JP2009225724A - Composition containing arachidonic acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide arachidonic acid oil and fat excellent in oxidation stability. <P>SOLUTION: A composition containing an arachidonic acid is used for adding arachidonic acid or enhancing its content. The composition contains tocopherol and a rosemary extract together with arachidonic acid. The arachidonic acid may be an alcohol ester of arachidonic acid or triglyceride, phospholipid, or glycolipid arachidonic acid whose part or whole of the constituent fatty acid is arachidonic acid. It is desirable that the composition contain 1 wt.% or above of arachidonic acid. The rosemary extract is preferably an oil soluble extract, more preferably carnosic acid. The composition is added to food and drink-favorite food, bait and feed, health care-medicine, or cosmetics so as to add arachidonic acid or enhance its content. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an arachidonic acid-containing composition used to add arachidonic acid or enhance its content. More specifically, the present invention relates to an arachidonic acid oil / fat composition having excellent oxidation stability and containing a tocopherol and rosemary extract.

  Arachidonic acid (ARA; cis-5,8,11,14-eicosatetraenoic acid) is a kind of long chain ω-6 highly (polyvalent) unsaturated fatty acids and is obtained from animal organs and tissues. Present in lipids. This is a kind of essential fatty acid and an important compound that is a precursor of synthesis such as prostaglandins, thromboxanes and leucotoluenes. It has also been pointed out that arachidonic acids (hereinafter abbreviated as ARAs) have physiological effects such as promoting the development of the infant's brain and preventing the deterioration of the brain of the elderly.

Focusing on the function of such arachidonic acid, conventionally, various compositions such as fats and oils and foods for the purpose of enhancing nutrition or imparting various physiological effects to long-chain highly unsaturated fatty acids such as arachidonic acid and esters thereof. Attempts have been made to add to. The nutrition fortifying composition described in JP-A-10-99048 contains arachidonic acid in an amount of 0.1 to 10% by weight as one of the components added to realize an ingredient close to breast milk. Moreover, in the synthetic lipid composition similar to human milk fat described in JP-A-11-89513, a long-chain n-6 highly unsaturated fatty acid containing arachidonic acid is used as one kind of fatty acid constituting triglyceride. Yes. Furthermore, JP-A-10-70992 and JP-A-10-191886 describe edible fats and oils derived from microorganisms containing abundant arachidonic acid in the form of triglycerides, and suitable uses thereof include formulas for premature infants, Examples include infant formula, infant food, and pregnant food.

  Polyunsaturated fatty acids such as docosahexaenoic acids and eicosapentaenoic acids are not limited to arachidonic acids, but each has its own physiological functions, but all of them are unstable due to many unsaturated bonds in the molecule. As time passes, it is oxidized by the action of oxygen, light, heat, etc., and a nasty odor is generated. In addition, it has been pointed out that the produced lipid peroxide causes aging and cancer, and when highly unsaturated fatty acids are used, the prevention of oxidation is an urgent issue to be solved.

  Several proposals have already been made to solve the above-mentioned problems. For example, a lipophilic antioxidant is proposed in which an aqueous solution containing tea extract is emulsified with one or more specific amounts of a lipophilic emulsifier together with a synergist of hydroxycarboxylic acid and an oil-soluble antioxidant active substance as necessary. According to this invention, it is described that it is effective in preventing the oxidation of animal and vegetable oils such as butter and fish oil (see Japanese Patent Publication No. 3-49315). In addition, a tea leaf extract component, one or more polyhydroxy compounds, one or two or more organic acids and water quality preservation agents (see Japanese Patent Publication No. Sho 5-66084), and highly unsaturated fatty acids Fish odor masking method (see Japanese Patent Laid-Open No. 6-189717) in which a fat-soluble ginger flavor is present in a food containing lipids containing fatty acids (mainly DHA, EPA), and further contains docosahexaenoic acid oil and vitamin C An emulsified composition (see JP-A-7-107938) has been proposed. In addition, an extract of Nanten leaves and a docosahexaenoic acid and / or fish oil stabilizer containing vitamin C as active ingredients (Japanese Patent Application No. 7-47188) have been proposed. However, these are mainly intended for DHA and EPA among polyunsaturated fatty acids. The reason for this is that the raw materials for DHA and EPA are intended for fish oil, so that a rot odor derived from the raw material is generated by oxidation, and DHA and EPA are more likely to be oxidized because they have a higher degree of unsaturation than ARA. And so on.

For the prevention of oxidation of ARA, it is customary to use antioxidants that have been known and used in common. For example, the use of tocopherols and ascorbic acid esters as antioxidants against ARA-rich oils produced by microorganisms has been proposed (Japanese Patent Laid-Open No. 10-139673). However, there is an optimum amount of tocopherol that gives the strongest antioxidant power, and there is a limit to the expected antioxidant power (Japanese Patent Laid-Open No. 2004-107599).

  The present inventors compared purely purified DHA, EPA and ARA ethyl esters with respect to their oxidizability, and found that ARA was most likely to be oxidized, contrary to expectations from the number of unsaturated bonds. The most urgent issue is to discover and consider the anti-oxidation method of ARA among polyunsaturated fatty acids, and to develop antioxidants that act individually on ARA, not the general anti-oxidation of fats and oils. In view of this, further research was conducted, and a combination of antioxidants preferable for ARA oxidation prevention was established, and the present invention was completed.

The arachidonic acid-containing composition of the present invention originates from an unexpected and surprising discovery as described above, and is specified as an invention having the following constitution.
The present invention is a composition used to add or enhance the content of arachidonic acid, and is characterized by containing tocopherol and rosemary extract together with arachidonic acids.

  The arachidonic acid may be an alcohol ester of arachidonic acid or a triglyceride, phospholipid or glycolipid in which part or all of the constituent fatty acid is arachidonic acid. It is desirable to contain 1% by weight or more of arachidonic acids.

The rosemary extract is preferably a fat-soluble extract, more preferably carnosic acid.
In order to add or strengthen the content of arachidonic acid, it is characterized by being added to foods / beverages / preference items, feedstuffs, health / pharmaceuticals or cosmetics. Therefore, food / beverage / preference products, feedstuffs, health / pharmaceutical products or cosmetics to which the composition is added are also included in the present invention.

  As another embodiment of the present invention, there is an antioxidant method for arachidonic acids using tocopherol and rosemary extract.

Among the highly unsaturated fatty acids, ie DHA, EPA and ARA, oxidation of arachidonic acid, which is particularly susceptible to oxidation, is very effectively prevented by using tocopherol and rosemary extract as an antioxidant, so that it is oxidatively stable. It is possible to provide an arachidonic acid oil / fat composition excellent in the above. The combined use of tocopherol and rosemary extract has a synergistic antioxidant effect on arachidonic acids, so the combination of both can effectively prevent deterioration of arachidonic acid even at low doses. Acts so that physiological functions can be maintained for a long time. The composition of the present invention can be added to a wide range of preparations and products for which arachidonic acid is desired to be added or whose content is required to be increased. Since the tocopherol and rosemary extract to be added are derived from natural products, the composition of the present invention is an additive that has no problem in terms of safety even when added to foods and drinks, pharmaceuticals, and the like.
Detailed Description of the Invention
The arachidonic acid-containing composition of the present invention is a composition used to add or enhance the content of arachidonic acid, and contains tocopherol and rosemary extract together with arachidonic acid. . That is, the present invention is a composition characterized by containing tocopherol and rosemary extract as active ingredients together with arachidonic acid as an antioxidant. Preferably, it is added to foods and drinks / preference items, feedstuffs, health / pharmaceuticals or cosmetics as a material, raw material or additive for enhancing nutrition based on arachidonic acid or imparting physiological functions. “Arachidonic acids (ARAs)” refers to arachidonic acid (ARA), a salt thereof, or an alcohol ester of arachidonic acid or a triglyceride, phospholipid or glycolipid in which a part or all of the constituent fatty acid is arachidonic acid. However, it is not limited to these.

  As a result of comparisons of the oxidizability of purely purified DHA, EPA and ARA ethyl esters, the present inventors found that ARA is most easily oxidized (FIG. 2). In addition, it is composed based on the following new findings.

Spices are conventionally known as naturally-occurring antioxidant materials, but the order of their effects varies depending on the type of oil and fat, and the oxidation-inhibiting effect on ARA, which is a ω-6 highly unsaturated fatty acid, is one of the spices. However, the present inventors have found that rosemary is particularly good. Rosemary has been conventionally known to have an antioxidant function. For example, in Japanese Patent Application Laid-Open No. 2004-107599, linoleic acid, linolenic acid, an oil deterioration preventing agent, comprising a 60% ethanol extract of rosemary having active oxygen scavenging ability and a film agent dispersible in water. Use for acid, eicosapentaenoic acid and docosahexaenoic acid has been proposed. However, the rosemary extract was not particularly superior in antioxidant effect against fats and oils other than ARA compared to other spices (FIG. 3). For example, for the antioxidant effect of soybean oil, oregano, thyme and tarragon extracts are more active than rosemary extract.

  As described above, the present inventors have found that the rosemary extract is specifically excellent in the antioxidant against ARAs, and the fat-soluble extract is particularly excellent (FIG. 4). Until now, there has been no known one that exhibits an antioxidant action specifically and effectively against arachidonic acid, which is an individual oil or fat. In addition, this discovery that there is a compatibility between the types of fats and oils and the types of spices is interesting for the antioxidant deterrent action of antioxidant spices. In this connection, as an antioxidant for docosahexaenoic acids, a preparation containing tocopherol, L-ascorbic acid fatty acid ester and tea extract as active ingredients has been proposed (JP-A-9111237), No mention is made of ARAs.

  It has also been clarified that the fat-soluble extractive component containing carnosic acid as the main polyphenol component is further excellent in antioxidant effect. In addition, the present invention further exhibits an antioxidant effect on ARAs by using together with tocopherols that are conventionally known to have an antioxidant function as a single component, compared to the case where each is used alone. Relying on the new knowledge that it can be, it has a feature that can solve the conventional problems at once.

Hereinafter, embodiments of the present invention will be described more specifically.
Examples of ARAs that are active ingredients that occupy a major position in the composition of the present invention and to which antioxidants (combinations of tocopherol and rosemary) are applied include fats and oils extracted and purified from microbial fermentation broth Can do. ARA (arachidonic acid) is present as a free fatty acid or its triglyceride in fungi such as Mortierella. As other ARAs, alcohol esters of arachidonic acid or triglycerides, phospholipids or glycolipids in which a part or all of the constituent fatty acid is arachidonic acid can be used.

  As such ARAs, not only ARAs single fats and oils but also ARA fats and oils mixed with, for example, DHAs or EPAs are preferable. Furthermore, it can be used for a mixture in which other fat-soluble vitamins and functional components are dissolved in an ARA-containing oil.

  The content of ARAs in the composition of the present invention is generally 1% by weight or more of the composition weight. Preferably, ARAs are contained in the composition in the range of 2 to 70% by weight, more preferably 5 to 50% by weight.

  Both tocopherol and rosemary used in the composition of the present invention can be easily obtained on the market. The tocopherol used in the present invention is an oil-soluble compound called vitamin E. Tocopherols are known to have various chemical structures such as α-type, β-type, γ-type, and δ-type, and any of them can be used in the present invention. In addition, natural products collected from natural products or synthetic products synthesized by chemical methods can be used without distinction.

In addition, the rosemary extract used in the present invention can be either a water-soluble or oil-soluble extract, but it is preferable that the rosemary extract is dissolved together in an oil and fat containing ARAs. It is preferred to use a fat-soluble rosemary extract. Their preparation methods are described in Examples 3 and 4 below. The method for preparing the rosemary extract may also follow the method specifically described in JP-A-2004-107599. Since the polyphenol component carnosic acid contained in the fat-soluble rosemary extract has an excellent antioxidant effect, this substance can also be used as a rosemary extract.

  The blending ratio of the rosemary extract and tocopherol in the present invention is not particularly limited. For example, the rosemary extract is 0.5 to 50 parts by weight, more preferably 5 to 5 parts by weight with respect to 1 part by weight of tocopherol. A range of 20 parts by weight is preferred. If a lot of rosemary extract is blended out of this range, there is a problem that the astringency derived from the extract becomes strong, and if it is too small, a synergistic effect by combined use is not recognized, and the effect of ARAs as an antioxidant is I can't expect much.

  The amount of antioxidant (ie, tocopherol and rosemary extract) to be included in the composition of the present invention and subject to antioxidant action is generally based on the weight of ARAs contained. A range of about 2 to 70% by weight, preferably about 5 to 50% by weight, can often be employed. If the added amount is less than 2% by weight, the effect is insufficient, and even if added over 70% by weight, the effect is not changed, which is uneconomical and has an adverse effect on the ARA-containing composition. .

  In the composition of the present invention, the antioxidant for arachidonic acids may be used only in the above-mentioned combination of tocopherol and rosemary extract, or an appropriate dilution with these mixtures. It may be used in the form of a composition with an agent, extender or carrier. Examples of such diluents, extenders or carriers include solid diluents such as gum arabic, dextrin, glucose and sucrose, extenders or carriers, alcohols such as water, ethanol, propylene glycol and glycerin, and polyglycerin. And liquid diluents such as fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters and glycerin fatty acid esters, extenders or carriers. Furthermore, in the range which does not impair the effect | action of the said component, it can be made to contain in a composition suitably combining arbitrary additives for general compositions, such as a fragrance | flavor, a pigment | dye, a pH adjuster, and a stabilizer.

  The composition of the present invention can be used as an arbitrary dosage form. For example, it can be used in a powdery form, a granular form, a liquid form, an emulsion form, a paste form, or any other suitable form. For example, gum arabic, dextrin, etc. may be added and used in a powder form, granule form, etc. using a drying means such as spray drying method, freeze drying method, etc., for example, ethanol, propylene glycol, It can also be used as a liquid dosage form which is dissolved in glycerin, an emulsifier or a mixture thereof and emulsified and dispersed. Further, as an embodiment of the composition of the present invention, together with a mixture of tocopherol and rosemary extract, other known antioxidants such as vitamin C, tea extract, enzyme-treated rutin, licorice extract, lecithin, gallic acid ester, You may use with the form of the mixture which mix | blended oxidation spices.

  The arachidonic acid-containing composition of the present invention is a composition used to add arachidonic acid or to enhance its content, and there is no particular limitation on the product to which this composition is added. However, in the present invention, addition to various compositions such as fats and oils is the most preferable application mode for the purpose of imparting nutritional enhancement and various physiological effects of arachidonic acid that have been tried. That is, if the composition of the present invention is added to a product that further increases the ARA content or a product that essentially does not contain ARAs but wants to impart its physiological action, the ARAs in the product and the product It is also possible to effectively prevent the generation of a deteriorated odor or a return odor accompanying a change with time due to light, oxygen, heat or the like. Specific examples of such products include foods and drinks / preference items, feeds, health / pharmaceuticals, cosmetics, and the like. For example, individual products include beverages such as fruitless beverages, beverages containing fruit juice, lactic acid bacteria beverages, and powdered beverages; frozen desserts such as ice cream, sherbet and ice confectionery; desserts such as pudding, jelly, bavaroa and yogurt; other drops Foods and beverages, candy, chocolate, rice cake, processed meat products, grilled meat, pickles, etc .; enteral nutrients, supplements, tablets, liquid oral medicines, powdered oral medicines, poultices, etc. Health / pharmaceuticals such as; cosmetics such as soaps, detergents and shampoos. However, the present invention is not limited to these examples, and various products and preparations are included in the addition target as necessary. Since the addition amount of the composition of the present invention to the above product varies depending on the type, characteristics, state, purpose of addition, etc. of the product, the preferred range cannot be determined unconditionally. Therefore, in practice, the amount of addition will be set as appropriate in each product or according to the purpose of addition. Generally, the addition amount is 0.01% by weight or more based on the product weight.

  From the above, the best mode of the present invention is a composition added to foods and beverages / preference products, feedstuffs, health / pharmaceutical products or cosmetics in order to add arachidonic acid or increase its content. And it is an oil-and-fat composition containing arachidonic acid characterized by containing tocopherol and a rosemary fat-soluble extract together with arachidonic acid.

As another embodiment of the present invention, a specific antioxidant method for arachidonic acids using tocopherol and rosemary extract is shown. As demonstrated in the examples below, the combined use of tocopherol and rosemary extract is expected to produce a synergistic oxidation inhibiting effect of arachidonic acids. The preferable blending, addition amount, and the like of the tocopherol and rosemary extract are easily derived from the description regarding the composition. According to the unique antioxidant method of the present invention, a mixture comprising a tocopherol and rosemary extract is added to and mixed with ARAs directly, and the ARAs change with time due to light, oxygen, heat, etc. Deterioration odor or return odor can be prevented. Antioxidants containing a mixture of tocopherol and rosemary extract or a combination thereof may also be used for antioxidant protection of ARA or ARAs, or products containing ARA or ARAs, such as food and drink It may be in a form that is added to taste products, feedstuffs, health / pharmaceuticals, cosmetics and the like to suppress oxidation of ARAs in the product.
[Example]
The present invention will be specifically described with reference to examples, but these examples do not limit the scope of the present invention. In addition, the materials used are only preferred examples within the scope of the present invention, and the numerical conditions such as the concentration, amount used, processing time, processing temperature, etc. of the materials used in the examples are within the scope of the present invention. This is only a preferred example.

In the studies shown in the following examples, the following TBA modification was used for the evaluation of fat oxidation and its oxidation inhibition. Soybean oil 0.1ml as sample oil, 0.2 M acetic acid hydrochloride buffer (pH 3.7) was added 1.5 ml, TBA (thiobarbituric acid) solution 1.5 ml, the FeCl ₃ solution (27,000ppm) 0.1ml, 100 ℃ · 15 minutes The red reaction product generated by the reaction between the fat oxide and TBA when held is measured by absorption at 532 nm. During the overheating oxidation of the fats and oils, BHT known as an antioxidant was added at various concentrations to evaluate the formation of red pigment in the reaction solution. The results are shown in FIG. The vertical axis represents the fat oxidation inhibition rate (%), and it was evaluated by how much the production of red pigment was suppressed, assuming that the absorbance when BHT was not added (oil oxidation inhibition rate was 0%) was 100. . It is known that the production of red pigment, that is, the oxidation of fats and oils is suppressed as the BHT addition amount increases.

  0.1 ml of an oil sample obtained by diluting arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, and ethyl ester of γ-linolenic acid 30 times each with chloroform was added in place of the soybean oil of Example 1, The absorbance of the red pigment produced by heat oxidation at 15 ° C. for 15 minutes was measured. When arachidonic acid was oxidized, the absorbance of the most produced red pigment was high. FIG. 2 shows the absorbance of each fat sample when the absorbance of the reaction solution of arachidonic acid is 100. As is apparent from the figure, the oxidizability of arachidonic acid is 3 to 10 times that of docosahexaenoic acid, eicosapentaenoic acid, and γ-linolenic acid. From this result, it was found that arachidonic acid is very easily oxidized compared to other highly unsaturated fatty acids.

Crush various spices (taragon, thyme, oregano, rosemary), add 9 times the amount of 60% aqueous ethanol solution, extract by shaking at 50 ° C for 2 hours, then centrifuge (5000rpm for 10 minutes) The supernatant was obtained as a 60% ethanol spice extract. When evaluating the oxidation of fats and oils using the sample fats and oils of Example 1 as soybean fats and oils or arachidonic acid-containing fats and oils, 0.1 ml of each spice extract was added, and the inhibitory activity of fat and oil oxidation by the respective extracted samples was compared. The results are shown in FIG.

  Oxidation of soybean oil and fat was suppressed in the order of tarragon, thyme, oregano and rosemary, but oxidation of oil containing arachidonic acid was in the order of rosemary, thyme, oregano and tarragon, and rosemary was arachidon. It was found to be suitable for acid oxidation inhibition.

  When evaluating the fat oxidation using the sample fat of Example 1 as arachidonic acid, a 5000 ppm solution of non-volatile components derived from rosemary 60% ethanol extraction and fat-soluble extraction (100% acetone extraction) was prepared. ml was added to compare the antioxidant activity against arachidonic acid. The results are shown in FIG. Among the rosemary extract components, it became clear that the oxidation-inhibiting activity was particularly high due to the fat-soluble fraction.

Regarding the inhibition of the oxidation of ARAs, the combined effect of the tocopherol and rosemary extract was examined from the viewpoint of quality stabilization for the following four samples.
(Sample 1) A tocopherol / rosemary-containing fat / oil comprising 10 g of 20% ARA-containing purified fat / oil, 0.2 g of tocopherol, and 0.2 g of rosemary fat-soluble extract was obtained.
(Sample 2) A tocopherol-containing fat / oil comprising 10 g of 20% by weight ARA-containing purified fat / oil and 0.4 g of tocopherol was obtained.
(Sample 3) A rosemary-containing fat and oil consisting of 10 g of 20% by weight ARA-containing purified fat and oil and 0.4 g of rosemary fat-soluble extract was obtained.
(Sample 4) 10 g of 20% by weight ARA-containing purified fat / oil was obtained.
-Storage stability test of fats and oils of samples 1, 2, 3 and 4 The prepared fats and oils samples were placed in 50 cc clear glass bottles and stored for 30 days at 50 ° C in the dark, on the 10th, 20th and 30th days. The temporal changes in flavor in the eyes were compared. The results are shown in Table 1. Each evaluation symbol in the table represents the following evaluation criteria.

  As is clear from the results in Table 1, the fats and oils of Sample 1 were stable with no change in flavor even after 10 days, while those of Samples 2, 3 and 4 to be compared were found to have a different taste and smell. Obviously, degradation due to oxidation of ARA fats and oils has occurred. In particular, the fats and oils of Sample 4 were already found to have an unpleasant taste and odor after 10 days, and the storage stability of the flavor was poor. In addition, by comparing the results of Sample 1 with the results of Sample 2 or Sample 3, the tocopherol / rosemary-containing oil / fat was found to have a synergistic antioxidant activity as compared to the tocopherol / rosemary-only oil / fat.

FIG. 1 shows the antioxidant activity of BHT on fats and oils measured by a modified TBA method. FIG. 2 shows the ease of oxidation of various polyunsaturated fatty acids. FIG. 3 shows the difference in antioxidant activity due to the difference in fats and oils of the antioxidant ethanol extract obtained from the spices. The target fats and oils are soybean fat (left) and arachidonic acid-containing fat (right). FIG. 4 represents a comparison of the antioxidant activity of the 60% etanol extract and the fat-soluble fraction of rosemary. (Sample oil and fat: Arachidonic acid ethyl ester, extract component concentration 5000ppm)

Claims (7)

  An arachidonic acid-containing composition comprising a arachidonic acid and a tocopherol and rosemary extract, wherein the composition is used to add or enhance the content of arachidonic acid.   The composition according to claim 1, wherein the arachidonic acid is an alcohol ester of arachidonic acid or a triglyceride, phospholipid or glycolipid in which a part or all of the constituent fatty acid is arachidonic acid.   The composition of Claim 1 or 2 containing 1 weight% or more of arachidonic acids.   The composition according to any one of claims 1 to 3, wherein the rosemary extract is a fat-soluble extract.   The composition according to any one of claims 1 to 4, wherein the rosemary extract is carnosic acid.   6. The composition according to any one of claims 1 to 5, which is added to foods / beverages / preference items, feedstuffs, health / pharmaceuticals or cosmetics in order to add arachidonic acid or enhance its content. object.   Antioxidation of arachidonic acids using tocopherol and rosemary extract.

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