CN111198119A - Method for detecting octylphenol in textile based on molecular imprinting technology - Google Patents
Method for detecting octylphenol in textile based on molecular imprinting technology Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004753 textile Substances 0.000 title claims abstract description 24
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 229920000767 polyaniline Polymers 0.000 claims abstract description 17
- 238000007650 screen-printing Methods 0.000 claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
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- 239000007788 liquid Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000012417 linear regression Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- STFNYVGJFSEPJG-UHFFFAOYSA-N NC1=CC=CC=C1.C(CCCCCCC)C1=C(C=CC=C1)O Chemical compound NC1=CC=CC=C1.C(CCCCCCC)C1=C(C=CC=C1)O STFNYVGJFSEPJG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012445 acidic reagent Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000008363 phosphate buffer Substances 0.000 claims description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013076 target substance Substances 0.000 abstract 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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Abstract
The invention provides a method for detecting octylphenol in textiles based on a molecular imprinting technology, and belongs to the field of analysis and detection. Aiming at a detection target substance octylphenol, the method takes aniline as a monomer, detection target Octylphenol (OP) as a template molecule and nano titanium dioxide as a carrier, and uses FeCl as an oxidant3Obtaining OP-MIP/PPY/TiO through free radical polymerization under the action2A molecularly imprinted nanocomposite. The hydroxyl groups on the octylphenol form hydrogen bonds with the nitrogen atoms on the polyaniline, and thus the octylphenol can intercalate into the polymer backbone during polymerization to form pores. The nano titanium dioxide is a good carrier due to the large specific surface area. Obtained after elution of the template molecule octylphenolThe compound is modified on the surface of a screen printing electrode, so that the specific recognition of the octylphenol can be realized, and a rapid, sensitive and strong-specificity octylphenol detection method is established.
Description
Technical Field
The invention belongs to the field of analysis and detection, and particularly relates to a method for detecting octylphenol in textiles based on a molecular imprinting technology.
Background
The alkylphenol mainly comprises octylphenol and nonylphenol, and is mainly used as a pretreatment auxiliary agent in a printing and dyeing auxiliary agent in the production process of textiles, such as a scouring agent, a wetting agent, a penetrating agent and the like. The biodegradation rate of the alkylphenol is only 0-9%, and the alkylphenol can exist in the environment for a long time; meanwhile, the substances are similar to estrogen substances and can disturb the normal hormone secretion process of a human body. The EU directive No. 2003/53/EC states that the content of octylphenol and nonylphenol in chemicals and their preparations for the textile industry cannot be higher than 0.1%. The value of textiles and clothing exported to Europe every year in China reaches 100 hundred million dollars, and the method has very important significance for achieving foreign detection technical indexes, ensuring smooth export of the textiles in China and establishing accurate and rapid determination of the residual quantity of octylphenol and nonylphenol in the textiles.
The existing detection methods related to determination mainly comprise a high performance liquid chromatography, a gas chromatography-mass spectrometry method, a liquid chromatography-mass spectrometry combined method and the like. The traditional analysis method has high accuracy, but the operation process is complex, the cost of the instrument is high, and the detection time is long.
Disclosure of Invention
The invention aims to solve the problems and provides a method for detecting octylphenol in textiles based on a molecular imprinting technology.
The purpose of the invention can be realized by the following technical scheme:
a method for detecting octylphenol in textiles based on a molecular imprinting technology comprises the following steps:
the first step is as follows: adding aniline and octylphenol into isopropanol, and mixing and stirring uniformly at room temperature to form an aniline-octylphenol mixed solution;
the second step is that: water solution of titanium dioxide nano particles dispersed in isopropanolAdding an acidic reagent into the solution, and adding FeCl3·6H2O, continuously stirring for 20-40 min to form titanium dioxide particle dispersion liquid;
the third step: uniformly mixing the mixed solution obtained in the first step and the titanium dioxide particle dispersion liquid obtained in the second step, introducing nitrogen, deoxidizing, stirring for 24 hours, then repeatedly precipitating by using acetone as a precipitator until the solution is colorless, and performing suction filtration and drying to obtain the octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite;
the fourth step: preparing 5-15 mg/mL suspension of the octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite, mixing the suspension and 5-15 mg/mL chitosan solution uniformly in equal volume, dripping 5 mu L of the mixed solution onto the surface of a screen printing electrode, and drying;
the fifth step: placing the screen electrode in a disodium hydrogen phosphate solution with the concentration of 0.2mol/L, and eluting a template molecule octylphenol in the molecularly imprinted layer by using a potentiostatic method to obtain a screen printing electrode with the template removed;
and a sixth step: placing the screen printing electrode without the template in phosphate buffer solutions with different concentrations of octylphenol and pH values of 5.0, stirring for 3-8 minutes, then performing differential pulse scanning to generate an oxidation peak at 0.54V, wherein the current intensity value of the oxidation peak is in positive correlation with the adsorption quantity of the octylphenol on the surface of the electrode, and thus establishing a linear regression equation;
the seventh step: and (3) placing the screen printing electrode without the template in the pretreated solution of the sample to be detected, stirring for 3-8 minutes, then performing differential pulse scanning, and substituting the value of the oxidation peak into a linear regression equation, so as to calculate the concentration of the octylphenol in the sample to be detected.
The technical scheme of the invention is as follows: in the first step: the molar volume ratio of the aniline to the octylphenol to the isopropanol is 1-3 mmol: 0.3-0.8 mmol: 3-8 mL.
The technical scheme of the invention is as follows: the molar volume ratio of the aniline to the octylphenol to the isopropanol is 1-2 mmol: 0.4-0.6 mmol: 3-8 mL.
The technical scheme of the invention is as follows: in the second step: titanium dioxide nanoparticles: isopropyl alcohol: acid reagent: feCl3·6H2O: the mass ratio of water is 0.1-0.3: 2-3: 0.5-1: 0.1-0.3: 20 to 30.
The technical scheme of the invention is as follows: the volume ratio of the mixed solution in the first step to the titanium dioxide particle dispersion liquid in the second step is 1: 3-8.
The technical scheme of the invention is as follows: the operating voltage of the potentiostatic method in the fifth step is 1.3V.
The technical scheme of the invention is as follows: the scanning speed in the sixth step was 50 mV/s.
The technical scheme of the invention is as follows: the linear regression in the sixth step was i (μ a) ═ 0.2010c1(μ M) +2.2232, R20.997; the detection limit is as low as 8.36 multiplied by 10-9mol/L。
The technical scheme of the invention is as follows: the concentration of octylphenol was 5X 10 at various concentrations-8mol/L，3×10-7mol/L，6×10-7mol/L，3×10-6mol/L，6×10-6mol/L，1×10-5mol/L，2×10-5mol/L and 3X 10-5mol/L。
The technical scheme of the invention is as follows: the method for pretreating the textile in the seventh step comprises weighing 1.0g of sample, cutting into pieces of 5mm × 5mm or less, adding 10mL of methanol, extracting in 60 deg.C ultrasonic bath for 30min, collecting 1mL of extractive solution, and collecting N2Blow-dry, dissolve with 100. mu.L of a complex solution of 20. mu.L methanol and 80. mu.L of 0.01M PBS pH 7.4.
The technical scheme of the invention is as follows: aiming at detecting target octylphenol, according to the principle of surface molecular imprinting technology (as shown in figure 1), aniline is taken as a monomer, target Octylphenol (OP) is taken as a template molecule, nano titanium dioxide is taken as a carrier, and oxidizing agent FeCl is added3Obtaining OP-MIP/PPY/TiO through free radical polymerization under the action2A molecularly imprinted nanocomposite. The hydroxyl groups on the octylphenol form hydrogen bonds with the nitrogen atoms on the polyaniline, and thus the octylphenol can intercalate into the polymer backbone during polymerization to form pores. The nano titanium dioxide is a good carrier due to the large specific surface area. After the octylphenol of the template molecule is eluted, the obtained compound is modified on the surface of a screen printing electrode, so that the specificity to the octylphenol can be realizedAnd (3) performing sexual identification, and establishing a rapid, sensitive and strong-specificity octylphenol detection method.
The invention has the beneficial effects that:
the invention provides the octylphenol detection method with low detection cost and high detection sensitivity. The method can realize the specific recognition of the octylphenol, and establish a rapid, sensitive and strong-specificity detection method for the octylphenol and the nonylphenol.
Drawings
FIG. 1 is a scanning electron microscope image of (A) octylphenol-polyaniline titanium dioxide molecularly imprinted nano-composite and (B) polyaniline titanium dioxide molecularly imprinted nano-composite.
FIG. 2(A) is a graph of differential pulse voltammetry for octyl phenol, and (B) is a graph of the corresponding linear regression equation.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
Test instrument and consumable
The electrochemical experiment was performed on an electrochemical workstation CHI-660E (shanghai chenhua instruments ltd), a screen printed electrode (Nanjing Zhongke electrodes ltd), a conductive carbon paste working electrode, and a silver/silver chloride reference electrode.
Octylphenol-polyaniline titanium dioxide mixture
1.5mmol of aniline and 0.5mmol of octylphenol were added to 5mL of isopropanol and stirred for 1 hour to obtain an aniline-octylphenol mixed solution.
0.15g titanium dioxide nanoparticles, 3ml isopropanol, 0.8mol HCL, 0.7mmol FeCl3·6H2O, 27ml of secondary water and stirring at 0 ℃ for 30min to form a titanium dioxide particle dispersion.
Mixing 5mL of aniline-octylphenol mixed solution with 30mL of titanium dioxide particle dispersion liquid, introducing nitrogen, removing oxygen, stirring for 24 hours, then repeatedly precipitating by using acetone as a precipitator until the solution is colorless, and performing suction filtration and drying to obtain the dark green polyaniline. Grinding the dried substance into powder, and storing in a refrigerator at 4 deg.C, wherein the dried substance is octylphenol-polyaniline titanium dioxide molecularly imprinted nano-composite.
FIG. 1 shows the scanning electron microscope images of the synthesized octylphenol-polyaniline titanium dioxide molecularly imprinted composite and the polyaniline titanium dioxide molecularly imprinted nanocomposite without the added octylphenol, and it can be seen from FIG. 1 that the average pore diameter of the nanoparticles is about 10 nm. The hydroxyl on the nonyl phenol forms hydrogen bonds with nitrogen atoms on the polyaniline, and the nonyl phenol can be embedded into the polymer skeleton during polymerization to form pores.
Preparation of electrode of octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite
And preparing the octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite into a suspension of 10 mg/mL. The chitosan was formulated into a 10mg/mL chitosan solution. Mixing the two solutions 1:1, dripping 5 mu L of the mixed solution on the surface of a screen printing electrode, and drying.
And then placing the screen electrode in a disodium hydrogen phosphate solution with the concentration of 0.2mol/L to elute the template molecule octylphenol in the molecularly imprinted layer by a potentiostatic method (the working voltage is 1.3V). In the process, because a positive potential is applied under an alkaline condition, the imprinted polymer film is oxidized in the elution process, so that the aniline skeleton loses the electropositivity, meanwhile, the template molecules are negatively charged under the alkaline condition, and the template and the functional monomer are separated due to static repulsion, namely the polyaniline molecular imprinted electrode screen printing electrode without the template is obtained.
Octylphenol test
After screen printing electrodes with the stencil removed were placed at pH5.0 with various concentrations of octylphenol (5X 10)-8mol/L，3×10-7mol/L，6×10-7mol/L，3×10-6mol/L，6×10-6mol/L，1×10-5mol/L，2×10-5mol/L and 3X 10-5mol/L) phosphate buffer solution, stirred for 5 minutes. Differential pulse scanning is carried out, the scanning range is 0.3V-0.8V, and the scanning speed is 50 mV/s.
Mixing Fe3O4The polydopamine molecularly imprinted nanoparticles are fixed on the surface of screen printing, after a porous molecularly imprinted layer adsorbs target molecule octylphenol, the octylphenol is embedded into moleculesIn the imprinting layer, octyl phenol molecules specifically adsorbed on the surface of the electrode are oxidized by using Differential Pulse Voltammetry (DPV), an oxidation peak is generated at 0.54V, the current intensity value of the oxidation peak is positively correlated with the adsorption quantity of the octyl phenol on the surface of the electrode, and is further positively correlated with the concentration of the octyl phenol in the solution, so that the quantitative basis of detection is established. As shown in FIG. 2, 5X 10 adsorption-8To 3X 10-5The relation between the DPV response curve generated by the octylphenol solution of mol/L and the oxidation peak current and the concentration of the octylphenol, the oxidation peak current I (mu A) and the concentration c (mu mol/L) of the octylphenol are 5 multiplied by 10-8～3×10- 5The regression equation of the linear relation in the mol/L range is that i (mu A) is 0.2010c1 (mu M) +2.2232 (R)20.997). The detection limit is as low as 8.36 multiplied by 10-9mol/L。
Recovery and precision of the process
And (3) respectively adding 0.5 and 50 mu g/L of octylphenol to 2 kinds of linings without octylphenol in the background by adopting a standard adding method, performing standard adding recovery measurement, independently measuring each level for 5 times, and calculating the recovery rate and the precision of the method. The test results are shown in Table 1.
TABLE 1 recovery and relative standard deviation of blank sample spiking recovery test
Determination of octylphenol in textiles by screen-printed electrodes
Weighing 1.0g sample, cutting to pieces of 5mm × 5mm or less, adding 10mL methanol, extracting in 60 deg.C ultrasonic bath for 30min, collecting 1mL extractive solution, and collecting N2Blow-dry, dissolve with 100. mu.L of a complex solution of 20. mu.L methanol and 80. mu.L of 0.01M PBS pH 7.4. The test was carried out using the method described above. The measured results are compared with the gas chromatography-mass spectrometry method as shown in the table below, and from the results, the method has high consistency with the results of the traditional analysis method, which indicates that the method has good reliability.
TABLE 2 determination of positive samples and comparison of results with conventional methods
Claims (10)
1. A method for detecting octylphenol in textiles based on a molecular imprinting technology is characterized by comprising the following steps: the method comprises the following steps:
the first step is as follows: adding aniline and octylphenol into isopropanol, and mixing and stirring uniformly at room temperature to form an aniline-octylphenol mixed solution;
the second step is that: dispersing titanium dioxide nano particles in isopropanol water solution, adding an acid reagent, and then adding FeCl3·6H2O, continuously stirring for 20-40 min to form titanium dioxide particle dispersion liquid;
the third step: uniformly mixing the mixed solution obtained in the first step and the titanium dioxide particle dispersion liquid obtained in the second step, introducing nitrogen, deoxidizing, stirring for 24 hours, then repeatedly precipitating by using acetone as a precipitator until the solution is colorless, and performing suction filtration and drying to obtain the octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite;
the fourth step: preparing 5-15 mg/mL suspension of the octylphenol-polyaniline titanium dioxide molecularly imprinted nano composite, mixing the suspension and 5-15 mg/mL chitosan solution uniformly in equal volume, dripping 5 mu L of the mixed solution onto the surface of a screen printing electrode, and drying;
the fifth step: placing the screen electrode in a disodium hydrogen phosphate solution with the concentration of 0.2mol/L, and eluting a template molecule octylphenol in the molecularly imprinted layer by using a potentiostatic method to obtain a screen printing electrode with the template removed;
and a sixth step: placing the screen printing electrode without the template in phosphate buffer solutions with different concentrations of octylphenol and pH values of 5.0, stirring for 3-8 minutes, then performing differential pulse scanning to generate an oxidation peak at 0.54V, wherein the current intensity value of the oxidation peak is in positive correlation with the adsorption quantity of the octylphenol on the surface of the electrode, and thus establishing a linear regression equation;
the seventh step: and (3) placing the screen printing electrode without the template in the pretreated solution of the sample to be detected, stirring for 3-8 minutes, then performing differential pulse scanning, and substituting the value of the oxidation peak into a linear regression equation, so as to calculate the concentration of the octylphenol in the sample to be detected.
2. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: in the first step: the molar volume ratio of the aniline to the octylphenol to the isopropanol is 1-3 mmol: 0.3-0.8 mmol: 3-8 mL.
3. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 2, characterised in that: the molar volume ratio of the aniline to the octylphenol to the isopropanol is 1-2 mmol: 0.4-0.6 mmol: 3-8 mL.
4. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: in the second step: titanium dioxide nanoparticles: isopropyl alcohol: acid reagent: FeCl3·6H2O: the mass ratio of water is 0.1-0.3: 2-3: 0.5-1: 0.1-0.3: 20 to 30.
5. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: the volume ratio of the mixed solution in the first step to the titanium dioxide particle dispersion liquid in the second step is 1: 3-8.
6. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: the operating voltage of the potentiostatic method in the fifth step is 1.3V.
7. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: the scanning speed in the sixth step was 50 mV/s.
8. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: in the sixth stepIs i (μ a) ═ 0.2010c1(μ M) +2.2232, R20.997; the detection limit is as low as 8.36 multiplied by 10- 9mol/L。
9. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: the concentration of octylphenol was 5X 10 at various concentrations-8mol/L，3×10-7mol/L，6×10-7mol/L，3×10-6mol/L，6×10-6mol/L，1×10-5mol/L，2×10-5mol/L and 3X 10-5mol/L。
10. The method for detecting octylphenol in textiles based on molecular imprinting technology as claimed in claim 1, characterised in that: the method for pretreating the textile in the seventh step comprises weighing 1.0g of sample, cutting into pieces of 5mm × 5mm or less, adding 10mL of methanol, extracting in 60 deg.C ultrasonic bath for 30min, collecting 1mL of extractive solution, and collecting N2Blow-dry, dissolve with 100. mu.L of a complex solution of 20. mu.L methanol and 80. mu.L of 0.01M PBS pH 7.4.
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