JP5000782B1 - Garlic crushed material, active oxygen scavenger, and method for producing garlic crushed material - Google Patents

Abstract

Disclosed is a crushed garlic having a high active oxygen scavenging ability, an active oxygen scavenger using the same, and a high active oxygen scavenging ability from raw garlic without going through a ripening process that has been indispensable for the production of black garlic. It aims at providing the method of manufacturing efficiently the garlic crush which has.
A garlic crushed product obtained by crushing garlic by steam explosion treatment, preferably a supernatant obtained by mixing 1 g of dried garlic product and 100 g of ion-exchanged water. It is a garlic crushed product having a total polyphenol content in the liquid of 0.2 g / L or more in terms of gallic acid equivalent.
[Selection] Figure 1

Description

  The present invention relates to a garlic crushed product, an active oxygen scavenger, and a method for producing a garlic crushed product. More specifically, the present invention relates to a garlic crush and an active oxygen scavenger having extremely high active oxygen scavenging ability, and a method for producing a garlic crush.

  Garlic is known to contain polyphenolic antioxidants. If you eat garlic that contains a lot of such antioxidants, garlic antioxidants are expected to prevent various lifestyle-related diseases such as arteriosclerosis by eliminating free radicals in the body. Has been.

  Conventionally, blackened aged garlic (referred to as black garlic) obtained by subjecting raw garlic to aged fermentation by the action of an enzyme is known. Such black garlic is known to contain more antioxidants than raw garlic.

  For example, Patent Document 1 below discloses a fermented black garlic extract produced by fermenting and aging raw garlic under conditions of a temperature of 55 to 80 ° C. and a humidity of 70 to 95% for 8 to 30 days.

  In order to produce black garlic, it was necessary to pass a long aging period, and there was a problem that productivity was low. In order to solve such a problem, for example, the following Patent Document 2 discloses that raw garlic and an enzyme containing cellulase or an enzyme containing cellulase and water, which are inserted and sealed in a flexible bag, Disclosed is a method for preparing an aged garlic extract by holding it at a pressure of 200 MPa within a range of 30 to 80 ° C. for 2 to 6 days, preferably 3 to 4 days. However, even the method disclosed in Patent Document 2 requires a aging period of about 2 to 6 days.

  By the way, when garlic is used as a component of health foods, it is usually pulverized or granulated using a miller, crusher, freeze pulverization method or the like. Specifically, for example, Patent Document 3 discloses as a crushing process, for example, a compression crusher such as a jaw crusher, a gyre crusher, and a cone crusher, a shear crusher such as a cutter mill and a shredder, an impact crusher such as a hammer crusher, Roll crusher such as roll crusher, rotary crusher such as disintegrator, cage mill, screw mill such as coffee mill, roll rolling mill such as edge runner, striking mill such as stamp mill, centrifugal roller mill, ball bearing mill, bowl mill, High-speed rotating mills such as roller mills such as Zegomir and Ong mills, swing hammer mills, pin mills, cage mills, turbo type mills, and centrifugal classification mills, rolling ball mills, vibratory ball mills, planetary ball mills, CF mills and other container vibratory mills, distribution pipes Milling, stirring tank mill, annular mill, airflow suction, airflow collision, collision plate collision, fluid bed type jet mill, grinding machine such as ultrasonic crusher, stone mill, mortar, etc. Etc. are disclosed. Patent Document 4 discloses producing black garlic pulverized material by pressurizing black garlic to about 200 ° C. while pressurizing to 5 to 60 MPa, and then instantaneously reducing the pressure to normal pressure. .

JP 2007-151436 A JP 2011-87540 A JP 2011-055811 A JP 2011-184281 A

  The present invention is a garlic crushed material having a high active oxygen scavenging capacity exceeding that of black garlic, an active oxygen scavenger using the same, and a raw garlic without going through a ripening step that has been indispensable for the production of black garlic. It aims at providing the method of manufacturing the garlic crushed material which has high active oxygen scavenging ability in a short time.

Garlic crushed material of the invention is a garlic crushed material was crushed broken by steam explosion processes Nin'ni click. Also, preferably, Drying and garlic crushed 1g and isolated from a mixture obtained by mixing the ion-exchanged water 100 g, 0.2 g in total polyphenols content of gallic acid equivalents in the supernatant / It is a garlic crush that is L or more . Conventionally, as described above, it takes a long time and labor to produce black garlic containing a large amount of an antioxidant. Moreover, even if it takes such a long time and effort, the active oxygen scavenging ability inherent in garlic has not been sufficiently extracted. On the other hand, as a method of pulverizing raw garlic, methods such as a miller, a mixer, a crusher and freeze pulverization were used, but the active oxygen scavenging ability of crushed garlic that was simply pulverized by such a method was Significantly lower than black garlic. The garlic crushed product of the present invention is a processed garlic product that sufficiently brings out the active oxygen scavenging ability of garlic, and it is extremely short from raw garlic without going through a aging process that takes a long time like when producing black garlic. Garlic crushed material having extremely high active oxygen scavenging ability over time can be produced. Moreover, since the garlic crushed material thus obtained can be produced in a short time, it can be preferably used as a low-cost active oxygen scavenger blended in health foods and pharmaceuticals.

  In addition, the method for producing crushed garlic according to the present invention includes a step of pressurizing raw garlic with saturated steam at a predetermined temperature for a predetermined processing time, and steam crushing garlic by instantaneously reducing the pressure of the pressurized garlic. And a step of allowing According to such a method, a garlic crushed product having high active oxygen scavenging ability can be produced in a short time. This mechanism is probably due to the high-temperature and high-pressure environment in the steam explosion process that allows water to sufficiently penetrate into the hard cell walls of raw garlic, and the garlic is cooked in the high-temperature and high-pressure environment, resulting in high molecular weight antioxidants in garlic. This is considered to be because the polyphenol component is hydrolyzed and converted into a lower molecular weight polyphenol antioxidant.

In the above production method, the conditions for the steam explosion treatment include the following formula (1):
S = Log [t · exp {(T−100) /14.75}] (1)
(T is processing time (min), T is temperature (° C))
It is preferable that the strength factor of steam explosion calculated from the above is a condition satisfying 3 or more. Further, the saturated steam pressure is 1 MPa or more and the treatment time is 5 minutes or more, or the saturated steam pressure is 3 MPa. It is preferable that the treatment time is 1 minute or longer from the viewpoint of obtaining a garlic crushed product having extremely high active oxygen scavenging ability.

  ADVANTAGE OF THE INVENTION According to this invention, the garlic crushed material which has high active oxygen scavenging ability can be provided. Moreover, such a garlic crushed product can be produced from raw garlic in a short time by a simple production process.

It is a schematic explanatory drawing of the steam explosion processing apparatus used by one Embodiment of this invention. In embodiments, an example of a graph used to determine free radical scavenging activity (EC _50). In embodiments, a plot of free radical scavenging activity (EC ₅₀₎ with respect to gallic acid equivalent. In embodiments, a plot of free radical scavenging activity (EC ₅₀₎ with respect to the strength factor S of steam explosion.

Hereinafter, an embodiment of the present invention will be described in detail.
The garlic crushed material in the present embodiment can be obtained, for example, by steam explosion treatment of raw garlic. The manufacturing method will be described below.

  The kind and production area of raw garlic used in the present embodiment are not particularly limited, and for example, garlic production areas such as Aomori Prefecture in Japan and raw garlic cultivated in China are used without particular limitation.

  In the production method of the present embodiment, raw garlic is subjected to steam explosion treatment to obtain a garlic crushed material. For example, as shown in FIG. 1, a steam explosion treatment apparatus 10 used for the steam explosion treatment includes a steam generator 1, a pressure vessel 2 provided with a heater 3, a steam introduction pipe 4, a product receiver 5, a coagulator 6, And valves V1 and V2.

  In the steam explosion process, first, for example, a plurality of raw garlic grains peeled off and housed in bunch are accommodated in a pressure-controlled container 2 controlled in temperature. Then, the valve V2 is closed, the valve V1 is opened, water vapor having a predetermined pressure and temperature is introduced into the pressure vessel 2 from the water vapor introduction pipe 4 connected to the water vapor generator 1, and then the valve V1 is closed. To do. As a result, the pressure in the pressure vessel 2 is increased by saturated steam and maintained as it is for a predetermined time. At this time, high-pressure water enters the garlic tissue. And after maintaining raw oil in this state for a predetermined time, the internal pressure in the sealed pressure-resistant vessel 2 is reduced by opening the valve V2 and, for example, reducing the pressure to atmospheric pressure. Due to the pressure difference, the water that has entered the tissue of raw garlic vaporizes and expands at once. And the raw garlic is crushed by the expansion force into juice. Then, the crushed juice-like garlic crushed material is received by the product receiver 5 connected to the pressure vessel 2. The water vapor discharged from the pressure vessel 2 to the product receiver 5 is cooled by the aggregator 6 and received by the product receiver 5. And the garlic crushed material remains in the product receiver 5.

  As the steam explosion treatment, the saturated steam pressure is preferably about 0.5 to 10 MPa, more preferably about 1 to 8 MPa. If the saturated water vapor pressure is too low, the temperature will not rise sufficiently, so it will take a long time to produce antioxidants and the garlic will not be sufficiently crushed. If the saturated water vapor pressure is too high Tend to have high energy costs. The saturated water vapor pressure and temperature can be converted. That is, when the saturated water vapor pressure is 0.5 to 10 MPa, the temperature is 151 to 310 ° C., and when the saturated water vapor pressure is 1 to 8 MPa, the temperature is about 180 to 295 ° C.

  The treatment time is preferably adjusted as appropriate depending on the saturated water vapor pressure to be treated. For example, it is preferable that the pressure is rapidly reduced after the steaming treatment is performed for 1 to 60 minutes, and further for 1 to 30 minutes. In the steam explosion process, it is preferable to select steaming conditions that are severe to some extent. The mechanism of antioxidant production of garlic fragments obtained by steam explosion treatment has not been elucidated at this time, but if the steaming conditions are too mild, the ability to scavenge active oxygen will be reduced Tend.

As the strength of the steam explosion process conditions, the following formula (1)
S = Log [t · exp {(T−100) /14.75}] (1)
(T is processing time (min), T is temperature (° C))
It is preferable that the strength factor (Severity factor) of steam explosion calculated from the above is 3 or more, more preferably 3.3 or more. By processing under such processing conditions, garlic crushed material having high active oxygen scavenging ability is generated. More specifically, the saturated water vapor pressure is 1 MPa or more and the treatment is performed for 5 minutes or more, or the saturated water vapor pressure is 3 MPa or more and the treatment for 1 minute or more has extremely high active oxygen scavenging ability. It is preferable from the point that a garlic crushed material is produced.

  In addition, in the thing which boiled raw garlic using the autoclave and grind | pulverized the obtained steamed material with the miller, as shown in the comparative example mentioned later, high active oxygen scavenging ability was not expressed.

The garlic crushed product thus produced has a high active oxygen scavenging ability. Specifically, for example, the supernatant liquid separated by filtering a mixed liquid obtained by mixing 1 g of dried garlic crushed material (dry weight, hereinafter also referred to as dry crushed material) and 100 g of ion-exchanged water is filtered. When the free radical scavenging ability (EC ₅₀ ) of 1,1-diphenyl-2-picrylhydrazyl (DPPH) is measured, it is 3000 μg / mL or less, further 1000 μg / mL or less, particularly 800 μg / mL or less. Is preferably 400 μg / mL or less. EC ₅₀ is an index used for evaluating active oxygen scavenging ability. The lower the EC ₅₀ , the higher the active oxygen scavenging ability. Further, a specific evaluation method is as follows.

A predetermined amount of garlic crushed material obtained by steam explosion treatment is freeze-dried to obtain a dried crushed material, and after thoroughly mixing 1 g of dried crushed material and 100 g of ion-exchanged water, the supernatant is separated by filtration. . Then, this supernatant is used as a sample stock solution, and a diluted solution of a predetermined concentration prepared from this sample stock solution is reacted with DPPH. Then, the absorbance at 517 nm of DPPH is measured, and DPPH with a known concentration measured in advance is measured. The relative value (%) with respect to the absorbance of the solution is calculated. Then, for example, as shown in FIG. 2, the relative value of the absorbance with respect to the concentration of a plurality of diluted solutions is plotted, a graph is drawn by drawing a straight line passing through each point, and the diluted solution when the relative value corresponds to 50% EC ₅₀ (50% effect concentration) is determined.

For example, when a raw garlic pulverized product obtained by pulverizing raw garlic with a miller or a mixer, which is a widely used garlic pulverization method, is used as a sample, as shown in a later example, Since the relative value of the absorbance of the DPPH solution never reached 50%, EC ₅₀ could not be calculated.

  The garlic crushed material obtained by steam explosion treatment of raw garlic described in this embodiment can exhibit a high active oxygen scavenging ability exceeding that of black garlic. Moreover, it can produce in a short time compared with manufacture of the black garlic manufactured through the aging process. Therefore, a garlic product having a high active oxygen scavenging ability can be produced at a low cost.

The garlic crushed material described in the present embodiment was separated from a mixed solution obtained by mixing 1 g of dried garlic crushed material and 100 g of ion-exchanged water, and 0.2 g / kg of gallic acid equivalent in the supernatant. When it contains L or more polyphenols, it exhibits extremely high active oxygen scavenging ability. Specifically, as shown in the graph of FIG. 3 to be described later obtained from Examples, when the supernatant contains polyphenols having a gallic acid equivalent of 0.2 g / L or more, the DPPH of the above-described supernatant is used. EC ₅₀ of about 1000 μg / mL or less. In the range of 0.2~1.6g / L as shown in FIG. 3, it is equivalent gallic acid amount is increased, EC ₅₀ has not changed significantly. From this, it is considered that the active oxygen scavenging ability of garlic can be maximized when the supernatant contains polyphenols having a gallic acid equivalent of 0.2 g / L or more.

  The total amount of polyphenols can be determined by the foreign thiocult method. Specifically, the following method is used. First, 1 g of dried garlic crushed material is collected in a test tube and mixed with 100 g of ion-exchanged water to obtain a mixed solution. And a supernatant liquid is isolate | separated by filtration from a liquid mixture. Then, 200 μL of the supernatant is taken, and 1 mL of the folin-thiocult-phenol reagent is added and stirred for 3 seconds. Thereafter, 1 mL of 10% aqueous sodium carbonate solution is added, and the mixture is stirred for 3 seconds and allowed to stand for 1 hour. The absorbance at 760 nm is measured with a spectrophotometer. Moreover, the light absorbency at the time of using deionized water instead of a supernatant liquid as a blank is measured. And the amount of total polyphenols is calculated from the standard curve calculated | required with the gallic acid solution, The gallic acid in the supernatant liquid isolate | separated from the liquid mixture obtained by mixing 1g of dried garlic crushed materials and 100g of ion-exchange water. Calculate the equivalent

  The garlic crushed material thus obtained remains in the form of juice, or even if the extract is taken out and used as an active oxygen scavenger, the garlic crushed material is dried and pasty or granulated to be active. It may be used as an oxygen scavenger. Further, such an active oxygen scavenger is used without particular limitation for the same use as that of a conventionally known garlic material. Specifically, for example, it can be preferably used as a material for garlic powder, garlic paste, garlic preparation, garlic-containing health food, and the like.

  Next, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited at all by the contents of the examples.

[Example 1]
Raw garlic was steam blasted using a steam blasting apparatus equipped with a steam generator, a pressure vessel, a steam inlet tube, a product receiver, an aggregator and the like as shown in FIG. The steam explosion treatment conditions were a saturated steam pressure of 3.0 MPa (temperature 234 ° C.), a treatment time of 10 minutes, and a strength factor S = 4.95. In this way, a garlic crushed material was obtained. And the free radical scavenging ability of the obtained garlic crushed material was measured by the following method.

The garlic crushed product was dried by a freeze dryer to obtain a dried crushed product. And after mixing 1 g of dry crushed materials and 100 g of ion-exchanged water, the supernatant was separated by filtration. This supernatant was used as a sample stock solution having a concentration of 10,000 μg / mL. Then, after reacting a diluted solution having a predetermined concentration prepared from the sample stock solution with DPPH, the absorbance of DPPH at 517 nm is measured, and the relative value (%) with respect to the absorbance of the DPPH solution having a known concentration measured in advance. ). Then, the relative value of DPPH radical scavenging ability with respect to a plurality of dilute solutions having different concentrations is plotted, a graph is drawn by drawing a straight line passing through each point, and EC is the concentration of the dilute solution when the relative value is 50%. ₅₀ (50% effective concentration) was determined. The EC ₅₀ was 178 μg / mL.

  Moreover, the gallic acid equivalent of the total amount of polyphenols in the supernatant liquid separated from the liquid mixture obtained by mixing 1 g of dried garlic crushed material and 100 g of ion-exchanged water was determined by the following method. . 1 g of dried garlic crushed material was collected in a test tube and mixed with 100 g of ion-exchanged water to obtain a mixed solution. And the supernatant liquid was isolate | separated by filtration from the liquid mixture. Then, 200 μL of the supernatant was taken, 1 mL of a forin-thiocult-phenol reagent was added, and the mixture was stirred for 3 seconds. Thereafter, 1 mL of a 10% aqueous sodium carbonate solution was added, and the mixture was stirred for 3 seconds and allowed to stand for 1 hour. The absorbance at 760 nm was measured with a spectrophotometer. Moreover, the light absorbency at the time of using deionized water instead of a supernatant liquid as a blank was measured. Then, the total polyphenol amount is calculated from the standard curve obtained with the gallic acid solution, and the gallic acid in the supernatant liquid separated from the mixed liquid obtained by mixing 1 g of dried garlic crushed material and 100 g of ion-exchanged water. The acid equivalent was calculated. As a result, the gallic acid equivalent was 1.41 g / L.

Table 1 shows the evaluation results of steam explosion conditions, EC ₅₀ and gallic acid equivalent.

[Examples 2 to 16]
A garlic crushed material was obtained and evaluated in the same manner as in Example 1 except that the steam explosion conditions were changed as shown in Table 1. The results are shown in Table 1. Further, in FIG. 2, as an example, shows a graph used to calculate the EC ₅₀ for Examples 3, 10 and 16.

[Comparative Example 1]
Instead of obtaining garlic crushed by steam explosion treatment of raw garlic, the garlic crushed was obtained and evaluated in the same manner as in Example 1 except that crushed raw garlic was obtained by pulverizing raw garlic using a miller. . The results are shown in Table 2.

[Comparative Example 2]
Instead of steam crushed raw garlic to obtain garlic crushed material, garlic was obtained by crushing raw garlic obtained by steaming raw garlic at 0.2 MPa (121 ° C) for 60 minutes using an autoclave, using a miller. A garlic crushed material was obtained and evaluated in the same manner as in Example 1 except that the crushed material was obtained. The results are shown in Table 2.

[Comparative Example 3]
Instead of obtaining raw garlic by steam explosion to obtain garlic crushed material, garlic was obtained in the same manner as in Example 1 except that garlic crushed material was obtained by pulverizing black garlic that had been fully aged for 30 days using a miller. Crushed material was obtained and evaluated. The results are shown in Table 2.

Here, a graph plotting the free radical scavenging activity (EC ₅₀₎ with respect to gallic acid equivalents in the embodiment in FIG. As shown in FIG. 3, Example 16 with a gallic acid equivalent of 0.08 g / L has an EC ₅₀ of 7444 μg / mL, whereas Example 15 with a gallic acid equivalent of 0.15 g / L has an EC of ₅₀ is 2150 μg / mL, and as the gallic acid equivalent increases, the ability to scavenge active oxygen is greatly reduced. However, in other examples in which the gallic acid equivalent exceeded 0.2 g / L, even when the gallic acid equivalent was significantly increased, the EC ₅₀ was not significantly reduced accordingly. Therefore, it can be seen that when the gallic acid equivalent exceeds 0.2 g / L, the active oxygen scavenging ability of garlic is extracted to the maximum.

On the other hand, as shown in Table 2, in the case of the garlic crushed material of Comparative Example 1 having a gallic acid equivalent of 0.028 g / L obtained by grinding raw garlic with a miller, the active oxygen scavenging ability is low. Thus, even a relative value of 50% was not obtained, and EC ₅₀ was not obtained. In addition, in the case of the garlic crushed product of Comparative Example 2 having a gallic acid equivalent of 0.035 g / L obtained by pulverizing a steamed product treated with a saturated water vapor pressure of 0.2 MPa using an autoclave, EC ₅₀ is 4412 μg / mL. Thus, a certain level of active oxygen scavenging ability was obtained, but a sufficiently high active oxygen scavenging ability was not obtained even after treatment for as long as 60 minutes. In the case of the garlic crushed material of Comparative Example 3 having a gallic acid equivalent of 0.153 g / L obtained by pulverizing black garlic obtained through a long aging step with a miller, EC ₅₀ is 902. It was 0.5 μg / mL, and some active oxygen scavenging ability was obtained.

Further, it shows a graph plotting the free radical scavenging activity (EC ₅₀₎ with respect to the strength factor S of steam explosion in the embodiment in FIG. From Table 1 and FIG. 4, in Examples 1 to 15 where the steam explosion treatment conditions are such that the steam explosion strength factor S described above satisfies about 3.2 or more, EC ₅₀ is about 2150 μg / mL. It was the following. Further, in Examples 1 to 9 where the saturated water vapor pressure of saturated water vapor is 1 MPa or more and the treatment time is 5 minutes or more, the gallic acid equivalent is 0.8 g / L or more, and EC ₅₀ is also 265 μg / L. It was less than mL and showed extremely high active oxygen scavenging ability. Furthermore, in Examples 12 and 13 where the saturated water vapor pressure of saturated water vapor is 3 MPa or more and the treatment time is 1 minute or more, the gallic acid equivalent is about 0.8 g / L or more, and EC ₅₀ is also 310 μg. / ML or less, showing extremely high active oxygen scavenging ability.

  The garlic crushed product obtained by the method for producing a garlic crushed product of the present invention can be preferably used as a garlic material blended in garlic products such as garlic powder, garlic paste, garlic preparation, and garlic-containing health food.

DESCRIPTION OF SYMBOLS 1 Steam generator 2 Pressure-resistant container 3 Heater 4 Steam introduction pipe 5 Product receiver 6 Coagulator 10 Steam explosion processing apparatus V1, V2 valve

Claims (8)

Garlic garlic crushed material characterized that you obtained by steam explosion process.   A total polyphenol content in a supernatant liquid separated from a mixed liquid obtained by mixing 1 g of dried garlic crushed material and 100 g of ion-exchanged water is 0.2 g / L or more in terms of gallic acid equivalent. 1. Garlic crushed material according to 1.   The garlic crushed material according to claim 1 or 2, wherein the garlic to be subjected to the steam explosion treatment is raw garlic. A reactive oxygen scavenger comprising the garlic crushed product according to any one of claims 1 to 3 or an extract thereof. Pressurizing raw garlic with saturated steam at a predetermined temperature for a predetermined treatment time;
And crushing the garlic with steam by instantaneously reducing the pressure of the pressurized garlic. The steam explosion process conditions are:
Following formula (1)
S = Log [t · exp {(T−100) /14.75}] (1)
(T is processing time (min), T is saturated water vapor temperature (° C))
The method for producing crushed garlic according to claim 5, wherein the strength factor of steam explosion calculated from is a condition satisfying 3 or more. The method for producing a garlic crushed product according to claim 5 or 6, wherein a saturated water vapor pressure of the saturated water vapor is 1 MPa or more and a treatment time is 5 minutes or more. The method for producing crushed garlic according to claim 5 or 6, wherein a saturated water vapor pressure of the saturated water vapor is 3 MPa or more and a treatment time is 1 minute or more.

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