WO2004007511A1

WO2004007511A1 - Mangostine extract

Info

Publication number: WO2004007511A1
Application number: PCT/JP2003/006936
Authority: WO
Inventors: Eishin Katoh; Shinya Hosoda
Original assignee: Hosoda Shc Inc.
Priority date: 2002-07-15
Filing date: 2003-06-02
Publication date: 2004-01-22
Also published as: JPWO2004007511A1

Abstract

It is intended to provide an extract having various effects, which is obtained from an unripe mangostine fruit without resort to any special operations and has no red color, and a process for producing the same. Namely, an unripe mangostine fruit is extracted with water and/or an organic solvent to give an extract.

Description

Description Mangosteen extract Technical field

The present invention relates to a mangosteen extract and a method for producing the same.

Background art

Mangosteen extract is said to have the following useful physiological actions (medicinal effects).

(1) Antioxidant action that suppresses the oxidation of lipids in foods and protects organisms from oxidative damage (Japanese Patent Application Laid-Open No. Hei 8-2258573, etc.),

(2) Suppresses the biosynthesis of prostaglandins and inhibits xygenase (Japanese Unexamined Patent Publication No. 2002-47180),

(3) Anti-allergic action that inhibits the binding of chemical mediators to receptors (Japanese Patent Application Laid-Open No. H10-732357)

美 Whitening effect that suppresses pigmentation due to sunburn (Japanese Patent Application Laid-Open No. 424/004, etc.),

テ Testosterone 5α-reductase inhibitory action that suppresses the progression of male pattern hair loss (Japanese Patent Laid-Open No. 5-173635)

異 Offensive odor due to the growth of harmful microorganisms · Excellent antibacterial action against foul odors · Deodorant action

(Japanese Unexamined Patent Publication No. Hei 7 — 1 4 7 9 5 1 · 2 5 0 6 5 8, Japanese Unexamined Patent Publication No. Hei 8 — 2 3 1 3 9 6, Japanese Unexamined Patent Application Publication No. 9-95 4 5 3 And Japanese Unexamined Patent Application Publication No. 2001-224747.

However, they all use what is clearly judged to be ripe mangosteen skin, and there is no mention of using immature fruit skin. The ripe mangosteen peel is brown, and the mangosteen extract obtained by extraction with a water-soluble organic solvent (polar solvent) such as methanol, ethanol, or acetate or an aqueous solution thereof is colored red. Therefore, there was a problem that it could not be used for those affected by color.

For this reason, the antibacterial composition of the mangosteen extract from which the red color and the hygroscopic substance have been removed is described in JP-A-9-195453. Disclosure of the invention

In view of the above, an object of the present invention is to provide a mangosteen extract having no various effects, without red coloring, and having various actions, and a method for producing the same.

The present inventors have found that unripe mangosteen fruit has a red pigment-free green color, and that if the fruit is damaged, a pale yellow emulsion will leach out (but not ripe mangosteen fruit). As a result, the present invention was completed in view of the use of the leachate.

That is, a configuration of the present invention is a mangosteen extract obtained by extracting unripe (unripe) mangosteen fruit with water and Z or an organic solvent. In the above configuration, it is desirable that the extract be extracted together with the anti-browning agent. Browning during storage of the mangosteen extract can be prevented. Embodiments of the mangosteen extract are both water-soluble and water-insoluble. As a method for producing the mangosteen extract having the above-mentioned constitutions, there are the following methods.

One is to immerse immature mangosteen fruit in water or Z or an organic solvent in the presence or absence of a browning inhibitor, filter the immersion liquid, and separate and remove the solvent from the filtrate. It is characterized by being manufactured by The other is to remove unripe mangosteen fruit in the presence of browning inhibitors or After immersion in water and / or an organic solvent in the presence, filtration of the immersion liquid, and a concentration step of removing the solvent of the filtrate, a yellow water-insoluble mangosteen extract that precipitates was obtained, and the solvent was further removed. A water-soluble mangosteen extract is obtained by distilling off the solvent from the liquid. The other is to immerse immature mangosteen fruit in water and / or organic solvent in the presence or absence of anti-browning agent, and to separate yellow substance precipitated by heating treatment. A water-insoluble mangosteen extract, and a water-soluble mangosteen extract is obtained by removing the solvent from the filtrate.

According to the present invention, a mangosteen extract obtained from an unripe mangosteen fruit has no red color as compared with a ripe mangosteen, so that it is not limited to a colored product, and can be applied to a product with no (white) color or light color. There is no need to worry about coloring, the product value is not reduced, the range of use is wide, and it can be used in various fields such as food, cosmetics, clothing, and sanitary goods. The mangosteen extract obtained from immature mangosteen fruit has a higher polyphenol content than that obtained from ripe mangosteen and has a higher antioxidant effect. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a process chart showing an example of the production method of the present invention.

(A) and (B) of FIG. 2 are chromatograms showing the results of high-performance liquid chromatography analysis of extracts extracted from immature mangosteen and ripe mangosteen, respectively. BEST MODE FOR CARRYING OUT THE INVENTION

In the following description, the amounts and ratios are based on mass unless otherwise specified. The mangosteen extract of the present invention is a mangosteen extract obtained by extracting unripe (unripe) mangosteen fruit with water and Z or an organic solvent, if necessary, in the presence of a browning inhibitor.

Here, “extracted matter (extracted material)” refers to Γextractant (solvent: sol vent) j, which is transferred to “extracted material (raw material: raw material)” in a dissolved state. Each) or eluting (eluting, dissolving) includes not only substances that have been eluted (the original extract) but also substances that have migrated in a non-dissolved state.

Mangosteen is a group of plants that are called "Garc inia mangos tana L. J" and are widely cultivated in Southeast Asia. The flesh of the pulp is favored for its elegant taste with a moderate balance of sweetness and sourness, and the peel is used as a treatment for cholera and dysentery, as an antidiarrheal agent, and as a central nervous system sedative and blood pressure increasing agent. ing.

"Immature mangosteen fruit" is an unripe mangosteen fruit that has a green or slightly brownish color, and when damaged, a yellowish milky viscous liquid oozes out and exposes the glass plate The yellow liquid adheres to the surface in contact with.

“Fruit” means whole fruit or pericarp, and includes both dried and undried (raw) dried after being heat-treated and cut into small pieces. Both dry and undried products are usually ground to the size of intermediate particles (3 to 20 mm) with a crusher, crushed with a crusher (thickness of about 3 mm), or Slice thinly (for example, about 1 mm) with a slicer to make the extract (raw material).

“Water and organic solvents (polar solvents)” used as extractants are water and water, such as methanol, ethanol, 1-propanol, and 2-propanone (acetone). , Butanol, ethyl ethoxide, etc. Organic solvent, used alone or as a mixture. Naturally, choose one with low toxicity.

Extractant (solvent: solvent) The amount of extractant used is 1 to 50 parts, preferably 2 to 30 parts per 1 part of mangosteen fruit. If the amount is too small, the yield of the extract will be low. If the amount is too large, it takes time to remove and separate the solvent, which is not preferable.

Then, a browning inhibitor is appropriately added to the mangosteen extract obtained by the method of the present invention. This addition time may be added to the extractant at the time of the extraction treatment or prior to the extraction treatment, or may be added to the mangosteen extract (extract) after extraction (after separation and recovery). Extraction of mangosteen fruit with water or an organic solvent alone causes browning of the leachate and the extract due to the action of browning enzymes, which are to be suppressed (prevented).

As the "browning inhibitor", one or more of the following organic acids and inorganic acids can be appropriately selected and used. Furthermore, brewed vinegar, vinegar, and the like can be used. Can also be used.

Monocarboxylic acids: ethaneic acid (acetic acid), lactic acid (2-hydroxypropanoic acid), propionic acid (propanoic acid), etc.

Polycarboxylic acids: adipic acid (hexanedioic acid), tartaric acid (2,3-dihydroxybutanedioic acid), succinic acid (butanedioic acid), fumaric acid (trans-butenedioic acid), Lingoic acid (2—hydroxybutanedioic acid), citric acid (2—hydroxypropane-1,2,3—tricarboxylic acid), etc.

Sugar alcohol derivatives: ascorbic acid (vitamin C), erythorbic acid (isoryscorbic acid; erythorbic acid), dalconic acid, darconon lactone (darcononate lactone), phytic acid ( Inositol hexanoic acid) etc.

Amino acids: aspartic acid, glutamate, etc.

Inorganic acid: hydrochloric acid, sulfuric acid, phosphoric acid, sodium phosphate The amount of the browning inhibitor to be added is such that the added strain becomes 0.001 to 5 wZv%, preferably 0.01 to 2 wZv%. If the additive concentration is too low, it is difficult to obtain a browning preventing effect, and if it is too high, the amount of the browning inhibitor remaining in the mangosteen extract is not preferable.

To suppress (prevent) the coloring of the mangosteen extract means to suppress (prevent) the discoloration (browning) of the water-soluble extract or the water-insoluble extract (yellow liquid) extracted (leached) from the fruit. For this purpose, it is necessary to suppress the function of the enzyme in the fruit or to make it inactive so that the enzyme does not work. It is desirable to add an anti-browning agent when the content of the organic solvent (solvent) in the solvent component constituting the extractant used for extraction is small, so that the anti-browning effect is increased. And the main component is mangostin described in “THE MERCK INDEX (TWELFTH EDITION) 5785” (p. 978).

The mangosteen extract of the present invention can be produced as follows. An example of the manufacturing method is shown below (see Fig. 1).

(1) Lottery preparation process

Prepare extract by crushing, slicing or crushing immature mangosteen fruit. The size of the crushed material, sliced material, crushed material, etc. at this time shall be as follows.

Crushed material: 1 to 50 mm, preferably 2 to 30 mm

Slices: 0.2 to 2 mm thick, preferably 0.3 to lmm (size 10 to 50 mm)

Pressed material: 0.5 to 5 mm in thickness, preferably 1 to 3 mm (size 2

(0 to 70 mm) And If the size is too small, the extract (active ingredient) in mangosteen tends to leak into the slicing machine or crusher before the extraction operation when crushing the fruit. On the other hand, if the size is too large, the specific surface area of the extract becomes large, and the extraction efficiency is reduced, and the extraction takes time.

(2) Extraction process

Mix and contact the extract with the extractant. At this time, the mixing mass ratio of the extractant (the extractant may contain a browning inhibitor) to the extract (extractant extractant) = 1Z1 to 1/50, preferably 1/2 to 1Z30. And more preferably 1/3 to 120. If the amount of extractant is too small, the extraction efficiency will decrease. If the amount of extractant is excessive, it will be wasteful and the workability of extracting and collecting the extractant will decrease.

The extraction conditions vary depending on the extraction mode and the form of the pulverized material. For example, in the case of immersion (batch), the conditions are as follows.

Pulverized material: room temperature to boiling temperature X several hours to several days, preferably 50 to 90 ° C X 2 to 24 h

Sliced or crushed material: room temperature to boiling temperature X several minutes to several hours, preferably 5 to 120 min

The extraction process may be performed in any of batch, semi-continuous, and continuous operation modes. The contact state of the extract Z and the extraction agent may be fixed-bed (immersion), moving-bed, or dispersed-contact. Either may be used.

(3) Solid-liquid separation process

Solid-liquid separation of the solution (extract) and residue (raft residue). The method of solid-liquid separation is not particularly limited, such as sedimentation separation and centrifugation, but usually filtration (centrifugal filtration, compression filtration, etc.).

(4) Extract recovery process

The extract is recovered by separating and removing the solvent from the extract. The solvent is separated and removed by evaporation crystallization or after cooling crystallization, followed by filtration. Here, when an organic solvent or an organic solvent Z water mixed solvent is used as the extractant, a water-insoluble extract (a yellow water-insoluble substance) can be obtained together with the water-soluble extract. .

The extract is usually dried to obtain the mangosteen extract of the present invention. The drying method is arbitrary such as freeze drying, room temperature drying, heat drying, vacuum drying, spray drying and the like.

If necessary, extract the mangosteen extract from silica gel, alumina, alkylsilylated silica gel (filler for reversed-phase chromatography, such as 0DS), porous polymer (such as styrene, hydroxymethacrylate). Mangostin, β-mangostin, α-mangosteen, epicatechin, liposome, resin-based), cross-linked dextran, etc. by a known method using gel filtration agents (eg, Shephadex, BioGel) and the like. It can be separated and purified into a single substance such as procyanidin.

In addition, the above extraction method may be supercritical extraction.

Since the water-insoluble mangosteen extract obtained above and the mangosteen extract containing the same are not soluble in water by themselves, the following water-soluble or water-dispersible preparations can be prepared by the following preparation methods (1) to (3). It is desirable to do it.

① Inclusion agents such as α-, β- and α-cyclodextrin, and branched (or branched) cyclodextrin for uniform dissolution or dispersion when mixed with water. ion agent), mix with alcohol and water, knead, dry or dissolve, dry (including spray-drying and freeze-drying), etc., then pulverize and sieve. Perform granulation (granulation).

In this preparation, water-soluble saccharides such as dextrin and oligosaccharides, organic acids such as acetic acid and ascorbic acid and salts thereof, and amino acids such as glycine and sodium glutamate as necessary. Acid, potassium phosphate, sodium chloride Excipients such as inorganic salts such as aluminum can also be added.

The mixing ratio of the clathrate to 1 part of the water-insoluble mangosteen extract is set to be 1/2 to 130, preferably 1 to 3 to 120.

② Low amount of surfactants such as glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, pyrene glycol fatty acid ester, and lecithin to dissolve or disperse uniformly when mixed with water. Both can be directly mixed and melted or once dissolved in the above-mentioned organic solvent such as alcohol, and then the solvent can be distilled off to obtain a paste-like mangosteen extract preparation. If necessary, water-soluble sugars such as dextrin and oligosaccharides, organic acids such as citric acid and ascorbic acid and salts thereof, amino acids such as glycine and sodium glutamate, and phosphoric acid Inorganic salts such as lithium and sodium chloride, and excipients such as ethanol, propylene glycol, and fats and oils can also be added. The surfactant is used in an amount of 0.5 to 20 parts, preferably 1 to 10 parts, per part of the water-insoluble mangosteen extract.

③ Mangosteen extract contains water, monohydric alcohols such as ethanol and 2-propanol, and polyvalents such as propylene glycol, dipropylene glycol, glycerin, and sorbitol as excipients. Alcohol, etc .; emulsifying agents such as the above surfactants; PH regulators: acetic acid, adipic acid, fumaric acid, lactic acid, lingoic acid, cunic acid, tartaric acid, darconic acid, ascorbic acid, phytin Organic acids such as acids and their salts, inorganic acids such as hydrochloric acid, carbonic acid, phosphoric acid, sulfuric acid and polyphosphoric acid and their salts, glycine, alanine, lysine, glutamic acid, histidine, arginine A liquid or pasty mangosteen extract preparation can be obtained by appropriately combining amino acids such as betain and salts thereof and bases such as sodium hydroxide. it can. In addition, the antioxidants tocopherol (vitamin E), ascorbic acid, Palmitic acid ester, erythorbic acid, ascorbic acid stearic acid ester and the like can also be blended.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, “peel” and “fruit” mean non-dried products of “immature mangosteen” unless otherwise specified, and “extract” means “mangosteen extract”. is there.

Further, “slightly yellowish brown” and “pale yellowish brown” respectively mean a slightly yellow and pale yellowish brown.

(Example 1)

Extract (crushed material in pericarp extract; crushed size about 2 to 5 mm) Extract 3464 g (70% ethanol) in 1.1 kg at 70 ° C x 5 h After the extraction, the extract was filtered through a paper filter to obtain an extract (extract Z extractant 1/3).

The solvent was separated and removed from the extract (filtrate) by vacuum evaporation to prepare a concentrate, and the concentrate was freeze-dried to recover 48.2 g of extract (pale tan powder). (Recovery rate of lottery ½ 14%).

(Example 2)

Extract 3 kg of extract (dried fruit cut into cuts of fruit; average thickness 4 mm) in 30 kg of extractant (60% ethanol) at 60 ° C overnight, and extract the filter. An extract was obtained by one press filtration (extract / extractant 1/10).

The extract was vacuum-strained and freeze-dried in the same manner as in Example 1 to recover 810 g of the extract (pale yellow-brown powder) (recovery rate of extract: 27%).

(Example 3)

Extract 835 g of extract prepared as extract (fruit slice; average thickness 0.5 mm) by immersing it in 4.6 kg of extractant (water) at 50 ° C for 1 h. Perform processing It became (extraction fee / extraction agent 1 / 5.5).

A yellow-brown substance floating in the extraction solution was collected (scooped and captured) with a filter cloth, dried at 65 ° C for 6 h, and 9.9 g of a water-insoluble extract (yellow-brown powder) was recovered. . On the other hand, the filtrate was spray-dried to recover 60.1 g of a water-soluble extract (light brown powder) of the present invention (recovery rate of extract: 1.1% + 7.1%).

(Example 4)

Extraction (fruit slice; average thickness approx. 0.7 mm) 91 1 g is added to 5 kg of extractant (water; 50 ° C) and boiled for 10 min for extraction. (Extraction fee extraction agent.

From the extracted solution, 17.8 g of a water-insoluble extract (yellow powder) and 70.7 g of a water-soluble extract (pale yellow-brown powder) were recovered through the same operation as in Example 3. Percentage collection rate = 2.0% + 7.8%).

(Example 5)

Extract (Pulverized pericarp in extractant; crushed size: approx. 5 to 20 mm) 5 28 g was immersed in 1 kg of extractant (40% ethanol) for 3 days at room temperature. The sheets were stacked and filtered with gauze to obtain a filtrate (extracting agent 1Z5).

The filtrate was concentrated under reduced pressure, and the yellow substance floating and precipitated was filtered through a filter cloth, and dried under reduced pressure at 40 ° C. to collect 12.6 g of a water-insoluble extract (yellow powder). On the other hand, the filtrate was lyophilized to recover 43.7 g of a water-soluble extract (light brown powder) (recovery rate of extract: ^ 2.4% + 8.3%).

(Example 6)

Extraction (pulverized pericarp extract in extractant; crushed size: about 5 to 20 mm) Extraction treatment is performed by heating and refluxing 574 g of 4.7 kg of extractant (aceton) for 5 h. Tsuta (extraction agent extraction agent.

After cooling the extracted solution, two sheets were layered and filtered with gauze. The solvent is evaporated from the filtrate in vacuo, and the remaining yellow suspension is lyophilized and the water-insoluble extract ( 12.1 g was recovered (yellow powder) (vs. the rate of recovery of the extract: about 2.1%).

(Example 7)

Add 686 g of fruit (fruit slice; average thickness about 0.5 mm) to 10 kg of extractant (10% ethanol containing 6% vinegar), boil for 10 min and extract Processing was performed (extraction fee Z extraction agent 2).

After cooling the extract, the floating yellow substance was collected with a filter cloth and dried under reduced pressure at 60 to recover 14.3 g of a water-insoluble extract (yellow powder). The filtrate was spray-dried to recover 67.5 g of the water-soluble extract (light yellow-brown powder) of the present invention (recovery rate of extract: 1.6% + 7.8%).

(Example 8)

Extract (crushed fruit; average thickness about 2 mm) 642 g of extractant (0.2% aqueous solution of citric acid) is crushed in 2.3 kg and boiled for 20 min. An extraction treatment was performed (extract solvent 1 Z 3.6).

After cooling the extracted solution, the same operations as in Example 5 were performed, and the collected filter cloth was dried under reduced pressure to obtain 15.7 _g of a water-insoluble extract (yellow powder) and a water-soluble extract ( 79.6 g was recovered (slightly collected rate of about 2.4% + 12.4%).

(Reference example 1)

8 g of the water-soluble extract obtained in Example 1, 72 g of branched cyclodextrin (Niken Kagaku; Isoelite P) and dextrin (Matsuya Chemical; Pindex 1) After dissolving 40 g in 400 ml of 50% ethanol, it was spray-dried to prepare 107 g of a pale yellow powder extract preparation as an inclusion complex of the extract.

(Reference example 2)

In 20 ml of a hot ethanol solution containing 2 g of the water-insoluble extract obtained in Example 8, 3 g of glycerin fatty acid ester (RIKEN vitamin; Poem M—100) was added. Was dissolved and concentrated under reduced pressure, and 2 g of propylene glycol was added to prepare 7 g of a yellow base extract preparation.

(Reference example 3)

10 g of the extract of Example 2 and 0.2 g of citric acid were dissolved in 89.8 g of ethanol, followed by filtration to prepare 99 g of a pale yellow liquid extract preparation.

(Comparative example)

Ripe mangosteen peel (346 g) was crushed in 1.1 kg of 70% ethanol, immersed at 70 ° C. for 5 hours, subjected to an extraction treatment, and filtered with a filter paper. The filtrate was concentrated under reduced pressure to remove ethanol, and the concentrate was lyophilized to recover 40.lg of the extract as a red powder.

(Test Example 1)

A 0.01% solution of each extract obtained in Example 1 and Comparative Example 1 was injected into a high-performance liquid chromatograph (ODS column; detection wavelength: 280 nm), and the chromatogram shown in FIG. Got.

The peak corresponding to polyphenol in Example 1 was larger than the comparative example (particularly peaks at retention times of around 12 minutes and 16 minutes), suggesting that the polyphenol component was large.

(Test Example 2)

As a sample, 0.5 ml of a 10% methanol solution containing 200 ig of each of the extracts and catechins obtained in Example 1 and Comparative Example 1 was 2.4% varnish. Then, 1.5 ml of concentrated hydrochloric acid was added to 3 ml of the methanol solution, mixed well, and allowed to react at 20 ° C for 15 minutes. The absorbance at 500 nm of these reaction solutions was measured.

As shown in Table 1, the absorbance of the extract of Example 1 was about 2.1 times that of the extract of Comparative Example and about 1.1 times that of catechin, as shown in Table 1. The result was the same. 【table 1 】

(Test Example 3)

As a sample, each extract of Example 1 and Comparative Example and each of the tocopherols in a 50% ethanol solution containing 20 ig of each were added with 2 ml of a 0.1 M acetate buffer.

After adding (pH 5.5) 2 ml, 1 ml of an ethanol solution of 0.2 mM 1,1, -diphenyl-2-picrylhydrazyl (DPPH) was added to each. After 30 minutes, the absorbance at 517 nm of these reaction solutions was measured. As a result, as shown in Table 2, the decrease in absorbance (absorbance difference) based on the DPPH radical was about 2.0 times that of the comparative example in Example 1 and about 1.7 times that of the tocopherol.

From this, it was found that the DPPH radical scavenging action (scavenging ability) of the extract of the present invention extracted from the immature fruit was about 2.0 times higher than that of the extract extracted from the ripe fruit.

[Table 2]

Control: Add 50% ethanol solution without sample Absorbance difference: (Absorbance of control)-(Absorbance of sample) (Test Example 4)

The antibacterial activity of the extract of Example 1, the water-insoluble extract of Example 4 and the extract of Comparative Example against Bacillus subtilis (Bacch Mul sasbtilis Marburg, 68) was measured by the agar dilution method. The minimum inhibitory concentrations were 0.0775% .0.02% and 0.0075%, respectively.

Examples 1 and Comparative Examples are water-soluble and water-insoluble mixed extracts.

Claims

The scope of the claims

1. A mangosteen extract, which is an extract obtained by extracting an immature mangosteen fruit or pericarp with an extractant comprising water and / or an organic solvent.

2. The mangosteen extract according to claim 1, wherein the extractant further contains a browning inhibitor.

3. The mangosteen extract according to claim 1, wherein the extract is water-soluble.

4. The mangosteen extract according to claim 1 or 2, wherein the extract is water-insoluble.

5. Immature mangosteen fruit is immersed in water or Z or an organic solvent in the presence or absence of a browning inhibitor, and after filtering the immersion liquid, the solvent is evaporated off from the filtrate to concentrate or concentrate. A method for producing a mangosteen extract, comprising recovering the extract through the process.

6. Immature mangosteen fruit is immersed in water and / or an organic solvent in the presence or absence of a browning inhibitor, and after filtering the immersion liquid, the filtrate is concentrated to remove the solvent. A method for producing a mangosteen extract, characterized in that a water-soluble extract is separately obtained by distilling off a yellow water-insoluble extract that precipitates out and further removing a solvent from a removing solution thereof.

7. Immature mangosteen fruit is immersed in water and / or an organic solvent in the presence or absence of an anti-browning agent, and the yellow substance that precipitates due to the heating treatment is separated to obtain a water-insoluble extract. A water-soluble extract is separately obtained by distilling a solvent from a filtrate to obtain a mangosteen extract.