JP2987365B1 - Antioxidant - Google Patents

Abstract

A sesame-derived fraction having a novel antioxidant and an antioxidant activity. Further, a pharmaceutical composition containing the compound is provided. SOLUTION: An antioxidant containing as an active ingredient a compound represented by at least one of the following structural formulas: Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel antioxidant, a sesame-derived fraction having an antioxidant action, and a pharmaceutical composition containing any one of them as an active ingredient.

[0002]

2. Description of the Related Art At present, nature-oriented products are becoming more and more attractive. Many foods have been studied in many fields, and new substances and new activities have been discovered one after another. In the field of pharmaceuticals, search for active substances having excellent safety and unique medicinal properties and action mechanisms in foods has been actively conducted. Seeds such as sesame, seafood such as salmon and sardines, and many foods represented by beverages such as Japanese tea and red wine are the targets of such research, and in fact, excellent drugs such as salmon calcitonin are created. Have been.

It has long been said that sesame is a food that prevents aging. In recent years, several effects of sesame have been scientifically proven. Examples thereof include an antioxidant effect and a metabolic activating effect (Japanese Patent Application No. 10-52097), which are supported by the results of scientific experiments. On the other hand, it is said that one of the causes of aging is oxidation by active oxygen or the like. Therefore, the antioxidant activity of sesame is very likely to be a means of preventing aging. In addition, some lignans and lignan glycosides have already been extracted as antioxidant components of sesame and their analysis has been performed. However, such known compounds alone have not been able to comprehensively explain the antioxidant action of sesame.

[0004] Sesame is washed with water in the process of being commercialized. Washing is usually performed by putting sesame seeds into water and stirring. At this time, a large amount of waste liquid is generated, all of which has been discarded as industrial waste. The inventors used this waste liquid as an aqueous extract of sesame seeds and searched for an active ingredient.

[0005]

An object of the present invention is to provide a novel antioxidant and a fraction derived from sesame having antioxidant activity. It is a further object of the present invention to provide a pharmaceutical composition or food containing the antioxidant or the fraction as an active ingredient.

[0006]

In order to achieve the above-mentioned object, the present invention provides a compound having an antioxidant activity and a fraction obtained from an aqueous extract of sesame seeds. Specifically, the present invention relates to compounds X and Y represented by the following formula, namely, hydroxymatairesinol (hydroxy).
mataresinol) and allohydroxymataresinol
(Sinol), as well as a fraction containing them.

[0007]

Embedded image

Embedded image

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound X and a compound Y represented by the following structural formulas, namely, hydroxymatairesinol.
And allohydroxymatairesinol (allohy
at least one of hydroxymethylresinol)
And an antioxidant and a fraction containing Where compound Y
Is a stereoisomer of compound X.

[0009]

Embedded image

Embedded image Compounds X and Y, which are active ingredients of the present invention, and a fraction can be obtained by the following methods. First of all,
Obtain sesame water extract. The sesame water extract may be a washing waste liquid obtained in a usual washing step when sesame is processed into a product. The sesame to be used may be black sesame or white sesame (when comparing white sesame and black sesame, the total amount of antioxidant components contained in each case is larger in black sesame).

Second, the sesame water extract obtained above is passed through an Amberlite XAD-7 column, and the adsorbed portion is eluted with 40% ethanol and collected. Subsequently, the collected liquid is freeze-dried to obtain a 40% ethanol fraction.

Third, the 40% ethanol fraction is dissolved in methanol and separated into a methanol-soluble fraction and a methanol-insoluble fraction. By this operation, a low-polarity part and a high-polarity part can be separated. Many representative lignan compounds are generally in the less polar portion, whereas the compounds of the present invention are in the more polar portion.

Fourth, the methanol-soluble fraction is passed through a Sephadex LH-20 column. This is 100
% Methanol, fraction 1-1 to fraction 1-9
Separate into nine.

Next, a fifth step is performed. The fractions 1-4 obtained in the previous step are subjected to HPLC using ODS-10. This gives a fraction 2-HPLC fraction from fraction 2-1. The active fraction of the present invention comprises fraction 2-
4. In addition, fractions 2-6 and 2-7 obtained here include known lignans having antioxidant activity (compounds A and B having the following structural formulas).

[0014]

Embedded image

Embedded image Further, in order to purify the compounds X and Y which are the active ingredients of the present invention, the sixth step is performed. The fraction 2-4 obtained in the previous step is subjected to HPLC using ODS-10. The resulting fraction 3-4 contains compound X and fraction 3-5 contains compound Y.

The fraction of the present invention has a strong antioxidant effect. Specifically, compounds X and Y, which are active forms thereof,
Has a radical scavenging ability. In particular, hydroxyl radical (.OH) and superoxide radical (.O
₂ ^-) is superior to erase. These things are
This is supported by experimental results in examples described later.

Therefore, the compounds X and Y of the active ingredient of the present invention and the pharmaceutical composition containing the fraction of the present invention as an active ingredient can be used for various active oxygen-related diseases (for example,
Ischemic disease, arteriosclerosis, diabetes, nephritis, aging, cancer, etc.). Foods to which compounds X and Y of the present invention and a fraction are added can be used as enriched foods or foods for specified health use.
Further, it can be used as an antioxidant in foods and the like.

On the other hand, the sesame seed washing waste liquid also contains known compounds A and B having an antioxidant effect. As mentioned above, compounds A and B can be obtained during the extraction process to obtain the fraction of the present invention. The antioxidant activity of compound X and / or compound Y, which is the active form of the present invention, is equivalent to or stronger than that of compounds A and B, which are known lignans. Specified.

The compound X or Y or the fraction of the present invention can be used together with the compound A and / or B. Further, the fraction obtained in any of the purification steps can be used as it is or through a process such as concentration. Further, the sesame seed washing waste liquid can be used after being subjected to concentration or the like as required without going through a further purification step. Further, it is similarly possible to use the compound X and / or Y obtained by further purifying the fraction of the present invention, alone or in combination with other active ingredients.

The compound of the present invention has an antioxidant activity equal to or higher than that of α-tocopherol which is a well-known antioxidant. Therefore, the compound X or Y or the fraction of the present invention can obtain an intended antioxidant effect by using a dose equal to or less than the effective amount of α-tocopherol.

Hereinafter, a pharmaceutical composition containing the compound X or Y or the fraction of the present invention will be described.

The pharmaceutical composition of the present invention contains the compounds X and Y obtained by the above-mentioned method and at least one of the fractions as an active ingredient. Further, the pharmaceutical composition of the present invention can contain an antioxidant other than compound X or Y together with compounds X and Y and at least one of the fractions. Furthermore, the pharmaceutical composition of the present invention comprises a compound X
And Y and at least one of the fractions can also contain other various drugs having various medicinal effects. In this case, it is well known to those skilled in the art to confirm that there is no problem in the efficacy, safety, etc. of each drug by the combination.

The pharmaceutical composition of the present invention comprises a compound X and / or
Or Y is from about 15 mg / kg of body weight / day to about 6
An effective amount in the range of 00 mg / kg of body weight / day may be administered once or in several divided doses. Alternatively, an effective amount of any of the fractions of the present invention corresponding to the above dose range may be administered once or in several divided doses.
The exact dose will vary widely depending on the mode of administration, dosage form of the drug administered, the condition and weight of the subject being treated, and should be determined by the experience and choice of the responsible physician or veterinarian.

The route of administration can be oral or parenteral, such as rectal, transdermal, subcutaneous, intravenous, intraurethral, as long as the active substance is effectively delivered to the appropriate and desired site of action.
Administration by any route, such as intramuscular, intranasal, ophthalmic, etc. is possible, but oral is preferred.

A typical pharmaceutical composition of the invention comprises a compound X and Y of the invention and at least one of the fractions in combination with a pharmaceutically acceptable carrier. In the production of such a pharmaceutical composition, the extract or compound can be contained in a carrier containing pharmaceutically usable excipients and auxiliaries. Such pharmaceutical compositions can be prepared in a manner known per se, for example, by means of conventional mixing, granulating, sugar-coating, dissolving or lyophilizing processes. For example, the compound or the active extract may be mixed with a carrier, diluted with the carrier, or encapsulated in the carrier.

The pharmaceutical composition containing the present invention can be sterilized. If desired, any adjuvant, emulsifier, salt for adjusting osmotic pressure, buffer and / or coloring agent may be added and mixed as long as it can be mixed harmlessly with the active extract of the present invention.

In addition, any dosage form of the pharmaceutical composition containing the present invention can be selected as long as it is effective according to the administration route.

Next, foods containing the compounds X and Y of the present invention and at least one of the fractions as an antioxidant additive will be described.

The compound or fraction of the present invention can be contained in foods of any type and in any form as additives having antioxidant activity. The quality of the obtained food is maintained for a long time by antioxidation. Furthermore, the addition of the additive can convert various foods into health foods,
It can also be used as fortified food or food for specified health use.

Ingestion of the food of the present invention prevents various active oxygen-related diseases (eg, ischemic disease, arteriosclerosis, diabetes, nephritis, aging, cancer, etc.), thereby maintaining health. It is possible to contribute to improvement of physical condition. A similar effect could also assist the medical effect provided by a physician or veterinarian.

Examples of foods that can be used as foods of the present invention include rice, beans, flour, starch, sugar, starch sugar, breads, noodles, confectionery, edible oils, dairy products (butter, cheese,
Ice cream, lactic acid bacteria products, etc.), bean products, processed horticultural products (cans, jams, dried fruits, fruit drinks, etc.), soft drinks,
Fermented foods (alcohol, vinegar, soy sauce, sauce, miso, natto,
Pickles), meat products (ham, bacon, sausage, canned foods), egg products, hydroxylated foods, various frozen foods, dried foods, instant foods, retort foods, and the like. It can also be added to seasonings, enzyme products and the like. However, it is not limited to these.

The method of adding to the food can be performed by any method known to those skilled in the art.

It is also possible to use the fraction at any stage for purifying the fraction.

It is well known to those skilled in the art that the present invention can be modified and used without departing from the scope claimed by the present invention.

[0034]

[Example] <Extraction method from sesame seed> Black sesame seed washing waste liquid (manufactured by Kadoya Oil Co., Ltd.) was subjected to Amberlite XAD-7 column chromatography. 40% of the adsorption part
It was eluted and recovered with ethanol and freeze-dried. This was used as a 40% ethanol fraction. Methanol was added to the freeze-dried product to separate into a methanol-soluble fraction and a methanol-insoluble fraction. The obtained methanol-soluble fraction was subjected to Sephadex LH-20 column (φ; 2.8 cm,
1; 27.5 cm). Nine fractions, fractions 1-1 to 1-9, were obtained using 100% methanol as eluent.

Next, Fractions 1-4 were combined with Develosil ODS
-10 (Devellosil ODS-10, manufactured by Nomura Chemical Co., Ltd.) was used, and a methanol aqueous solution (H ₂ O: MeOH) was used as an eluent.
= 1: 1) and reverse phase HPL at a flow rate of 5 mL / min.
C was performed. Detection was performed at UV 280 nm, and each peak was fractionated. Thereby, 9 of fractions 2-1 to 2-9 are obtained.
One fraction was obtained. The fraction 2-4 obtained here is a fraction containing the compound X and the compound Y of the present invention. Incidentally, fractions 2-6 and 2-7 contain compounds A and B having known antioxidant effects, respectively.

Fractions 2-4 were further purified to identify their active ingredients. Fraction 2-4 is Divelosil O
Column packed with DS-10 (20 mm x 250 mm)
And an aqueous methanol solution (H ₂ O: Me)
OH = 3: 2) at a flow rate of 5 mL / min.
PLC was performed. Compound X and compound Y were purified as fractions 3-4 and 3-5, respectively, by detection at UV 280 nm.

The obtained compound X and compound Y were analyzed by mass spectrometry and NMR spectroscopy (FIG. 2).
And FIG. 3). The results show that both compounds X and Y have a molecular weight of 374 and a molecular formula of C ₂₀ H ₂₂ O ₇ and correspond to the above-mentioned structural formulas, and furthermore, that these compounds are mutually stereoisomers. Was.

Further, the yields of the obtained compounds X and Y and the known compounds A and B were calculated based on the ratio (g / g%) to the weight of the used black sesame and the ratio (g / g) to the weight of the used washing waste liquid. g%) (FIG. 4). From these results, it can be seen that compounds X and Y of the present invention and known compound A
It was clarified that B and B can be recovered more efficiently by using an aqueous extract such as washing waste liquid than by using the whole black sesame.

FIG. 5 shows that each of the aqueous extracts of black sesame and white sesame was packed with Diverosil ODS-HG-5 (4.6 φ × 250 mm), and an aqueous methanol mixture (H ₂ O) was used as an eluate. : MeOH = 1: 1)
The results obtained by performing PLC (flow rate 0.8 mL / min) and detecting the eluate at UV 280 nm are shown.
Each sample used was a water extract obtained by using 100 mL of water for 20 g of black sesame and white sesame, respectively. The obtained water extract was freeze-dried,
A sample was dissolved at a concentration of mg / ml. This sample 10
μL was applied to the HPLC. FIG. 5 shows the difference in composition between the respective liquids. The water extract of black sesame had a higher content of the antioxidant active substance than the water extract of white sesame.

<Antioxidant Action> AAPH-added rodan iron method The rodan iron method, also called the thiocyanate method, is a commonly used method for measuring the antioxidant activity of a sample. The method consists of two steps. A first step of oxidizing linoleic acid and a second step of measuring the degree of oxidation. In the first step, the presence of the test substance reduces the degree of linoleic acid oxidation according to its antioxidant activity. The Rodin iron method is a measurement method utilizing this principle.

AAPH indicates 2,2-azobis (2-amidinopropane) dihydrochloride. AAPH is a radical accelerator. Therefore, the addition of AAPH promotes the oxidation of linoleic acid. The AAPH-added rhodan iron method is a method in which the first step is shortened by adding AAPH to promote the oxidation reaction of linoleic acid. When linoleic acid is new or the sample to be evaluated has a strong antioxidant property, the oxidation of linoleic acid progresses very slowly, so that it takes a very long time to complete the first step. However, by adding AAPH, the oxidation rate of linoleic acid can be increased without affecting the experimental results, and the first step can be completed in a relatively short time.

Since it was confirmed that the addition of AAPH had no effect on the evaluation of the compound of the present invention,
The AAPH-added rhodane iron method was applied to compounds X and Y of the present invention.
Was used to evaluate the antioxidant activity of

The specific method implemented is described below.
First, perform the first step. In a glass test tube with a screw screw cap, 1.0 mL of distilled water, 2.5 mL of 0.2 M phosphate buffer (pH 7.0), 2.5 mL of 1.3% linoleic acid in ethanol solution, and 0.1 mL of ethanol solution. 5m 1m
g / mL test substance solution (ethanol solution) and 0.2
5 mL of 46.4 mM 2,2-azobis (2-amidinopropane) dihydrochloride (Wako Pure Chemical Industries, Ltd.) was added and stirred. This was incubated in a thermostat at 50 ° C. After an arbitrary time (0 hour, 2 hours, 4 hours, 6 hours, 8 hours), the sample was taken out and used as each oxidized sample. The following second step was performed for each oxidized sample.

Into a 10 mL test tube with a screw screw cap, 0.1 mL of each oxidized sample (obtained in the first step), 4.7 mL of 75% ethanol, and 0.1 m
L of a 30% ammonium thiocyanate solution was added.
Thereto, 0.1 mL of ferrous chloride (3.5% hydrochloric acid solution) was added, stirred well, and the absorbance at 500 nm was measured exactly 3 minutes after the addition of ferrous chloride. The measurement was performed three times for each oxidized sample.

FIG. 6 shows the experimental results. The vertical axis is 500n
The absorbance at m is shown, and the horizontal axis shows the oxidation time of each sample. The control is an oxidized sample to which ethanol was added during the oxidation reaction in the first step. As a positive control, 0.5 ml of 0.2 mM butylhydroxytoluene (1 mg / ml EtOH) as an antioxidant was similarly used. The graph shows compounds X, Y, A, and B, an aqueous extract (a solution obtained by washing 10 g of black sesame with three times 50 mL of water), and a 40% ethanol fraction (1 mg / mL in ethanol). The results are shown when each was used at a concentration of 1 mg / mL.

From these results, it was found that the compounds X and Y of the present invention
Was found to have antioxidant activity. Compounds X and Y had comparable antioxidant activity to known compounds A and B.

2. DPPH method The DPPH method measures that the antioxidant is a radical D
It utilizes the conversion of PPH. Into a non-radical form. Actually, the amount of radical decrease when the test sample and the radical are present at the same time is measured, and the radical scavenging ability of the test sample is evaluated.

In this experimental method, a stable free radical, phenoxy radical, is used instead of the lipid hydroperoxy radical generally used in the experiment. This generally increases the accuracy of a radical measurement system that is easily affected by experimental conditions and the like to a system capable of quantitative measurement. Specifically, α, α-diphenyl-β-picrylhydrazyl (DPPH.) Is used. Measurement is DP
The decrease in absorbance at 517 nm of the sample accompanying the decrease in PH is used as an index.

A specific measuring method will be described below. Each test substance was dissolved in 100% ethanol at a concentration of 1 mg / mL to prepare a sample. 2 mL of 0.1 M acetate buffer (pH 5.
To 5), 2 mL of the above-mentioned ethanol solution of each test substance was added. To this, 1 mL of a 0.5 mM DPPH · (Wako Pure Chemical) ethanol solution was added to make a total volume of 5 mL. Immediately thereafter, the absorbance at 517 nm was measured. After 30 minutes,
The absorbance at 517 nm was measured again. As a control, instead of a sample in which the test substance was dissolved in ethanol,
The same operation was performed using only ethanol as a solvent as a sample. The absorbance immediately after the addition of the DPPH / ethanol solution was almost constant in all samples.
The radical scavenging ability of each test substance was evaluated by the radical scavenging rate (A) calculated by the following equation. A = {(absorbance of control after 0 min) − (absorbance of each sample after 30 min)} / (absorbance of control after 30 min) × 100 The results are shown in FIG. 7. The horizontal axis shows the control value as 10
The radical scavenging rate is shown as 0%. The graph is
Compounds X, Y, A, and B each having a final concentration of 2 mM, and an aqueous extract (black sesame or white sesame 2) having a final concentration of 20 μg / ml.
0 g was washed three times with 100 mL of water), and the results obtained when a 40% ethanol fraction having a final concentration of 20 μg / mL was used. As a positive control, α-tocophenol (2 mM, in ethanol)
Was used.

It has been found that the compounds X and Y of the present invention have a very strong radical scavenging ability. These were stronger than the existing Compounds A and B, and more potent for Compound Y than α-tocophenol. In addition, when the black sesame water extract was compared with the white sesame water extraction, the black sesame water extract had higher activity. this is,
This is probably due to differences in the amounts of compounds X, Y, A and B contained therein.

3. Electron Spin Resonance (ESR) At present, ESR has become an important means for obtaining information about the state of electrons and molecules in various fields. Measurement of free radicals using the ESR method is
It is widely applied in fields such as pharmacy and environmental hygiene. On the other hand, in order to obtain stable experimental results,
Various measurements are being studied. Further, from the ESR spectrum obtained by the measurement, it is possible to obtain much information such as the type and amount of the free radical.

In the measurement, DMPO (5,5-dimethyl-
A spin trapping method using 1-pyrruloline-1-oxide) was used (Kuriyama Kenichi, Inui Takeo; Journal of the Japanese Society of Agricultural Chemistry, vol. 69, No. 6, 703-705, 19).
95). In addition, as a free radical species, humans Russia hexyl radical (OH ·) and the superoxide radical _- were studied using the (· O ^2). The experimental method performed is shown below.

3-1. Hydroxyl radical scavenging activity Each test substance was dissolved at a concentration of 800 μM in a 5% acetonitrile aqueous solution to prepare each sample. 50 μL of 6.7 μM
Ascorbic acid (AsA), 35 μL of 1.4 MH
₂ O2, 50 μL of 0.1 mM FeCl ₂ , and 50 μL of the sample prepared above were mixed. 15 μL of DM
Sixty seconds after the addition of PO, the spin adduct (DMPO-OH.) Was measured using ESR. As a control, 50 μL of 5% acetonitrile was used.

3-2. Superoxide radical scavenging activity Each test substance was dissolved in a 5% aqueous solution of acetonitrile at a concentration of 800 μM (it was confirmed that 5% acetonitrile did not interfere with the measurement). 50 μL of 2.0 mM
Hypoxanthine (Wako Pure Chemical Industries, Ltd.), 35 μL of 5.5
mM DTPA, 15 μL of 9.2 M DMPO and 50 μL of the sample prepared above were mixed. 50μ there
After addition of L of 0.33 units / mL xanthine oxidase (Wako Pure Chemical Industries, Ltd.), spin adduct using ESR after 40 seconds (DMPO- · _{O 2} ^-) was measured. 50 μL of 5% acetonitrile as control
Using.

The results are shown in FIG. The horizontal axis of the graph indicates the amount of decrease due to the addition of each sample when the height (indicating the spin amount) of the twice integrated curve of the ESR signal of the control is 100. Water-soluble tocopherol (Trolox: 800 μM in 5% acetonitrile) was used as a positive control.
Was used. The compound X of the present invention had an ability to scavenge hydroxyl radicals and superoxide radicals. In particular, for superoxide radicals, 7
It has a very good activity of eliminating 0.2% of superoxide radicals.

[0056]

EFFECTS OF THE INVENTION A fraction having a very strong antioxidant activity was isolated from the sesame water extract. Further, it was revealed that the active components of the fractions were Compounds X and Y. Thus, compounds X and / or Y can be used as antioxidants with excellent activity. In addition, a pharmaceutical composition containing compounds X and Y and at least one of the fractions of the present invention exerts excellent preventive and therapeutic effects on diseases associated with active oxygen. In addition, foods to which compounds X and Y and at least one of the fractions of the present invention are added can contribute to maintaining health and improving physical condition. Further, the compounds X and Y of the present invention can be efficiently recovered from sesame washing waste liquid which has been conventionally industrial waste. Therefore, it is possible to effectively use industrial waste, and it is economically effective.

[Brief description of the drawings]

FIG. 1 is a block diagram showing a scheme of an extraction step of compounds X, Y, A and B.

FIG. 2 shows the results of an instrumental analysis of compound X.

FIG. 3 shows the results of an instrumental analysis of compound Y.

FIG. 4 is a view showing the yields of compounds X, Y, A and B obtained by the extraction step shown in FIG.

FIG. 5 is a chart showing the results of UV 280 nm detection of each fraction obtained when the aqueous extract was subjected to HPLC.

FIG. 6 is a graph showing the results of antioxidant activity measurement by the AAPH-added rodan iron method.

FIG. 7 is a graph showing the results of radical scavenging ability measurement by the DPPH method.

FIG. 8 is a graph showing the results of measurement of radical scavenging ability by an electron spin resonance method.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 15/06 A23L 1/30 A61K 31/34 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. An antioxidant containing, as an active ingredient, a compound represented by at least one of the following structural formulas: Embedded image 2. An antioxidant active fraction extracted from sesame, which contains any one of the following compounds: Embedded image 3. The antioxidant-active fraction according to claim 2, wherein the water-washed sesame solution is freeze-dried, and the obtained freeze-dried product is dissolved in methanol to obtain ODS-HG-5 (4.6 φ). ×
250 mm) (eluent; H ₂ O: MeOH = 1: 1, flow rate 0.8 mL / m)
fraction, characterized by being obtained in a range between about 6 minutes and about 8 minutes when subjected to UV absorption at 280 nm. 4. The antioxidant-active fraction according to claim 2, which is extracted by the following steps: adding sesame seeds to water and stirring to obtain a sesame seed water extract. Passing the aqueous extract obtained in the above step through Amberlite XAD-7 column chromatography and eluting and collecting with 40% ethanol; and lyophilizing the collected liquid to obtain a 40% ethanol fraction. Said 40
Adding methanol to the% ethanol fraction to obtain a methanol-soluble fraction; subjecting the methanol-soluble fraction to a Sephadex LH-20 column, eluting with 100% methanol, and confirming by thin layer chromatography. Collecting the fraction containing the fourth peak obtained by the above step;
The solution was subjected to high performance liquid chromatography using an S-10 column (eluent; H ₂ O: MetOH = 1: 1), and UV28
Collecting the fraction containing the fourth peak obtained while confirming by detection at 0 nm. 5. The compound according to claim 1 or claim 2.
5. A pharmaceutical composition containing the fraction according to any one of items 1 to 4 as an antioxidant active ingredient, for preventing and / or treating a disease associated with active oxygen. 6. The compound according to claim 1 or claim 2.
5. A food containing the fraction according to any one of items 1 to 4 as an additive having antioxidant activity.