CN105363394A - Preparation and application of magnetic fluorescent molecule imprinting nano-microspheres for detecting nitrobenzene - Google Patents
Preparation and application of magnetic fluorescent molecule imprinting nano-microspheres for detecting nitrobenzene Download PDFInfo
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- CN105363394A CN105363394A CN201510615058.1A CN201510615058A CN105363394A CN 105363394 A CN105363394 A CN 105363394A CN 201510615058 A CN201510615058 A CN 201510615058A CN 105363394 A CN105363394 A CN 105363394A
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000004005 microsphere Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007885 magnetic separation Methods 0.000 claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 11
- 238000010791 quenching Methods 0.000 claims abstract description 9
- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 230000008859 change Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002077 nanosphere Substances 0.000 claims description 18
- 239000012086 standard solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920000547 conjugated polymer Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 10
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000005576 amination reaction Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
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- 238000005303 weighing Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IOFGMNBDIDEBIQ-UHFFFAOYSA-N 3,5-dibromobenzamide Chemical compound NC(=O)C1=CC(Br)=CC(Br)=C1 IOFGMNBDIDEBIQ-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000006070 nanosuspension Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 2
- QFWOJNOZWMHNTK-UHFFFAOYSA-N (7-borono-9,9-dihexylfluoren-2-yl)boronic acid Chemical compound C1=C(B(O)O)C=C2C(CCCCCC)(CCCCCC)C3=CC(B(O)O)=CC=C3C2=C1 QFWOJNOZWMHNTK-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 229920001109 fluorescent polymer Polymers 0.000 abstract description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- SHZXKQJLRLVYGP-UHFFFAOYSA-N 2-[7-(1,3,2-dioxaborinan-2-yl)-9,9-dihexylfluoren-2-yl]-1,3,2-dioxaborinane Chemical compound C1=C2C(CCCCCC)(CCCCCC)C3=CC(B4OCCCO4)=CC=C3C2=CC=C1B1OCCCO1 SHZXKQJLRLVYGP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
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- 230000036952 cancer formation Effects 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 238000002848 electrochemical method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to preparation and application of magnetic fluorescent molecule imprinting nano-microspheres for detecting nitrobenzene. Magnetic ferroferric oxide nano-particles serve as a solid-phase supporting medium to prepare the fluorescent molecule imprinting nano-microspheres, and nitrobenzene in water is selectively and quantitatively detected according to the change of fluorescence intensity. According to the method, the monodisperse ferroferric oxide nano-particles are prepared through a hydrothermal method; the surfaces of the ferroferric oxide nano-particles are chemically modified, the ferroferric oxide nano-particles are connected with fluorescent polymers through a covalent bond reaction, and then the fluorescent molecule imprinting nano-microspheres are prepared; the concentration of nitrobenzene in water is detected through magnetic separation and enrichment, it is detected through tests that a good linear relation is formed between fluorescence quenching intensity and nitrobenzene within the concentration range of 5.0*10<-8>-1.0*10<-7> mol/L, and the lower detection limit is 2.0*10<-8> (S/N=3). By combining the ferroferric oxide nano-particles and the fluorescent molecule imprinting material with high specificity, a trace amount of nitrobenzene in water can be detected in an enrichment and high-selectivity mode.
Description
Technical Field
The invention belongs to the technical field of nano material science and analytical chemistry, and particularly relates to preparation and application of a magnetic fluorescent molecularly imprinted nano microsphere for detecting nitrobenzene.
Background
The nitrobenzene compounds are substances with high toxicity and difficult degradability, have accumulation in the environment and have great harm to human bodies, animals and plants after long-term contact. For example, nitrobenzene washing wastewater contains a particularly high amount of nitrobenzene in addition to a small amount of benzene, nitrobenzene, dinitrobenzene, dinitrotoluene, trinitrotoluene, dinitrochlorobenzene, and the like. It is generally twice as toxic as other compounds and will be harmful toHuman productSudden onset or carcinogenesis. In addition, if the wastewater containing nitrobenzene substances is directly discharged into a natural water environment, serious pollution is caused to water bodies, and the nitrobenzene has extremely high stability in the water, so that the caused water body pollution lasts for a long time.
At present, various methods are used for detecting nitrobenzene compounds, such as gas chromatography, high performance liquid chromatography, capillary electrophoresis, chromatography-mass spectrometry, photometry, electrochemical methods and the like. The photometric method is widely applied to the determination of nitrobenzene compounds due to the advantages of simple instrument and equipment, convenient operation and the like. The national standard GB/T15501-1955 stipulates that zinc powder is applied to reduce nitrobenzene compounds in experimental operation, and certain system errors are caused because porous zinc slag and filter paper generated after the zinc powder is reduced have certain adsorption force. Therefore, the pollution of the nitrobenzene compounds to human health and environment is not negligible, and some methods for quickly, sensitively and accurately detecting the nitrobenzene compounds are awaited to be developed.
Since the theme of the teaching of Swager of the science and engineering university of ma province in 1998 made a breakthrough progress in detecting the vapor of the nitroaromatic compound by using the fluorescent conjugated polymer film, the fluorescence sensing technology based on photoinduced electron transfer was considered as a better detection means for the nitroaromatic compound, and the detection sensitivity was 30 times higher than that of the other technologies. Fluorescent conjugated polymers are understood to mean polymers having a pi-pi*The linear conjugated polymer with conjugated electronic structure makes the light collected by each monomer capable of being transmitted in the form of aggregate to produce signal multiplication effect. The property determines that the method has the capability of detecting the ultra-low content of the substance to be detected, and provides a good method for realizing high-sensitivity detection of the nitroaromatic.
The invention relates to preparation and application of magnetic fluorescent molecularly imprinted nanospheres for detecting nitrobenzene. According to the method, the monodisperse ferroferric oxide nanoparticles are prepared by a hydrothermal method, and the ferroferric oxide is superparamagnetic and is not easy to agglomerate. After the ferroferric oxide surface is subjected to amination modification, good monodispersity can be kept; connecting a conjugated fluorescent polymer on the surface of the aminated ferroferric oxide nano particle by adopting a covalent bond reaction to prepare a magnetic fluorescent molecularly imprinted nano microsphere; providing a high specific surface area by ferroferric oxide nanoparticles, so that nitrobenzene molecules enter recognition sites in a more solution manner; the concentration of nitrobenzene in water is detected by magnetic separation and enrichment, so that the detection sensitivity can be improved. The ferroferric oxide nano particles are combined with a fluorescent molecular imprinting material with strong specificity, and can be used for enriching trace nitrobenzene in water and detecting the nitrobenzene with high selectivity.
Disclosure of Invention
According to the invention, the fluorescent molecularly imprinted nanospheres are prepared by taking the ferroferric oxide nanoparticles as a solid-phase support medium, and the conjugated polymer material is modified on the surface of the ferroferric oxide nanoparticles by a covalent bond bonding method, so that the fluorescent molecularly imprinted nanospheres have molecular imprinting and fluorescence properties. After magnetic separation and enrichment, the fluorescence intensity change is measured to realize the high selectivity and high sensitivity measurement of the nitrobenzene in the water.
The technical scheme of the invention is as follows:
the preparation and application of the magnetic fluorescent molecularly imprinted nanosphere for detecting nitrobenzene comprise the following steps:
(1) preparing superparamagnetic ferroferric oxide nano particles and performing surface amination modification by a hydrothermal method;
(2) preparing fluorescent molecularly imprinted nanospheres by taking ferroferric oxide nanoparticles as a solid phase;
(3) and (3) determining the content of nitrobenzene in the water through the change of the fluorescence intensity of the magnetic fluorescence molecular imprinting nano-microspheres.
The step (1) of preparing superparamagnetic ferroferric oxide nano particles and surface amination modification by a hydrothermal method specifically comprises the following steps
Weighing 2.0g of ferric chloride, 1.6g of polyethylene glycol (PEG) and 5.8g of anhydrous sodium acetate, dissolving in 60mL of ethylene glycol, fully stirring to completely dissolve, transferring to a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, sealing, and placing in an oven at 200 ℃ for reaction for 12 hours; the reaction is completed, and then the mixture is naturally cooled to room temperature to obtain black ferroferric oxide nano suspension; taking out the solution in the high-pressure kettle, performing magnetic separation and washing by using absolute ethyl alcohol, then performing magnetic separation and washing by using secondary distilled water, and storing the washed material in the absolute ethyl alcohol;
b, performing ultrasonic dispersion on the ferroferric oxide nanoparticles by using 38mL of absolute ethyl alcohol and 2mL of ultrapure water, transferring the mixture into a 100mL round-bottom flask, and mechanically stirring at the rotating speed of 400 rpm. 200 μ L of 3-Aminopropyltriethoxysilane (APTES) was quickly added dropwise to the solution, stirred well and reacted for 12h under nitrogen protection. The reaction solution is sequentially magnetically separated and washed for 3 times by ethanol and deionized water to prepare the amination modified ferroferric oxide nano particles,as shown in figure 1AndFIG. 2As shown.
The step (2) of preparing the fluorescent molecularly imprinted nanosphere by taking the ferroferric oxide nanoparticles as the solid phase specifically comprises the following steps:
a, adding 25mL of tetrahydrofuran, 279mg of 3, 5-dibromobenzamide and 502mg of 9, 9-dihexylfluorene-2, 7-diboronic acid di (1, 3-propanediol) ester into a 100mL three-neck flask in sequence, stirring until the mixture is dissolved, adding 15mL of K with the concentration of 2mol/L2CO3An aqueous solution; introducing nitrogen for 30min, heating to 69 ℃ for reflux, and rapidly adding 24mgPd (PPh) under the protection of nitrogen3)4. After 48h at 69 ℃, 200mg of 9, 9-dihexylfluorene-2, 7-diboronic acid bis (1, 3-propanediol) ester was added under nitrogen protection and the reaction was continued for 6 h. After the reaction, the reaction mixture was transferred to a beaker containing 100mL of methanol, and after suction filtration, the insoluble matter was washed three times in the order of distilled water, methanol and distilled water. Extracting the washed solid in a Soxhlet extractor for 24 hours by using acetone, transferring the product to a vacuum oven for vacuum drying at 25 ℃ to obtain solid powder of the conjugated polymer terminated by the borate;
and b, weighing 0.2g of amination-modified ferroferric oxide nano particle and borate-terminated conjugated polymer solid powder, adding the solid powder into 50mL of Nitrobenzene (NT) ethanol solution with the concentration of 1mmol/L, and slowly stirring for 2h to saturate the adsorption of NT. 1mL of glutaraldehyde (50% strength) as a crosslinking agent was added and the reaction was stirred slowly at room temperature for 12 h. And after the reaction is finished, repeatedly centrifuging and washing the product by using acetone and distilled water to remove the template molecules, and drying in vacuum to obtain the nitrobenzene fluorescent molecularly imprinted magnetic nanospheres.
The step (3) of determining the content of nitrobenzene in water through the change of fluorescence intensity of the magnetic fluorescence molecular imprinting nano-microspheres specifically comprises the following steps:
a, preparing a series of nitrobenzene standard solutions with different concentrations by taking absolute ethyl alcohol as a solvent, wherein the concentration of the nitrobenzene standard solutions is 5.0 × 10-8mol/L、1.0×10-7mol/L、2.0×10-7mol/L、5.0×10-7mol/L、1.0×10-6mol/L. Respectively adding 50mg of magnetic fluorescent molecularly imprinted microspheres into 20mL of anhydrous ethanol and 20mL of nitrobenzene standard solution, mechanically dispersing, and standing for 5 minutes; removing the absolute ethyl alcohol and the nitrobenzene standard solution by magnetic separation, respectively adding 2mL of absolute ethyl alcohol, mechanically dispersing into a homogeneous suspension, and transferring into a fluorescent cuvette; and (3) measuring the fluorescence intensity of 2mL of magnetic fluorescent molecular imprinting microsphere solution in the fluorescent cuvette. The experimental tests used an RF-5301PC fluorometer (Shimadzu, Japan) with its accompanying computer software for the acquisition and processing of experimental data. During the test, the excitation slit width is 5nm, and the emission slit width is 10 nm; the maximum excitation wavelength is 330nm and the maximum emission wavelength is 380 nm. Measurement of F0Adding the fluorescence intensity of the treated magnetic fluorescent molecular imprinting microspheres into absolute ethyl alcohol, FSThe fluorescence intensity of the nitrobenzene standard solution after being added with the magnetic fluorescent molecular imprinting microsphere is shown, the fluorescence quenching process is analyzed by a Stern-Volmer equation,as shown in fig. 3As shown. According to the obtained fluorescence F0/FSAnd NT concentration the working curve was plotted when the NT concentration was 5.0 × 10-8~1.0×10-6The mol/L range shows a linear relation, and the linear equation is F0/FS=1.65×106 c+0.942, a linear correlation coefficient of 0.993,as shown in fig. 4The NT concentration detection limit was found to be 2 × 10 based on a triple standard deviation-8mol/L；
b. Detection of nitrobenzene samples of unknown concentration: measuring fluorescence intensity F in a fluorescence cuvette containing a fluorescent molecularly imprinted microsphere solution0(ii) a Quantitative addingAdding nitrobenzene sample solution with unknown concentration, and measuring fluorescence intensity FS(ii) a The experimental tests used an RF-5301PC fluorometer (Shimadzu, Japan) with its accompanying computer software for the acquisition and processing of experimental data. During the test, the excitation slit width is 5nm, and the emission slit width is 10 nm; the maximum excitation wavelength is 330nm and the maximum emission wavelength is 380 nm. F is to be0/FSAnd (4) substituting the linear equation obtained in the step (4) to calculate the concentration of the nitrobenzene in the liquid to be detected.
Advantageous results of the invention
(1) The invention takes magnetic ferroferric oxide nano particles as a solid phase support and prepares the nitrobenzene fluorescent molecularly imprinted microsphere by a covalent bond bonding method. The molecularly imprinted material forms a molecularly imprinted membrane on the surface of the nano ferroferric oxide, and the ferroferric oxide nanoparticles provide a high specific surface area, so that nitrobenzene molecules enter recognition sites in a more solution manner;
(2) the monodisperse ferroferric oxide nano particles prepared by the hydrothermal method have uniform particle size and form a monodisperse phase. After surface functional group modification and polymer crosslinking, no agglomeration occurs, the polymer is easy to disperse in a solution, and further analysis and application are easy;
(3) the molecularly imprinted polymer used on the surface of the ferroferric oxide nano particle is a conjugated polymer, and has high selectivity and high sensitivity on nitrobenzene. The synthesized fluorescent molecularly imprinted nanospheres are used for detecting nitrobenzene, and have the advantages of simple operation, good linear range and low detection limit;
(4) the ferroferric oxide nano particles are subjected to magnetic separation in the analysis process, so that a low-concentration sample can be enriched, and the high-sensitivity detection of trace nitrobenzene in water is realized.
DrawingsDescription of the drawings:
drawing (A)1 Synthesis of magnetic fluorescent molecular imprinting nano-microsphereDrawing (A)；
Drawing (A)2 transmission electron microscope of ferroferric oxide magnetic nano particles with modified fluorescent molecular imprintingDrawing (A)；
Drawing (A)3 magnetic fluorescent molecular imprinting nano microsphere fluorescence quenching spectrumDrawing (A) ‘
FIG. 4Shows the fluorescence F of the magnetic fluorescent molecular imprinting microsphere0/FSWith nitrobenzenecLinear relationDrawing (A)。
Wherein,FIG. 2Middle curve a fluorescence intensity F without addition of Nitrobenzene0Curve b shows the fluorescence intensity F after quenching of the fluorescence after addition of nitrobenzeneS。
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Step 1, weighing 2.0g of ferric chloride, 1.6g of polyethylene glycol (PEG) and 5.8g of anhydrous sodium acetate, dissolving the ferric chloride, the polyethylene glycol (PEG) and the anhydrous sodium acetate in 60mL of ethylene glycol, fully stirring the mixture to completely dissolve the mixture, transferring the mixture into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, sealing the autoclave, and placing the autoclave in an oven at the temperature of 200 ℃ for reaction for 12 hours; the reaction is completed, and then the mixture is naturally cooled to room temperature to obtain black ferroferric oxide nano suspension; taking out the solution in the autoclave, performing magnetic separation and washing by using absolute ethyl alcohol, then performing magnetic separation and washing by using secondary distilled water, and storing the washed material in the absolute ethyl alcohol.
And 2, ultrasonically dispersing the ferroferric oxide nano particles by using 38mL of absolute ethyl alcohol and 2mL of ultrapure water, transferring the mixture into a 100mL round-bottom flask, and mechanically stirring at the rotating speed of 400 r/min. 200 μ L of 3-Aminopropyltriethoxysilane (APTES) was quickly added dropwise to the solution, stirred well and reacted for 12h under nitrogen protection. And (3) centrifugally washing the reaction solution by using ethanol and deionized water for 3 times in sequence to obtain the amination modified ferroferric oxide nano particles.
Step 3. adding 25mL of tetrahydrofuran, 279mg of 3, 5-dibromobenzamide and 502mg of 9, 9-dihexylfluorene-2, 7-diboronic acid di (1, 3-propanediol) ester into a 100mL three-neck flask in sequence, stirring until the mixture is dissolved, adding 15mL of K with the concentration of 2mol/L2CO3An aqueous solution; introducing nitrogen for 30min, heating to 69 ℃ for reflux, and rapidly adding 24mgPd (PPh) under the protection of nitrogen3)4. After 48h at 69 ℃, 200mg of 9, 9-dihexylfluorene-2, 7-diboronic acid bis (1, 3-propanediol) ester was added under nitrogen protection and the reaction was continued for 6 h. After the reaction, the reaction mixture was transferred to a beaker containing 100mL of methanol, and after suction filtration, the insoluble matter was washed three times in the order of distilled water, methanol and distilled water. Extracting the washed solid in a Soxhlet extractor for 24 hours by using acetone, transferring the product to a vacuum oven for vacuum drying at 25 ℃ to obtain solid powder of the conjugated polymer terminated by the borate; 0.2g of amination-modified ferroferric oxide nano-particle and borate-terminated conjugated polymer solid powder are weighed and immersed into 50mL of Nitrobenzene (NT) ethanol solution with the concentration of 1mmol/L, and the mixture is slowly stirred for 2 hours, so that the adsorption of NT is saturated. 1mL of glutaraldehyde (50% strength) as a crosslinking agent was added and the reaction was stirred slowly at room temperature for 12 h. And after the reaction is finished, repeatedly centrifuging and washing the product by using acetone and distilled water to remove the template molecules, and drying in vacuum to obtain the nitrobenzene fluorescent molecularly imprinted magnetic nanospheres.
Step 4, using absolute ethyl alcohol as solvent to prepare a series of nitrobenzene standard solutions with different concentrations, wherein the concentration is 5.0 × 10-8mol/L、1.0×10-7mol/L、2.0×10-7mol/L、5.0×10-7mol/L、1.0×10-6mol/L. Respectively adding 50mg of magnetic fluorescent molecularly imprinted microspheres into 20mL of anhydrous ethanol and 20mL of nitrobenzene standard solution, mechanically dispersing, and standing for 5 minutes; removing the absolute ethyl alcohol and the nitrobenzene standard solution by magnetic separation, respectively adding 2mL of absolute ethyl alcohol, mechanically dispersing into a homogeneous suspension, and transferring into a fluorescent cuvette; and (3) measuring the fluorescence intensity of 2mL of magnetic fluorescent molecularly imprinted microsphere solution in the fluorescence cuvette. Experimental testing was conducted using an RF-5301PC fluorometer (Shimadzu, Japan) with its associated computer software for experimental countingCollecting and processing the data. During the test, the excitation slit width is 5nm, and the emission slit width is 10 nm; the maximum excitation wavelength is 320nm and the maximum emission wavelength is 380 nm. Measurement of F0Adding the fluorescence intensity of the treated magnetic fluorescent molecular imprinting microspheres into absolute ethyl alcohol, FSAnd (3) representing the fluorescence intensity of the nitrobenzene standard solution after being added with the magnetic fluorescent molecularly imprinted microspheres, and analyzing the fluorescence quenching process by using a Stern-Volmer equation. According to the obtained fluorescence F0/FSAnd NT concentration when NT is at 5.0 × 10-8~1.0×10-6The concentration range of mol/L is in a linear relation, and the linear equation is F0/FS=1.65×106 c+0.942, linear correlation coefficient of 0.993, NT concentration detection limit of 2 × 10 according to three times standard deviation-8mol/L。
Step 5, detecting a m-Dinitrobenzene (DNT) standard sample by using the fluorescent molecularly imprinted microspheres obtained in the step 3, drawing a working curve in the same step as the step 4, forming the fluorescent molecularly imprinted nanospheres by virtue of NT molecular surface imprinting, wherein the quenching constants of the NT on the fluorescent molecularly imprinted nanospheresK SVIs 1.65 × 106M-1And the quenching constant of fluorescence quenching efficiency of DNT to itK SVIs only 0.6 × 106M-1The size and shape of the holes in the polymer thin layer on the surface of the fluorescent molecularly imprinted microsphere are highly matched with those of NT, but are not matched with DNT. Therefore, the NT concentration can be selectively detected by using the fluorescent molecularly imprinted microspheres in the research.
And 6, detecting a nitrobenzene sample with unknown concentration: measuring fluorescence intensity F in a fluorescence cuvette containing a fluorescent molecularly imprinted microsphere solution0(ii) a Quantitatively adding nitrobenzene sample solution with unknown concentration, and measuring fluorescence intensity FS(ii) a The experimental tests used an RF-5301PC fluorometer (Shimadzu, Japan) with its accompanying computer software for the acquisition and processing of experimental data. During the test, the excitation slit width is 5nm, and the emission slit width is 10 nm; the maximum excitation wavelength is 320nm and the maximum emission wavelength is 380 nm. F is to be0/FSAnd (4) substituting the linear equation obtained in the step (4) to calculate the concentration of the nitrobenzene in the liquid to be detected.
Claims (4)
1. Preparation and application of magnetic fluorescent molecularly imprinted nanospheres for detecting nitrobenzene, comprising the following steps:
(1) preparing superparamagnetic ferroferric oxide nano particles and performing surface amination modification by a hydrothermal method;
(2) preparing fluorescent molecularly imprinted nanospheres by taking ferroferric oxide nanoparticles as a solid phase;
(3) and (3) determining the content of nitrobenzene in the water through the change of the fluorescence intensity of the magnetic fluorescence molecular imprinting nano-microspheres.
2. The preparation and application of the magnetic fluorescent molecularly imprinted nanosphere for detecting nitrobenzene according to claim 1, wherein the step (1) is specifically as follows:
weighing 2.0g of ferric chloride, 1.6g of polyethylene glycol (PEG) and 5.8g of anhydrous sodium acetate, dissolving in 60mL of ethylene glycol, fully stirring to completely dissolve, transferring to a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, and placing in an oven at 200 ℃ for reaction for 12 hours; naturally cooling to room temperature to obtain black ferroferric oxide nano suspension; performing magnetic separation and washing by using absolute ethyl alcohol, performing magnetic separation and washing by using secondary distilled water, and storing the washed material in the absolute ethyl alcohol;
b, ultrasonically dispersing the ferroferric oxide nano particles by using absolute ethyl alcohol and ultrapure water, transferring the nano particles into a round-bottom flask, and mechanically stirring the nano particles uniformly;
quickly dripping 200 mu L of 3-Aminopropyltriethoxysilane (APTES) into the solution, stirring uniformly, and introducing nitrogen to protect reaction overnight; and (3) magnetically separating and washing the reaction solution by using ethanol and deionized water in sequence for 3 times to obtain the amination modified ferroferric oxide nano particles.
3. The preparation and application of the magnetic fluorescent molecularly imprinted nanosphere for detecting nitrobenzene according to claim 1, wherein the step (2) is specifically as follows:
a, 279mg of 3, 5-dibromobenzamide and 502mg of 9, 9-dihexylfluorene-2, 7-diboronic acid di (1, 3-propanediol) ester are sequentially added into a 100mL three-neck flask, 25mL of tetrahydrofuran is added and stirred until the tetrahydrofuran is dissolved, and K with the concentration of 2mol/L is added2CO315mL of aqueous solution; introducing nitrogen for 30min, heating to 69 ℃ for reflux, and rapidly adding 24mgPd (PPh) under the protection of nitrogen3)4(ii) a After reacting for 48h at 69 ℃, adding 200mg of 9, 9-dihexylfluorene-2, 7-diboronic acid di (1, 3-propylene glycol) ester under the protection of nitrogen, and continuing to react for 6 h; after the reaction is finished, transferring the mixture into a beaker filled with methanol, and washing insoluble substances for three times in sequence of distilled water, methanol and distilled water after suction filtration; the washed solid was in a Soxhlet extractorExtracting with acetone for 24h, transferring the product to a vacuum oven for vacuum drying at 25 ℃ to obtain borate-terminated conjugated polymer solid powder;
b, weighing a proper amount of amination-modified ferroferric oxide nano particles and borate-terminated conjugated polymer solid powder, adding the solid powder into 50mL of 1mmol/L Nitrobenzene (NT) ethanol solution, and slowly stirring for 2h to saturate the adsorption of NT; adding cross-linking agent glutaraldehyde (50% concentration), and slowly stirring at room temperature for reaction for 12 h; and after the reaction is finished, repeatedly centrifuging and washing the product by using acetone and distilled water to remove the template molecules, and drying in vacuum to obtain the nitrobenzene fluorescent molecularly imprinted magnetic nanospheres.
4. The method for synthesizing and using the fluorescent molecularly imprinted nanospheres for the determination of nitrobenzene in water according to claim 1, wherein the step (3) is specifically as follows:
a, preparing a series of nitrobenzene standard solutions with different concentrations by taking absolute ethyl alcohol as a solvent;
respectively adding the magnetic fluorescent molecular imprinting microspheres into absolute ethyl alcohol and nitrobenzene standard solution, mechanically dispersing and standing for 5 minutes; removing the anhydrous ethanol and nitrobenzene standard solution by magnetic separation, respectively adding a small amount of anhydrous ethanol, mechanically dispersing into homogeneous suspension, and transferring into a fluorescent cuvette; measuring the fluorescence intensity of the magnetic fluorescent molecularly imprinted microsphere solution in the fluorescent cuvette; the experimental test uses an RF-5301PC fluorometer (Shimadzu, Japan) with its associated computer software for experimental data acquisition and processing;
the maximum excitation wavelength is 330nm, and the maximum emission wavelength is 380 nm; measurement of F0Adding the fluorescence intensity of the treated magnetic fluorescent molecular imprinting microspheres into absolute ethyl alcohol, FSThe fluorescence intensity of the nitrobenzene standard solution after being added with the magnetic fluorescent molecular imprinting microspheres is shown, and the fluorescence quenching process is analyzed by a Stern-Volmer equation; according to the obtained fluorescence F0/FSAnd NT concentration, drawing a working curve, and obtaining the NT concentration detection limit when the NT concentration is in a standard deviation three times;
b. of samples of nitrobenzene of unknown concentrationAnd (3) detection: measuring fluorescence intensity F in a fluorescence cuvette containing a fluorescent molecularly imprinted microsphere solution0(ii) a Quantitatively adding nitrobenzene sample solution with unknown concentration, and measuring fluorescence intensity FS(ii) a The experimental test uses an RF-5301PC fluorometer (Shimadzu, Japan) with its associated computer software for experimental data acquisition and processing; the maximum excitation wavelength is 330nm, and the maximum emission wavelength is 380 nm; f is to be0/FSAnd (c) substituting the linear equation obtained in the step (a) to calculate the concentration of the nitrobenzene in the liquid to be detected.
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