CN116396496A - Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof - Google Patents
Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof Download PDFInfo
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- CN116396496A CN116396496A CN202310582141.8A CN202310582141A CN116396496A CN 116396496 A CN116396496 A CN 116396496A CN 202310582141 A CN202310582141 A CN 202310582141A CN 116396496 A CN116396496 A CN 116396496A
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- ketoprofen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The invention discloses a preparation method of a molecularly imprinted Zr-MOF fluorescent probe material, which comprises the following steps of S10: zrCl is added to 4 Uniformly dispersing the ketoprofen and the ketoprofen in a DMF solution to obtain a first mixed solution; s20: adding ligand terephthalic acid into the first mixed solution to obtain a second mixed solution; s30: reacting, washing and separating to obtain a solid template containing ketoprofen; s40: removing ketoprofen in the template; s50: and carrying out plasma modification on the template to obtain the Zr-MOF fluorescent probe material. The invention has good selectivity to ketoprofen, high sensitivity and resistanceHigh interference power, low cost and less pollution.
Description
Technical Field
The invention belongs to the technical field of fluorescence sensing, and relates to a molecularly imprinted Zr-MOF fluorescent probe material, a preparation method and application thereof.
Background
The medicine pollution and pesticide residue can be enriched into human body through food chain, so that the risks of cancer, teratogenesis and mutation exist, and potential threat is formed to human health. Ketoprofen belongs to nonsteroidal anti-inflammatory drugs (NSAIDs) and has analgesic, anti-inflammatory and antipyretic effects. The mechanism of action is to block Cyclooxygenase (COX) so as to inhibit the synthesis of prostaglandin and achieve the effects of relieving fever and pain. However, ketoprofen has serious gastrointestinal side effects, and long-term administration may lead to a series of adverse effects such as headache and somnolence, cardiovascular reactions (peripheral oedema), platelet dysfunction, inhibition of the synthesis of prostaglandins, which may lead to altered renal blood flow, and to kidney damage, electrolyte imbalance and hypertension. The medicine can flow into the nature through the metabolism of the human body, thereby causing water pollution. Therefore, it is particularly important to develop a method for detecting ketoprofen with high sensitivity and high selectivity.
Currently, the detection means of ketoprofen mainly comprise liquid chromatography, ultraviolet fluorescence, ion chromatography, electrochemical detection and the like. The fluorescent probe is an important method for detecting ketoprofen, and has the advantages of low cost, high sensitivity, good stability and the like, and is considered as one of the most promising detection methods, but substances with different spatial structures or containing different functional groups can also influence the luminescence of the substances, so that the detection selectivity and the sensitivity of the fluorescent probe are improved.
Molecular imprinting utilizes molecularly imprinted polymers (Molecular Imprinting Polymers, MIPs) to mimic enzyme-substrate or antibody-antigen interactions for specific recognition of imprinted molecules (also known as template molecules).
The molecular imprinting technology is widely applied to some polymer materials and some inorganic materials, but is not reported in MOFs materials, and the MOFs materials are not used for detecting ketoprofen.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a molecularly imprinted Zr-MOF fluorescent probe material, and a preparation method and application thereof.
A preparation method of a molecularly imprinted Zr-MOF fluorescent probe material comprises the following steps of S10: zrCl is added to 4 Uniformly dispersing the ketoprofen and the ketoprofen in a DMF solution to obtain a first mixed solution; s20: adding ligand terephthalic acid into the first mixed solution to obtain a second mixed solution; s30: reacting, washing and separating to obtain a solid template containing ketoprofen; s40: removing ketoprofen in the template; s50: and carrying out plasma modification on the template to obtain the Zr-MOF fluorescent probe material.
Optionally, the step S10 includes performing ultrasonic treatment on the first mixed solution; the step S20 includes performing ultrasonic treatment on the second mixed solution; the step S30 comprises the steps of centrifugally washing by utilizing a mixed solution of ethanol and DMF to obtain a solid template containing ketoprofen; the step S40 comprises the steps of adding the solid template into DMF containing concentrated hydrochloric acid, stirring, washing and drying the solid template, so as to remove ketoprofen in the template; the step S50 includes passing through a low temperature H 2 S plasma to modify the template; said low temperature H 2 The S plasma is modified under the voltage of 10V-30V and the time of 15 min-35 min.
The Zr-MOF fluorescent probe material prepared by the preparation method has a controllable porous structure.
A fluorescence detection method utilizes the Zr-MOF fluorescent probe material to carry out fluorescence detection on ketoprofen.
The beneficial effects of the invention are as follows: compared with polymer materials and inorganic materials, MOFs have the advantages of large specific surface area, easiness in functional modification, controllable porous structure and the like. The MOFs fluorescent material is improved and synthesized by using a molecular imprinting technology, has the advantages of large specific surface area, easiness in functional modification and controllable porous structure, and simultaneously has high selectivity on an object to be detected, and the fluorescence intensity of the MOFs and the sensitivity of the probe are enhanced through H2S plasma modification. The invention provides a Zr-MOF fluorescent probe material prepared based on a molecular imprinting technology and application thereof, and the MOF is mainly used in the field of fluorescence sensing. Compared with the LTP@UiO-66 (NIP) probe, the white granular LTP@UiO-66 (MIP) fluorescent probe material provided by the invention has the advantages of good ketoprofen selectivity, high sensitivity, strong stability, strong anti-interference capability, low cost and small pollution.
Drawings
FIG. 1 is a scanning electron microscope image of a Zr-MOF fluorescent probe material prepared by the invention;
FIG. 2 is a schematic XRD spectrum of a Zr-MOF fluorescent probe material prepared by the invention;
FIG. 3 is a schematic diagram of an infrared spectrum of a Zr-MOF fluorescent probe material prepared by the invention;
FIG. 4 shows fluorescence emission spectra and fluorescence excitation spectra of Zr-MOF fluorescent probe materials prepared by the invention;
FIG. 5 is a graph showing the quenching of ketoprofen by Zr-MOF fluorescent probe material prepared by the present invention;
FIG. 6 is a schematic diagram showing the selectivity of ketoprofen and various organic matters of a Zr-MOF fluorescent probe material prepared by the invention;
FIG. 7 is a graph showing the comparison of fluorescence intensity of Zr-MOF fluorescent probe materials prepared by the invention in the presence of different organic interferents;
FIG. 8 is a graph showing the comparison of fluorescence intensity of Zr-MOF fluorescent probe material prepared by the invention under the condition of plasma modification and no plasma modification.
Detailed Description
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of the invention, as illustrated in the accompanying drawings. Like reference numerals refer to like parts throughout the several views of the drawings. The drawings are not intended to be drawn to scale, emphasis instead being placed upon illustrating the principles of the invention.
The terms and words used in the following description and claims are not limited to written meanings, but are used only by the inventors to enable a clear and consistent understanding of the invention. It will be apparent to those skilled in the art, therefore, that the following description of the various embodiments of the invention is provided for illustration only and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
It should be understood that the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a module" includes reference to one or more such modules. Advantages and features of the present invention and methods of accomplishing the same may be understood more readily by reference to the following detailed description of embodiments and the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present disclosure will only be defined by the appended claims.
The preparation method of the Zr-MOF fluorescent probe material comprises the following steps: s10: zrCl is added to 4 Uniformly dispersing the ketoprofen and the ketoprofen in a DMF solution to obtain a first mixed solution; s20: adding ligand terephthalic acid into the first mixed solution to obtain a second mixed solution; s30: reacting, washing and separating to obtain a solid template containing ketoprofen; s40: removing ketoprofen in the template; s50: and carrying out plasma modification on the template to obtain the Zr-MOF fluorescent probe material.
The step S10 may be performed at room temperature, and the operation of step S20 may be performed after the first mixed solution is subjected to the ultrasonic treatment, and the second mixed solution may also be subjected to the ultrasonic treatment in step S20. The reaction of step S30 was performed in a polytetrafluoroethylene liner, followed by centrifugal washing with a mixed solution of ethanol and DMF to obtain a solid template containing ketoprofen. Adding a solid template to D in step S40MF (containing 0.4ml of concentrated hydrochloric acid) and washed and dried to obtain a ketoprofen-removed template. By low temperature H of the stencil in step S50 2 S plasma is modified to improve the fluorescence characteristic of the Zr-MOF fluorescent probe material.
Example 1
At first, 0.686mmol of ZrCl is added in the room temperature environment 4 Uniformly dispersing the mixed solution with 0.343mmol of ketoprofen in 40mL of LDMF solution, adding 0.343mmol of terephthalic acid after ultrasonic treatment for 20min, transferring the mixed solution into a 60mL polytetrafluoroethylene lining after ultrasonic treatment for 20min, and reacting at 120 ℃ for 48h; after the reaction, naturally cooling to room temperature, centrifugally washing the cooled product with ethanol and DMF mixed solution for three times, stirring in 100 mM (containing 0.4ml of concentrated hydrochloric acid) at 90 ℃ for 24 hours, and repeating once to remove the ketoprofen template. Washing, drying, and cooling to low temperature H 2 The S plasma voltage was maintained at 10V for 15min and the modification time was taken to give Zr-MOF, designated LTP@UiO-66 (0.5 MIP).
Example 2
At first, 0.686mmol of ZrCl is added in the room temperature environment 4 Uniformly dispersing the mixed solution with 0.686mmol of ketoprofen in 40mL of LDMF solution, adding 0.343mmol of terephthalic acid after ultrasonic treatment for 20min, transferring the mixed solution into a 60mL polytetrafluoroethylene lining after ultrasonic treatment for 20min, and reacting at 120 ℃ for 48h; after the reaction, naturally cooling to room temperature, centrifugally washing the cooled product with ethanol and DMF mixed solution for three times, stirring in 100 mM (containing 0.4ml of concentrated hydrochloric acid) at 90 ℃ for 24 hours, and repeating once to remove the ketoprofen template. Washing, drying, and cooling to low temperature H 2 The S plasma voltage was maintained at 10V for 15min and the modification time was taken to give Zr-MOF, designated LTP@UiO-66 (1.0 MIP).
Example 3
At first, 0.686mmol of ZrCl is added in the room temperature environment 4 Uniformly dispersing 1.029mmol of ketoprofen in 40mL of the solution, adding 0.343mmol of terephthalic acid after ultrasonic treatment for 20min, transferring the mixed solution into a 60mL polytetrafluoroethylene lining after ultrasonic treatment for 20min, and reacting at 120 ℃ for 48h; naturally cooling to room temperature after the reaction is finished, and centrifugally washing the cooled product by using ethanol and DMF mixed solution respectivelyThree times, followed by stirring in 100mL of LDMF (containing 0.4mL of concentrated hydrochloric acid) at 90℃for 24h and repeating once to remove the ketoprofen template. Washing, drying, and cooling to low temperature H 2 The S plasma voltage was maintained at 10V for 15min and the modification time was taken to give Zr-MOF, designated LTP@UiO-66 (1.5 MIP).
Comparative example 1
At first, 0.686mmol of ZrCl is added in the room temperature environment 4 Dispersing the mixture with 0.343mmol of terephthalic acid in 40mL of LDMF solution, uniformly stirring, transferring the mixed solution into a 60mL polytetrafluoroethylene lining, and reacting at 120 ℃ for 48h; naturally cooling to room temperature after the reaction, centrifugally washing the cooled product with ethanol and DMF mixed solution for three times, drying at 50 ℃, and cooling at low temperature H 2 The S plasma voltage was maintained at 10V for 15min and the modification time was set to Zr-MOF, designated LTP@UiO-66 (NIP).
Comparative example 2
Firstly, uniformly dispersing 0.686mmol of ZrCl4 and 1.029mmol of ketoprofen in a 40mLDMF solution at room temperature, adding 0.343mmol of terephthalic acid after 20min of ultrasound, transferring the mixed solution into a 60mL polytetrafluoroethylene lining after 20min of ultrasound, and reacting at 120 ℃ for 48h; after the reaction is finished, naturally cooling to room temperature, centrifugally washing the cooled product with ethanol and DMF mixed solution for three times respectively, stirring in 100 mM (containing 0.4mL of concentrated hydrochloric acid) at 90 ℃ for 24 hours, and repeating once to remove the ketoprofen template. After washing, the resultant was dried to give Zr-MOF, which was designated UiO-66 (1.5 MIP).
Fluorescence detection
Fluorescence detection was performed on the materials obtained in examples 1, 2, and 3 and comparative examples 1 and 2. The method comprises the following steps: firstly, 10 mu L of a potassium permanganate solution with the concentration of 2mM is taken; then, the fluorescent probe materials obtained in examples 1, 2 and 3 and comparative examples 1 and 2 were respectively dropped into 10mg/L of the aqueous solution by a pipette, and fluorescence detection was performed.
Performance detection
1. The Zr-MOF fluorescent probe materials prepared in examples 1 to 3 of the present invention and comparative example 1 were subjected to morphological analysis by a scanning electron microscope. As shown in fig. 1, it can be seen that ltp@uio-66 (NIP) is not very uniform in size (fig. 1, panel a) and exhibits a cubic type of stereo structure, while in the synthesis process, ketoprofen is still in an octahedral structure (fig. 1, panel b) when added in an amount of 0.5 times the amount of zirconium chloride, but the morphology is changed from an octahedral to a spherical shape when the added amount reaches 1.0 or 1.5 times (fig. 1, panels c and d).
2. The Zr-MOF fluorescent probe materials prepared in examples 1 to 3 and comparative example 1 of the present invention were subjected to X-ray diffraction to analyze the crystal phase and surface chemical structure of the Zr-MOF. As shown in FIG. 2, the XRD pattern of the Zr-MOF exhibited good crystallinity and was substantially coincident with the main peak of the simulated diffraction peak.
3. Surface chemical structural analysis of Fourier Infrared Spectroscopy (FT-IR) was performed on the Zr-MOF fluorescent probe materials prepared in examples 1 to 3 and comparative example 1 of the present invention, as shown in FIG. 3, 1650cm -1 The nearby absorption peak is a characteristic peak caused by C=O stretching vibration in carboxyl, 1480cm -1 The peak near is COO in the ligand - Is caused by the telescopic vibration of the device; at 1580cm -1 、1500cm -1 There are two medium intensity absorption peaks, which are characteristic peaks of benzene-containing ring compounds; fingerprint area 750cm -1 The characteristic peak at the position is deformation vibration of Zr-O bond.
4. The Zr-MOF fluorescent probe materials prepared in examples 1-3 and comparative example 1 of the present invention were subjected to detection of fluorescence excitation spectrum and fluorescence emission spectrum, thereby obtaining a schematic diagram of fluorescence excitation spectrum and fluorescence emission spectrum shown in FIG. 4. Clearly, LTP@UiO-66 (NIP) showed fluorescence emission at 390nm when excited at 264 nm. The luminescence of LTP@UiO-66 (NIP) is due to charge transitions within its energy level. In contrast, LTP@UiO-66 (1.5 MIP) exhibited stronger fluorescence intensity at the same excitation (FIG. 5 a), probably due to the presence of defects that allowed the imprinted molecule to be modified with more functional groups under the same modification conditions. More sulfhydryl groups cause an increase in the number of excited electrons during energy transfer.
5. The Zr-MOF fluorescent probe materials prepared in examples 1 to 3 and comparative example 1 of the present invention were subjected to fluorescence detection experiments of permanganate ions of different concentrations, in particular, as follows: the fluorescence test is carried out at 298K, and a 10mg/L fluorescent probe suspension is obtained by adopting a stepwise dilution method. 2mL of the sample was dropped into the cuvette by using a pipette, 1. Mu.L of ketoprofen ethanol solution with a concentration of 2mmol/L was gradually dropped, and the change of fluorescence intensity was tested at an excitation wavelength of 264nm until the fluorescence intensity was no longer quenched. The fluorescence signal was then obtained by adding different concentrations of ketoprofen in the range of 0-100. Mu.M. Similarly, fluorescence response at different temperatures fluorescence tests were performed at 288 and 318K temperatures using the same method. For comparison, probe samples with different proportions of ketoprofen (0.5, 1.0 and 1.5) were added for sensory evaluation. All spectra were collected in triplicate. When the ketoprofen concentration increases from 0 to 10 μm, LTP@UiO-66 (NIP) K sv 1.08X10 5 M -1 LOD was 0.41. Mu.M. More importantly, template molecules are added in the synthesis process, so that the sensitivity of the sample is greatly improved. In addition, LTP@UiO-66 (1.5 MIP) has a higher K than LTP@UiO-66 (NIP) sv Up to 5.77×10 5 M -1 LOD values reach 0.04. Mu.M. Therefore, the molecularly imprinted MOFs are very effective for improving fluorescence detection performance. More importantly, the LOD value (0.04. Mu.M, 10.16. Mu.g/kg) of LTP@UiO-66 (1.5 ketoprofen@MIP) was far below the highest safe level (50. Mu.g/kg) of ketoprofen in milk specified by the national ministry of health, which indicates that it is an excellent fluorescent probe for detecting ketoprofen. In the process of exploring and adding different proportions of templates to perform fluorescence detection on ketoprofen, the fluorescence quenching of the material on ketoprofen gradually increases along with the increase of the proportion of the templates, and the corresponding K sv And also increases as shown in fig. 5f, g and h. K of LTP@UiO-66 (0.5 MIP) and LTP@UiO-66 (1.0 MIP) sv Less than LTP@UiO-66 (1.5 MIP), 4.7X10 respectively 5 M -1 And 5.65X10 5 M -1 . The reason is that as the amount of template added increases, the number of corresponding specific wells increases. However, as the proportion of template molecules increases from 1.0 to 1.5, the magnitude of the change in fluorescence response decreases significantly, indicating that the formation of holes becomes progressively saturated.
6. The Zr-MOF fluorescent probe materials prepared in examples 1 to 3 and comparative example 1 of the present invention were subjected to a selective experiment on permanganate ions and an experiment on resistance to other ions, and the specific experimental methods are as follows: a series of different medicines and pesticides (diclofenac sodium, flurbiprofen, malachite green, chlorothalonil, chlorpropham, atrazine, roxithromycin, secnidazole and gibberellin) are prepared as target objects to be detected, and the selectivity of detection is evaluated. To 2ml of the suspension, an ethanol solution of the interfering substance at a concentration of 2mmol/L was added, 10. Mu.l was added dropwise at a time, followed by ultrasound for 5min, to complete the reaction, and the fluorescence intensity was measured and all spectra were collected three times in parallel. For the interference experiments, 10. Mu.L of the above interfering organic compound at a concentration of 2mmol/L was added to 2mL of the fluorogenic substrate suspension, and the fluorescence emission results were recorded. The same volume and concentration of ketoprofen solution was then added to the mixture for fluorescence measurement. For LTP@UiO-66 (NIP), the fluorescence intensity was quenched by the ketoprofen moiety with a quenching efficiency of 36%, while other organic compounds had a slight effect on the fluorescence intensity of LTP@UiO-66 (NIP). However, LTP@UiO-66 (MIP) obtained by molecular imprinting technique showed high selectivity to ketoprofen (FIG. 6). LTP@UiO-66 (0.5 MIP) showed high responsiveness to ketoprofen, and quenching efficiency of up to 71% for 10ul of ketoprofen. By observing the fluorescence intensity of LTP@UiO-66 (1.0 MIP), the quenching efficiency of LTP@UiO-66 (1.0 MIP) reached 75% by increasing the addition amount of ketoprofen. Further increasing the addition amount of ketoprofen, the quenching efficiency of LTP@UiO-66 (1.5 MIP) reaches 85%. The response of LTP@UiO-66 (MIP) to ketoprofen was significantly improved compared to LTP@UiO-66 (NIP), while the response to other small organic molecules was unchanged. Notably, the reaction of LTP@UiO-66 (MIP) on sodium diclofenac and flurbiprofen was also improved. This is because sodium diclofenac and flurbiprofen have similar spatial structures as ketoprofen, and thus the specific pores formed by ketoprofen also enhance the binding of ltp@uio-66 (MIP) to sodium diclofenac and flurbiprofen, resulting in an increase in reactivity. In conclusion, the molecular imprinting technology effectively improves the selectivity of LTP@UIO-66 (MIP) to template molecules. The anti-interference ability of the fluorescent probe was further investigated (fig. 7). As shown in fig. 7, ketoprofen was added to the suspension of the fluorescent agent in the presence of the interferents, exhibiting some degree of quenching. However, the degree of quenching by different interferents varies greatly. For LTP@UiO-66 (0.5 MIP), LTP@UiO-66 (1.0 MIP) and LTP@UiO-66 (1.5 MIP) obtained by molecular imprinting, ketoprofen was added to the fluorescent probe suspension containing the interfering substance, the fluorescence intensity was still lowered, and the fluorescence quenching degree was almost uniform (panels b, c and d in FIG. 7). The LTP@UiO-66 (MIP) has better anti-interference capability.
8. As a result of fluorescence detection of the Zr-MOF fluorescent probe materials obtained in example 3 and comparative example 2 of the present invention, as shown in FIG. 8, it can be seen from FIG. 8 that UiO-66 (1.5 MIP) which was not plasma-modified had a weak fluorescence intensity, whereas LTP@UiO-66 (1.5 MIP) which was fluorescence-modified had a significantly enhanced fluorescence intensity.
Although the technology has been illustrated and described with respect to one or more implementations, alterations and/or modifications may be made to the illustrated examples without departing from the spirit and scope of the appended claims. In particular regard to the various functions performed by the above described components or structures (assemblies, devices, circuits, systems, etc.), the terms (including a reference to a "means") used to describe such components are intended to correspond, unless otherwise indicated, to any component or structure which performs the specified function of the described component (e.g., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary implementations. In addition, while a particular feature may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application. Furthermore, to the extent that the terms "includes," including, "" has, "" containing, "or variants thereof are used in either the detailed description or the claims, such terms are intended to be inclusive in a manner similar to the term" comprising.
In the above description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The foregoing description is only of a preferred embodiment of the invention, which can be practiced in many other ways than as described herein, so that the invention is not limited to the specific implementations disclosed above. While the foregoing disclosure has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes and modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the technical solution of the present invention still falls within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a molecular imprinting Zr-MOF fluorescent probe material is characterized by comprising the following steps,
s10: zrCl is added to 4 Uniformly dispersing the ketoprofen and the ketoprofen in a DMF solution to obtain a first mixed solution;
s20: adding ligand terephthalic acid into the first mixed solution to obtain a second mixed solution;
s30: reacting, washing and separating to obtain a solid template containing ketoprofen;
s40: removing ketoprofen in the template;
s50: and carrying out plasma modification on the template to obtain the Zr-MOF fluorescent probe material.
2. The method according to claim 1, wherein the step S10 comprises subjecting the first mixed solution to ultrasonic treatment.
3. The method according to claim 1, wherein the step S20 comprises subjecting the second mixed solution to ultrasonic treatment.
4. The method according to claim 1, wherein the step S30 comprises centrifugal washing with a mixed solution of ethanol and DMF to obtain a solid template containing ketoprofen.
5. The method according to claim 1, wherein the step S40 comprises adding the solid template to DMF containing concentrated hydrochloric acid, stirring, washing, and drying to remove ketoprofen from the template.
6. The method according to claim 1, wherein the step S50 comprises passing through a low temperature H 2 S plasma modifies the template.
7. The method of claim 6, wherein the low temperature H 2 The S plasma is modified under the voltage of 10V-30V and the time of 15 min-35 min.
8. A Zr-MOF fluorescent probe material prepared according to the preparation method of any one of claims 1 to 7.
9. The Zr-MOF fluorescent probe material according to claim 8, wherein said Zr-MOF fluorescent probe material has a controllable porous structure.
10. A fluorescence detection method, characterized in that ketoprofen is subjected to fluorescence detection by using the Zr-MOF fluorescent probe material according to any one of claims 8 to 9.
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