KR100913228B1 - Solid phase extraction method using Hanji adsorption Ssamjiwai used for volatile aroma component analysis - Google Patents

Abstract

The present invention relates to a Hanji adsorption swab used in the analysis of volatile aroma components and a solid phase extraction method using the same, which can be useful for extracting volatile aroma components from natural products in order to analyze volatile aroma (fragrance) components of a specific natural product. The present invention relates to a solid phase extraction method for extracting aromatic components from a natural product sample using Hanji adsorption swab and the Hanji adsorption swab made by adding an adsorbent to the inside of the bag.

According to the Hanji adsorption swab of the present invention and the solid phase extraction method using the same, it is possible to extract and analyze the components very economically in terms of cost by not using an expensive device such as a conventional SPME device, and in particular, Inexpensive solid-phase extraction media can be manufactured and used in large quantities, greatly reducing the cost of extracting components.

Natural product, Natural, Aroma, Fragrance, Hanji, Adsorption, Ssamzie, Solid phase, Extraction

Description

Korean Mulberry Paper Bag-Solid Phase Extraction for the Analysis of Volatile Aroma Components}

The present invention relates to a Hanji adsorption swab used for the analysis of volatile aroma components and a solid phase extraction method using the same, and more particularly, to extract volatile aroma components from natural products in order to analyze volatile aroma (fragrance) components of a specific natural product. The present invention relates to a solid phase extraction method for extracting an aromatic component from a natural product sample using a hanji adsorption bag which can be easily used, and the Hanji adsorption bag made by putting an adsorbent inside the bag.

Generally, fragrances of natural products in fields such as the discovery of new fragrance ingredients and new fragrance combinations, organic fragrance synthesis, food, medicine, cosmetics and disease treatment (Aromatherapy), improvement of daily necessities and varieties of natural plants. The technology of extracting and analyzing (Aroma) components is very important and high value technology.

Therefore, the development of new methods or devices that can efficiently and precisely extract and analyze volatile aroma components in natural products is very important.

Natural fragrances widely used in food, medicine, cosmetics, aromatherapy, household goods, etc. are mainly extracted and used by methods such as vacuum distillation, solvent extraction, and pomade method.

However, the conventional extraction methods, such as steam distillation method has the disadvantage of generating component changes and unstable decomposition products by pyrolysis and hydrolysis, and in the case of solvent extraction method, tissue components including toxic alkaloid components are extracted and mixed at the same time. Disadvantages and disadvantages of toxic organic solvent remain despite solvent removal after solvent extraction.

In addition, when using the pomade method, not only takes a long time, but also it is not easy to re-separate the aromatic component from the pomade again, and there is a disadvantage.

In addition, solid phase extraction (Solid Phase Extraction, SPE), solid phase micro extraction (SPME), solid phase trapping solvent extraction method (Solid Phase Trapping micro solvent Extraction) , SPTE).

Here, the solid phase extraction method (SPE) uses a solid phase extraction medium (Sepak C18 extraction tool) containing an adsorbent (C8, C18 silica particles), and the target component to be extracted is adsorbed and separated from the adsorbent. The solvent is extracted from the adsorbent by using a solvent, in which a large amount of solvent is used and there is a disadvantage in that it must be concentrated for analysis after separation.

In addition, the SPME is a method of adsorbing and desorbing a target component onto a fiber coated with an adsorbent on a thin pin surface inserted into a syringe needle, which is applicable to various samples and can be extracted in a short time. However, since the device is expensive and the needle-shaped adsorption medium breaks well, there are disadvantages in terms of cost, such as replacement after approximately 20 times of use.

Therefore, the present invention is invented in view of the above, by making a low-cost solid-phase extraction medium made by putting the adsorbent in a sheet of paper so that the components can be extracted using a simple tool such as adsorption vessel and syringe-type desorption vessel The purpose of the present invention is to provide a Hanji adsorption bag and a solid phase extraction method using the same, which can be used to analyze volatile aroma components, which can greatly reduce the cost of extracting components and reduce the amount of solvent used.

In order to achieve the above object, the present invention is used as a solid adsorption medium for extracting a volatile aroma component from a sample, and a solid state adsorbent capable of adsorbing the aroma component of the sample is placed on paper. By laminating Hanji so that the adsorbent is put inward, it provides Hanji adsorption swab used for volatile aroma component analysis, which is produced by folding the nested Hanji.

In a preferred embodiment, the adsorbent is placed on a rectangular hanji and folded to make the adsorbent inward to make the hanji long, followed by folding the elongated hanji twice at an angle, and further folding one end of the crossed hanji. It is characterized by being manufactured by sandwiching between the nested portion of the rear back.

In addition, after fixing one end of the connecting string to one side of the folded Hanji to put the adsorbent, it is characterized in that completed by attaching a display paper that can describe the necessary matters while acting as a handle on the opposite end of the connecting string.

In addition, the present invention, which is used as a solid adsorption medium for extracting the volatile aroma component from the sample, it is possible to adsorb the aroma component of the sample to the inside of the bag after making the paper in the form of a bag (bag) After inserting the solid adsorbent, it is characterized in that it is produced in the form of a tea bag (tea bag).

As a preferred embodiment, after fixing one end of the connecting string to one side of the paper-packed paper of the adsorbent is inserted into the handle, the end of the other side of the connecting strap is completed by attaching a label that can describe the necessary matters It is done.

On the other hand, the present invention, in the solid phase extraction method for extracting the volatile aroma component from the sample for analysis of the volatile aroma component contained in the sample, to prepare a Hanji adsorption swab made by putting a solid adsorbent inside the bag Steps; Placing the hanji adsorption swab in an adsorption vessel containing a sample and leaving the sample at the upper layer for a predetermined time so that the volatile aroma component of the sample is adsorbed to the adsorbent of the hanji adsorption swab; Remove the Hanji adsorption swab from the adsorption vessel, transfer it to the inside of the syringe-type desorption vessel, insert a very small amount of extraction solvent into the desorption vessel, and pressurize the extracting solvent. Characterized in that it comprises a step of extracting the solvent.

In a preferred embodiment, the step of extracting the solvent, using a syringe as the desorption vessel, putting a suction paper into the inside of the syringe, and then injecting a solvent for extraction and then pressurized with a plunger (pruner, syringe rod), It characterized in that the process of discharging the solvent containing the aroma component passed through the Hanji adsorption bag to the syringe outlet.

In addition, it is characterized by using petroleum ether (petroleum ether) as the extraction solvent.

According to the Hanji adsorption swab of the present invention having the above characteristics and the solid phase extraction method using the same, it is possible to extract and analyze components very economically in terms of cost by not using an expensive apparatus such as a conventional SPME apparatus, and in particular, an adsorbent. It is possible to use a large amount of low-cost solid-phase extraction medium made by putting in a paper can greatly reduce the cost of extracting the ingredients.

In addition, since a small amount of the solvent is put into the syringe and pressurized with a plunger, the solvent is extracted from the adsorbed component, thereby reducing the amount of solvent used compared to the conventional solid phase extraction method.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a Hanji adsorption bag and a solid phase extraction method using the same, which can be usefully used to extract volatile aroma components from natural products for analyzing volatile aroma (fragrance) components of a specific natural product.

1 is a view showing an embodiment of the hanji adsorption wrapper according to the present invention, Figure 2 is a view showing a process of making the hanji adsorption wrapper of Figure 1 by putting the adsorbent.

As shown, the volatile aroma component extracting Hanji adsorption sack paper (10a) according to the present invention is produced using a traditional domestic Hanji (韓 紙), an adsorbent (for example, 100mg, such as Tenax TA, Tenax GR, etc.) inside The Korean paper 12 is folded and made so that (13) is put.

At this time, as a preferred embodiment of folding the hanji, as shown in Figure 2, first put the adsorbent 13 in the center of the rectangular hanji (12), and then folded twice so that the adsorbent is put inside the hanji long nested To be in a state.

That is, the adsorbent 13 is placed between two imaginary side-by-side fold lines 12a on which the hanji 12 is folded, and the hanji is folded along the two fold lines so that the adsorbent is put inward to make it long.

Then, the long paper made of paper (12) is folded two times obliquely, and one side end of the crossed paper is further folded and sandwiched between the nested parts of the rear and fixed.

When the Korean paper is folded in this way, the Hanji adsorption wrapper 10a having the adsorbent 13 inserted therein is completed, and the end of the connecting string 14 is taped on one side of the Hanji 12 surrounding the adsorbent 13. After fixing by gluing or the like, the other end of the connecting string is attached to the display paper 15 which can describe the necessary matters while serving as a handle.

As the adsorbent in the Hanji adsorption bag according to the present invention 'Tenax TA' or 'Tenax GR' provided by the 'Supelco' company can be used.

These adsorbents are widely known as adsorbents useful for adsorbing volatile components including natural aromatic components.

FIG. 3 is a view showing another embodiment of the hanji adsorption swab according to the present invention, and shows a tea bag adsorption swab in the form of a tea bag made by adding an adsorbent to the inside of the bag.

Hanji adsorption wrapper (10b) of the present embodiment is made by folding the Hanji in the form of a bag, the adsorbent 13 inside the bag 11 made of Hanji and sealed.

Referring to a specific example, the embodiment of FIG. 3 is prepared by sealing two sheets of rectangular hanji and then folding the edge of one sheet of one sheet of paper and bonding it to the edge of the other sheet, the adsorbent 13 between the two sheets of Korean paper. Insert and seal to complete the Hanji adsorption wrapper (10b).

In addition, as described above, the connecting strap 14 is connected to one side of the bag 11 made of Hanji, which is made of the adsorbent 13 inside the bag, and serves as a handle at the end of the connecting strap 14 to describe necessary matters. The display paper 15 which can be attached is attached.

As described above for the hanji adsorption ssamji according to the present invention, it will be described for the method of extracting the volatile aroma component from the natural product sample using the following.

4A and 4B are diagrams illustrating an aroma component extraction process according to the present invention, and FIG. 4A illustrates the case of using the Hanji adsorption swab of FIG. 1, and FIG. 4B illustrates the use of the Hanji adsorption swab of FIG. 3. The case is shown.

First, the Hanji adsorption swabs 10a and 10b containing the adsorbent 13 are prepared, placed in the adsorption vessel 20 containing the natural product sample 1 to be analyzed, and then in a vacuum atmosphere in the adsorption vessel 20. It is left to the upper layer part of the sample 1 for about 60 to 90 minutes, and the volatile aroma component of the sample 1 is made to adsorb | suck to the adsorbent of Hanji adsorption bag 10a, 10b.

At this time, the suction paper (10a, 10b) in the suction paper (10a, 10b) while holding the display paper 15 by hand, the inside of the adsorption vessel 20, a portion of the connecting string 14 and the display paper 15 After coming out to close the cap 21 to seal the adsorption vessel.

When the adsorption is completed for a predetermined time as described above, take out the Hanji adsorption bag (10a, 10b) from the adsorption vessel 20 into the syringe-shaped desorption vessel 30, the extraction solvent is put into the desorption vessel (As an example, about 0.6mL), the aroma component is extracted by allowing the solvent to pass through the Hanji adsorption bag 10a, 10b at the same time as the plunger (syringe rod) 31 is pressurized.

As the detachable container 30, a syringe made of hard glass may be used, and when the solvent is extracted, the Hanji adsorption bag (10a, 10b) is put into the syringe 30, and the extraction solvent is put therein, and then the plunger 31 is inserted. Pressurize.

When the solvent containing the aroma component is discharged through the syringe outlet 30a while pressing the plunger 31 as described above, it is collected in a separate container such as a microtube 40, and then about 1 Small amounts of microliters can be directly analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), or various other analytical methods to precisely analyze volatile aroma components in natural products.

In this way, according to the Hanji adsorption bag and the aroma component extraction method using the same according to the present invention, it is possible to extract and analyze the components very economically in terms of cost by not using an expensive device such as a conventional SPME device, in particular Inexpensive solid-phase extraction media made of adsorbents can be manufactured and used in large quantities, thereby greatly reducing the cost of extracting components.

5 is a result of a screening experiment on the type and amount of the adsorbent in the Hanji adsorption bag to adsorb the volatile aroma component.

Four adsorbents Tenax TA, Porapak Q, Carbowax, and OV-1, weighing from 0.01g to 0.30g, were adsorbed to a standard concentration of 100 ppm of o-cymene (hereinafter referred to as standard solution). Peak area values were compared.

As a result, the two adsorbents of Carbowax and OV-1 had little adsorption force to the standard solution, so there was no mechanical response. However, Tenax TA and Porapak Q showed the most efficient adsorption of the aromatic components when the amount was 0.1g as shown in the graph. Among them, Tenax TA was confirmed to be the most effective as the adsorbent.

The extraction efficiency decreases when the amount of the adsorbent increases by more than 0.1 g because the amount of the solvent injected into the adsorbent itself decreases rapidly.

FIG. 6 shows an example of adsorption of a standard solution using three solvents, petroleum ether, methylene chloride, and chloroform, to extract the volatile aromatic components adsorbed. peak areas) were compared.

As a result, it was confirmed that petroleum ether was the most effective, and in the case of chloroform, the melting of the hanji and the adsorbent occurred, which was not suitable.

7 is a result of a screening experiment regarding the amount (mL) of the solvent for extraction injected into the Hanji adsorption bag to extract the adsorbed volatile aroma component.

In the volume of 0.5mL or less, the solvent penetrated into the Hanji adsorption sack was hardly extracted, and when confirmed in the volume of 0.6mL ~ 0.9mL it was confirmed that the most effective when extracted with 0.6mL.

At volumes above 0.6 mL, the aromatic components were diluted in the solvent, resulting in poor mechanical response, and above 0.9 mL there was no mechanical response.

8 is a screening experiment of temperature conditions for most efficiently adsorbing volatile aroma components.

As a result of adsorbing a constant standard solution at 30 ° C. to 60 ° C. for a certain time, it was confirmed that the most effective at 40 ° C.

At a high temperature of 60 ° C., moisture was filled inside the vial, which prevented the adsorption of the volatile aroma component, thereby degrading the mechanical response.

9 is an adsorption time screening experiment for most efficiently adsorbing volatile aroma components.

As a result of adsorbing a standard solution at 30 minutes, 1 hour, and 1 hour and 30 minutes, respectively, the adsorption time after 1 hour was higher than that of 30 minutes. It can be seen that there is almost no difference in the results.

10 is an experimental result comparing Jeonju-Hanji, Poongsan-Hanji, Poongsan-Oji, and China-Sunji to select Hanji for making Hanji adsorption paper.

Using a certain amount of the selected adsorbent to make the same Hanji adsorption swab was experimented under the same conditions.

As a result, it was confirmed that Jeonju-Hanji, Poongsan-Hanji, and Wind Oxidation Line were more effective than the Chinese Ship, and the most effective paper was Wind Oxidation Line, but had the disadvantage that it was easy to tear when using the thinnest paper.

11 is a graph of extracting and analyzing the fragrance components of bay leaf (Bay, Laurus nobilis L. ) using the extraction method according to the present invention.

Laurel leaves of the camphor tree (Lauraceae) are widely used as spices, tea, antibacterial, antioxidants, promotes appetite, removes fishy smell during cooking, and has the effect of antioxidants and preservatives.

After extracting the aromatic aroma component of the bay leaf using the Hanji adsorption ssam according to the present invention it was possible to directly obtain the GC-MS total ion chromatogram (Total Ion Chromatogram, TIC) without going through the concentration process.

Attached Figure 12 is the Korean Mint, Huoxiang, Agastache of Lamiaceae using the extraction method according to the present invention rugosa ) is a GC-MS TIC graph extracted from the fragrance components.

Attached Figure 13 is an octagonal fennel (Star anise, scientific name Illicium) using the extraction method according to the present invention verum Hooker fil . ) Is a GC-MS TIC graph obtained by extracting and analyzing the fragrance components.

Attached Figure 14 is a sign using the extraction method according to the invention (Amomum fruit, scientific name Amomum villosum ) is a graph extracting the fragrance components of the extract.

1 is a view showing an embodiment of the hanji adsorption swab according to the present invention,

Figure 2 is a view showing a process of making a hanji adsorption swab shown in Figure 1 by folding the adsorbent so that the adsorbent,

Figure 3 is a view showing another embodiment of the hanji adsorption paper according to the invention,

4a and 4b is a view showing the aroma component extraction process according to the present invention,

5 is a test result diagram according to the type and amount of the adsorbent in the Hanji adsorption bag;

Figure 6 is an experimental result showing the effect of the solvent used to extract the volatile aroma component adsorbed on the Hanji adsorption ssam

7 is a test result diagram according to the amount (mL) of the solvent for extraction to be injected into the Hanji adsorption bag to extract the volatile aroma components adsorbed on the Hanji adsorption bag

Figure 8 is a result of the temperature conditions for the most efficient adsorption of volatile aroma components on the Hanji adsorption swab according to the present invention,

9 is a result of the adsorption time for the most efficient adsorption of volatile aroma components on the Hanji adsorption swab according to the present invention.

10 is a test result diagram according to the hanji material for making hanji adsorption paper according to the present invention,

11 is a GC-MS TIC graph of an embodiment of extracting and analyzing the fragrance component of bay leaf using the extraction method according to the present invention,

12 is a GC-MS TIC graph of an embodiment of extracting and analyzing the fragrance components of the quarantine using the extraction method according to the invention,

13 is a GC-MS TIC graph of an embodiment of extracting and analyzing the fragrance component of octagonal fennel using the extraction method according to the present invention;

14 is a GC-MS TIC graph of the embodiment of the extraction analysis of the fragrance components of the signature using the extraction method according to the present invention.

<Explanation of symbols for the main parts of the drawings>

10a, 10b: Hanji adsorption wrapped paper 12: Hanji

13: adsorbent 14: connecting string

15: indicator 20: adsorption vessel

30: detachable container (syringe) 31: plunger

40: microtube

Claims (8)

It is used as a solid adsorption medium for extracting the volatile aroma component from the sample (1), and on top of the paper (12), a solid adsorbent (13) capable of adsorbing the aroma component of the sample is placed on top of Hanji adsorption sack paper used for volatile aroma component analysis, characterized in that the adsorbent (13) to be put inward and then folded to make a hanji in a folded state. The method according to claim 1, wherein the adsorbent 13 is placed on the rectangular hanji 12, and the hanji 12 is folded and made long so that the adsorbent 13 is put inward, and the long hanji is folded at an angle twice to cross. , Hanji adsorption sack paper used in the analysis of volatile aroma components, characterized in that by folding the one end portion of the crossed Korean paper and then sandwiched between the nested parts of the back. The method according to claim 1, after fixing one end of the connecting string 14 to one side of the Hanji 12 folded to be inserted into the adsorbent 13, the necessary information while serving as a handle on the opposite end of the connecting string 14 Hanji adsorption wrapped paper used in the analysis of volatile aroma components, characterized in that completed by attaching the display paper 15 that can be. Used as a solid adsorption medium for extracting the volatile aroma component from the sample (1), the solid phase adsorbent (13) capable of adsorbing the aroma component of the sample inside the bag after making Korean paper into a bag form Hanji adsorption sack paper used in the analysis of volatile aroma components, characterized in that it is produced in the form of tea bags after sealing. The method according to claim 4, after fixing the one end of the connecting strap 14 to one side of the bag 11 of the Hanji material into which the adsorbent 13 is inserted, and acts as a handle on the opposite end of the connecting strap 14 Hanji adsorption wrapped paper used for analysis of volatile aroma components, characterized in that completed by attaching a display paper 15 that can be described. In the solid phase extraction method for extracting the volatile aroma component from the sample (1) for the analysis of the volatile aroma component contained in the sample (1), Preparing hanji adsorption wrappers (10a, 10b) made by putting a solid adsorbent (13) inside the hanji (12) bag; The Hanji adsorption swabs 10a and 10b are placed in the adsorption vessel 20 containing the sample 1, and left in the upper portion of the sample for a predetermined time so that the volatile aroma components of the sample 1 are absorbed by the Hanji adsorption swabs 10a and 10b. Adsorbing to the adsorbent (13); Taking out the Hanji adsorption bag 10a, 10b from the adsorption vessel 20 and transferring it to the inside of the syringe-type desorption vessel 30 and putting the extraction solvent into the desorption vessel 30 and pressurizing it, the extraction solvent Solvent extraction of the aromatic components while passing through the Hanji adsorption bag (10a, 10b); Solid phase extraction method using a paper adsorption ssam paper comprising a. The method of claim 6, wherein the solvent extraction step, using a syringe as the detachable container 20, the hanji adsorption bag (10a, 10b) is put into the syringe and the extraction solvent is put in the plunger (31) Pressurizing to, and the solid phase extraction method using a hanji adsorption sack paper, characterized in that proceeding to discharge the solvent containing the aromatic component passed through the hanji adsorption sackcloth (10a, 10b) to the syringe outlet (30a). The method of claim 6, wherein the petroleum ether (petroleum ether) is used as the extraction solvent.

Images