JP7163052B2 - Method for producing S-allylcysteine - Google Patents

Description

The present invention relates to a method for producing S-allylcysteine.

Conventionally, plants of the genus Allium, such as garlic and onions, are known to contain various sulfur-containing amino acids. Attention has been paid.

However, the content of S-allylcysteine contained in, for example, garlic is very small.

For example, Patent Literature 1 discloses an invention relating to a method for processing an Allium plant including a step of adding cysteine. Cited Document 1 discloses that the processing method increases the amount of S-allylcysteine produced in about several days.

JP-A-3-167129

According to the processing method described in Patent Document 1, it is possible to increase the production amount of S-allylcysteine in about several days, but from the viewpoint of industrially producing S-allylcysteine, There is the problem that the formation of S-allylcysteine is too slow.

Under such circumstances, the main object of the present invention is to provide a method for producing S-allylcysteine in a short period of time.

The present inventors have made intensive studies to solve such problems. As a result, by allowing allicin and L-cystine to coexist in a solvent in the presence of an alkaline earth metal hydroxide or alkaline earth metal oxide, S-allyl cysteine can be efficiently produced in a short time. found to generate The present invention is an invention completed by further studies based on these findings.

That is, the present invention provides inventions in the following aspects.
Section 1. allicin and L-cystine in the presence of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides in a solvent, S-allyl A method for producing cysteine.
Section 2. Item 2. The method for producing S-allylcysteine according to item 1, wherein at least one selected from the group consisting of plants belonging to the genus Allium, juices of the plants, and extracts of the plants is used as the allicin.
Item 3. The method for producing S-allylcysteine according to any one of claims 1 and 2, wherein the plant belonging to the genus Allium is at least one selected from the group consisting of garlic, onion, Chinese shallot, Chinese garlic, and chives.
Section 4. the alkaline earth metal hydroxide is at least one of magnesium hydroxide and calcium hydroxide;
Item 4. The method for producing S-allylcysteine according to any one of Items 1 to 3, wherein the alkaline earth metal oxide is at least one of magnesium oxide and calcium oxide.
Item 5. In the above step, a mixture of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides and L-cystine is prepared, and the mixture and allicin are combined with the solvent. Item 5. The method for producing S-allylcysteine according to any one of Items 1 to 4, wherein the S-allylcysteine is mixed in.
Item 6. Item 6. The method for producing S-allylcysteine according to any one of Items 1 to 5, wherein the temperature in the step is 20 to 60°C.
Item 7. Item 7. The method for producing S-allylcysteine according to any one of Items 1 to 6, wherein in the step, the solvent has a pH of 9 or more and an oxidation-reduction potential of −300 mV or less.
Item 8. An S-allylcysteine-containing composition containing 1% by mass or more of at least one selected from the group consisting of calcium and magnesium.
Item 9. A food, drug, quasi-drug, or cosmetic comprising the S-allylcysteine-containing composition of Item 8.

According to the present invention, it is possible to provide a method for producing S-allylcysteine in a short period of time.

1 is a graph showing changes in the amount of S-allylcysteine (SAC) produced in Example 1. FIG. 4 is a graph showing pH value transition in Example 1. FIG. 4 is a graph showing ORP value transition in Example 1. FIG. 4 is a graph showing changes in the amount of S-allylcysteine (SAC) produced in Example 2. FIG. 4 is a graph showing pH value transition in Example 2. FIG. 4 is a graph showing ORP value transition in Example 2. FIG. 4 is a graph showing changes in the amount of S-allylcysteine (SAC) produced in Comparative Example 1. FIG. 4 is a graph showing pH value transition of Comparative Example 1. FIG. 4 is a graph showing ORP value transition in Comparative Example 1. FIG. 1 is a graph comparing changes in the amount of S-allylcysteine (SAC) produced in Examples 1 and 2 and Comparative Example 1. FIG. 4 is a graph comparing pH value transitions of Examples 1 and 2 and Comparative Example 1. FIG. 4 is a graph comparing ORP value transitions of Examples 1 and 2 and Comparative Example 1. FIG.

In the method for producing S-allylcysteine of the present invention, allicin and L-cystine are combined in the presence of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides, It is characterized by including a step of coexistence in a solvent (hereinafter sometimes referred to as a reaction step). Since the method for producing S-allylcysteine of the present invention has such a configuration, it is possible to efficiently produce S-allylcysteine in a short period of time (for example, within about 24 hours). The method for producing S-allylcysteine of the present invention is described in detail below.

S-allylcysteine produced by the production method of the present invention has a chemical structure represented by the following general formula. In addition, about the three-dimensional structure of the following general formula, the general structure as a natural product is shown.

In the present invention, the product S-allylcysteine may be S-allylcysteine having the above structure, an optical isomer thereof, or a mixture of these optical isomers.

In the present invention, allicin, which is a raw material, is a kind of sulfur-containing amino acid. Chemically synthesized allicin may be used as allicin as a raw material. Purified allicin may also be used.

In addition, in the present invention, a material containing allicin can also be used as allicin. The material containing allicin is preferably at least one selected from the group consisting of plants of the genus Allium, juices of plants of the genus Allium, and extracts of plants of the genus Allium. It is known that allicin is converted from alliin to produce allicin, for example, by destroying alliin-containing plant tissues belonging to the genus Allium and allowing endogenous enzymes to act. Therefore, when a plant belonging to the genus Allium is used as a raw material allicin, the plant belonging to the genus Allium is injured or cut to destroy the tissue, and alliin is allowed to act on alliin to produce allicin. A plant of the genus Allium (that is, a plant of the genus Allium in a state containing allicin) is used.

Alliinase contained in plants belonging to the genus Allium is known to be inactivated by heating at high temperatures. Therefore, when a plant of the genus Allium is used as a source of allicin, allicin is produced by destroying the tissue of the plant of the genus Allium, which has not been subjected to alliinase inactivation treatment, and allowing alliin to act on alliin. It is preferred to use plants of the genus Allium that have been fermented.

When a plant of the genus Allium (that is, a plant of the genus Allium containing allicin) is used as allicin, it is preferably in the form of a cut product, crushed product, ground product, powder, or the like of the plant. A cut product, crushed product, ground product, or powder of a plant belonging to the genus Allium can be obtained, for example, by cutting, crushing, grinding, or pulverizing the plant using a crusher, mixer, food processor, pulper fisher, or the like. Moreover, the juice of a plant belonging to the genus Allium can be prepared using, for example, a filter press, a juicer-mixer, or the like. Squeezed juice can also be prepared by filtering the ground product using a filter cloth or the like. Allium plant cuts, grinds, grinds and juices may be diluted or concentrated. Dilutions include, for example, a cut product, crushed product, ground product, squeezed juice, etc. of the plant, diluted with water about 1 to 50 times. Concentrates include, for example, cut products, crushed products, ground products, squeezed juices, etc. of the plant, which are concentrated 1- to 100-fold by means of freeze concentration, vacuum concentration, and the like. A cut product, crushed product, ground product, or squeezed juice of a plant belonging to the genus Allium may be frozen. An extract of a plant belonging to the genus Allium can be obtained by extracting the above-mentioned plant belonging to the genus Allium, the cut product, or the like, with a solvent such as water. In the present invention, the materials containing allicin may be used singly or in combination of two or more.

More than 700 kinds of plants belonging to the genus Allium are known, and any plant can be used as a material as long as it can supply allicin. Specific examples of plants belonging to the genus Allium include garlic, onion, allium leek, leek, chive, leek, ittle scallion, yellow scallion, mountain scallion, nobil, wild scallion, chive, chive, chive, chive, Tree onions, green onions, scallions, leeks, shallots, scallions, shallots, shallots, green onions, chives, scallions, white onions, and the like. Among these, garlic (Allium sativum L.), onion (Allium cepa L.), chives (Allium schoenoprasum L.), scallion (Allium chinense G.Don) are considered to contain high concentrations of sulfur-containing amino acids such as alliin. , Allium victorialis subsp. platyphyllum, etc. are preferred, and garlic (Allium sativum L.) is more preferred.

In the present invention, L-cystine (3,3'-dithiobis(2-aminopropionic acid)) as a raw material is a kind of sulfur-containing amino acid. Cystine has a structure in which two molecules of cysteine are linked via a disulfide bond (-SS-) generated by oxidation of a thiol group (-SH). In the present invention, as L-cystine as a raw material, chemically synthesized L-cystine may be used as a raw material, or a material containing L-cystine may be used as a raw material.

L-cystine is readily available in purified form. In addition, from the viewpoint of increasing the production rate of S-allylcysteine, it is preferable to use purified L-cystine. Purified products of L-cystine generally include those commercially available as reagents, pharmaceutical ingredients, food ingredients, and the like.

In the production method of the present invention, the ratio of allicin and L-cystine is not particularly limited as long as S-allylcysteine is produced. The amount of L-cystine is preferably 300 mol or more, more preferably 500 mol or more, still more preferably 700 mol or more. In addition, in the present invention, when the material containing allicin, the material containing L-cystine, or the like is used, the amount of these materials used should preferably be such that the ratio of allicin and L-cystine is such a ratio. can be set appropriately.

In the production method of the present invention, by allowing allicin and L-cystine to coexist in the presence of at least one of an alkaline earth metal hydroxide and an alkaline earth metal oxide, S-allylcysteine is produced for a short period of time. efficiently generated by

Alkaline earth metal hydroxides preferably include magnesium hydroxide and calcium hydroxide. Alkaline earth metal oxides preferably include magnesium oxide and calcium oxide. Alkaline-earth metal hydroxides and alkaline-earth metal oxides may be used singly or in combination of two or more. Alkaline earth metal hydroxides and alkaline earth metal oxides may be used alone, or two or more of them may be used in combination. Among these, from the viewpoint of increasing the production rate of S-allylcysteine, it is preferable to use at least one of alkaline earth metal hydroxides and alkaline earth metal oxides, and alkaline earth metal oxides are more preferably used. preferable. In particular, it is preferable to use at least one of magnesium oxide and calcium oxide.

The amount of alkaline earth metal hydroxide and alkaline earth metal oxide used (total amount) is not particularly limited, but the pH of the solvent in the reaction step of the production method of the present invention is, for example, 9.5 or higher. , preferably 9.5 to 12, more preferably about 10 to 12, more preferably about 11 to 12.

The solvent is not particularly limited as long as it does not inhibit the production of S-allylcysteine, but preferably water, ethanol or the like can be used. Only one type of solvent may be used, or two or more types may be mixed and used.

The concentration of allicin in the solvent is not particularly limited as long as S-allylcysteine is produced, but is preferably about 800 to 2,000 mg/L, more preferably about 1,500 to 2,000 mg/L. From the same point of view, the concentration of L-cystine in the solvent is preferably about 7,000 to 17,000 mg/L, more preferably about 12,000 to 17,000 mg/L. As S-allylcysteine is produced, allicin and L-cystine are consumed, and the concentrations of allicin and L-cystine in the solvent decrease. In the present invention, when the material containing allicin, the material containing L-cystine, or the like is used, the amounts used are such that the concentrations of allicin and L-cystine in the solvent are preferably within the above range. and set appropriately.

In the present invention, the temperature of the reaction step is not particularly limited as long as S-allylcysteine is produced. About 30 to 60°C, more preferably about 35 to 55°C, particularly preferably about 40 to 50°C.

In addition, the pH of the solvent in the reaction step is not particularly limited as long as S-allylcysteine is produced. is more preferable, and about 11 to 12 is even more preferable. The pH of the solvent may be the above pH value in at least a part of the reaction process. It is more preferable to have the above pH value.

Further, the oxidation-reduction potential of the solvent in the reaction step is not particularly limited as long as S-allylcysteine is produced, but it is preferably -300 mV or less, more preferably about -400 to -650 mV, and -500 to -500 mV. More preferably, it is about -650 mV. The oxidation-reduction potential of the solvent may be the above-mentioned oxidation-reduction potential in at least a part of the reaction process. It is more preferable that the above oxidation-reduction potential is achieved within the time limit.

The time for the reaction step is not particularly limited as long as the desired amount of S-allylcysteine is produced, and varies depending on the type and amount of the raw material used, but is usually about 1 to 24 hours, preferably 4 to 12 hours. It is preferable to set

In the production method of the present invention, allicin and L-cystine may coexist in a solvent in the presence of at least one of an alkaline earth metal hydroxide and an alkaline earth metal oxide. The mixing order is not particularly limited. For example, in the reaction step, a mixture of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides and L-cystine is prepared, and the mixture and allicin are combined. They may be mixed in a solvent. Further, in the reaction step, after uniformly mixing at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides, allicin, and L-cystine in a solvent, these may be stirred or allowed to stand still. The stirring method is not particularly limited, and examples thereof include a method of stirring using a stirring blade, a mixer, a stirrer, or the like.

After the reaction step, an isolation step of separating S-allylcysteine from the mixture by ordinary isolation procedures such as filtration, centrifugation, concentration and extraction can be performed. Furthermore, in order to increase the purity of S-allylcysteine, a purification step of purifying S-allylcysteine can be carried out by ordinary purification procedures such as column chromatography and recrystallization. The reaction mixture can also be dried into solids (powder, granules, etc.) by methods such as freeze-drying and spray-drying. The purified product of S-allylcysteine obtained by the production method of the present invention and the reaction mixture containing S-allylcysteine can be suitably used as pharmaceuticals, quasi-drugs, food and drink, cosmetics, feeds, health foods, and the like. can be done.

As described above, in the method for producing S-allylcysteine of the present invention, allicin and L-cystine are combined with at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides. It comprises a step of coexisting in a solvent in the presence. Therefore, according to the production method of the present invention, an S- An allylcysteine-containing composition is preferably obtained. The present invention can suitably provide foods, pharmaceuticals, quasi-drugs, cosmetics, etc. containing the S-allylcysteine-containing composition.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the invention is not limited to the examples. The measurement methods used in Examples and Comparative Examples are as follows.

(HPLC analysis conditions)
Column: Unison US-C18 5 μm (250 mm×4.6 mm) manufactured by Intact Co., Ltd. Column temperature: 45° C.
Mobile phase: [A solution] 10 mM potassium dihydrogen phosphate buffer (pH 2.5/phosphoric acid), [B solution] acetonitrile Flow rate: 1 mL/min
Measurement wavelength: 210 nm

(Example 1)
100 g of garlic (variety name: Fukuchi White) was peeled, the pedestal was removed, and scaly pieces were added to 100 g of garlic (variety name: Fukuchi White). Crush to obtain a garlic paste. To 100 parts by mass of garlic paste, 6 parts by mass of magnesium oxide (manufactured by Nacalai Tesque) and 4 parts by mass of L-cystine (manufactured by Protein Chemical) are added, respectively, and ion-exchanged water is added twice the weight of garlic. was added, warmed to 40-50° C. and stirred. Sampling was performed at 0, 2, 4, 6, 8, and 24 hours after the addition of magnesium oxide and L-cystine, and the content of S-allyl cysteine in the sample solution was measured by HPLC. , it was confirmed that a maximum of 4.06 g/kg of S-allylcysteine was produced. FIG. 1 shows a graph showing changes in the amount of S-allylcysteine (SAC) produced. Further, when the pH and oxidation-reduction potential (ORP) of the sample solution were measured, the maximum pH was 9.82 and the minimum oxidation-reduction potential was -465 mV. Graphs showing pH value transition and ORP value transition are shown in FIGS. 2 and 3, respectively.

(Example 2)
Except for using calcium oxide instead of magnesium oxide, the same procedure as in Example 1 was performed, and it was found that a maximum of 4.15 g / kg of S-allyl cysteine was produced with respect to the weight of garlic. confirmed. FIG. 4 shows a graph showing changes in the amount of S-allylcysteine (SAC) produced. Further, the maximum pH was 11.9 and the minimum oxidation-reduction potential was −593 mV. Graphs showing pH value transition and ORP value transition are shown in FIGS. 5 and 6, respectively.

(Comparative example 1)
The same procedure as in Example 1 was performed except that sodium hydroxide, which is an alkali metal hydroxide, was used instead of magnesium oxide to adjust the initial pH to 12. It was confirmed that 0.54 g/kg of S-allyl cysteine was produced. FIG. 7 shows a graph showing changes in the amount of S-allylcysteine (SAC) produced. Moreover, the maximum pH was 9.97 and the minimum oxidation-reduction potential was -336 mV. Graphs showing pH value transition and ORP value transition are shown in FIGS. 8 and 9, respectively.

10 to 12 show comparisons of changes in the amount of S-allylcysteine (SAC) produced, changes in pH, and changes in redox potential in Examples 1 and 2 and Comparative Example 1, respectively. From a comparison between Examples 1 and 2 and Comparative Example 1, the method of allowing allicin and L-cystine to coexist in a solvent in the presence of an alkaline earth metal (hydroxide or metal oxide) is The amount of S-allyl cysteine (SAC) produced is very large and the production rate is very high compared to the method of coexisting in a solvent in the presence of hydroxide), and S-allyl cysteine is produced in a short time. I know you can.

Claims (5)

A step of allowing allicin and L-cystine to coexist in a solvent in the presence of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides ,
As the allicin, using at least one selected from the group consisting of plants belonging to the genus Allium, juices of the plants, and extracts of the plants,
A method for producing S -allylcysteine, wherein the plant belonging to the genus Allium is at least one selected from the group consisting of garlic, onion, shallot, Chinese garlic, and chives . the alkaline earth metal hydroxide is at least one of magnesium hydroxide and calcium hydroxide;
2. The method for producing S-allylcysteine according to claim 1 , wherein the alkaline earth metal oxide is at least one of magnesium oxide and calcium oxide. In the above step, a mixture of at least one selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides and L-cystine is prepared, and the mixture and allicin are combined with the solvent. The method for producing S-allylcysteine according to claim 1 or 2 , wherein the S-allylcysteine is mixed in. The method for producing S-allylcysteine according to any one of claims 1 to 3 , wherein the temperature in said step is 20 to 60°C. 5. The method for producing S-allylcysteine according to any one of claims 1 to 4 , wherein in said step, said solvent has a pH of 9 or higher and an oxidation-reduction potential of -300 mV or lower.

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