JP3498728B2 - Environmental sample processing method and polymer material used for it - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to rivers, lake water, groundwater,
Methods for concentrating, separating, capturing, detecting, extracting or recovering trace substances contained in or possibly contained in environmental samples such as soil, and polymeric materials used therefor (treatment Material). Furthermore, the polymer material recognizes the trace substance (target substance), and the target substance contained in the environmental sample is concentrated by capturing or capturing it.
The present invention relates to methods and materials for performing separation, capture, detection, extraction or recovery processes.

[0002]

2. Description of the Related Art Gas chromatography or liquid chromatography is generally used as a method for analyzing target substances such as exogenous endocrine disrupting substances (environmental hormone substances, etc.) in environmental samples such as rivers, lake water, groundwater and soil. Is used for.

Although the target substance pretreatment method using activated carbon can adsorb or retain the target substance, it is not easy to take out only the specific target substance adsorbed or retained from the activated carbon. Not only the number of processing steps increases and the number of repetitive operations increases, but it may cause an error.

Further, in high performance liquid chromatography using a C18 column, which is generally used as a separating material for endocrine disruptors, the concentration, recovery and separation of the target substance are not sufficient, and accurate identification is possible. It's difficult.

In the actual measurement and analysis of environmental samples, there has been the inconvenience that a large amount of environmental samples must be brought to a place where measurement and analysis equipment is provided.

Further, environmental samples usually contain a large amount of humic acid, and it is difficult to efficiently concentrate, separate, capture, extract or recover the target substance of interest. In other words, since the content of humic acid is large, it interferes with the measurement of the target substance, which is usually contained in a small amount, and makes accurate measurement difficult. Further, the pretreatment for removing humic acid requires a complicated step, and the target substance may be removed depending on the pretreatment method.

[0007]

In the conventional chromatography, it was not sufficient to selectively concentrate, separate, capture, detect, extract or recover the target substance of interest from the environmental sample. Moreover, in measuring and analyzing environmental samples, a considerable amount of environmental samples had to be transported and brought.

Therefore, a simple and convenient method for treating the target substance has been desired.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a part of a target substance such as an exogenous endocrine disrupting substance or a toxic substance such as a phenolic or organochlorine compound or Removal of a target substance analog from a fragment obtained by reacting a reactive compound in the presence of a target substance analog having at least one of chemical structure, size, or shape of fragments in common or similar The resulting polymeric material is a low-molecular-weight organic material that may or may be contained in an environmental sample containing humic acid.
It has been found that it is effective for concentration, separation, capture, detection, extraction or recovery of a target substance which is a compound .

The first invention is an environmental material containing humic acid.
At least one of the chemical structure, size or shape of a part or fragment of the target substance (A), which is a low molecular weight organic compound contained in or possibly contained in the environmental sample, , A common or similar polymer material obtained by removing the target substance analog (B) from a substance obtained by reacting a reactive compound in the presence of the target substance analog (B) , Enriching the target substance (A) contained in or possibly contained in environmental samples,
It is a method for treating an environmental sample, characterized by separating, removing, capturing, detecting, extracting or collecting.

A second invention is an optionally substituted hydrocarbon group having a carbon number of 4 or more, an aromatic hydrocarbon group, which is contained in the chemical structural formula of a part or fragment of the target substance (A). At least one of the cyclo ring group or the heterocyclic group is common or similar, and the target substance analog (B) is removed from the product obtained by reacting the reactive compound in the presence of the target substance analog (B). Of an environmental sample using a polymer material having the property of concentrating, separating, capturing, detecting, extracting or collecting the target substance by adding or contacting the target substance containing the target substance (A) It is a processing method.

A third aspect of the present invention is a method for treating an environmental sample using, as a reactive compound, a polymer material containing a crosslinkable compound having two or more reactive groups.

A fourth aspect of the present invention is the method for treating the environmental sample, wherein the target substance (A) is bisphenol A and the target substance analog (B) is tert-butylphenol.

A fifth aspect of the present invention is a method for treating an environmental sample containing bisphenol A and humic acid.

[0015]

A sixth invention is an environmental sample containing a target substance (A) and humic acid, wherein the ratio of the target substance (A) / humic acid is 100 or more before and after the treatment. Is the processing method of.

A seventh aspect of the present invention is a method for treating an environmental sample in which the ratio of the target substance (A) / humic acid is 500 or more before and after the treatment.

The eighth invention is a polymer material (treatment material) used in the method used in the above method.

Further, the present invention also relates to a method for treating an environmental sample using a polymer material synthesized by the molecular imprinting method, wherein the template polymerization method uses bulk polymerization or suspension polymerization. It is also used as a kit in which a polymer material is packed in a column (cartridge).

In addition, polymer materials prepared by the molecular marking method or the molecular imprinting method are disclosed in JP-A-6-510474, JP-A-5-194617, JP-A-8-506320, and US Pat. No. 5,110,833. It is known to be used as a catalyst, enzyme, antibody and the like.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the polymer material is humin.
Utilizing the fact that it functions as a hydrophobic polymer in environmental samples containing acid , it adsorbs hydrophobic exogenous endocrine disrupting substances and toxic substances in environmental samples and elutes other substances,
Selective concentration, separation, capture, detection, detection and extraction of target substances such as exogenous endocrine disrupters and toxic substances by the operation of extracting or separating the remaining target substances such as exogenous endocrine disrupters and toxic substances Or it is something to collect.

The molecular imprinting method is
It is said to be the creation of artificial affinity materials, and is a method that has been studied for the production of artificial enzymes and artificial antibodies. The present invention is
At least one of an optionally substituted hydrocarbon group having 4 or more carbon atoms, an aromatic hydrocarbon group, a cyclocyclic group or a heterocyclic group contained in the chemical structure of the target substance itself or the target substance (atom The target substance analog (print molecule) having a group or fragment) and a monomer are polymerized and the print molecule is removed by extraction or the like, and the polymer material retains complementarity to the target substance, and the target substance is selectively Can be adsorbed or bound. Further, in the present invention,
It may be a covalently bound molecular imprinting or a non-covalently bound molecular imprinting.

The target substance (A) is an organic compound having a relatively low molecular weight, and it is usually a compound that is preferably not present, and may be contained or possibly contained in the environmental sample. It is a substance. For example, substances that have a bad effect on the living body, substances that have been suggested to have problems with the environment, hygiene, etc., such as nonylphenol, butylphenol, dichlorophenol, bisphenol A, styrene, styrene dimer, styrene trimer, octachlorostyrene, Butyl phthalate, propyl phthalate, hexyl phthalate, pentyl phthalate, dichlorohexyl phthalate, butylbenzyl phthalate, diethylhexyl phthalate, polybrominated biphenyl, diethylhexyl adipate, vinyl acetate, vinyl chloride and the like. The target substance may be a useful compound.

The toxic substance is a substance contained in an environmental sample, and, for example, environmental toxic substances such as microcystin (blue-green venom) and saxtoxin (red tide) can also be the target substance.

The target substance analogue (B) is a compound in which at least one of the chemical structure, the size of the molecule or the shape of the molecule of the target substance or a part or fragment of the target substance is common or similar. In the present invention, when the target substance is a toxic substance, at least one of the chemical structure, the molecular size or the molecular shape of the toxic substance is common or similar without using the toxic substance. It has the advantage that safe compounds can be used to produce the polymeric materials according to the invention. That is, the present invention, even if the target substance is a highly toxic substance,
It has an advantage that a polymer material capable of capturing the target substance can be produced without handling the substance itself.

In molecular imprinting using the target substance (A) itself, the target substance (A)
However, there is a drawback in that the separation, recovery, capture or concentration of can not always be processed properly. That is, the polymer material obtained by using the target substance (A) may remain even if the target substance (A) is sufficiently removed. Therefore, when an environmental sample that does not contain the target substance (A) is used to perform separation and recovery with the polymer material, the target substance (A) is The measurement result will be included. In addition, target substances (A)
When the environmental sample containing is treated, the target substance (A) remaining in the polymer material may be measured as an error.

Further, since environmental samples usually contain a large amount of humic acid, it is difficult to efficiently concentrate, separate, capture, detect, detect, extract or recover the target substance of interest. In other words, since the content of humic acid is large, it interferes with the measurement of the target substance, which is usually contained in a small amount, and makes accurate measurement difficult. Further, the pretreatment for removing humic acid requires a complicated step, and the target substance may be removed depending on the pretreatment method.

A part or fragment of the target substance (A),
The target substance analog (B) having at least one of the chemical structure, the size of the molecule, and the shape of the molecule being common or similar is not the target substance (A) itself, but, for example, one of the chemical structural formulas of the target substance. Target substance analogues whose parts are common or similar, target substance analogues whose chemical structural formulas of part of the target substance are common (same) or similar, molecular size of the target substance or partial size of the target substance , Common target substances, chemical structure formulas of target substances or partial chemical structure formulas of target substances, and target substance analogs in which the size and shape of molecules are similar.

At least one of optionally substituted hydrocarbon group having 4 or more carbon atoms, aromatic hydrocarbon group, cyclo ring group or hetero ring group contained in the chemical structural formula of the target substance (A). As the target substance analog having (atomic group or fragment), one of substituents such as halogen atom, hydroxyl group, amino group, carboxyl group, sulfonic acid group, cyano group, alkyl group, cycloalkyl group, carbonyl group, etc. Alternatively, an alkyl group having 4 or more carbon atoms, a phenyl group, an alkylphenyl group, a cycloalkyl group, and the like, which may be substituted by two or more.

The target substance analogs include (1) various isomers, (2) the presence or absence of substituents, for example, phenol and nonylphenol, (3) different types of substituents, nonylphenol and octylphenol, ( 4) Compounds having different numbers of alkylene groups, (5) Compounds of the same system, such as octane and decane in alkanes. In addition, the target substance analog also includes a reaction product or a decomposition product of the target substance, and an organic solvent can also be used.

As the method for synthesizing the polymer material of the present invention,
After reacting the target substance analog (B) and a reactive compound, preferably a polymerizable compound, the target substance analog (B)
Is a method of removing by means of solvent treatment or the like.

As the reactive compound, (meth) acrylates, vinylbenzenes, which are known as compounds of the molecular marking method or the molecular imprinting method,
A compound such as a heterocyclic aromatic compound can be used, but a cross-linking agent having a polymerizable group such as two or more vinyl groups, a polymerizable group containing a functional group such as a carboxyl group, a sulfonic acid group, a hydroxyl group, an amino group or a cyano group. A monomer having a group and another monomer having a polymerizable group can be used. Preferably, a cross-linking agent having two or more polymerizable groups such as vinyl groups and a monomer having a polymerizable group containing a functional group, and optionally other monomers are used. Generally, a monomer having a polymerizable group containing a functional group can be a ligand for an exogenous endocrine disruptor (print molecule). It is desirable to use a reactive compound having a basic group or an acidic group or a reactive compound having a hydroxyl group as the reactive compound.

Examples of the cross-linking agent having two or more polymerizable groups such as vinyl groups include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glycerol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate and the like. Is a compound having two or more double bonds. It is also preferable to use a compound having 3 to 4 or more polymerizable groups.

Examples of the monomer having a polymerizable group having a functional group such as a basic group or an acidic group include, for example, acrylic acid, tacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-hydroxy acrylic acid. One or more of ethyl, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl pyridine, vinyl imidazole, glycidyl methacrylate, vinyl acetate and the like are used.

Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic. Examples include lauryl acid and styrene.

The target substance analog (B) is, for example, 0.1 moles per mole of the monomer having a functional group-containing polymerizable group.
It is present in an amount of 01 to 1 mol, preferably 0.05 to 0.8 mol, more preferably 0.1 to 0.5 mol.

In the reaction, in addition, a porosifying solvent,
A polymerization initiator, a solvent, a surfactant, a dispersion stabilizer, etc. are used. The polymerization initiator is azobisisobutyronitrile, benzoyl peroxide, etc., and the solvent is benzene, toluene, xylene, lower alcohol,
Examples include chloroform and hexane.

The reaction method includes suspension polymerization, bulk polymerization, seed polymerization, dispersion polymerization and the like, and the polymerization conditions are, for example, heating at 40 to 120 ° C., or ultraviolet light.
Irradiation with active energy rays such as electron beams. Preferably,
Seed polymerization is a method in which particles having a uniform particle size are easily obtained.

In the case of a separating material packed in a column, which is one of the methods of using the polymer material of the present invention, a rod having a filter at the bottom, if necessary, is provided with a reactive material. A material for separation can be produced simultaneously with the molecular imprinting reaction by filling, carrying out a reaction, and removing the target substance analog (B).

Furthermore, the environment of the target substance (A) can be measured by using the separating material of the material of the present invention packed in a column or the like.

The obtained polymer material is extracted or washed with a solvent or the like capable of dissolving the target substance analog (B) to remove the target substance analog (B) from the polymer material. It is also possible to carry out solvent extraction and then remove with Soxhlet. Other removal methods may be used.

If necessary, the polymer material from which the target substance analog (B) has been removed is pulverized, and the particle size is adjusted according to the purpose of use. For example, the particle size may be 50 to 300 μm, but the particle size of the obtained polymer compound may be used as it is. Preferably, a polymeric material obtained by a polymerization method having a uniform particle size is used. The target substance analog (B) may be removed from the polymer material after pulverization.

By subjecting the polymer material to a conditioning treatment with a low molecular weight alcohol or a low molecular weight alcohol containing water, the characteristics of the adsorption rate can be remarkably improved.

Since humic acid is often contained in a large amount in environmental samples, it is necessary to reduce the influence of humic acid in measurement as much as possible. In the present invention, however, the ratio of the target substance (A) / humic acid is The treatment method or the polymer material is 100 or more, preferably 500 or more, more preferably 1000 or more before and after the treatment. That is,
It is desirable that the target substance (A) is 100 times or more, preferably 500 times or more, more preferably 700 times or more, or a treatment method or a polymer material.

In the present invention, the polymer material can also be used as a predicting or detecting method or a predicting or detecting material for functionality such as toxicity with respect to an environmental sample which may contain a target substance. Furthermore, it is also possible to evaluate potential functionality (toxicity, hygiene, etc.) and estimate functionality.

In the present invention, inclusion compounds such as cyclodextrin, activated carbon, and other materials capable of concentrating, separating, removing, capturing, detecting, extracting or recovering the target substance may be used as the material of the present invention. It can also be used together.

The present invention will be described below with reference to examples. The example is one embodiment of the present invention, and the present invention is not limited to the example. In addition, "part" in the example,
"%" Indicates parts by weight and% by weight, respectively. Example 1 Ethylene glycol dimethacrylate / 1-vinylimidazole / tert-butylphenol (molar ratio 46
/ 4/1) as a polymerization initiator (2,2-azobis (2,4
-Dimethylvaleronitrile)) and toluene (a porosifying solvent) at 50 ° C. for 24 hours for bulk polymerization, and then pulverized by a pulverizer to give granules. Collecting particles of 20 μm or more, methanol and THF (tetrahydrofuran)
Washed with.

Polymer materials 2 obtained in Example 1 respectively
Gram, wash with stirring with acetone, remove the supernatant fine particles by decantation, after complete drying,
0.5 gram was filled in a glass cartridge. After filling, water was used for conditioning.

A sample of a mixed solution obtained by adding 30 ml of humic acid to a 2 ppm aqueous solution of bisphenol A was continuously poured into a cartridge, washed with water, and concentrated or recovered with methanol.

The collected sample was analyzed by HPLC (high performance liquid chromatography). The results are shown in FIGS. 1 and 2.

Chromatograms of humic acid in mobile phases of water and methanol are shown in FIG. As is clear from (1) of FIG. 1, it can be seen that humic acid was eluted in the mobile phase of water, and was hardly eluted in the case of methanol in (2) of FIG.

As is clear from (1) before concentration of the target substance in FIG. 2 and (2) after concentration, when water is used as the mobile phase,
Bisphenol A did not elute, but did elute with methanol. It is considered that some humic acids are not captured and adsorbed by the polymer material, and some are captured and adsorbed by the polymer material and do not elute even with methanol.

In (1) before concentration in FIG. 2, the peak area of the humic acid chromatogram was 85244 and the peak area of bisphenol A was 2976. In (2) after concentration in FIG. 2, the peak area of the humic acid chromatogram was 3033 + 4169 + 5571 (12773 in total), and the peak area of bisphenol A was 342859. Therefore, the target substance / humic acid before concentration was 2976/85244 = 0.0349, and the target substance / humic acid after concentration was 342859/12773 = 2
6.842, the ratio before and after concentration is 26.842 / 0.0349 = 769.1
It became 26. That is, it can be seen that the concentration can be about 700 times or more.

As is clear from FIG. 2, the bisphenol A has a large concentration effect, while the humic acid has no concentration effect. The polymer material filled in the cartridge was white before the sample was injected, whereas the brown color of humic acid was attached after the concentration operation. This and this could not be removed even by washing with methanol. This also shows that a part of the humic acid used is strongly adsorbed on the polymer material. Therefore, in concentrating a small amount of bisphenol A in the environmental sample, it was found that a part of the humic acid contained in the environmental sample can be removed by elution and a part can be removed by adsorption.

As a sample, bisphenol A
2 ppm aqueous solution (containing no humic acid) was poured into the above cartridge and separated or collected in the same manner, whereby about 1000-fold concentration was possible. Comparative Example 1 In the polymer material of Example 1, bisphenol A was used instead of tertiary butylphenol to prepare a polymer material.

The polymer material obtained was used to fill a glass cartridge in the same manner as in Example 1.

An aqueous solution of humic acid containing no bisphenol A was continuously poured into a cartridge, washed with water, and concentrated or recovered with methanol.

When the collected sample was analyzed by HPLC (high performance liquid chromatography), a peak of bisphenol A was observed.

Therefore, it is understood that accurate measurement is difficult with the polymer material of this comparative example.

As described above, according to the present invention, the selectivity is increased, non-specific trapping and adsorption of contaminants are reduced, and the target bisphenol A (BPA) is concentrated, separated, trapped, detected and extracted. Or collection is accurate and easy.

[0061]

As is clear from FIGS. 1 and 2, in capturing, recovering or separating a target substance contained in an environmental sample,
It has been shown that the polymeric material according to the present invention is effective. In addition, the method and polymer material of the present invention made it possible to remove humic acid by a substantially single-step treatment.
Furthermore, in the method and polymer material of the present invention, an environmental sample is treated in-situ (flowing to a column), washed with water, and humic acid is removed to concentrate the target substance,
It can be transported and brought to a place with analysis / measurement equipment, providing a highly convenient means.

[Brief description of drawings]

FIG. 1 shows chromatograms of humic acid in mobile phases of water and methanol.

FIG. 2 is a chromatograph using a polymer material according to the present invention before and after a concentration operation.

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP 2000-254490 (JP, A) JP 2001-55399 (JP, A) JP 2000-107597 (JP, A) JP 2000-254491 (JP, A) JP-A-11-21294 (JP, A) JP-A-2000-135435 (JP, A) JP-A-2000-79394 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 1/10-1/44 B01J 20/26 C02F 1/00 ZAB G01N 33/00

Claims (8)

(57) [Claims] 1. An environmental material containing humic acid, which may be or may be contained in an environmental sample.
A reactive compound in the presence of a target substance analog (B) in which at least one of the chemical structures, sizes or shapes of a part or fragment of the target substance (A) which is a low molecular weight organic compound is common or similar. By using the polymer material obtained by removing the target substance analog (B) from the product obtained by reacting the target substance (A) which is or may be contained in the environmental sample (A ) Concentration, separation, capture, detection,
A method for treating an environmental sample, characterized by extracting or recovering. 2. The target substance analog (B), which may be substituted, is a hydrocarbon group having 4 or more carbon atoms, which is contained in the chemical structural formula of a part or fragment of the target substance (A). The method for treating an environmental sample according to claim 1, wherein at least one of the aromatic hydrocarbon group, the cyclocyclic group, and the heterocyclic group is a polymeric material obtained by using a common or similar target substance analog. 3. The method for treating an environmental sample according to claim 1, wherein the reactive compound is obtained by including a crosslinkable compound having two or more reactive groups. 4. The method for treating an environmental sample according to claim 1, wherein the target substance (A) is bisphenol A, and the target substance analog (B) is tert-butylphenol. 5. The method for treating an environmental sample according to claim 4, wherein the environmental sample contains bisphenol A and humic acid. 6. Containing a target substance (A) and humic acid
An environmental sample that contains the target substance (A) /
Characterized by the ratio of myonic acid being 100 or more
4. The method for treating an environmental sample according to claim 1,
Law. 7. The target substance (A) / humic acid before and after treatment
7. The processing of environmental samples according to claim 6, wherein the ratio is 500 or more.
Method. 8. A method according to any one of claims 1 to 7.
Polymer materials used.