CN111171806A - Preparation method and application of molecular imprinting ratio type fluorescent probe based on up-conversion nano material - Google Patents
Preparation method and application of molecular imprinting ratio type fluorescent probe based on up-conversion nano material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a molecular imprinting ratio type fluorescent probe based on an up-conversion nano material4,Er,Yb@NaGdF4After the amidation bonding, the substrate and the light-emitting material are coated with a silicon dioxide layer. Then, PFOS is used as a template molecule, APTES is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, and the initiation is carried out under the alkaline condition to form the analysis and identification material NaYF coated by the silicon dioxide imprinted layer4,Er,Yb@NaGdF4/SiO2@ MIP (UCNPs @ MIP). The invention realizes the PFOS treatment by using the up-conversion nano particles with better water solubility as the luminescent material and constructing the molecular imprinting ratio type fluorescent probe based on the surface molecular imprinting and ratio fluorescence methodSelectivity and high sensitivity quantitative detection. The method is green and pollution-free, and has the characteristics of simplicity, convenience, rapidness and sensitivity.
Description
Technical Field
The invention relates to the technical field of environmental analytical chemistry, in particular to a preparation method and application of a molecular imprinting ratio type fluorescent probe based on an up-conversion nano material.
Background
Perfluorinated compounds (PFCs) are artificially synthesized endocrine disrupting substances of artificial organic fluorine, consist of hydrophilic end groups and fully fluorinated hydrophobic carbon chains, and have chemical and thermal stability, amphiphilicity and high surface activity. Among them, perfluorooctanesulfonic acid (PFOS) is one of typical perfluoro compounds for the final conversion of PFCs in the environment. Because the carbon-fluorine bond has extremely strong bond energy, the carbon-fluorine bond is difficult to degrade after entering the environment. PFOS has been found to have systemic toxicity to animals and humans, such as neurotoxicity, hepatotoxicity, immunotoxicity and reproductive toxicity and to constitute a potential risk to humans through the food chain. And is widely distributed in the environment, so that the analysis and detection of the compound are very important.
Because of the special structure of PFOS and related compounds, the current main methods for detecting PFOS in environment and other samples are chromatography-mass spectrometry, chromatography tandem mass spectrometry and the like. However, the application and popularization of the analysis methods are limited due to the complex operation and long analysis period of the analysis methods. The fluorescence spectrophotometry has been paid much attention to due to the advantages of high sensitivity, high analysis speed and the like, and the application of the fluorescence spectrophotometry to the detection of PFOS in an environmental water sample has also been reported. The existing fluorescent marker has the defects of high toxicity, low chemical stability, high fluorescence background interference and the like. Therefore, the research on the fluorescent material with low cytotoxicity, high penetration depth and high chemical stability has very important significance for the analysis and detection of PFOS.
The upconversion nanoparticles are a unique lanthanum ion-doped optical nanomaterial and have a rich electronic energy level structure in a 4f electron shell. So far, hexagonal phase NaYF4Yb, Er is considered to be one of the most efficient fluorescent nanomaterials in upconversion. Compared with organic fluorescent dye and quantum dot，NaYF4Yb and Er have high chemical stability, long fluorescence life and low potential biological toxicity. The method adopts 980nm near infrared light for excitation, has the advantages of deep penetration, low background, no interference and the like compared with the traditional ultraviolet visible light excitation, and is suitable for the analysis and detection of target objects in complex samples.
Molecularly imprinted polymers have been widely recognized as materials with selective binding cavities that are complementary to the template molecule in terms of shape, size, and arrangement of functional groups. Since they are tailored to the respective target molecules, they have a strong specific recognition effect on the target molecules. Among them, the surface molecularly imprinted material has a high mass transfer rate and has easily accessible recognition sites, and thus is widely used in practical detection applications.
Disclosure of Invention
The invention aims to solve the problems that: the preparation method and the application of the molecular imprinting ratio type fluorescent probe based on the up-conversion nano material are provided, and compared with the existing luminescent material, the molecular imprinting ratio type fluorescent probe has the advantages of higher biocompatibility, higher fluorescence stability and larger application prospect.
The technical scheme provided by the invention for solving the problems is as follows: a preparation method of a molecular imprinting ratio type fluorescent probe based on an up-conversion nano material comprises the following steps,
(1) firstly, preparing nano-scale up-conversion nano-particle NaYF4Er, Yb and NaYF4Tm, Yb; then the upconversion nano particle NaYF is carried out4Er, Yb and NaYF4Tm, Yb for NaGdF4Coating the passivation layer to obtain the upconversion nano particle NaYF on the passivation structure4,Er,Yb@NaGdF4And NaYF4,Tm,Yb@NaGdF4(ii) a For the passivated up-conversion nano particle NaYF4,Er,Yb@NaGdF4Carrying out APTES surface modification to obtain up-conversion nanoparticles modified by amino; to pair
Carrying out carboxylation modification on the monodisperse silicon dioxide microspheres prepared by the method to obtain carboxylated silicon dioxide microspheres; by carboxylated SiO2Amidating and combining substrate and aminated up-conversion nano particle to obtain NaYF4,Er,Yb@NaGdF4/SiO2(UCNPs) composite materials; the passivated up-conversion nano particle NaYF is treated4,Tm,Yb@NaGdF4Coating a silicon dioxide layer to obtain an analysis reference material NaYF4,Tm,Yb@NaGdF4@SiO2；
(2) Adding 20-30 mg of template molecule PFOS into 30-40 mL of ethanol, performing ultrasonic treatment to dissolve the template molecule PFOS, and adding 20-30 mg of NaYF into the solution4,Er,Yb@NaGdF4/SiO2(UCNPs), ultrasonically dispersing the composite material uniformly, then dropwise adding 80 mu LAPTES, 200 mu L TEOS and 100 mu L ammonia water into the system while stirring, and stirring at 500rpm for 8-12 h to complete the polymerization reaction;
(3) centrifuging the reaction solution at 8500rpm/min for 5min, and collecting the solid;
(4) repeatedly eluting template molecules in the solid by using an eluent under the condition of 100W through an ultrasonic reaction, centrifuging at 8500rpm/min to separate the solid from the liquid, placing the product in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the NaYF material4,Er,Yb@NaGdF4/SiO2@ MIP, with analytical reference material NaYF4,Tm,Yb@NaGdF4@SiO2Mixing the components according to a certain proportion to finally obtain the molecular imprinting ratio type fluorescent probe.
Preferably, the particle size of the up-conversion nano material is 15-40 nm.
Preferably, the mass ratio of the PFOS to the APTES is 1: 4-2: 3; the mass ratio of TEOS, ammonia water and APTES is 10:5: 4.
Preferably, the eluent is a 9:1 mass ratio mixed solution of methanol and 5% acetic acid, a 5% acetic acid and NaCl solution, or a 0.01M NaOH methanol solution.
Preferably, the NaYF4,Er,Yb@NaGdF4/SiO2@ MIP and NaYF4,Tm,Yb@NaGdF4@SiO2The mass ratio of (A) to (B) is 4: 1-3: 2.
A method for selectively detecting perfluorooctane sulfonate comprises the steps of adding a certain amount of molecular imprinting ratio type fluorescent probe prepared by the preparation method of any one of claims 1-5 into a colorimetric tube, adding a PFOS solution with a certain concentration, fixing the volume to 10mL by using a Tris-HCl buffer solution, carrying out ultrasonic treatment for 1min, mixing uniformly, standing at room temperature for 10min, recording fluorescence spectrum data at 546.6nm and 478.0nm under the excitation of 980nm light, and realizing quantitative detection of PFOS according to the difference of fluorescence intensity ratios of two peaks under different PFOS concentrations.
Preferably, the pH value of the Tris-HCl buffer solution is 2-5.
Compared with the prior art, the invention has the advantages that: the luminescent material adopted by the invention is an up-conversion material NaYF4Er, Yb and NaYF4Compared with the existing luminescent materials, Tm and Yb have larger biocompatibility, higher fluorescence stability and larger application prospect. The fluorescent probe adopts a surface molecular imprinting method, so that high selectivity of PFOS is realized; meanwhile, a ratio fluorescence method is adopted, so that double-signal amplification detection is realized, and the reliability of an analysis result is improved. The invention has stronger anti-interference capability, higher sensitivity for detecting PFOS, wider linear range and better potential application value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph of the fluorescence response of UCNPs @ MIP and UCNPs @ NIP for different concentrations of PFOS (a, c); standard graphs (b, d) of UCNPs @ MIP and UCNPs @ NIP for different concentrations of PFOS;
FIG. 2 is a graph showing the effect of pH of the buffer solution used on the sensitivity of the fluorescent probe for PFOS detection;
FIG. 3 is a graph showing the effect of NaCl solutions of different concentrations on the sensitivity of a fluorescence probe for detecting PFOS;
FIG. 4 is a graph showing the effect of different incubation temperatures on the sensitivity of a fluorescent probe for PFOS detection;
FIG. 5 is a graph showing the results of selectivity of a fluorescent probe for PFOS and its structural analogs at pH 3.8;
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example one
In the invention, the two up-conversion nano materials and the passivation layer coating are prepared by a high-temperature pyrolysis method. Preparation of NaYF by reported high-temperature pyrolysis method4Yb, Er and NaYF4Yb, Tm and coating it with a passivation layer. 6mL of oleic acid and 15mL of 1-octadecene were weighed into a 100mL three-necked flask, and 0.78mmol of YCl was accurately weighed3、0.2mmol YbCl3And 0.02mmol ErCl3Adding into a three-neck flask, stirring at room temperature under nitrogen atmosphere for 10min to remove O2,Slowly heating the solution to 110 ℃ and keeping the temperature for 10min, evaporating water, then slowly heating the solution to 160 ℃ and keeping the temperature for 30min to completely dissolve the rare earth chloride to form a light yellow solution, then stopping heating, and cooling to room temperature. Will contain 4mmol of NH4Slowly adding a methanol mixed solution of F and 2.5mmol NaOH into a flask, stirring at 50 ℃ for 30min until all methanol is evaporated, rapidly heating the solution to 310 ℃ under the protection of nitrogen atmosphere, maintaining the temperature, stirring for 1.5h, cooling the obtained solution to room temperature, washing with ethanol to obtain a white solid precipitate, and repeatedly washing with cyclohexane, methanol and ethanol for several times to obtain NaYF4Yb, Er nanoparticles. NaYF4Yb, Tm is prepared as above, except that the proportion of the rare earth chloride is 0.75mmol YCl3、0.1803mmolYbCl3And 0.00214mmol of TmCl3Added to a three-necked flask. The preparation method of NaYF4 Yb, Er @ NaGdF4 and NaYF4 Yb, Tm @ NaGdF4 is the same as that of the method. 1mmol of GdCl3Added to the flask and charged with a solution containing 0.06g NaYF4Yb, Er in 10mL of methanol.
In the invention, the up-conversion nano-particles modified by amination are prepared by the following method: respectively dispersing CO-520 and up-conversion nanoparticles in cyclohexane with a certain volume, then mixing the two, performing ultrasonic treatment for a certain time, adding 0.3mL of ammonia water after the solution is clarified, simultaneously adding 0.07mL of tetraethoxysilane into the system, continuously and gently stirring for 24h at the temperature of 25-40 ℃, then repeatedly washing by using an ethanol/water (1:1, V/V) solution, and dispersing the obtained solid in deionized water for storage.
In the present invention, SiO prepared2Ultrasonically dispersing nano microspheres in a methanol and DMF solution, placing the solution in an oil bath pot for stirring, then adding carboxyethyl silanetriol sodium salt, refluxing for 12 hours at the temperature of 60 ℃ under the protection of nitrogen, continuing stirring and cooling to room temperature, pouring the solution into a centrifuge tube, centrifuging, washing the solution to be neutral by using ethanol, a dilute nitric acid solution and deionized water, and drying the solution in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carboxylated silicon dioxide spheres.
In the present invention, carboxylated SiO2Ultrasonically dispersing microspheres in PBS buffer solution, adding certain amount of EDC and NHS (V/V,1:1), ultrasonically stirring for 2min, magnetically stirring for 15min, activating under weakly acidic condition, and centrifuging to obtain activated SiO2. Dispersing the obtained product and the aminated up-conversion nano particles obtained in the third step into a PBS buffer solution, performing ultrasonic treatment for 5min to uniformly disperse the solution, performing magnetic stirring overnight, centrifuging to obtain white precipitate, repeatedly washing with ethanol and deionized water, and drying at 60 ℃ for 12h to obtain NaYF4,Er,Yb@NaGdF4/SiO2(UCNPs) composite materials;
in the invention, a template molecule PFOS is added into ethanol, the template is dissolved by ultrasonic treatment for 2min, then an up-conversion nano composite material is added, the material is dissolved by ultrasonic treatment for 2min, then 80 mu LAPTES functional monomer, 200 mu L TEOS cross-linking agent and 100 mu L ammonia water are added as an initiator while stirring, and after stirring overnight, the obtained solid is collected by centrifugation. Ultrasonically washing off the template with methanol/acetic acid (9:1V/V) at 100W, centrifuging with centrifuge, separating solid and liquid, repeatedly washing until the template molecules are completely eluted, and vacuum drying in a vacuum drying oven at 60 deg.C for 12 hr. The upconversion surface molecular imprinting ratio type fluorescent probe takes PFOS as a template molecule and adopts an imprinting layer formed by a reverse microemulsion method.
The invention also provides a method for detecting perfluorooctane sulfonate by using the imprinting system, 20mg of UCNPs @ MIP and UCNPs @ NIP powder are obtained after vacuum drying, 10mg of UCNPs @ MIP and UCNPs @ NIP powder are respectively weighed and dispersed in 100mL of water to prepare UCNPs @ MIP and UCNPs @ NIP solutions with the concentration of 0.1g/L, and a certain amount of the solutions are taken for carrying out recombination experiments with PFOS. The specific method comprises the following steps: adding 4ml of UCNPs @ MIP solution and 1ml of reference fluorescent material solution into a 10ml colorimetric tube, then adding a series of PFOS solutions with different concentrations, carrying out constant volume with the PFOS solutions, carrying out ultrasonic mixing for 5min, and standing for 5min at room temperature.
In the present invention, when the above-mentioned molecular imprinting ratio fluorescence system is applied to the selective detection of perfluorooctyl sulfonate in water, it preferably comprises the following steps: mixing the imprinting system, the perfluorooctane sulfonate and the buffer solution to fix the volume, and measuring the fluorescence spectrum of the system under the excitation wavelength of 980 nm. In the present invention, the buffer solution is preferably Tris-HCl buffer solution.
Example two
The molecular imprinting ratio fluorescent probe synthesized by the method is subjected to fluorescence detection performance analysis.
The molecular imprinting ratio fluorescent probe synthesized by the specific embodiment is applied to detecting PFOS in water, and the specific steps are as follows: 10mg of UCNPs @ MIP material was weighed out and dissolved in 100mL of deionized water to make up a stock solution of MIP at 0.1 g/L. A series of 4mL UCNPs @ MIP stock solutions and 1mL analytical reference material stock solutions are placed in a series of 10mL colorimetric tubes, 5mL PFOS solutions with different concentrations are respectively added, and fluorescence spectra of 478nm and 546.7nm are recorded under excitation light of 980 nm. According to the Stern-Volmer equation (I)546/I478)0/(I546/I478) Fluorescence spectrum data at 478nm and at 546nm are recorded, and the ratio of fluorescence intensity between the two peaks is calculated as the ordinate. FIG. 1 is a fluorescence spectrum diagram of the UCNPs @ MIP and UCNPs @ NIP probes after being combined with PFOS with different concentrations. As shown in a and c in FIG. 1, the fluorescence of both UCNPs @ MIP and UCNPs @ NIP can be quenched by PFOS, but the interaction of UCNPs @ MIP and PFOS is quenched to a greater extent, so that a specific binding site is provided for PFOS in the process of molecular imprinting. The PFOS is able to enter the cavity close to the upconversion nanoparticles,thereby, electron transfer occurs, and fluorescence is quenched. UCNPs @ NIP has no site for specific binding, and therefore, the degree of quenching is small. The quenching constant of UCNPs @ MIP is larger than that of UCNPs @ NIP, so that the quenching effect of the molecular imprinting ratio fluorescent probe on PFOS is more obvious, as shown in b and d in figure 1, the molecular imprinting ratio fluorescent probe is divided into two standard curves in 0.001-1 nM, a good linear relation exists between 0.001-0.2 nM, and the linear equation is that y is 4.03CPFOS+1.05(R20.974). The linear relation is good between 0.2nM and 1nM, and the linear equation is that y is 9.44CPFOS+1.54(R20.96), the effect of PFOS concentration changes on UCNPs @ MIP fluorescence satisfies the Stern-Volmer equation. According to equation F0/F＝1+KSVC,F0And F is the fluorescence intensity in the absence or presence of PFOS, KSVAnd C is the concentration of PFOS, and the quenching constant, namely the linear slope, shows the quenching capability of the PFOS to UCNPs @ MIP. From the figure, the quenching constant of UCNPs @ MIP is larger than that of UCNPs @ NIP, so that the quenching effect of the molecular imprinted polymer on PFOS is more obvious, and further, the specificity of the molecular imprinted polymer on PFOS is demonstrated.
EXAMPLE III
The system was studied for the selectivity of PFOS detection with molecular imprinting ratiometric fluorescent probes at different pH values of the buffer solutions used: placing a series of MIP stock solutions of 4mL and analytical reference material stock solutions of 1mL into a series of 10mL colorimetric tubes, diluting the volume to 10mL by using a 1nM PFOS solution prepared from a 6-9 PBS buffer solution and a 2-5 Tris-HCl buffer solution, and measuring the fluorescence intensity of 478.0nM and 546.7nM under the excitation of 980 nM. As can be seen from FIG. 2, when the fluorescence intensity ratio of 478nm to 546.7nm is obtained under excitation of 980nm, the fluorescence quenching efficiency is increased continuously at the final pH of 2 to 3.8, and when the pH is higher than 3.8, the fluorescence intensity ratio is decreased, the quenching efficiency is also decreased, and the system is more easily combined with the target perfluorooctane sulfonic acid under the weakly acidic condition of pH 3.8.
Example four
The influence of the system on the sensitivity of the fluorescent probe for detecting PFOS in NaCl solutions with different concentrations is researched: a series of 4mL MIP stock solutions and 1mL analytical reference material stock solutions were placed in a series of 10mL colorimetric tubes, 5mL NaCl solutions with different concentrations were added, and the fluorescence intensities at 478.0nm and 546.7nm were measured under 980nm excitation. As can be seen from FIG. 3, in the excitation at 980nm, the fluorescence intensity ratio between 478nm and 546.7nm was found to decrease continuously with increasing NaCl concentration and the fluorescence quenching efficiency was reduced continuously in the range of 0.05 to 0.5M, so that the detection was performed without adding NaCl solution.
EXAMPLE five
The influence of the system on the sensitivity of the fluorescent probe for detecting PFOS at different incubation temperatures is researched: 4mL of UCNPs @ MIP stock solution and 1mL of analysis reference material stock solution are placed in a 10mL colorimetric tube, 1nM PFOS solution is added, and fluorescence intensity of 478nM and 546.7nM is measured under excitation of 980 nM. As can be seen from FIG. 4, the fluorescence intensity ratio of 478nm to 546.7nm under excitation of 980nm is relatively stable at room temperature of 15-35 ℃, while the fluorescence quenching efficiency is reduced at temperature of 35-60 ℃. Therefore, the test was carried out at room temperature.
EXAMPLE six
In order to research the analysis selectivity of the molecular imprinting ratio fluorescence probe for PFOS, surfactant substances (SDBS, Phenol, CTAB) such as PFOS structural analogues (PFOA, F-53B, PFSF, OSA, PFBSK, PFHSK) and long-chain and benzene rings common in water are researched to evaluate the selectivity of the imprinting system for PFOS. Placing a series of MIP stock solutions with a volume of 4mL and analytical reference material stock solutions with a volume of 1mL into a series of 10mL colorimetric tubes, respectively adding 5mL of PFOS or above compound solutions with the same concentration, measuring the fluorescence intensity of the system at 478.0nm and 546.7nm under the condition of 980nm excitation light, and measuring the fluorescence intensity according to Stern-Volmer equation (I)546/I478)0/(I546/I478) Fluorescence spectrum data at 478nm and at 546nm are recorded, and the ratio of fluorescence intensity between the two peaks is calculated as the ordinate. As can be seen from FIG. 5, both UCNPs @ MIP and UCNPs @ NIP undergo some degree of fluorescence quenching after PFOS addition, wherein UCNPs @ MIP has higher selectivity for PFOS and higher sensitivity than UCNPs @ NIP, UCNPs @ MIP has relatively good selectivity for structural analogs, indicating successful encapsulation of the imprinting layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (7)
1. A preparation method of a molecular imprinting ratio type fluorescent probe based on an up-conversion nano material is characterized by comprising the following steps: the preparation method comprises the following steps of,
(1) firstly, preparing nano-scale up-conversion nano-particle NaYF4Er, Yb and NaYF4Tm, Yb; then the upconversion nano particle NaYF is carried out4Er, Yb and NaYF4Tm, Yb for NaGdF4Coating the passivation layer to obtain the upconversion nano particle NaYF on the passivation structure4,Er,Yb@NaGdF4And NaYF4,Tm,Yb@NaGdF4(ii) a For the passivated up-conversion nano particle NaYF4,Er,Yb@NaGdF4Carrying out APTES surface modification to obtain up-conversion nanoparticles modified by amino; to pair
Carrying out carboxylation modification on the monodisperse silicon dioxide microspheres prepared by the method to obtain carboxylated silicon dioxide microspheres; by carboxylated SiO2Amidating and combining substrate and aminated up-conversion nano particle to obtain NaYF4,Er,Yb@NaGdF4/SiO2(UCNPs) composite materials; the passivated up-conversion nano particle NaYF is treated4,Tm,Yb@NaGdF4Coating a silicon dioxide layer to obtain an analysis reference material NaYF4,Tm,Yb@NaGdF4@SiO2；
(2) Adding 20-30 mg of template molecule PFOS into 30-40 mL of ethanol, performing ultrasonic treatment to dissolve the template molecule PFOS, and adding 20-30 mg of NaYF into the solution4,Er,Yb@NaGdF4/SiO2(UCNPs), ultrasonically dispersing the composite material uniformly, and then stirringSequentially dropwise adding 80 mu of LAPTES, 200 mu of TEOS and 100 mu of ammonia water into the system, and stirring at 500rpm for 8-12 h to complete the polymerization reaction;
(3) centrifuging the reaction solution at 8500rpm/min for 5min, and collecting the solid;
(4) repeatedly eluting template molecules in the solid by using an eluent under the condition of 100W through an ultrasonic reaction, centrifuging at 8500rpm/min to separate the solid from the liquid, placing the product in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the NaYF material4,Er,Yb@NaGdF4/SiO2@ MIP, with analytical reference material NaYF4,Tm,Yb@NaGdF4@SiO2Mixing the components according to a certain proportion to finally obtain the molecular imprinting ratio type fluorescent probe.
2. The method for preparing the molecular imprinting ratio-type fluorescent probe based on the up-conversion nano-material according to claim 1, wherein the method comprises the following steps: the particle size of the up-conversion nano material is 15-40 nm.
3. The method for preparing the molecular imprinting ratio-type fluorescent probe based on the up-conversion nano-material according to claim 1, wherein the method comprises the following steps: the mass ratio of the PFOS to the APTES is 1: 4-2: 3; the mass ratio of TEOS, ammonia water and APTES is 10:5: 4.
4. The method for preparing the molecular imprinting ratio-type fluorescent probe based on the up-conversion nano-material according to claim 1, wherein the method comprises the following steps: the eluent is any one of a mixed solution of methanol and acetic acid with the concentration of 5% in a mass ratio of 9:1, a 5% acetic acid and NaCl solution, or a 0.01M NaOH methanol solution.
5. The method for preparing the molecular imprinting ratio-type fluorescent probe based on the up-conversion nano-material according to claim 1, wherein the method comprises the following steps: the NaYF4,Er,Yb@NaGdF4/SiO2@ MIP and NaYF4,Tm,Yb@NaGdF4@SiO2The mass ratio of (A) to (B) is 4: 1-3: 2.
6. A method for selectively detecting perfluorooctane sulfonate is characterized by comprising the following steps: adding a certain amount of molecular imprinting ratio type fluorescent probe prepared by the preparation method of any one of claims 1-5 into a colorimetric tube, adding a PFOS solution with a certain concentration, fixing the volume to 10mL by using a Tris-HCl buffer solution, carrying out ultrasonic treatment for 1min, mixing uniformly, standing at room temperature for 10min, recording fluorescence spectrum data at 546.6nm and 478.0nm under the excitation of 980nm light, and realizing quantitative detection of the PFOS according to the difference of the fluorescence intensity ratios of two peaks under different PFOS concentrations.
7. The method for selectively detecting perfluorooctane sulfonic acid according to claim 6, wherein: the pH value of the Tris-HCl buffer solution is 2-5.
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| CN113174045A (en) * | 2020-10-16 | 2021-07-27 | 杭州美迪生物医药技术开发有限公司 | Molecularly imprinted polymer for fluorescence detection, application thereof and detection kit |
| CN113174046A (en) * | 2020-11-27 | 2021-07-27 | 杭州美迪生物医药技术开发有限公司 | Prealbumin detection molecularly imprinted polymer, application thereof and detection kit |
| CN114486825A (en) * | 2021-12-31 | 2022-05-13 | 江苏大学 | Rapid detection method of carbendazim based on up-conversion-molecular imprinting fluorescence sensor |
| CN115015190A (en) * | 2022-04-20 | 2022-09-06 | 天津科技大学 | Preparation method of temperature-sensitive molecularly imprinted polymer for cow milk beta-lactoglobulin allergen detection |
| CN115386375A (en) * | 2022-09-05 | 2022-11-25 | 河北农业大学 | Preparation method of sulfanilamide drug imprinted bionic antibody-up-conversion fluorescent probe |
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| CN114486825A (en) * | 2021-12-31 | 2022-05-13 | 江苏大学 | Rapid detection method of carbendazim based on up-conversion-molecular imprinting fluorescence sensor |
| CN115015190A (en) * | 2022-04-20 | 2022-09-06 | 天津科技大学 | Preparation method of temperature-sensitive molecularly imprinted polymer for cow milk beta-lactoglobulin allergen detection |
| CN115430468A (en) * | 2022-07-20 | 2022-12-06 | 中南大学 | Series-connection 3D ratio fluorescence microfluidic device and method for detecting organophosphorus pesticide |
| CN115430468B (en) * | 2022-07-20 | 2023-06-23 | 中南大学 | Tandem 3D ratio fluorescence microfluidic device and method for detecting organophosphorus pesticides |
| CN115386375A (en) * | 2022-09-05 | 2022-11-25 | 河北农业大学 | Preparation method of sulfanilamide drug imprinted bionic antibody-up-conversion fluorescent probe |
| CN115386375B (en) * | 2022-09-05 | 2024-05-24 | 河北农业大学 | Preparation method of sulfonamide imprinting bionic antibody-up-conversion fluorescent probe |
| CN116144360A (en) * | 2023-01-08 | 2023-05-23 | 北方工业大学 | Preparation method of rare earth up-conversion fluorescent probe |
| 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 |
| CN117447335B (en) * | 2023-12-26 | 2024-03-05 | 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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