JP2007155519A - Solid phase extraction cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid phase extraction cartridge capable of extracting stably an object material from a sample. <P>SOLUTION: In this solid phase extraction cartridge, the sample which is an analysis target is allowed to flow into a cartridge body 10a, and the object material in the sample is adsorbed onto a filling material 11 in the cartridge body 10a, and then a solvent is allowed to flow into the cartridge body 10a, to thereby recover eluate formed by eluting the object material into the solvent from the filling material 11. The filling material 11 includes an adsorbent 11a for adsorbing the object material and a swelling material 11b swelled by the solvent S, and the filling material 11 is swelled when the solvent is allowed to flow into the cartridge body 10a, and a cavity in the cartridge body 10a is reduced furthermore than the case wherein the sample is allowed to flow, and a pressure loss at the outflow time is heightened, to thereby mitigate the outflow speed of the eluate flowing out from the cartridge body 10a. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid phase extraction cartridge and a solid phase extraction method using the same.

  Conventionally, a liquid-liquid extraction method has been frequently used for extracting a target substance (substance to be analyzed) from a liquid. However, this liquid-liquid extraction method has problems such as complicated work and time and experience, and the use of a large amount of solvent. For this reason, at present, a solid phase extraction method is used which is easy to work, uses a small amount of solvent, and can process a large amount of sample by automation (see, for example, Patent Documents 1 and 2). .)

  In this solid-phase extraction method, a solid-phase extraction cartridge in which a cartridge body is filled with a filler is used, and a sample to be analyzed such as atmospheric gas or tap water is allowed to flow through the solid-phase extraction cartridge. After the substance is adsorbed on the filler, a solvent is passed through the solid-phase extraction cartridge, and an eluate in which the target substance is eluted from the filler into the solvent is recovered.

  By the way, in a general solid phase extraction method, when the sample is flowed to the solid phase extraction cartridge, the sample should flow quickly. On the other hand, when the solvent is flowed to the solid phase extraction cartridge and the target substance is recovered, In order to ensure the extraction of the target substance with the solvent, it is desirable that the solvent flows gently.

  However, when a solid-phase extraction cartridge with good sample aeration (liquid) property is used, the flow rate of the eluate flowing out from the solid-phase extraction cartridge increases when the solvent is flowed. Therefore, there is a problem that the time for elution of the target substance from the solvent becomes insufficient, and it is difficult to stably extract the target substance.

On the other hand, a metering pump may be used to adjust the flow rate of the solvent flowing out from the solid-phase extraction cartridge. However, since it is expensive, a cheaper and easier method is desired. In addition, in order to slow the outflow rate of the solvent flowing out from the solid-phase extraction cartridge, it may be possible to attach an injection needle to the nozzle of the solid-phase extraction cartridge. It is necessary to pay attention to.
JP 2000-514704 gazette JP 2001-246245 A

  The present invention has been made in view of such a situation, and when flowing a solvent to a solid phase extraction cartridge while quickly flowing a sample to be analyzed to the solid phase extraction cartridge, the outflow from the solid phase extraction cartridge is performed. Phase extraction cartridge capable of slowing the flow rate of the solvent to be removed, and solid phase extraction capable of stably extracting the target substance from the sample by using this solid phase extraction cartridge It aims to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have swelled the filler when the solvent is passed through the solid-phase extraction cartridge, and the pressure loss in the cartridge body is higher than when the sample is passed. By utilizing this fact, it was found that the outflow rate of the solvent flowing out from the solid-phase extraction cartridge can be adjusted, and the present invention has been completed.

That is, the present invention provides the following means.
(1) A sample to be analyzed is flowed through the cartridge body, and a target substance in the sample is adsorbed on the filler in the cartridge body, and then a solvent is flowed through the cartridge body so that the filler is transferred from the filler to the solvent. A solid phase extraction cartridge for recovering an eluate from which the target substance has been eluted, wherein the filler includes an adsorbent that adsorbs the target substance, and a swelling material that swells with the solvent, and the cartridge body The solid phase extraction cartridge is characterized in that the filling material swells when the solvent is flowed through and the pressure loss in the cartridge body is higher than when the sample is flowed.
(2) The solid phase extraction according to (1) above, wherein the filler has a first layer mainly composed of the adsorbent and a second layer mainly composed of the swelling material. cartridge.
(3) The solid phase extraction cartridge according to item (2), wherein the first layer and the second layer are alternately stacked at least three layers.
(4) The solid solution according to any one of (1) to (3) above, wherein an outflow rate of the eluate flowing out from the cartridge main body is 0.3 to 1.5 ml / min. Phase extraction cartridge.
(5) A solid-phase extraction method using the solid-phase extraction cartridge according to any one of (1) to (4), wherein a sample to be analyzed is caused to flow through the cartridge body, After the target substance is adsorbed on the filler in the cartridge body, a solvent is allowed to flow through the cartridge body, and the eluate obtained by eluting the target substance from the filler into the solvent is recovered. Phase extraction method.
(6) The solid phase extraction method as described in (5) above, wherein a liquid sample is flowed as the sample.
(7) The solid phase extraction method as described in (5) or (6) above, wherein an organic solvent is passed as the solvent.
(8) The solid phase extraction method according to (7), wherein any one of acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, ethyl acetate, n-hexane, methyl ethyl ketone, and toluene is used as the organic solvent.

  As described above, according to the present invention, the swelling material contained in the filler swells when a solvent is passed through the cartridge body, and the pressure loss in the cartridge body is higher than when the sample is passed. The solvent (eluent) that flows out from the solid-phase extraction cartridge when the target substance is extracted by flowing the solvent through the solid-phase extraction cartridge while quickly flowing the sample to be analyzed through the solid-phase extraction cartridge It is possible to make the outflow speed of the vehicle moderate. Therefore, by using such a solid phase extraction cartridge, it is possible to stably extract the target substance from the sample.

  Hereinafter, a solid phase extraction cartridge and a solid phase extraction method to which the present invention is applied will be described in detail with reference to the drawings. In addition, in the drawings used in the following description, in order to make the features easy to understand, there are cases where the portions that become the features are enlarged for the sake of convenience, and the dimensional ratios of the respective components are not always the same as the actual ones. Absent.

(Solid phase extraction method)
The solid-phase extraction method to which the present invention is applied is a process in which a target substance contained in a gas or liquid sample is subjected to processing such as purification, concentration, analysis and fractionation using a solid-phase extraction cartridge to which the present invention is applied. is there. Here, the “target substance” refers to a chemical substance to be subjected to purification, concentration, analysis, fractionation, and the like. Examples of such target substances include environmental pollutants, chemical pollutants, dioxins, environmental hormones, agricultural chemicals, pharmaceuticals, surfactants, biotoxins, natural drugs, natural pigments, natural flavors, natural seasonings, and the like. be able to.

  In the solid-phase extraction method to which the present invention is applied, in order to efficiently purify, concentrate, analyze, and fractionate a very small amount of a target substance present in such a gas or liquid sample, for example, according to the procedure shown in FIG. Extract the target substance. Specifically, first, (a) sample gas Gs such as indoor air or air, or (b) sample water Ld such as river water or tap water is sucked with a pump P while being extracted with a solid phase extraction cartridge. 10 is ventilated or passed through from one side. Thereby, (c) the target substance in the sample gas Gs or the sample water Ld is adsorbed (collected) on the filler 11 in the solid-phase extraction cartridge 10. Next, (d) the solvent contained in the cylinder 30 from the other side of the solid-phase extraction cartridge 10 with one side of the solid-phase extraction cartridge 10 facing down and the test tube 20 disposed under the one side. Run S. As a result, the eluate S ′ from which the target substance is eluted (detached) from the filler 11 into the solvent S flows out from one side of the solid-phase extraction cartridge 10, and (e) the test tube 20 underneath. To be recovered. Then, (f) the recovered eluate S ′ is sent to an analysis step (measurement of chromatogram) using, for example, a liquid chromatography measuring device.

(Solid phase extraction cartridge)
A solid-phase extraction cartridge 10 to which the present invention is applied includes a cartridge body 10a formed in a substantially cylindrical shape, for example, as shown in FIG. 2, and nozzles are respectively provided at both ends in the longitudinal direction of the cartridge body 10a. 10b and 10c are provided. The solid-phase extraction cartridge 10 includes a filler 11 and a pair of frits (also referred to as filters) 12a and 12b arranged so as to sandwich the filler 11 from the longitudinal direction inside the cartridge body 10a. I have. In addition, since this cartridge main body 10a accommodates the filler 11 and frit 12a, 12b inside, it can be divided between a lid portion provided with the nozzle 10b side and a container portion provided with the nozzle 10c. Yes.

  The material of the cartridge body 10a may be any material that is insoluble in the organic solvent and does not leak the filler 11 during the sample concentration operation. Examples thereof include polypropylene and polyethylene. Further, the shape, size, etc. of the cartridge main body 10a are not particularly limited to those shown in FIG. 1, for example, a syringe barrel syringe or a barrel type having a volume of 1 to 500 ml, preferably 2 to 100 ml. And what was set with the filter made from resin or porous glass etc. may be sufficient.

  As the solvent S used for extraction of the target substance, any organic solvent can be used according to the target substance to be extracted. As such an organic solvent, for example, acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, ethyl acetate, n-hexane, methyl ethyl ketone, toluene and the like can be used.

  The filler 11 is filled in the cartridge main body 10a and is held by a pair of frits 12a and 12b so as not to leak from the nozzles 10b and 10c of the cartridge main body 10a.

  Examples of the filler 11 include silica-based materials such as silica gel having functional groups such as silica gel, octadecyl group, octyl group, butyl group, trimethylsilyl group, cyanopropyl group, nitrophenylethyl group, and perenyl group, activated carbon particles, Carbonaceous materials such as activated carbon fibers and carbon graphite, and porous inorganic materials such as alumina zeolite can be used.

  Further, as the filler 11, a material made of an organic material in addition to the above-described inorganic material can be used as long as it is made of a porous material. For example, a synthetic porous polymer or cork is used. Natural products such as, synthetic porous polymers, activated carbon obtained by firing and activating natural products, and the like can be used. Among these, it is particularly preferable to use a synthetic porous polymer (polymer).

  As the synthetic porous polymer, for example, a crosslinked (co) polymer having a three-dimensional network structure, a polymer in which bubbles are dispersed by a foaming agent such as fluorocarbon or carbon dioxide, and the like can be used. . Among these synthetic porous polymers, a crosslinked (co) polymer is particularly preferable, and a crosslinked (co) polymer having a three-dimensional network structure obtained by polymerizing a crosslinkable polyvinyl monomer having two or more double bonds as a crosslinking agent. It is preferable to use a polymer.

  Examples of crosslinkable polyvinyl monomers include aromatic polyvinyl monomers, polyhydric alcohol poly (meth) acrylic acid ester monomers, polyallyl ethers, N, N′-lower alkylene bis (N-vinylcarboxylic acid amides), and the like. Can be mentioned. Here, “(meth) acryl” means “acryl” or “methacryl” (hereinafter the same).

Specifically, examples of the aromatic polyvinyl monomer include divinylbenzene, divinylxylene, divinylnaphthalene, trivinylbenzene, divinylphenol, and the like.
Polyhydric alcohol poly (meth) acrylic acid ester monomers include, for example, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc. Can do.
Examples of the polyallyl ether include diallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and tetraallyloxyethane.
Examples of N, N′-lower alkylene bis (N-vinylcarboxylic amide) include N, N′-1,3-propylene bis (N-vinylacetamide), N, N′-1,2-methylene bis ( N-vinylacetamide) and the like.
Among these, aromatic polyvinyl monomers are preferable, divinylbenzene, divinylxylene, divinylnaphthalene, trivinylbenzene and divinylphenol are more preferable, and divinylbenzene is more preferable.
Moreover, these crosslinkable polyvinyl monomers can be used individually or in combination of 2 or more types.

When producing a cross-linked (co) polymer, a non-cross-linkable vinyl monomer copolymerizable with these may be used together with the cross-linkable polyvinyl monomer, if necessary. Here, the non-crosslinkable vinyl monomer refers to a compound having one polymerizable double bond.
Examples of such non-crosslinkable vinyl monomers include aromatic monovinyl monomers, (meth) acrylic acid ester monomers, carboxylic acid unsaturated ester monomers, maleic acid monomers, monomers having a carboxyl group, and unsaturated ethers. And monomers based on N-alkenylcarboxylic acid amide and acrylonitrile.

Specifically, examples of the aromatic monovinyl monomer include styrene, o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene, o-, m-, p- (chloromethyl). Examples include styrene, hydroxystyrene, acetoxystyrene, (diethylaminoethylstyrene), vinylnaphthalene, N-vinylpyridine, and the like.
Examples of (meth) acrylic acid ester monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, octadecyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth). Examples thereof include acrylate, 2-hydroxypropyl (meth) acrylate, glycerin (meth) acrylate, and polyethylene glycol (meth) acrylate.
Examples of the carboxylic acid unsaturated ester monomer include vinyl acetate, allyl acetate, and vinyl propionate.
Examples of maleic monomers include maleic acid, maleic anhydride, 2,3-dimethylmaleic anhydride, dimethyl maleate, and diethyl maleate.
Examples of the monomer having a carboxyl group include (meth) acrylic acid and crotonic acid.
Examples of the unsaturated ether monomer include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, butyl allyl ether, and the like.
Examples of N-alkenylcarboxylic acid amide monomers include N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, N- (2-propenyl) formamide, N- (2-propenyl) acetamide, N-vinylbutyrate. Examples include rhoamide, N-vinylbenzamide, N-vinyl (o-toluamide), N-vinyl (p-toluamide), and the like.
Among these, styrene, ethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, and N-vinylacetamide are preferable.
Moreover, these non-crosslinkable vinyl monomers can be used individually or in combination of 2 or more types.

  In addition, in order to obtain a polymer having a wide range of application with a high possibility of introducing a functional group after polymerization, for example, o-, m-, p- (chloromethyl) styrene, glycidyl (meth) acrylate, 2- What has reactive groups, such as a chloromethyl group, an epoxy group, and a hydroxyl group, like a hydroxyethyl methacrylate, glycerol mono (meth) acrylate, etc. can also be used.

Examples of the polymerization method of the crosslinked (co) polymer include normal radical polymerization such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
Here, the case where copolymer particles are produced by, for example, aqueous suspension polymerization will be described as an example. The present invention is not particularly limited to this.

First, a polymerization initiator is added to a mixture of a monomer and a solvent or a dispersion medium to prepare an oil phase used for aqueous suspension polymerization.
The solvent or dispersion medium is added to the monomer mixture for the purpose of making the resulting crosslinked (co) polymer particles porous, and the type thereof is used when water is not used as a medium such as bulk polymerization. Is not particularly limited, but when water is used as a medium such as aqueous suspension polymerization, an organic compound that is hardly soluble in water is preferable.

  Examples of the solvent or dispersion medium include toluene, xylene, diethylbenzene, heptane, octane, dodecane, butyl acetate, dibutyl phthalate, isoamyl alcohol, 1-hexanol, cyclohexanol, 2-ethylhexanol, 1-dodecanol, and non-crosslinked polystyrene. Etc.

  These solvents or dispersion media can be used alone or in combination of two or more. In particular, the BET specific surface area of the crosslinked polymer can be controlled if these combinations are determined by the affinity with the selected monomer. That is, the BET specific surface area can be increased by combining the selected monomer with a high affinity.

  Moreover, it is preferable that the addition amount of these solvent or a dispersion medium shall be 10-300 mass parts with respect to 100 mass parts of total amounts of a monomer, More preferably, it is 30-200 mass parts, More preferably, it is 40. -150 parts by mass. This is because when the addition amount is less than 10 parts by mass, the porosity of the porous copolymer particles becomes insufficient, and when the addition amount exceeds 300 parts by mass, the physical strength of the porous copolymer particles becomes insufficient. Because.

  On the other hand, examples of the polymerization initiator include azo compounds such as 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, Commonly used organic peroxides such as dicumyl oxide, di-t-butyl peroxide, tert-butyl perbenzoate, and methyl ethyl ketone peroxide can be used. Moreover, these polymerization initiators can be used individually or in combination of 2 or more types. Moreover, although the density | concentration of a polymerization initiator is suitably determined by the kind etc. of a monomer and cannot be defined unconditionally, it shall be 0.1-5 mass parts with respect to 100 mass parts of total amounts of a monomer, for example. Is preferred.

Next, a dispersion stabilizer is added to adjust the aqueous phase.
Examples of the dispersion stabilizer include water-soluble polymer compounds such as polyvinyl alcohol, alkyl cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, sodium polyacrylate, and gelatin. Moreover, although the density | concentration of a dispersion stabilizer is not specifically limited, For example, it is preferable to set it as 0.1-5 mass parts with respect to 100 mass parts of water.

  In order to prevent a part of the monomer from dissolving in the aqueous phase, it is preferable to add salts to the aqueous phase. Examples of salts to be added include sodium chloride, calcium chloride, sodium sulfate and the like. Moreover, these salts can be used individually or in combination of 2 or more types. The concentration of the salt is not particularly limited, but is preferably as high as possible within the range allowed by the solubility. For example, in the case of sodium chloride, the amount is preferably 1 to 15 parts by mass with respect to 100 parts by mass of water, and in the case of calcium chloride, the amount is preferably 1 to 40 parts by mass with respect to 100 parts by mass of water.

  Moreover, when the ratio of the water phase to the oil phase is too large, the amount of a part of the monomer dissolved in the water phase increases. Conversely, when the ratio is too small, coalescence of oil droplets is likely to occur. For this reason, it is preferable that the mass of water to be used shall be 200-1000 mass parts with respect to 100 mass parts of total amounts of a monomer, a solvent, or a dispersion medium.

  Next, the oil phase and the aqueous phase are mixed and dispersed so that the oil droplets have a target particle diameter (particle diameter). For this dispersion, a stirrer equipped with a stirring blade for atomization or a high-speed disperser (homogenizer) can be used. Among these, when preparing an adsorbent having a relatively large particle size (for example, for solid phase extraction), it is preferable to use an agitator equipped with a stirring blade for atomization, and an adsorbent having a relatively small particle size. When producing (for example, an adsorbent for liquid chromatography), it is preferable to use a high-speed disperser (homogenizer).

  Next, aqueous suspension polymerization is performed. The polymerization reaction by this aqueous suspension polymerization is carried out at a temperature range of 40 to 100 ° C. for 5 to 16 hours under ordinary stirring. As described above, spherical and porous copolymer particles can be obtained.

  The average particle diameter of the copolymer particles is preferably 0.1 to 2000 μm, more preferably 1 to 500 μm, and still more preferably 2 to 200 μm. This is because if the average particle diameter is smaller than 0.1 μm, the strength is not sufficient, and if it exceeds 2000 μm, the adsorption rate per certain weight decreases and the performance as an adsorbent decreases.

  The shape of the filler 11 is not particularly limited, and for example, various shapes such as spherical particles, crushed particles, membranes, fibers, and massive continuous bodies can be used. In addition, a lump continuous body is a rod-like polymer obtained by extracting the lump polymerized in a cylindrical container, for example. The crushed particles are, for example, irregular or regular particles obtained by crushing massive continuum or spherical particles into smaller pieces with a hammer, mortar, pulverizer or the like.

The specific surface area measured by the BET method of the filler 11 is preferably 50 m ² / g or more, and more preferably 400 m ² / g or more. When the specific surface area of the filler 11 is smaller than 50 m ² / g, the adsorption efficiency of the target substance is deteriorated.

  The pair of frits 12a and 12b hold the filler 11 in the cartridge body 10a so that the filler 11 does not leak from the nozzles 10b and 10c of the cartridge body 10a. And also has a function for allowing the solvent to uniformly pass therethrough. As the frits 12a and 12b, those that do not elute unnecessary components when a solvent is flowed are preferably used. For example, polyethylene particles, glass particles, metal particles, etc. are sintered to have a thickness of 0. What was shape | molded by the porous disk shape of about 5-3 mm, or the filter etc. which consist of paper, glass fiber, etc. can be used. Moreover, it is preferable to use the frit 12a, 12b having a strength that can withstand the pressure accompanying the swelling of the filler 11 described later.

  When the target substance is extracted by the above-described solid-phase extraction method using the solid-phase extraction cartridge 10 having the above structure, first, analysis is performed from the nozzle 10c side (or the nozzle 10b side) of the cartridge body 10a. By flowing a target gas or liquid sample, the target substance in the sample is adsorbed on the filler 11. Next, as shown in FIG. 3, while inserting the nozzle 30a of the cylinder 30 containing the solvent S to be passed through the solid phase extraction cartridge 10 into the female nozzle 10b on the upper side of the cartridge body 10a, the lower part of the cartridge body 10a A test tube 20 serving as a container for collecting the eluate S ′ flowing out from the solid-phase extraction cartridge 10 is disposed under the male nozzle 10c on the side. Then, the solvent S is quantitatively injected into the cylinder 30 using the dropper 40, and the solvent S accommodated in the cylinder 30 is caused to flow from the nozzle 10b side of the cartridge body 10a, whereby the target substance is transferred from the filler 11 to the solvent S. Elute. The eluate S 'containing the target substance flows out from the nozzle 10c side of the cartridge body 10a and is collected in the test tube 20 therebelow.

  By the way, in the solid-phase extraction cartridge 10 to which the present invention is applied, the filler 11 adsorbs a target substance (hereinafter referred to as an adsorbent) and the substance that swells with the solvent S (hereinafter referred to as a swollen material). When the solvent S is caused to flow through the cartridge body 10a, the filler 11 swells, and the pressure loss in the cartridge body 10a is higher than when the sample is caused to flow.

  Specifically, as shown in FIG. 4A, the filler 11 includes a first layer 11a mainly composed of an adsorbent and a second layer 11b mainly composed of a swelling material. The first layer 11a and the second layer 11b are stacked in the longitudinal direction of the cartridge body 10a.

  For the first layer 11a, an adsorbent that hardly swells with the solvent S for extraction can be used. As such an adsorbent, for example, a porous inorganic material or a fibrous substance having a large surface area can be used. Specifically, silica gel, or octadecyl group, octyl group, butyl group, trimethylsilyl group, cyanopropyl group, At least one or more selected from silica gel having any functional group of nitrophenylethyl group and perenyl group, activated carbon particles, activated carbon fiber, carbon graphite, and alumina zeolite can be used.

  On the other hand, the second layer 11b is preferably a swelling material that swells with the solvent S but does not affect the adsorption of the target substance by the first layer (adsorbent) 11a. As such a swelling material, for example, fine particles or fibers of a synthetic organic polymer can be used. Specifically, polystyrene gel crosslinked with about 1% with divinylbenzene, or SX-1 manufactured by Bio-Red Co., Ltd. TentaGel manufactured by Aldrich or the like can be used.

  The first layer 11a may be an adsorbent that swells with the solvent S, that is, an adsorbent that adsorbs the target substance and swells with the solvent S may be used. Examples of such a substance that adsorbs the target substance and swells with the solvent S include, for example, styrene-divinylbenzene copolymer, silica gel in which octadecyl group is chemically bonded, divinylbenzene-ethylene dimethacrylate-N-vinylacetamide ternary copolymer. A synthetic porous polymer such as a polymer, divinylbenzene-glycerin dimethacrylate-N-vinylacetamide terpolymer can be used.

  In addition to the layered structure shown in FIG. 4 described above, the layered structure of the filler 11 has a structure in which at least three or more first layers 11a and second layers 11b are alternately stacked, for example, The number of layers, the combination of layers, and the like, such as the one layer 11a stacked so as to be sandwiched between the second layers 11b, can be changed as appropriate. Further, when the specific gravity or particle size of the adsorbent or swelling material formed by each layer of the filler 11 is greatly different, the first layer 11a and the second layer 11b are separated by a frit as necessary. You may do it.

  Further, as the filler 11, it is possible to fill the cartridge body 10 a with a mixture of the adsorbent and the swelling material described above in advance. In this case, the filler 11 does not necessarily have a layer structure, and can have a single layer structure in which an adsorbent and a swelling material are mixed.

  In the solid-phase extraction cartridge 10 to which the present invention is applied, when the solvent S is passed through the cartridge body 10 a filled with such a filler 11, the filler 11 swells and the cartridge body more than when the sample is passed. The outflow speed of the solvent (eluent S ′) flowing out from the cartridge main body 10a can be adjusted by utilizing the fact that the voids in 10a are reduced and the pressure loss during extraction is increased.

  Specifically, in the solid-phase extraction cartridge 10 to which the present invention is applied, as shown in FIG. 4A, the ratio of the second layer 11b in the cartridge main body 10a is swollen, and the cartridge main body 10a is previously stored. A gap D can be provided in the space. Such a gap D can be provided between any of the pair of frits 12a and 12b sandwiching the filler 11 and both ends in the longitudinal direction of the cartridge body 10a. Or it can also be provided between any of the pair of frit 12a, 12b and the filler 11. In the solid-phase extraction cartridge 10 shown in FIG. 4A, a gap D is formed between one frit 12a and the upper surface portion inside the cartridge main body 10a and between the other frit 12b and the lower surface portion inside the cartridge main body 10a. Is provided.

  Further, when such a gap D is provided, it is preferable that at least one of the pair of frits 12a and 12b is movable within the cartridge body 10a. In the solid-phase extraction cartridge 10 shown in FIG. 4A, a pair of frits 12a and 12b are movable in the cartridge body 10a.

  In the solid-phase extraction cartridge 10, as shown in FIG. 4B, the second layer 11b swells when the solvent S is passed through the cartridge body 10a. At this time, the pair of frit 12a, 12b is pressed by the filler 11 whose volume is increased by the swelling of the second layer 11b, and moves in the cartridge body 10a. When the movement of the pair of frits 12a and 12b is restricted at both ends of the cartridge main body 10a, the gap D in the cartridge main body 10a disappears, and the filler 11 can no longer swell. Thereby, the filler 11 is brought into a compacted state in the cartridge body 10a.

In the solid-phase extraction cartridge 10 to which the present invention is applied, it is possible to arbitrarily adjust the outflow rate of the eluate S ′ flowing out from the cartridge body 10 a depending on the degree of compaction of the filler 11.
Specifically, in the solid-phase extraction cartridge 10 to which the present invention is applied, the outflow rate of the eluate S ′ that flows out from the nozzle 10c of the cartridge body 10a when about 10 ml of the solvent S is placed in the cylinder 30 and is naturally dropped. However, it is preferable to perform the above setting so as to be 0.3 to 1.5 ml / min. Thereby, the outflow rate of the eluent S ′ flowing out from the nozzle 10c of the cartridge body 10a can be made gentle.

  In the solid-phase extraction cartridge 10 shown in FIG. 4A, the filler 11 is set to be in an appropriate compacted state by eliminating the gap D in the cartridge body 10a. Therefore, if the gap D is not provided, when the filler 11 swells, the increase in the volume of the filler is strongly restricted, so that the compacted state becomes too large. As a result, the outflow rate of the eluate S ′ Will be significantly reduced. This is not preferable in terms of shortening the analysis time.

  If the gap D is not provided, the pair of frits 12a and 12b must be firmly fixed in the cartridge body 10a so that the pair of frits 12a and 12b do not move due to swelling of the filler 11. On the other hand, in the solid-phase extraction cartridge 10 shown in FIG. 4A, the pair of frits 12a and 12b are lightly fixed in the cartridge body 10a by frictional force with the inner surface of the cartridge body 10a in order to avoid the bias of the filler 11. However, the cartridge 11 can be moved in the longitudinal direction by the swelling of the filler 11.

The flow rate of the eluent S ′ flowing out of the cartridge body 10 a is determined by the filling amount of the filler 11, the gap between the particles of the filler 11, the particle size of the filler 11, and the pressure when filling the filler 11. Therefore, it is possible to adjust without providing the gap D in some cases. For example, when the particle size of the filler 11 is large (the cartridge for atmospheric analysis), the gap D is not always necessary. For example, by adjusting the void ratio in the filler 11, an effect equivalent to that of the gap can be obtained. Can be given.
Further, in order to make the flow rate of the eluate S ′ flowing out from the nozzle 10c of the cartridge body 10a gentle, the particle diameter of the filler 11 is preferably 50 to 500 μm.

Further, in the solid-phase extraction cartridge 10 to which the present invention is applied, it is possible to provide a restricting means for restricting movement of at least one or both of the fillers 11 among the pair of frits 12a and 12b.
Specifically, as the restricting means, for example, as shown in FIG. 5, a pair of stoppers 13a and 13b for restricting the movement of the pair of frits 12a and 12b can be provided in the cartridge body 10a. As shown in FIG. 5A, the pair of stoppers 13a and 13b are formed so as to protrude from the upper surface portion and the lower surface portion inside the cartridge main body 10a, respectively. Further, as shown in FIG. 5A, a plurality of these pair of stoppers 13a and 13b are radially arranged at the same height around the nozzles 10b and 10c so as to be in uniform contact with the frit 12a and 12b. Has been. A gap D is provided between the upper frit 12a and the stopper 13a.

  In this case, when the solvent S is caused to flow into the cartridge body 10a, the filler 11 swells and one frit 12a moves upward, and when the gap D disappears, the pair of stoppers 13a and 13b are paired with the pair of frit 12a, By pressing 12b inward, the filler 11 becomes a consolidated state. Thereby, the outflow speed of the eluent S 'flowing out from the cartridge main body 10a can be arbitrarily adjusted according to the height (gap D) of the stoppers 13a and 13b. In this case, the flow rate of the eluate S ′ flowing out from the cartridge body 10a is set while setting the filling amount of the filler 11 filled in the cartridge body 10a to an optimal value for extracting the target substance. Can also be set to an optimal value.

  Further, as the restricting means, for example, a pair of spacers 14a and 14b as shown in FIG. 6A can be provided. The pair of spacers 14a and 14b are ring-shaped members disposed outside the frits 12a and 12b in the cartridge main body 10a. When the solvent S is passed through the cartridge main body 10a, the pair of frits 12a and 12b. The movement accompanying the swelling of the filler 11 is regulated.

  In this case as well, the outflow rate of the eluent S 'flowing out from the cartridge body 10a can be arbitrarily adjusted according to the thickness of the spacers 14a and 14b. Therefore, while setting the filling amount of the filler 11 filled in the cartridge body 10a to an optimum value for extracting the target substance, the outflow rate of the eluent S ′ flowing out from the cartridge body 10a is also an optimum value. Can be set to

  Further, as the restricting means, for example, a pair of stoppers 15a and 15b as shown in FIG. 6B can be provided. The pair of stoppers 15a and 15b are projections that are disposed outside the frit 12a and 12b in the cartridge body 10a and project from the inner surface of the cartridge body 10a, and have the solvent S flow through the cartridge body 10a. Sometimes, the movement of the pair of frit 12a, 12b with the swelling of the filler 11 is restricted.

  In this case as well, the outflow rate of the eluent S 'flowing out from the cartridge body 10a can be arbitrarily adjusted according to the arrangement of the stoppers 15a and 15b. Therefore, while setting the filling amount of the filler 11 filled in the cartridge body 10a to an optimum value for extracting the target substance, the outflow rate of the eluent S ′ flowing out from the cartridge body 10a is also an optimum value. Can be set to

  Further, as the restricting means, for example, as shown in FIG. 6C, stoppers 16a and 16b can be provided on the frits 12a and 12b. The pair of stoppers 16a and 16b are protrusions protruding from the surface of the frit 12a and 12b opposite to the filler 11, and when the solvent S flows through the cartridge body 10a, Abutting on the upper surface portion and the lower surface portion, the movement of the pair of frits 12a and 12b with the swelling of the filler 11 is restricted.

  In this case as well, the outflow rate of the eluent S 'flowing out from the cartridge body 10a can be arbitrarily adjusted according to the heights of the stoppers 16a and 16b. Therefore, while setting the filling amount of the filler 11 filled in the cartridge body 10a to an optimum value for extracting the target substance, the outflow rate of the eluent S ′ flowing out from the cartridge body 10a is also an optimum value. Can be set to

  As the restricting means, for example, as shown in FIG. 6D, the cartridge body 10a can be provided with reduced diameter portions 17a and 17b. The pair of reduced diameter portions 17a and 17b are portions where the diameter of the cartridge body 10a is reduced outside the frit 12a and 12b in the cartridge body 10a, and when the solvent S is allowed to flow through the cartridge body 10a. In addition, the movement of the pair of frits 12a and 12b accompanying the swelling of the filler 11 is restricted.

  In this case as well, the outflow rate of the eluent S 'flowing out from the cartridge main body 10a can be arbitrarily adjusted according to the positions of the reduced diameter portions 17a and 17b. Therefore, while setting the filling amount of the filler 11 filled in the cartridge body 10a to an optimum value for extracting the target substance, the outflow rate of the eluent S ′ flowing out from the cartridge body 10a is also an optimum value. Can be set to

  As described above, according to the present invention, the filler 11 swells when the solvent S is passed through the cartridge body 10a, and the pressure loss in the cartridge body 10a is higher than when the sample is passed. When flowing the solvent S to the solid phase extraction cartridge 10 while quickly flowing the sample to be analyzed through the extraction cartridge 10, the outflow rate of the solvent (eluent S ′) flowing out from the solid phase extraction cartridge 10 is set. It can be gradual. That is, even when the solid phase extraction cartridge 10 having good sample aeration (liquid) property is used, the flow rate of the eluate S ′ flowing out from the solid phase extraction cartridge 10 is made slow so that the target substance is obtained. The extraction rate can be increased.

  Therefore, in the solid phase extraction method using such a solid phase extraction cartridge 10, the target substance can be stably extracted from the sample while shortening the operation time. In addition, when such a solid-phase extraction cartridge 10 is used, it is not necessary to attach a special instrument such as the above-described injection needle, so that it is very inexpensive and can be operated safely. In addition, it is possible to prevent impurities from interfering during analysis.

Hereinafter, the effects of the present invention will be clarified by examples. In addition, this invention is not limited to a following example, In the range which does not change the summary, it can change suitably and can implement.
Example 1
In Example 1, the above-described solid-phase extraction cartridge 10 shown in FIG. 4 was actually produced.
In Example 1, the inner diameter of the cartridge body 10a is 13 mm, and TentaGel (polystyrene gel having a particle diameter of 140 to 17 μm) manufactured by Aldrich is used as a swelling material so that no gap D (= 0) is generated in the cartridge body 10a. ) And 100 mg of silica gel having an average particle diameter of 150 μm as an adsorbent, so that the filler 11 has a two-layer structure of a first layer 11a and a second layer 12a.

  Then, when pure water (ion exchange water) as a sample was passed through the solid phase extraction cartridge 10 of Example 1 at 20 ml / min, the differential pressure became 0.05 MPa or less, and there was a problem with liquid permeability. There wasn't. Moreover, when the cylinder 30 was connected to the solid phase extraction cartridge 10 of Example 1, and 10 ml of acetonitrile was put into the cylinder 30 as the solvent S and dropped spontaneously, the outflow rate of the solvent S was 0.5-2 ml / min. Thus, a moderate outflow rate was obtained.

(Comparative Example 1)
Comparative Example 1 was carried out except that 450 mg of silica gel having an average particle diameter of 150 μm was filled as an adsorbent and the filler 11 had a single-layer structure so that no gap D (= 0) occurred in the cartridge body 10a. A solid-phase extraction cartridge 10 similar to that in Example 1 was produced.

  Then, when pure water (ion exchange water) was passed through the solid phase extraction cartridge 10 of Comparative Example 1 at a rate of 20 ml / min, the differential pressure became 0.05 MPa or less, causing a problem in liquid permeability. There wasn't. On the other hand, when the cylinder 30 was connected to the solid-phase extraction cartridge 10 of Comparative Example 1 and 10 ml of acetonitrile was added to the cylinder 30 as a solvent S and dropped spontaneously, the outflow rate of the solvent S became 2 ml / min or more and the outflow The result was too fast.

FIG. 1 is a schematic diagram showing the procedure of a solid-phase extraction method to which the present invention is applied. FIG. 2 is a perspective view showing a solid-phase extraction cartridge to which the present invention is applied. FIG. 3 is a perspective view showing the operation by the solid phase extraction method using the solid phase extraction cartridge shown in FIG. 4A is a cross-sectional view showing a state before flowing the solvent of the solid phase extraction cartridge shown in FIG. 2, and FIG. 4B is a view after flowing the solvent of the solid phase extraction cartridge shown in FIG. It is a cross section which shows the state. FIG. 5A is a cross-sectional view showing a state in which the regulating means is arranged in the solid phase extraction cartridge shown in FIG. 2, and FIG. 5B is a plan view showing the stopper. FIG. 6 is a cross-sectional view showing another restricting means.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Solid phase extraction cartridge 10a ... Cartridge main body 10b, 10c ... Nozzle 11 ... Filler 11a ... 1st layer (adsorbent) 11b ... 2nd layer (swelling material) 12a, 12b ... Frit 13a, 13b ... Stopper ( Regulatory measures)

Claims (8)

A sample to be analyzed is flowed through the cartridge body, and the target substance in the sample is adsorbed to the filler in the cartridge body, and then a solvent is passed through the cartridge body to pass the solvent from the filler to the solvent. A solid phase extraction cartridge for recovering the eluate from
The filler includes an adsorbent that adsorbs the target substance, and a swelling material that swells with the solvent, and the filler swells when the solvent flows through the cartridge body, and the sample flows. The solid phase extraction cartridge is characterized in that pressure loss in the cartridge body increases.   2. The solid-phase extraction cartridge according to claim 1, wherein the filler includes a first layer mainly composed of the adsorbent and a second layer mainly composed of the swelling material.   The solid phase extraction cartridge according to claim 2, wherein at least three or more layers of the first layer and the second layer are alternately laminated.   The solid-phase extraction cartridge according to any one of claims 1 to 3, wherein an outflow rate of the solvent flowing out from the cartridge body is 0.3 to 1.5 ml / min. A solid phase extraction method using the solid phase extraction cartridge according to any one of claims 1 to 4,
A sample to be analyzed is flowed through the cartridge body, and a target substance in the sample is adsorbed to the filler in the cartridge body, and then a solvent is flowed through the cartridge body to pass the solvent from the filler to the solvent. A solid phase extraction method comprising collecting an eluate from which a substance is eluted.   The solid phase extraction method according to claim 5, wherein a liquid sample is flowed as the sample.   The solid phase extraction method according to claim 5 or 6, wherein an organic solvent is passed as the solvent.   The solid-phase extraction method according to claim 7, wherein any one of acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, ethyl acetate, n-hexane, methyl ethyl ketone, and toluene is used as the organic solvent.

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