JPH0327293A - Production of alpha-glycosyl rutin and use thereof - Google Patents

Abstract

PURPOSE:To produce the subject compound on an industrial scale at a low cost by allowing a sugar transferase to act upon a rutin-rich liquid containing rutin and starch at high concentrations. CONSTITUTION:Rutin is dissolved at a concentration of >=0.5w/v% in an aqueous solution of an organic solvent containing methanol, etc., a starchy substance such as amylose is added to the solution in an amount of 0.5-50 pts. per 1 pt. of rutin, a sugar transferase such as alpha-amylase is added to the mixture and the components are made to react with each other at pH4.5-6.5 and 70-90 deg.C for 5-80hrs to obtain a reaction product containing a large amount of alpha-glucosyl rutin and a small amount of unreacted rutin and having a total rutin content of 1-20w/v% in terms of rutin. The reaction product is purified with a porous synthetic adsorbent resin and treated with beta-amylase to form alpha-glucosyl rutin and/or alpha-maltosyl rutin, from which alpha-glucosyl rutin is collected. As necessary, the rutin is used as an active component of a remedy for sensitive diseases.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing α-glycosyl ludine and its use, and more specifically, to a method for producing α-glycosyl ludine and its use, and more particularly, to a method for producing α-glycosyl ludine, and more specifically, to a rutin-rich liquid containing a high concentration of rutin and starch. α-
Glycosyl rutin is produced and collected.
A method for producing α-glycosyl rutin, characterized in that a glycosyltransferase is allowed to act on a solution containing rutin and starch, and then amylase is allowed to act to produce α-glucosyl rutin and/or α-maltosyl rutin. A method for producing α-glycosyl rutin, which is characterized by producing and collecting the same, as well as beverages, processed foods, and other food products containing α-glycosyl rutin obtained by these methods; Preventive agents for susceptible diseases,
The present invention relates to methods for producing therapeutic agents, such as anti-sensitivity disease agents, cosmetics such as skin beautifying agents and skin whitening agents, and furthermore, antioxidants.

[Prior art] Rutin has the chemical structure shown below, and has the ability to strengthen capillaries,
It has been known for a long time as vitamin P, which has physiological effects such as preventing bleeding and regulating blood pressure, and as a yellow pigment, and is used in foods, medicines, cosmetics, etc.

Vitamin P is involved in the physiological activities of vitamin C in vivo, such as the hydroxylation reaction of brolin and lysine, which are necessary for the synthesis of collagen, which is the main component of biological connective tissue.
It also participates in oxidation-reduction reactions such as reducing F, $+4 of cytochrome C to Fe"+, and further acid,
It is known to enhance activities such as those involved in the immune-enhancing effect caused by increased white blood cells, and plays an important role in maintaining and increasing the FL store of the living body.

Rutin is used not only as a vitamin aP fortifier as a nutrient, but also as a yellow coloring agent, antioxidant, etc., either alone or in combination with other vitamins, due to its chemical structure and physiological effects. It is used in foods and drinks, as a preventive and therapeutic agent for susceptibility diseases such as circulatory system diseases, that is, as an anti-sensitivity disease agent, and even in cosmetics as skin beautifying agents such as yellow colorants and ultraviolet absorbers, and skin whitening agents. , its range is extremely wide.

However, rutin is poorly soluble in water, and only about 1 g (about 0.011 J/V%) dissolves in 8 L of water at room temperature, making it extremely difficult to use.

As a method to improve this, for example,
As shown in Japanese Patent Publication No. 677, a method of increasing water solubility by adding an aliphatic compound having an aano group to rutin, and a method of adding monohalogenated acetic acid to rutin as shown in Japanese Patent Publication No. 26-2724. A method of increasing water solubility by making it a sodium acetate compound by acting on
As shown in Japanese Patent No. 5, a method has been known in which rutin is treated with Rongalit to convert it into a sulfite compound and increase its water solubility.

However, all of these methods use amino compounds, mono-octogenacetic acid, sulfite compounds, etc., and there are concerns that the produced substances may have other physiological activities or toxicity, and their purification is also difficult.

Therefore, the present inventors first proposed the
In the publication, as a safer water solubilization method, the action of glycosyltransferase using a biosynthetic reaction is used to transfer more than the same mole of glucose residue from a starch partial hydrolyzate to rutin. -We proposed a method to change the water solubility of rutin by producing glycosyl rutin.

α-Glycosyl rutin obtained by this method has no concerns about toxicity, has the same physiological activity as the raw material rutin, has high solubility in water, is extremely convenient to handle, and is expected to have a wider range of uses. , its realization has been confirmed.

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

However, conventionally, the a degree of preparation in the biosynthesis reaction is about 0 for rutin. It is only about IW/V%, and the amount of water used, amount of purified water, energy cost, etc. relative to α-glycosyl rutin in the product are excessive, making its industrialization difficult.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned drawbacks, and in particular, it focuses on a reaction method in which the concentration of rutin is increased during preparation, and tlI of α-glycosyl rutin after the reaction. We conducted extensive research on manufacturing methods, etc.

As a result, by allowing various transferases to act on a rutin-rich liquid containing high concentrations of rutin and starch, it is possible to desirably produce rutin in a highly concentrated suspension form or in an alkaline @p
It is prepared in the form of a highly concentrated solution dissolved in H or an organic solvent aqueous solution, and its preparation aIJf. is about 0.5 W/V% or more as rutin, preferably about 1.0 to 20
．． 0W/V%, in other words, α-glycosyl rutin is produced by allowing the glycosyltransferase to act at 0W/V%, which is about 5 times higher than the conventional technology (desirably, about 10 to 200 times higher). We found that the 112m method was well-generated,
Then, glycosyltransferase is applied to a solution containing rutin and starch, and then amylase is applied to a solution containing α-glucosyl rutin and/i: or α-maltosyl rutin. Found that it is often produced, its manufacturing method, and these methods! The present invention has been completed by confirming the use of α-glycosyl rutin produced in foods and drinks, preventive and therapeutic agents for sensitive diseases, cosmetics, antioxidants, etc.

In addition, when purifying the α-glycosylrutin produced by this reaction, we discovered that it can be easily purified by bringing the reaction solution into contact with a porous synthetic adsorbent and taking advantage of the difference in adsorption properties of the two. In particular, when the reaction solution contains an organic solvent, the organic solvent w.
It was found that similar purification could be achieved by bringing the solution to a low σ4 concentration and then contacting the solution with a porous synthetic adsorbent.

Therefore, it has been found that the method for producing α-glycosyl rutin of the present invention can eliminate the shortcomings of conventional methods at once, and can significantly reduce the amount of water used, the amount of water used for purification, and the energy cost, making it extremely possible to realize its industrialization. It makes it easier.

The present invention will be explained in detail below.

The rutin used in the present invention is not limited to highly purified rutin, and may include mixtures of rutin and flavonoid glycosides such as citronin, naringin, and hesveridin, or even rutin. Oil extracts derived from various plants or partially purified products thereof can be used as appropriate.

Examples of plant tissues that can be advantageously used are buckwheat leaves and stems, Japanese apricots (clumps or rice lumps), Japanese brooms, eucalyptus leaves and stems, citrus fruits, and the like.

The starch used in the present invention binds at least an equimolar amount of glucose residues to rutin using a glycosyltransferase that is used simultaneously;
Any material can be used as long as it can produce α-glycosyl rutin, and examples include starch partial hydrolysates such as amylose, dextrin, cyclodextrin, and maltooligosaccharides, as well as liquefied starch and gelatinized starch. .

Therefore, in order to facilitate the production of α-glycosyl ludine, a starch substance suitable for glycosyltransferase is selected.

For example, α-glucosidase (E
C 3.2.1.20), maltose,
Lutooligosaccharides such as malto-1-liose and maltotetraose, or starch partial hydrolysates with a DE of about 10 to 70 are suitable, and cyclomaltodextrin glucanotransferase (EC2.4.1.19) is suitable. When used, cyclodextrin or starch lakes with a DEI of about 60 or a starch partial hydrolyzate with a DEI of about 60 are suitable.
), suitable are starch gelatinized products with a D of 1 or less, dextrins with a DE of about 3◇, starch partial hydrolysates, and the like.

In addition, the starch concentration during the reaction is approximately 0.5 relative to rutin.
A range of 50 to 50 times is preferred.

The rutin-rich liquid as used in the present invention may be any liquid containing rutin at a high concentration.
Alternatively, a solution containing a high concentration in the form of a solution dissolved at an alkaline pH exceeding pH 7.0 or dissolved in an aqueous organic solvent solution is suitable, and the concentration is approximately 0.5V.
/V% or higher concentration, preferably about 1.0 to 20%.
It means a solution containing 0 W/V%.

The breeding solvent used in the present invention is desirably one in which the solubility of rutin is higher than that in water (e.g., methanol, ethanol, n-probanol, t'so-probanol, which can dissolve rutin in water, ethanol, n-probanol, t'so-probanol, Lower alcohols such as n-butanol, acetol, and acetone, lower ketones, and the like are suitable.

Concerning the organic solvent concentration of the flI solvent aqueous solution, conditions are selected in which rutin is dissolved in as high a concentration as possible, starch and glycosyltransferases are not insolubilized as much as possible, and α-glycosylrutin is produced satisfactorily. Selected from the range of 3 to 70 V/V%, preferably <U, about 5 to 130 V/V%.

Also, t = tunpu? : In order to easily dissolve rutin at 4a degrees, it is possible to dissolve rutin in advance in an alkaline aqueous solution such as caustic soda water or aqueous ammonia, combine it with an aqueous organic solvent solution, and further neutralize it before using it for transglycosylation reaction. This will be done as appropriate.

The glycosyltransferase used in the present invention may be one that produces α-glycosyl rutin without degrading rutin when it acts on a rutin-rich liquid containing rutin and a starchy substance with properties suitable for this enzyme. Bye.

For example, α-glucosidase is an enzyme derived from animal and plant tissues such as pig liver and buckwheat seeds, or mucor (l)
4ueor) genus, Benicillium (Pen ie i l
Enzymes derived from roasted products obtained by culturing microorganisms such as molds of the genus Saccharomyces or yeasts of the genus Saccharomyces in a nutrient medium are cyclomaltodextrin and glucano. Transfer Iase is derived from Patylus (Bae I lus).
) area, Klebsiola (Klebsiola), etc., α-alpha-reforming enzyme is found in Hosokan, which belongs to the genus Pachylus, etc., or Asbergillus (
Enzymes derived from roasted molds belonging to the genus Asperginae and the like can be appropriately selected.

These glycosyltransferases do not necessarily need to be purified before use as long as they satisfy the above conditions, and the purpose of the present invention can usually be achieved using crude enzymes.

If necessary, it may be used after being purified by various known methods. Furthermore, commercially available glycosyltransferases can also be used.

r>H and temperature during the reaction are usually selected from pH 3 to 10 and temperature 10 to 90°C, as long as glycosyltransferase acts to produce α-glycosyl rutin.

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

In addition, by repeating the immobilized glycosyltransferase using a patch method,
Alternatively, it can be appropriately selected to be used in the reaction in a continuous manner.

Furthermore, if necessary, mold organisms or animals that have glycosyltransferases,
It is also possible to produce α-glycosyl ludin by roasting the tissue of the vertebrate in a medium containing starch and rutin.

The reaction method of the present invention can be carried out by allowing a glycosyltransferase to act on a rutin-rich liquid containing high concentrations of rutin and starch.

For example, when rutin is reacted in the form of a high-altitude suspension, approximately O. 5W/V% or more, preferably about 1.0~5
．． OW/V% suspended rutin and a suitable amount of starchy L, a high rutin-rich liquid with a pH of about 4.5 to 6.5;
The temperature is as high as possible for the action of glycosyltransferase, specifically copper,
When maintained at about 70 to 90°C and treated with glycosyltransferase for 1 ton, rutin is converted to α-glycosylrutin. ! The cloudy rutin gradually dissolves, and at the same time, α-glucosyl rutin, α-maltosyl rutin, α-mal-1 triosyl rutin, α-mal-I tetraosyl
Rutin, α-maltobentaosyl ludin, α-mal I
- Hexaosyl rutin and α-glycosyl rutin are easily produced in high concentrations. a obtained in this way
-Glycosyl rutin-containing solutions usually contain a large amount of α-glycosyl rutin and unreacted rutin dissolved at room temperature and near neutrality, and the total amount of α-glycosyl rutin is approximately 0.5 V in terms of ludin. /V% or more, preferably reaching concentrations as high as about 1.0 to 5.0 W/V%.

Also, for example, ludine should not be dissolved in an alkaline solution with a pH higher than 7.0; when reacting in a highly concentrated solution,
p1 {about 7.5 to 10.0 (7) about 0.5 W/V in water
% or more, preferably about 1.0 to 5.0 W/V%, is heated and dissolved, and an appropriate amount of starch is dissolved therein to obtain a high rutin-rich solution, which can be processed by glycosyltransferases. Possible t double high pH, high temperature, specifically r + H about 785 to 1
io. o. When the temperature is maintained at about 50 to 80°C and glycosyltransferase is allowed to act on it, α-glycosyl rutin is easily produced in high concentration.

At this time, since rutin in an alkaline solution is prone to decomposition, in order to prevent this, it is desirable to keep it under anaerobic conditions and shield it from as much light as possible.

The α-glycosyl rutin-containing solution obtained in this way usually contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin dissolved at room temperature and near neutrality, and the total amount of rutin Converted to approximately 0.5 W/V% or more,
It has been found that concentrations as high as about 1.0 to 5 Ov/v% can be reached.

For example, when rutin is dissolved in an organic solvent aqueous solution and reacted in the form of a highly concentrated solution, rutin is first dissolved in an organic solvent by heating, and then this is mixed with a starchy aqueous solution. A glycosyltransferase is added to the molasses, or rutin and starch are dissolved in an organic solvent aqueous solution by heating, cooled to a predetermined temperature, and a glycosyltransferase is added thereto to initiate a reaction.

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

Furthermore, a method combining the above conditions may be used, for example, to prepare a rutin-rich liquid containing about 2.0 to 20.0 W/V% of suspended ludin and an appropriate amount of starch. 5 to 10.

When the temperature is maintained at about 50°C to 80°C and glycosyltransferase is applied thereto, α-glycosyl rutin is similarly easily produced in high concentrations.

In addition, ludine can be added to a strong alkaline aqueous solution such as about 0.1 to 1.0 N of caustic soda aqueous solution, caustic potash aqueous solution, soda carbonate aqueous solution, calcium hydroxide Yagi, ammonia water, etc. to about 5.0 to 20 N. Using the undissolved material at a high concentration of OW/V%, add an acidic aqueous solution of sulfuric acid or sulfuric acid to adjust the pH to a level at which the enzyme can act, add starch, and immediately transfer. It is extremely advantageous to use enzymes because α-glycosylrutin can be easily produced in high concentrations. At this time, even if the rutin solution is dissolved at a high concentration, rutin tends to precipitate by adjusting the pH with an acidic aqueous solution, so the pH
It may also be advantageous to start the transglycosylation reaction while suppressing the precipitation of rutin by coexisting starch or a small amount of α-glycosyl ludin before H adjustment. Ru. The iW solution containing α-glycosyl rutin obtained in this way usually contains a large amount of α-glycosyl rutin and a small amount of unreacted rutin dissolved at room temperature and around neutrality, and the total amount of The amount is approximately 5 in terms of rutin. It was found that concentrations as high as 0% i/V% were reached.

Furthermore, if necessary, in order to increase the solubility of rutin before the reaction and facilitate the sugar transfer reaction to rutin, an organic solvent dissolved in water 76 Ti L'1 is added to the rutin-rich liquid, For example, it may be appropriately selected that lower alcohols such as methanol, ethanol, n-probanol, iso-probanol, n-butanol, acetol, and acetone, lower alcohols, and the like are not co-existed.

As described above, the method of the present invention allows the preparation a degree of luden to be about 5 times or more than that of the conventional method, preferably about 10 to 200.
It was found that when the reaction rate was increased by as much as 2 times, α-glycosyl rutin could be easily produced at a high concentration.

That is, at the end of the reaction, the dissolved M contains α-glycosyl ludin of Daikei and a small amount of unreacted rutin, and the combined mass is about 0.5 W/V% or more in terms of rutin.
'J! t, <l; l:, about 1.0 to 20.0
%l/V%, about 5 times more than the conventional technology, and the desired L.
<I, about 10 to 200 j? It turns out that J is also expensive.

Relatively high molecular weight (×・−
Glycosyl ludine, if necessary, as is or after purification using a porous synthetic adsorption resin, can be used as gnorecoal sulfurase (EC 3.2.1.3) or β-arylase (EC 3.2. 1.2) Nato's amberase, 7
α-D- of α-glycosyl rutin is partially hydrolyzed with
It is possible to reduce the number of glucosyl groups. for example,
If glucoamylase is not used, it may hydrolyze a polymer higher than α-maltosyl rutin to produce glucose, and α-glucosyl rutin may be produced as an M product at t+. When β-amylase is used, it hydrolyzes a polymer higher than α-maltotriosyl rutin to produce maltose and mainly produces α-amylase.
It is possible to generate a mixture of -glucosyl rutin and α-maltosyl rutin.

The reaction solution containing α-glycosyl rutin produced as described above can be used as it is to produce an α-glycosyl rutin product. Usually, the reaction solution is filtered,
It is condensed into a syrup-like form, and then dried and powdered into a powdered α-glycosyl rutin product.

This product is not only a vitamin P fortifier, but also a highly safe natural coloring agent, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, UV absorber,
As a deterioration prevention agent, etc., it can be used in foods, snacks, feed, and 11f.
It can be advantageously used for applications such as anti-sensitivity agents, cosmetics, and plastic products. Furthermore, when producing unpurified α-glycosyl rutin products, it is possible to separate and purify α-glycosyl rutin from impurities such as starch by utilizing the difference in adsorption properties of porous synthetic adsorbents. good.

The porous resin used in the present invention is a porous resin with a large adsorption surface area, and is a synthetic resin such as non-ionic styrene-divinylbenzene polymer, phenol-formalin resin, acrylate resin, methacrylate resin, etc. resin, such as the commercially available Rohrn & Haa
Product name of s company an: Amberlight X80=1, A>Hurler i'to
4. Amberlight XAD-7, Amberlight XAD
-8, amparai l- XAT) -11, 7 t<-
Light XAD-12, product name Diaion HP-10, Diaion HP P-20 manufactured by Mitsubishi Chemical Industries, Ltd.
, Diaion HP-30, Diaion HP P-40
, Diamond Ion HP-50, Imact I product name Imact I Syn-42, Imact Rsyn-4
4, Imakuti syn-46, etc.

In the method for purifying the reaction solution that produced α-glycosyl rutin according to the present invention, the reaction solution is passed through a column packed with a porous synthetic adsorbent, and α-glycosyl rutin and a relatively small amount of unreacted While rutin is adsorbed to the porous synthetic adsorbent, the starch and water-soluble sugars that coexist in the process flow out without being absorbed.

In particular, when the reaction solution contains an organic solvent, the concentration of the organic solvent is reduced to prevent the solution from coming into contact with the porous synthetic adsorbent. Glycosyl rutin and rutin can be purified together.

If necessary, after the end of the transtransferase reaction and before contact with the porous synthetic adsorbent, for example, the reaction solution may be heated to remove insoluble matter by filtration, or aluminum silicate may be removed. Absorption and removal of proteinaceous substances in the reaction solution by rinsing with magnesium acid, magnesium alkali phosphate, etc., strongly acidic ion exchange resin (■ type), medium basic or weak basic ion exchange resin. It is also optional to use a combination of purification methods such as treatment with cells (QH type) and desalting.

As mentioned above, the relatively small amount of α-glycosyl ludine selectively adsorbed on the porous synthetic adsorbent ram is the relatively small amount of unreacted ludine that is removed after washing with dilute alkali, water, etc. When a mixed solution of an organic solvent or an organic solvent and water, such as methanol water or ethanol water, is passed through, α-glycosyl rutin is first eluted, and if the R solution is increased or the organic solvent concentration is increased, Unreacted rutin begins to elute.

By distilling this eluate containing a high content of α-glycosyl ludine to first distill off the organic solvent and then concentrating it to an appropriate concentration, a syrup-like product containing α-glycosyl ludine as a main component can be obtained. Furthermore, the drying and powdering process results in a powdered product containing α-glycosyl rutin as its main component.

This elution operation of α-glycosyl rutin and unreacted rutin using an organic solvent also serves as a regeneration operation of the porous synthetic adsorbent, thereby making it possible to use the porous synthetic adsorbent repeatedly.

Further, purification using the porous synthetic adsorbent of the present invention has the advantage that not only starch and water-soluble sugars but also impurities such as water-soluble salts can be removed in a timely manner.

The α-glycosyl ludine thus obtained has the following features.

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

(2) Compared to rutin, α-glycosyl rutin has greater strength, light resistance, and stability.

(3) α-Glycosyl rutin has strong antioxidant ability. As an antioxidant, it can be advantageously used to prevent the oxidation of oil-based foods and drinks, oil-based anti-sensitivity disease agents, oil-based cosmetics, etc.

In particular, when used as an anti-sensitivity disease agent, it exerts effects such as removing active oxygen and suppressing the production of lipid peroxide through antioxidant action, and is effective in preventing and treating various susceptibility diseases.
It is convenient for maintaining and increasing integrity.

In addition, unlike other antioxidants such as vitamin E and vitamin C, α-glycosyl rutin is virtually tasteless and odorless, so it can be used with confidence without worrying about discoloration, discoloration, or odor. can.

(4) α-Glycosyl Rutin is hydrolyzed into rutin and glucose by enzymes in the body, and exhibits the inherent physiological activity of lutin (vitamin aP).

In addition, when used in combination with vitamin C and vitamin C, their physiological activities can be enhanced.

(5) In the case of products containing starch, the starch not only exhibits the effects of α-glycosyl rutin, but also has the effect of shaping, bulking, and sweetening. ,
In the case of refined products from which starch has been removed, excipients,
The effects of α-glycosyl rutin can be exerted without increasing the scenery, and since it is virtually tasteless and odorless, it can be used to season and flavor Mt. Hakusan.

Due to these features, α-glycosyl rutin is not only a highly safe natural vitamin P fortifier, but also used alone or in combination with one or more other ingredients for coloring. agents, antioxidants, stabilizers, anti-fading agents, quality improvers, viral diseases, bacterial diseases, cardiovascular diseases,
Used in preventive and therapeutic agents for sensitive diseases such as malignant ulcers, ultraviolet absorbers, etc., as well as in food and beverages, recreational foods, feeds, feedstuffs, anti-sensitivity disease agents, skin beautifying agents, cosmetics such as skin whitening agents, and even plastic products. Preferably 0.001W/W
% or more can be used advantageously.

It also harmonizes well with various substances that have star tastes such as sour, salty, astringent, stomach, and bitter, and has great acid resistance and heat resistance, so it can be used in common foods and drinks,
Favorite foods, such as soybean oil, powdered oil, miso, powdered miso, moromi, fillet, burikake, mayonnaise, dressing,
Vinegar, Sanbai Vinegar, Powdered Sushi Vinegar, Nakagusa Soup, Tempura Soup, Mentsuyu, Sauce, Ketchup, Yakiniku Sauce, Curry Roux, Stew Base, Soup Base, Dashi Base, Complex Seasonings, Mirin, New Mirin, Table Shiko . Various seasonings such as gar, coffee sugar, amabei, arare, okoshi, karin I
・Cormorant, gyuhi, kasuri, manshu, ushiichirou, bean paste,
A variety of Japanese sweets, such as sheep fat, mizuhitsu oku, nishikidama, jelly, castella, candy, bread, biscuits, crackers, cookies,
fS such as pies, puddings, cream puffs, waffles, sponge cakes, donuts, di3cholates, chewing gum, galamels, and cassidy. Western confectionery, frozen desserts such as ice cream and sorbet, syrups such as pickled fruits, ice honey, pastries such as putter cream, custard cream, flower paste, peanut paste, and fruit paste, pastes, jams, marmalades, Syrup pickles, fructose and ink seeds, processed vegetable foods, buns, noodles, cooked rice, processed grain foods such as artificial meat, oil and fat foods such as salad oil and margarine,
Pickles such as Fukujinzuke, Bettarazuke, Senmaizuke, Rakki J, Usei, pickles such as takuan pickle mix, Chinese cabbage pickle mix,
Meat products such as ham and sausage, fish meat products such as fish ham, fish sausage, chikubo 1, chikuwa, and hamben,
Various delicacies such as sea urchin, salted squid, vinegar kelp, dried squid, mirin-dried blowfish, seaweed, wild vegetables, dried squid, small fish,
9J with shellfish etc. Vegetables such as boiled Tsukuda, boiled beans, potato salad, kelp rolls, tempura, etc., eggs such as Kinshi tamago, milk drinks, butter, cheese, dairy products, fish, meat, meat, fruits, vegetables, etc., bottled and canned. alcoholic beverages such as synthetic alcoholic beverages, fermented sake, fruit alcoholic beverages, Western alcoholic beverages, coffee, cocoa, juice, carbonated beverages, lactic acidic beverages, lactic acidic beverages and other pure drinking water, pudding mixes, pancake mixes, instant jiko, and one-sip beverages. ,
It can be advantageously added to instant food and drinks such as instant coffee, instant shiruko, instant soup, etc. for purposes such as vitamin P fortifier, yellow coloring agent, antioxidant, quality improver, and stabilizer. It is also convenient to use it as a vitamin P fortifier, an antioxidant, and to improve palatability in feed for fR breeding animals such as housework, poultry, bees, silkworms, and fish. .

Other products include cigarettes, lozenges, cod liver oil drops, multivitamin preparations, mouth fresheners, oral pastilles, gargles, tube supplements,
Oral medicines, injections, toothpaste, lipstick, lip balm,
Sunscreen and more! It is also advantageous to use solid, pasty, and liquid favorite foods, preventive and therapeutic agents for sensitive diseases, as anti-sensitive disease agents, skin-beautifying agents, and cosmetics such as Kame Shirakei. Moreover, it can also be advantageously used as an ultraviolet absorber, anti-deterioration agent, etc. by blending it into brassic products.

Susceptible diseases as used in the present invention are diseases that can be prevented or treated by α-glycosylludin, such as viral diseases, III1 fungal diseases, and traumatic diseases. , immune diseases, rheumatism, diabetes,
It may also be a cardiovascular disease, a malignant tumor, etc. Preventive and therapeutic agents for diseases susceptible to α-glycosyl rutin can be selected depending on the desired shape. Examples include sprays, eye drops, nasal drops, gargles, liquids such as injections, ointments, plasters, base preparations such as creams, powders, granules, capsules, tablets, and the like. When preparing the formulation, one or more than 2 m of other ingredients such as therapeutic agents, physiologically active substances, antibiotics, adjuvants, enhancers, stabilizers, colorants, and flavoring agents may be added as necessary. It is also optional to use them together.

The administration location can be adjusted as appropriate depending on the content, route of administration, frequency of administration, etc. Generally, a suitable amount of α-glycosyl rutin is in the range of about 0.001 to 50.0 g per day for an adult.

Also, in the case of cosmetics, it can be used in the same manner as the preventive and therapeutic agents mentioned above.

There are several known methods for using α-glycosyl rutin, such as mixing, kneading, dissolving, soaking, permeating, scattering, applying, spraying, and pouring. Appropriately selected.

The non-toxicity of the α-glycosyl rutin of the present invention will be explained below through experiments.

Experiment Using 7-week-old DD dorsal mice, an acute toxicity test was conducted by orally administering t:α-glycosyl rutin prepared by the method of Example 8-3, and no mortality was observed up to 5&. However, it was difficult to administer this substance.Therefore, the toxicity of this substance is extremely low.

In addition, α-glucosyl prepared by the method of Example 812
When this test was conducted using rutin, similar results were obtained 9
: It was found that the toxicity was extremely low.

Hereinafter, as an example of the present invention, α-glycosylrutin! Examples of Iti are described in Example 8, and examples of uses of α-glycosylrutin are described in Example 8.

Example A-1 α-Glycosyl Rutin 3 parts by weight of rutin and 15 parts by weight of dextrin (DE18) were added to 80 parts by weight.
Mix with 97 parts by weight of ℃n hot water! I! A cloudy liquid with high rutin content is prepared, and Bacillus stearothermophilus (
Bacillus stearothermophil
20 units of cyclomaltodextrin glucanotransferase derived from US) (sold by Hayashibara Biochemical Research Institute Co., Ltd.) per dextrin ram, λ, pH 6.0, 75
The reaction was carried out for 64 hours while maintaining the temperature at °C and stirring. When the reaction solution was analyzed by Baber chromatography, approximately 85% of the rutin was found to be α-glucosyl rutin, α-maltosyl rutin, α-maltotriosyl rutin, α-maltotetraosyl rutin, α-maltopenta It was converted to α-glycosyl rutin such as osyl rutin. The reaction solution is heated to inactivate the enzyme, filtered, and the filtrate is concentrated to form a starch-like substance 9! Is the product containing α-glycosyl rutin per solid substance? The yield was about 90% based on quadruple dishes.

This product is not only used as a vitamin P fortifier, but also as a highly safe natural coloring agent, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, and ultraviolet absorber. As a result, it can be advantageously used in food and beverages, recreational foods, feeds, fodder, anti-sensitivity agents, cosmetics, brass snack products, and the like.

Example A-2 α-Glucosyl Rutin Example A-
Prepared according to method 1 and t. : Dissolve 1 part by weight of an α-glycosyl rutin product containing starchy starch in 4 parts by weight of water, adjust the pH to 5.0, and add glucoamylase (EC3.2.1.3, Seikagaku Corporation) to 4 parts by weight of water. company sales)
α-glycosyl rutin product solids per duram 100
unit was added and the reaction was carried out at 50°C for 5 hours. Analysis of the reaction solution by Baber chromatography revealed that α-glycosyl rutin had been 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, trade name Diaion HP-10 (sold by Mitsubishi Chemical Industries, Ltd.) at SV2. As a result, α-glucosyl rutin L and unreacted rutin in the solution were adsorbed to the porous synthetic adsorbent, and glucose, salts, etc. were adsorbed and flowed out. Next, after passing the column with water and washing it, the column was passed through the column while gradually increasing the concentration of the ethanol aqueous solution, and the α-glucosyl rutin fraction was collected.
The mixture was concentrated under reduced pressure and powdered to obtain powdered α-glucosyl rutin at a yield of about 80% based on the raw material rutin based on solid matter.

This α-glucosyl rutin is hydrolyzed with acid,
For every mol of quercetin, 1 mol of L-rhamnose, 1 mol of D-
It was found that 2 moles of glucose were produced, and when α-glucosyl rutin was treated with α-glucosidase extracted from pig liver and partially prepared, it was hydrolyzed into rutin and D-glucose. .

This α-glucosyl rutin is a highly purified water-soluble vitamin aP fortifier, and is also a yellow coloring agent, antioxidant, stabilizer, anti-inflammatory agent, quality improver, preventive agent, It can be advantageously used as a therapeutic agent, ultraviolet absorber, etc., as well as in foods and drinks, recreational foods, anti-sensitivity disease agents, cosmetics, etc.

Example A-3 α-Glycosyl RutinRutin 4-layer dish was heated and dissolved in 90-layer water at pH 9.5. Separately, 20 parts by weight of dextrin (DE8) was heated and dissolved in 10 parts by weight of water, and then these solutions were dissolved. A rutin-rich solution is obtained by mixing the rutin-rich solution, and cyclomaltodextrin glucanotransferase is added to this solution at a concentration of 30% per dextrin gram.
The reaction mixture was stirred and reacted for 40 hours while maintaining the pH at 8-2 and 65°C.

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

The reaction solution was heated to inactivate the # element, filtered, and the filtrate was mixed with a porous synthetic adsorbent, trade name Amparai 1/XAD-7 (Ro
The liquid was passed through a column (manufactured by HM & Haas) at SV1.5.

As a result, α-glycosyl rutin and unreacted rutin in the solution were adsorbed onto the porous synthetic adsorbent, while dextrins, oligosaccharides, salts, etc. flowed out without being adsorbed.

After passing water through this column and washing it, 50V/V% methanol was passed through the column to concentrate and powder the α-glycosyl rutin and rutin dissolved IU L.
A mono-glycosyl rutin product was obtained at a yield of about 140% based on the rutin weight of the R material.

This product is not only a highly water-soluble vitamin P fortifier, but also a highly safe natural yellowing agent, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, It can be advantageously used as an ultraviolet absorber, anti-deterioration agent, etc. in foods and beverages, favorite foods, feeds, feedstuffs, medicines for pile-sensitive diseases, cosmetics, plastic products, and the like.

Example 8-4 α-Glycosyl Rutin 1 part by weight of rutin is dissolved in 1 N caustic soda TL! 1'4 parts by weight of dextrin (DEIO) was added to the hh mixture, which was neutralized by adding 0.01N hydrochloric acid solution, and immediately dissolved in cyclomalt. Add 10 units of dextrin glucanotransferase per 1 lingram of dextrin, and
The reaction mixture was reacted for 40 hours while maintaining the temperature at 6.0°C and 70°C. When the reaction solution was analyzed by paper chromatography, it was found that about 80% of rutin had been converted to α-glycosylrutin.

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

Like Example A-3 and lQ, this product is not only a highly water-soluble vitamin P fortifier, but also a highly safe natural yellow colorant, antioxidant, stabilizer, and anti-fading agent. agent,
It can be used for a variety of purposes, including as a quality improver, preventive agent, therapeutic agent, and ultraviolet absorber.

Example 815 α-Glycosyl rutin (1) Preparation of α-glucosidase specimen 7.4. Ov/V%, +J acid 1 force r) UmO. HI/V%, ammonium nitrate 0.1W
/V%, magnesium sulfate 0.05V/V%, potassium chloride 0.05W/V%, polybeptone 0.2W/V%,
Mueor javanica was added to 500 parts by weight of a liquid medium consisting of calcium carbonate IW/V% (separately sterilized by dry heat and added aseptically at the time of planting) and water.
us) IFO 4570 was cultured with shaking at a temperature of 30°C for 44 hours. After culturing, the mycelia were collected, and 0.5M acetate buffer (pH 5.
Add 500 parts by weight of 4M urea solution dissolved in 3) and heat at 30°C.
After standing for 40 hours, the mixture was centrifuged. After dialyzing this supernatant overnight in running water, it was saturated with ammonium sulfate by 0.9%, left at 4°C for a wedge, and the salted out product was collected by filtration, and
t! to 50 parts by weight of Ij liquid (pH 5.3). After lysis, two supernatants were collected by centrifugation and used as an α-glucosidase preparation.

(2) Preparation of α-glycosyl rutin 5 parts by weight of rutin was heated and dissolved in 40 parts by weight of 0.5N caustic soda solution, and this was diluted with 5N sodium acid solution to pH 9.5.
Separately, 20 parts by weight of dextrin (DE30) was heated and dissolved in 10 parts by weight of water, and then these dissolved wIi.
Mix it up! ! A cloudy rutin-rich solution was prepared, and (1
10 parts by weight of the α-glucosidase preparation prepared by the method described in ) was added, and the mixture was reacted at 55° C. for 40 hours while maintaining pi-[8.5 and stirring.

Analysis of the reaction solution by paper chromatography revealed that about 60% of the ludine had been converted to α-glycosylrutin.

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

As in Example A-3, this product is not only a highly water-resistant vitamin P fortifier, but also a highly safe natural yellow colorant, antioxidant, stabilizer, and fading agent. As an inhibitor, quality improver, prophylactic agent, therapeutic agent, ultraviolet absorber, etc.
Can be used for various purposes.

Example A-6 α-Glycosyl ludin rutin monomer and 15 parts by weight of dextrin (DE18) were dissolved in 99 parts by weight of a 50V/V% methanol aqueous solution heated to 40°C, cooled to 25°C, and added to this. 20 units of cyclomaltodextrin glucanotransferase (sold by Hayashibara Biochemical Research Institute, Inc.) was added per dextrin gram, the pH was adjusted to 6.0, and the mixture was reacted for 72 hours. Analysis of the reaction solution by bar chromatography revealed that approximately 80% of the rutin was α-glucosyl rutin, α-maltosyl rutin, α-maltotriosyl rutin, α-maltotetraosyl rutin, α-maltobentaosyl rutin. α-glycosyl rutin such as rutin was converted to rutin. The reaction solution is concentrated under reduced pressure to distill off methanol, heated to inactivate the enzyme, filtered, and the filtrate is further concentrated to obtain a syrup-like starch-containing α-glycosyl rutin product on a solid basis. The yield was about 95% based on the weight of the raw materials.

This product is not only a vitamin P fortifier, but also a highly safe natural yellow coloring agent, antioxidant, stabilizer, anti-fading agent, quality improver, preventive agent, therapeutic agent, and ultraviolet absorber. It can be advantageously used for applications such as food, drinks, recreational foods, feeds, feedstuffs, anti-sensitivity agents, cosmetics, and plastic products.

Example A-7 α-Glucosyl Rutin Example A-
1 part by weight of a syrup-like starch-containing α-glycosyl rutin product prepared according to method 6 was dissolved in a 4-layer dish of water, and glucoamylase (EC 3.2.1.
3, sold by Toyobo Co., Ltd.) was added at 1001 points per duram of the solid α-glycosyl rutin product, and the mixture was reacted at 50°C for 5 hours. Analysis of the reaction solution by Baber chromatography revealed that α-glycosyl rutin had been converted to α-glucosyl rutin.

The reaction solution was heated to inactivate the enzyme, filtered, and the filtrate was passed through a column of porous synthetic adsorbent, trade name Diaion HP-No (sold by Mitsubishi Chemical Industries, Ltd.) at SV2. As a result, α-glucosyl rutin and unreacted rutin in the solution were adsorbed to the porous synthetic adsorbent, and dextrin, merigosaccharides, glucose, salts, etc. were absorbed and flowed out. Next, after passing water through the column and washing it, the column was passed through the column while gradually increasing the concentration of ethanol aqueous F&, and the α-glucosyl rutin fraction was collected, concentrated under reduced pressure, and powdered to form powdered α- Glucosyl rutin was obtained at a yield of about 80% per solid based on the raw material rutin.

As in Example A-2, this α-glucosyl rutin can be used as a highly purified water-soluble vitamin P fortifier, as well as a coloring agent, an antioxidant, a stabilizer, and an anti-fading agent. It can be advantageously used as a quality improver, preventive agent, therapeutic agent, ultraviolet absorber, etc. in foods and beverages, luxury foods, anti-sensitivity disease agents, cosmetics, etc.

Example A-8 α-glycosyl rutin rutin i,
wt part was dissolved by heating in 5 parts by weight of a 50 V/V% ethanol aqueous solution, and separately, 103,111 parts of dextrin (DE8) was dissolved by heating in 45 parts by weight of water, and then these il[
E was mixed, 10 units of cyclomaltodextrin glucanotransferase was added per dextrin, the pH was adjusted to 8.0, and the mixture was stirred at 50°C for 24 hours.

When the reaction solution was analyzed using Baberk zero chromatography, it was found that about 90% of the rutin had been converted to α-glycosylrutin.

Reaction lol! i. After concentrating under reduced pressure and distilling ethanol, it is heated to inactivate the enzyme, filtered, and the filtrate is mixed with a porous adsorbent, trade name Amberlite XAD-7 (Rohm
& 1laas (11m) column at SV1.5.

As a result, α-glycosyl rutin and unreacted rutin in the solution were absorbed into the porous synthetic absorbent, and dextrin, oligosaccharides, salts, etc. were washed away without being adsorbed.

After washing the column with wood pipe, pass 50V/V% methanol through it to remove α-glycosyl rutin and rutin, concentrate it, and powder it. The yield was about 140% based on the weight of rutin.

This product contains not only highly water-soluble Vita-Kin P strengthening agents, but also highly safe natural yellow coloring agents, antioxidants, stabilizers, anti-fading agents, quality improvers, and antioxidants. It can be advantageously used as a preventative agent, therapeutic agent, ultraviolet absorber, etc. in foods and beverages, recreational foods, feeds, fodder, anti-sensitivity disease agents, cosmetics, plastic products, etc.

Example 819 α-Glycosyl Rutin One part of rutin was dissolved by heating in five parts of an 80 V/V% methanol aqueous solution, and separately, 20 parts of dextrin (DE30) was dissolved by heating in 27 parts by weight of water, and then, These solutions were mixed, 8 parts by weight of α-glucosidase prepared by the method of Example A-5(1) was added thereto, and the mixture was allowed to react at 40° C. for 40 hours while maintaining the pH at 5.3.

Analysis of the reaction solution by paper chromatography revealed that approximately 60% of the rutin had been converted to α-glycosylrutin.

After concentrating the reaction solution under reduced pressure to distill off methanol, it was purified in the same manner as in Example 8-8, compressed, and powdered to obtain powdered α-
A glycosyl rutin product was obtained with a yield of about 110% based on the weight of the raw material rutin.

This product was developed by Mr. L@J of Example 818, and not only contains a highly water-soluble vitamin P fortifier, but also a highly safe natural coloring agent, antioxidant, and a stable agents, anti-fading agents, quality improvers, preventive agents, therapeutic agents, ultraviolet absorbers, etc.
Can be used for various purposes.

Example A-=10 α-Glycosyl Rutin According to the method of Example A-6 *mt, 1 part by weight of α-Glycosyl Rutin product containing syrupy starch was dissolved in 4x IPf% water, This is supplemented with β-amylase (EC 3.
2.1.2, 100 units of α-glycosyl rutin product (sold by Toyobo Co., Ltd.) was added per solid duram, and the mixture was heated to 50°C.
, and reacted for 5 hours.

Analysis of the reaction solution by Baber chromatography revealed that α-glycosyl rutin had been converted to α-glycosyl rutin mainly consisting of α-glucosyl rutin and α-maltosyl rutin.

The reaction solution was heated to inactivate the enzyme, filtered, and the filtrate was passed through a column of porous synthetic adsorbent, trade name Diaion HP-10 (sold by Mitsubishi Kawei Industries, Ltd.) at SV2. As a result, α-glycosyl rutin and unreacted rutin in the solution were adsorbed to the porous synthetic adsorbent, and maltose, oligosaccharides, glucose, salts, etc. flowed out without being adsorbed. Next, after passing water through the column and washing it, the column was passed through the column while gradually increasing the concentration of the ethanol aqueous solution, and the α-glycosyl rutin fraction was collected, compressed under reduced pressure, and powdered.
Powdered α-glycosyl rutin was obtained at a yield of about 85% based on the weight of the raw material rutin per solid.

When glucoamylase is applied to this α-glycosyl rutin, it is hydrolyzed into α-glucosyl rutin and D-glucose, and when α-glucosidase extracted from pig liver and partially purified is applied, it is hydrolyzed into rutin and D-glucosidase. −
It was found that it was hydrolyzed into glucose.

This α-glycosyl rutin is a highly purified and highly water-soluble biku1P strengthening agent. It can be advantageously used in foods and drinks, recreational foods, anti-sensitivity disease agents, cosmetics, plastic products, etc., as well as UV absorbers.

Example 8-1 Hard candy = reduced maltose starch syrup (sold by Hayashibara Shoji Co., Ltd., registered trademark Mavit) 1,5
00-layer plate was heated and concentrated under reduced pressure until the water content was about 2% or less, and 15 parts by weight of citric acid and one layer of powdered α-glycosyl rutin obtained by the method of Example 813 were added. and a small plate of lemon flavor were mixed, followed by molding and packaging according to a conventional method to obtain a hard candy.

This product is a yellow lemon candy enriched with vitamin AP, and has low cariogenicity and low strength.

Example B-2 Boiled Japanese Butterbur Peeled Japanese Butterbur, cut it into appropriate lengths, soaked it in hard saline water for several hours, and kneaded it with the method of Example A-1. A vivid green butterbur boiled in water was obtained by boiling it in a liquid containing a green coloring agent prepared by blending Ruchinhi Blue No. 1 Flax.

This product can be used as an ingredient in various Japanese dishes to add color, and it also has physiological effects as a good fiber.

Example B-3 1 liter of mochi Enoki starch! 162 parts by weight of water f! While mixing and heating to gelatinize, 1111.5 parts by weight of sand and crystalline β
- Maltose (manufactured by Hayashibara Co., Ltd., registered trademark Sunmalt) 0.7jl mouth portion, starch syrup 0.3-layer plate portion and Example A
-Syrup-like α-glycosyl rutin 0 obtained by method 6
．． After mixing 2 parts by weight, the gyuhi is purified by molding and packaging according to conventional methods. This product is a millet-dango-like Japanese confectionery made from gyuhi with good flavor and texture.

Example B-4 100 parts by weight of mixed sweetener honey, 50 parts by weight of high fructose sugar, 2 parts of brown sugar
Parts by weight of the powdered α-glycosyl rutin obtained by the method of Example A-9 were mixed to remove the mixed sweetness.

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

Example 8-5 Sand cream crystalline α-maltose (manufactured by Hayashibara Co., Ltd., registered trademark Finetose) 1.200! Okibe, Shi91toning i
, ooo parts by weight, tOW part of powdered α-glycosyl rutin obtained by the method of Example A-8, 1 part by weight of lecithin, 1 part by weight of lemon oil, and 1 part by weight of vanilla oil are mixed in a conventional manner to make a sand cream. was manufactured.

This product is a vitamin P-enriched, yellow-colored sand cream that prevents oxidation of fats and oils, and has a good texture, meltability, and flavor.

Example B-6 Orange juice 501,111 parts of orange juice, 0.1 part by weight of citric acid,
Sand Ills Judong Department, 0.5 parts by weight of powdered α-glycosyl rutin obtained by the method of Example/1-5, 0.111 parts by weight of L-ascorbic acid (L?Tamine C), perfume application and water The mixture was mixed in a 46-layer plate, and then filled into containers and sterilized according to a conventional method in step 1 to obtain an orange juice product.

This product is an orange juice enriched with vitamin P1 and vitamin C, and has good color and flavor.

Example B-7 Tablet Ascorbic acid 20-layer plate contains crystalline β-maltose 13
Parts by weight, 4 parts by weight of cornstarch and Example/l-7
After 3 parts by weight of the powdered α-glucosylrutin obtained by the method described above was mixed uniformly, the mixture was compressed using a 20R punch with a diameter of 12 mm to obtain tablets.

This product is a complex multivitamin with ascorbic acid Lα-glucosylrutin, and the ascorbic acid has good stability.
It is an easy-to-swallow tablet.

It is a multivitamin preparation with rutin, has good stability of ascorbic acid, and is an easy-to-swallow tablet.

Example ! 1-8 Capsules Calcium acetate - 10 parts by weight, l4 monolactate V-gnesium - Sansuiba 50 parts by weight, Maltose 57 parts by weight,
Powdered α-glucosyl rutin 20% rutin and 20% eicosabentaenoic acid 7- obtained by the method of Example A-2
After uniformly combining 12 liters of dextrin clathrate compound and granulating it in a granule molding machine, it was encapsulated in gelatin capsules according to a conventional method, and each capsule had a length of 150 m.
We manufactured capsules for g people.

This product prevents the oxidation of eicobencunsanoic acid and is used as a high-quality blood cholesterol lowering agent, immunostimulant, skin beautifying agent, etc., and is used as a preventive agent for sensitive diseases, a therapeutic agent, and a health promotion agent. You can use it to your advantage by increasing the number of items.

Example B-=-9 Ointment Sodium acetate/trihydrate 11 tl 1 part, DL calcium monolactate 4 parts by weight Glycerin 10 parts L Evenly mixed, this mixture was mixed with 50 parts by weight of vaseline, 10 parts by weight of wood wax. In addition to a mixture of 10 parts by weight of lanolin, 14.5 parts by weight of sesame oil, 1 part by weight of powdered α-glycosyl ludine and 0.5 parts by weight of peppermint oil obtained by the method of Example 8-4. , and then mix it evenly to make 12 ointments: 6 This product has antioxidant properties, is highly stable, and can be used as a high-quality sunscreen, skin beautifier, coloring agent, etc. It can be advantageously used as a burn healing accelerator.

Example R-10 Injection Powdered α-glucosyl rutin obtained by the method of Example 817 was dissolved in water, purified and filtered according to a conventional method, and the solution was diluted with 20 ml of 4-volume asible. α−
Glucosyl rutin was dispensed into 200 m cores, dried under reduced pressure, and sealed to form an injection.

This cough injection can be administered alone or in combination with other vitamins, minerals, etc. intramuscularly or intravenously. Mugita,
This product does not require vomiting or IQ during low-temperature storage, and has extremely good solubility in physiological saline water when used.

This product is effective not only for supplementing Vitasen P, but also as an antioxidant, removing active oxygen and suppressing the production of lipid peroxide, and is effective against viral diseases, bacterial diseases, and cardiovascular diseases. organ disease,
It is widely used as a preventive and therapeutic agent for various diseases.

Example B-11 Injection Sodium chloride exa part, potassium chloride 0.3 part by weight,
0.2 parts by weight of calcium chloride, 3.1 parts by weight of sodium lactate, 45 parts by weight of maltose, and powdered α-glucosylludine 2 obtained by the method of Example A-2! Water for Otoribe 1.00
The solution was dissolved in a 0-fold leaf portion, purified and filtered to make it pyrogen-free according to a conventional method, and the solution was filled in 25 (lsL) portions into a sterilized plastic container to obtain an injection.

Is this product Vitan aP? It is an injection that is not only used as a full supplement, but also provides calories, minerals, removes active oxygen, and suppresses the production of peroxide, facilitating treatment during and after illness, promoting recovery, and It can be used as a prophylactic and therapeutic agent for various diseases such as viral diseases, epilepsy diseases, circulatory diseases, and malignant tumors.

Example 8-12 Management nutritional supplement 20 parts by weight of crystalline α-maltose, 1.1 parts by weight of glycine
1: fil$, sodium glutamate 018 heavy acid part,
1.23 parts by weight of common salt, 1 part by weight of citric acid, 0.4 parts by weight of calcium lactate, 0.1 parts by weight of magnesium carbonate, 0.1 part by weight of powdered α-glycosyl rutin obtained by the method of Example 818. A formulation is prepared consisting of 0.01 parts by weight of Chiayan, and 0.01 parts by weight of riboflavin. 24g each of this mixture was filled into sachets made by Lacutate Alcho and heat-sealed to make a management supplement.

One bag of this oral nutritional supplement can be dissolved in approximately 300 to 500 aL of water and can be advantageously used as an oral or non-daily nutritional supplement to the Jl cavity, helmet, intestines, etc., depending on the management method.

Example B-13 Bath agent DL Sodium monolactate 21 parts, sodium pyruvate 8! Amount, syrupy α- obtained by the method of Example 811
5 parts by weight of glycosyl rutin and 40 parts by weight of ethanol were mixed with 26 parts by weight of purified water and appropriate amounts of coloring and fragrance to produce a bath additive.

This product is suitable for use as a skin beautifying agent and skin whitening agent, and can be used by diluting it 100 to 10,000 times in bathing water. , water for face washing,
It is also advantageous to use it by diluting it in lotions, etc.

Example B-14 Emulsion 0.5 parts by weight of polyoxyethylene behenyl ether, 1 part by weight of polyoxyethylene sorbitol, 1 part by weight, 1 part by weight of polyoxyethylene behenyl ether
Parts by weight, 1 liter of lipophilic glycerin monostearate! Weight part, 0.5 parts of rubic acid, 0.5 parts of phenyl alcohol
Heavy plate part, 1 part of avocado oil, 1 part of powdered α-glycosyl rutin obtained by the method of Example A-3, dinner plate E
and an appropriate amount of anti-flag agent are heated and dissolved according to a conventional method, and to this are added lli parts of sodium L-lactate, 5 parts by weight of L3-butylene glycol, 0.1 parts of carboxyvinylbonimer, and 85.3 parts of purified water. Parts by weight were added, emulsified using a homogenizer, and an appropriate amount of fragrance was added and crystallized with stirring to produce a milky lotion.

This product has antioxidant properties and is highly stable (it can be advantageously used as a high-quality sunscreen, skin beautifier, skin whitening agent, etc.).

Example B-15 Cream polyoxyethylene glycol monostearate 2 parts by weight, self-emulsifying glyceryl monostearate 5 parts by weight,
Powdered α-glucosyl rutin double hydroxide obtained by the method of Example A-2, 1 part by weight of liquid paraffin, 10 parts by weight of glyceryl trioctanoate, and a preservative were dissolved by heating according to a conventional method. Add 2 parts of monolactic acid, 5 parts by weight of 1,3-butylene glycol, and 06 parts of purified water, emulsify by using a homogenizer, and add 1 part of fragrance.
7 products were added and stirred and mixed to form a cream.
A high-quality sunscreen with antioxidant properties and high stability.
It can be advantageously used as a skin beautifier, skin whitening agent, etc.

Example 8-16 Antioxidant powdered α-glycosil obtained by the method of Example A-10
An antioxidant was obtained by mixing 1 part by weight of Rutin 10 weight I, 2 parts by weight of Gotamin E, 0.1 part by weight of linocytin, and 0.5 part by weight of sodium citrate.

This product is suitable for use in oil-based foods such as margarine and putter cream, unsaturated fatty acids, oil-based foods, anti-sensitivity disease agents such as oil-based hormones, and cosmetics such as emulsions and creams. %, it can be advantageously used as an antioxidant, stabilizer, quality improver, etc.

Examples B-1, 7 Antioxidant 10 parts of powdered α-glucosyl rutin obtained by the method of Example A-2 and 0.2 parts by weight of sodium citrate were mixed to obtain an antioxidant.

This product is suitable for use in oil-based foods such as margarine and butter cream, anti-sensitivity disease agents such as unsaturated fatty acids, oil-based vitamins and oil-based hormones, and cosmetics such as emulsion and cream. 0.01 to 2.0 W/W for foods and drinks containing natural pigments that easily discolor.
%, it can be advantageously used as an antioxidant, stabilizer, anti-fading agent, quality improver, etc.

[Effects of the Invention] As mentioned in the main text, the present invention involves interfering with the action of glycosyltransferase in a rutin-rich liquid containing high-alkalinity ludin and starch during the production of α-glycosyl rutin. By carrying out the transglycosylation reaction, it is desirable to carry out the transglycosylation reaction by containing lugin in a highly concentrated suspension form, or in a highly concentrated solution form dissolved in an alkali@pH or dissolved in an aqueous solution of a 4M solvent. The reaction can be carried out at a feed concentration of rutin of about 5 times or more, preferably about 10 to 200 times higher than that of the conventional technique, and α-glycosyl rutin can be easily produced at a high concentration. Find, tt:
When glycosyltransferase is applied to a solution containing rutin and starch, and amylase is then applied, α-glycosyl rutin, which is mainly composed of α-glucosyl rutin and/or α-maltosyl rutin, is often produced. Furthermore, during the purification of these reaction solutions, they discovered that α-glycosyl rutin can be purified by contacting the reaction solution with a porous synthetic adsorbent, and especially when the reaction solution contains an organic solvent. If the organic solvent d
They found that similar purification could be achieved by contacting the solution with a porous synthetic adsorbent after reducing the concentration of α-glycosyl rutin, which significantly reduced the amount of water used, water storage for purification processing, and energy costs required to produce α-glycosyl rutin. This makes it extremely easy to realize industrialization.

In addition, α-glycosylludin obtained in this way has good water solubility, good light resistance and stability, and is hydrolyzed into rutin and glucose by enzymes in the body, exerting its original physiological activity. It is not only a highly safe natural vitamin P fortifier, but also a yellowing agent, antioxidant, stabilizer, anti-fading agent, quality improver,
Advantageously used as prophylactic agents, therapeutic agents, ultraviolet absorbers, anti-deterioration agents, etc., in food and beverages, luxury foods, feed, fodder, anti-sensitivity disease agents, skin beautifying agents, cosmetics such as color 8 agents, and even plastic products. be done.

Therefore, the industrial production method L of α-glycosyl rutin according to the present invention has been established for use in foods and beverages, cosmetics, pharmaceuticals,
It has extremely great industrial significance in the plastics industry.

Patent applicant Kentsu Hayashibara Biochemistry Co., Ltd. Representative name: Kentsu Hayashibara Procedural amendment November 6, 1995 Director of the Patent Office Fumi Takeshi Yoshida 1, @Indication of patent application No. 217893, 2008 , Name of the Invention Method for producing α-glycosyl rutin and its uses 3. Relationship with the case of the person making the amendment Patent applicant 1-2-3 Shimoishi, Okayama City, Okayama Prefecture & Contents of the amendment (1) The chemical structural formula of rutin stated on page 5 of the specification has been amended as follows. Masu.

"4. "Detailed Description of the Invention" section to be clicked in the specification subject to amendment" (2) "With a complex vitamin preparation" written in line 17 on page 50 of the specification was changed to "with a multivitamin preparation," ” will be corrected.

(3) Delete the line 19-20 of the same page: "Complex vitamin with rutin...Easy-to-swallow tablets."

The correction will be made to "eicobentansananoic acid Jer eicozabentaenoic acid" as stated in page 51, line 11 of the specification.

(5) "8 parts by weight of lithium" written in line 19 of page 54 of the specification will be corrected to "8 parts by weight of thorium."

(4)

Claims (10)

[Claims] (1) A method for producing α-glycosyl rutin, which comprises producing α-glycosyl rutin by causing a glycosyltransferase to act on a rutin-rich liquid containing high concentrations of rutin and starch, and collecting the same. . (2) The scope of claims characterized in that the high concentration rutin is high concentration suspension rutin, or high concentration solution rutin dissolved at alkaline pH or dissolved in an aqueous organic solvent solution. The method for producing α-glycosylrutin according to item (1). (3) Claim No. 1, characterized in that the high concentration rutin is high concentration rutin of 0.5 W/V% or more.
The method for producing α-glycosylrutin according to item or item (2). (4) A solution obtained by allowing a glycosyltransferase to act on a rutin-rich organic solvent aqueous solution containing high concentrations of rutin and starch to produce α-glycosylrutin, and then reducing the organic solvent concentration of this solution. 1. A method for producing α-glycosylrutin, which comprises purifying α-glycosylrutin by bringing it into contact with a porous synthetic adsorbent to collect α-glycosylrutin. (5) A glycosyltransferase is allowed to act on a solution containing rutin and starch, and then amylase is made to act to produce α-glucosylrutin and/or α-maltosylrutin, which is then collected. A method for producing α-glycosylrutin. (6) A glycosyltransferase is allowed to act on a solution containing rutin and starch, and then amylase is made to act to produce α-glucosylrutin and/or α-maltosylrutin, and this solution is further made porous. A method for producing α-glycosylrutin, which comprises purifying α-glucosylrutin and/or α-maltosylrutin by contacting it with a synthetic adsorbent. (7) A rutin-rich liquid containing high concentrations of rutin and starch is made to act with a glycosyltransferase to produce α-glycosylrutin, which is collected and the resulting α-glycosylrutin is contained. A method for producing characteristic food and drink products. (8) A-glycosylrutin is produced by causing a glycosyltransferase to act on a rutin-rich liquid containing high concentrations of rutin and starch, and the resulting α-glycosylrutin is contained as an active ingredient. 1. A method for producing an anti-sensitivity disease agent. (9) A rutin-rich solution containing high concentrations of rutin and starch is reacted with a glycosyltransferase to mainly form α-glycosylrutin, which is collected, and the resulting α-glycosylrutin is used as an active ingredient. A method for producing cosmetics characterized by containing (10) A method for producing an antioxidant, which comprises containing α-glycosylrutin as an active ingredient.