CN111122555B - Tetrabromobisphenol A imprinted composite material and application thereof - Google Patents
Tetrabromobisphenol A imprinted composite material and application thereof Download PDFInfo
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- CN111122555B CN111122555B CN201811282263.0A CN201811282263A CN111122555B CN 111122555 B CN111122555 B CN 111122555B CN 201811282263 A CN201811282263 A CN 201811282263A CN 111122555 B CN111122555 B CN 111122555B
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 238000011161 development Methods 0.000 claims abstract description 11
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 12
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 2
- 230000004069 differentiation Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000005375 photometry Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 102000004190 Enzymes Human genes 0.000 abstract description 3
- 108090000790 Enzymes Proteins 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003556 assay Methods 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 2
- RVHUMFJSCJBNGS-UHFFFAOYSA-N 2-[2,6-dibromo-4-[2-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C(Br)=C(OCCO)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCCO)C(Br)=C1 RVHUMFJSCJBNGS-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 2
- -1 amino modified ferroferric oxide Chemical class 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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Abstract
The invention provides a molecular imprinting/enzyme-like catalysis composite material for recognizing tetrabromobisphenol A with high selectivity, and provides an ultrasensitive high-selectivity method for detecting tetrabromobisphenol A on the basis. On one hand, the imprinted composite material can identify TBBPA with high selectivity, avoid sample matrix interference and ensure the sensitivity of the analysis method, and meanwhile, the adsorbed TBBPA can be degraded by an enzyme-like catalytic material-H2O 2 system to consume the content of H2O 2; on the other hand, the adsorption of TBBPA on the surface of the imprinting material leads to the reduction of the activity of the enzyme-like catalytic material in the residual holes and the reduction of the catalytic capability on the substrate. Therefore, due to the selective adsorption of TBBPA, not only the catalytic activity of the enzyme is weakened in the substrate color development process, but also the content of H2O2 is reduced, and the ultrasensitive high-selectivity detection of TBBPA can be realized. This dual signal amplification strategy can significantly improve the sensitivity and selectivity of the assay.
Description
Technical Field
The invention belongs to the field of chemical detection and analysis, and particularly relates to a tetrabromobisphenol A imprinted composite material.
Background
Tetrabromobisphenol a (TBBPA) is one of the most commonly used brominated flame retardants in the world today. It is widely added to electronic products and plastic products as a reactive brominated flame retardant to slow or stop the spread of fire. Due to the large amount of TBBPA used, the detection can be carried out in various environmental media. Research shows that TBBPA has various toxic effects on human bodies, including endocrine disrupting effects, liver/kidney toxicity, neurotoxic effects and immune system toxicity, wherein the endocrine disrupting effects are the most obvious. Recently, the world health organization international agency for research on cancer (in the published list of carcinogens, TBBPA has been classified as a 2A (possibly carcinogenic to human) carcinogen.
At present, mass spectrometry is a common method for detecting TBBPA, but the technology requires complex instrument and equipment, professional technicians and high operation cost. The development of rapid, convenient, cheap and sensitive analysis technology is imperative. The molecular imprinting technology, as a high molecular material, can selectively recognize target molecules, and remarkably reduce sample matrix interference, but how to improve the sensitivity of the method is a difficult problem of a rapid detection technology. The traditional method is to combine a molecular imprinting material and an enzyme-like catalytic material into a whole to prepare a composite material, selectively identify target molecules by means of a surface molecular imprinting film, and simultaneously reduce residual imprinting holes due to selective adsorption and reduce the activity of an internal enzyme-like catalytic material, so that the chromogenic reaction of substrate molecules is reduced, and the detection of the target molecules is realized. Namely: selective adsorption target molecules are increased, residual imprinting holes are reduced, enzyme-like catalytic activity is weakened, and substrate color development capability is reduced.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a tetrabromobisphenol A imprinted composite material and a method for detecting TBBPA with ultrasensitiveness and high selectivity.
One of the objectives of the present invention is to provide a molecular imprinting/enzyme-like catalytic composite material that recognizes tetrabromobisphenol a with high selectivity.
The technical scheme for realizing the invention is as follows:
the method for preparing the ultrasensitive high-selectivity tetrabromobisphenol A imprinted/enzyme-like catalytic composite material comprises the following steps:
(1) ultrasonically dispersing a material with the enzyme-like catalysis characteristic in ethanol, adding 3-aminopropyltriethoxysilane, tetraethoxysilane and acetic acid, and reacting for 2-10 hours at the temperature of 20-80 ℃ to obtain an amino-modified enzyme-like catalysis material;
(2) adding 3-aminopropyltriethoxysilane, tetraethoxysilane, tetrabromobisphenol A and acetic acid into ethanol, adding the amino-modified enzyme-like catalytic material obtained in the step (1), reacting for 6-24 hours at the temperature of 20-80 ℃, and washing off the template tetrabromobisphenol A by using ethanol to obtain the tetrabromobisphenol A imprinted composite material.
The enzyme-like catalytic material in the step (1) can be one of ferroferric oxide nanoparticles, graphene materials, carbon nanotube materials, nanogold and metal organic framework materials, and the concentration of the enzyme-like catalytic material is 0.5-5% of ethanol in terms of mass (g)/volume (ml) percentage concentration (W/V);
preferably, the volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane in the step (1) is 1: the total volume of the 2-5, 3-aminopropyltriethoxysilane and the tetraethoxysilane accounts for 1-10% of the volume of the ethanol.
Preferably, the concentration of the acetic acid in the step (1) is 5-20% of that of ethanol by volume percentage;
preferably, the volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane in the step (2) is 1: the total volume of 0.5-2, 3-aminopropyltriethoxysilane and tetraethoxysilane accounts for 1-10% of the volume of ethanol.
Preferably, the tetrabromobisphenol A in the step (2) is 1-5% of ethanol in terms of mass (g)/volume (ml) percentage concentration (W/V), and the concentration of the acetic acid is 0.5-5% of the ethanol in terms of volume percentage.
The invention provides a tetrabromobisphenol A imprinted composite material prepared by the preparation method.
The invention provides an application of a tetrabromobisphenol A imprinted composite material prepared by the preparation method of the tetrabromobisphenol A imprinted composite material in detecting tetrabromobisphenol A.
The invention also aims to provide an ultrasensitive high-selectivity method for detecting tetrabromobisphenol A, which comprises the following steps:
s1: preparing a tetrabromobisphenol A imprinted composite material by the method according to any one of claims 1 to 6;
s2: detecting tetrabromobisphenol A:
setting a control group: incubating the imprinted composite material prepared in the step S1 with a tetrabromobisphenol A methanol solution with a known concentration at normal temperature, centrifuging, and washing with triple distilled water; adding H with the concentration of 50-500 mmol/L2O2Incubating the solution for 10-20 minutes; adding 3,3',5,5' -tetramethyl benzidine with the concentration of 2-20mmol/L and 0.2mol/L, pH, 3-5 acetic acid buffer solution, and incubating for 20-50 minutes;
setting an experimental group: incubating the imprinted composite material prepared in the step S1 with tetrabromobisphenol A methanol solution with unknown concentration to be detected at normal temperature, centrifuging and washing with triple distilled water; adding H with the concentration of 50-500 mmol/L2O2Incubating the solution for 10-20 minutes; adding 3,3',5,5' -tetramethylbenzidine with the concentration of 2-20mmol/L and acetic acid buffer solution with the concentration of 0.2mol/L, pH ═ 3-5, and incubating for 20-50 minutes;
s3: color development and contrast:
if tetrabromobisphenol A is contained, the catalytic color development reaction of 3,3',5,5' -tetramethylbenzidine can occur, and the higher the concentration of tetrabromobisphenol A is, the lighter the blue color is, compared with the color of a control group in the color of an experimental group; when the tetrabromobisphenol A in the experimental group and the tetrabromobisphenol A in the control group are close to each other in color, an instrument is used for distinguishing.
The differentiation performed by the instrument in step S3 may be specifically performed by photometric measurement using an ultraviolet spectrophotometer or a microplate reader, or gray value analysis performed by scanning colors using a scanner.
The detection method provided by the invention has the specific mechanism that: on one hand, the imprinted composite material can identify TBBPA with high selectivity, avoid sample matrix interference and ensure the sensitivity of the analysis method, and meanwhile, the adsorbed TBBPA can be degraded by an enzyme-like catalytic material-H2O 2 system to consume the content of H2O 2; on the other hand, the adsorption of TBBPA on the surface of the imprinting material leads to the reduction of the activity of the enzyme-like catalytic material in the residual holes, the catalytic capability of the substrate is weakened, and the high-sensitivity and high-selectivity detection of the TBBPA is realized. Namely: the selective adsorption target molecules are increased, the H2O2 required by degradation is increased, residual imprinting holes are reduced, the catalytic activity of enzyme-like enzymes is weakened, and the substrate color development capability is reduced. Due to the selective adsorption of TBBPA, not only the catalytic activity of the enzyme-like enzyme is weakened, but also the content of H2O2 is reduced in the substrate color development process. This dual signal amplification strategy can significantly improve the sensitivity and selectivity of the assay.
The invention has the following advantages and beneficial effects: tetrabromobisphenol A (TBBPA) is one of the most commonly used brominated flame retardants in the world at present and can be detected in various environmental media. At present, mass spectrometry is a common method for detecting TBBPA, but the technology requires complex instrument and equipment, professional technicians and high operation cost. Although the electrochemical analysis method is simple and convenient, the method has low sensitivity, is easily interfered by a sample matrix, and is difficult to be used for an actual sample with a complex matrix. The method for detecting TBBPA provided by the invention provides a technical support for environmental pollution monitoring and population health hazard research.
Drawings
FIG. 1(A) is HKUST-1, FIG. 1(B) is amino modified HKUST-1 and FIG. 1(C) is electron microscope image of TBBPA molecular imprinting/HKUST-1 composite material;
FIG. 2 shows the adsorption effect of the molecularly imprinted/HKUST-1 composite material on TBBPA;
FIG. 3 is the selectivity of the analysis method based on the molecularly imprinted/HKUST-1 composite material for TBBPA. The abbreviations for the various substances in the figures are as follows: TBBPA: tetrabromobisphenol A; TCBPA: tetrachlorobisphenol A; BPA: bisphenol A; TBBPA-BHEE: tetrabromobisphenol a-bis (2-hydroxyethyl) ether; TBBPA-BAE: tetrabromobisphenol a-diallyl oxide; TBBPS: tetrabromobisphenol S; and (2) BPS: bisphenol S; in the figure, Δ G is a gray scale difference;
FIG. 4 shows the linear range of the ultrasensitive high selectivity detection method proposed in this patent, where Δ G is the gray scale difference.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
(1) Preparation of tetrabromobisphenol A imprinted composite material
1.1) dispersing 500mg of ferroferric oxide magnetic particles into 10mL of ethanol, and carrying out ultrasonic dispersion for 5 minutes. And then, adding 3-aminopropyltriethoxysilane, tetraethoxysilane and 5% acetic acid into the solution, and reacting for 2 hours at the temperature of 40 ℃ to ensure the modification of amino groups on the surface of the enzyme-like catalytic material. The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1:2, the total volume of the two accounts for 1 percent of the volume of the ethanol.
1.2) adding tetrabromobisphenol A, 3-aminopropyltriethoxysilane, tetraethoxysilane and 0.5 percent acetic acid into ethanol, adding the amino modified ferroferric oxide magnetic particles, and reacting for 6 hours at the temperature of 40 ℃. And washing the template tetrabromobisphenol A by using ethanol to obtain the tetrabromobisphenol A imprinted composite material.
The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1: 0.5, and the total volume of the two accounts for 1 percent of the volume of the ethanol. Tetrabromobisphenol A is 1 percent of ethanol in terms of mass/volume percentage concentration (W/V), and acetic acid is 0.5 percent of ethanol in terms of volume percentage.
(2) Ultrasensitive high-selectivity detection of tetrabromobisphenol A
And (3) incubating the prepared imprinted composite material with a methanol solution of tetrabromobisphenol A for 15 minutes at normal temperature, centrifuging, and washing with triple distilled water of not more than 1mL for 2 times to further remove sample impurities. Add 20 μ L H2O2The solution (100mM) was incubated for 10 minutes to effect degradation of tetrabromobisphenol A adsorbed onto the imprinted composite material. Subsequently, 50. mu.L of 3,3',5,5' -tetramethylbenzidine (2mM) and 50. mu.L of acetic acid buffer (0.2M, pH 3) were added and incubated for 20 minutes to effect catalytic color development of 3,3',5,5' -tetramethylbenzidine, establishing a novel method for trace detection of tetrabromobisphenol A.
Example 2
(1) Preparation of tetrabromobisphenol A imprinted composite material
1.1) dispersing 500mg of carbon nanotubes in 100mL of ethanol, and ultrasonically dispersing for 30 minutes. And then, adding 3-aminopropyltriethoxysilane, tetraethoxysilane and 20% acetic acid into the solution, and reacting for 10 hours at the temperature of 50 ℃ to ensure the modification of amino groups on the surface of the enzyme-like catalytic material. The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1:5, and the total volume of the 3-aminopropyltriethoxysilane and the tetraethoxysilane accounts for 10% of the volume of the ethanol.
1.2) adding tetrabromobisphenol A, 3-aminopropyltriethoxysilane, tetraethoxysilane and acetic acid into ethanol, adding the amino modified carbon nano tube, and reacting for 24 hours at the temperature of 50 ℃. And washing the template tetrabromobisphenol A by using ethanol to obtain the tetrabromobisphenol A imprinted composite material.
The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1:2, and the total volume of the 3-aminopropyltriethoxysilane and the tetraethoxysilane accounts for 10% of the volume of the ethanol. Tetrabromobisphenol A is 5% of ethanol by mass/volume percentage concentration (W/V), and acetic acid is 5% of ethanol by volume percentage.
(2) Ultrasensitive high-selectivity detection of tetrabromobisphenol A
And (3) incubating the prepared imprinted composite material with a methanol solution of tetrabromobisphenol A for 60 minutes at normal temperature, centrifuging, and washing with triple distilled water of not more than 1mL for 2 times to further remove sample impurities. Add 20 μ L H2O2The solution (50mM) was incubated for 20 minutes to effect degradation of tetrabromobisphenol a adsorbed onto the imprinted composite material. Subsequently, 50. mu.L of 3,3',5,5' -tetramethylbenzidine (20mM) and 50. mu.L of acetic acid buffer (0.2M, pH 5) were added and incubated for 50 minutes to effect catalytic color development of 3,3',5,5' -tetramethylbenzidine, establishing a novel method for trace detection of tetrabromobisphenol A.
Example 3
(1) Preparation of tetrabromobisphenol A imprinted composite material
1.1) 500mg of metal organic framework material (HKUST-1) was dispersed in 10mL of ethanol and ultrasonically dispersed for 10 minutes. And then, adding 3-aminopropyltriethoxysilane, tetraethoxysilane and 10% acetic acid into the solution, and reacting for 6 hours at the temperature of 60 ℃ to ensure the modification of amino groups on the surface of the enzyme-like catalytic material. The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1: 4, the total volume of the two accounts for 5 percent of the volume of the ethanol.
1.2) adding tetrabromobisphenol A, 3-aminopropyltriethoxysilane, tetraethoxysilane and acetic acid into ethanol, adding the amino modified material metal organic framework material, and reacting for 12 hours at the temperature of 60 ℃. And washing the template tetrabromobisphenol A by using ethanol to obtain the tetrabromobisphenol A imprinted composite material. The volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane is 1: 1, the total volume of the two accounts for 2 percent of the volume of the ethanol. Tetrabromobisphenol A is 2 percent of ethanol by mass/volume percentage concentration (W/V), and acetic acid is 1 percent of ethanol by volume percentage.
(2) Ultrasensitive high-selectivity detection of tetrabromobisphenol A
And (3) incubating the prepared imprinted composite material with a methanol solution of tetrabromobisphenol A for 20 minutes at normal temperature, centrifuging, and washing with triple distilled water of not more than 1mL for 2 times to further remove sample impurities. Add 20 μ L H2O2The solution (50mM) was incubated for 15 minutes to effect degradation of tetrabromobisphenol a adsorbed onto the imprinted composite material. Subsequently, 50. mu.L of 3,3',5,5' -tetramethylbenzidine (10mM) and 50. mu.L of acetic acid buffer (0.2M, pH 4) were added and incubated for 30 minutes to effect catalytic color development of 3,3',5,5' -tetramethylbenzidine, establishing a novel method for trace detection of tetrabromobisphenol A.
FIG. 1 shows an electron micrograph of a TBBPA molecularly imprinted/HKUST-1 composite material prepared in example 3. The results show that: the HKUST-1 material has a large specific surface area, the amino modified HKUST-1 material presents a porous characteristic, and a subsequently prepared TBBPA imprinted film is uniformly distributed on the surface of the material and is stably combined.
The TBBPA molecular imprinting/HKUST-1 composite material (20mg) prepared in example 3 was soaked in 10ml ethanol solutions containing TBBPA with different concentrations, and then dried for 4 hours under oscillation at normal temperature. After being washed by deionized water, the TBBPA content in the supernatant is determined by adopting a liquid chromatography, and the adsorption capacity of the TBBPA molecular imprinting/HKUST-1 composite material to the TBBPA is further calculated. As shown in FIG. 2, the adsorption capacity of TBBPA molecularly imprinted/HKUST-1 composite material for TBBPA reaches 187.3mg/g, while the adsorption capacity of the control non-imprinted material is 24.6mg/g, and the selectivity factor reaches 7.6. The selectivity factor of TBBPA molecular imprinting material reported in literature is between 1.8 and 4.3, and the adsorption capacity is 45 to 95mg/g, which proves that the preparation method provided by the patent has excellent selective adsorption effect on TBBPA.
FIG. 3 shows the selectivity of the ultrasensitive high selectivity method for detecting tetrabromobisphenol A as set forth in example 3. The content of TBBPA and structural analogues was 1 ng/mL. The results show that: 1/10 of the gray value caused by the structural analogue with the same concentration and the gray value lack of TBBPA is far lower than the lowest limit value of the linear range of the method, which shows that the selectivity of the analysis method is extremely high, the TBBPA detection is not interfered by the structural analogue, and the method can be really used for the analysis of the actual sample.
FIG. 4 shows the linear range of the ultrasensitive high selectivity method for detecting tetrabromobisphenol A as set forth in example 3. The results show that: in the concentration range of 0.01-10ng/mL, the log value of the concentration and the gray value of the color reaction present a good linear range. The detection limit of the method is 3 pg/mL. The literature reports that: the detection limit of the liquid chromatography mass spectrum is generally 600pg/mL, the detection limit based on the biological antibody color reaction is 30ng/mL, and the detection limit based on the molecular imprinting material electrochemical sensor is 120-
480pg/mL, the detection limit of the molecular imprinting material-based fluorescence sensor is 814pg/mL, and the detection limit of the recommended method of the invention is 1/10-1/271 of the reported method, which shows that the analysis method can detect tetrabromobisphenol A with ultra-sensitivity and high selectivity.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of tetrabromobisphenol A imprinted composite material is characterized by comprising the following steps:
(1) ultrasonically dispersing a material with the enzyme-like catalysis characteristic in ethanol, adding 3-aminopropyltriethoxysilane, tetraethoxysilane and acetic acid, and reacting for 2-10 hours at the temperature of 20-80 ℃ to obtain an amino-modified enzyme-like catalysis material; the enzyme-like catalytic material is one of ferroferric oxide nanoparticles, graphene materials, carbon nanotube materials, nanogold and metal organic framework materials;
(2) adding 3-aminopropyltriethoxysilane, tetraethoxysilane, tetrabromobisphenol A and acetic acid into ethanol, adding the amino-modified enzyme-like catalytic material obtained in the step (1), reacting for 6-24 hours at the temperature of 20-80 ℃, and washing off the template tetrabromobisphenol A by using ethanol to obtain the tetrabromobisphenol A imprinted composite material.
2. The method of claim 1, wherein the concentration of the enzyme-like catalytic material is 0.5-5% by mass/volume (W/V).
3. The method of preparing a tetrabromobisphenol a imprinted composite material according to claim 1, wherein: the volume ratio of the 3-aminopropyltriethoxysilane to the tetraethoxysilane in the step (1) is 1: the total volume of the 2-5, 3-aminopropyltriethoxysilane and the tetraethoxysilane accounts for 1-10% of the volume of the ethanol.
4. The preparation method of the tetrabromobisphenol A imprinted composite material according to claim 1, wherein the concentration of the acetic acid in the step (1) is 5-20% by volume of ethanol.
5. The method of preparing tetrabromobisphenol a imprinted composite material according to claim 1, wherein the volume ratio of 3-aminopropyltriethoxysilane to tetraethoxysilane in step (2) is 1: the total volume of 0.5-2, 3-aminopropyltriethoxysilane and tetraethoxysilane accounts for 1-10% of the volume of ethanol.
6. The method for preparing tetrabromobisphenol A imprinted composite material according to claim 1, wherein the concentration of tetrabromobisphenol A in step (2) is 1-5% by mass/volume percent (W/V), and the concentration of acetic acid is 0.5-5% by volume percent of ethanol.
7. A tetrabromobisphenol A imprinted composite material prepared by the method of any one of claims 1 to 6.
8. Use of the tetrabromobisphenol a imprinted composite material of claim 7 for detecting tetrabromobisphenol a.
9. A method for detecting tetrabromobisphenol a, comprising the steps of:
s1: preparing a tetrabromobisphenol A imprinted composite material by the method according to any one of claims 1 to 6;
s2: detecting tetrabromobisphenol A:
setting a control group: incubating the imprinted composite material prepared in the step S1 with a tetrabromobisphenol A methanol solution with a known concentration at normal temperature, centrifuging, and washing with triple distilled water; adding H with the concentration of 50-500 mmol/L2O2Incubating the solution for 10-20 minutes; adding 3,3',5,5' -tetramethylbenzidine with the concentration of 2-20mmol/L and acetic acid buffer solution with the concentration of 0.2mol/L, pH ═ 3-5, and incubating for 20-50 minutes;
setting an experimental group: incubating the imprinted composite material prepared in the step S1 with tetrabromobisphenol A methanol solution with unknown concentration to be detected at normal temperature, centrifuging and washing with triple distilled water; adding H with the concentration of 50-500 mmol/L2O2Incubating the solution for 10-20 minutes; adding 3,3',5,5' -tetramethylbenzidine with the concentration of 2-20mmol/L and acetic acid buffer solution with the concentration of 0.2mol/L, pH ═ 3-5, and incubating for 20-50 minutes;
s3: color development and contrast:
comparing the color of the experimental group with the color of the control group, the higher the concentration of tetrabromobisphenol A is, the lighter the blue color is; when the tetrabromobisphenol A in the experimental group and the tetrabromobisphenol A in the control group are not distinguishable by naked eyes, an instrument is used for distinguishing.
10. The method according to claim 9, wherein the differentiation in step S3 is performed by using an instrument, specifically, by performing photometric analysis using an ultraviolet spectrophotometer, a microplate reader, or by performing gray value analysis by scanning colors using a scanner.
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