MgO aqueous solution 72.0 76.1 27.41 3.0 8.5 Example 7 0.3% MgO aqueous solution 73.1 76.3 29.63 3.1 10.3 Example 8 0.5% MgO aqueous solution 72.7 71.9 30.27 3.1 11.3

As shown in Table 5, the pH was changed to 8-11 depending on the concentration of MgO, which showed a difference in antioxidant capacity. That is, the extraction rate was not significantly different according to the concentration of MgO, but the free radical scavenging activity (DPPH) and lipid peroxidation inhibitory activity (TBA) at the antioxidant power showed the best antioxidant power at pH 10 of 0.3% MgO aqueous solution, and 0.5% MgO When the pH of the aqueous solution was above 11, the lipid peroxide inhibitory activity (TBA) did not show much difference, but the free radical scavenging activity (DPPH) showed a tendency to decrease.

Examples 9-11

An alkali extract was extracted in the same manner as in Example 7, except that the extraction was performed at the extraction temperature as shown in Table 6.

Temperature (℃) Antioxidant power Extraction rate TBA (%) DPPH (%) Polyphenol Amount (mg / g) Brix Example 9 60 51.9 54.6 23.54 1.9 Example 10 80 72.2 72.6 24.42 1.9 Example 7 100 73.1 76.3 29.63 3.1 Example 11 121 72.3 79.4 30.18 3.2

As shown in Table 6, the extraction rate increased with increasing temperature, free radical scavenging activity (DPPH) increased with increasing temperature, the highest at 121 ℃, lipid peroxidation inhibitory activity (TBA) was the highest at 100 ℃, At higher temperatures, the results were decreased.

Examples 12-16

An alkali extract was extracted in the same manner as in Example 7, except that the extraction time was performed as shown in Table 7 below.

Hours (h) Antioxidant power Extraction rate TBA (%) DPPH (%) Polyphenol Amount (mg / g) Brix Example 7 One 73.1 76.3 29.63 3.1 Example 12 2 79.7 76.0 30.83 3.3 Example 13 3 79.9 77.2 30.61 3.4 Example 14 4 78.7 79.1 31.74 3.5 Example 15 5 81.6 79.5 31.18 3.5 Example 16 6 78.6 79.0 30.69 3.5

As shown in Table 7, as the extraction time increases, the antioxidant power and the extraction rate increased up to 2 hours, but did not show a significant difference from the time after that.

Example 17 Antioxidant Preparation

A water-soluble natural antioxidant was prepared by a conventional spray dry method using the alkali extract prepared in Example 7. When spray drying, the temperature of the inlet was adjusted to 175 ℃ to 185 ℃, the temperature of the outlet was adjusted to 90 ℃ to 110 ℃.

The components of the prepared antioxidants were analyzed and the results are shown in Table 8 below.

ingredient carbohydrate protein Polyphenols Ash and inorganic matter moisture Sum Available Carbohydrates Crude fiber unit(%) 53.2 11.4 22.3 3.1 7.2 2.8 100

As shown in Table 8, the antioxidant prepared in the present invention contains carbohydrates and proteins as the main constituents, it can be seen that other polyphenols and minerals.

Test Example 1

In order to determine the antioxidant power according to the concentration of the natural antioxidant prepared in the present invention, the antioxidant prepared in Example 17 was dissolved in water at a concentration of 0.01% to 0.15% and the final concentration compared to the volume of the TBA and DPPH liquid After adding 0.1%, the antioxidant power was measured, and the results are shown in Table 9.

Analytical Concentration (%) Antioxidant power TBA (%) DPPH (%) 0.01 51.1 29.6 0.03 74.7 70.8 0.05 81.6 84.7 0.07 82.2 88.5 0.1 87.2 90.7 0.15 86.8 91.5

As shown in Table 9, as the concentration of the antioxidant increases, the antioxidant power increases, but it can be seen that the difference does not show much from the concentration of 0.05% or more.

Test Example 2

In order to examine the safety of the heat of the natural antioxidant, the antioxidant prepared in Example 17 was dissolved in an aqueous solution at a concentration of 10% and heated for 90 minutes in a 100 ° C sterilizer and sampled hourly, and then the final concentration. Was added to 0.1% of the volume of TBA and DPPH solution to measure the antioxidant power and the results are shown in Table 10.

Analysis time (min) Antioxidant power TBA (%) DPPH (%) 0 86.6 88.6 15 85.6 88.4 30 85.4 88.2 60 85.6 88.3 90 85.5 88.1

As shown in Table 10, the water-soluble natural antioxidant prepared by the present invention can be seen that it is stable for 90 minutes at 100 ℃ excellent heat resistance.

Test Example 3

In order to compare the heat resistance of the water-soluble natural antioxidant prepared in the present invention and the conventional natural antioxidant tocopherol (Vit.E), the antioxidant and tocopherol obtained in Example 17 were added to DMSO (dimethyl sulfoxide) at a 10% concentration. After dissolving each other and heating at 100 ° C. for 60 minutes, the final concentration was added to 0.1% of the volume of TBA and DPPH solution to measure the antioxidant power. The results are shown in Table 11.

Analytical Antioxidants TBA (%) DPPH (%) Antioxidant of the Invention (Example 17) Before heat treatment 88.6 90.1 After heat treatment 87.1 89.6 Vit. E Before heat treatment 86.7 92.5 After heat treatment 61.1 91.6

As shown in Table 11, in the case of the most widely used tocopherols, the active oxygen scavenging ability is stable regardless of heat treatment, but the lipid peroxide inhibitory activity (TBA) is reduced by about 25% after heat treatment. On the contrary, the antioxidant of the present invention showed that both active oxygen scavenging activity (DPPH) and lipid peroxide inhibiting activity (TBA) were excellent in thermal stability regardless of heat treatment.

As described above, it can be seen that the antioxidant according to the present invention can be applied to various formulations by supplementing a natural antioxidant that is weak against heat such as Vit.E, which has been industrially restricted.

Test Example 4

Water-soluble natural antioxidants prepared by the present invention and existing natural antioxidants, tocopherol (Honen, Japan) and synthetic antioxidants BHT (Sigma, USA), BHA (Sigma, USA) and EDTA (Compared to the antioxidant power of Akzo Nobel (Akzonobel), the Netherlands) is shown in Figure 1 the results.

In addition, in order to find out the trend of oxidative power over time, the antioxidant peroxidation inhibitory ability of each antioxidant was measured by time-dependent inhibition rate and the results are shown in FIG. 2. This was measured at 533 nm when the reaction product of malon aldehyde and TBA reagent produced by fat and oil of fats and fats gave a red pigment. To lose. DMSO solution was used instead of the antioxidant.

1 and 2, the antioxidant of the present invention was higher than the existing natural antioxidant Vit.E in the lipid peroxidation inhibitory activity (TBA), higher than EDTA among other synthetic antioxidants, but significantly different from BHA, BHT Did not look. In addition, free radical scavenging activity was much higher than that of EDTA and similar to other antioxidants.

Alkali extract of the skim bran and onion skin mixture of the present invention is very excellent in the antioxidant power and stability can be useful as an antioxidant, such as antioxidants, food additives for preventing rancidity of food and health supplements.

Claims (6)

A method for producing an alkali extract of degreasing rice bran and onion skin, wherein the mixture of degreasing rice bran and onion skin is extracted at 0 to 150 ° C. using a metal oxide or an alkali salt aqueous solution as an extraction solvent. The method of claim 1, The degreasing rice bran and onion blood mixture is characterized in that the mixture in a weight ratio of 1: 0.1 to 1: 2. The method of claim 1, The amount of the metal oxide or alkali salt is characterized in that 0.01 to 10% by weight based on the total amount of the extraction solvent. The method according to any one of claims 1 to 3, The metal oxide is characterized in that at least one selected from the group consisting of magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, manganese oxide and copper oxide. The method according to any one of claims 1 to 3, Wherein said alkali salt is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, calcium hydroxide and magnesium hydroxide. Antioxidant containing an alkali extract of skim bran and onion skin mixture prepared by the method of claim 1 as an active ingredient.