JPH0565482A - Antioxidant and method for extracting the same - Google Patents

Abstract

PURPOSE:To obtain an inexpensive and more powerful and safe antioxidant, containing a Maillard reaction product prepared by heating a mixture of grains with saccharides and mass-producible at a low cost by using simply and abundantly available raw materials. CONSTITUTION:An antioxidant containing a Maillard reaction product obtained by heating a mixture of grains with saccharides. Furthermore, since the Maillard reaction product is browned and has unique flavor, an extract from the above- mentioned product is preferably used for a food in which the color and flavor are unfavorable. The extract is obtained by mixing the grains with saccharides and, as necessary, proteins, carrying out hot pressing treatment of the mixture in an extruder, then dissolving the resultant Maillard reaction product in water and filtering the prepared solution. Furthermore, the ratio of the raw materials is 1-50 pts.wt. saccharides and 0-200 pts.wt. proteins based on 100 pts.wt. grains.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antioxidant and a method for extracting the same for the purpose of processing a natural product to produce an antioxidant or extracting an antioxidant.

[0002]

Conventionally, an antioxidant containing one or more amino acids selected from alanine, leucine, histidine and the like and a browning reaction product of dihydroxyacetone as components has been known (JP-A-49). -125578
issue).

Further, there has been known a method for producing an antioxidant substance in which an amino acid and a saccharide are adjusted in pH and then heated, the resulting browning product solution is purified, and the antioxidant substance is eluted (JP-A-64). -10971).

[0004]

Among the above-mentioned conventional techniques,
The former antioxidant is obtained as a browning reaction product (Maillard reaction product) using alanine, leucine or the like as a raw material, and dihydroxyacetone, which is not recognized as a food additive, is used, which is not preferable. Further, since amino acids are used as a raw material, an increase in the manufacturing cost of antioxidants cannot be avoided.

This also applies to the above-mentioned conventional antioxidants based on amino acids and sugars.

Further, in the above patent, the reaction time is relatively long (1 to 6 hours), and there are many problems in fitting in a series of production lines.

[0007]

[Means for Solving the Problems] Oxidation of fats and oils in conventional foods not only causes deterioration of food quality along with putrefaction, but also induces the production of lipid peroxides in the living body to prevent aging and cancer. It is said to be the cause. Therefore, research and development was conducted on antioxidants, and refined products or synthetic agents (for example, BHT) are known, but since processed products of natural products or extracts thereof are still unsatisfactory, This invention was obtained as a result of research and development for the purpose of inexpensively mass-producing effective substances.

[0008] The present invention uses cereals, which are available at a relatively low cost, as a main raw material, and adds sugars and, if necessary, proteins to the materials to cause a Maillard reaction and extract the product or the product. According to the present invention, an effective antioxidant was obtained to solve the above conventional problems. Furthermore, the antioxidant thus obtained is a polymer Maillard reaction product of protein and sugar, and has a stronger antioxidant effect than the low molecular weight Maillard reaction product of amino acid and sugar described in the above conventional problems. have. In addition, by using an extruder in the Maillard reaction, the purpose of processing can be achieved easily and quickly, enabling mass production.

That is, the invention of the product is an antioxidant characterized by containing a Maillard reaction product obtained by heating a mixture of cereals and sugars as a component. Further, it is an antioxidant characterized by containing a Maillard reaction product obtained by heating a mixture of cereals, sugars and proteins as a component. Next, it is an antioxidant characterized by containing a Maillard reaction product obtained by mixing grains and sugars with proteins if necessary, and heating and pressurizing the mixture with an extruder. Further, the invention of the method is characterized in that grains and sugars are mixed with proteins if necessary, and the Maillard reaction product obtained by heat-pressurizing the mixture with an extruder is dissolved in water and filtered. It is a method of extracting an antioxidant. Further, grains and sugars are mixed with proteins if necessary, and the Maillard reaction product obtained by heat-pressurizing the mixture with an extruder is dissolved in water and filtered, and the filtrate thus obtained is subjected to electrochemical detection. Method A method for extracting an antioxidant characterized by detecting a peroxide by fractionating it by gel filtration chromatography and removing it. Next, the cereal is wheat,
Rice, corn, barley, rye, oats, fluff, hie, acne, and soybeans, adzuki beans, broad beans, peas, and other beans, including coarse grains or powders,
It is not limited to the examples given here. Further, the saccharides are glucose, sucrose, fructose, maltose, starch syrup, galactose, honey, glucose-fructose syrup, etc., and are not limited to the examples given here. Proteins are sodium casein, casein, skim milk powder, whey, soybean powder, concentrated soybean powder, soybean powder isolate, vital gluten, egg white powder, egg yolk powder,
It is a substance with a high protein content such as whole egg powder and gelatin, and is not limited to the examples given here.

In the above, even when the Maillard reaction product is used as it is, a considerable effect is recognized as shown in FIG. 1. However, the extract from the Maillard reaction product has a further excellent effect. It was accepted to show. Further, since the extract contains a small amount of a peroxidative substance detected by an electrochemical detector (A in FIG. 3), except for this, and for the use in which color adhesion is not preferable,
In FIG. 3, except for part B (not shown in the figure, coloring is observed in this part by a visible detector), but by separating only part C, only colorless active ingredient can be obtained.

In the above, cereals are the main raw material, but other raw materials are 1 to 50 parts of sugar and 0 parts of protein to 100 parts of cereals.
~ 200 parts are used. When the saccharide content is 1 part or less, the Maillard reaction product is not sufficiently produced and is wasteful. When the amount is 50 parts or more, the amount of sugar is large compared to the protein content of cereals, so that there is much waste. Further, in the case of the extruder treatment, if the sugar content is 50 parts or more, the amount of self-heating will decrease and the target temperature will not be reached.

[0012] Further, since the protein is intended to supplement the protein deficiency in cereals (including beans), it is necessary to add the protein to those having a relatively high protein content (such as soybean). It may be reduced or not added. For the above reasons, it is not necessary to add more than 200 parts of protein. Also, in the case of the extruder treatment, 20
If it is 0 parts or more, the torque of the extruder during the heating and pressurizing process increases, and it becomes difficult to operate the extruder.
Further, the extruder treatment causes the extrudate to be structured, which makes subsequent treatments such as water extraction difficult.

A large antioxidant effect is also observed when the Maillard reaction product is used as it is (FIG. 1).
Since the product is browned and has a unique flavor, it is preferable to use the extract for foods which are not preferable for such color and flavor. The extract is
Since it still contains a peroxide substance, a substantially colorless antioxidant can be obtained by separating the peroxide substance and, if necessary, the coloring component.

[0014]

Example 1 (1) Blend wheat flour 10 g + glucose 1 g +
Ion-exchanged water 200 ml Wheat flour 10 g + Vital gluten 10 g + Glucose 1 g + Ion-exchanged water 200 ml Wheat flour 10 g + Soy protein isolate 10 g + Glucose 1 g
+ Ion-exchanged water 200 ml wheat flour 10 g + casein 10 g + glucose 1 g + ion-exchanged water 200 ml (2) Heat treatment method Heat treatment is carried out at 120 ° C for 20 minutes by an autoclave. (3) Measurement of antioxidative ability Heat treatment solution 5 ml + 5% linoleic acid ethanol solution 20 ml + 0.2 M phosphate buffer (pH 7.0) 20 ml ↓ Storage at 45 ° C for 48 hours ↓ Extract linoleic acid with chloroform, and extract its POV ( (4) Result (POV) No heat treatment liquid added 743.4meq / Kg Heat treatment liquid added 94.2meq / Kg Heat treatment liquid added 42.4meq / Kg Heat treatment liquid added 64.1meq / Kg Addition of heat treatment liquid 31.7 meq / Kg As described above, the heat treatment product of wheat flour and glucose, and the heat treatment product to which protein was added exhibited the antioxidant ability of suppressing the oxidation of linoleic acid.

[0015]

Example 2 (1) Blend 100 parts wheat flour + 20 parts glucose 100 parts wheat flour + 20 parts glucose + 20 parts casein 100 parts wheat flour + 20 parts glucose + soybean protein 2 isolate
0 parts Wheat flour 100 parts + Glucose 20 parts + Vital gluten 20 parts Wheat flour 100 parts + Glucose 20 parts + Egg white powder 20 parts (2) Heat treatment Heat-pressurized by an extruder, extruded and then finely pulverized.

(Conditions) Model used: Toshiba Machine Co., Ltd. TEM-50 L / D: 24 Feed amount: 100 Kg / hr Water content: 10% Heating temperature: 160 ° C. Die: 4 mmφ × 2 (3) Measurement of antioxidant capacity Finely pulverized product of extrudate 5 g + 5% ethanol solution of linoleic acid 20 ml + 0.2 M phosphate buffer (pH 7.0) 25 ml ↓ Storage at 45 ° C for 48 hours ↓ Extract linoleic acid with chloroform and extract its POV (peroxide value) Measurement (4) Result (POV) Extrudate-free 796.5 meq / Kg Extrudate-added 119.5 Extrudate-added 39.8 Extrudate-added 71.7 Extrudate-added 80.1 Extrudate-added 73.7 Thus In addition, the extrudate produced by the extruder was found to have an antioxidant ability to suppress the oxidation of linoleic acid. Among them, the one to which casein was added had a strong antioxidant ability.

[0017]

Example 3 (1) Blending 100 parts wheat flour + 20 parts glucose + 20 parts casein (2) Heat treatment The mixture was extruded by heating and pressurizing with an extruder, and then pulverized.

(Conditions) Model used: Toshiba Machine Co., Ltd. TEM-50 L / D: 24 Feed amount: 100 Kg / hr Water content: 10% Heating temperature: 160 ° C. Die: 4 mmφ × 2 (3) Measurement of antioxidant capacity To 500 mg of the extrudate, 20 ml of 0.1 M linoleic acid ethanol solution and 20 ml of 0.1 M phosphate buffer (pH 7.0) were added, and the mixture was adjusted to 50 ml with water to give an antioxidant measurement solution. In this case, the extrudate added contains about 18 mg of nitrogen. On the other hand, in the case of the water extract of the extrudate, the amount of the solution containing 1 mg of nitrogen is 0.1
20 ml of M linoleic acid ethanol solution and 20 ml of 0.1 M phosphate buffer (pH 7.0) were added to make 50 ml with water to obtain an antioxidant measurement liquid.

This solution for measuring antioxidant capacity was stored at 40 ° C. protected from light. During that period, the POV of linoleic acid was measured every few days by the Rhodan iron method. That is, 0.1 ml was taken from the antioxidant measuring solution, and 4.7 ml of 75% ethanol was added thereto. After that, 0.1% aqueous solution of 30% rhodan ammonium
ml and 20 ml of 20 mM ferrous chloride / 3.5% hydrochloric acid solution were added, and after 3 minutes, the absorbance at 500 nm was measured. As the POV of linoleic acid increases, so does the absorbance at 500 nm. (4) Results (POV) The results shown in FIGS. 1 and 2 were obtained as described above.

As shown in the figure, the extrudate had a strong antioxidant capacity equal to or higher than BHT, and the oxidation of linoleic acid was suppressed over 60 days.

Further, even a small amount of the water extract of the extrudate had a strong antioxidant ability.

[0022]

Example 4 Column: TSKgel G3000SW _XL (7.8 mm ID × 3)
0 cm) Pump; Tosoh Co., Ltd. liquid chromatography pump CCPM Detector; Tosoh Co., Ltd. UV-Visible Detector UV-801
Electrochemical detector EC-8010 manufactured by Tosoh Co., Ltd. Eluent; 0.2M phosphate buffer (pH 6.8) Flow rate; 1.0 ml / min Column temperature; RT injection amount; 20 μl detection; UV (290 nm, 0. 2ABU / FS), ECD (Pt, 50
0 mV, 50 nA / FS) sample; water extract of extrudate of Example 3 (Result) By using an electrochemical detector, peroxide could be detected in the water extract. By removing this fraction, a stronger antioxidant could be obtained.

That is, the chart of FIG. 3 was obtained by gel filtration chromatography. Therefore, parts A and B were removed to obtain a colorless antioxidant extract having higher antioxidant properties.

[0024]

INDUSTRIAL APPLICABILITY According to the present invention, cereals are used as a main raw material, sugars, and if necessary proteins are added thereto and mixed, and the mixture is heated to obtain a Maillard reaction product. There is an effect that it can be obtained inexpensively and in large quantities. Further, since an antioxidant substance is extracted from the Maillard reaction product, there is an effect that a strong antioxidant can be produced in a large amount. However, the raw materials are easily and abundantly available, the processing cost is relatively low, and since they are processed products of natural raw materials, they have the characteristics that they can be used as food additives with peace of mind.

[Brief description of drawings]

FIG. 1 is a comparative graph showing the antioxidant effect of the Maillard reaction product of the present invention.

FIG. 2 is a comparative graph showing the antioxidant effect of a water extract from the Maillard reaction product.

FIG. 3 is a gel filtration chromatogram of electrochemical detection method which also detects peroxides in the water extract of Maillard reaction product.

Claims (5)

[Claims] 1. An antioxidant comprising a Maillard reaction product obtained by heating a mixture of cereals and sugars as a component. 2. An antioxidant comprising a Maillard reaction product obtained by heating a mixture of grains, sugars and proteins as a component. 3. Grains and sugars are mixed with proteins if necessary,
An antioxidant characterized by containing as a component a Maillard reaction product obtained by heat-pressurizing the mixture with an extruder. 4. A grain and a sugar are mixed with protein if necessary,
A method for extracting an antioxidant characterized in that a Maillard reaction product obtained by heating and pressurizing the mixture with an extruder is dissolved in water and filtered. 5. A mixture of grains and sugars, if necessary, with proteins,
The Maillard reaction product obtained by heating and pressing the mixture with an extruder was dissolved in water and filtered, and the filtrate thus obtained was fractionated by gel filtration chromatography with electrochemical detection to detect peroxides. Extraction method of antioxidants characterized by removing