KR101144992B1 - Detecting method of garlic in mixed seasoning - Google Patents

Abstract

PURPOSE: A method for verifying garlic in mixed seasoning is provided to prevent the inconsistent distribution of seasoning by discovering the false report of components contained in the seasoning. CONSTITUTION: Volatile components are collected from mixed seasoning using a headspace sampler. Whether the collected volatile components contain allyl sulfide or diallyl disulfide is verified by using a gas chromatography-mass spectrometer. When the headspace sampler is used, at least one solvent is selected from a sodium chloride aqueous solution, a potassium chloride aqueous solution, and calcium carbonate aqueous solution. The column of the gas chromatography is a capillary column. The mobile phase of the gas chromatography column is helium, and the flux of the mobile phase is 1ml/minute.

Description

DETECTING METHOD OF GARLIC IN MIXED SEASONING}

The present invention relates to a method for checking whether garlic is contained in a mixed seasoning, and more specifically, a headspace sampler and a gas chromatography-mass spectroscopy (GC-MS). It relates to how to easily check the presence of garlic in the mixed seasoning using.

Red pepper powder seasoning (also known as multi daegi) is a product with a large tariff difference depending on its composition, and is mainly imported as a powdered red pepper powder seasoning (aka dry) and paste type red pepper dae (aka wet).

The major components of the many atmospheres are red pepper powder, grain flour, garlic, onion, glucose and salt.

In the case of red pepper powder, UV-Vis can be used to directly analyze the content, and glucose (HPLC method), salt (potentiometric titration method) and grain meal (starch quantitative method) can be analyzed by instrumental or wet analysis.

However, garlic (raw garlic or garlic powder) and onion (fresh onion or onion powder), which are the main ingredients of the many atmospheres, do not yet have a method for analyzing the contents directly, so it is determined by indirect method to determine whether the contents are included. In most cases, the content of the data was recognized.

According to Articles 23 and 24 of the Korea Customs Service Notification No. 2010-129 on the Classification of Red Pepper Powders, Article 23 and Article 24 of the Tariff Act, “In the whole ingredient, garlic, leeks, onions, ginger, etc. At least two kinds of articles imparting characteristics should be mixed in an appropriate ratio and their weight ratio should be at least 10%. ” Should contain at least 8% by weight of spices or seasonings. ”

Therefore, qualitative and quantitative analysis methods of garlic and onion, which are mainly used as a spice of many waiting, should be prepared to determine whether or not it is a legitimate item in the standard notification.

Recently, customs have discovered that the customs manufacture a red pepper powder with a high tariff rate (270%) after drying it on the market after customs clearance at low tariff rate (45%). For example, after mixing only red pepper powder with water, customs may report that garlic or onions are also mixed and pass through customs at a rate of 45%.

In view of such a situation, the present inventors pay attention to the fact that garlic has a unique fragrance component, and then, a method of effectively measuring the fragrance component and a method for confirming the presence or absence of garlic based on the measured result are investigated and the present invention. Reached.

It is an object of the present invention to provide a method for easily checking whether or not garlic is included in a mixed seasoning using a headspace sampler and gas chromatography-mass spectrometry (GC-MS).

Garlic containing confirmation method of the mixed seasoning of the present invention,

The headspace sampler is used to collect the volatile components included in the mixed seasoning, and the gas chromatography-mass spectrometer is used to identify allyl sulfide or diallyl disulfide in the collected volatile components.

By using the method of confirming the presence of garlic in the mixed seasoning of the present invention, it is possible to confirm the presence of garlic in the mixed seasoning within a short time.

In addition, the use of the garlic seasoning method in the mixed seasoning of the present invention facilitates the detection of shippers who falsely declare the ingredients of the red pepper powder mixed seasoning in order to lower the tariff. There is an effect that can be blocked.

1 is a view showing the results of GC-MS measurement of raw garlic Examples 1-4.
Figure 2 is a diagram showing the results of GC-MS measurement of garlic powders 5 to 8.
Figure 3 is a view showing the results of GC-MS mixed seasoning Examples 9-13.
Figure 4 is a diagram showing the results of GC-MS mixed seasoning Examples 14-17.
5 is a graph showing the results of GC-MS measurement of pepper, grains, ginger, glucose, MSG, which are comparative examples.

The method of confirming the presence of garlic in the mixed seasoning of the present invention is to collect volatiles contained in the mixed seasoning using a headspace sampler, and allyl sulfide in the collected volatiles using a gas chromatography-mass spectrometer. (Common name Garlic oil)] or diallyl disulfide.

In the method of confirming the presence of garlic in the mixed seasoning of the present invention, the headspace sampler and the gas chromatography-mass spectrometer are connected to know the information of the unknown sample.

The headspace sampler is a device that can detect volatile organic compounds contained in complex samples composed of various compounds.

The principle of the headspace sampler is as follows: When the sample to be analyzed and the solvent which helps to move the volatiles in the sample are put into a vial and heated to a certain temperature, the volatile components in the sample are evaporated into the empty space of the vial. It exists as a phase. A certain amount of this evaporated gaseous phase is transported to GC to obtain information on volatiles with MS.

The solvent preferably used in the mixed seasoning method of the present invention in the presence of garlic is a solvent selected from the group consisting of an aqueous sodium chloride solution, an aqueous calcium chloride solution and an aqueous calcium carbonate solution. The solvent used more preferably is aqueous sodium chloride solution. This minimizes the generation of moisture and effectively transfers the volatiles to be measured from the sample into the gas phase due to the salting effect.

In the method of confirming the presence of garlic in the mixed seasoning of the present invention, the heating temperature when using the headspace sampler is preferably 40 ~ 50 ℃. If the heating temperature is less than 40 ℃ there is a problem that the component detection is not good, if the heating temperature exceeds 50 ℃ there is a problem that the excessive moisture is introduced into the column due to the large amount of water evaporation, causing cracks in the column.

In the method of confirming the presence of garlic in the mixed seasoning of the present invention, it is preferable that the column of the gas chromatography is a capillary column, the mobile phase is helium, and the flow rate of the mobile phase is 1 ml / min.

The temperature of the column in the present invention is characterized in that the temperature is raised for 20 to 35 minutes from 30 to 40 ℃ to 260 ~ 280 ℃.

In the method of confirming the presence of garlic in the mixed seasoning of the present invention, the retention time of allyl sulfide is 6 to 7 minutes. In addition, the residence time of diallyl disulfide is 12 to 13 minutes. That is, when garlic is contained in the mixed seasoning, allyl sulfide component is detected in 6-7 minutes, and diallyl disulfide component is detected in 12-13 minutes. By checking at least one of these two ingredients, it can be seen that the mixed seasoning contains garlic. Allyl sulfide and diallyl disulfide components may vary in intensity of the peak depending on the processing state of garlic.

In the present invention, the mixed seasoning can be used any mixture of ingredients used to enhance the taste of the food. That is, a mixed spice selected from red pepper powder, grain flour, garlic, onion, glucose, salt, sugar, soy sauce, pepper, sesame salt, broth, sesame oil, maltodextrin, MSG, and the like is available. However, the mixed seasoning used in the present invention is not limited to the above, and may be further included seasoning ingredients commonly used.

In particular, in the present invention, the mixed seasoning is preferably used red pepper powder seasoning. The red pepper powder seasoning is a red pepper powder seasoning or hot pepper paste preparation for making red pepper paste.

According to the current Korea Customs Service, red pepper powder mixed seasoning for red pepper paste manufacturing has red pepper powder weight ratio of 40% or less, and when meju powder is mixed with more than 16% by weight of all ingredients, the powdered powder, which is a glycosylating agent, is 13% or more by weight ratio. If meju powder is not mixed or is mixed at a weight ratio of 16% or less, the weight ratio of grain flour should be 25% or more, and the weight ratio of sugars (starch syrup, glucose, sugar) should be 4% or more.

According to the current Korea Customs Service notice, the red pepper stand has a weight ratio of 40% or less of all the ingredients, and two or more kinds of ingredients that give the characteristics of the stand, such as garlic, leeks, onions, and ginger, must be mixed in an appropriate ratio. The weight ratio of these sums shall be at least 10%. In addition, the weight ratio of salt in all components should be 20% or less, and the weight ratio of total moisture (including the water content of the raw material itself) in all components should be 45% or more.

Hereinafter, the method of confirming the presence of garlic in the mixed seasoning of the present invention through the following examples and test examples in more detail.

< Example  1-8>

A headspace sampler (Agilent G1888), a gas chromatography-mass spectrometer (Agilent 7890GC-5975MSD) were prepared and run under the conditions shown in Table 1.

G1888 Headspace 7890GC, 5975MSD Loop size 1 mL Injection temp 250 ℃ Vial pressure 10 psig Split ratio 2: 1 HS oven temp 50 ℃ Carrier flow 1 mL / min, Helium Loop temp 100 ℃ Oven temp 40 ° C 2min, 6 ° C / min 140 ° C,
40 ℃ / min 220 ℃, post 260 ℃ 2min Transfer line temp 120 DEG C Equilibration time 20 min Column Agilent 19091S-433
(30m × 250㎛ × 0.25㎛) Shake Low GC cycle time 30 min Scan 30-550 amu Pressurization time 0.2 min Source temp 230 ℃ Vent (loop fill) time 0.2 min Quad temp 150 ℃ Inject time 1 min

Four kinds of fresh garlic (Examples 1 to 4) and four garlic types (Examples 5 to 8) were prepared and used as a sample. 1 g of each sample was placed in a headspace measuring vial (20 mL), and 5 mL of saturated sodium chloride aqueous solution was added thereto, followed by homogeneous stirring and sealing.

1 and 2 shows the results of GC-MS measurement of fresh garlic of Examples 1-4 and garlic garlic of Examples 5-8. Examples 1-4 fresh garlic and Examples 5-8 garlic powder both showed peaks at residence times 6.41 and 12.17.

< Examples 9-17>

Mixed spices were prepared from the ingredients in Table 2 and were carried out in the same manner as in the above examples.

shape Constituent Example 9 Wet atmosphere 1 Red pepper 39.5%, garlic powder 5%, onion powder 7%, salt 2%, water 46.5% Example 10 Atmospheric atmosphere 2 Pepper 40%, Garlic 1%, Onion 1%, Salt 5%, Water 53% Example 11 Wet atmosphere 3 Hot pepper 40%, fresh garlic 1%, fresh onion 1%, salt 5%, water 53% Example 12 Atmospheric atmosphere 4 Hot pepper 40%, fresh garlic 3%, fresh onion 3%, salt 5%, water 49% Example 13 Atmospheric atmosphere 5 Hot pepper 40%, fresh garlic 5%, fresh onion 5%, salt 5%, water 45% Example 14 Atmospheric atmosphere 6 Red pepper 39.5%, fresh garlic 7%, fresh onion 5%, salt 0.5%, water 48% Example 15 Wait 1 Hot pepper 20%, garlic powder 3%, onion powder 3%, grain flour 65%, glucose 6%, salt 2%, MSG 1% Example 16 Waiting 2 Hot pepper 20%, garlic powder 5%, onion powder 5%, grain flour 65%, glucose 5% Example 17 Waiting 3 Red pepper 20%, garlic powder 1%, onion powder 1%, grain flour 65%, glucose 5%, salt 8%

3 and 4 shows the results of the GC-MS measurement of the mixed seasonings of Examples 9 to 17. Examples 9-17 mixed seasonings all showed peaks at residence times 6.41 and 12.17. Therefore, it was confirmed that the garlic ingredient is contained in the mixed seasoning example.

< Comparative example >

Red pepper, wheat flour, ginger powder, glucose, and MSG were used as a sample, and it carried out by the same method as Example.

Figure 5 shows the results of GC-MS measurement of red pepper, wheat flour, ginger powder, glucose, MSG. There were no peaks at residence times 6.41 and 12.17 in red pepper, grain flour, ginger powder, glucose and MSG. Therefore, it was confirmed that the garlic component was not contained in the material of the comparative example.

Specific embodiments of the present invention have been presented above, but the present invention is not limited to the above, and various modifications can be made within the technical spirit of the present invention, and such modifications will belong to the following claims.

Claims (9)

A headspace sampler is used to capture the volatiles contained in the mixed seasoning, and a gas chromatography-mass spectrometer is used to identify allyl sulfide or diallyl disulfide in the collected volatiles,
The solvent used when using the headspace sampler is at least one selected from the group consisting of aqueous sodium chloride solution, calcium chloride solution and calcium carbonate solution,
When using the headspace sampler, the heating temperature is 40 ~ 50 ℃ mixed seasoning, characterized in that the garlic containing method characterized in that. delete delete The method according to claim 1,
The gas chromatography column is a capillary column, the mobile phase is helium and the flow rate of the mobile phase is 1ml / min characterized by the presence of garlic in the mixed seasoning method. The method of claim 4,
The temperature of the column is 30 to 40 ℃ to 260 ~ 280 ℃ 20 to 35 minutes in the mixed season, characterized in that the temperature of the garlic containing method. The method according to claim 1,
The residence time of the allyl sulfide is 6 ~ 7 minutes characterized in that the garlic containing method in the mixed seasoning. The method according to claim 1,
The residence time of the diallyl disulfide is 12 ~ 13 minutes, characterized in that the garlic containing method of mixing seasoning, characterized in that. The method according to claim 1,
Wherein the mixed seasoning is a method of confirming the presence of garlic in the mixed seasoning, characterized in that the red pepper powder mixed seasoning for manufacturing red pepper paste. The method according to claim 1,
The mixed seasoning is a chili pepper waiting method for checking the presence of garlic in the mixed seasoning, characterized in that the atmosphere.

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