JPH0654664A - Food and drink - Google Patents

Abstract

PURPOSE:To sufficiently color a food and a drink with rutin as an antioxidant and a natural coloring matter and to prevent oxidation even in the case of an acidic and/or a low-temperature food and drink. CONSTITUTION:Rutin is included in cyclodextrin even under an alkali condition so that rutin is stabilized to ultraviolet light and water solubility is extremely improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to foods and drinks to which an inclusion compound in which rutin is included in cyclodextrin is added.

BACKGROUND OF THE INVENTION Rutin is one of the flavonol glycosides, and is contained in flower buds of the legume family Enju and buckwheat of the Polygonaceae family. The main physiological activities are fragility and abnormalities of capillaries. Cerebral hemorrhage,
It is effective in preventing radiation damage and hemorrhagic diseases. Furthermore, since rutin has an antioxidant action, it is extremely useful as an antioxidant for foods, and because it exhibits a bright yellow color, it is extremely useful as a natural pigment for foods.

[0003] Yellow pigments such as rutin absorb light having a wavelength in the ultraviolet region, so that yellow is visually emphasized as a complementary color, but ultraviolet has a wavelength shorter than visible light and energy. It is also higher than visible light and infrared light, and therefore, natural yellow dyes such as rutin are much more susceptible to damage to the molecule by absorbing ultraviolet light than other dyes that absorb visible light and infrared light.

Therefore, foods and drinks using a yellow natural pigment such as rutin will fade in a short time under the sunlight or the light of a fluorescent lamp, and therefore, should be put in a light-shielding container or a transparent container. It is necessary to store it in a cool and dark place, and this will hinder the handling at food factories, and the display and exhibition at food stores.

Furthermore, since rutin has a low solubility in water, it has been difficult to use rutin in an amount sufficient to color food by taking advantage of its bright yellow color.

[0006]

2. Description of the Related Art In order to compensate for the above-mentioned drawbacks of rutin, it has been conventionally proposed to include rutin with cyclodextrin (for example, JP-A-59-137499). According to this method, since rutin forms an inclusion compound with cyclodextrin without being chemically changed, rutin is exposed to ultraviolet rays by cyclodextrin while maintaining the properties such as antioxidation of rutin. The cyclodextrin is highly water-soluble, so that the water-solubility of rutin can be greatly improved.

[0007]

However, the above inclusion compounds have low water solubility at low temperature or acidity. For example, a saturated aqueous solution of the above inclusion compounds forms a precipitate of the above inclusion compounds at a temperature of 10 ° C. or below, and has a pH of 6 or less. A similar precipitate is formed below.

Therefore, when the inclusion compound is used in acidic or low-temperature foods and drinks such as soft drinks, ice creams and jellies, turbidity due to the above precipitation occurs in beverages and the tongue becomes rough in solid foods due to the above precipitations. It gives an unpleasant texture. In order to prevent the formation of such a precipitate, the addition amount of the inclusion compound may be reduced, but if the addition amount is reduced, it is naturally impossible to expect sufficient coloring.

[0009]

Means for Solving the Problems As a means for solving the above-mentioned conventional problems, the present invention provides foods and drinks in which a clathrate compound in which rutin is included in cyclodextrin under alkaline conditions is added. The cyclodextrin which is particularly preferable as the cyclodextrin is a branched cyclodextrin, and more preferable branched cyclodextrin is a branched β-cyclodextrin in which one or more oligosaccharides are bonded to one molecule of cyclodextrin and / or Or branched γ-cyclodextrin.
Further, the desirable pH during inclusion is 7 to 10.

The present invention is described in detail below. [Rutin] The rutin of the present invention has the following structural formula as described above.

[Chemical 1] Is a flavonol glycoside, which is usually extracted from plants such as flower buds and legumes of the leguminaceae, buckwheat, tobacco leaves, plants such as tomatoes with a solvent such as hot water or alcohol, and concentrated and purified from the extract. It is isolated as an anhydrate or a trihydrate crystal by the means of. However, in the present invention, rutin can be used as it is as an extract without being isolated, or can be used in a mixed state with other components contained in the plant. Further, it may be one in which an oligosaccharide such as glucose, maltose or maltotriose is bound to the rutinose portion of rutin.

[Cyclodextrin] The cyclodextrin used in the present invention has 6 to 12 D-glucoses forming a cyclic structure with an α1 → 4 bond, and a cyclodextrin producing enzyme such as Bacillus macerans is added to starch. Manufactured by working.

As the cyclodextrin, α-cyclodextrin having a degree of polymerization of 6, β-cyclodextrin having a degree of polymerization of 7 and γ-cyclodextrin having a degree of polymerization of 8 can be industrially used at a low cost. It is not limited to.

Further desirable cyclodextrins are branched cyclodextrins derived from β- or γ-cyclodextrins. The branched cyclodextrin is a cyclodextrin in which a monosaccharide such as glucose or an oligosaccharide such as maltose or maltotriose is bound to the cyclodextrin with an α1 → 6 bond to 1 mol of β- or γ-cyclodextrin. . The branched cyclodextrins have even higher water solubility than cyclodextrins.

The branched cyclodextrin is usually a starch degradation product containing cyclodextrin obtained by reacting a starch with an amylase of Bacillus macerans as described above, and a cyclodextrin such as α-amylase, β-amylase or glucoamylase. An enzyme that is not decomposed or is not easily decomposed is added to decompose the acyclic dextrin remaining in the decomposed product of starch to generate oligosaccharides, and the high-concentrated decomposed product of starch is further supplemented with pullulanase and isoamylase. It is produced by allowing a debranching enzyme to act and binding the oligosaccharide thus produced to cyclodextrin. Alternatively, the debranching enzyme is allowed to act on a high-concentration solution prepared by mixing separately prepared maltose or maltotriose with pure cyclodextrin obtained by various methods from a starch degradation product containing these cyclodextrins. Can also be obtained by Furthermore, since branched cyclodextrin is also contained in the mother liquor obtained by reacting starch with a cyclodextrin-forming enzyme, these can also be used.

In the present invention, the cyclodextrin and / or the branched β- or γ-cyclodextrin may be used as a mixture of two or more kinds. When cyclodextrin and branched β- or γ-cyclodextrin are used in combination,
The saturation point and the inclusion molar ratio of the inclusion compound of rutin / cyclodextrin are improved, and the water solubility of rutin is improved as compared with the case of using cyclodextrin alone.

In the present invention, the cyclodextrin or the branched β- or γ-cyclodextrin may be an isolated and purified product, or the cyclodextrin and / or the branched β- or γ-cyclodextrin may be used. It can also be used up to the starch degradation product containing it.

[Production of Inclusion Compound] The inclusion compound is formed by mixing a rutin-containing substance such as rutin or a rutin extract with a cyclodextrin-containing substance such as cyclodextrin or a starch degradation product. Since the rate of crystal precipitation of rutin is faster than the rate of inclusion of cyclohexyl in cyclodextrin, it is performed under alkaline conditions in order to moderate the crystallization rate.

In order to keep the above alkaline conditions,
One of the alkalis usually used as food additives such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate, sodium citrate, potassium hydroxide, potassium carbonate, potassium phosphate, calcium hydroxide, calcium carbonate, kansui, or the like. Use a mixture of two or more. A desirable alkaline condition is pH 7-1.
0, and more preferably pH 7-8.

When using a rutin solid substance, it is desirable to add it in the form of a solution in order to carry out the inclusion more quickly. At this time, an organic solvent used as a food additive such as ethanol, glycerol, propylene glycol, the above aqueous solution of alkali metal salt, or a mixed solution thereof may be used as the solvent.

In the production of the clathrate compound, the mixing ratio of rutin and cyclodextrin is 0.1 to 0.5 times the mole of the cyclodextrin generally used. Usually, in the production of an inclusion compound, 1 to 3 parts by weight of the above cyclodextrin or a cyclodextrin-containing substance is dispersed in 5 to 10 parts by weight of water, and heated and stirred at 60 to 80 ° C. to be completely dissolved. Usually, about 0.5 to 5% by weight of alkali is added. 60-8 the above solution
While maintaining at 0 ° C. and stirring gently, the amount of rutin or rutin extract or rutin-containing solution as planned above is added, and the pH is adjusted to preferably 7 to 10, more preferably 7 to 8, Stir for 0.5-2 hours. The rutin-cyclodextrin clathrate compound is produced in this manner, and the clathrate compound may be made into a solution, or may be dried by freeze-drying, spray-drying, drum-drying or the like to be powdered.

[Food and Drink] The clathrate compound of the present invention is added to various foods and drinks. Examples of food and drink to which the inclusion compound of the present invention is added include soft drinks (cider, ramune, etc.), powdered juice, dairy products (milk, yogurt, ice cream, butter, margarine, cheese, whipped cream, etc.) , Frozen desserts, confectionery (anko, yokan, buns, chocolate, gum, jelly, agar, almond tofu, cakes, castella, cookies, rice crackers, snacks, etc.), bread,
Mochi, marine products (kamaboko, chikuwa, etc.), processed meat (sausage, ham, etc.), fruit processed products (jam, marmalade, fruit sauce, etc.), seasonings (dressing, mayonnaise, miso, etc.), noodles (udon, Buckwheat etc.), pickles, meat storage, fish meat, fruit bottling, canned foods and the like.

No special step is required to add the clathrate compound of the present invention to the food or drink, and the inclusion compound may be added together with the raw materials at the beginning of the manufacturing process of the food or drink, or added during the manufacturing process, or Add at the end of the manufacturing process. As an addition method, a usual method such as kneading, kneading, dissolving, dipping, spraying, spraying, coating, etc. is selected according to the type and properties of food and drink. In the food and drink, lecithin together with the inclusion compound of the present invention,
The coexistence of glycine and the like synergistically increases the antioxidant effect of rutin.

[0023]

In the present invention, since rutin is clathrated by cyclodextrin having good water solubility, the antioxidant effect of rutin is maintained as it is, and the stability of rutin to ultraviolet light and the water solubility are improved. Such water-solubility improving effect is further improved by using branched β or γ-cyclodextrin. Furthermore, in the present invention, since the inclusion is carried out under alkaline conditions, the solubility of rutin is improved and the amount of inclusion of rutin is increased. Foods containing the clathrate of the present invention, compared to conventional foods using rutin alone, dramatically increased resistance to ultraviolet rays that also cause fading, and therefore does not require a special storage means, and There is no problem in terms of food safety.

[0024]

EXAMPLES Examples will be given to explain the present invention in more detail, but the present invention is not limited thereto. [Example 1] Maltosyl-β-cyclodextrin 10
To 50 g of water, add 50 g of water and add 0.1 g of sodium carbonate.
Was added to adjust the pH to 8.5, and then the mixture was heated and kept at 70 ° C. and completely dissolved. Thereafter, 6 ml of an ethanol solution containing 25% by volume of rutin was added and cooled to 40 ° C. with gentle stirring for 1 hour to obtain a rutin-cyclodextrin inclusion compound solution. As the [sample], the inclusion compound 10
77.2 g of water was added to g, and granulated sugar 15
g, citric acid 0.3 g, sodium citrate 0.15 g
Add, heat so that it does not boil, and finally gelatin 2
g was added, and when it was completely dissolved, it was transferred to two petri dishes with a diameter of 12 cm and cooled and solidified at 4 ° C. to prepare rutin-containing jelly. As [Control 1], 5 g of a 0.2% aqueous sodium carbonate solution containing 300 mg of rutin was added, and as [Control 2], 10 g of β-cyclodextrin was added with 10 ml of distilled water and 0.6 g of rutin, and the mixture was heated to room temperature using an automatic mortar. 3
As a [Control 3], 5 g of the clathrate compound obtained by the time kneading was added to 10 g of maltosyl-β-cyclodextrin and 1 part of distilled water.
0 ml and 0.6 g of rutin were added, and 5 g of the clathrate compound obtained by kneading at room temperature for 3 hours in an automatic mortar was dispersed and dissolved in 82.2 g of distilled water to prepare an aqueous solution, each containing 15 g of granulated sugar. , 0.3 g of citric acid and 0.15 g of sodium citrate were added and heated without boiling, and finally 2 g of gelatin was added.
It was transferred to a 2 cm Petri dish and cooled to 4 ° C. to solidify to prepare a rutin-containing jelly.

Of the two jelly samples, [Sample], [Control 1], [Control 2] and [Control 3], one was placed in a refrigerator at 4 ° C. and the other was placed 40 cm under a UV lamp for sterilization. Leave in position for 6 hours. Then, 3 g of the jelly was dispensed into a 50 ml volumetric flask, about 40 ml of distilled water was added, and the jelly was completely dissolved while keeping the temperature in boiling water, then cooled to room temperature and made up to volume with distilled water. . Each solution was filtered, and the filtrate was measured for absorbance in the range of 200 to 500 nm using a spectrophotometer. The evaluation of the measured value is the percentage obtained by dividing the measured absorbance value of the solution exposed to the germicidal UV lamp at the wavelength measured at the absorption maximum wavelength (λmax a) of the solution stored in the refrigerator, at the wavelength showing the absorption maximum. The value obtained by subtracting from was shown as the fading rate.
Also, 300-40 of the solution exposed to a UV lamp for sterilization
The absorption maximum wavelength (λmaxb) in the range of 0 nm was subtracted from the absorption maximum wavelength (λmax a) of the solution stored in the refrigerator, and the result was shown as the degree of color change (Δλ).

After 6 hours, [Control 1], [Control 2] and [Control 3] were turbid in pale yellow, while [Sample] was transparent. The results of absorbance measurement are shown in Table 1.

[Table 1]

As shown in Table 1, in rutin which is not included in cyclodextrin [Control 1], and in which it is not included under alkaline conditions [Control 2] and [Control 3], the absorption maximum is increased. Discoloration that the wavelength shown changes,
And the fading was observed, but in the [Sample] using the rutin-cyclodextrin clathrate compound aqueous solution clathrated under alkaline conditions, no change was observed in the color tone and no change in the degree of fading was observed.

Example 2 To 20 g of mixed sugar containing 50% maltosyl-γ-cyclodextrin, 50 g of water was added, 0.5 g of sodium carbonate was added to adjust the pH to 8, and the mixture was heated to 70 ° C. and kept warm. Dissolved in. After that, 6 ml of an ethanol solution containing 25% by volume of rutin was added,
It was cooled to 40 ° C. with gentle stirring for 1 hour and dried with a spray dryer to obtain a rutin-cyclodextrin inclusion compound solution. As a [sample], 1 g of the inclusion compound and 10 g of grapefruit juice, 0.2 g of citric acid, 0.02 g of vitamin C, and 12 granulated sugars
g, orange essence 0.03g, add water to 100ml
And the juice was prepared. Two 20 ml sealed transparent test tubes were prepared and one was exposed to direct sunlight for 5 days in a cool dark place and the other outdoors.
[Control 1] 2.5 g of a 0.2% sodium carbonate aqueous solution containing 150 mg of rutin, and [Control 2] 10 g of β-cyclodextrin with 10 ml of distilled water and 150 mg of rutin were added at room temperature using an automatic mortar. At 3
1g of clathrate compound obtained by time kneading was prepared, and 10g of grapefruit juice, 0.2g of citric acid, 0.02g of vitamin C, 12g of granulated sugar and 0.03g of orange essence were added with water to a constant volume of 100ml, The juice was prepared. As in the case of [Sample], each was sealed in two transparent test tubes capable of sealing 20 ml each, and one was exposed to direct sunlight for 5 days in a cool and dark place and the other outdoors.

After 5 days, each solution was filtered, and the filtrate was measured for absorbance in the range of 300 to 400 nm using a spectrophotometer. The evaluation of the measured value is the absorbance measured value at the absorption maximum wavelength (λmax a) of the solution stored in a cool dark place, at the wavelength showing the absorption maximum, the percentage obtained by dividing the absorbance measured value of the solution exposed to direct sunlight is 100. And the value was shown as the fading rate. In addition, the maximum absorption wavelength (λ) in the range of 300 to 400 nm of the solution exposed to direct sunlight
max b) absorption maximum wavelength (λma
The value obtained by subtracting from xa) was shown as the degree of color change (Δλ).

After 5 days, a pale yellow flocculent precipitate was observed in the solutions of [Control 1] and [Control 2] exposed to a cool dark place and direct sunlight, but no precipitation was observed in [Sample]. It was The absorbance measurement results are shown in Table 2.

[Table 2]

As shown in Table 2, in the case of rutin which is not clathrated with cyclodextrin [Control 1] and when it is not clathrated under alkaline conditions [Control 2], the wavelength showing the absorption maximum varies. Although the so-called discoloration and fading were observed, in the [Sample] using the rutin-cyclodextrin inclusion compound clathrated under alkaline conditions, almost no change was observed in the color tone and the degree of fading.

Example 3 To 10 g of maltosyl-β-cyclodextrin, 50 g of water was added, 0.5 g of sodium carbonate was added, and the mixture was heated and kept at 70 ° C. to be completely dissolved. Thereafter, 6 ml of an ethanol solution containing 25% by volume of rutin was added, cooled to 40 ° C. with gentle stirring for 1 hour, and dried with a spray dryer to obtain rutin-cyclodextrin inclusion compound powder. [Sample]
White sugar 171g, butter 332g, egg 20g, salt 3
g and 474 g of medium strength wheat flour were kneaded with a mixer to prepare a cookie dough. The inclusion compound 0.5 is added to 30 g of this dough.
And 0.5 g of lecithin were added and thoroughly kneaded. The prepared cookie dough is spread and molded at 220 ° C.
Baked in the oven. As [Control 1], 150 mg of rutin was added, and as [Control 2], 10 g of β-cyclodextrin was added with 10 ml of distilled water and 1.5 g of rutin,
1 g of clathrate compound obtained by kneading and drying at room temperature for 3 hours using an automatic mortar was added to 30 g of the above cookie dough and kneaded sufficiently. Spread these prepared cookie dough,
It was molded and baked in an oven at 220 ° C. [Control 3]
30 g of the above cookie dough to which nothing was added was spread, molded, and baked in an oven at 220 ° C.

As a result, [Sample] had a smooth texture like [Control 3] to which nothing was added. Further, in comparison with the color of the non-inclusion rutin [Control 1] and the color of the non-inclusion ruthenium [Control 2], [Sample] has a bright yellow color, which is remarkable when observed over time. No fading was observed.

[Example 4] 50 g of Mitsukan vinegar (produced by Nakanozu Co., Ltd.), 100 g of solar corn salad oil (produced by Nippon Shokuhin Kako Co., Ltd.), 40 g of sucrose, 10 g of salt, 2 g of white pepper, Ajinomoto (AGF Co., Ltd.) 3g, water 30g
g and 2 g of garlic powder were mixed and stirred with a homogenizer for 30 seconds to prepare a French dressing. As a [sample], 0.1 g of the inclusion compound prepared in Example 2 and 0.1 g of lecithin, and as a [control 1] 2.5 g of a 0.2% sodium carbonate solution containing 15 mg of rutin.
As [Control 2], 10 ml of β-cyclodextrin, 10 ml of distilled water and 1.5 g of rutin were added, and kneaded for 3 hours at room temperature with an automatic mortar and dried to obtain 0.1 g of the inclusion compound, As [Control 3], only 0.1 g of the clathrate compound prepared in Example 2 was used, and as [Control 4] lecithin 0.
1 g, 0.1 g of maltosyl β-cyclodextrin as [Control 5], respectively, in the above French dressing 25
What was added to g was prepared.

The obtained [Sample] and [Control 1] to [Control 5] were placed in a hermetically sealed 100 ml glass container, and 4
The sample was allowed to stand and stored in a thermostat kept at 0 ° C. Once a day, 1
After storing for 5 and 30 days with vigorous shaking for 5 minutes, they were taken out from the incubator and visually compared to each other, and in [Control 1] and [Control 2], a pale yellow precipitate of rutin was generated and coloration was also deteriorated. However, no change was observed in [Sample] and [Control 3] as compared with immediately after preparation. Furthermore, each sample was subjected to centrifugation (10,000 rpm / 60 minutes), the upper salad oil layer was recovered, and the peroxide value (PV) was measured by iodometry. The results are shown in Table 3.

[Table 3]

As shown in Table 3, the peroxide value (PV) showed the minimum value in [Sample]. As shown by the results of [Control 1] to [Control 3], no inhibition of the antioxidative performance of rutin by inclusion was observed. Further, the antioxidant performance evaluated from the value of [Sample] is considered to be due to the synergistic effect of rutin-lecithin, since the antioxidant performance is hardly observed when lecithin alone is used.

[0037]

Therefore, in the present invention, a sufficient amount of rutin as an antioxidant and a natural yellow pigment can be used in acidic and / or low temperature foods and drinks without causing precipitation, and the above foods and drinks can be used. Hardly fades when exposed to UV light.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location A23L 3/3562 A61K 31/70 ACA 8314-4C

Claims (4)

[Claims] 1. A food or drink obtained by adding a clathrate compound in which rutin is clathrated in cyclodextrin under alkaline conditions. 2. The food or drink according to claim 1, wherein the cyclodextrin is a branched cyclodextrin. 3. The branched cyclodextrin is a branched β-cyclodextrin and / or a branched γ-cyclodextrin in which one or more monosaccharides or oligosaccharides are linked to one molecule of cyclodextrin. Food and drink described in 2. 4. The food or drink according to claim 1 or 2, wherein the clathrate compound is obtained by clathrating rutin with cyclodextrin under alkaline conditions of pH 7 to 10.