KR20060083280A - Extacct method of natural antioxidant from an agriculture byproducts and material thereof - Google Patents

Abstract

The present invention provides a method for producing a natural antioxidant extract and antioxidant properties extracted by the production method, characterized in that the agricultural by-products are far-infrared or heat-treated to freely activate the natural antioxidants to increase the use of agricultural by-products. do. The present invention is a very useful invention in the food industry to improve the functionality of herbal medicines and natural plant materials by securing the natural source processing technology using far-infrared treatment and heat treatment.

Sesame gourd, peanut peel, citrus peel, grape seed, far infrared ray treatment, heat treatment, antioxidant activity, total phenol content, radical scavenging activity, lipid peroxidation degree, GC, HPLC

Description

Extraction method of natural antioxidants from agricultural by-products and their substances

Figure 1 is a schematic diagram of the glass activation of the components of the natural antioxidant material present in the polymerization state using a heat and a far infrared heater in the present invention.

Figure 2 is a graph of the results of gas chromatograms (GC) for methanol extract of sesame gourd, Figure 2a is a non-treated, Figure 2b is a result of treatment in the far infrared treatment.

FIG. 3 is a graph of gas chromatograms (GC) of grape seed ethanol extract, FIG. 3A is a non-heated grape seed, FIG. 3B is a pulverized grape seed, and FIG. 3C is a whole grape seed.

Figure 4 is a graph showing the catechins, epicatechins and caffeine content change of the grape seed extract through HPLC.

The present invention relates to a method of extracting antioxidants by far-infrared or heat treatment of agricultural by-products. More specifically, the present invention relates to a method of freely activating natural antioxidants from agricultural by-products through the far-infrared or heat treatment, and to natural antioxidants extracted by the method.

There is a large distribution of unidentified natural antioxidants in most plants, most of which are known as polyphenol compounds. They are called tannins of polymers and exist as inert concentrated tannins that are not decomposed or absorbed by the human body by being combined with proteins and sugars. In order to be absorbed by the human body and have high activity, it must be present as hydrolyzable tannins that are well decomposed by water or enzymes, or their degradation products, ellagitannin or gallotannins. Therefore, for the production of highly efficient tannins, chemical methods through acid and physical methods such as grinding have been commonly used. However, they often do not have high efficacy on acid screens or react more quickly with oxygen, which causes rancidity.

On the other hand, sesame gourd, peanut peel, citrus peel, grape seed, etc. of agricultural by-products generally occupy most of the fiber and exist as a polymer inert rather than a low molecular antioxidant. Therefore, millions of tonnes of agricultural by-products are thrown away every year, and some of them are used as heating materials for herbal medicine, animal feed and manure, and their range of use is limited. Their processing is not only limited to drying, heat treatment, fermentation, etc., but also has insufficient evidence to properly demonstrate the physiological changes of processed by-products and the change of antioxidants, and thus does not enhance the use efficiency. Among the antioxidants present in foods, macromolecular antioxidants such as superoxide dismutase, catalase, and peroxidase are active due to decomposition by gastric fluid during heating or absorption in human body. This is lost and ineffective. In addition, low molecular weight antioxidants, such as flavonoids, carotenoids, and polyphenols, are present in the form of repetitive polymers in plants and are not liberated even when food is ingested. In an attempt to increase the solubilization of these low-molecular-weight antioxidants, studies have been reported on various treatments such as far-infrared treatment, fermentation, microwave treatment and gamma-ray treatment.

However, when treated with radiation including gamma rays, excessive oxygen species are generated in the living body, causing radiological damage and causing fatal damage to the human body. Due to high energy, oxygen-hydrogen bonds of water molecules are decomposed to generate hydroxyl radicals. Induced low molecular weight of proteins, but the brain disease of the living organisms often occur, there was a problem that increased oxidative stress.

The present invention has been made in order to overcome the above-mentioned problems, the object of the present invention is to increase the use of agricultural by-products, the natural antioxidants, characterized in that by extracting by activating the natural antioxidants by far-infrared or heat treatment It is to provide a method for producing an extract.

Another object of the present invention to provide an antioxidant extracted by the above production method.

In order to achieve the above technical problem, the present invention provides a method for producing a natural antioxidant extract, characterized in that the agricultural by-products are far-infrared or heat-treated to extract the natural antioxidant by free activation. Preferably, the agricultural by-product of the present invention uses sesame gourd, peanut peel, citrus peel, grape seed.

Moreover, it is most preferable that the heat processing temperature of this invention is 50-200 degreeC. If the heat treatment temperature is less than 50 ℃ temperature is low, the effect of the heat treatment does not appear properly, if the heat treatment temperature is 200 ℃ or more, the agricultural by-products and antioxidants can not withstand the high temperature is destroyed.

The present invention provides a natural antioxidant extracted through the above manufacturing method. The natural antioxidants are preferably p-hydroxybenzoic acid, o-coumaric acid, vanillic acid, p-coumaric acid, isoperulic acid, 2-methoxyphenol, catechin, epicatechin, caffeine, gallic acid and mixtures thereof It is characterized by containing a phenol derivative selected from the group consisting of.

In the present invention, a general heat heater and a far-infrared radiation heater having a wavelength of 2-14 μm were used as part of the present invention after drying or removing fat to enhance the acceptance of antioxidant capacity.

In order to process far-infrared rays, ovens of 750 × 600 × 900 mm in width, length, and height were prepared. In the center of the oven, two far-infrared heaters were installed to raise the temperature up to 250 ° C. The samples were placed in a disc so that the samples could be rotated evenly. On the other hand, Figure 1 is a schematic diagram for freely activating the components of the natural antioxidants present in the polymerization state using a heat and a far infrared heater in the present invention.

On the other hand, the present invention can be variously produced as a functional food material, functional cosmetics, pharmaceuticals, etc. in animal feed or herbal medicine.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention. The following examples are intended to illustrate the invention, the scope of the invention is not limited to the following examples.

Example 1 Preparation of Sesame Gourd Extract

To prepare sesame gourd, 20 g of sesame seeds are maintained at a temperature of the far-infrared radiant heater at 200 ° C. and treated for 10, 20, 30, 40, 50, 60, 90 and 120 minutes for each hour, and then oil is removed by a milking machine. In order to completely remove the fats and oils, hexane (n-hexane) is completely removed three times, and volatile hexane is blown off completely with nitrogen gas. The oil was completely removed from the sample 10g with 100mL 99.5% (v / v) methanol overnight stirring (12 hours), and then separated from the clean liquid and foreign matter through a filter and concentrated. The sample thus prepared was 1 mg / mL and dissolved again in 99.5% (v / v) methanol to assay antioxidant results.

Example 2 Preparation of Peanut Shell Extract

Peanut shells were rinsed through drying after washing with water, and then treated with 5, 10, 15, 20, 40, 60 minutes of normal heat heater or far-infrared radiant heater at 150 ° C for different time. The mixture was extracted overnight with 10 mL of distilled water, filtered and subjected to antioxidant assay.

Example 3 Preparation of Citrus Peel Extract

Citrus peel was washed with water and dried with citrus unshiu , and then the pulverized peel was kept at 10, 20, 30, 40, and 50 minutes at a temperature of 150 ℃ far-infrared radiation heater. 0.1 g of far-infrared irradiated citrus peel was extracted with 10 mL of 70% ethanol solution in an incubator (at room temperature, 100 rpm) for 12 hours, and diluted 5 times after the filter, and assayed.

Example 4 Preparation of Grape Seed Extract

Grape seeds are prepared from whole pulverized grape seeds and pulverized grape seeds, and treated with a general heat heater at a temperature of 50, 100, 150, 200 ° C and 10, 20, 30, 40, 60, 90, 120 minutes per hour and 70%. Extracted with an ethanol solution in an incubator (room temperature, 100 rpm) 12 hours, and diluted 5 times after the filter assayed.

Experimental Example 1 Measurement of the Antioxidant Activity of Sesame Leaf Extract Obtained by Irradiation with Far Infrared Radiation Heater

Table 1 shows the results of investigating changes in antioxidant capacity by measuring total phenolic content, radical scavenging activity, and lipid peroxidation-induced time of sesame foil extracts obtained by treatment with far-infrared radiation heater. Changes in total phenolic content (TPC) increased sharply from 33.98 to 79.74 μM after 120 minutes of exposure to the far-infrared irradiated control. Radical scavenging activity (RSA,%) and lipid peroxidation inhibition induction time (IT) were also increased from 26.40% to 77.78% and 0.643 to 0.793 hours, respectively, in the extracts irradiated with far-infrared rays for 120 minutes. This result means that the far-infrared radiation heat treatment freely activated the phenolic compounds present in inert form in sesame foil.

Meanwhile, all the measurements of the following experimental examples of the present invention were repeated three times, and the results were tested for the mean and standard deviation using a SAS (Statistical Analysis System), and the Newman-Keul`s multiple range test (Newman-Keul`). s multiple range tests).

Table 1 Results of Antioxidant Activity of Methanol Extract of Sesame gourd

Note: a ~ e: significance of row (P <0.05, n = 3), x ~ y: significance of column, SEM: standard deviation

Experimental Example 2 GC / MS Analysis of Sesame Foil by Investigating Far-Infrared Radiant Heater

2 is a graph of the results of gas chromatograms (GC) for the methanol extract of sesame gourd. Meanwhile, the methanol extract of the sesame gourd was prepared by the method of Example 1. New phenolic compounds were detected in the sesame gourd extract treated with far-infrared rays, and it can be confirmed from Table 2 that the change in the content thereof was also significantly increased. Meanwhile, in FIG. 2 (A) is that the far-infrared non-treated peak numbers 1: p- hydroxybenzoic acid (p -hydroxybenzoic acid), 2: banil acid (vanillic acid), 3: p- Kumar acid (p -coumaric acid ), 4: isoferulic acid. (B) is 200 ℃ a peak to the number 1 for 30 minutes in a far infrared ray treatment: p- hydroxybenzoic acid (p -hydroxybenzoic acid), 2: o- Kumar acid (o -coumaric acid), 3: banil acid (vanillic acid ), 4: shows the iso-ferulic acid (isoferulic acid): p- Kumar acid (p -coumaric acid), 5.

[Table 2] Effect of Non-far-infrared or Far-infrared Irradiation through GC / MS on Major Phenol Components in Fat-derived Sesame Leaves

compound Non Far Infrared Treatment Far Infrared Treatment p-hydroxy benzoic acid 483 2842 o-comic acid 0 1233 Vanillic acid 4563 8899 p-comic acid 2371 25286 Isoferulic acid 3027 3437 Sum 10444 41697

Note) The numerical value indicates total ionized water * 10 ⁴

Experimental Example 3 GC / MS Analysis of Sesame Foil by Investigating Far-Infrared Radiant Heater

Table 3 shows the effect of heat or far-infrared treatment of peanut shell extract on the total phenolic content. Meanwhile, the peanut shell extract was prepared by the method of Example 2. As time passed, the content of phenol contained in peanut extracts treated with far infrared rays or heat treatment began to increase. On the other hand, treatment with far-infrared had more phenol content after a certain period of time than heat treatment.

[Table 3] Effect of Heat or Far Infrared Rays on Peanut Shell Extracts on Total Phenolic Content

Note: a ~ e: significance of row (P <0.05, n = 3), x ~ y: significance of column, SEM: standard deviation, unit: μm

Table 4 shows the effect of heat or far-infrared treatment of peanut shell extract on radical scavenging activity. As time passed, all of the experimental groups treated with heat or far infrared rays improved radical scavenging ability, but the radical scavenging ability was higher in the far infrared treated groups.

[Table 4] Effect of heat or far-infrared ray treatment on peanut scavenging activity of peanut shell extract

Note) a ~ e: significance of row (P <0.05, n = 3), x ~ y: significance of column, SEM: standard deviation, unit:%

Table 5 shows the effect of heat treatment and far-infrared treatment of peanut shell extract on reducing power. As time passed, the reducing power of the experimental group treated with far infrared rays was remarkable.

[Table 5] Effect of heat or far infrared ray treatment on reducing power of peanut shell extract

Note: a ~ e: significance of row (P <0.05, n = 3), x ~ y: significance of column, SEM: standard deviation, unit: absorbance

Experimental Example 4 Analysis of Increased Phenols of Peanut Shell Extract by GC / MS

Table 6 shows the types of phenols increased through GC / MS analysis. Three were compared: first, untreated, second, heat treated, and far-infrared. As a result of analysis, the new low molecular weight phenols were the highest in far-infrared treatment group. Especially, in case of 2-methoxy phenol, the treatment with far-infrared ray showed more than 8 times increase than untreated treatment. On the other hand it was confirmed that the general heat treatment can also produce phenol derivatives.

[Table 6] Types of Phenols Increased by GC / MS Analysis (150 ℃, 60min)

RT compound Total ionized water (* 10 ⁴ ) No treatment 4.23 2-methoxy phenol 217 7.24 2-methoxy-5-vinyl phenol 55 10.98 4-hydroxy-3-methoxy benzeneacetic acid 143 Heat treatment 7.24 2-methoxy phenol 253 9.12 4-hydroxy-3-methoxy benzaldehyde 197 10.95 4-hydroxy-3-methoxy benzeneacetic acid 168 11.77 4-hydroxy-3-methoxy benzoic acid 93 14.02 4-hydroxy-3-methyl benzacetic acid 120 Far Infrared Ray Treatment Zone 4.29 2-methoxy phenol 1736 4.33 2-hydroxy-4-methoxy benzoic acid 1617 7.24 2-methoxy-5-vinyl phenol 143 9.12 4-hydroxy-3-methoxy benzaldehyde 795 9.52 2,4-bis (1,1-dimethylethyl) phenol 446 10.98 4-hydroxy-3-methoxy benzeneacetic acid 115 11.06 Vanillyl alcohol 75 11.40 Methyl cinnamate 152

Experimental Example 5: Increased Antioxidant Effect of Citrus Peel Extracts

Table 7 shows the total phenolic content of the citrus peel extracts treated with far infrared rays. The extracts of the citrus peels were prepared by the method of Example 3. In the case of far-infrared treatment, the highest value was found within about 30 minutes.

Table 7 Measurement of total phenolic content by treating far citrus peel with citrus peel

Minutes 0 10 20 30 40 50 SEM TPC (μM) 71.9 ^d 62.8 ^e 116.0 ^c 133.9 ^a 132.3 ^b 117.5 ^c 0.5

Note) TPC: Amount of phenolic compounds such as tannic acid contained in 70% ethanol extract of citrus peel, a ~ e: Significance of row (P <0.05, n = 3), SEM: Standard deviation

Table 8 shows the effect of 70% ethanol extract prepared from far-infrared-treated citrus peel on radical scavenging activity. Similar to the phenol total amount measurement, the efficiency of the scavenging activity was the highest at around 30 minutes in radical scavenging.

[Table 8] Effect of far-infrared ray treatment on the radical scavenging activity of citrus peel extract

Minutes 0 10 20 30 40 50 SEM RSA (%) 29.64 ^f 16.69 ^e 42.07 ^d 51.27 ^a 50.30 ^b 47.68 ^c 0.15

Note) a ~ f: Significance of row (P <0.05, n = 3), SEM: Standard Deviation

Table 9 shows the effect of 70% ethanol extract prepared from citrus peel treated with far infrared rays on reducing power. As in the other experiments of Experimental Example 5, when the far-infrared ray was treated for 30 minutes, the reducing power was the highest. Therefore, in the case of citrus peel, it is most preferable to treat far infrared rays for about 30 minutes.

TABLE 9 Effect of Far-Infrared Irradiation on 70% Ethanol Extract Prepared from Citrus Peel

Minutes 0 10 20 30 40 50 SEM Reducing power 0.451 ^c 0.321 ^d 0.653 ^ab 0.675 ^a 0.637 ^ab 0.610 ^b 0.015

A) c: significance of horizontal rows (P <0.05, n = 3), SEM: standard deviation

Experimental Example 6 Increased Antioxidant Effect of Grape Seeds

Tables 10, 11 and 12 show the total phenol content, radical scavenging activity and reducing power of antioxidant activity according to the pulverized form of grape seed, roasting temperature and baking time using a heat heater. Meanwhile, the grape seed was prepared by the method of Example 4. In the experiment, the total phenolic content of the whole grape seed showed a significant increase of 0.575 mM in the 40 min treatment at 150 ° C. in the untreated 0.380 mM, and the pulverized grape seed had the highest temperature of 0.555 mM at the high treatment time of 100 ° C. for 10 minutes. The content increased. Even in the case of% radical scavenging activity, whole grape seeds increased from 83.91% up to 40 minutes at 150 ° C in 63.13% untreated, and increased to 82.94% after 10 minutes irradiation at 100 ° C in untreated 78.19%. appear. Reduction power was also increased, and whole grape seed showed the maximum increase from 0.866 at 100 ℃ 60 min at 0.766 to 0.865 at 40 ℃ at 150 ℃ without treatment.

[Table 10] Effect of heat treatment on total phenolic content according to the physical shape of grape seeds

Note) a ~ f: significance of row (P <0.05, n = 3), x ~ w: significance of column, SEM: standard deviation, WGSE (whole grape seed extract): whole grape seed, PGSE (powder grape seed): Crushed grape seeds

 [Table 11] Effect of heat treatment on radical scavenging activity according to the physical shape of grape seed

Note) a ~ f: significance of row (P <0.05, n = 3), x ~ w: significance of column, SEM: standard deviation, WGSE (whole grape seed extract): whole grape seed, PGSE (powder grape seed): Crushed grape seeds

[Table 12] Effect of heat treatment on reducing power according to the physical shape of grape seeds

Note) a ~ f: significance of row (P <0.05, n = 3), x ~ w: significance of column, SEM: standard deviation, WGSE (whole grape seed extract): whole grape seed, PGSE (powder grape seed): Crushed grape seeds

Experimental Example 7 GC Measurement of Grape Seed Ethanol Extract

3 is a graph showing the results of gas chromatograms (GC) of grape seed ethanol extract. As a result, it was confirmed that a lot of low-molecular phenols appeared through the heat treatment.

Meanwhile, in FIG. 3, (A) is a non-heated grape seed, and the peak numbers in the figure are 1: glycerol, 2: erythritol, 3: xylitol, 4: alpha-Arabinofuranoside, 5: 1H-indole-2-carboxylic acid, 6: 2-Azathianthrene, 7: Glucopyranose, 8: 6-methylthio benzoti 6-methylthio benzothieno quinoline, 9: Palmitic acid, 10: 2,2-[(1-methyl-1,2-ethane)] phenol (2,2, '-[(1 -methyl-1,2-ethane)] phenol), 11: 4-amino-2- (2-quinolyl) -5H- [1] benzopyran [3,4-C] pyridin-5-one (4- amino-2- (2-quinolyl) -5H- [1] benzopyran [3,4-c] pyridin-5-one), 12: linoleic acid, 13: stearic acid, 14: brown Lactofuranose (Galactofuranose), 15: Arabinofuranose (Arabinofuranose).

(B) is pulverized grape seed, 1: glycerol, 2: trimethyl silanol benzoate, 3: xylitol, 4: arabinofuranose, 5: 2- Azathianthrene, 6: Galactofuranoside, 7: Mannitol, 8: Glucopyranose, 9: 1H-indole-carboxylic acid (1H-indole-) 2-carboxylic acid), 10: palmitic acid, 11: 4-amino-2- (2-quinolyl) -5H- [1] benzopyran [3,4-C] pyridin-5-one (4-amino-2- (2-quinolyl) -5H- [1] benzopyran [3,4-c] pyridin-5-one), 12: linoleic acid, 13: stearic acid, 14: dibenzoazcyclodecane, 15: N-phenyl dibenzocarbazole, 16: hexaethyldisloxane.

(C) is the whole grape seed, 1: glycerol, 2: trimethyl silanol benzoate, 3: 1,2,3-benzenetriyltris silane (1,2,3-benzenetriyltris silane) ), 4: Xylitol 5: Arabinofuranose, 6: 2-Azathianthrene, 7: Azelaic acid, 8: 3,4-Dihydroxy 3,4-dihydroxy benzoic acid, 9: mannitol, 10: glucitol, 11: 6-methylthio benzothieno quinoline 12, o-cinnamic acid (o-Cinnamic acid), 13: Palmitic acid, 14: 4-amino-2- (2-quinolyl) -5H- [1] benzopyran [3,4-C] pyridin-5-one (4-amino-2- ( 2-quinolyl) -5H- [1] benzopyran [3,4-c] pyridin-5-one), 15: linoleic acid, 16: stearic acid, 17: dibenzazocyclodecane ( Dibenzoazcyclodecane), 18: beta-D-Galactofuranose (beta-D-Galactofuranose).

Experimental Example 8 Changes in the Contents of Catechins, Epicatechins, Caffeine, and Gallic Acid in Grape Seed Extracts by HPLC

Figure 4 shows the change of catechins, epicatechins, caffeine, gallic acid, etc. that grape seed is said to have excellent antioxidant capacity through HPLC. In the figure, except for EGC (epigallocatechin), all the contents were increased compared to the untreated group.

The present invention is an innovative invention that can develop agricultural processing by-products, which are unused resources, as natural antioxidants, which are high value-added products. Therefore, the recycling of waste resources provided the possibility of extending the use from animal feed or herbal medicine to functional food materials and functional cosmetics. It is a very useful invention in the food industry that aims to improve the functionality of herbal medicines and natural plant materials by securing natural source processing technology using far-infrared treatment and heat treatment.

Claims (5)

A method for producing a natural antioxidant extract, characterized in that by extracting the agricultural product by far-infrared or heat treatment by free activation of natural antioxidants. The method of claim 1, The agricultural by-products are sesame gourd, peanut peel, citrus peel, grape seed, characterized in that the production method of natural antioxidant extract. The method of claim 1, The heat treatment temperature is a method for producing a natural antioxidant extract, characterized in that 50 ~ 200 ℃. Natural antioxidant extracted by the method of any one of claims 1 to 3. The method of claim 4, wherein The natural antioxidants include p-hydroxybenzoic acid, o-comic acid, vanillic acid, p-comic acid, isoperulic acid, 2-methoxyphenol, catechin, epicatechin, caffeine, gallic acid and mixtures thereof. Natural antioxidants, characterized in that it contains a phenol derivative selected from the group consisting of.

Images