CN113308248A - Preparation and application of perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on up-conversion material - Google Patents
Preparation and application of perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on up-conversion material Download PDFInfo
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Abstract
The invention discloses preparation and application of a perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on an up-conversion material, and the method is amino modified NaYF4Yb and Er as core, N, O-bistrifluoroacetamide as functional monomer, hexadecyl trimethyl ammonium bromide as pore-creating agent, perfluorooctane sulfonic acid as template molecule, ethyl orthosilicate as cross-linking agent, and NaYF modified by amino under alkaline condition4Forming a silicon dioxide thin layer with a specific recognition site for perfluorooctane sulfonate on the surface of Yb and Er, removing a template and a pore-forming agent to obtain a mesoporous molecular imprinting fluorescent probe material, and applying the mesoporous molecular imprinting fluorescent probe material to the detection of perfluorooctane sulfonate in water to achieve a better effectThe conversion molecular imprinting fluorescent probe has higher detection sensitivity and selectivity, the preparation method is scientific, the operation is simple, and the reaction condition is easy to control; the prepared material is green and has good application prospect.
Description
Technical Field
The invention relates to the technical field of molecular imprinting fluorescent probes, in particular to preparation and application of a perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on an up-conversion material.
Technical Field
Perfluorooctanesulfonic acid (PFOS) has been widely produced worldwide and used as a raw material for textiles, lubricating oils, cosmetics, water-proofing materials and fire-extinguishing foams since the 50 s of the 20 th century because of its hydrophobic and oleophobic properties. Because of the high bond energy of the C-F bond in the PFOS structure (about 110kcal/mol), it has high thermal stability and chemical inertness in the environment. It is difficult to decompose in strong acids, strong bases and oxidizing agents, and photolysis, hydrolysis and biodegradation do not occur, so that the PFOS is difficult to decompose once it is discharged to the environment. PFOS has been widely reported as a ubiquitous contaminant. Toxicology studies indicate that even trace amounts of PFOS may cause serious functional damage to the liver and kidney of a human body, and have adverse effects on fatty acid metabolism, reproductive system and hormone secretion system. Therefore, it is of great significance to develop a high-sensitivity analysis method for detecting perfluorooctane sulfonate in the environment.
At present, the detection methods of perfluorooctane sulfonate mainly comprise a liquid chromatography-mass spectrometry (LC-MS), a liquid chromatography-tandem mass spectrometry (LC-MS-MS) and a gas chromatography-mass spectrometry (GC-MS). Although these analytical methods have good sensitivity, these instruments are relatively expensive and involve complicated sample preparation, complicated and time-consuming instrument operation, limiting their application.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides preparation and application of a perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on an up-conversion material.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method and application of perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on up-conversion material comprises the following steps,
(1) amino-modified up-conversion nanoparticles NaYF4Yb, Er (UCNPs) is added into 30mL deionized water and is fully dispersed by ultrasonic treatment for 10 min;
(2) adding template molecule perfluorooctane sulfonate (PFOS) and functional monomer for preassembling;
(3) stirring for 30min, sequentially adding a pore-foaming agent and a sodium hydroxide solution, and stirring for reaction for 30 min;
(4) adding catalyst ammonia water and cross-linking agent ethyl orthosilicate, and stirring for 12 hours at room temperature to react;
(5) centrifuging the reaction solution after the reaction is finished, and eluting the template molecules and the pore-forming agent in the solid product by using an eluent;
(6) putting the product in a vacuum drying oven to dry to constant weight;
the application method is that,
(5) sequentially adding a molecularly imprinted fluorescent probe dispersion liquid and a Britton-Robinson buffer solution into a 10mL colorimetric tube with a plug to adjust the acidity of the system, and uniformly mixing, wherein the ratio of the molecularly imprinted fluorescent probe dispersion liquid to the Britton-Robinson buffer solution is 8: 1;
(6) adding PFOS standard solution, and then using deionized water to fix the volume to 10 mL;
(7) reacting at room temperature for 10min, and transferring to a cuvette after the reaction is complete;
(8) and (3) exciting by using a 980nm laser, recording the fluorescence emission spectrum and intensity of the system at 545nm, and realizing quantitative detection of the PFOS according to the change value of the fluorescence intensity at 545 nm.
Preferably, the mass ratio of the amino-modified UCNPs to the PFOS to the functional monomer to the pore-forming agent to the sodium hydroxide to the TEOS to the ammonia water is (1-5) to (60-100) to (10-15) to (5-10).
Preferably, the eluent is a mixed solution of a polar organic solvent and a low-concentration acid or alkali solution in a volume ratio of 8: 2.
Preferably, the concentration of the molecular imprinting fluorescent probe dispersion used is 0.01-0.2 g/L.
Preferably, the pH value of a Britton-Robinson buffer solution adjusting system is 2-8.
The invention has the beneficial effects that: the invention combines the surface molecular imprinting technology and the up-conversion fluorescence technology to modify NaYF on amino4The surface of Yb and Er forms a silicon dioxide thin layer with a specific recognition site for perfluorooctane sulfonate. Based on PFOS and NaYF4The specific combination of amino group and fluorine-containing group on the surface of Yb and Er is realized by NaYF4The quenching mechanism of charge transfer of Yb, Er to PFOS leads to fluorescence quenching of molecularly imprinted fluorescent probes. And the quantitative detection of the PFOS can be realized according to the change of the fluorescence intensity. The invention combines the upconversion particles with low cytotoxicity with the mesoporous imprinting material with excellent selectivity, and has good application prospect in the fields of nanotechnology, biological detection and the like.
The invention has the advantages that:
(1) adopting NaYF4Yb and Er are used as fluorescent signal materials, compared with the traditional organic fluorescent dye, the fluorescent dye has the advantages of low cytotoxicity, high penetration depth, high photochemical stability, small fluorescent background interference and the like, and has huge application prospects in the fields of fluorescence biological detection and imaging.
(2) By adopting the surface molecular imprinting technology, the imprinting sites are positioned on the surface of the upconversion material and have a highly-through hole structure, so that the transfer capacity of target molecules is greatly improved, and the efficient and rapid detection of the PFOS can be realized.
(1) The prepared molecularly imprinted polymer can be used for detecting PFOS in an environmental water sample, the method is quick, simple and convenient, high in sensitivity and good in selectivity, and compared with an analysis method of a chromatographic mass spectrum, the method has the advantages of reducing detection cost and improving detection efficiency.
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The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows N of MIP2Adsorption-desorption isothermal curve and aperture distribution diagram;
figure 2 is a graph of the results of fluorescence emission spectra of mip (a) and nip (c) binding to different concentrations of PFOS at pH 3.38 and of the linear results of the Stern-Volmer equation fitting of mip (b) to nip (d);
FIG. 3 is the effect of pH of the solution on the fluorescence response of the system after binding of PFOS and MIP;
figure 4 is a selectivity study of MIPs for PFOS and analogues at the same concentration.
Detailed Description
The invention is explained in more detail below by means of specific embodiments and figures, but the following detailed description is only exemplary and not restrictive, and the technical features or combinations of technical features described in the embodiments should not be considered in isolation, but they can be combined with one another to achieve better technical features.
Example 1
Preparing a perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of an up-conversion material:
(1) upconversion material NaYF4Preparation of Yb and Er: will contain 1mmol of LnCl3(Ln ═ Y: Yb: Er, 80:18:2) in a 50mL beaker, 2mmol of sodium citrate and 10mL of water were added, the mixture was magnetically stirred for 10min, NaCl (2.88mmol) and NH were added4F (6mmol) in 5mL of an aqueous solution, OA (10mL) and ethylene glycol (5mL) were added to the above solution, and after stirring for 30min, the mixed solution was transferred to a 50mL reaction vessel and reacted at 180 ℃ for 6 hours. After the reaction is finished, centrifugally washing the reaction product for 3 times by using ethanol, and finally drying the obtained solid in a vacuum drying oven at 60 ℃ for 6 hours to obtain the up-conversion material NaYF4:Yb,Er(UCNPs)。
(2) Preparation of amino-modified UCNPs: 100mg of UCNPs are weighed into a 100mL round-bottom flask, 10mL of cyclohexane and 1mL of ammonia water-520 are added, the mixture is stirred vigorously for 10min, then 4mL of ammonia water-520 and 800 μ L of 25% ammonia water are respectively weighed and added into the flask in sequence. Sealing with a plug, and ultrasonically dispersing for 20min to obtain transparent emulsion. 400. mu.L of ethyl orthosilicate was added dropwise thereto with a microsyringe. After stirring overnight, 500. mu.L of APTES was added dropwise to the above solution. And continuing to react for 3-4 h, stopping stirring, and aging the reaction solution at room temperature for 2 h. And (3) centrifugally separating the aged reaction liquid, washing the reaction liquid for 3 times by using ethanol, and finally drying the obtained solid in a vacuum drying oven at the temperature of 60 ℃ for 6 hours to obtain the amino modified up-conversion nano material.
Preparing a molecular imprinting fluorescent probe: accurately weighing up-conversion nano particle NaYF modified by amino4Yb, Er (UCNPs)50mg is added into 30mL deionized water, the deionized water is subjected to ultrasonic treatment for 10min to fully disperse the PFOS, then 30mg of template molecule perfluorooctane sulfonate (PFOS) and 100 muL of functional monomer N, O-bis (trimethylsilyl) trifluoroacetamide are added for preassembly, after stirring for 30min, 1.6mL of 0.2MCTAB and 0.2mL of 0.2M sodium hydroxide solution are sequentially added for stirring reaction for 30min, then 200 muL of ammonia water and 200 muL of TEOS are added, and the reaction is carried out by stirring for 12h at room temperature. And after the reaction is finished, centrifuging the reaction solution, eluting PFOS and CTAB by using ethanol and 0.1M HCl (8:2, v/v) eluent, then centrifugally cleaning by using deionized water to remove redundant hydrochloric acid solution, and drying the product in a vacuum drying oven to constant weight to obtain the up-conversion-based perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe. The preparation process of the non-imprinted fluorescent probe is the same as the preparation process except that no template molecule PFOS is added, wherein the functional monomer used is preferably fluorine-containing silylation reagent such as N, O-bis (trimethylsilyl) trifluoroacetamide, (3,3, 3-trifluoropropyl) methyldichlorosilane, (3,3, 3-trifluoropropyl) methyldimethoxysilane or (3,3, 3-trifluoropropyl) triethoxysilane, but is not limited thereto.
Example 2
The application of the perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of the up-conversion material comprises the following steps:
sequentially adding 800 mu L of molecular imprinting fluorescent probe dispersion liquid (0.05g/L) and a certain volume of BR buffer solution into a 10mL colorimetric tube with a plug, uniformly mixing, adding a PFOS standard solution with a certain concentration, then using deionized water to perform constant volume to 10mL, reacting for 10min at room temperature, transferring to a cuvette after the reaction is sufficient, using a 980nm laser for excitation, recording the fluorescence emission spectrum and intensity of a system at 545nm, and realizing quantitative detection of the PFOS according to the change value of the fluorescence intensity at 545 nm; PFOS and non-blotting fluorescent probe combined condition experiment is carried out under the same condition.
Example 3
Characterizing the perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of the synthesized upconversion material:
(1) FIG. 1 shows N of MIPs2The adsorption-desorption isothermal curve (a) and the pore size distribution diagram (b) can judge the pore characteristics of the sample according to the type of the adsorption-desorption isothermal curve, and N can be known from the graph (a) in FIG. 12The adsorption-desorption isothermal curve is a typical Langmuir type IV curve when P/P0Above 0.4, a wider hysteresis loop occurs, indicating that the MIP surface channels have narrower openings. Further, the MIP had a specific surface area of 38.123m2Per g, pore volume 0.033cm3(ii) in terms of/g. As shown in FIG. 1(b), the pore size distribution of MIP is broad and mainly concentrated at 2 to 50nm, and the average pore size of mesopores is 3.786 nm. The larger specific surface area and the pore size of the MIP are moderate, so that the transfer capability of the target molecule PFOS is improved.
(2) FIG. 2(a), (c) are fluorescence emission spectra of MIP and NIP combined with different concentrations of PFOS and (b) and (d) are graphs of fitting linear results of Stern-Volmer equation of MIP and NIP, and the specific steps are as follows: sequentially adding 800 mu L of molecular imprinting fluorescent probe dispersion liquid (0.05g/L) and a certain volume of BR buffer solution into a 10mL colorimetric tube with a plug, uniformly mixing, adding PFOS standard solution with a certain concentration, then using deionized water to perform constant volume to 10mL, reacting for 10min at room temperature, transferring to a cuvette after the reaction is sufficient, using a 980nm laser to excite, and recording the fluorescence emission spectrum and intensity of a system at 545nm, as can be seen from figures 2(a) and (c), PFOS can quench the fluorescence of MIP and NIP, and the quenching constant of PFOS to MIP is larger than that of NIP, so that the quenching effect of the molecular imprinting polymer to PFOS is more obvious, and further, the specificity of the molecular imprinting polymer to PFOS is further illustrated. PFOS causes fluorescence quenching due to high electronegativity, fluorescence quenching is caused by electrostatic interaction with a fluorescence probe MIP and fluorine-fluorine interaction, when the pH of a system is adjusted to be 3.38, the electrostatic interaction with the fluorine-fluorine causes fluorescence quenching of both the MIP and the NIP, and as can be seen from graphs (b) and (d), the fluorescence quenching system has good linearity in the range of 0.01-1.5 nmol/LThe relationship is that MIP has larger quenching degree after the action of PFOS, and the linear equation is that y is 0.8559x +0.0402, R20.9962, and the fluorescence is quenched after the NIP and PFOS are acted, the linear equation is that y is 0.2361x +0.0424, R2Calculated imprinting factors of 3.63, 0.9951, indicate higher selectivity of MIPs than NIP due to the presence of a large number of specific recognition sites on the MIP surface.
(3) As the pH not only affects the surface environment of the composite material, but also affects the charge of surface groups of the composite material, so as to affect the combination of target molecules and the probe, the influence of the pH value on the detection of PFOS by MIP is considered in the range of pH value 3-10, and BR buffer solution is selected to adjust the acidity; the method comprises the following specific steps: sequentially adding 800 mu L of molecular imprinting fluorescent probe dispersion liquid (0.05g/L) and BR buffer solutions with different volumes into a 10mL colorimetric tube with a plug, uniformly mixing, adding a PFOS standard solution with a certain concentration, then using deionized water to fix the volume to 10mL, reacting at room temperature for 10min, and transferring to a cuvette after the reaction is complete. Recording the fluorescence emission spectrum and intensity of the system at 545nm by using a 980nm laser for excitation; as can be seen from FIG. 3, the fluorescence quenching degree of PFOS on MIP decreases with the increase of system pH, and PFOS has a lower pK in water due to its negative chargeaAnd 4, the amino group on the MIP surface is positively charged after protonation under an acidic condition, and simultaneously, because the fluorine-containing functional monomer exists, the MIP fluorescence quenching value can be enhanced by taking the electrostatic interaction with fluorine-fluorine as a receptor to bind PFOS. When the pH value of the solution is increased, the amino group on the surface of the MIP is deprotonated to enable the MIP to be negatively charged, and the MIP is blocked from fluorescence quenching due to the electrostatic repulsion effect of PFOS in an anionic form, but the MIP still can interact with the PFOS under an alkaline condition to cause fluorescence quenching due to the fact that the fluorine-containing group for identifying the PFOS is arranged on the surface of the MIP. Under alkaline conditions, the MIP fluorescence is quenched to a lesser extent than when the pH is acidic. In order to obtain higher sensitivity, the system was therefore selected to have a pH of 3.38 for subsequent experiments.
(4) To examine the detection selectivity of the molecular imprinting fluorescent probe for PFOS, we selected the structural analogs of PFOS, chromium fog inhibitor (F-53B), perfluorooctanoic acid (PFOA), perfluorohexyl sulfonate (PFHxS), and potassium perfluorobutyl sulfonate (PFBS), for study. The method comprises the following specific steps: sequentially adding 800 mu of LMIP dispersion liquid (0.05g/L) and a certain volume of BR buffer solution into a 10mL colorimetric tube with a plug, uniformly mixing, adding PFOS structural analogs with different concentrations, then using deionized water to fix the volume to 10mL, reacting for 10min at room temperature, transferring to a cuvette after full reaction, using a 980nm laser to excite, and recording the fluorescence emission spectrum and intensity of a system at 545nm, as can be seen from FIG. 4, the MIP has certain recognition capability on template molecules PFOS, has the maximum quenching intensity, has an imprinting factor of 3.63, and has certain quenching amount on the PFOS structural analogs, but the specific selectivity is not high; in addition, F-53B, PFOA has the same structure as PFOS, but F-53B, PFOA has obviously lower quenching effect on the MIP fluorescent probe than PFOS and F-53B has higher quenching effect than PFOA, which shows that C-F bond plays an important role in forming imprinting sites with sulfonic functional groups. Because the PFHxS, PFBs and PFOS have different structures in terms of carbon chain length, the quenching effect on the MIP fluorescent probe is more obvious along with the increase of the carbon chain length, which indicates that the C-F bond influences the recognition effect; the result shows that, because a plurality of specific recognition sites are formed on the surface of the MIP in the process of imprinting synthesis, the template molecule PFOS can generate strong fluorine-fluorine and electrostatic interaction with the MIP to cause obvious quenching of fluorescence, and secondly, because F-53B, PFOA, PFHxS, PFBs and PFOS have different spatial configurations and molecular masses, the F-53B, the PFOA, the PFHxS and the PFBs can also generate electrostatic interaction with the MIP and the fluorine-fluorine, but because the recognition configurations of the imprinting sites can not be completely matched with the F-53B, the F-PFHxS and the PFBs, the fluorescence quenching is not obvious.
While embodiments of the present invention have been described herein, it will be understood by those skilled in the art that changes may be made to the embodiments herein without departing from the spirit of the invention. The above examples are merely illustrative and should not be taken as limiting the scope of the invention.
Claims (5)
1. Preparation and application of perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe based on up-conversion material are characterized in that: the preparation method comprises the following steps of,
(1) amino-modified up-conversion nanoparticles NaYF4Adding Yb and Er into 30mL deionized water, and performing ultrasonic treatment for 10min to fully disperse the Yb and Er;
(2) adding template molecule perfluorooctane sulfonate and a functional monomer for preassembly;
(3) stirring for 30min, sequentially adding a pore-foaming agent and a sodium hydroxide solution, and stirring for reaction for 30 min;
(4) adding catalyst ammonia water and cross-linking agent ethyl orthosilicate, and stirring for 12 hours at room temperature to react;
(5) centrifuging the reaction solution after the reaction is finished, and eluting the template molecules and the pore-forming agent in the solid product by using an eluent;
(6) putting the product in a vacuum drying oven to dry to constant weight;
the application method is that,
(1) sequentially adding a molecularly imprinted fluorescent probe dispersion liquid and a Britton-Robinson buffer solution into a 10mL colorimetric tube with a plug to adjust the acidity of the system, and uniformly mixing, wherein the ratio of the molecularly imprinted fluorescent probe dispersion liquid to the Britton-Robinson buffer solution is 8: 1;
(2) adding PFOS standard solution, and then using deionized water to fix the volume to 10 mL;
(3) reacting at room temperature for 10min, and transferring to a cuvette after the reaction is complete;
(4) and (3) exciting by using a 980nm laser, recording the fluorescence emission spectrum and intensity of the system at 545nm, and realizing quantitative detection of the PFOS according to the change value of the fluorescence intensity at 545 nm.
2. The preparation and application of the upconversion material based perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of claim 1 are characterized in that: the mass ratio of the amino-modified UCNPs to the PFOS to the functional monomer to the pore-forming agent to the sodium hydroxide to the TEOS to the ammonia water is 1-5: 1: 1-5: 60-100: 10-15: 5-10.
3. The preparation and application of the upconversion material based perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of claim 1 are characterized in that: the eluent is a mixed solution of a polar organic solvent and a low-concentration acid or alkali solution in a volume ratio of 8: 2.
4. The preparation and application of the upconversion material based perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of claim 1 are characterized in that: the concentration of the molecular imprinting fluorescent probe dispersion liquid is 0.01-0.2 g/L.
5. The preparation and application of the upconversion material based perfluorooctane sulfonate mesoporous molecular imprinting fluorescent probe of claim 1 are characterized in that: the pH value of a Britton-Robinson buffer solution adjusting system is 2-8.
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| CN117447335A (en) * | 2023-12-26 | 2024-01-26 | 应急管理部天津消防研究所 | PFOS fluorescent probe and application and preparation method thereof |
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