JP2003033143A - Lecithin-containing active oxygen scavenger, method for producing the same and method for scavenging active oxygen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new active oxygen scavenger capable of scavenging active oxygen existing in coffee or tea as XY or XZ and difficult to be scavenged with a conventionally known or suggested active oxygen scavenger. SOLUTION: The method for producing an active oxygen scavenger comprises (1) contacting at least one kind of material selected from the group consisting of starch, hemicellulose, glucan and protein with the hexane solution of lecithin, (2) removing hexane from the product to produce a lecithin-containing material and (3) treating the lecithin-containing material in an alkali hydroxide water solution followed by washing the product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an active oxygen scavenger containing lecithin, a method for producing the same, and a method for scavenging active oxygen. More specifically, the present invention relates to an active oxygen scavenger that adsorbs active oxygen in an oxygen-existing environment and emits erasure light, a method for producing the same, and a method for eliminating active oxygen. Using this substance,
Active oxygen causing various harmful functions can be safely detoxified, and various applications such as improvement of foods and cosmetics are possible.

[0002]

BACKGROUND OF THE INVENTION Oxygen is essential molecules for life maintenance of biological (O _2), many of the biological water molecules from O ₂ (H ₂
Energy is obtained using four-electron reduction to O).
The highly reactive intermediate generated during the energy acquisition process by the reduction of oxygen is called active oxygen (X).
In recent years, it has been pointed out that active oxygen and free radicals promote aging, cause damage to living organisms, and cause various diseases. The elucidation of chemical reactivity and physicochemical properties and the damage to living organisms, and the elucidation of in vivo active oxygen defense mechanisms have attracted attention from a wide range of fields.

[0003] carcinogenesis, initiation, but occurs through the promotion process, O ₂ is one-electron reduced superoxide anion ^- by suppressing, (O ₂ ·)
It is said that this promotion process can be hindered.
It has also been reported that peroxides such as hydrogen peroxide (H ₂ O ₂ ) in which O ₂ has been reduced by two electrons have a cancer promoting effect, and the involvement of active oxygen in carcinogenesis is being clarified. . On the other hand, active oxygen or free radicals are often used for the treatment of cancer. in this way,
Active oxygen having both sides of physiological action is used and eliminated in aerobic organisms in a well-balanced manner, and it is considered that a disease occurs when the balance is lost. The narrow active oxygen, the above-mentioned O ₂ · ^-, the H ₂ O _2, refers generally to four plus hydroxyl radical (HO ·) and singlet oxygen ⁽¹ O _2).

[0004] O ₂ · ^- is caused by the one-electron reduction of molecular oxygen, in vivo has been known to occur over a wide range in macrophages or white blood cells in the granules, the system such as enzymes. However, O ₂ · ^- is relatively reactive low, it has been found to be toxic. In vivo, superoxide dismutase (SO
By the action of such D) O ₂ · ^- occurs disproportionation, is further one-electron reduction H ₂ O ₂ is produced. Although H ₂ O ₂ also does not show very high reactivity, it causes damage inside and outside the cell because it crosses the cell membrane rapidly and reacts with transition metals to produce highly reactive HO.

[0005] Lipid peroxide generated by the radical chain reaction is converted to an alkoxy radical (RO) or an alkylperoxy radical (ROO) by a catalytic reaction of a transition metal.
・) Occurs, the RO generated in the process of lipid peroxidation
Theories that ROO and ROO affect living organisms have come to be claimed.

Catalase which decomposes these peroxides,
Glutathione peroxidase, enzymes such as peroxidase, transferrin inactivate metal ions, ferritin, lactoferrin, contributes protein group to metal stabilization such as ceruloplasmin, O ₂ · ^- and SOD to disproportionation in vivo It is thought to work as an antioxidant to prevent the generation of free radicals. It is also believed that water-soluble substances such as ascorbic acid, uric acid, and albumin-bound pyrilvin and fat-soluble substances such as tocopherol, ubiquinol, and estrogens of female hormones capture free radicals in vivo. In addition, searches for natural antioxidants have been actively conducted, and antioxidant components mainly derived from plants, such as tocopherols, phenol compounds (flavonoids, tannins, etc.), carotenoids, peptides, melanoidins, β-diketones, etc. Have been found.

[0007] Under the circumstances described above, the present inventor has determined that three types of active oxygen (hereinafter sometimes referred to as X), hydrogen donor (hereinafter sometimes referred to as Y) and mediator (hereinafter sometimes referred to as Z) can be obtained. XYZ-based active oxygen-eliminated luminescence, in which luminescence is generated and X is extinguished when they are gathered, is being serialized in Monthly Japan Food Science: Nippon Food Publishing Co., Ltd. This luminescence leads to the recognition that the energy at the time of elimination of active oxygen is converted into light, and the phenomenon of XYZ-based active oxygen elimination luminescence is a universal phenomenon occurring inside and outside the living body. It has been revealed. In addition, it is rare that X existing inside and outside the living body is single, and the generated X is adsorbed on Y or Z and exists as XY or XZ. Therefore, Z can be searched and quantified by XY, and Y can be searched and quantified by XZ, and analysis and distribution analysis using luminescence can be expected. Further, detection of XZ by Y and erasure of X thereof, detection of XY by Z and erasure of X thereof are also possible.

Further, the present inventor has recognized that XYZ-based active oxygen erasure emission is a basic phenomenon in an oxygen environment.
Z as a mediator is a completely new concept, X is easily generated by heating, etc., and exists in a relatively stable state as XY and XZ. X, Y, Z, XY and XZ are not necessarily in water. It has been clarified that this is a completely new luminous phenomenon characterized by not requiring melting. Furthermore, active oxygen scavengers obtained by immersing a material selected from carbohydrates, proteins, quaternary amine compounds, etc. in an aqueous alkali hydroxide solution, followed by washing and neutralization, active oxygen containing water-insoluble polyphenol as a main component Scavengers and methods for removing active oxygen using them have been elucidated. However, it has been difficult to completely eliminate active oxygen such as coffee and tea even with these individual or combined scavengers.

[0009]

An object of the present invention is to provide a novel active oxygen scavenger. Another object of the present invention is to eliminate active oxygen present as XY or XZ in coffee or tea or the like, which has been difficult to eliminate with conventional known or proposed active oxygen scavengers. It is to provide a novel active oxygen scavenger which can be used. Still another object of the present invention is to provide a method for producing the above active oxygen scavenger of the present invention. Still another object of the present invention is to provide a method for eliminating active oxygen in a beverage or liquid food with the active oxygen scavenger of the present invention. Still other objects and advantages of the present invention will become apparent from the following description.

[0010]

According to the present invention, the above objects and advantages of the present invention are firstly achieved by (1) at least one material selected from the group consisting of starch, hemicellulose, glucan and protein; Contacting a hexane solution of lecithin, (2) removing hexane to form a lecithin-containing material, and (3) treating the lecithin-containing material with an aqueous alkali hydroxide solution and washing with water. This is achieved by a method for producing an erasing agent.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by an active oxygen scavenger obtained by the above method of the present invention. Further, according to the present invention, the above object and advantages of the present invention are: Thirdly, in the beverage or liquid seasoning, the active oxygen scavenger of the present invention is brought into contact with a beverage or liquid seasoning. Is achieved by a method for eliminating active oxygen. This novel active oxygen scavenger of the present invention, coffee, tea, soup, miscellaneous beverages such as miso soup, cooking, just put into food processing raw material liquid,
It has been revealed that active oxygen existing as XY and XZ can be almost completely eliminated.

[0012]

During DETAILED DESCRIPTION OF THE INVENTION The herein, O ₂ · The active oxygen _{^{(X) -, H 2 O}} 2, HO ·, HOO ·, ROOH, RO ·
And ROO. These active oxygens are generated and exist as XY and XZ in foods, living bodies, smoke and the like. Hydrogen donor (Y) is hydrogen (H
), Proton (H ⁺ ) and electron (e ⁻ ) donors, such as catechins, tannins, melanoidins, gallic acid, flavonoids and anthocyanins. Examples of the mediator (Z) include, for example, acetaldehyde, carbonate, heme / non-heme protein, quaternary amine, etc., as well as skin, digestive organ, respiratory organ, heart, blood vessel, eye, brain, bone marrow, genital organ, etc. Serum and the like can be mentioned. It has already been clarified that there is a synergistic effect by these alone or in combination, and an amplification effect by minerals and the like.

The process for producing an active oxygen scavenger of the present invention comprises the steps (1) to (3) as described above. In the step (1), at least one material selected from the group consisting of starch, hemicellulose, glucan, and protein is brought into contact with a hexane solution of lecithin. These materials are preferably hardly water-soluble or water-insoluble. These materials need not necessarily be purely composed of the above components, and may be available in many cases as foods containing the above components as main components. These materials can take various forms depending on the actual usage of the active oxygen scavenger of the present invention, for example, fibrous, porous, flat, and the like.

Lecithin is a phosphatidyl choline.
ne), a diacyl-L-3- represented by the following formula (1):
Glyceryl phosphorylcholine (diacyl-L-3-
glycerylphosphorylcholine
Is equivalent to

[0015]

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Lecithin is hydrolyzed by phospholipases A and B to produce lysophosphatidylcholine represented by the following formula (2) and glycerol phosphocholine represented by the following formula (3).

[0017]

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[0018]

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The lecithin in hexane solution preferably has a lecithin concentration of 5 to 60% by weight, more preferably 12.5 to 50% by weight. The hexane solution of lecithin may optionally further contain a hydrocarbon solvent other than hexane, to the extent that the desired lecithin concentration is maintained.

The contact between the raw material and the hexane solution of lecithin can be carried out by various methods. For example, it can be performed by applying a solution to a material, spraying the material, or immersing the material in the solution. In the above-mentioned XYZ-based active oxygen-eliminated luminescence, how the lecithin functions as a Y reagent or an X reagent was examined as follows.

The measurement of light emission was performed using the CCD camera No. Light emission was detected for 10 minutes according to 1 (sensitivity 10). 2% hydrogen peroxide (H ₂ O ₂ ) aqueous solution as X reagent, 10% acetaldehyde (MeCHO) aqueous solution of gallic acid (GA) saturated and dissolved as Y reagent, 10% MeCHO aqueous solution as Z reagent A solution obtained by dissolving KHCO ₃ in water was used.

Soybean lecithin is applied to the bottoms of the wells of the multiplate, and the wells are coated with the X reagent, X reagent and Y reagent (hereinafter referred to as XY reagent) or X reagent and Z reagent (hereinafter referred to as XZ reagent) in each well. And 1 ml of Z reagent were added, and luminescence was measured. As a result, lecithin is converted to Y reagent (XZ
120 luminance (cd / m ² ), Z
As a reagent (detected by the XY reagent), 30 luminance was shown.
It can be seen that Y and Z coexist on the lecithin molecule.

Next, in step (2), the material containing or supporting the hexane solution of lecithin obtained in step (1) is subjected to removal of hexane and optionally other hydrocarbon solvent to remove the lecithin-containing material. Is generated. The removal of hexane can be by natural drying or forced drying. The conditions for forced drying vary depending on the amount and the state of the material to be dried, but can be, for example, 50 to 100 ° C. for 10 minutes to 1 hour. The drying atmosphere can be air or an inert gas, and can be at normal pressure or reduced pressure.

Further, in step (3), the lecithin-containing material obtained in step (2) is brought into contact with an aqueous alkali hydroxide solution. Examples of the alkali hydroxide include an alkali metal or alkaline earth metal hydroxide and a quaternary organic ammonium hydroxide. Of these, hydroxides of alkali metals or alkaline earth metals are preferred. Preferred examples of the alkali hydroxide include sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. Especially, sodium hydroxide is preferable.

The aqueous alkali hydroxide solution is, for example, 0.5 to 0.5%.
It is preferable to have a 4N concentration of alkali hydroxide. The contact between the lecithin-containing material and the aqueous alkali hydroxide solution can be performed by, for example, immersing the lecithin-containing material in the aqueous alkali hydroxide solution, or spraying or applying the aqueous alkali hydroxide solution to the lecithin-containing material. In step (3), after treatment with an aqueous alkali hydroxide solution, washing with water is performed. The alkali hydroxide is removed by washing with water. Therefore, it is preferable to carry out the water washing until the pH of the washing liquid after washing hardly changes.

In the same manner as described above, when the lecithin was treated with an alkali hydroxide (sodium hydroxide), XYZ-based active oxygen extinction luminescence was examined.

Soy lecithin was applied to the bottoms of the wells of the multiplate and 1 ml of water was poured into the wells other than the first. Then 4N to the first well and the next well containing water
After injecting 1 ml of NaOH each, 1 ml was collected from the well containing water and injected into the adjacent well. By repeating this operation sequentially, 4N × 2 ⁰ , × 2
^-1 , × 2 ^-2 ,... × 2 ^-11 diluted solution was prepared, washed with water, and Z luminescence by the same XY reagent was measured. As a result, the luminance was 500 as Z in 4N NaOH, but doubled to 1000 in 2N, and decreased at higher dilution, ie, the conversion of lecithin to OH foam was efficient with 2N NaOH. Was found to occur.

Soybean lecithin was applied to the bottom of the wells of the multiplate, and 2N NaOH was allowed to stand at 1 minute intervals, followed by washing with water to examine the effect of time on OH foam conversion. As a result, the luminance was 100 as Z up to 7 minutes, but doubled to 2000 luminance after 8 minutes, and was substantially constant thereafter. It has been found that efficient conversion to OH foam requires at least 8 minutes of standing.

Further, the optimum concentration of OH foam lecithin was examined as follows. That is, 50% of soy lecithin
Prepare a hexane solution and add 50%
^{2 0, × 2 -1, ×} 2 -2, × 2 -2, to prepare a hexane diluent ··· × 2 ^-11. A filter paper of 21 mmφ was put into each of the diluents and allowed to adsorb, then taken out and air-dried. These adsorbed papers were transferred to another multiplate, treated with sodium hydroxide to convert to OH foam, and Z luminescence by the same XY reagent was examined at a sensitivity of 8.0. As a result, 5
0% × 2 ⁰ in was 700 luminance, but as high as 1500 brightness about twice the × 2 ^-1, was reduced to 250 luminance in × 2 ^-2. 25% means that there is clearly an optimal concentration
Hexane solution adsorbed paper corresponds to this.

The novel active oxygen scavenging composition obtained by the above-mentioned method of the present invention is characterized by having both functions of Y and Z.
X of Z is efficiently deleted.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples. Example (1) X of Canned Beverage Commercially Available The X amounts of coffee A and B, oolong tea and green tea of commercially available canned beverage were examined. For measuring the luminance, the CCD camera No. was used.
Emission was detected for 10 minutes at a sensitivity of 10 according to 1. As a Y reagent, a solution obtained by dissolving GA in a 10% aqueous MeCHO solution was used. As a Z reagent, a solution obtained by dissolving KHCO ₃ in a 10% aqueous MeECHO solution was used. As a result, in coffee A, XY: 80, XZ: 30, a total of 11
0 brightness; coffee B: XY: 15, XZ: 60, total 7
5 luminance; oolong tea: XY: 60, XZ: 0,60 in total
The luminance and green tea were XY: 40 and XZ: 0, for a total of 40 luminances. All are DNA damage lines, 1 mM HOO
The luminance is 30 or more corresponding to H. Therefore, X of canned beverage
Is important.

(2) Elimination of X in canned beverages with OH-form lecithin Elimination of X in canned beverages with OH-form lecithin was attempted by the following method. 21% soybean lecithin in 25% hexane solution
After dipping the mmφ filter paper, it was taken out and air-dried. The air-dried filter paper was immersed in 2N NaOH for 10 minutes and washed with water to prepare OH foam lecithin paper. This paper was spread on a multi-plate, and 1 ml of canned beverage was added thereto, and erasing luminescence was observed. As a result, coffee A, coffee B, oolong tea, and green tea exhibited 20, 20, 15, and 10 luminances, respectively, and clear erasure light emission was observed. From the X amounts obtained with the Y and Z reagents, the respective erasure rates were 18.2, 26.7, 25.0 and 25.0%.

(3) Comparison of X Elimination Rate of Canned Drinks X elimination of canned beverages with soy lecithin is noteworthy from the viewpoint of practicality. The results of X elimination of canned beverages tried so far are summarized in Table 1 as comparative erasure rates. This means that X present as XZ is erased with the Y reagent and X as XY is erased with the Z reagent, resulting in a total elimination rate of 100%.

[0034]

[Table 1]

Hemoglobin, siberium sawfish, laver powder, and kelp powder, which have relatively strong Y and Z luminous abilities, could not eliminate X in canned beverages, but a little in DDMP saponin and some in serum. X of coffee could be erased. However, OH foam lecithin is not available in OH foam AG1 × 8 resin (R-CH ₂ N ⁺ (C
H ₃ ) ₃ , BIO-RAD), but it was found that X in canned beverages was eliminated relatively efficiently. Therefore, by combining with another Z material, an erasing rate comparable to that of the standard reagent can be expected.

(4) OH foam lecithin paper and O
X-form active oxygen-eliminated luminescence of H-form lecithin rice cracker XYZ-type active oxygen-eliminated luminescence of OH-form lecithin paper was examined.
Brightness. However, in the case of OH foam lecithin rice cracker using rice cracker instead of paper, a clear synergistic effect of 750 brightness as Z and 60 brightness as Y was observed. That is, the synergistic effect between lecithin and the OH form of starch, another Z protein, glucan,
The same happens with hemicellulose.

(5) Comparison of Z Luminescence with XY Reagent A rice cracker or the like was used instead of paper to prepare a combined material of OH foam lecithin and Z material, and the XYZ active oxygen-eliminated luminescence was measured. Table 2 shows the results of comparison of Z luminescence by the XY reagent.

[0038]

[Table 2]

The highest luminance of 2,000 for wheat crackers, followed by potato chips, fu, agar> shiitake mushrooms, frozen tofu> white ball dumplings> rice crackers> mung bean vermicelli> paper has a synergistic effect higher than expected. Such high Z emission means that XY in a solution state is easily erased, and development as an erasing agent is strongly expected. Moreover, all of these materials are ingredients,
It can be arbitrarily processed into fibrous, porous, planar, etc., and its use is immeasurable.

(6) Comparison of Y luminescence by XZ reagent Table 3 shows the results of comparison of Y luminescence by the XZ reagent.

[0041]

[Table 3]

The highest brightness of wheat crackers at 150, followed by fu and frozen tofu> rice crackers, rice balls, potato chips, agar>
In the order of shiitake mushroom, mung bean vermicelli, and paper, the synergistic effect is higher than expected as in the case of Z. As high as the Z light emission, the Y light
Means that it is easily erased.

As is apparent from the above (5) and (6), a material having a high Z function and a certain Y function has been successfully produced. Since it has both YZ functions, it is expected that XZ and XY of solution foods such as soy sauce and canned beverages can be easily erased.

(7) New active oxygen scavenger Elimination of X in canned coffee with OH foam lecithin sheet A new active oxygen scavenger prepared from various Z materials and lecithin is named OH foam lecithin sheet, and various sheets such as rice crackers are used. Created. These sheets were spread on a multi-plate, and 1 ml of canned coffee was added thereto, and X erasing luminescence was observed. As a result, outstanding erasing luminescence was observed.
Table 4 shows the results.

[0045]

[Table 4]

Comparing the elimination rates, the rice cracker sheet was the most efficient at 144%, followed by frozen tofu and potato chips>fu> wheat biscuit> shiitake mushroom, banana, mung bean vermicelli>
Agar> Oolong tea, Shiratama dumpling> Paper.

(8) A novel active oxygen scavenger OH foam lecithin sheet An OH foam lecithin sheet was prepared by using canned beverages, soy sauce X-erased rice crackers and lecithin. Spread on a multi-plate, soy sauce 1 on top
Points, 6 cans of coffee and 5 cans of tea 1 ml each and add X
Of the sample was observed. As a result, comparing the erasing rates from the observed erasable erasing light, all of the erasing rates were 100% or more of the standard reagent ratio, 429% for soy sauce, and 6 canned coffee.
134-200% for points, 200-950 for 5 points of canned tea
%Met.

Seasonings, canned food, soup, ramen soup,
It has already been clarified that unexpected Xs occur in daily meals such as miso soup. By utilizing this new material, the generation X can be suppressed and erased, and commercialization is expected as soon as possible.

Continuation of front page    (72) Inventor Yumiko Yoshiki             2-2-38 Kakyoin, Aoba-ku, Sendai, Miyagi Prefecture             702 F term (reference) 4B027 FB01 FB10 FB22 FC03 FE06                       FK08 FP78 FQ20                 4B035 LC09 LG13 LK11                 4B039 LB01 LC17 LG45 LR30

Claims (11)

[Claims] (1) contacting at least one material selected from the group consisting of starch, hemicellulose, glucan and protein with a hexane solution of lecithin, and (2) removing hexane to produce a lecithin-containing material. And (3) treating the lecithin-containing material with an aqueous alkali hydroxide solution and washing with water. 2. The method according to claim 1, wherein the material used in the step (1) is water-inactive or hardly water-soluble. 3. The method according to claim 1, wherein the hexane solution of lecithin used in the step (1) has a lecithin concentration of 5 to 60% by weight. 4. The method according to claim 1, wherein the step (1) is performed by immersing the raw material in a hexane solution of lecithin. 5. The method according to claim 1, wherein the removal of hexane in the step (2) is carried out by natural drying. 6. The method according to claim 1, wherein the alkali hydroxide in the aqueous alkali hydroxide solution in the step (3) is an alkali metal or alkaline earth metal hydroxide. 7. The method according to claim 1, wherein the aqueous alkali hydroxide solution in the step (3) has an alkali hydroxide concentration of 2 to 16% by weight. 8. The method according to claim 1, wherein the treatment in the step (3) is performed by immersing the lecithin-containing material in an aqueous alkali hydroxide solution. 9. The method according to claim 1, wherein the water washing in the step (3) is carried out until the pH of the washing liquid of the washing liquid hardly changes. 10. An active oxygen scavenger obtained by the method of claim 1. 11. A method for eliminating active oxygen in a beverage or liquid food, which comprises contacting the active oxygen scavenger obtained by the method of claim 1 with a beverage or liquid food.