JP6272421B1 - Method for stabilizing carotenoid and method for producing carotenoid compound - Google Patents

Abstract

There has been a demand for a carotenoid stabilization method and a carotenoid compound production method capable of maintaining a stable state in air for a long period of time. The carotenoid stabilization method according to the present invention is characterized by mixing carotenoids with Ca ions and / or Mg ions. [Selection] Figure 1

Description

The present invention relates to carotenoids used for pigments, pharmaceuticals, cosmetics, drugs, foods, beverages, feeds and the like. Specifically, the present invention relates to a carotenoid compound that can keep a carotenoid that is usually unstable in the air in a stable state for a long time even in the air.
Further, the present invention relates to a carotenoid stabilization technique that can make a carotenoid stable in air by using an inexpensive raw material and a simple method.

A carotenoid is a kind of natural pigment that exists widely in nature, and is a substance composed of isoprene as a basic unit and various groups bonded to a basic structure (skeleton) in which such isoprene units are linked. Carotenoids are compounds used not only as pigments but also as raw materials for various uses such as pharmaceuticals, cosmetics, drugs, foods, beverages and feeds.
Among the carotenoids, β-cryptoxanthin has been reported to show the suppressive effect on various diseases such as cancer, osteoporosis, diabetes, and periodontal disease, and has recently been attracting attention.

However, these carotenoids typified by β-cryptoxanthin have the property of being easily decomposed by light and oxygen, so it is difficult to store them in a stable state in the air. Is currently used in a state of being dissolved and dispersed in a liquid such as water.
In addition, even in the liquid state, carotenoids are decomposed by a slight amount of light, and as described in [0003] of Patent Document 1, there is a problem that the decomposition proceeds before use. .

  Then, the technical development for stabilizing carotenoid is performed, for example, the technique etc. which are described in patent documents 1-5 are developed.

  Specifically, the invention described in Patent Document 1 aims to improve the stability of color tone by dissolving and emulsifying carotenoids in fats and oils having a specific composition. The invention described in Patent Document 2 is intended to improve the stability of a pigment by adding an extract extracted from a plant of the genus department with an organic solvent to a pigment such as carotenoid. The invention described in Patent Document 3 is intended to improve the stability of color tone by adding an extract extracted from licorice with an organic solvent to a pigment such as carotenoid. The invention described in Patent Document 4 aims to improve the stability of β-cryptoxanthin by adding vitamin C at a specific concentration to water in which β-cryptoxanthin is mixed at a specific concentration. In the invention described in Patent Document 5, the stability of the pigment is improved by adding an organic acid having two or more carboxyl groups to the carotenoid.

Japanese Patent Publication No. 1-59303 JP-A-6-234935 Japanese Examined Patent Publication No. 7-62116 Japanese Patent No. 5909084 Japanese Patent No. 3665084

As described above, various technical developments for stabilizing carotenoids have been carried out in the past, but since the inventions described in Patent Documents 1 to 4 are all used as liquids, they are used and used. There is a problem that is limited. In other words, since the inventions described in Patent Documents 1 to 4 are in a liquid state, the amount of light and oxygen acting on the carotenoid is less than that in the solid state (in the air). Therefore, any of the inventions described in Patent Documents 1 to 4 can be used even when the stabilizing effect expressed by the additive component itself used is low (at a level that can withstand use).
Therefore, the inventions described in Patent Documents 1 to 4 have a problem that they cannot be used in a solid state (in the air) with a large amount of light and oxygen acting on carotenoids (the level cannot withstand use). .

  On the other hand, although the invention described in Patent Document 5 is in a solid state as a final form, an organic acid having two or more carboxyl groups used as an additive component (specifically, malic acid, malonic acid, etc.) ) Is expensive (also described as “relatively inexpensive raw material” in [0005] of Patent Document 5).

  Now, the present inventors have found that in the air, one or more metal ions (especially alkaline earth metal ions) selected from divalent to hexavalent metal ions are contained or combined with carotenoids. It was found that stable carotenoids can be kept stable in air for a long period of time.

  Here, it is not known at all that one or more metal ions (especially alkaline earth metal ions) selected from divalent to hexavalent metal ions are used as carotenoid stabilizers, There is no such description or suggestion in the prior art documents represented by Patent Documents 1 to 5 and the like.

  As described above, the present invention includes one or two or more metal ions (especially alkaline earth metal ions) selected from divalent to hexavalent metal ions with carotenoids, or even in the air. The object is to provide a carotenoid compound capable of maintaining a stable state for a long period of time.

In order to achieve the above object, the carotenoid stabilization method according to claim 1 of the present invention is characterized by mixing carotenoids with Ca ions and / or Mg ions .

Method for stabilizing carotenoids according to claim 2 of the present invention, the Ca ion and / or Mg ions, and mixing to said Rukoto so that the half molar equivalents relative to carotenoids.

The carotenoid stabilization method according to claim 3 of the present invention is characterized in that the carotenoid is β-carotene or / and β-cryptoxanthin .

The method for producing a carotenoid compound according to claim 4 of the present invention includes a mixing step of mixing an aqueous solution of Ca ion or Mg ion hydroxide and a pulverized product of a carotenoid source, and after the mixing step. A residue collecting step for collecting the residue by filtering the mixture, an extraction step for extracting a soluble fraction by mixing an organic solvent with the residue obtained by the residue collecting step, and an organic solvent from the soluble fraction after the extraction step It is removed with the recovery process of obtaining a carotenoid compound characterized Rukoto.

The method for producing a carotenoid compound according to claim 5 of the present invention is characterized in that the carotenoid source is derived from sputum .

According to the method for stabilizing a carotenoid according to the present invention, the carotenoids, by Rukoto be mixed with Ca ions and / or Mg ions, carotenoids that perform stabilization that holds a long period in a stable state even in the air Can do. In addition, such stabilization can be performed by an inexpensive raw material and a simple method.

According to the method for stabilizing carotenoids according to claim 2 of the present invention, the Ca ion or / and Mg ions, the mixture to Rukoto so that half molar equivalents relative to carotenoids, turn into more stable carotenoid Can be.

According to the method for stabilizing carotenoids according to claim 3 of the present invention, by using a specific carotenoids can Rukoto to more effectively exhibit the effect of stabilizing.

According to the manufacturing method of the carotenoid compounds according to the present onset bright, an aqueous solution of hydroxides of Ca ions or Mg ions, a mixing step of preparing a mixture by mixing a pulverized carotenoid source, a mixture after the mixing step A residue collecting step for collecting the residue by filtration, an extraction step for extracting a soluble fraction by mixing an organic solvent with the residue obtained by the residue collecting step, and an organic solvent from the soluble fraction after the extraction step. by providing a recovery step of obtaining the carotenoid compounds was removed, carotenoid can it to hold a long time in a stable state even in the air. Further, it is possible to produce according the cheaper raw materials and simple method.

3 is a graph showing the results of fluorescent X-ray analysis of the carotenoid compound of Example 1. It is the graph which expanded a part of FIG. 3 is a graph showing the results of fluorescent X-ray analysis of the carotenoid compound of Example 2. It is the graph which expanded a part of FIG. It is a graph which shows the result of the fluorescent X ray analysis of the carotenoid compound of a comparative example. It is the graph which expanded a part of FIG.

  An embodiment of the present invention will be described. The embodiment described below is merely an example embodying the present invention, and does not limit the technical scope of the present invention.

(Basic structure)
The carotenoid compound of the present invention has one or more metal ions selected from divalent to hexavalent metal ions and carotenoid as essential constituent requirements.
Thus, by containing a specific metal ion in a carotenoid, it is possible to obtain a carotenoid compound that can maintain a stable state for a long time even in air, which has been difficult in the past. One of the reasons that a stable state can be maintained for a long period of time is that carotenoids are decomposed by bonding the specific metal ions described above to the hydroxyl group, carbonyl group, epoxy group, methyl group, etc. of carotenoid. It is conceivable that this is suppressed.

In addition, about the form of a coupling | bonding, the form which has couple | bonded by the metal ion and these groups couple | bonded by ionic bond, the form which the metal ion and several carotenoids coordinated, etc. (complexation) etc. Various forms can be adopted.
In addition, when the metal ion and a plurality of carotenoids are linked (complexed) by coordination bonds, various structures such as a linear structure, a planar structure, a tetrahedral structure, and an octahedral structure with the metal ion as the nucleus It is configured by forming a three-dimensional structure.
Specific examples include structures represented by the following structural formulas.

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Wherein M is one or more metal ions selected from 2 to 6 metal ions, n is the same as the valence of M or the coordination number of M, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are any groups selected from H, OH, O, and CH ₃ )

(Metal ions)
The metal ion used for the carotenoid compound of the present invention needs to be one or more metal ions selected from divalent to hexavalent metal ions. Thus, by using a metal ion having a specific valence, the carotenoid can be held in a stable state for a long time even in the air.

In addition, the metal ion used for the carotenoid compound of the present invention is not particularly limited as long as it is a metal ion having a valence of 2 to 6, and a metal ion or transition metal of a typical metal belonging to Group 1 to Group 15 Various metal ions having a valence of 2 to 6 can be used. These metal ions can be used alone or in combination.
Among them, it is preferable to use a metal ion of an alkali metal or an alkaline earth metal from the point that the carotenoid can be held in a more stable state (a point where the bonding state between the carotenoid and the metal ion can be further improved). Of these, metal ions of alkaline earth metals are preferably used, and Ca ions and / or Mg ions are more preferably used.

  In addition, the metal ion source of the metal ion used in the present invention is not particularly limited as long as it can be dissociated with a polar solvent such as water and alcohols. Salts (fluoride, chloride, bromide, iodide, etc.), sulfates, nitrates, acetates, carbonates, organic acid salts (oxalates, etc.) and the like can be used.

(Carotenoid)
The carotenoid used in the carotenoid compound of the present invention is not particularly limited, and various carotenoids can be exemplified. Specifically, α-carotene, β-carotene, γ-carotene, δ-carotene, ε-carotene, ζ-carotene, lycopene, neurosporene, phytoene, phytofluene, xanthophyll, anthaxanthin, astaxanthin, canthaxanthin, citrana Xanthine, α-cryptoxanthin, β-cryptoxanthin, diazinoxanthine, diatoxanthine, dinoxanthine, flavoxanthin, fucoxanthin, lutein, neoxanthine, lactucaxanthin, amalasia xanthine A, tunaxanthin, halocinthia Xanthine, 3-hydroxy-β, ε-carotene-3′-one, deinochrome, capsanthin, capsanthin 3,6-epoxide, capsorbine, pitosporamxanthine, rhodoxanthine, rubixanthine, violaxane Emissions can zeaxanthin, apocarotenoid, abscisic acid, apocarotenal, bixin, crocetin, crocin, ionone, be mentioned peridinin, retinal, retinoic acid, retinol and the like. These carotenoids can be used alone or in combination.
Among them, a carotenoid having a hydroxyl group or a carbonyl group can be used because it can hold the carotenoid in a more stable state (a point where the bonding state between the carotenoid and the metal ion can be further improved). Among them, carotene (α-carotene, β-carotene, γ-carotene, δ-carotene, ε-carotene, ζ-carotene) or cryptoxanthin (α-cryptoxanthin, β-cryptoxanthin) is considered preferable. .

  The carotenoid sources of carotenoids used in the present invention include fruits such as citrus fruits and persimmons, vegetables such as various carrots and tomatoes, plants such as tomorrow, and those contained in animals such as crustaceans (derived from Can be used.

(Mixing ratio)
In the carotenoid compound of the present invention, the number of carotenoids used (number of moles) is preferably the same as the valence or coordination number of the metal ions used. Carotenoids can be improved in the bonding state between carotenoids and metal ions by the ionic bond or coordination bond of metal ions used in this way without excess or deficiency, and as a result, carotenoids are stable even in the air. It can be held for a long time.

  Therefore, in summary, when an alkaline earth metal ion is used as the metal ion and a carotenoid having a hydroxyl group is used as the carotenoid, it is preferable to use one alkaline earth metal ion and two carotenoids. In addition, when the structure is specifically expressed, it is considered that the following structure is preferable when Ca ion or Mg ion is used as the metal ion and β-cryptoxanthin is used as the carotenoid.

(M is Ca ion or Mg ion)

(M is Ca ion or Mg ion)

(Production method: Carotenoid stabilization method)
The carotenoid compound production method (carotenoid stabilization method) of the present invention is particularly a method that can contain a carotenoid and a metal ion, or a method that can ionically bond or coordinate a carotenoid and a metal ion. It is not limited. For example, a method of removing the solution after dissolving or dispersing the carotenoid source and the metal ion source in a solution such as water or alcohol, or removing the solution after dissolving the metal ion source in a solution obtained by extracting the carotenoid from the carotenoid source. And the like.

Of various production methods, a production method including the following steps 1) to 4) is preferably employed because the carotenoid compound of the present invention can be produced more efficiently.
1) A solution of divalent to hexavalent metal ions prepared by dissolving one or more metal ion sources in water or alcohol, and a carotenoid source (for example, fruit or vegetable fruit or skin containing carotenoids) 2) Mixing step of mixing the pulverized product with 2) Residue collecting step of collecting the residue by filtering the mixture after the mixing step 3) Mixing the organic solvent to the residue obtained by the residue collecting step Extraction process for extracting soluble fraction 4) Recovery process for removing carotenoid compounds from the soluble fraction after extraction process In addition, recovery between the residue recovery process of 2) and the extraction process of 3) It is also possible to add a drying step for drying the residue, and in each step, heating may be appropriately performed as necessary in order to efficiently produce the carotenoid compound of the present invention.

  In addition, when fruits and vegetables are used as the carotenoid source, the yield may decrease due to binding of sugars and impurities contained in the carotenoid source with metal ions (the carotenoid compound of the present invention can be efficiently used). Therefore, it is preferable to perform a treatment for removing sugar and impurities as necessary, such as a washing treatment.

  Next, the carotenoid compound according to the present invention will be described in detail based on Examples and Comparative Examples. In addition, this invention is not limited to a following example.

Example 1
First, 2.5 kg of skin of straw (produced in Kudoyama-cho, Wakayama Prefecture) was pulverized to a size of 15 to 20 mm and dispersed in 3000 ml of water.
Next, magnesium hydroxide (manufactured by Kishida Chemical Co., Ltd.) was used as a metal ion source, and 50 g of such magnesium hydroxide was dissolved in 300 ml of water.
Next, the above-mentioned solution was mixed with stirring in the dispersion, and then stirring was continued for 10 minutes. In addition, when adding the solution, it was added with care so that the pH of the mixed solution was maintained from neutral to weakly alkaline (pH 7 to 9).
Next, the mixed solution was filtered to recover the residue. During filtration, the residue on the filtration filter was washed several times with water.
Next, the collected residue was dried at 40 ° C. for 10 hours.
Next, 2000 ml of IPA was mixed with the dried residue, stirred, and left for 2 days to extract a soluble fraction in the residue.
Finally, the carotenoid compound of Example 1 was produced by removing IPA from the soluble fraction under reduced pressure using an evaporator. The recovered carotenoid compound was 3.0 g of a yellowish powder.

(Example 2)
The carotenoid compound of Example 2 was produced in the same manner as in Example 1 except that magnesium hydroxide was changed to 30 g of calcium hydroxide (manufactured by Kishida Chemical). The recovered carotenoid compound was 3.2 g of a yellowish powder.

(Comparative example)
A carotenoid compound of a comparative example was produced in the same manner as in Example 1 except that magnesium hydroxide was not used. The recovered carotenoid compound was 3.2 g of a yellowish powder.

  Next, the stability over time of the produced carotenoid compounds of Examples 1 and 2 and the carotenoid compound of the comparative example was evaluated. Specifically, visual observation, high-performance liquid chromatographic analysis (HPLC analysis), fluorescent X-ray analysis, liquid chromatograph mass spectrometry for each carotenoid compound immediately after production and after standing for 6 months at room temperature in a room where sunlight enters Evaluation by (LCMS analysis) was performed.

(Visual observation)
First, for evaluation by visual observation, each of the carotenoid compounds of Example 1, Example 2, and Comparative Example was placed in a transparent glass container, and left for 6 months at room temperature in a room where the carotenoid compound and sunlight were inserted immediately after preparation. Each of the subsequent carotenoid compounds was visually evaluated for color tone.
As a result, the carotenoid compounds of Examples 1 and 2 retained orange to yellow even after being left for 6 months, whereas the carotenoid compounds of Comparative Examples gradually became paler after 1.5 months. After 3 months, it was almost white, and after 6 months, it was completely white. Here, it is known that β-cryptoxanthin and β-carotene occupy most of the carotenoids contained in the cocoon, and such β-cryptoxanthin and β-carotene show orange to yellow.
Therefore, the carotenoid compound of Examples 1 and 2 (carotenoid compound of the present invention) that retains orange to yellow even after being left for 6 months retains the carotenoid in a stable state in air for a long period of time. I understood.

(High-performance liquid chromatographic analysis)
Next, quantitative analysis of β-cryptoxanthin and β-carotene in each of the carotenoid compounds of Example 1, Example 2, and Comparative Example was performed by high performance liquid chromatographic analysis. Specifically, an HPLC system (model: 1100 series HPLC system, manufactured by Agilent Technologies) was used, and the procedure was performed according to the following procedure according to the 5th edition Japanese Food Standard Component Table Analysis Manual. The results are shown in Table 1.
1) First, 0.1 g of each carotenoid compound was collected, extracted with ethanol and hexane, and then separated by adding water.
2) The solvent layer of 1) was collected and distilled under reduced pressure.
3) After the residue of 2 was made up with acetone, β-cryptoxanthin and β-carotene were measured by high performance liquid chromatography.

As a result, it is obvious that the carotenoid compounds of Examples 1 and 2 have a high content of β-cryptoxanthin and β-carotene immediately after the production, and a yellowish powdery state after being left for 6 months. And β-cryptoxanthin and β-carotene also showed high contents.
On the other hand, the carotenoid compound of the comparative example showed a higher content than the carotenoid compounds of Examples 1 and 2 immediately after production, but the yellow color began to fade gradually after 1.5 months. It was observed that the degradation of xanthine and β-carotene progressed. Then, when the contents of β-cryptoxanthin and β-carotene were measured at the time when 3 months passed, the contents of β-cryptoxanthin and β-carotene were already in the carotenoid compounds of the examples in the stage of 3 months. It was confirmed that it was significantly lower than that. Furthermore, when it was allowed to stand for 6 months, it became a completely white powder. From this, it was confirmed that in the carotenoid compound of the comparative example, β-cryptoxanthin and β-carotene in the compound were decomposed by light or oxygen.

(X-ray fluorescence analysis)
Next, β-cryptoxanthin and β-carotene in each carotenoid compound of Example 1, Example 2, and Comparative Example were analyzed by fluorescent X-ray analysis. Specifically, an energy dispersive X-ray fluorescence analyzer (model: EDX-800HS, manufactured by Shimadzu Corporation) was used. The results are shown in Table 2 and FIGS.

  As a result, for the carotenoid compound of Example 1 using Mg ions as metal ions, Mg was detected as shown in Table 2, FIG. 1 and FIG. 2, and the carotenoid compound of Example 2 using Ca ions as metal ions. As shown in Table 2, FIG. 3, and FIG. 4, Ca was detected, and it was confirmed that the carotenoid was in a state of binding to metal ions. On the other hand, no metal ions were detected for the carotenoid compounds of Comparative Examples that did not use metal ions, as shown in Table 2, FIG. 5, and FIG.

  Therefore, from the results of high performance liquid chromatographic analysis and fluorescent X-ray analysis, the carotenoid compounds of Examples 1 and 2 (the carotenoid compound of the present invention) retain carotenoids in air in a stable state for a long period of time. I found out.

Further, from the results of fluorescent X-ray analysis, it was also confirmed that the carotenoid compounds of Examples 1 and 2 had a structure in which metal ions were bonded to β-cryptoxanthin and β-carotene. On the other hand, it was confirmed that the carotenoid compound of the comparative example had β-cryptoxanthin and β-carotene as they were.
Therefore, also from the viewpoint of chemical structure (bound state), it was found that the carotenoid compounds of Examples 1 and 2 (the carotenoid compound of the present invention) hold carotenoids in a stable state in the air for a long period of time. It was.

The carotenoid compound of the present invention can maintain a stable state even in the air for a long period of time and can be used in a solid or powder state for pigments, pharmaceuticals, cosmetics, drugs, foods, beverages, feeds, and the like.

Claims (5)

To carotenoids,
A method for stabilizing carotenoids, comprising mixing Ca ions or / and Mg ions.
Ca ions and / or Mg ions,
The carotenoid stabilization method according to claim 1, wherein the carotenoid is mixed so as to have a ½ molar equivalent to the carotenoid.
The carotenoid is
The method for stabilizing carotenoid according to claim 1 or 2, wherein the method is β-carotene or / and β-cryptoxanthin.
A mixing step in which an aqueous solution of Ca ion or Mg ion hydroxide and a pulverized carotenoid source are mixed to produce a mixture;
A residue collecting step of collecting the residue by filtering the mixture after the mixing step;
An extraction step of extracting a soluble fraction by mixing an organic solvent with the residue obtained by the residue collection step;
A method for producing a carotenoid compound, comprising a recovery step of removing the organic solvent from the soluble fraction after the extraction step to obtain a carotenoid compound.
The carotenoid source is
The method for producing a carotenoid compound according to claim 4, wherein the carotenoid compound is derived from straw.