JP2016003210A - Anthocyanin stabilizer and anthocyanin stabilization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anthocyanin stabilizer which exhibits an excellent improving action of anthocyanin stability, to provide an anthocyanin-containing composition containing it, and to provide an anthocyanin stabilization method.SOLUTION: An anthocyanin stabilizer added into anthocyanin contains at least one kind of amino acid of lysine or histidine as an active ingredient. Preferably, the lysine is contained at a mass ratio in the range of 0.01-1 to delphinidin-based anthocyanin, or preferably, the histidine is contained at a mass ratio in the range of 0.005-1 to the delphinidin-based anthocyanin.

Description

  The present invention relates to an anthocyanin stabilizer for improving the stability of anthocyanins, an anthocyanin-containing composition containing the same, and a method for stabilizing anthocyanins.

  Conventionally, anthocyanins are known as natural components having an antioxidant action. Anthocyanins are present in plants in the form of glycosides in which flavonoid anthocyanidins are linked to sugars and sugar chains as aglycones.

  Since anthocyanin is a pigment component, it is also used in various fields such as foods and drinks, pharmaceuticals, and cosmetics in the use of natural pigments. Anthocyanins are abundantly contained in berries such as blueberries, raspberries, lingonberries, and bilberries, and these anthocyanin-containing plants are applied as health foods and the like for the purpose of exhibiting an antioxidant effect and the like.

  On the other hand, it is known that anthocyanins have low stability, and fading proceeds especially under conditions such as light, heat, air oxidation, and alkali. Therefore, conventionally, attempts have been made to improve the stability of anthocyanins by adding various substances to anthocyanins (see, for example, Patent Documents 1 to 5).

  Patent Document 1 discloses a technique for stabilizing anthocyanins by adding a compound having an SH group, such as cysteine-containing peptides, to anthocyanins.

  Patent Document 2 discloses a technique for preventing fading of an anthocyanin pigment contained in the beverage by adding iron ions to the anthocyanin pigment-containing beverage.

  Patent Document 3 discloses a technique for suppressing the fading of an anthocyanin pigment and stabilizing it by adding an extract of a plant belonging to the department of an antaceae to the anthocyanin pigment.

  Patent Document 4 discloses a technique for preventing fading of an anthocyanin pigment by an emulsified composition containing tocopherol.

  Patent Document 5 discloses a technique for suppressing and stabilizing fading of an anthocyanin dye by adding glycyrrhizin to the anthocyanin dye.

JP 2009-136187 A Japanese Patent Laying-Open No. 2005-104841 JP-A-6-234935 JP 2012-75340 A JP-A-9-263707

  However, even if the techniques of Patent Documents 1 to 5 are applied, anthocyanins cannot be sufficiently stabilized.

  An object of the present invention is to provide an anthocyanin stabilizer that exhibits an excellent effect of improving the stability of anthocyanins, an anthocyanin-containing composition containing the same, and a method for stabilizing anthocyanins.

  The present inventor has found that a specific amino acid exhibits an effect of improving the stability of anthocyanins.

  Therefore, in order to achieve the above object, the anthocyanin stabilizer of the present invention is characterized by containing as an active ingredient at least one amino acid selected from the group consisting of lysine and histidine.

  According to the anthocyanin stabilizer of the present invention, the stability of anthocyanins can be improved.

  The anthocyanin stabilizer of the present invention is effective in improving the stability of delphinidin-based anthocyanins when the amino acid is lysine. By including lysine at a mass ratio in the range of 0.01 to 1 with respect to delphinidin-based anthocyanins, the effect of improving the stability of delphinidin-based anthocyanins can be reliably obtained.

  If the mass ratio of lysine is less than 0.01, the effect of improving the stability may not be sufficient. If it exceeds 1, the lysine as the additive is larger than the delphinidin-based anthocyanin as the additive, and the additive As meaningless.

  The anthocyanin stabilizer of the present invention is effective in improving the stability of delphinidin-based anthocyanins and cyanidin-based anthocyanins when the amino acid is histidine. By including histidine at a mass ratio in the range of 0.005 to 1 with respect to delphinidin-based anthocyanins, the effect of improving the stability of delphinidin-based anthocyanins can be reliably obtained.

  If the mass ratio of histidine is less than 0.005, the stability improving effect may not be sufficient. If it exceeds 1, the amount of histidine as an additive is larger than that of the delphinidin-based anthocyanin as an additive. As meaningless.

  Moreover, the anthocyanin stabilizer of this invention can be added to an anthocyanin containing composition.

  According to the anthocyanin-containing composition of the present invention, the stability of the anthocyanin contained in the anthocyanin-containing composition can be improved by the effect of the anthocyanin stabilizer.

  Examples of the anthocyanin-containing composition include mulberry, cranberry, boysenberry, currant, lotus cup, blueberry, blackberry, prune, bilberry, acai, grape, raspberry, strawberry, red cabbage, eggplant, colored rice, black bean, black sesame, Mention may be made of those extracted from at least one plant selected from colored potatoes, red potatoes, strawberries, red beans, red onions, purple onions, perillas, iwaki berries, usvenia oysters, purple corn, huckleberries, lingonberries, and gooseberries.

  Furthermore, the anthocyanin stabilizer of this invention can be used for the anthocyanin stabilization method which improves the stabilization of anthocyanin by adding to the anthocyanin containing composition.

The graph which shows the effect of the anthocyanin stabilizer of this embodiment.

  Next, embodiments of the present invention will be described in more detail.

  The anthocyanin stabilizer of this embodiment contains at least one amino acid selected from the group consisting of lysine and histidine as an active ingredient. The anthocyanin stabilizer can improve the stabilization of anthocyanins contained in the anthocyanin-containing composition by being added to the anthocyanin-containing composition.

  Here, anthocyanins are configured as glycosides in which anthocyanidins, which are flavonoids, are linked to sugars and sugar chains as aglycones. The type of anthocyanin in which the anthocyanin stabilizer of the present embodiment is effective is not particularly limited, and examples thereof include pelargonidin, cyanidin, delphinidin, peonidin, petunidin, and malvidin anthocyanins.

  An anthocyanin stabilizer containing lysine as an active ingredient is effective in improving the stability of delphinidin-based anthocyanins. An anthocyanin stabilizer containing histidine as an active ingredient is effective in improving the stability of delphinidin-based anthocyanins and cyanidin-based anthocyanins.

  Since lysine and histidine contained in the anthocyanin stabilizer of the present embodiment are easily available as amino acids, the stabilization of anthocyanins can be improved easily and inexpensively.

  In addition, lysine and histidine are water-soluble amino acids, and there is no risk of health damage even if an anthocyanin-containing composition to which an anthocyanin stabilizer is added is excessively consumed. Can be applied.

  The amino acids may be used alone or in combination of two. The amino acid may be an L-form amino acid, a D-form amino acid, or a DL-form amino acid (amino acid in which a D-form and an L-form are mixed), or may be formulated as a salt.

  The anthocyanin stabilizer containing lysine has the effect of improving the stability of delphinidin-type anthocyanins when the mass ratio of lysine to delphinidin-type anthocyanins is in the range of 0.01 to 1, more preferably in the range of 0.05 to 1. You can definitely get it.

  An anthocyanin stabilizer containing histidine has an effect of improving the stability of delphinidin-based anthocyanins when the mass ratio of histidine to delphinidin-based anthocyanins is in the range of 0.005 to 1, more preferably 0.05 to 1. You can definitely get it.

  The anthocyanin stabilizer of this embodiment can be added to a known anthocyanin-containing composition containing anthocyanin, and the origin of the anthocyanin is not particularly limited. As the anthocyanin-containing composition, natural materials containing anthocyanins, extracts from the natural materials, biosynthetic products, chemically synthesized products, and the like can be used.

  Natural materials containing anthocyanins include, for example, mulberry, cranberry, boysenberry, currant, lotus cup, blueberry, blackberry, prune, bilberry, acai, grape, raspberry, strawberry, red cabbage, eggplant, colored rice, black bean, black sesame Colored potatoes, red potatoes, persimmons, red beans, red onions, purple onions, perillas, iwaki berries, usvenia oysters, purple corns, huckleberries, lingonberries, gooseberries and the like. These natural materials may be used alone or in combination of two or more.

  In the anthocyanin-containing composition, the content of the anthocyanin before the anthocyanin stabilizer is added is not particularly limited, but when the purpose is to take anthocyanin or when the anthocyanin is used as a main component for various uses Is preferably 30% by mass or more. Moreover, in order to take anthocyanin more effectively, 40 mass% or more is preferable.

  The anthocyanin-containing composition containing the anthocyanin stabilizer may be either liquid or solid. The liquid state includes forms such as fluid liquid, gel, and jelly. The solid state includes forms such as powder, particles, and tablets.

  The anthocyanin-containing composition containing the anthocyanin stabilizer can be used in various dosage forms such as tablets, capsules, granules, drinks, syrups, and troches.

  The anthocyanin-containing composition containing the anthocyanin stabilizer can be applied to various fields such as pharmaceuticals, quasi-drugs, foods and drinks, cosmetics, research reagents, and the like. It can be applied to a colorant or dye using a fatigue recovery solvent or a natural pigment.

  When the anthocyanin-containing composition containing the anthocyanin stabilizer is applied as a food or drink, it can be applied to various food materials or beverage materials such as health foods and supplements. When the anthocyanin-containing composition is applied as a food or drink, a gelling agent, saccharide, flavor, sweetener, fats and oils, base material, excipient, food additive, auxiliary material, extender, etc. may be appropriately blended. .

  Moreover, when applying the said anthocyanin containing composition as liquid food-drinks, in order to improve the stability of anthocyanin more, it is preferable to make pH into the range of 3.5-7.5. Further, when the anthocyanin-containing composition is in a liquid state, the anthocyanin-containing composition may be filled into a soft capsule in order to improve storage stability.

  When applying the anthocyanin containing composition containing the said anthocyanin stabilizer as cosmetics, it can manufacture by mix | blending with a cosmetic base material. The form of the cosmetic can be a lotion, emulsion, cream, powder or the like. The cosmetic base material is a base material that is generally blended in common with cosmetics, and mainly contains oil, purified water, and alcohol. When applying the anthocyanin-containing composition as a cosmetic, a surfactant, a humectant, an antioxidant, a thickener, an antiseborrheic agent, a blood circulation promoter, a pH adjuster, a pigment, an antiseptic, a fragrance, and the like are appropriately blended. May be.

  When the anthocyanin-containing composition containing the anthocyanin stabilizer is applied as a pharmaceutical product, it can be administered by various methods such as oral administration, coating, intravascular administration, and transdermal administration. The pharmaceutical can be in the form of a liquid, ointment, spray, sheet, powder, powder, granule, tablet, capsule, pill, suppository, or injection. When the anthocyanin-containing composition is applied as a pharmaceutical product, excipients, base materials, emulsifiers, solvents, stabilizers and the like may be appropriately blended.

  Next, an Example and a comparative example are shown about the anthocyanin stabilizer of this embodiment.

[Test 1: Stability test of anthocyanins with various amino acids]
In this test, the anthocyanin anthocyanin is mixed with an anthocyanin stabilizer containing any one amino acid of lysine and histidine, and the amount of anthocyanin remaining after a predetermined period of time is measured. The effect of the stabilizer was measured.

  First, an anthocyanin stabilizer having a concentration of various amino acids or antioxidants of 3.27 mg / mL (Example 1) by adding 6.54 mg of amino acids or antioxidants to 2 mL of pH 6.8 phosphate buffer. -2 and Comparative Examples 1-14) were prepared.

  As the amino acid, L-lysine (Wako Pure Chemical Industries, Ltd. Lot.HCJ9046) (hereinafter abbreviated as lysine) is used in Example 1, and L-histidine (Nacalai Tesque, Lot.M8K9101) (hereinafter, referred to as “lysine”) is used in Example 2. In Comparative Example 1, L-glutamic acid (Nacalai Tesque Co., Ltd., Lot.M8R9515) (hereinafter abbreviated as glutamic acid) is used. In Comparative Example 2, L-threonine (Tokyo Chemical Industry Co., Ltd., Lot. TNXTL-LG) (hereinafter abbreviated as threonine), L-alanine (Nacalai Tesque Co., Ltd., Lot.M8R9380) (hereinafter abbreviated as alanine) in Comparative Example 3, and L-aspartic acid (Nacalai Tesque in Comparative Example 4). Co., Ltd., Lot.M4E3671) (hereinafter abbreviated as aspartic acid), in Comparative Example 5, L-leucine (Nacalai Tesque, Ltd., Lot.M9E4265) (hereinafter abbreviated as leucine), In Comparative Example 6, L-methionine (Nacalai Tesque, Inc., Lot.M2A8983) (hereinafter abbreviated as methionine), and in Comparative Example 7, L-proline (Nacalai Tesque, Inc., Lot.M1E7764) (hereinafter, abbreviated as proline). In Comparative Example 8, L-glutamine (Kishida Chemical Co., Ltd., Lot.H30411S) (hereinafter abbreviated as glutamine), and in Comparative Example 9, L-arginine (Nacalai Tesque Co., Ltd., Lot. M2F0711) (hereinafter referred to as arginine) In Comparative Example 10, L-valine (Nacalai Tesque, Inc., Lot.M3A9803) (hereinafter abbreviated as valine), and in Comparative Example 11, L-tyrosine (Nacalai Tesque, Lot. M8G2206) (hereinafter, abbreviated). In Comparative Example 12, L-cystine (Nacalai Tesque Co., Ltd., Lot. M4E4835) (hereinafter abbreviated as cystine) was used.

  Further, as the antioxidant, (+)-catechin (Tokyo Chemical Industry Co., Ltd., Lot.FJN01) (hereinafter abbreviated as catechin) is used in Comparative Example 13, and Trolox (CALBIOCHEM, Lot.D00042958) is used in Comparative Example 14. (Hereinafter abbreviated as Trolox) was used.

  The phosphate buffer solution is composed of 17.0 g of potassium dihydrogen phosphate (Nacalai Tesque, Ltd., Lot.M6P2693) and 17.75 g of anhydrous disodium hydrogen phosphate (Kishida Chemical Co., Ltd., Lot. E39656T). The sample was diluted to 1000 mL and diluted 10-fold with ultrapure water immediately before this test.

  Next, 200 μL of the anthocyanin stabilizers of Examples 1-2 and Comparative Examples 1-14 were dispensed into a 15 mL tube, and the phosphate buffer was added to make a total volume of 9 mL. In addition, as Reference Example 1 (control), 200 μL of water was put into a 15 mL tube, and the phosphate buffer was added to make a total volume of 9 mL.

  Next, the tube containing the anthocyanin stabilizer or water and the phosphate buffer is shaken by a shaking water bath (Taitec Co., Ltd., Water Bath Shaker MM-10) adjusted to a temperature of 37 ° C. Then, 1 mL of anthocyanin-containing solution was added to the tube to prepare a test solution. The test solution corresponds to the anthocyanin-containing composition of the present invention.

  In the 25 mL volumetric flask, 16.35 mg of Delphinidin-3-Glucoside Chloride (Tokiwa Plant Chemistry Laboratory Co., Ltd., Lot. 111140201) (hereinafter abbreviated as delphinidin-based anthocyanin) was added to the 25-mL volumetric flask. , Made up with 0.01N hydrochloric acid aqueous solution.

  When the test solution was prepared, 0.65 mg of delphinidin-based anthocyanin was contained in 10 mL of the test solutions of Examples 1-2, Comparative Examples 1-14, and Reference Example 1. Further, Examples 1-2 and Comparative Examples The test solutions of Examples 1 to 14 contain 0.65 mg of the amino acid or antioxidant. That is, in the test solution, the mass ratio of amino acid to delphinidin-based anthocyanin is 1.

  Next, immediately after preparing the test solution (immediately after adding the anthocyanin-containing solution), 60 minutes, 120 minutes, and 240 minutes, 1 mL of the test solution was taken from the tube, A sample for analysis was prepared by dispensing 200 μL into a 5 mL microtube and diluting 4 times with a 10% aqueous formic acid solution. The aqueous formic acid solution is obtained by adding 50 mL of formic acid (Kishida Chemical Co., Ltd., Lot. G11625C) to 450 mL of pure water.

  Next, 300 μL of the sample for analysis was dispensed into a 96-well microplate, and the absorbance of light having a wavelength of 535 nm was measured using a microplate reader (DS Pharma Biomedical Co., Ltd., POWERSCAN HT).

  For the analytical samples of Examples 1-2, Comparative Examples 1-14, and Reference Example 1, the absorbance ratios immediately after preparing the test solution, after 60 minutes, after 120 minutes, and after 240 minutes are shown in Table 1. . The absorbance ratio is a relative value when the absorbance immediately after preparing the test solution is 100%.

  FIG. 1 shows the change in absorbance ratio over time for the analytical samples of Example 1 (lysine), Example 2 (histidine) and Reference Example 1.

  According to Table 1 and FIG. 1, the anthocyanin stabilizers of Examples 1 and 2 containing any one amino acid of lysine and histidine were compared with Reference Example 1 containing no amino acids, and the test The degree of decrease in the absorbance ratio with time after preparation of the solution is small. Moreover, the anthocyanin stabilizer of Examples 1-2 compared with the anthocyanin stabilizer of Comparative Examples 1-14 containing amino acids or antioxidants other than lysine and histidine, and the time passage after preparation of the test solution. The degree of decrease in the absorbance ratio is small.

  Therefore, the anthocyanin stabilizer containing any one amino acid of lysine and histidine is more effective than the anthocyanin stabilizer containing other amino acids or antioxidants. It is clear that it is excellent in suppressing and improving the stability of anthocyanins.

[Test 2: Test for mixing ratio of amino acids]
Next, the stability of anthocyanins was tested by changing the blending ratio of amino acids blended in the anthocyanin stabilizer.

  First, lysine is used as an amino acid, and the mass ratio of amino acid to delphinidin-based anthocyanin is 1 (Example 3), 0.5 (Example 4), 0.1 (Example 5), 0.05 (Example 6). , 0.01 (Example 7), 0.005 (Example 8), 0.001 (Example 9) except that the anthocyanin stabilizer was prepared in exactly the same manner as in Example 1, and the test solution Was prepared.

  Further, test solutions were prepared in the same manner as in Examples 3 to 9 except that histidine was used as an amino acid (Examples 10 to 16).

  Further, as Reference Example 2, a test solution containing no amino acid was prepared in exactly the same manner as Reference Example 1.

  Then, an analytical sample was prepared exactly as in Example 1 except that the obtained test solution was used, and the absorbance of light having a wavelength of 535 nm was measured for the analytical sample.

  The absorbance ratios immediately after preparing the test solution, 120 minutes later, and 240 minutes later are shown in Table 2.

  According to Table 2, in the anthocyanin stabilizer containing any one amino acid of lysine and histidine, the larger the mass ratio (blending ratio) of amino acids to delphinidin-based anthocyanins, the longer the time after preparation of the test solution. It is clear that the degree of decrease in the absorbance ratio with the progress is small and tends to be excellent in improving the stability of anthocyanins.

  When the amino acid is lysine, when the mass ratio of lysine to delphinidin-based anthocyanins is in the range of 0.01 to 1, more preferably in the range of 0.05 to 1, the effect of improving the stability of anthocyanins is reliably obtained. Obviously it can be.

  In addition, when the amino acid is histidine, when the mass ratio of histidine to delphinidin-based anthocyanins is in the range of 0.005 to 1, more preferably in the range of 0.05 to 1, the effect of improving the stability of anthocyanins is ensured. It is clear that can be obtained.

[Test 3: Test for anthocyanins]
Next, the anthocyanin stability was tested by changing the type of anthocyanin to which the anthocyanin stabilizer was added.

  In this test, instead of delphinidin-based anthocyanin, Cyanidin 3-Glucoside Chloride (manufactured by Joban Plant Chemistry Laboratory, Lot. 112130504) (hereinafter abbreviated as cyanidin-based anthocyanin) was used as the anthocyanin. An anthocyanin-containing solution was prepared exactly the same as 1.

  Also, an anthocyanin stabilizer containing histidine was prepared in exactly the same manner as in Example 2 to prepare a test solution (Example 17). In addition, an anthocyanin stabilizer containing leucine, arginine, valine or catechin was prepared in exactly the same manner as Comparative Examples 5, 9, 10 or 13, and test solutions were prepared (Comparative Examples 15 to 18).

  Further, as Reference Example 3, a test solution containing no amino acid at all was prepared in the same manner as Reference Example 1.

  Then, an analytical sample was prepared in the same manner as in Example 1 except that the anthocyanin-containing solution and the test solution obtained in this test were used, and the absorbance of light having a wavelength of 535 nm was measured for the analytical sample.

  Table 3 shows the absorbance ratio immediately after preparing the test solution, after 60 minutes, after 120 minutes, and after 240 minutes.

  From Reference Example 3 (Control) in Table 3 and Reference Example 1 (Control) in Table 1, cyanidin-based anthocyanins were compared with delphinidin-based anthocyanins in the degree of decrease in absorbance ratio over time after the test solution was prepared. It is clear that it is small and relatively stable.

  And from Table 3, the anthocyanin stabilizer of Example 17 containing histidine has a smaller degree of decrease in the absorbance ratio with the passage of time after the preparation of the test solution compared to Reference Example 3, and is relatively stable. It is clear that the stability of cyanidin-based anthocyanins, which are excellent in the resistance, is further improved.

  On the other hand, the anthocyanin stabilizers of Comparative Examples 15 to 18 containing amino acids other than histidine have a greater degree of decrease in the absorbance ratio with the passage of time after the preparation of the test solution compared to Reference Example 3, and cyanidin anthocyanins. It is apparent that fading is promoted by deteriorating the stability of the color.

Therefore, in order to achieve the above object, anthocyanin stabilizers of the present invention as an active ingredient Rishi down, characterized in that it is effective in delphinidin-based anthocyanins.

According to the anthocyanin stabilizer of the present invention, the stability of delphinidin-based anthocyanins can be improved.

Anthocyanin stabilizer of the present invention contains a weight ratio ranging from 0.01 to re thin relative delphinidin-based anthocyanins, it is possible to reliably obtain the stability improvement of delphinidin-based anthocyanins.

The anthocyanin stabilizer of the present invention is, for example, mulberry, cranberry, boysenberry, currant, lotus cup, blueberry, blackberry, prune, bilberry, acai, grape, raspberry, strawberry, red cabbage, eggplant, colored rice, black bean Delphinidin-type anthocyanins extracted from at least one plant selected from sesame, black sesame, colored potato, red potato, persimmon, red bean, red onion, purple onion, perilla, iwaki berry, usbenia, purple corn, huckleberry, lingonberry, and gooseberry It is effective for.

Claims (8)

  An anthocyanin stabilizer characterized by comprising at least one amino acid selected from the group consisting of lysine and histidine as an active ingredient. The anthocyanin stabilizer according to claim 1, wherein
The amino acid is lysine;
An anthocyanin stabilizer characterized by being effective for delphinidin-based anthocyanins. The anthocyanin stabilizer according to claim 2,
An anthocyanin stabilizer comprising the lysine at a mass ratio in the range of 0.01 to 1 with respect to the delphinidin-based anthocyanin. The anthocyanin stabilizer according to claim 1, wherein
The amino acid is histidine;
An anthocyanin stabilizer characterized by being effective for delphinidin-based anthocyanins and cyanidin-based anthocyanins. The anthocyanin stabilizer according to claim 4,
An anthocyanin stabilizer comprising the histidine in a mass ratio in the range of 0.005 to 1 with respect to the delphinidin-based anthocyanin.   An anthocyanin containing composition containing the anthocyanin stabilizer of any one of Claims 1-5. The anthocyanin-containing composition according to claim 6,
The anthocyanin-containing composition is mulberry, cranberry, boysenberry, currant, lotus cup, blueberry, blackberry, prune, bilberry, acai, grape, raspberry, strawberry, red cabbage, eggplant, colored rice, black bean, black sesame, colored potato An anthocyanin-containing composition extracted from at least one plant selected from the group consisting of potato, potato, persimmon, red bean, red onion, purple onion, perilla, iwaki berry, usvenia oyster, purple corn, huckleberry, lingonberry, and gooseberry .   An anthocyanin stabilizing method according to any one of claims 1 to 5, wherein the anthocyanin stabilizing agent according to any one of claims 1 to 5 is added to an anthocyanin-containing composition.

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