KR101430638B1 - Fabrication Method of Extracting needle inserted a Metal Wire Coated with Adsorbent and In-Needle Micro-Extraction Method Using thereof - Google Patents

Abstract

The present invention relates to a method of preparing an injector for extraction in an injection needle by coating an adsorbent such as polyethylene glycol, polydimethylsiloxane or a mixture thereof on a surface of a fine metal wire with a specific thickness and length, And more particularly to a method of coating and curing an organic or inorganic substance adsorbent on the surface of a metal wire such as stainless steel wire or nichrome wire with a specific thickness and length, And then extracting, concentrating, refining, and injecting the sample prior to the gas chromatography (GC). In this method, the volatile components are saturated and adsorbed, , And since no extraction solvent is used at all, the toxic organic solvent It is eco-friendly because it does not have any exposure and waste generation and it does not need any separate equipment and equipment. It not only simplifies the scale of the experiment, but also greatly increases the extraction efficiency, reduces the extraction speed, reduces the economic cost, The present invention also relates to a method of preparing a needle which can be repeatedly used for analyzing composition components of various volatile samples such as solids and gases as well as liquid samples,

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of preparing an extractive injection needle containing a metal wire coated with an adsorbent and a method of extracting a micro-

The present invention relates to a method for producing an injection needle for extraction in an injection needle in which an adsorbent such as polyethylene glycol, polydimethylsiloxane or a mixture thereof is coated on the surface of a fine metal wire with a specific thickness and length, Thereby extracting the sample.

Many extraction methods are known for analyzing volatile components from analytical samples. Conventionally, solvent extraction has been widely used, and this method has been mainly applied prior to the separation step of GC or Gas Chromatography-Mass Spectroscopy (GC-MS). However, the above-mentioned solvent extraction method requires a relatively large amount of sample, and there is a problem that the concentration process is additionally required before GC analysis. In addition to the contamination of the instrument and the destruction, degradation and loss of the analyte, exposure to a large amount of toxic solvent A large amount of waste was generated and it took a long time.

For this reason, the development of new alternative methods has been required. One of them is solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE), which were introduced in the 1990s. Recent trends in analytical chemistry are to simplify, miniaturize, and automate sample preparation. Recently developed sample preparation techniques are being improved to reduce the amount of analytical sample, volume of extraction solvent, extraction time and cost. As a typical example, SPME and SBSE have a basic principle of using polydimethylsiloxane (PDMS) as an adsorbent, and it is important that they are detoxified without using an extraction solvent.

The application of adsorbents such as PEG and PDMS was first applied to the stationary phase of GC column, and it is mainly applied to adsorption fibers of SPME in pretreatment. In addition, PDMS is applied to a magnetic stirring bar to analyze volatile substances in liquid samples by SBSE sample pretreatment process. However, these analytical methods have some disadvantages. In case of SPME, separate expensive special assembly is required for analysis and expensive thermal desorption equipment for thermal desorption is needed. In addition, since the hardness is low, the adsorption fibers are liable to be damaged in the thermal desorption process and have a relatively short life span. Therefore, it is necessary to pay close attention to handling when extracting, and it is difficult to use it repeatedly many times because of lack of robustness. In the case of SBSE, it is not suitable for application to solid samples other than liquid samples. In addition, expensive thermal desorption equipment and separate parts are required as in SPME.

The inventors of the present invention have developed a method for extracting volatile compounds using a needle having a metal wire coated with an adsorbent.

Therefore, the present invention can be applied to various types of adsorbents in order to significantly reduce the amount of the sample, completely eliminate the amount of the organic solvent used for volatile component extraction, and reduce the extraction time and cost, And a method of manufacturing a special syringe inserted and inserted into a syringe needle.

It is an object of the present invention to provide a robust extraction method capable of efficiently adsorbing and desorbing various volatile substances using the syringe, capable of repeated use, and a robust extraction method.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention,

(i) mixing polyethyleneglycol (PEG) and polydimethylsiloxane (PDMS) base solution (A) with polydimethylsiloxane curing agent ratio (B) and coating the metal wire, heat resistant fiber or fine silica rod to cure; And

(ii) inserting the coated metal wire, fiber or fine silica rod into a stainless steel injection needle; Preparing an extraction needle;

The present invention also provides a method of manufacturing an extraction needle for analyzing a volatile component containing a volatile component.

According to another aspect of the present invention,

The injector needle manufactured by the extraction needle manufacturing method for analyzing the volatile components is connected to the long-desorption type gas-tight syringe barrel and the syringe barrel, and the vial containing the sample is sealed so that the sample is inserted into the metal wire, (PEG-PDMS) coated on a polyethylene glycol-polydimethylsiloxane (PEG-PDMS).

According to still another aspect of the present invention, there is provided a method of analyzing a sample, comprising the step of inserting a sample extracted using a microextraction method of a sample into an analyzer and analyzing the sample.

According to another aspect of the present invention, there is provided an injection needle for extracting a trace amount of a sample prepared through a method for preparing an injection needle.

The features and advantages of the present invention are summarized as follows.

(i) When the injection needle of the present invention is used, the extraction, concentration, purification, and sample injection are integrated into one process step before the GC process, and since no extraction solvent is used, exposure to toxic organic solvents and waste generation There is no environmentally friendly.

(ii) The method of extracting volatile compounds by using a syringe inserted with a metal wire coated with the adsorbent of the present invention inside the injection needle significantly reduces the amount of sample, completely eliminates the amount of organic solvent used for volatile component extraction, The cost can be reduced.

(iii) By using the injection needle of the present invention, it is possible to perform a very small amount extraction using a needle which can be repeatedly used for analysis of composition components of various volatile samples such as solids and gases as well as liquid samples.

(iv) Extraction method of the present invention is applied to various essential oils and spices, woods, superhomes as well as environmental samples, petrochemical samples, food samples, pesticide and fertilizer samples, medical chemical samples, biochemical samples and non- The analysis is possible with high efficiency and improved accuracy and accuracy.

Fig. 1 is a schematic view of a method of preparing an injection needle having a metal wire coated with an adsorbent thereon, and a method of extracting a very small amount of an injection needle.
2 is a photograph of a needle manufacturing process and a reciprocating piston in which a metal wire coated with an absorbent is inserted into a material used for making a needle.
3 is an enlarged photograph of a non-coated nichrome wire with a biomicroscope, Panel B is a photograph of a coated nichrome wire with a biomicroscope, and Panel C shows a PEG-PDMS coated surface with a scanning electron microscope (FE-SEM, Tescan, TUV Mira II - LMH, 50/60 Hz, 230 ~ 2200 VA), and panel D shows a photograph of the PDMS coated surface observed with a scanning electron microscope to be.
FIG. 4 shows the results of comparing the peak areas of the 10 target compounds in which the weight ratio of the PEG-PDMS mixed solution was changed to 0:10, 3: 7, and 5: 5. E: benzaldehyde, F: benzaldehyde, G: trans- cinnamaldehyde, H: benzyl acetate, I: linalyl, acetate, J: (+) - limonene, and K: β-caryophyllene.
FIG. 5 is a comparative chart of the peak areas of 10 target components while varying the coating length of the PEG-PDMS adsorbent to 5, 10, 15 and 20 mm.
6 is a comparative chart of the extraction efficiency according to the adsorption temperature in the WC-INME of the present invention.
7 is a comparative chart of the extraction efficiency according to the adsorption time in the WC-INME of the present invention. A and B are the results when the piston is used and C and D are the results when the piston is not used.
Figure 8 is a comparison of desorption efficiencies according to desorption temperatures in the WC-INME of the present invention.
9 is a comparative diagram of desorption efficiency according to desorption time in the WC-INME of the present invention.
10 is a comparative chart of the extraction efficiencies of the WC-INME method of the present invention in which citron essential oil samples are analyzed and the HS-SPME (red) and HS-INME methods using PDMS as an adsorbent. C: (+) - limonene, D: p-cymene, E: gamma-terpinene, F: terpinolene, G: linalool, H:? -Caryophyllene.
11 is a graph showing the results of measurement of A: essential oil of Yuza: Korean citron, Citrus inchangenius Swingle x C. reticulata Blanco, Jeollanamdo Agricultural Research and Extension Services, Najusi, Korea), B: Lavender Essential Oil (true lavender: Huile Essentielle de Lavande vraie, Lavandula angustifolia Miller, Distillerie Vallondes Lavandes, Sault, France) and C: Bulgarian rose perfume: Rosa Damasceina Mill, Lema, Kazanlak, Bulgaria) is a typical chromatogram obtained from the GC-FID analysis of Example 2. The peak numbers correspond to the peak numbers in Table 8.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention,

(i) mixing polyethyleneglycol (PEG) with polydimethylsiloxane (PDMS) base solution (A) and polydimethylsiloxane curing agent ratio (B) and coating the metal wire, heat resistant fiber or fine silica rod to cure; And

(ii) inserting the coated metal wire, fiber or fine silica rod into a stainless steel injection needle; Preparing an extraction needle;

The present invention also provides a method of manufacturing an extraction needle for analyzing a volatile component containing a volatile component.

In a preferred embodiment of the present invention, the weight composition ratio of the solution obtained by mixing the polyethylene glycol with the polydimethylsiloxane base solution (A) and the polydimethylsiloxane curing agent ratio (B) is 1: 10: 1 - 10: . More preferably, PEG and PDMS A and B are mixed at a weight ratio of 10: 10: 1 and then coated on a surface of nichrome wire, stainless steel wire or the like to have a specific thickness and length and cured. More specifically, PDMS is a polymer having ethyl-siloxane as a basic unit. The physical properties of the PDMS are shown in Table 1 below.

division Solution A (base) Solution B (curing agent) product name Sylgarg (R) 184 silicone elastomer kit Chemical classification Silicone compound Chemical name % (w / w) Chemical name % (w / w) Dimethylsiloxane,
dimethylvinylterminated > 60 Dimethyl, methylhydrogen siloxane 30 to 60 Dimethylvinylated and trimethylated silica 30 to 60 Dimethylsiloxane,
dimethylvinylterminated 10 ~ <30 tetra (trimethylsiloxy) silane <10 Dimethylvinylated and trimethylated silica 10 ~ <30 tetramethyl tetravinyl cyclotetrasiloxane <10 condition Liquid color Colorless smell slightly Boiling point > 100 ° C importance 1.11 1.03 Dynamic viscosity
(cSt) 5000 110

In a preferred embodiment of the present invention, the metal wire may be stainless steel or a nichrome metal wire, but is not limited thereto, and may be replaced with a heat resistant fiber, a fine silica wire, a glass fiber or a nanotube.

In a preferred embodiment of the present invention, the thickness of the coated polyethylene glycol-polydimethylsiloxane (PEG-PDMS) in step (i) is 10-50 μm and the coating length is 5-30 mm. More preferably, for example, a metal wire coated with a 10 mm long and 35 탆 thick metal wire is prepared as an injection needle and inserted into a stainless steel needle needle of a certain size, for example, 21 gauge or 39 mm long, So that an injection needle for extraction can be manufactured. The injection needle is inserted into the GC injection port at 250 ^° C for 30 minutes to remove impurities before use in the experiment.

In a preferred embodiment of the present invention, polyacrylic acid, polyacrylate, poly (phenyl dimethyl siloxane), and poly (vinylpyrrolidone) are added to polyethylene glycol-polydimethylsiloxane (PEG-PDMS) coated on the metal wires, Tenax TA, Tenax GR, Porapak N, Activated Carbon, Graphite, Graphite Carbon Black, Carbon Nanoparticles, Carbon Nanoparticles, Poly (styrene divinyl benzene), Tenax TA, It is also possible to use a variety of polymers such as graphene, florisil, zeolite, silica gel, fused silica, alumina, metal catalyst, polymeric polymer, octadecyl silane (ODS), monolithic material, molecularly imprinted polymer, polyurethane, cellulose, ion exchanger, The physicochemical properties of the compound to be analyzed by addition of the enzyme, the substrate, the antigen, and the antibody alone, or a mixture of two or more thereof, Depending on the chemical properties, polarity, reactivity to properly adjust the type and the amount of the adsorbent can be applied (modify).

According to another aspect of the present invention,

The injector needle manufactured by the extraction needle manufacturing method for analyzing the volatile components is connected to the long-desorption type gas-tight syringe barrel and the syringe barrel, and the vial containing the sample is sealed so that the sample is inserted into the metal wire, the heat resistant fiber, Or polyethyleneglycol-polydimethylsiloxane (PEG-PDMS) coated on a nanotube. The present invention also provides a method for extracting a trace amount of a sample to be analyzed.

In a preferred embodiment of the present invention, the sample to be adsorbed to the injection needle of the present invention is (-) - acetoxy-p-menthane, (+) - aromadendrene, 4-allyl veratrole, 4-allyl- 4-allylanisole, allicin, allyl, 4-aminobenzoic acid, acetaldehyde, acetic acid 2-ethylhexyl ester, acetic acid 2-phenylethyl ester, acetic acid benzyl ester, acetic acid isoamyl ester, acetic acid n-hexyl ester, acetoacetic acid n- anhydrous anisole, isoamyl alcohol, isoamyl amine, trans-anethole, anthracene, 2,3-benzanthracene, benzaldehyde, benzoic acid, anhydrous anisole, anisaldehyde, allyl sulfide, allyl n-propyl sulfide, cis-3-hexenyl ester, benzoic acid ethyl ester, benzoic acid methyl ester, benzoic acid, benzyl acetate, benzyl alcohol, benzyl methyl ether, benzene, bergamotene, borneol, bornyl acetate, butyl acetate, iso -butanal, iso - butylaldehyde, iso- butylamine, n-butyl alcohol, n-butyric acid ethyl ester, n-butyraldehyd (-) - (-) - carvone, (-) - n-butyric acid, n-butyric acid amyl ester, n-butanol, p-bromobenzyl bromide, p-bromophenacyl bromide, bromocresol green R) - (-) - citramalic acid, (S) - (+) - carvone, (-) - α-cubebene, (+) - 3-carene, , camphor, (+) - camphor, 1,3,5,7-cyclooctatetraene, 1,3,5-cycloheptatriene, 2-carene, 2-cyclohexane-1-one, cadaverine, caryophylleneoxide, choline, cineole , cinnamaldehyde, cinnamic acid benzyl ester, cinnamic acid cinnamyl ester, cinnamyl acetate, cinnamyl alcohol, citral, citronellol, citronellyl acetate, coumarin, crotonaldehyde, cuminaldehyde, curcumin, cyclohexane, cyclohexene, cyclohexanol, cyperene, D, caproic acid ethyl ester, n-capric acid isopropyl ester, n-capric acid methyl ester, n-caprylic acid ethyl ester, n-capronaldehyde, n-caprylaldehyde, n-caprylic acid isopropyl ester, trans -cinnamaldehyde, trans -cinnamic acid, α-caryophyllene, α-cyclodextrin, α-caryophyllene, β-caryophyllene, β-cyclodextrin, 1,3-dithiolane, 1,3-dithiolane, 1,4-dianobutane, 1,5-decadienes, 2,5-decadienes, dimethyl pyrazine, 2,5-dimethyl thiophene, 2,6-dimethoxy toluene, 2,6-di-tert-butyl-p-cresol, 2-dodecene-1-ylsuccinic anhydride, diallyl disulfide, diallyl trisulfide, diallyl tetrasulfide, dimethyl 2-decane, n-decane, n-dodecane, n-dodecane, trans-2,4-dicyclohexylamine, diethyl phthalate, dimethyl phthalate, eugenol acetate, eugenol methylether, n-eicosane, o-caprolactone, ethylbenzene, ethylene sulfide, ethylene chlorohydrine, eugenol, eugenol acetate, ethyl 2-methylbutyrate, farnesene, formic acid isoamyl ester, fusel oil, furfural, furfuryl alcohol, fluorobenzene, (-) - fenchone, (+) - fenchone, farnesol, p-ethylbenzaldehyde, ethyl vanillin, fatty acid methyl esters, 1-hexene-1-ol, cis-3-hexene-1-ol, cis-3-hexene- 1- cis-jasmone, lavandulol, lavandulyl acetate, cis-3-hexyl acetate, hexanal, n-heptadecane, n-heptyl aldehyde, hepenal, n-hexadecanol, 1-hexadecanol, indole, (+) - linalool, (-) - linalool, (-) - linalool, (+) - linalool, , laurinaldohyde, linalool, linalool oxide, linalool oxide, longifolene, (-) - menthol, (-) - p-mentha-1,5-diene, (+) - isomenthol, , 2-methyl pyrazine, 2-methyl-3-pentanol, 4-methoxycinamic acid, 5-methyl-2-furfural, 6-methyl-5-heptene- methyl n-caproate, methyl n-caprylate, methyl pelargonate, methyl phenylacetate, methyltrimethoxysilane, methyl propyl disulfide, methyl 2-propynyl sulfide, α-iso-methylionone, β-mycrene, (+) - neomenthol, n-octanol, n-octanol, n-octanol, n-octanol, n-octanol, n-octanol, n-hexanol, nerol acetate, neoclovene, nicotinic acid methyl ester, n-nonadecane, (1R) - (-) - α-pinene, (1S) - (-) - α-propanediol 2-phenylethyl alcohol (2), sec-phenethyl alcohol, 2-phenyl-ethylamine (2) N-propyl alcohol, o-phthalaldehyde, pelargonic acid ethyl ester, penta fluorobenzyl bromide, pentacene, n-propyl alcohol, propylene sulfide, (-) - α-phellandrene, β-phellandrene, phenol, poly (ethylene glycol), reserpine, salicylic acid, stearic acid, phenylacetic acid ethyl ester, phthalic acid, acid, succinic acid, sabi (Z) -β-cantalol, epi-β-cantalol, (E) -β-cantalol, santolina triene, styrene, sec, secene, salicylic acid methyl ester, α-santalene (-) - terpinen-4-ol, (+) - δ-tocopherol, 1-tetradecanol, 2-tridecanone, n- tricosane, triirane, iso-thymol, N, o-bis-TMS-trifluoroacetamide, n-tetradecane, n-tridecane, terpinolene, terpinyl acetate, toluene, thujone, thujene, thymol, thymoquinone, tyramine, , 2-undecanone, n-undecane , uraine, (1S) -cis-verbenol, iso-valeric acid ethyl ester, valeric acid, n-valeraldehyde, (+) - valencene, vanillin, vanilic acid, verbenone, 2-vinyl- 1,3-dithiine, 3-vinyl-1,2-dithiocyclohex-5-ene, (m) -xylene, (o) -xylene or (p) -xylene.

In addition, it can be applied to most polar and nonpolar materials, but it is most useful for volatile polar materials and is effective for analysis of alcohols, aldehydes and esters.

In a preferred embodiment of the present invention, the piston is compressed and adsorbed by moving the plunger up and down using a reciprocating piston to facilitate extraction and adsorption of analytical components in the step.

More specifically, the extraction needle is inserted into a syringe plunger made of a long-terminated gas-tight syringe barrel, for example, 1 mL of Hamilton 1001 N, Luer lock gas tight syringe barrel and polytetrafluoroethylene (PTFE, Teflon) . Teflon is effective in analyzing volatile samples because it does not adsorb organic materials and seals the syringe smoothly and tightly. For the extraction of the analytical components, a 50 mL vial containing 0.5 μL of essential oil is sealed with a mini-nut cap, and the needle is exposed to the upper part of the sample and the adsorption process is performed at 50 ^° C for 30 minutes. At this time, the reciprocating piston is used to move the plunger up and down to automatically extract and adsorb the analytical components present in the upper layer of the sample through the needle, thereby accelerating the extraction and adsorption process. It is preferable that the reciprocating speed of the piston is 180 reciprocations during an extraction time of 30 minutes at 6 cycles / min (10 s / cycle).

In a preferred embodiment of the present invention, the needle is exposed by exposing the upper layer of the sample, but is not limited thereto. For liquid samples in vials of varying volumes, they can be directly immersed in liquid samples.

In a preferred embodiment of the present invention, it is preferable to carry out the analysis characterized in that the adsorption temperature during the adsorption step is 30 to 70 ° C. More preferably at 40 - 60 &lt; 0 &gt; C.

In a preferred embodiment of the present invention, the adsorption time during the adsorption step may be in the range of 5 to 60 minutes. More preferably, the adsorption time is in the range of 20 to 40 minutes.

In a preferred embodiment of the present invention, the step of adsorbing and extracting the sample may further include the step of desorbing the adsorbed extracted sample to inject the sample component into the analyzer.

In a preferred embodiment of the present invention, the desorption temperature may be 150 to 300 ° C. and the desorption time may be 1 to 30 minutes in the step of desorbing the adsorbed sample.

More preferably, after the extraction process is completed, the needle is detached from the vial, replaced with a new syringe of the same product, immediately inserted into a GC or GC-MS inlet, and then detached at 240-250 ^° C for 2-5 minutes. The analytical components are injected and separated into the GC column simultaneously with the thermal desorption.

According to still another aspect of the present invention, there is provided a method of analyzing a sample, comprising the step of inserting a sample extracted using a microextraction method of a sample into an analyzer and analyzing the sample.

Analytical instruments are not limited to GC or GC-MS and can be used for fast GC, multidimensional GC, GC-olfactometry (GC-O), tandem MS, HPLC, ultra-HPLC, LC-MS, supercritical fluid chromatography ), capillary electrophoresis (CE), lab-on-a-chip, UV-visible spectrometer, atomic absorption spectrometry (AAS), inductively coupled plasma (ICP) And so on.

According to another aspect of the present invention, there is provided an injection needle for extracting a trace amount of a sample prepared through a method for preparing an injection needle. A schematic diagram of extraction analysis of essential oils using the extraction method using the extraction needles of the present invention is shown in FIG.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, and it is to be understood by those skilled in the art that the present invention is not limited thereto It will be obvious.

[ Example ]

(One) Example  1: coated with adsorbent Metal wire  Inserted Inject needle  Used Needle  Coated with an adsorbent for internal microextraction Metal wire  Inserted Needle  How to make

Using stainless steel injection needle (Edge Co., Korea, 21 gauge; 819 μm OD, 514 μm ID, 39 mm length) and nichrome wire (Teikoku Alloy Industry, Japan, 200 μm OD) A disposable stainless steel needle and a plastic syringe (Sofjec, Hwajin Medical Co., Ltd, Korea, 25 gauge, 25 mm length) were used to coat the nichrome wire with adsorbent material. The injection needle was connected to a plunger made of PTFE (polytetrafluoroethylene, Teflon) and a long-terminated gas-tight syringe barrel (1 mL Hamilton 1001N, luer lock gas tight syringe barrel).

Poly (ethylene glycol) (PEG) used as an adsorbent for coating was prepared from 50% (wt / wt) aqueous solution by purchasing 20,000 Number Average Molecular Weight from Aldrich (St. Louis, Mo., USA). Poly (dimethylsiloxane) (PDMS) was purchased from Dow Corning Inc. PDMS solution kit (Sylgard 184 Silicone Elastomer Kit) consisting of PDMS base solution A (Sylgard 184A) and curing agent solution B (Sylgard 184B) was purchased and used.

0.500 g of PEG 50% aqueous solution was weighed into a cleanly washed 5 mL vial, and 0.500 g of PDMS base solution A and 0.050 g of curing agent solution B were weighed in a weight ratio of 10: 1 and mixed thoroughly to obtain a 1: 1 (5: 5) ratio of PEG-PDMS mixed solution was prepared. The coated nichrome wire (200 μm OD) was straightened with a round pipe (6 cm OD, 15 cm length) made of stainless steel, cut into a length of 10 cm, wiped clean with methanol, and dried in a 100 ^° C oven Min to remove impurities. Disposable needles to fill the PEG-PDMS mixed solution were connected to the syringe barrel and the push rod, and the methanol was pulled up to the inside of the injection needle and released to remove the impurities inside the injection needle.

PEG-PDMS mixed solution was prepared by disposing a sterile steel disposable needle (25 gauge) with 1 mL of a disposable syringe made of plastic and immersing it in PEG-PDMS mixed solution for 15 seconds. I swallowed it into the needle. After 15 seconds, the injection needles and the syringe were separated, the injection needle filled with the PEG-PDMS mixed solution was set up vertically in the septum for GC, and the prepared nichrome wire was inserted into the center of the injection needle so that the adsorbent was coated Respectively.

After curing in a 100 ^o C oven for 15 minutes, the nichrome wire was carefully pulled out of the disposable needles and a metal wire coated with PEG-PDMS was prepared. The length of the PEG-PDMS coated on the nichrome wire was cut with a nipper so that the length was 10 mm, the length of the entire nichrome wire was cut to 39 mm so as to be equal to the length of a stainless steel injection needle (21 gauge, 39 mm length) The upper portion was rolled into a circular spiral coil so that the metal wire could be attached to the injection needle.

A nichrome wire with a thickness of about 35 μm was carefully placed in a stainless steel injection needle (21 gauge, 39 mm length) to fix the PEG-PDMS adsorbent. The materials used in the production of the needles and the manufacturing process are shown in Fig.

The thickness of the coated PEG-PDMS adsorbent is 35 μm, and a photograph of the PEG-PDMS adsorbent is shown in FIG. 3 through a biomicroscope and a scanning electron microscope. The coated nichrome wire was coated with an inverted microscope (IM, Nikon Eclipse, TS100) connected with a lens (Q-Emaging Micropublisher 3.3, 40 magnification) to confirm the thickness of the PEG-PDMS adsorbent coated on the nichrome wire No nichrome wires were compared. The surface of the adsorbent was analyzed using a field emission-scanning electron microscope (FE-SEM, Tescan, TUV Mira II - LMH, 50/60 Hz, 230-2200 VA) .

(2) Example  2: coated with adsorbent Metal wire  Inserted Inject needle  Extraction method

The injection needle prepared by the method of Example 1 was inserted into a GC injection port of 250 ^° C for 30 minutes to remove impurities before use in the experiment and then connected to a 1 mL long desorption type gas tight syringe barrel and a Teflon material bar . Teflon is effective in analyzing volatile samples because it does not adsorb organic materials and seals the syringe smoothly and tightly. For the extraction of the analytical components, a 50 mL vial containing 0.5 μL of essential oil was sealed with a mini-nut cap made of Teflon and the needle was exposed to the upper part of the sample and the adsorption process was performed at 50 ^° C for 30 minutes. At this time, by using a self-reciprocating piston as shown in FIG. 2, the analyzing components existing in the upper part of the sample are automatically sucked into the needle through automatic compression and suction by moving the plunger up and down Thereby promoting the extraction and adsorption process. The reciprocating speed of the reciprocating piston was 6 cycles / min (10 s / cycle) for a total of 180 revolutions over 30 minutes of extraction time. After the extraction procedure was completed, the injection needle was detached from the vial, replaced with a new syringe of the same product, immediately inserted into the GC inlet, and thermally desorbed at 240 ^° C for 2 minutes. The analytical components were separated and injected into the GC column simultaneously with the thermal desorption.

(3) Example  3: Example  Analysis of samples using 1 to 2 extraction procedures

Was prepared in the same manner as in Example 1, and analyzed using yuza essential oil, lavender essential oil, and rose perfume samples.

[Evaluation of physical properties]

1) gas chromatography ( gas chromatography , GC )

Optimization of the analytical method was performed using an HP 5890 (Hewlett-Packard GC) equipped with a flame ionization detector (FID) and an HP 3396A integrator. Optimization of analysis method The detailed analysis conditions of the GC used in the study are shown in Table 2 below.

GC  Operating conditions ( HP  5890)  column (DB-624, length 30 m x ID 0.25 mm x film thickness 1.4 m, J & W Scientific, Folsom, Calif., USA)  Oven temperature  50 DEG C (3 min) -5 DEG C / min-220 DEG C (10 min)  Injection temperature  240 ℃  Detector temperature  250 ℃  Split ratio  1: 30  Carrier gas N ₂ (99.99%) at a flow rate of 1.0 ml / min,  FID gas H ₂ at 30 ml / min, air at 300 ml / min

2) Gas Chromatography-Mass Spectrometry ( gas chromatography - mass spectrometry , GC - MS )

GC 2000 (Thermoquest-Finnigan, Austin, TX, USA) was used to qualitatively analyze the volatile flavor components of essential oils (GC-Q plus ion trap MS ⁿ ). Identification of aroma components was performed by comparing the mass spectra of the reference materials and the corresponding NIST and Wiley libraries. The detailed analysis conditions of GC-MS for qualitative analysis of volatile flavor components of essential oils are shown in Table 3 below.

GC - MS  Operating Conditions GC  ( Trace GC  2000)  column 6% cyanopropyl phenyl-94% -dimethylsiloxane copolymer (DB-624, length 30 m x ID 0.25 mm x film thickness 1.4 m, J & W Scientific, Folsom, CA, USA  Oven temperature  50 ℃  Injector temperature  240 ℃  Split ratio  1: 30  Carrier gas  99.999% He (at a flow rate constant of 1.0 ml / min) MS (a GC -A plus ion trap MS ⁿ )  Ionization voltage  70 eV  Transfer line temperature  230 ℃  Ion source temperature  200 ℃  Mass range (m / z)  50 to 500

(4) Comparative Example

One) Comparative Example  1: Extraction method of upper layer solid phase HS - SPME )

SPME parts and adsorption coated fibers were made by Supelco (Bellefonte, PA, USA), which is coated with 100 ㎛ PDMS (red). Before being used in the experiment, it was inserted into a GC injection part and heated at 250 ° C for 30 minutes to remove impurities to confirm that contaminated peaks appeared. As in Example 2, a sample of yuzu essential oil was taken in a 50 ml vial, sealed with a Teflon mini-cap, and left at 40 캜 for 30 minutes to adsorb a perfume component. At the end of the adsorption, the SPME fibers were taken out and immediately inserted into the GC-MS injection port and analyzed by thermal desorption for 1 minute.

2) Comparative Example  2: Micro Inner Turf  have PDMS Extraction Method of Needle in the Upper Layer of a Sample Using a Needle Filled with HS - INME )

200 μm diameter of the micro-bore tunnel before use in the experiment with the filled needles PDMS (ca. 106 μm thickness, l cm in length) with, after removing the impurities for 30 minutes heated at 250 ^o C, Chapter 1 mL A detachable gas-tight syringe barrel and a Teflon plunger. As in Example 2, the present invention was applied to the analysis of fragrance components of a small amount of citrus essential oil samples. A 50 mL vial containing 0.5 μL essential oil was sealed with a mini-nut cap, and the needle was exposed to the upper part of the sample, and saturation and adsorption process was performed at 50 ^° C for 20 minutes. At this time, using the reciprocal piston manufactured by the laboratory itself, the analytical components existing in the upper part of the sample were sucked into the needle to promote the extraction and adsorption process. After the extraction procedure was completed, the injection needle was removed from the vial, replaced with a new syringe of the same product, immediately plugged into the GC inlet, and desorbed at 240 ^° C for 2 minutes.

(5) Example  4: WC - INME  Optimization experiments for various parameters that can affect the analysis results

1) Suitable for analysis PEG - PDMS  Determination of weight ratio of mixed solution

FIG. 4 shows the results of experiments in which the weight composition ratio of the PEG-PDMS mixed solution was changed to 0:10, 3: 7, 5: 5 and 7: 3 in order to find the optimum composition ratio of the PEG-PDMS adsorbent. The peak areas of 10 target compounds were compared with those of benzaldehyde (log P _ow = 1.48) and (+) - limonene (log P _ow = 4.45) was the best detected, and benzyl acetate (log P _ow = 1.96) and linalyl acetate (log P _ow = 3.93) were best detected at 3: 7. However, when the PEG-PDMS mixed solution has a composition ratio of 7: 3, it has a disadvantage that the coating on the nichrome wire is not well performed. This is because PEG has a property of being rapidly liquefied at room temperature when it is used alone without being mixed with PDMS see. Therefore, in the case of the 7: 3 mixed solution containing a large amount of PEG, it was difficult to produce a coating metal wire because the coating metal wire could not be hardened sufficiently to produce a coating metal wire. PEG-PDMS composition ratio of the mixed solution was 5: 5 in the case _{linalool (log P o / w =} 2.97), β-phenethyl alcohol (log P o / w = 1.36), eugenol (log P o / w = 2.27), trans ( P _{o / w} = 1.90) and β-caryophyllene (log P _{o / w} = 6.30) showed the largest peak area of all five components. Can be detected, and it can be confirmed that the peak areas of the other five components are also substantially large. The large peak area means that the sensitivity is high and the affinity of the polar material PEG and the analyte is high. The octanol / water partition coefficient ( P _{o / w} ) is generally used to evaluate the partition coefficient ( P _{PDMS / w} ) of the analytical target component between the aqueous solution and the PDMS coating layer as P _{o / w} P _{PDMS / w} . Therefore, analytes with large P _{o / w} can be said to be more distributed to non-polar PDMS. Therefore, the PEG-PDMS adsorbent has the highest sensitivity for the analysis of 5 of the 10 components when the composition ratio of the adsorbent is 5: 5. Therefore, it is most suitable for extracting analytes of a specific category such as alcohol, aldehyde, I decided it was a composition rate.

2) Suitable for analysis PEG - PDMS  Judging coating length of mixed solution

When the WC-INME method of the present invention was used, the coating length of the PEG-PDMS mixed solution was measured by changing the coating length of the PEG-PDMS adsorbent to 5, 10, 15, and 20 mm. The experimental results are shown in Fig. The peak areas of 10 target substances were the highest at 10 mm, and the standard substances of alcohol type such as benzyl alcohol, linalool, β-phenethyl alcohol and eugenol show a drastic decrease in peak area as the coating length increases . This means that as the coating length increases, more extraction time and higher extraction temperature are required. That is, the most important parameter for performing this analysis method is the kind, length, and thickness of the adsorbent.

Therefore, the length of PEG-PDMS adsorbent for HS-WC-INME was chosen as 10 mm.

3) Determination of extraction efficiency according to adsorption temperature and adsorption time

Comparison of extraction efficiency according to the adsorption temperature when using the WC-INME method of the present invention is shown in FIG. 6 in a temperature range of 30 ^o C to 70 ^o C. And the largest peak area at 50 ^° C. It can be seen that the extraction efficiency decreases drastically at 60 ^o C and 70 ^o C in all 10 components because the adsorbed analytical components are back extracted by high temperature.

The effect on the adsorption time was evaluated in the range of 5 minutes to 40 minutes and is shown in FIG. The adsorption time is related to the number of reciprocating movements of the piston. The time taken for the piston to reciprocate once was set to be 10 seconds, that is, 6 times per minute. As a result of the experiment with the adsorption time changed at 50 ^o C, it was confirmed that the nine components except linalyl acetate were detected most at 30 minutes (180 reciprocations). It can be seen that the analytical components reached equilibrium between the PEG-PDMS adsorbent and the sample upper layer during the adsorption time of 30 minutes. The peak area decreases after 30 min, which is probably due to the fact that the extraction time in the HS extraction method does not depend on the concentration of the analyte in the sample. FIGS. 7-C and D show the results of the extraction efficiency according to the use of the piston during the same adsorption process without using the piston in the same time range. It can be confirmed that the peak area is reduced to about 50 times as compared with Figs. 7-A and 7-B. It was confirmed that the use of the reciprocating piston is very important to reduce the adsorption time and increase the extraction efficiency.

Therefore, the optimal adsorption temperature and adsorption time for WC-INME were selected to be 50 ^° C and 30 minutes (180 times), respectively.

5) Determination of optimum condition of adsorption temperature and desorption time

Selection for the desorption conditions were evaluated through a first peak area obtained by the second desorption A _d1 and two desorption efficiency as shown in the following formula 1 using the peak area A _d2, obtained by the second desorption (desorption efficiency,%) calculated.

[Formula 1]

Desorption efficiency  (%) = { A _d1 / ( A _d1 + A _d2 )} X 100

When the desorption efficiency reaches 100%, it can be said that all of the adsorbed components are desorbed and can be the ideal conditions. After the adsorption process at 50 ^° C for 30 minutes, the desorption temperature was tested by desorption at 150 ^° C to 250 ^° C for 2 minutes. As a result, as shown in FIG. 8, it was confirmed that the four components of the alcohol type were desorbed at 240 ^° C. and 2 minutes to 100%, indicating reproducible desorption efficiency. However, trans- cinnamaldehyde among the six components showed 96 and 95% desorption efficiency at 240 ^° C and 250 ^° C, respectively, so that about 4 to 5% of the trans- cinnamaldehyde remained in the needle. Therefore, after the desorption, the injection needle was heated at 250 ^° C for 30 minutes to remove the trans- cinnamaldehyde present in the needle.

In addition, FIG. 9 shows the results of experiment on the desorption time while changing the temperature from 240 ^o C to 0.5, 1, 2, and 3 minutes. As at the desorption temperature, the four components of the alcohol species can be seen to reach equilibrium at two minutes. The remaining 6 components also reached equilibrium at 2 min, whereas trans- cinnamaldehyde showed 96% desorption efficiency at 2 min and 3 min.

Therefore, the optimal desorption temperature and desorption time were selected to be 240 ^° C and 2 minutes, respectively.

(6) Example  5: Verification of analysis method after optimization experiment

After the optimization experiment, the preparation of the calibration curve, the detection limit, and the quantitation limit were verified to evaluate whether the designed HS-WC-INME method is an appropriate method for analyzing the aroma components of the essential oil. Correlation coefficient ( r ² ) of all 10 components showed excellent linearity with a value of 0.98 ~ 0.99. The detection limit and the quantitation limit were calculated as 3 s / m and 10 s / m , respectively, using the standard deviation ( s ) of the peak area and the slope of the calibration curve ( m ) from the lowest concentration of the 7 concentrations . The detection limits obtained from the experiments ranged from 1.3 ng to 17.9 ng. The limits of quantification ranged from 4.5 ng to 59.7 ng and the linear range ranged from 4 ng to 450,000 ng.

Calibration curve No. Compounds Equation r ² LOD LOQ Dynamic range (ng) A Benzylalcohol y = 19.6 x + 4495.6 0.990 2.4 8.1 8 ~ 225,000 B Linalool y = 89.0 x + 4307.1 0.998 9.1 30.3 30 ~ 200,000 C β-Phenethylalcohol y = 19.7 x - 1575.0 0.996 1.3 4.5 4 ~ 275,000 D Eugenol y = 19.0 x + 1373.2 0.992 8.9 29.7 30 ~ 175,000 E Benzaldehyde y = 26.2 x + 781.1 0.996 6.2 20.8 21 ~ 300,000 F trans- cinnamaldehyde y = 31.2 x + 2183.5 0.988 16.1 53.7 54 ~ 200,000 G Benzylacetate y = 64.4 x - 3744.9 0.999 8.2 27.2 27 ~ 200,000 I Linalylacetate y = 13.6 x + 591.9 0.994 17.9 59.7 60 ~ 325,000 J (+) - Limonene y = 19.5 x + 3318.7 0.995 7.6 25.3 25 ~ 450,000 K β-Caryophyllene y = 86.8 x + 2696.0 0.999 1.8 5.9 6 ~ 325,000

The accuracy shown in the following Tables 5 and 6 was performed through the standard addition method. The recovery was obtained by adding 0.5 μL of citron essential oil, lavender essential oil and standard solution (absolute amount: 10 μg, 100 μg) known to the concentration of rose perfume. When 10 μg was added, it was 95.6% ~ 111.8% % And 100 μg, respectively, the results were excellent in the range of 89.7% ~ 101.7%. The relative standard deviation (RSD%) was calculated by measuring intraperitoneal (run to run) and inter assay (needle to needle) precision of the essential components of citron essential oil and lavender essential oil, respectively. As a result, the RSD% value of the intra-assay (run to run) between the same injection needles was 1.9% or less. In the inter assay (needle to needle) experiment comparing 5 different injection needles, 3.2 % To 7.2%.

Recovery% (mean ± RSD%, n = 3) Sample Compounds 10 μg spiked (lower level) 100 μg spiked (upper level) Yuza Linalool 101.9 ± 6.7 101.7 ± 6.5 (+) - Limonene 111.8 ± 9.9 98.7 ± 1.0 Lavender Linalyl acetate 107.4 ± 9.1 89.7 ± 8.5 Rose β-Phenethylalcohol 95.6 ± 2.6 98.6 ± 3.5

Reproducibility% (RSD%, n = 10) Sample Compounds Intraassay
(run to run, n = 10) Interassay
(needletoneedle, 5 needles x 10 measurements) Yuza Linalool 1.9 3.2 (+) - Limonene 1.9 4.1 Lavender Linalool 0.9 3.9 Linalyl acetate 0.8 7.2

Among the existing analytical methods used for the analysis of volatile aroma components, the extraction efficiencies of the HS-SPME (red) and HS-INME methods using PDMS as adsorbents and the WC-INME method were compared. For each method, 0.5 μL citron essential oil was analyzed under optimized conditions, and the peak area and enrichment factor ( EF ) for the characteristic eight components were calculated and compared. The concentration factor is an indicator of the degree to which the analytical components volatilized into the upper layer of the sample are concentrated in the adsorbent through the pretreatment process. The concentration factor can be calculated by the following equation, and the larger the value, the greater the extraction efficiency.

EF = A ₁ / A ₀

Where A ₁ is the peak area of the analytical components obtained by the WC-INME, HS-SPME, and HS-INME methods, and A ₀ is the peak area of the analytical components obtained by the static HS method. For the Static HS method, 10 mL of Hamilton 1010RN gas-tight syringe (Supelco) was used to collect the analytical components from the upper layer of the vials saturated with 0.5 μL citron essential oil and injected into the GC inlet. The calculated enrichment factors are shown in Table 7 below, and the comparison results through the absolute peak area obtained from GC-FID are shown in FIG.

Peak
No. Components Enrichmentfactor ( EF )
(mean ± RSD%, n = 3) HS-WC-INME HS-INME
(PDMS, tunnel) HS-SPME
(PDMS, red) A α-Pinene 4.62 ± 5.16 3.53 ± 2.68 2.09 ± 2.15 B α-Phellandrene 6.41 + - 6.08 6.23 ± 3.64 6.24 ± 0.61 C (+) - Limonene 38.91 + - 0.99 37.72 ± 2.03 33.99 + - 3.01 D p-Cymene 46.01 + - 1.62 40.18 + - 3.50 37.04 + - 2.60 E γ-Terpinene 8.72 ± 1.36 7.82 + - 1.23 7.40 ± 2.59 F Terpinolene 12.18 + - 4.55 12.21 + - 0.83 10.07 ± 1.60 G Linalool 57.47 ± 3.78 44.67 ± 3.66 54.45 + - 8.13 H β-Caryophyllene 24.39 ± 2.17 20.08 + - 9.56 35.84 + 1.42

α-pinene, α-phellandrene, (+) - limonene, ρ-cymene, γ-terpinene and terpinolene showed similar or slightly higher extraction efficiencies than the HS-INME and HS-SPME methods in the WC-INME method. This is due to the increase of the sample capicity due to the increase of the porosity that can adsorb volatile aroma components due to PEG. linalool showed higher extraction efficiency than HS-INME method using HS-SPME method and showed the highest extraction efficiency in WC-INME than both methods. This means that linalool with high polarity is extracted most efficiently in the WC-INME method which can extract polar substances more effectively by mixing PEG with polarity higher than PDMS than HS-INME, HS-SPME method consisting of PDMS only. β-Caryophyllene showed the highest extraction efficiency in the HS-SPME method because the WC-INME method requires a passive adsorption process by a reciprocating piston, so that it is relatively light and has a boiling point lower than the boiling point. This is considered to be an effective extraction method. Therefore, β-caryophyllene with a high molecular weight and high octanol / water partition coefficient ( P _{o / w} ) and a high boiling point seems to be the best extracted from HS-SPME.

The results of the GC-FID analysis of Example 2 in which citron, lavender essential oil and rose perfume samples were analyzed using the WC-INME method of the present invention are shown in FIG. The GC-FID analysis results of Comparative Examples 1 and 2 in which citron samples were analyzed using the HS-INME and HS-SPME methods of the prior art are shown in Table 8 below.

Peak
No.        Compounds Normalized peak area%
(mean ± RSD%, n = 3) Yuza oil Lavender oil Rose perfume One Thujene 0.11 + - 0.64 - - 2 α-Pinene 0.38 ± 1.16 tr - 3 β-Pinene 0.11 ± 5.31 tr - 4 β-Myrcene 1.54 + - 5.22 13.85 ± 2.59 - 5 3-Octanone - 0.41 ± 18.08 - 6 Benzaldehyde - - 0.54 + - 5.36 7 α-Phellandrene 0.30 ± 1.62 - - 8 α-Terpinene 0.16 + - 4.78 - - 9 β-Phellandrene - 7.27 ± 6.67 - 10 (+) - Limonene 72.87 ± 1.48 - 0.44 0.43 11 p-Cymene 2.95 + - 4.50 - - 12 Cineol - 11.71 + - 7.92 - 13 Ocimene 0.32 ± 3.07 - - 14 γ-Terpinene 9.24 + - 4.52 - - 15 Terpinolene 0.61 + - 4.76 - - 16 Linalool 3.54 + - 8.40 25.57 ± 1.57 1.31 ± 3.91 17 β-Phenethyl alcohol - - 22.92 + - 7.84 18 Camphor - 0.34 3.35 - 19 Octanal 0.03 ± 2.69 - - 20 Lavandulol - 0.51 ± 7.12 - 21 Terpinene-4-ol - 1.09 ± 0.57 - 22 Borneol - 0.90 + 0.42 - 23 α-Terpineol 0.37 + - 11.80 0.19 ± 10.21 - 24 Citronellol - - 17.95 + - 9.54 25 Nerol - - 3.80 ± 8.84 26 Linalyl acetate - 12.05 ± 10.41 - 27 Geraniol - - 3.17 ± 4.30 28 Lavandulyl acetate - 4.25 + 4.50 - 29 Thymol 0.36 5.80 - - 30 Citronellyl acetate - - 1.66 ± 4.13 31 Neryl acetate - - 4.64 ± 10.11 32 Bergamotene 0.34 + - 3.74 - - 33 β-Caryophyllene 2.39 ± 13.28 5.67 ± 3.31 - 34 alpha-caryophyllene 0.80 + - 8.66 - - 35 Farnesene 0.39 + - 16.77 - - 36 α-Isomethyl ionone - - 7.93 ± 3.42 * tr: trace <0.1% * -: not detection

As is apparent from the above results, in the case of extracting by conventional methods, it is possible to easily perform extraction with excellent extraction efficiency without using any commonly used organic solvent and without a separate thermal desorption facility. Therefore, it was confirmed that WC-INME is effective for analyzing most volatile aroma components, and particularly, it is possible to effectively extract polar components.

Claims (14)

(i) mixing polyethyleneglycol and polydimethylsiloxane (PEG-PDMS) base resin (A) with polydimethylsiloxane curing agent ratio (B) and coating the metal wire, heat resistant fiber, fine silica rod or nanotube to cure; And
(ii) inserting the coated metal wire, fiber or fine silica rod into a stainless steel injection needle; Preparing an extraction needle;
Wherein the method comprises the steps of:
The method of claim 1, wherein the weight ratio of the polyethylene glycol and the polydimethylsiloxane base curing agent (B) is 1 - 10: 1 - 10: 1 - 10.
The method of claim 1, wherein the metal wire is a stainless steel or a nichrome wire.
The method according to claim 1, wherein the thickness of the coated polyethylene glycol-polydimethylsiloxane (PEG-PDMS) in step (i) is 10-50 μm and the coating length is 5-30 mm.
The method of claim 1, wherein the polyethyleneglycol-polydimethylsiloxane (PEG-PDMS) coated on the metal wire, the heat resistant fiber, or the fine silica rod is coated with polyacrylic acid, polyacrylate, poly (phenyl dimethyl siloxane), cyano propylphenyl dimethyl polysiloxane, poly Tenax TA, Tenax GR, Porapak N, activated carbon, graphite, graphite carbon black, carbon nanoparticles, graphene, florisil, Polymer, Polymers, Octadecyl silane (ODS), Monolithic material, Molecularly imprinted polymer, Polyurethane, Cellulose, Ion Exchanger, Surfactant, Cyclodextrin, Enzymes and Substrates, Antigens and Antibodies Characterized in that a single or a mixture of two or more selected from the group consisting of Way.
The injector needle manufactured by the extraction needle making method for analyzing the volatile component according to any one of claims 1 to 5 is connected to the long-term removable gas tight syringe barrel and the syringe barrel, the vial containing the sample is sealed, To a polyethylene glycol-polydimethylsiloxane (PEG-PDMS) coated on metal wires, heat resistant fibers, fine silica rods or nanotubes.
7. The method of claim 6, wherein the sample is selected from the group consisting of (-) - acetoxy-p-menthane, (+) - aromadendrene, 4-allyl veratrole, 4-allyl-1,2-dimethoxybenzene, 4-allylanisole, allicin, acid, acetaldehyde, acetic acid 2-ethylhexyl ester, acetic acid 2-phenylethyl ester, acetic acid benzyl ester, acetic acid isoamyl ester, acetic acid n-hexyl ester, acetoacetic acid n-butyl ester, acetophenone, anhydrous alcohol, allyl methyl sulfide , allyl n-propyl sulfide, allyl sulfide, anisaldehyde, anhydrous anisole, anethol, isoamyl alcohol, isoamyl amine, trans-anethole, anthracene, 2,3-benzanthracene, benzaldehyde, benzoic acid cis-3-hexenyl ester, benzoic acid ethyl ester , benzoic acid methyl ester, benzoic acid , benzyl acetate, benzyl alcohol, benzyl methyl ether, benzene, bergamotene, borneol, bornyl acetate, butyl acetate, iso -butanal, iso- butylaldehyde, iso -butylamine, n-butyl alcohol, n- butyric acid ethyl ester, n-butyraldehyde, n-butyric acid, n-butyric acid amyl ester, n-butanol, (R) - (-) - carvone, (R) - (-) - citramalic acid, (S) - (+) - carvone, bromobenzene bromide, bromocresol green, (+) - camphor, (+) - 3-carene, (+) - 8 (15) -caten-9-ol, (+) - camphor, -cyclooctatetraene, 1,3,5-cycloheptatriene, 2-carene, 2-cyclohexane-1-one, cadaverine, caryophylleneoxide, choline, cineole, cinnamaldehyde, cinnamic acid benzyl ester, cinnamic acid cinnamyl ester, cinnamyl acetate, , citronellol, citronellyl acetate, coumarin, crotonaldehyde, cuminaldehyde, curcumin, cyclohexane, cyclohexene, cyclohexanol, cyperene, D-L-camphene, n-caproic acid ethyl ester, n-capric acid isopropyl ester, -caprylaldehyde, n-caprylaldehyde, n-caprylic acid isopropyl ester, trans- cinnamaldehyde, trans- cinnamic acid, a-caryophyllene,? -cyclodextrin,? -caryophyllene,? -cyclodextrin, gamma -cyclodextrin, o-cymene, p-cymene, carbon tetrachloride, chlor oform, 1,3-dithiane, 1,2-dithiolane, 1,3-dithiolane, 1,4-Diaminobutane, 1,5-Decadienne, 2,5-dimethyl pyrazine, 2,5-dimethyl thiophene, 2,6- dimethoxy toluene, 2,6-di-tert-butyl-p-cresol, 2-dodecene-1-ylsuccinic anhydride, diallyl disulfide, diallyl trisulfide, diallyl tetrasulfide, dimethyl disulfide, dimethylfuran n-propyl disulfide, 2,7-dichlorofluorescein, n-decane, 2-decane, decanal, n-docosane, n-dodecane, trans-2,4-decadienal, 2-ethyl- ethoxy benzaldehyde, p-ethylbenzaldehyde, ethyl vanillin, ethyl benzene sulphate, ethyl benzene sulphate, ethyl benzene sulphate, , folic acid, fenchone, fenchone, farnesol, formic acid isoamyl ester, fusel oil, furfural, furfuryl alcohol, fluorobenzene, geranial, geraniol, geranyl acetate, geranyl acetone 1-ol, cis-3-hexene-1-ol, cis-3-hexyl acetate, hexanal, n-hexan-1-ol, cis-lanceol, cis-lanthanole, l-hexadecanol, indole, a-loneone, b-loneone, cis-jasmone, lavandulol, lavandulyl acetate, cis- linalool, (+) - linalool, (+) - limonene, (±) -limonene, (±) -linalool, (+) - menthol, (+) - menthol, 2-methyl pyrazine, 2-methyl-3- pentanol, 4-methoxycinamic acid, 5-methyl-2-furfural, 6-methyl-5-heptene-2-one, D, L-menthol, menthone, methyl enanthate, methyl n-caproate, methyl n-caprylate, methyl pelargonate , methyl phenylacetate, methyltrimethoxysilane, methyl propyl disulfide, methyl 2-propynyl sulfide, α-iso-methylionone, β-mycrene, (+) - neomenthol, 1-naphthylamine, narigin, naphthalene, nerol, neryl acetate, neoclovene, nicotinic aci d-methyl ester, n-nonadecane, n-nonane, nonanal, n-nonylaldehyde, 2-nonanone, n-octane, n-octanal, 1-octanol, n-octadecane, (+) - α-pinene, (1S) - (-) - α-pinene, β-pinene, 1-pentanol, 2 2-phenylethyl alcohol, 2-phenylethyl alcohol (β), sec-phenethyl alcohol, 2-phenylethylamine, 2-propanol, 1- (1-propenylthio) propane, propenyl 1-propynyl sulfide, 3-phenylpropionaldehyde, iso-phrone, n-propyl alcohol, o-phthalaldehyde, pelargonic acid ethyl ester, penta fluorobenzyl bromide, pentacene, n-pentadecane, phenyl ether, phenyl acetaldehyde, phenyl acetaonitrile, phenylacetic (ethylene glycol), reserpine, salicylic acid, stearic acid, succinic acid, sabinene hydrate, safrole, salicylic acid, propionic acid, propionaldehyde, propylene sulfide, methyl ester, α-pentanol e, (Z) -α-santalol, (Z) -β-pentanol, epi-β-cantalol, (-) - terpinen-4-ol, (±) -terpinen-4-ol, (+) - δ-tocopherol, 1-tetradecanol, 2-tridecanone, n-tricosane, n-tetradecane, n-tridecane, terpinolene, terpinyl acetate, toluene, thujone, thujene, thymol, thymoquinone, tyramine, α-terpineol, γ-terpinene, 2-undecanone, n-undecane, uraine 1S) -cis-verbenol, iso- valeric acid ethyl ester, valeric acid, n-valeraldehyde, (+) - valencene, vanillin, vanilic acid, verbenone, 2-vinyl-1,3-dithiine, 3-vinyl-1, 2-dithiocyclohex-5-ene, (m) -xylene, (o) -xylene or (p) -xylene.
The method according to claim 6, wherein the step of compressing and adsorbing the sample is performed by moving the stirrer up and down using a reciprocating piston to accelerate extraction and adsorption of analytical components.
[7] The method according to claim 6, wherein the adsorption temperature during the adsorption step is 30 to 70 [deg.] C.
The method according to claim 6, wherein the adsorption time is in the range of 5 to 60 minutes.
The method according to claim 6, further comprising the step of desorbing the adsorbed extracted sample to inject the sample component into the analyzer after the step of adsorbing and extracting the sample.
[12] The method according to claim 11, wherein the adsorbed sample is desorbed at a desorption temperature of 150 to 300 ° C. and a desorption time of 1 to 30 minutes.
A method for analyzing a sample, comprising the step of inserting a sample extracted using the method of extracting a trace of the sample of any one of claims 6 to 12 into an analyzer and analyzing the sample.
An injection needle for extracting a trace amount of a sample prepared by the method for producing an injection needle according to any one of claims 1 to 5.

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