JP2926411B2 - Production method of α-glycosyl rutin and its use - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to α-glycosyl rutin, a method for producing the same and use thereof, and more particularly, a rutin-rich liquid containing a high concentration of rutin and starch. Α-glycosyl rutin obtained by allowing a glycosyltransferase to act on the same, a method for producing the same, beverages and foods containing the α-glycosyl rutin, foods and drinks such as processed foods, prophylactic and therapeutic agents for susceptible diseases, ie, anti-sensitive diseases Cosmetics such as cosmetics
Furthermore, the present invention relates to use for various compositions such as an antioxidant.

[Related Art] Rutin has a chemical structure shown below, and has long been known as a vitamin P having a physiological action such as strengthening of capillaries, prevention of bleeding, blood pressure regulation, and as a yellow pigment, Are used in cosmetics.

Vitamin P participates in vivo in the physiological activity of vitamin C, for example, the hydroxylation reaction of proline and lysine necessary for the synthesis of collagen, which is a main component of biological connective tissue, and also, for example, Fe ^{+ of} cytochrome C. ^{Reduce ++} to F
It is known to be involved in redox reactions such as e ⁺⁺ and to enhance activities such as being involved in the immunopotentiating effect of leukocyte increase, and play an important role in maintaining and promoting the health of living bodies. No.

Rutin is used not only as a nutrient for vitamin P fortifiers, but also for its chemical structure and physiological effects, alone or in combination with other vitamins, for example, as a yellow colorant, antioxidant, etc. In addition, it is used as a prophylactic agent, a therapeutic agent for susceptibility diseases such as cardiovascular diseases, that is, an anti-sensitivity disease agent, and further, as a skin colorant such as a yellow coloring agent and an ultraviolet absorber, and as a skin lightening agent and the like. Is extremely wide.

However, rutin is sparingly soluble in water, and only about 1 g (about 0.01 W / V%) is dissolved in 8 L of water at room temperature, which is extremely difficult to use.

As a method for improving this, for example, Japanese Patent Publication No. 25-16
No. 77, a method of increasing the water solubility by adding an aliphatic compound having an amino group to rutin, and, as disclosed in Japanese Patent Publication No. There has been known a method of increasing the water solubility of a compound, as described in JP-B-29-1285, and a method of reacting rutin with Rongalit to increase the water solubility of a sulfite compound.

However, all of these methods use an amino compound, a monohalogenacetic acid, a sulfite compound, and the like.
The resulting substance is concerned about other physiological activities and toxicity, and its purification is also difficult.

Therefore, the present inventors have previously described in Japanese Patent Publication No. 54-32073, a method of water-solubilization with higher safety, in which starch is partially hydrolyzed to rutin by the action of a glycosyltransferase utilizing a biosynthesis reaction. A method was proposed to improve the water solubility of rutin by transferring α-glycosyl rutin by transferring more than equimolar glucose residues from the product.

The α-glycosyl rutin obtained by this method has no toxicity concerns, has the same physiological activity as the raw material rutin, has high solubility in water, is extremely convenient in handling, and is expected to be used in a wider range of applications. Its realization has been crane neck.

[Problem to be Solved by the Invention] As described above, α-glycosyl rutin has various advantages, and its industrialization is awaited.

However, conventionally, the charge concentration in the biosynthesis reaction is only about 0.1 W / V% as rutin, and α-
The amount of water used for glycosyl rutin, the amount of purified water,
Energy costs and the like become excessive, which makes industrialization difficult.

Means for Solving the Problems The present invention has been made to solve the above-mentioned drawbacks, and in particular, a reaction method in which the concentration of rutin at the time of charging is increased, and purification of α-glycosyl rutin after the reaction. I did research on the method.

As a result, desirably, by reacting the glycosyltransferase with a rutin-rich solution containing a high concentration of rutin and starch, the rutin is preferably in a high-concentration suspension or at an alkaline pH.
Or dissolved in an organic solvent aqueous solution in a high-concentration solution, and the charged concentration is about 0.5 W / V as rutin.
% Or more, preferably about 1.0 to 20.0 W / V%, in other words, about 5 times or more the prior art, preferably about 10 to 200 W / V.
It was found that α-glycosyl rutin was well produced by acting the glycosyltransferase in a state twice as high, and simultaneously, the glycosyltransferase was allowed to act on a solution containing rutin and starch. It has been found that α-glycosyl rutin mainly composed of α-glycosyl rutin and / or α-maltosyl rutin is produced by the action of amylase, and its production method is established, and the α-glycosyl rutin produced by these methods is established. The present invention has been completed by establishing uses for various compositions such as food and drink containing rutin, a preventive agent for susceptibility diseases, a therapeutic agent, cosmetics, and an antioxidant.

Also, when purifying α-glycosyl rutin produced by this reaction, it has been found that it can be easily purified by bringing the reaction solution into contact with a porous synthetic adsorbent and utilizing the difference in adsorption properties. When the reaction solution contained an organic solvent, it was found that after the concentration of the organic solvent was reduced, the solution could be brought into contact with a porous synthetic adsorbent to purify similarly.

Therefore, it has been found that the method for producing α-glycosyl rutin according to the present invention can alleviate the drawbacks of the conventional method at a glance and greatly reduce the amount of water used, the amount of purified water, and the energy cost, and it is extremely easy to realize the industrialization. Is what you do.

 Hereinafter, the present invention will be described in detail.

Rutin used in the present invention is not necessarily limited to highly purified rutin, and a mixture of rutin and, for example, flavonoid glycosides such as citronin, naringin, and hesperidin, and various types of plants containing rutin Extracts derived therefrom or partially purified products thereof can be used as appropriate.

As the plant tissue, for example, buckwheat leaf stems, enju buds (sophora or sophora rice), enishida buds, eucalyptus leaf stems, ginkgo leaf stems, citrus fruits and the like can be advantageously used.

The starch used in the present invention may be any as long as it can produce α-glycosyl rutin in which glucose residues are bonded in equimolar or more from rutin by simultaneously used glycosyltransferase, and examples thereof include amylose, dextrin, cyclodextrin, and the like. A partially hydrolyzed starch such as maltooligosaccharide, and further, a liquefied starch and a gelatinized starch are appropriately selected.

Therefore, in order to facilitate the production of α-glycosyl rutin, starches suitable for glycosyltransferases are selected.

For example, as a glycosyltransferase, α-glycosidase (EC
When 3.2.1.20) is used, maltooligosaccharides such as maltose, maltotriose, and maltotetraose, or partially hydrolyzed starch of about 10 to 70 DE are preferred, and cyclomaltodextrin glucanotransferase (EC When using 2.4.1.19), cyclodextrin or a partially gelatinized starch having a DE of 1 or less is preferably used as a partial hydrolysis portion of starch having a DE of about 60, and α-amylase (EC
3.2.1.1) When DE is used,
About 30 dextrins, partially hydrolyzed starch, and the like are preferred.

The starch concentration at the time of the reaction was about 0.5 to rutin.
A range of from 50 to 50 times is preferred.

The rutin-rich liquid referred to in the present invention may be any liquid containing rutin at a high concentration, for example, a high concentration in suspension, or dissolved in an alkaline pH exceeding pH 7.0 or an aqueous solution of an organic solvent. A solution containing a high concentration in the form of a solution dissolved in the above is suitable, and the concentration is a high concentration of about 0.5 W / V% or more, preferably a solution containing about 1.0 to 20.0 W / V%. Means

The organic solvent used in the present invention is desirably one in which the solubility of rutin is higher than that in the case of water, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, and acetol, which are mutually soluble in water. , Lower alcohols such as acetone, lower ketones and the like are preferred.

The concentration of the organic solvent in the aqueous organic solvent solution is selected so that rutin is dissolved in the highest possible concentration, starch and glycosyltransferase are not insolubilized as much as possible, and α-glycosyl rutin is produced well. 70V / V%, preferably selected from the range of about 5 to 60V / V%.

In addition, in order to easily dissolve rutin to the highest possible concentration, rutin is previously dissolved in an alkaline aqueous solution such as sodium hydroxide solution and aqueous ammonia, mixed with an aqueous organic solvent solution, and further neutralized to conduct a sugar transfer reaction. It is also used appropriately.

The glycosyltransferase used in the present invention may be any one that produces α-glycosyl rutin without decomposing rutin when acted on a rutin-rich solution containing rutin and starchy substances having properties suitable for this enzyme. Good.

For example, α-glucosidase is an enzyme derived from animal or plant tissues such as pig liver, buckwheat seed, or a mold belonging to the genus Mucor, Penicillium, or a yeast belonging to the genus Saccharomyces. Enzymes derived from cultures obtained by culturing such microorganisms in a nutrient medium are cyclomaltodextrins
Glucanotransferase, Bacillus
Genus, enzymes derived from bacterial cultures belonging to the genus Klebsiella, etc., α-amylase is a bacterium belonging to the genus Bacillus, or Aspergillus (Aspergillus)
s) An enzyme derived from a mold culture belonging to the genus or the like can be appropriately selected.

These glycosyltransferases do not necessarily need to be purified and used as long as the above conditions are satisfied. Usually, the purpose of the present invention can be achieved with a crude enzyme.

If necessary, it may be used after being purified by various known methods. Alternatively, a commercially available glycosyltransferase can be used.

The pH and temperature during the reaction may be adjusted so long as the glycosyltransferase acts to generate α-glycosyl rutin, and is usually pH 3 to 10,
The temperature is selected from 10 to 90 ° C.

There is a close relationship between the amount of enzyme used and the reaction time, and usually the amount of enzyme is selected so that the reaction is completed in about 5 to 80 hours from the viewpoint of economy.

In addition, the immobilized glycosyltransferase can be appropriately selected to be used for the reaction repeatedly or batchwise in the reaction.

Further, if necessary, a tissue of a microorganism, animal, or plant having a glycosyltransferase can be cultured in a medium containing starch and rutin to produce α-glycosyl rutin.

In the reaction method of the present invention, a glycosyltransferase may act on a rutin-rich solution containing a high concentration of rutin and starch.

For example, when reacting rutin in a high-concentration suspension, it is about 0.5 W / V% or more, preferably about 1.0 to 5.0 W / V%.
The rutin-rich solution containing the suspended rutin and an appropriate amount of starch is adjusted to a pH of about 4.5 to 6.5, and maintained at a temperature as high as possible for the action of glycosyltransferase, specifically about 70 to 90 ° C. ,
When glycosyltransferase is allowed to act on this, suspended rutin gradually dissolves as rutin is converted to α-glycosyl rutin, and at the same time, α-glycosyl rutin, α-maltosyl rutin, α-maltotriosyl rutin, α-glycosyl rutin -Maltotetraosyl rutin, α-maltopentaosyl
Α-Glycosyl rutin, such as rutin and α-maltohexaosyl rutin, is easily produced at high concentrations. The α-glycosyl rutin-containing solution thus obtained usually contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin at room temperature and near neutrality. Approximately 0.5W / V% or more, preferably approx.
It has been found that concentrations as high as 1.0 to 5.0 W / V% are reached.

Further, for example, when reacting in the form of a high-concentration solution in which rutin is dissolved on the alkaline side exceeding pH 7.0, a pH of about
About 0.5 W / V% or more in 7.5 to 10.0 water, desirably about 1.0
To 5.0 W / V% of rutin by heating, and dissolving an appropriate amount of starch in the rutin-rich solution, the pH being as high as possible at which the glycosyltransferase can act, high temperature, specifically, pH About 7.
When maintained at 5 to 10.0 at a temperature of about 50 to 80 ° C. and reacted with glycosyltransferase, α-glycosylrutin is easily produced at a high concentration.

At this time, rutin in the alkaline solution is liable to be decomposed. Therefore, in order to prevent this, it is desirable to maintain rutin under light shielding and anaerobic as much as possible. If necessary, an antioxidant such as L-ascorbic acid or erythorbic acid may be co-present.

The α-glycosyl rutin-containing solution thus obtained usually contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin at room temperature and near neutrality, and the total amount thereof is It was found that the concentration reached about 0.5 W / V% or more, and further reached a high concentration of about 1.0 to 5.0 W / V%.

Further, for example, when the rutin is transported in the form of a high-concentration solution in an organic solvent aqueous solution, rutin is dissolved in an organic solvent by heating in advance, and then mixed with an aqueous starchy solution. Add glycosyltransferase, or heat and dissolve rutin and starch in an aqueous organic solvent,
After cooling to a predetermined temperature, a reaction is performed by adding a glycosyltransferase thereto.

The α-glycosyl rutin-containing solution thus obtained also contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin dissolved therein, and the total amount is about 1.0 to 10 W / V% in terms of rutin. It was found that high concentrations were reached.

Further, a method of combining the above conditions, for example, a rutin-rich solution containing about 2.0 to 20.0 W / V% of suspended rutin and an appropriate amount of starch at a pH of about 7.5 to 10.0 and a temperature of about 50 to 80
When maintained at ℃ ° C. and subjected to glycosyltransferase, α-glycosylrutin is also readily produced in high concentrations.

Rutin was dissolved at a high concentration of about 5.0 to 20.0 W / V% in a strongly alkaline aqueous solution such as caustic soda aqueous solution, caustic potash aqueous solution, sodium carbonate aqueous solution, calcium hydroxide aqueous solution, and ammonia water having a concentration of about 0.1 to 1.0 N. It is possible to adjust the pH to a level at which the enzyme can act by adding an acidic aqueous solution such as hydrochloric acid or sulfuric acid, add starch, and immediately activate the glycosyltransferase. This is extremely convenient. At this time, even if the rutin solution is dissolved at a high concentration, rutin is likely to be precipitated by adjusting the pH with an acidic aqueous solution.Before the pH adjustment, starch and a small amount of α-glycosyl rutin are allowed to coexist. It is also advantageous to start the transglycosylation reaction while suppressing the deposition of rutin. The α-glycosyl rutin-containing solution thus obtained usually contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin at room temperature and near neutrality, and the total amount thereof is Approx.5.0
It was found that the concentration reached as high as 20.0 W / V%.

Further, if necessary, in order to increase the solubility of rutin before the reaction and facilitate the transglycosylation reaction to rutin, an organic solvent which can be mutually dissolved with water in a rutin-rich solution, for example, methanol, ethanol, n Coexistence of lower alcohols such as -propanol, iso-propanol, n-butanol, acetol, acetone and the like, lower ketones and the like can be appropriately selected.

As described above, according to the method of the present invention, the reaction can be performed by increasing the charged concentration of rutin about 5 times or more, and even about 10 to 200 times that of the conventional method, and can easily increase α-glycosyl rutin. It has been found that a concentration can be produced.

That is, at the end of the reaction, a large amount of α-glycosyl rutin and a small amount of unreacted rutin are dissolved and contained, and the total amount is about 0.5 W / V% or more in terms of rutin, and further about 1.0 to 20.0%. W / V%, which is more than about 5 times that of the prior art, and furthermore, about 10 to 200 times.

The relatively high-molecular α-glycosyl rutin produced by the glycosyltransfer reaction may be used as it is or after being purified by a porous synthetic adsorption resin, and then purified with glucoamylase (EC 3.2.1.3) or β-amylase (EC 3.2.
1.2) partially hydrolyzed by amylase and α-
The number of α-D-glucosyl groups of glycosyl rutin can be reduced. For example, when glucoamylase is allowed to act, α-maltosyl rutin or higher polymer can be hydrolyzed to generate glucose and accumulate and generate α-glucosyl rutin.
When β-amylase is allowed to act, high-molecular substances higher than α-maltotriosyl rutin are hydrolyzed to produce maltose, and α-glycosyl rutin and α
A mixture with maltosyl rutin can accumulate and form;

The reaction solution containing α-glycosyl rutin produced as described above is used as it is for α-glycosyl rutin.
It can also be a rutin product. Usually, the reaction solution is filtered and concentrated to a syrup-like, and further dried and pulverized to a powdered α-glycosyl rutin product.

This product is not only a vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, ultraviolet absorber, deterioration As an inhibitor and the like, it can be advantageously used for various compositions such as foods and drinks, favorite foods, feeds, feeds, antisensitizing agents, cosmetics and plastic products. Further, when producing a purified α-glycosyl rutin product, it is possible to separate α-glycosyl rutin from impurities such as starch by using the difference in adsorptivity of the porous synthetic adsorbent to purify the product. Good.

The porous synthetic resin referred to in the present invention is a synthetic resin such as a porosity, large adsorption surface area, and a nonionic styrene-divinylbenzene polymer, a phenol-formalin resin, an acrylate resin, and a methacrylate resin. For example, commercially available trade names Amberlite XAD-1, Amberlite XAD-2, Amberlite XAD-, Amberlite XAD-7, Amberlite XAD-8, Amberlite XAD-11, manufactured by Rohm & Haas. Amberlite XAD-12, manufactured by Mitsubishi Kasei Kogyo Co., Ltd. Diaion HP-10, Diaion HP-20, Diaion HP-
30, Diaion HP-40, Diaion HP-50, IMACTI
Imakti Syn-42, Imakti Syn-4
4, Imakti Syn-46 and others.

The method for purifying a reaction solution that has produced α-glycosyl rutin according to the present invention is characterized in that, when the reaction solution is passed, for example, through a column filled with a porous synthetic adsorbent, α-glycosyl rutin and a relatively small amount of unreacted rutin Is adsorbed to the porous synthetic adsorbent, whereas a large amount of coexisting starch and water-soluble saccharide flow out without being adsorbed.

In particular, when the reaction solution contains an organic solvent, the concentration of the organic solvent is reduced, and the solution is brought into contact with the porous synthetic adsorbent. Similarly, α-glycosyl rutin contained in the reaction solution And rutin may be adsorbed and purified.

If necessary, after the completion of the glycosyltransferase reaction and before contact with the porous synthetic adsorbent, for example, the reaction solution is heated to remove insolubles generated by filtration, or magnesium aluminate silicate, alumina Adsorb and remove proteinaceous substances in the reaction solution by treating with magnesium acid, etc., or treat with strong acidic ion exchange resin (H type), medium basic or weak basic ion exchange resin (OH type), etc. It is optional to use a combination of purification methods such as desalting.

As described above, α-glycosyl rutin selectively adsorbed on the porous synthetic adsorbent column and a relatively small amount of unreacted rutin are washed with a dilute alkali, water, etc., and then washed with a relatively small amount of an organic solvent or When a mixture of an organic solvent and water, for example, methanol water or ethanol water, is passed, first, α-glycosyl rutin is eluted, and unreacted rutin is increased by increasing the amount of liquid passed or increasing the concentration of the organic solvent. Elutes.

The eluate having a high content of α-glycosyl rutin is subjected to a distillation treatment, an organic solvent is first distilled off, and then concentrated to an appropriate concentration to obtain a syrup-like product containing α-glycosyl rutin as a main component. Further, by drying and pulverizing the product, a powdery product containing α-glycosyl rutin as a main component is obtained.

Since the elution operation of α-glycosyl rutin and unreacted rutin with the organic solvent is also a regeneration operation of the porous synthetic adsorbent, the porous synthetic adsorbent can be used repeatedly.

Further, the purification by the porous synthetic adsorbent of the present invention has a feature that not only starches and water-soluble saccharides but also impurities such as water-soluble salts can be removed at the same time. Α-Glycosyl rutin thus obtained has the following features.

(1) Compared with rutin, α-glycosyl rutin has extremely high water solubility.

(2) α-Glycosyl rutin has higher light resistance and stability than rutin.

(3) α-glycosyl rutin has strong antioxidant ability. As an antioxidant, it can be advantageously used to prevent oxidation of oily foods and drinks, oily anti-sensitivity agents, oily cosmetics, and the like.
In particular, when used as an anti-sensitivity drug, it exerts its effects as an antioxidant, such as removing active oxygen and suppressing the production of lipid peroxide, and prevents, treats, maintains and promotes various sensitivities. It is convenient. Also, α-glycosyl
Rutin, unlike thiamine, riboflavin, vitamin C, vitamin E and other vitamins and antioxidants,
It is practically tasteless and odorless, and can be used safely without fear of discoloration, browning and off-flavors. It is also possible to use α-glycosyl rutin in combination with one or more other vitamins and antioxidants. It is convenient.

(4) α-Glycosyl rutin is hydrolyzed into rutin and glucose by enzymes in the body, and exhibits the original physiological activity (vitamin P) of rutin. In addition, the combined use with vitamin C can enhance their biological activity.

(5) In the case of a product containing starch, not only the effect of α-glycosyl rutin is exerted, but also the starch can exert shaping, bulking and sweetening effects. In the case of a purified product by removing, the effect of α-glycosyl rutin can be exerted with almost no shaping or increase in volume, and it can be freely seasoned and flavored because it is virtually tasteless and odorless it can.

Because of these features, α-glycosyl rutin is not only a highly safe natural vitamin P enhancer,
A yellow colorant, an antioxidant, a stabilizer, a fading inhibitor, alone or in combination with one or more other components.
Food and drinks, foods, feeds, feeds, feeds, anti-sensitivity agents, skin care agents, as quality improvers, prophylactics, therapeutic agents, ultraviolet absorbers, etc. for susceptibility diseases such as viral diseases, bacterial diseases, cardiovascular diseases, malignant tumors, etc. Agents, cosmetics such as whitening agents, and further, are blended with various compositions such as plastic products.
More than 001 W / W% can be used advantageously.

Also, α-glycosyl rutin is well-harmonized with various substances having tastes such as sourness, salty taste, astringency, umami, and bitterness, and has high acid resistance and heat resistance. For example, soy sauce, powdered soy sauce, miso, powdered miso, moromi, Hishio, furikake, mayonnaise, dressing, vinegar, three vinegar vinegars, powdered sushi vinegar, Chinese ingredients, Tentsuyu,
Noodle soup, sauce, ketchup, grilled meat sauce, curry roux, stew ingredients, soup ingredients, dashi ingredients, compound seasonings, mirin, new mirin, table sugar, coffee sugar, and other seasonings, rice crackers, hail, oshi ,
Karinto, fertilizer, rice cakes, steamed buns, buns, seaweed, sweets such as yokan, mizuyokan, nishikidama, jelly, castella, candy, bread, biscuits, crackers, cookies, pies, puddings, cream puffs, waffles, sponges Cake, donut, chocolate, chewing gum,
Various confectionery such as caramel and candy, ice cream, sherbet and other frozen desserts, fruit syrup pickles, ice honey and other syrups, butter cream, custard cream, flower paste, peanut paste, fruit paste and other spreads, pastes, jams , Marmalade, syrup pickles, fruits such as sugar cane, processed foods of vegetables, breads, noodles, cooked rice, processed foods of shells such as artificial meat, oil and fat foods such as salad oil, margarine,
Pickles such as Fukujinzuke, Betarazuke, Senmaizuke, Rakkyozuke, pickles such as Takuan-zuke, Shimozuke-zuke, meat products such as ham and sausage, fish ham, fish sausage, kamaboko, chikuwa, hampen etc. Fish meat products,
Various delicacies such as sea urchin, salted squid, vinegar kelp, Sakisame, Fugu mirin dried, seaweed, wild vegetables, sardines, small fish,
Boiled tsukuda, boiled beans, potato salad, etc.
Vegetables such as kelp, tempura, kinshi egg, milk drink,
Eggs such as butter and cheese, dairy products, fish meat, meat, fruits,
Bottled vegetables, canned foods, synthetic liquor, brewed liquor, fruit liquor,
Alcoholic beverages such as Western liquor, coffee, cocoa, juice, tea, black tea, oolong tea, carbonated drinks, soft drinks such as lactic acid drinks, lactic acid drinks, pudding mix, hot cake mix, instant juice, instant Kobe, instant shiruko, instant soup, etc. It can be advantageously blended with instant foods and drinks for the purpose of vitamin P enhancer, yellow colorant, antioxidant, quality improver, stabilizer and the like. Livestock, poultry, bees,
It is also convenient to use it in feeds and feeds for breeding animals such as silkworms and fish for the purpose of enhancing vitamin P, an antioxidant, and improving palatability.

In addition, various solids and pastes such as tobacco, troches, liver oil drops, multivitamin preparations, oral fresheners, mouthwash tablets, gargles, tube nutrients, oral medications, injections, toothpaste, lipstick, lip balm, sunscreen, etc. State, liquid taste, prophylactic agent for susceptibility disease, therapeutic agent, ie, anti-sensitivity disease agent, skin beautifying agent, can be advantageously used in combination with cosmetics such as skin lightening agent, furthermore, ultraviolet absorber, It can also be advantageously implemented by blending it in a plastic product or the like as a deterioration inhibitor or the like.

In addition, the susceptibility disease referred to in the present invention is a disease that is prevented or treated by α-glycosyl rutin, and includes, for example, viral disease, bacterial disease, traumatic disease, immune disease, rheumatism, diabetes, It may be a circulatory disease, a malignant tumor or the like. The prophylactic or therapeutic agent for α-glycosyl rutin susceptibility disease can be freely selected in form according to the purpose. Examples thereof include liquid preparations such as sprays, eye drops, nasal drops, gargles, and injections, pastes such as ointments, plaques, creams, and solid preparations such as powders, granules, capsules, and tablets. In the preparation, if necessary, other components, for example, therapeutic agents, bioactive substances, antibiotics, adjuvants, bulking agents, stabilizers, coloring agents,
It is optional to use one kind or two or more kinds of flavoring agents and the like.

The dose can be appropriately adjusted depending on the content, administration route, administration frequency and the like. Usually, a range of about 0.001 to 50.0 g per day for an adult is preferable as α-glycosyl rutin.

Also, in the case of cosmetics, it can be used according to the above-mentioned prophylactic and therapeutic agents.

As a method of using α-glycosyl rutin, a known method such as kneading, kneading, dissolving, dipping, penetrating, spraying, coating, spraying, or pouring is appropriately used in the steps until the products of the various compositions are completed. To be elected.

Hereinafter, the non-toxicity of the α-glycosyl rutin of the present invention will be described by experiments.

Experiment Using a 7-year-old dd mouse, an acute toxicity test was conducted by oral administration of α-glycosyl rutin prepared by the method of Example A-3. As a result, deaths were observed up to 5 g per kg of body weight. Did not. Therefore, the toxicity of this substance is extremely low.

When this test was performed using α-glycosyl rutin prepared by the method of Example A-2, similar results were obtained, and it was found that the toxicity was extremely low. Hereinafter, as examples of the present invention, a production example of α-glycosyl rutin will be described in Example A, and application examples of α-glycosyl rutin in various compositions will be described in Example B.

Example A-1 α-Glycosyl rutin 3 parts by weight of rutin and 15 parts by weight of dextrin (DE18) were mixed with 97 parts by weight of hot water at 80 ° C. to form a suspension-rich rutin-rich solution, which was mixed with Bacillus stearo. Thermofils (Ba
Cylus stearothermophilus) -derived cyclomaltodextrin glucanotransferase (manufactured by Hayashibara Biochemical Laboratory Co., Ltd.) was added at 20 units per dextrin ram, and the mixture was reacted at pH 6.0, 75 ° C. and stirring for 64 hours while stirring. When the reaction solution was analyzed by paper chromatography, about 85% of the rutin was α-glycosyl rutin, α
-Converted to α-glycosyl rutin such as maltosyl rutin, α-maltotriosyl rutin, α-maltotetraosyl rutin and α-maltopentaosyl rutin. Deactivate the enzyme that heated the reaction, filter,
The filtrate is concentrated to give an α-glycosyl rutin product containing syrup-like starchy material in an amount of about
Obtained in 90% yield.

This product is not only a vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, ultraviolet absorber, etc. It can be advantageously used for various compositions such as foods and drinks, favorite foods, feeds, feeds, antisensitizing agents, cosmetics, and plastic products.

Example A-2 1 part by weight of α-glycosyl rutin product containing syrup-like starchy substance prepared according to the method of Example A-1 was dissolved in 4 parts by weight of water and adjusted to pH 5.0. Glucoamylase (EC 3.2.1.3, sold by Seikagaku Corporation)
-100 units per gram of solid product of glycosyl rutin was added and reacted at 50 ° C for 5 hours. When the reaction solution was analyzed by paper chromatography, α-glycosyl rutin was converted to α-glycosyl rutin.

The reaction solution was heated to deactivate the enzyme, filtered, and the filtrate was passed through a column of a porous synthetic adsorbent, trade name Diaion HP-10 (available from Mitsubishi Kasei Kogyo Co., Ltd.) at SV2. As a result, α-glycosyl rutin and unreacted rutin in the solution were adsorbed on the porous synthetic adsorbent, and glucose, salts, and the like flowed out without being adsorbed. Next, the column was passed through with water and washed, and then passed while increasing the concentration of the aqueous ethanol solution stepwise to collect an α-glycosyl rutin fraction,
After concentration under reduced pressure and pulverization, powdery α-glycosyl rutin was obtained in a yield of about 80% based on the weight of the raw material rutin per solid.

When the α-glycosyl rutin was hydrolyzed with an acid, 1 mol of L-rhamnose per 1 mol of quercetin,
It was found that 2 mol of D-glucose was produced, and when α-glycosidase, which was extracted from pig liver and partially purified, was allowed to act on α-glycosylrutin, it was hydrolyzed to rutin and D-glucose.

The α-glycosyl rutin is a highly purified and highly water-soluble vitamin P enhancer, as well as a yellow colorant,
Antioxidants, stabilizers, anti-fading agents, quality improving agents, prophylactic agents,
It can be advantageously used as a therapeutic agent, an ultraviolet absorber, and the like for various compositions such as foods and drinks, palatables, anti-sensitivity agents, and cosmetics.

Example A-3 α-Glycosyl rutin 4 parts by weight of rutin were dissolved in 90 parts by weight of water under heating at pH 9.5,
Separately, 20 parts by weight of dextrin (DE8) is dissolved by heating in 10 parts by weight of water, and then these solutions are mixed to obtain a solution-rich rutin-rich solution, to which is added 30 units of cyclomaltodextrin glucanotransferase per dextrin trauma. The reaction was continued for 40 hours with stirring at pH 8.2 and 65 ° C.

When the reaction solution was analyzed by paper chromatography, about 90% of the rutin was converted to α-glycosylrutin.

The reaction solution was heated to inactivate the enzyme, filtered, and the filtrate was filtered using a porous synthetic adsorbent, trade name Amberlite XAD-7 (Rohm &
(Manufactured by Haas) at SV 1.5.

As a result, α-glycosyl rutin and unreacted rutin in the solution are adsorbed on the porous synthetic adsorbent, and dextrin,
Oligosaccharides and salts flowed out without adsorption.

After the column was washed with water and washed with water, 50 V / V% methanol was passed through to elute α-glycosyl rutin and rutin, which were concentrated and powdered to obtain a powdered α-glycosyl rutin product. Approximately 140 based on the weight of rutin
% Yield.

This product is not only a highly water-soluble vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant,
Foods, foods, tastes, etc. as stabilizers, anti-fading agents, quality improving agents, prophylactic agents, therapeutic agents, ultraviolet absorbers, deterioration inhibitors, etc.
It can be advantageously used for various compositions such as feed, feed, anti-sensitivity agents, cosmetics, and plastic products.

Example A-4 α-Glycosyl rutin 1 part by weight of rutin was dissolved in 4 parts by weight of 1N sodium hydroxide solution, neutralized by adding a 0.01N hydrochloric acid solution, and 5 parts by weight of dextrin (DE10) was added. Maltodextrin glucanotransferase was added at 10 units per dextrin gram, and the mixture was reacted at pH 6.0 and 70 ° C. for 40 hours.

When the reaction solution was analyzed by paper chromatography, about 80% of the rutin was converted to α-glycosyl rutin.

The reaction solution was purified, concentrated and powdered in the same manner as in Example A-3 to obtain a powdery α-glycosyl rutin product in a yield of about 120% based on the weight of the raw material rutin.

This product is not only a highly water-soluble vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, as in the case of Example A-3. As quality improvers, prophylactics, therapeutics, UV absorbers, etc.
It can be used for applications to various compositions.

Example A-5 α-Glycosyl rutin (1) Preparation of α-glycosidase preparation Maltose 4.0 W / V%, potassium monophosphate 0.1 W / V%, ammonium nitrate 0.1 W / V%, magnesium sulfate 0.05 W / V
%, Potassium chloride 0.05W / V%, polypeptone 0.2W / V%,
Mucor javanicus IFO 4570 was shake-cultured at a temperature of 30 ° C. for 44 hours in 500 parts by weight of a liquid medium consisting of calcium carbonate 1 W // V% (separately dry-heat sterilized and aseptically added at the time of inoculation) and water. . After completion of the culture, the mycelium was collected, and to 48 parts by weight of the wet mycelium, 500 parts by weight of a 4 M urea solution dissolved in 0.5 M acetate buffer (pH 5.3) was added.
After leaving still for 40 hours, it was centrifuged. The supernatant was dialyzed overnight in running water, adjusted to 0.9 saturation with ammonium sulfate, allowed to stand at 4 ° C. overnight, and the formed salt precipitate was collected by filtration. A 0.01 M acetate buffer (pH 5.3) was used.
After suspending and dissolving in 50 parts by weight, the supernatant was collected by centrifugation to obtain an α-glucosidase preparation.

(2) Preparation of α-glycosyl rutin 5 parts by weight of rutin was dissolved in 40 parts by weight of 0.5N caustic soda solution, adjusted to pH 9.5 with a 5N hydrochloric acid solution, and 20 parts by weight of dextrin (DE30) was added to water. The resulting solution was dissolved by heating in 10 parts by weight, and then these solutions were mixed to obtain a suspended rutin-rich solution.
10 parts by weight of a glucosidase preparation was added, and the mixture was reacted at 55 ° C. for 40 hours with stirring while maintaining the pH at 8.5.

When the reaction solution was analyzed by paper chromatography, about 60% of the rutin was converted to α-glycosyl rutin.

The reaction solution was purified, concentrated and powdered in the same manner as in Example A-3 to obtain a powdery α-glycosyl rutin product in a yield of about 110% based on the weight of the raw material rutin.

This product is not only a highly water-soluble vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, as in the case of Example A-3. As quality improvers, prophylactics, therapeutics, UV absorbers, etc.
It can be used for applications to various compositions.

Example A-6 α-glycosyl rutin 1 part by weight of rutin and 15 parts by weight of dextrin (DE18) were added to 40 parts by weight.
Dissolved in 99 parts by weight of a 50V / V% methanol aqueous solution heated to 25 ° C, cooled to 25 ° C, and added with cyclomaltodextrin.
Glucanotransferase (available from Hayashibara Biochemical Laboratories, Inc.) is added at 20 units per dextrin trauma, and pH 6.
The reaction was adjusted to 0 and reacted for 72 hours. When the reaction mixture was analyzed by paper chromatography, about 80% of the rutin was
α-glucosyl rutin, α-maltosyl rutin, α
Α-maltotriosyl rutin, α-maltotetraosyl rutin, α-maltopentaosyl rutin, etc.
Had been converted to glycosyl rutin. After the reaction, the reaction mixture was concentrated under reduced pressure to distill off methanol, and then heated to inactivate the enzyme. It was obtained in a yield of about 95% based on the weight of the raw material.

This product is not only a vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, ultraviolet absorber, etc. It can be advantageously used for various compositions such as foods and drinks, favorite foods, feeds, feeds, antisensitizing agents, cosmetics, and plastic products.

Example A-7 α-Glycosyl rutin 1 part by weight of an α-glycosyl rutin product containing syrup-like starchy substance prepared according to the method of Example A-6 was dissolved in 4 parts by weight of water, and glucoamylase was added thereto. (EC 3.
2.1.3, sold by Toyobo Co., Ltd.) was added at 100 units per gram of solid α-glycosyl rutin product, and reacted at 50 ° C. for 5 hours. When the reaction solution was analyzed by paper chromatography, α-glycosyl rutin was converted to α-glucosyl rutin.

The reaction solution was heated to inactivate the enzyme, filtered, and the filtrate was passed through a column of a porous synthetic adsorbent, Diaion HP-10 (trade name, sold by Mitsubishi Chemical Industry Co., Ltd.) at SV2. As a result, α-glucosyl rutin and unreacted rutin in the solution were adsorbed on the porous synthetic adsorbent, and dextrin, oligosaccharides, glucose, salts and the like flowed out without being adsorbed. Next, the column was passed through with water and washed, and then the ethanol aqueous solution was passed while increasing the concentration stepwise, and the α-glucosyl rutin fraction was collected, concentrated under reduced pressure, and powdered.
The powdery α-glucosyl rutin was obtained in a yield of about 80% based on the weight of the raw material rutin per solid.

As in the case of Example A-2, the present α-glucosyl rutin was used as a highly purified water-soluble vitamin P enhancer, as well as a yellow colorant, an antioxidant, a stabilizer, a discoloration inhibitor, As a quality improving agent, a preventive agent, a therapeutic agent, an ultraviolet absorber, and the like, it can be advantageously used for various compositions such as foods and drinks, palatables, antisensitizing agents, and cosmetics.

Example A-8 α-Glycosyl rutin 1 part by weight of rutin was dissolved by heating in 5 parts by weight of a 50 V / V% aqueous ethanol solution, and 10 parts by weight of dextrin (DE8) was separately dissolved in water 4 parts.
Heat and dissolve in 5 parts by weight, then mix these solutions,
Cyclomaltodextrin glucanotransferase was added at 10 units per dextrin ram, adjusted to pH 6.0, and reacted at 50 ° C. for 24 hours.

When the reaction solution was analyzed by paper chromatography, about 90% of the rutin was converted to α-glycosyl rutin.

The reaction solution was concentrated under reduced pressure, ethanol was distilled off, and then the enzyme was deactivated by heating. The solution was filtered, and the filtrate was columnated with a porous synthetic adsorbent, trade name Amberlite XAD-7 (manufactured by Rohm & Haas). Through SV1.5.

As a result, α-glycosyl rutin and unreacted rutin in the solution are adsorbed on the porous synthetic adsorbent, and dextrin,
Oligosaccharides and salts flowed out without adsorption.

After the column was washed with water and washed with water, 50 V / V% methanol was passed through to elute α-glycosyl rutin and rutin, which were concentrated and powdered to obtain a powdered α-glycosyl rutin product. Approximately 140 based on the weight of rutin
% Yield.

This product is not only a highly water-soluble vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant,
As food stabilizers, fading inhibitors, quality improving agents, prophylactic agents, therapeutic agents, ultraviolet absorbers, etc.
It can be advantageously used for various compositions such as anti-sensitivity agents, cosmetics and plastic products.

Example A-9 α-Glycosyl rutin One part by weight of rutin was dissolved in 5 parts by weight of a 60 V / V% methanol aqueous solution while heating, and 20 parts by weight of dextrin (DE30) was separately dissolved in water.
Heat and dissolve in 27 parts by weight, then mix these solutions,
8 parts by weight of the α-glucosidase preparation prepared by the method of Example A-5 (1) was added thereto, and the mixture was maintained at 40 ° C. while maintaining the pH at 5.3.
For 40 hours.

When the reaction solution was analyzed by paper chromatography, about 60% of the rutin was converted to α-glycosyl rutin.

After the reaction solution was concentrated under reduced pressure and methanol was distilled off, the residue was purified in the same manner as in Example A-8, concentrated and powdered to obtain a powder α.
-A glycosyl rutin product is obtained in a yield of about 110% based on the weight of the raw rutin.

This product, as in Example A-8, is not only a highly water-soluble vitamin P enhancer, but also a highly safe natural yellow colorant, antioxidant, stabilizer, anti-fading agent, As quality improvers, prophylactics, therapeutics, UV absorbers, etc.
It can be used for applications to various compositions.

Example A-10 α-Glycosyl rutin 1 part by weight of a syrupy starch-containing α-glycosyl rutin product prepared according to the method of Example A-6 is dissolved in 4 parts by weight of water, and β- Amylase (EC 3.2.
1.2, sold by Toyobo Co., Ltd.) was added at 100 units per gram of solid α-glycosyl rutin product, and reacted at 50 ° C. for 5 hours. When the reaction solution was analyzed by paper chromatography, α-glycosyl rutin was mainly α-glycosyl rutin.
It had been converted to α-glycosyl rutin consisting of glucosyl rutin and α-maltosyl rutin.

The reaction solution was heated to deactivate the enzyme, filtered, and the filtrate was passed through a column of a porous synthetic adsorbent, trade name Diaion HP-10 (available from Mitsubishi Kasei Kogyo Co., Ltd.) at SV2. As a result, α-glycosyl rutin and unreacted rutin in the solution are adsorbed on the porous synthetic adsorbent, and maltose, oligosaccharide,
Glucose, salts and the like flowed out without being adsorbed. Next, the column was passed through with water and washed, and then passed while increasing the concentration of the ethanol aqueous solution in a stepwise manner.
The rutin fraction was collected, concentrated under reduced pressure, and pulverized to obtain powdery α-glycosyl rutin in a yield of about 85% based on the weight of the raw material rutin per solid.

When glucoamylase is allowed to act on this α-glycosyl rutin, it is hydrolyzed to α-glucosyl rutin and D-glucose, and when α-glucosidase extracted from pig liver and partially purified is allowed to act, rutin and D-glucosidase are reacted.
-Hydrolyzed to glucose.

The α-glycosyl rutin is a highly purified and highly water-soluble vitamin P enhancer, as well as a yellow colorant,
Antioxidants, stabilizers, anti-fading agents, quality improving agents, prophylactic agents,
It can be advantageously used as a therapeutic agent, an ultraviolet absorber and the like for various compositions such as foods and drinks, palatables, anti-sensitivity agents, cosmetics and plastic products.

Example B-1 Hard candy 1,500 parts by weight of reduced maltose syrup (manufactured by Hayashibara Shoji Co., Ltd., registered trademark: Mavit) were heated, concentrated under reduced pressure until the water content became about 2% or less, and 15 parts by weight of citric acid and One part by weight of the powdery α-glycosyl rutin obtained by the method of Example A-3 and a small amount of lemon flavor were mixed, and then molded and packaged according to a conventional method to obtain a hard candy.

This product is a yellow lemon candy fortified with vitamin P, and has low caries and low calories.

Example B-2 Boiled Butterfly Butterfly peeled, cut into appropriate lengths, immersed in thin saline for several hours, and syrup-shaped α-glycosyl rutin obtained by the method of Example A-1 And a blue color No. 1 were blended and the mixture was boiled with a liquid containing a green colorant to obtain boiled green butterflies in water.

This product not only adds color to various Japanese-style dishes, but also has a physiological effect as a dietary fiber.

Example B-3 1.2 parts by weight of water was mixed with 1 part by weight of fertilizer waxy seeds, and gelatinized by heating, and then 1.5 parts by weight of sugar and 0.7 parts of crystalline β-maltose (manufactured by Hayashibara Co., Ltd., San Mart) 0.7 Parts by weight, 0.3 parts by weight of starch syrup and 0.2 parts by weight of syrup-like α-glycosyl rutin obtained by the method of Example A-6,
Thereafter, the fertilizer was manufactured by molding and packaging according to a conventional method.

This product has good flavor and mouthfeel fertility, and is a kibidango-style Japanese confectionery.

Example B-4 100 parts by weight of a mixed sweetener, 50 parts by weight of isomerized sugar, 2 parts by weight of brown sugar, and 1 part by weight of powdered α-glycosyl rutin obtained by the method of Example A-9 are mixed and mixed. I got a sweetener.

This product is a sweetener enriched with vitamin P and is suitable as a health food.

Example B-5 Sand cream 1,200 parts by weight of crystalline α-maltose (manufactured by Hayashibara Co., Ltd., fine tose), 1,000 parts by weight of shortening, 10 parts by weight of powdered α-glycosyl rutin obtained by the method of Example A-8 Parts, lecithin 1 part by weight, lemon oil 1
1 part by weight of vanilla oil and 1 part by weight of vanilla oil were mixed by a conventional method to produce a sand cream.

This product is a sand cream enriched with vitamin P and colored yellow, prevents oxidation of fats and oils, and has good mouthfeel, melting condition and flavor.

Example B-6 Orange Juice 50 parts by weight of orange juice, 0.1 part by weight of citric acid, sugar 5
Parts by weight, 0.5 part by weight of powdery α-glycosyl rutin obtained by the method of Example A-5, 0.1 part by weight of L-ascorbic acid (vitamin C), an appropriate amount of flavor and 46 parts by weight of water,
Then, the mixture was filled in a container and sterilized according to a conventional method to obtain an orange juice product.

This product is orange juice fortified with vitamin P and vitamin C, and has good color tone and flavor.

Example B-7 Tablet 20 parts by weight of ascorbic acid were uniformly mixed with 13 parts by weight of crystalline β-maltose, 4 parts by weight of corn starch and 3 parts by weight of powdered A-glucosyl rutin obtained by the method of Example A-7. Thereafter, tablets were obtained using a 20R punch having a diameter of 12 mm to obtain tablets.

This product is a multivitamin preparation of L-ascorbic acid and α-glucosyl rutin, and is a tablet with good ascorbic acid stability and easy to drink.

Example B-8 Capsule formulation 10 parts by weight of calcium acetate / monohydrate, 50 parts by weight of L-magnesium lactate / trihydrate, 57 parts by weight of maltose, Example A
After uniformly mixing 20 parts by weight of powdery α-glucosyl rutin and 12 parts by weight of a γ-cyclodextrin clathrate compound containing 20% of eicosapentaenoic acid obtained by the method of -2, the mixture is subjected to a granulating machine to obtain granules. According to the method, the mixture was encapsulated in a gelatin capsule to produce a capsule containing 150 mg of one capsule.

This product prevents the oxidation of eicosapentaenoic acid and can be advantageously used as a high-quality blood cholesterol lowering agent, immunostimulant, skin-beautifying agent, prophylactic agent for susceptibility diseases, therapeutic agent, food for promoting health, etc. .

Example B-9 Ointment 1 part by weight of sodium acetate / trihydrate and 4 parts by weight of DL-calcium lactate were uniformly mixed with 10 parts by weight of glycerin, and this mixture was mixed with 50 parts by weight of petrolatum, 10 parts by weight of wood wax, Ointment is prepared by adding 10 parts by weight of lanolin, 14.5 parts by weight of sesame oil, 1 part by weight of powdery α-glycosyl rutin obtained by the method of Example A-4, and 0.5 part by weight of mint oil, and further uniformly mixing. did.

The product has an antioxidant property, a high stability, and can be advantageously used as a high-quality sunscreen, skin-beautifying agent, fairing agent, etc., and also as a healing promoter for external wounds and burns.

Example B-10 Injection The powdery α-glucosyl rutin obtained by the method of Example A-7 was dissolved in water, purified and filtered according to a conventional method to be pyrogen-free, and the solution was placed in a 20 mL ampoule. -Dispensed 200 mg of glucosyl rutin, dried under reduced pressure, and sealed to produce an injection.

The injection can be administered alone or mixed with other vitamins, minerals, etc., intramuscularly or intravenously. In addition, the product does not need to be stored at low temperature, and has extremely good solubility in physiological saline and the like when used.

This product is effective not only for supplementing vitamin P but also as an antioxidant to remove active oxygen and suppress the production of lipid peroxide, and is effective for various diseases such as viral diseases, bacterial diseases, cardiovascular diseases, and malignant tumors. It can be advantageously used as a prophylactic or therapeutic agent for diseases.

Example B-11 Propellant 6 parts by weight of sodium chloride, 0.3 part by weight of potassium chloride,
0.2 parts by weight of calcium chloride, 3.1 parts by weight of sodium lactate,
45 parts by weight of maltose and 2 parts by weight of powdery α-glucosyl rutin obtained by the method of Example A-2 were dissolved in 1,000 parts by weight of water, purified and filtered according to a conventional method to be pyrogen-free, and this solution was sterilized. Injections were prepared by filling each 250 mL into a plastic container.

This product is an injection for supplementing calories, supplementing minerals, removing active oxygen and suppressing the production of lipid peroxide, as well as vitamin P supplementation. Furthermore, viral diseases, bacterial diseases,
It can be advantageously used as a prophylactic or therapeutic agent for various diseases such as circulatory diseases and malignant tumors.

Example B-12 Tube feeding nutrient 20 parts by weight of crystalline α-maltose, 1.1 parts by weight of glycine, 0.18 parts by weight of sodium glutamate, 1.2 parts by weight of sodium chloride, 1 part by weight of citric acid, 0.4 parts by weight of calcium lactate, 0.1 parts by weight of magnesium carbonate Parts, 0.1 part by weight of powdery α-glycosyl rutin obtained by the method of Example A-8,
A formulation consisting of 1 part by weight and riboflavin 0.01 part by weight is prepared. Each 24 g of the blend was filled into a laminated aluminum pouch and heat sealed to prepare a tube nutritional supplement.

The tube-feeding nutrient can be advantageously used as an oral or parenteral nutritional supplement for the nasal cavity, stomach, intestine, etc. by dissolving one bag in about 300 to 500 mL of water by a tube-feeding method.

Example B-13 Bath preparation 21 parts by weight of DL-sodium lactate, 8 parts by weight of sodium pyruvate, 5 parts by weight of syrup-like α-glycosyl rutin obtained by the method of Example A-1 and 40 parts by weight of ethanol
26 parts by weight of purified water and an appropriate amount of a coloring agent and a fragrance were mixed to prepare a bath agent.

The product is suitable as a skin-beautifying agent and a skin-whitening agent, and may be used after being diluted 100 to 10,000 times with hot water for bathing. As in the case of hot water for bathing, this product can be advantageously used by diluting it in face wash water, lotion and the like.

Example B-14 Emulsion 0.5 parts by weight of polyoxyethylene behenyl ether, 1 part by weight of polyoxyethylene sorbitol tetraoleate, 1 part by weight of lipophilic glyceryl monostearate, 0.5 part by weight of pyruvate, 0.5 part by weight of behenyl alcohol, avocado 1 part by weight of oil, powdery α- obtained by the method of Example A-3
Glycosyl rutin (1 part by weight), an appropriate amount of vitamin E and a preservative are dissolved by heating according to a conventional method, and 1 part by weight of sodium L-lactate, 5 parts by weight of 1,3-butylene glycol,
0.1 part by weight of carboxyvinyl ponymer and 85.3 parts by weight of purified water were added, emulsified with a homogenizer, and an appropriate amount of a flavor was added, followed by stirring and mixing to produce an emulsion.

This product has antioxidant properties, is highly stable, and can be advantageously used as a high-quality sunscreen, skin-beautifying agent, skin-whitening agent, and the like.

Example B-15 Cream 2 parts by weight of polyoxyethylene glycol monostearate, 5 parts by weight of self-emulsifying glyceryl monostearate, powdered α-glucosyl obtained by the method of Example A-2
2 parts by weight of rutin, 1 part by weight of liquid paraffin, 10 parts by weight of glycerin trioctanoate and an appropriate amount of a preservative are dissolved by heating according to a conventional method, and 2 parts by weight of L-lactic acid, 5 parts by weight of 1,3-butylene glycol and 66 parts by weight of purified water was added, and the mixture was emulsified with a homogenizer, and an appropriate amount of a flavor was further added, followed by stirring and mixing to produce a cream.

The product has antioxidant properties, high stability, and can be advantageously used as a high-quality sunscreen, skin-beautifying agent, fair-skin agent and the like.

Example B-16 Antioxidant 10 parts by weight of powdery α-glycosyl rutin obtained by the method of Example A-10, 2 parts by weight of vitamin E, 0.1 part by weight of lecithin and 0.5 part by weight of sodium citrate were mixed together to form an antioxidant. Agent was obtained.

This product is for oily foods such as margarine and butter cream,
About 0.01 to 0.01 for cosmetics such as unsaturated fatty acids, oil-based vitamins, oil-sensitive hormones, and other anti-sensitive diseases, emulsions, and creams
It can be advantageously used as an antioxidant, a stabilizer, a quality improver, etc. by blending 5.0W / W%.

Example B-17 Antioxidant An antioxidant was obtained by mixing 10 parts by weight of powdery α-glucosyl rutin obtained by the method of Example A-2 and 0.2 part by weight of sodium citrate.

This product is for oily foods such as margarine and butter cream,
About 0.01 to 0.01 for cosmetics such as unsaturated fatty acids, oil-based vitamins, oil-sensitive hormones, and other anti-sensitive diseases, emulsions, and creams
5.0W / W% blended, moreover, about 0.01 ~ 2.0W / W% blended in foods and drinks containing natural pigments which are easy to fade, antioxidant, stabilizer, fading inhibitor, quality improver It can be used advantageously as such.

[Effects of the Invention] As described in the text, the present invention provides a method for producing a-glycosylrutin by reacting a glycosyltransferase with a rutin-rich solution containing a high concentration of rutin and starch to cause a glycosyltransferase reaction. Is desirably prepared by adding rutin in a high-concentration suspension or in a high-concentration solution in which the rutin is dissolved at an alkaline pH or dissolved in an organic solvent aqueous solution to carry out a sugar transfer reaction. It has been found that the reaction can be carried out at a concentration of about 5 times or more, preferably about 10 to 200 times that of the prior art, and that α-glycosyl rutin can be easily produced at a high concentration. Glycosyltransferase is allowed to act on the solution containing
By reacting amylase, α-glucosyl rutin and / or α-maltosyl rutin
Found that glycosyl rutin is well produced,
Furthermore, in the purification after the reaction, it was found that the α-glycosyl rutin can be purified by contacting the reaction mixture with a porous synthetic adsorbent. Particularly, when the reaction solution contains an organic solvent, the organic solvent is used. After reducing the concentration, the solution was brought into contact with a porous synthetic adsorbent, and it was found that the solution could be purified in the same way.The amount of water used for the production of α-glycosylrutin, the amount of purified water, and the energy cost could be significantly reduced. It is extremely easy to realize the industrialization.

The α-glycosyl rutin obtained in this way has good water solubility, good light fastness and stability, and is hydrolyzed to rutin and glucose by enzymes in the body to exhibit the original physiological activity of rutin. Not only as a highly safe natural vitamin P enhancer,
As a yellow colorant, antioxidant, stabilizer, anti-fading agent, quality improving agent, prophylactic agent, therapeutic agent, ultraviolet absorber, anti-deterioration agent, etc., food and drink, favorite food, feed, feed, anti-sensitivity agent,
The composition is advantageously used for cosmetics such as skin-beautifying agents and skin-whitening agents, and various compositions such as plastic products.

Therefore, establishment of the industrial production method of α-glycosyl rutin and its use according to the present invention has great industrial significance in the food and drink, cosmetics, pharmaceutical and plastic industries.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 31/71 A61K 31/71 // C07H 17/07 C07H 17/07

Claims (11)

(57) [Claims] The present invention relates to a rutin-rich solution containing a high concentration of rutin at a concentration of 0.5 w / v% or more and a starchy substance.
-A method for producing α-glycosyl rutin, which comprises producing and collecting glycosyl rutin. 2. The high-concentration rutin is a high-concentration suspended rutin, or a high-concentration solution rutin dissolved at an alkaline pH or dissolved in an organic solvent aqueous solution. 2. The method for producing α-glycosyl rutin according to 1. 3. The method for producing α-glycosyl rutin according to claim 1, wherein the high-concentration rutin is a high-concentration rutin of 1.0 w / v% or more. 4. A method according to claim 1, wherein a glycosyltransferase is acted on, and then amylase is acted on to produce α-glycosyl rutin and / or α-maltocin rutin, which is collected. The method for producing α-glycosyl rutin according to the above. 5. The reaction of a glycosyltransferase followed by the action of an amylaza to produce α-glycosyl rutin and / or α-maltosyl rutin, and the solution is contacted with a porous synthetic adsorbent for purification. The method for producing α-glycosyl rutin according to claim 1, 2, 3, or 4, wherein α-glycosyl rutin and / or α-maltosyl rutin are collected. 6. A glycosyltransferase is allowed to act on a rutin-rich solution containing rutin at a high concentration of 0.5 w / v% or more and starch, and α
-A method for producing a composition, comprising producing glycosyl rutin, collecting the glycosyl rutin, and adding the resulting α-glycosyl rutin. 7. The high-concentration rutin is a high-concentration rutin, or a high-concentration solution rutin dissolved at an alkaline pH or dissolved in an organic solvent aqueous solution. 7. A method for producing the composition according to 6. 8. The method for producing a composition according to claim 6, wherein the high-concentration rutin is a high-concentration rutin of 1.0 w / v% or more. 9. The composition according to claim 6, wherein the composition is a food or drink, an antisensitizing agent, a cosmetic, a yellow colorant, an antioxidant or an ultraviolet absorber. Production method. 10. The composition according to claim 6, 7, 8 or 9, wherein the composition contains a vitamin selected from thiamine, riboflavin, vitamin C and vitamin E together with α-glycosyl rutin. Production method. (11) the composition comprises α-glycosyl rutin in 0.1%;
6. The composition according to claim 6, wherein the content is 001 w / w% or more.
A method for producing the composition according to 8, 9, or 10.