Patent Application
20140186508
The present invention relates to an antioxidant for oils and fats or complex lipids such as phospholipids, an oil or fat composition or a complex lipid composition comprising the antioxidant, and a method for preventing oxidation of an oil or fat composition or a complex lipid composition.
Oils and fats are oxidized by, for example, heat, light, or oxygen to discolor or to generate an oxidized odor. The oxidized lipid not only has inferior color tone and flavor but is also considered to have adverse effects on health. In recent years, highly unsaturated fatty acids (a fatty acid having three or more double bonds) typified by linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and arachidonic acid (AA) have been known to have excellent physiological activities, and oils and fats containing a large amount of the highly unsaturated fatty acid, typified by a fish oil, should be more actively used as edible oils and fats. However, the oil or fat containing such a highly unsaturated fatty acid is readily oxidized to generate a characteristic unpleasant odor or to deteriorate in flavor, resulting in the limited usage in or processing to food products.
To prevent the oxidation of oils and fats, the addition of a synthetic antioxidant such as butylated hydroxyanisole (BHA) has been known to be effective. However, the synthetic antioxidant involves safety concerns. In consideration of the recent tastes of customers, there is a demand for the use of a substance derived from a natural product in place of a chemically synthesized substance. The antioxidant derived from natural products typically includes tocopherol and ascorbic acid. In addition, a green tea extract is also known to have the antioxidant activity.
Ginger is a food material used as a spice and has been used as a crude drug having the functions of warming the body and increasing metabolism since a long time ago. Patent Literature 1 discloses that a ginger oil effectively masks unpleasant odor derived from an aquatic animal oil or fat, but the ginger oils used therein were those produced by a steam distillation method.
Patent Literature 1: Japanese Patent Application Publication No. 2001-131575
The present invention has an object to provide a natural product-derived antioxidant having a higher inhibitory action on the increase in peroxide value than that of known natural product-derived antioxidants and having a higher masking action on an unpleasant odor than that of ginger oils produced by a steam distillation method.
In order to solve the problems, the present invention encompasses the inventions below.
The present invention can provide a natural product-derived antioxidant having a higher inhibitory action on the increase in peroxide value than that of a known natural product-derived antioxidant and having a higher masking action on an unpleasant odor than that of ginger oils produced by a steam distillation method.
An antioxidant for an oil or fat or a complex lipid of the present invention is characterized by comprising a ginger oil. The ginger oil means a natural essential oil obtained from the rhizomes of ginger (Amomum zingiber L.) belonging to the genus Amomum, the family Zingiberaceae. The natural essential oil contains various constituents exemplified by aromatic volatile oil constituents such as zingiberene, zingiberol, camphene, cineole, linalool, and citral and pungent constituents such as zingerol, zingerone, and shogaol.
The ginger oil used in the antioxidant of the present invention has at least one peak detected within 5 minutes before a peak of neral and at least three peaks within 7 minutes after a peak of geranial when subjected to a high-performance liquid chromatographic (hereinafter referred to as “HPLC”) analysis in the following analysis conditions.
Sample: an ethanol containing 0.1% (w/v) of the ginger oil
Column: an ODS column having a particle size of 5 μm, an inner diameter of 4.6 mm, and a length of 250 mm
Column oven temperature: 40° C.
Detection wavelength: 228 nm
Mobile phase: water (liquid A), acetonitrile (liquid B)
Flow rate: 1 mL/min
Gradient program:
The sample is prepared using ethanol (guaranteed reagent).
The column is packed with a chemically bonded porous spherical silica gel having a surface modified with ODS (octadecylsilyl group: C18H37Si) as the stationary phase and having a particle size of 5 μm and has an inner diameter of 4.6 mm and a length of 250 mm. The column is preferably “COSMOSIL 5C18-MS-II” manufactured by Nacalai Tesque, which is used by the inventors of the present invention, and may be a commercially available product equivalent to the column (for example, “COSMOSIL 5C18-AR-II” manufactured by Nacalai Tesque or “Wakosil II-5C18” manufactured by Wako Pure Chemical Industries, Ltd.).
The HPLC apparatus is not particularly limited and a commercially available HPLC apparatus may be used.
The amount of injection is not particularly limited, and the inventors of the present invention inject 10 μL of the sample.
The inventors of the present invention have analyzed an in-house ginger oil produced by a hexane extraction method and a commercially available ginger oil produced by a steam distillation method in the above HPLC conditions and have found that two peaks assigned to neral (also called cis-citral) and geranial (also called trans-citral) are detected around a retention time of 15 minutes in both chromatograms but there are marked differences regarding a peak detected within 5 minutes before the peak of neral and peaks detected within 7 minutes after the peak of geranial. Specifically, the in-house ginger oil produced by a hexane extraction method has one large peak about 3 minutes before the peak of neral and a plurality of peaks between the peak of geranial and about 7 minutes after the peak of geranial, but these peaks are not observed in the chromatogram of the commercially available ginger oil produced by a steam distillation method (see
The inventors of the present invention have further found that the in-house ginger oil produced by a hexane extraction method has a higher masking effect on the unpleasant odor of a fish oil and a higher photooxidation prevention effect (inhibition effect on the increase in peroxide value) than those of the commercially available ginger oil produced by a steam distillation method.
In the HPLC conditions, a signal having an area of at least 1% or more of the peak area of geranial is considered as a peak. The number of the peaks detected within 5 minutes before the peak of neral is at least one and may be two or more. The number is preferably one. The number of the peaks detected within 7 minutes after the peak of geranial is at least three and may be three or more. The number is preferably four, more preferably five, and even more preferably six.
The ginger oil used in the antioxidant of the present invention may be any ginger oil having the peaks defined as above when the HPLC analysis is carried out in the above conditions, and may be produced by any method. Examples of the known method for producing a ginger oil include a steam distillation method, a supercritical carbon dioxide extraction method, and a hexane extraction method.
The ginger oil by the steam distillation method can be produced as follows. For example, a raw material (rhizomes of ginger) is placed in a distillation container, then water vapor is fed into the distillation container, and oil constituents are extracted from the raw material to vaporize together with the water vapor. The water vapor with the oil constituents is cooled to be separated into two layers of an oil layer and a water layer, and the oil is collected. As far as the inventors of the present invention have examined, the ginger oil by the steam distillation method is considered not to fall into the ginger oil having the peaks defined as above.
The ginger oil by the supercritical carbon dioxide extraction method is produced as follows. For example, a raw material (rhizomes of ginger) is placed in an extraction tank, and heated and pressurized CO2 in a supercritical state is fed into the extraction tank to dissolve oil constituents in the raw material. Next, the pressure of the supercritical CO2 dissolving the oil constituents is reduced to vaporize CO2 and the oil is thus collected.
The ginger oil by the hexane extraction method is produced as follows. For example, a raw material (rhizomes of ginger) is placed in a reaction container, and n-hexane is added to come in contact with the raw material. Then, the n-hexane solution is collected, and n-hexane is removed with an apparatus such as a centrifugal thin-film evaporator and a vacuum evaporator. Thus the oil is collected.
When the ginger oil is produced by the hexane extraction method, vegetable ginger or the residue of squeezed ginger can be preferably used as the raw material. The residue of squeezed ginger is more preferred because the residue contains pungent constituents and aromatic constituents of the ginger and has a low water content: The residue of ginger after squeeze is preferably frozen to be stored for improved storage stability. The extraction solvent is preferably n-hexane for easy extraction of the pungent constituents and the aromatic constituents. The extraction is preferably carried out at room temperature or lower.
The oil or fat or the complex lipid applicable to the present invention may be any oil or fat or any complex lipid that contains an unsaturated fatty acid, and examples thereof include an oil or fat or a complex lipid derived from plants, animals, aquatic plants and animals, microorganisms, and other materials. Examples of the complex lipid includes phospholipids (glycerophospholipids, sphingophospholipids), glycolipids (glyceroglycolipids, sphingoglycolipids), lipoproteins, sulfolipids, and ceramides. Specific examples of the oil or fat derived from plants include tung oil, linseed oil, almond oil, perilla oil, olive oil, orange seed oil, pumpkin seed oil, kapok oil, mustard oil, Trichosanthes kirilowii seed oil, Catalpa ovata seed oil, a conjugated linoleic acid-containing oil or fat, Calendula officinalis seed oil, wheat germ oil, rice bran oil, corn oil, sesame oil, cherry seed oil, safflower oil, pomegranate seed oil, Perilla frutescens oil, snakeguard seed oil, soybean oil, tea seed oil, evening primrose seed oil, camellia oil, rapeseed oil, Momordica charantia seed oil, Campsis grandiflora seed oil, balsam apple seed oil, palm oil, sunflower oil, peanut oil, grape seed oil, Impatiens balsamina seed oil, macadamia nut oil, cottonseed oil, and ground nut oil. Specific examples of the complex lipid derived from plants include soybean phospholipid, rapeseed phospholipid, sunflower phospholipid, corn ceramide, rice ceramide, konjak ceramide, wheat ceramide, sugar beet ceramide, and pineapple ceramide. Specific examples of the oil or fat derived from animals include beef tallow, lard, and egg yolk oil. Specific examples of the complex lipid derived from animals include egg yolk phospholipid, sphingomyelins derived from egg yolk and milk, and galactosyl ceramide derived from bovine brain. Specific examples of the oil or fat derived from aquatic animals include fish body oils obtained from sardine, salmon, mackerel, saury, herring, tuna, and other fishes, liver oils of squid and Alaska pollack, an orbital oil of bonito, tuna, and the like, seal oil, and krill oil. Specific examples of the complex lipid derived from aquatic animals include phospholipids obtained from sand eel, salmon roe, and the like. Specific examples of the oil or fat derived from microorganisms include an oil derived from Schizochytrium sp., an oil derived from Nitzschia sp., an oil derived from Nannochloris sp., and an oil derived from Mortierella sp. These oils and fats and complex lipids may be used singly or as a mixture. Alternatively, these oils and fats and complex lipids may be hardened, fractionated, or transesterificated and the obtained products may be used singly or as a mixture of two or more of them. An oil or fat containing an unsaturated fatty acid may be mixed with an oil or fat free from an unsaturated fatty acid, and the mixture may be hardened, fractionated, or transesterificated. Preferred are an oil or fat derived from aquatic animals, an oil or fat derived from microorganisms, and various phospholipids.
The antioxidant of the present invention can be added to an oil or fat, a complex lipid, or a composition containing the same and be used. When the antioxidant of the present invention is added to an oil or fat or the like, the antioxidant is preferably, homogeneously mixed with an intended oil or fat or the like. The mixing method is not particularly limited and a known stirrer can be used, for example. The amount of the antioxidant of the present invention is not particularly limited. The antioxidant is preferably added in an amount of about 0.01 to about 25 parts by weight, more preferably about 0.1 to about 15 parts by weight, and even more preferably about 1 to about 10 parts by weight, in terms of ginger oil relative to 100 parts by weight of an oil or fat or a complex lipid.
The antioxidant of the present invention may contain other components in addition to the ginger oil unless the object of the invention is impaired. Examples of the additional component include food additives used in a common edible oil or fat.
The antioxidant of the present invention alone may be added to an oil or fat, a complex lipid, or a composition containing the same, but a higher oxidation prevention effect can be achieved by combination use with an additional antioxidant. Examples of the additional antioxidant specifically include commonly used antioxidants such as tocopherol, L-ascorbic acid, L-ascorbyl palmitate, a rosemary extract, a tea extract, a sunflower extract, and a coffee bean extract.
The antioxidant of the present invention can maintain a clear liquid form at ambient temperature for a long period of time. The antioxidant is preferably stored in a sealed container. The storage temperature is an ambient temperature and is preferably 20° C. to 30° C.
The present invention encompasses an oil or fat composition containing the antioxidant of the present invention added thereto and a complex lipid composition containing the antioxidant of the present invention added thereto. Examples of the oil or fat composition include an oil or fat, an emulsion containing an oil or fat, and a solubilized liquid containing an oil or fat. The emulsion may be a micro emulsion, and the solubilized liquid may be a nano emulsion. Examples of the complex lipid composition include a complex lipid, an emulsion containing a complex lipid, and a solubilized liquid containing a complex lipid. The oil or fat composition and the complex lipid composition may contain, in addition to the oil or fat, the complex lipid, and an emulsifier, other components such as a common food additive.
The addition of the antioxidant of the present invention to an oil or fat, a complex lipid, or a composition containing them can more strongly suppress an unpleasant odor caused by the deterioration of the oil or fat and can also more strongly inhibit the increase in peroxide value even in a harsh oxidation condition (for example, continuous irradiation with light at 6,000 Lux for 14 days, see Example 2) as compared with the ginger oil produced by a steam distillation method. In addition, the ginger oil used in the antioxidant of the present invention contains constituents different from those in the ginger oil produced by a steam distillation method, and thus may be excellent in osteogenesis promoting effect, bone metabolism inhibitory effect, bactericidal effect, immunocyte activation effect, cholesterol lowering effect, carbohydrate and lipid absorption inhibitory effect, fat degradation and burning acceleration effect, nausea or headache inhibitory effect, vasodilating effect, blood circulation promoting effect, and other effects.
The present invention will be described in detail with reference to Examples hereinbelow, but the present invention is not limited to them.
At −10° C. or lower, 60 kg of residue of squeezed ginger (having a water content of about 75% by mass) was frozen, and the frozen raw material was brought into contact with about a double volume of n-hexane at −5° C. for 15 minutes in a reaction container. Then, the n-hexane solution was collected, and n-hexane was removed with a centrifugal thin-film evaporator and a vacuum evaporator at a room temperature or lower, thus affording a ginger oil. The obtained ginger oil (hereinafter referred to as “in-house ginger oil”) was a brown transparent oil-soluble liquid having a refreshing aroma of freshly grated ginger and pungent constituents specific to ginger.
The in-house ginger oil was subjected to HPLC analysis in the conditions below. A Shimanto ginger essential oil (trade name, manufactured by ECO-SHIMANTO) produced by a steam distillation method was also subjected to HPLC analysis in the same conditions.
The in-house ginger oil or the Shimanto ginger essential oil was added to ethanol (guaranteed reagent) so as to give a concentration of 0.1% (w/v) and the obtained sample was analyzed.
Pump: HITACHI L-2130
Column oven: HITACHI L-2350
Detector: HITACHI L-2450
Column: COSMOSIL 5C18-MS-II, 4.6 mm×250 mm (manufactured by Nacalai Tesque, ODS column)
Column oven temperature: 40° C.
Injection amount: 10 μL
Detection wavelength: 228 nm
Mobile phase: water (liquid A), acetonitrile (liquid B)
Flow rate: 1 mL/min
Gradient program:
The purified fish oil used was “DD Oil Type 2” (trade name) manufactured by Nippon Suisan. The known antioxidant used was vitamin E (“Tocopherol AT-160 (trade name)” manufactured by J-OIL MILLS). The ginger oil used was two types as below:
Each sample was prepared in accordance with the formulation ratio shown in Table 1, then 5 g of each sample was placed in a 20-mL bottle, and the bottle was sealed with a cap. The bottle was continuously irradiated with light at 6,000 Lux. After 7 days and 14 days, each sample was subjected to a peroxide value measurement and a sensory evaluation. The increase in the amount of vitamin E added is known to lower the antioxidant effect, and therefore the formulation ratio was designed as shown in Table 1.
The peroxide value was determined in accordance with “Standard Methods for the Analysis of Fats, Oils and Related Materials (II), reference, 2.4-1996, Peroxide valup (chloroform method)” by The Japan Oil Chemists' Society. The sample was dissolved in a titration solvent of chloroform and acetic acid (2:3). To the sample solution, a potassium iodide solution was added while a nitrogen gas stream was passed through the sample solution to remove dissolved oxygen, and free iodine was titrated with 0.01 mol/L sodium thiosulfate solution by potentiometric titration. The peroxide value was calculated based on the amount of the sodium thiosulfate solution used in the titration.
In the sensory evaluation, ten panelists evaluated the direct odor of each sample. A sample with a strong unpleasant odor was evaluated as grade C, a sample with a weak unpleasant odor was evaluated as grade B, and a sample with a masked unpleasant odor was evaluated as grade A. The grade given by the largest number of panelists was regarded as the grade of the sample.
Table 2 shows the results. Each of the samples 3 and 4 to which the ginger oil was added inhibited the increase in the peroxide value as compared with the reference sample 1, and the inhibition degree by the in-house ginger oil (a) was higher than that by the Shimanto ginger essential oil (b). In the unpleasant odor masking effect evaluation, (a) had the masking effect, but (b) had a weak unpleasant odor. Vitamin E (Tocopherol AT-160) as a known antioxidant failed to achieve the oxidation prevention effect in the conditions in this Example.
The results revealed that the in-house ginger oil (a) achieved a higher oxidation prevention effect and unpleasant odor masking effect than those of the Shimanto ginger essential oil (b). Thus, the following experiments employed the ginger oil produced by the hexane extraction method or the supercritical carbon dioxide extraction method.
The purified fish oil used was “DD Oil Type 2” (trade name) manufactured by Nippon Suisan, the known antioxidant used was “Tocopherol AT-160 (trade name)” manufactured by J-OIL MILLS, and the ginger oil used was the in-house ginger oil produced in Example 1.
Each sample was prepared in accordance with the formulation ratio shown in Table 3. In a similar manner to that in Example 2, 5 g of each sample was placed in a 20-mL bottle, and the bottle was sealed with a cap. The bottle was continuously irradiated with light at 6,000 Lux. After 7 days and 14 days, each sample was subjected to the peroxide value measurement and the sensory evaluation.
Table 4 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor. The sample 4 containing the in-house ginger oil in an amount equivalent to that of vitamin E had a lower peroxide value than that with vitamin E and masked the unpleasant odor.
The same samples were prepared with the same materials as those in Example 3, and each bottle was stored in a thermostatic chamber at 60° C. In a similar manner to that in Example 3, each sample was subjected to the peroxide value measurement and the sensory evaluation after 7 days and 14 days.
Table 5 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The same samples were prepared with the same materials as those in Example 3, and each bottle was left without a cap at room temperature (26±2° C.). In a similar manner to that in Example 3, each sample was subjected to the peroxide value measurement and the sensory evaluation after 7 days and 14 days.
Table 6 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The study was carried out in a similar manner to that in Example 3 except that a soybean sirasimeyu (soybean refined oil) (manufactured by Tsuji Oil Mills) was used in place of the purified fish oil.
Table 7 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The study was carried out in a similar manner to that in Example 3 except that a corn sirasimeyu (cone refined oil) (manufactured by Tsuji Oil Mills) was used in place of the purified fish oil.
Table 8 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The study was carried out in a similar manner to that in Example 3 except that a cottonseed oil (manufactured by J-OIL MILLS) was used in place of the purified fish oil.
Table 9 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The study was carried out in a similar manner to that in Example 3 except that a high linoleic sunflower oil (manufactured by J-OIL MILLS) was used in place of the purified fish oil.
Table 10 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The used materials were a medium chain triglyceride oil (“Scholey 64G (trade name)” manufactured by The Nisshin OilliO Group, Ltd., caprylic acid (C8):capric acid (C10)=60:40), phospholipid derived from salmon roe (“Sunomega PC-DHA (trade name)” manufactured by NOF CORPORATION, vitamin E (see Example 2), and the in-house ginger oil (see Example 1).
Each sample was prepared in accordance with the formulation ratio shown in Table 11. In a similar manner to that in Example 2, the bottle was continuously irradiated with light at 6,000 Lux. After 7 days and 14 days, each sample was subjected to the peroxide value measurement and the sensory evaluation.
Table 12 shows the results. The sample 3 to which the in-house ginger oil was added had a lower peroxide value than those of the samples 1 and 2 and masked the unpleasant odor.
The present invention is not limited to each embodiment and each example described above and can be variously modified within the scope of claims. The technical scope of the present invention encompasses an embodiment obtained by an appropriate combination of different technical means disclosed in respective embodiments.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-284092 | Dec 2012 | JP | national |
