CN113567594B - Detection method of norfloxacin based on MOFs type molecularly imprinted polymer - Google Patents
Detection method of norfloxacin based on MOFs type molecularly imprinted polymer Download PDFInfo
- Publication number
- CN113567594B CN113567594B CN202111024140.9A CN202111024140A CN113567594B CN 113567594 B CN113567594 B CN 113567594B CN 202111024140 A CN202111024140 A CN 202111024140A CN 113567594 B CN113567594 B CN 113567594B
- Authority
- CN
- China
- Prior art keywords
- uio
- norfloxacin
- eluent
- mip
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
- G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8603—Signal analysis with integration or differentiation
- G01N2030/862—Other mathematical operations for data preprocessing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a detection method of norfloxacin based on MOFs molecular engram polymer, which comprises the following steps: s1: preparing MOFs type molecularly imprinted polymer UiO-66@MIP; s2: establishing a norfloxacin liquid phase standard working curve: s3: detecting an actual water sample: mixing the actual water sample with the UiO-66@MIP prepared in the step S1, incubating the mixture on a shaker for 40 minutes at 500rpm, and removing the supernatant by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; and enriching the eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of an initial actual water sample by using water, detecting the obtained water solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, substituting the peak area into a norfloxacin liquid phase standard working curve, and calculating to obtain the norfloxacin content in the actual water sample. The detection method effectively reduces the detection cost and the operation difficulty of norfloxacin and improves the detection efficiency.
Description
Technical Field
The invention belongs to the field of antibiotic detection, and particularly relates to a norfloxacin detection method based on MOFs molecular imprinting polymers.
Background
Norfloxacin (NOR) is one of the quinolone antibiotics, and is widely used as a broad-spectrum inexpensive antibiotic for the treatment and control of diseases in humans and animal products. According to incomplete statistics, the usage amount of antibiotics in China exceeds 50% of the total world usage amount, so that a plurality of problems are caused. Since it is only partially metabolized, a large amount of antibiotics are discharged into the environment with feces and urine, and thus, the phenomenon of antibiotic detection in lakes and rivers is not uncommon. Long-term drinking of water containing antibiotics can lead to human immunity reduction, intestinal flora imbalance, even cancer and teratogenesis. Therefore, it is urgent to develop a low-cost, simple and efficient norfloxacin separation detection method. Currently, solid Phase Extraction (SPE) or QuEChERS has been widely used for extracting norfloxacin from water, but has the problems of higher cost, lower adsorption capacity, no selectivity and the like. Thus, these methods still leave room for improvement.
Molecularly Imprinted Polymers (MIPs), commonly known as artificial antibodies, are polymers that can selectively bind template targets through a key and lock mechanism. Molecular imprinting is a common method for improving the selectivity of materials due to low cost, high stability and high selectivity. The polymer with high selectivity needs to be attached to the nano material with a certain specific surface area to exert the highest performance, so that a method for compounding the molecularly imprinted polymer on the surface of the nano material needs to be established.
In recent years, metal Organic Frameworks (MOFs) have become the focus of much research. MOFs and their composites are widely used in the fields of separation and enrichment, analysis and detection due to their large accessible surface area, uniform and adjustable pore size, chemical modularity, fluorescence and catalytic activity. In these fields, MOFs exhibit properties that are well documented for their potential to bind to molecular imprinting.
Disclosure of Invention
Aiming at the technical problems to be solved, the invention provides a detection method of norfloxacin based on MOFs type molecularly imprinted polymer, which can realize low-cost, simple and efficient qualitative and quantitative detection of norfloxacin by preparing MOFs type molecularly imprinted polymer UiO-66@MIP with high adsorption capacity, high selectivity and high stability and using the MOFs type molecularly imprinted polymer UiO-66@MIP in the adsorption detection of norfloxacin.
In order to achieve the above object, the present invention provides a detection method of norfloxacin based on MOFs type molecularly imprinted polymer, which is characterized in that: the method comprises the following steps:
s1: preparation of MOFs type molecularly imprinted polymer UIO-66@MIP: preparation of UiO-66-NH 2 As a carrier for molecular imprinting, the reaction between anhydride and amino is carried out in UiO-66-NH 2 After grafting double bonds on the surface, imprinting NOR on the surface of MOFs through free radical polymerization to prepare UiO-66@MIP;
s2: establishing a norfloxacin liquid phase standard working curve: mixing the norfloxacin standard solutions with serial concentrations with the UiO-66@mip prepared in the step S1 respectively, incubating the mixed solution on a shaker at 500rpm for 40 minutes, and removing the supernatant by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; enriching the eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of the initial norfloxacin standard solution by using water, and detecting the obtained aqueous solution by using a high performance liquid chromatography; drawing a norfloxacin liquid phase standard working curve by using the peak area of the obtained data;
s3: detecting an actual water sample: mixing the actual water sample with the UiO-66@MIP prepared in the step S1, incubating the mixture on a shaker for 40 minutes at 500rpm, and removing the supernatant by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; and enriching the eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of an initial actual water sample by using water, detecting the obtained water solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, substituting the peak area into a norfloxacin liquid phase standard working curve, and calculating to obtain the norfloxacin content in the actual water sample.
Compared with the prior art, the invention combines the molecular imprinting technology with MOFs and selects the UiO-66-NH with high stability 2 As a carrier for molecular imprinting, the reaction between anhydride and amino is carried out in UiO-66-NH 2 After grafting double bonds on the surface, NOR was imprinted on the MOFs surface by free radical polymerization to form UiO-66@MIP. The molecularly imprinted polymer has high adsorption capacity, high selectivity and high stability, is used for separating and detecting norfloxacin, effectively reduces detection cost and operation difficulty, and improves detection efficiency.
Preferably, in the step S2, the dosage ratio of the norfloxacin standard solution to the UIO-66@MIP is 3mL:10mg; in the step S3, the dosage ratio of the actual water sample to the UIO-66@MIP is 3mL:10mg.
Preferably, the chromatographic conditions of the high performance liquid chromatography in steps S2 and S3 are: in C 18 The chromatographic column is a stationary phase, 0.025mol/L phosphoric acid solution-acetonitrile is used as a mobile phase, the flow rate is set to be 0.8ml, and the wavelength of the PDA detector is set to be 277nm; the phosphoric acid solution is regulated with triethylamineThe pH is 3.0; the volume ratio of the phosphoric acid solution to acetonitrile is 80:20.
Preferably, in steps S2 and S3, the eluent is a methanol/acetic acid solution with a volume ratio of 9:1, and the addition amount of the eluent is the same as the volume of the initial norfloxacin standard solution or the volume of the actual water sample.
Preferably, step S1 comprises the steps of:
s1a: preparation of UiO-66-NH 2 As a carrier of molecular imprinting;
s1b: the UiO-66-NH obtained in the step S1a 2 Dispersing in dichloromethane, ultrasonic treating for 20 min, adding methacrylic anhydride into the solution, and continuously reacting at 25 ℃ for 96 hours; after the reaction was completed, the precipitate was collected by centrifugation at 9000rpm and washed 3 times with methylene chloride; vacuum drying the product at 45 ℃ to obtain UIO-66-M;
s1c: mixing the UiO-66-M prepared in the step S1b with acetonitrile, performing ultrasonic dispersion for 10 minutes, adding NOR and MAA, and stirring the mixture at room temperature for 2 hours; after heating the mixture to 60 ℃, EGDMA and AIBN were added and the mixture was reacted at 60 ℃ for 24 hours; centrifuging at 9000rpm after the reaction is finished, collecting precipitate, and washing with an eluent until the template is removed; finally, the product is dried in vacuum at 60 ℃ to obtain the UIO-66@MIP.
Preferably, in step S1b, uiO-66-NH 2 The ratio of dichloromethane to methacrylic anhydride was 1g:15mL:2.6mL.
Preferably, in step S1c, uiO-66-M, acetonitrile, NOR, MAA, EGDMA and AIBN are used in a ratio of 80mg:50mL:51 mg:68. Mu.L:400. Mu.L:70 mg.
Preferably, step S1a comprises the steps of: zrCl is added to 4 And acetic acid was dissolved in DMF by ultrasonic wave for 5 min; then 2-amino terephthalic acid is dissolved in the solution, and deionized water is added into the solution after ultrasonic treatment is carried out for 5 minutes; transferring the mixed solution into a polytetrafluoroethylene reactor, heating to 120 ℃ for 24 hours, and then cooling to room temperature; the product was repeatedly washed with DMF and ethanol and then dried under vacuum at 60 ℃.
Preferably, in step S1a, zrCl 4 Acetic acid, DMFThe dosage ratio of 2-amino terephthalic acid to deionized water was 0.78g:5.55mL:80mL:0.58g:0.24mL.
Preferably, the eluent in the step S1a is methanol/acetic acid solution with the volume ratio of 9:1.
Preferably, the concentration of the series of norfloxacin standard solutions in step S2 is 43.0mg/L, 21.5mg/L, 14.3mg/L, 10.8mg/L, 5.4mg/L, 2.2mg/L, 1.1mg/L, 0.54mg/L, 0.27mg/L, 0.1mg/L, respectively.
Drawings
FIG. 1 is a working curve of HPLC of norfloxacin
FIG. 2 is a comparison of HPLC chromatograms of an actual water sample and a UiO-66@MIP adsorption elution solution in an effect test example
FIG. 3 is a diagram of UiO-66-NH obtained in example 1 2 Infrared characterization graphs of UiO-66-M and UiO-66@MIP
FIG. 4 is a diagram of UiO-66-NH obtained in example 1 2 XRD characterization patterns of UiO-66-M and UiO-66@MIP
FIG. 5 is a diagram of UiO-66-NH obtained in example 1 2 Thermogram of UiO-66-M and UiO-66@MIP
FIG. 6 is a diagram of UiO-66-NH obtained in example 1 2 Nitrogen adsorption and desorption curve and pore size distribution diagram of UiO-66-M
FIG. 7 is a graph showing the nitrogen adsorption/desorption curve and the pore size distribution of UiO-66@MIP obtained in example 1
FIG. 8 is a diagram of UiO-66-NH obtained in example 1 2 TEM images of (a)
FIG. 9 is a TEM image of UiO-66-M obtained in example 1
FIG. 10 is a TEM image of the UiO-66@MIP prepared in example 1
FIG. 11 is a TEM image of UiO-66@NIP obtained in comparative example
FIG. 12 is a bar graph of the effect of template to functional monomer ratio on adsorption capacity in UiO-66@MIP
FIG. 13 is a bar graph showing the effect of functional monomer to crosslinker ratio on adsorption capacity in UiO-66@MIP
FIG. 14 is a bar graph showing the effect of pH on adsorption capacity in adsorption conditions
FIG. 15 is a graph showing the static adsorption of UiO-66@MIP prepared in example 1 and UiO-66@NIP prepared in comparative example
FIG. 16 is a Scatchard plot of UiO-66@MIP obtained in example 1
FIG. 17 is a Scatchard plot of UiO-66@NIP obtained in comparative example
FIG. 18 is a graph showing the dynamic adsorption of UiO-66@MIP prepared in example 1 and UiO-66@NIP prepared in comparative example
FIG. 19 is a bar chart showing the results of a selectivity test for UiO-66@MIP prepared in example 1 and UiO-66@NIP prepared in comparative example
FIG. 20 is a bar chart showing the reusability test of the UiO-66@MIP prepared in example 1
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The following examples, test examples and the apparatus used in the test examples are shown in Table 1, and the reagents are shown in Table 2.
Table 1 laboratory instrument table
Table 2 experiment reagent table
Example 1: detection method of norfloxacin in actual water sample
The norfloxacin in an actual water sample is detected according to the following steps:
s1: MOFs molecularly imprinted polymer UIO-66@MIP was prepared according to the following steps:
s1a: preparation of UiO-66-NH 2 Carrier as molecular imprintingThe body: 0.78g ZrCl 4 And 5.55mL of acetic acid were dissolved by sonication in 80mL of DMF for 5 minutes. Then, 0.58g of 2-amino terephthalic acid was dissolved in the solution. After additional 5 minutes of sonication, 0.24mL deionized water was added to the solution. The mixed solution was transferred to a polytetrafluoroethylene reactor, heated to 120 ℃ for 24 hours, and then cooled to room temperature. The product was repeatedly washed with DMF and ethanol and then dried under vacuum at 60 ℃.
S1b: by reaction of anhydride with amino group, in UiO-66-NH 2 Grafting double bonds on the surface to synthesize UIO-66-M: 1g of UiO-66-NH prepared in step S1a 2 Dispersed in 15mL of methylene chloride. After sonication for 20 minutes, 2.6mL of methacrylic anhydride was added to the solution. The entire reaction was continued at 25℃for 96 hours. After the reaction was completed, the precipitate was collected by centrifugation at 9000rpm and washed 3 times with methylene chloride. The product was dried under vacuum at 45 ℃.
S1c: NOR was imprinted on the surface of UiO-66-M by free radical polymerization to synthesize UiO-66@MIP: 80mg of UiO-66-M and 50mL of acetonitrile were added to a 100mL flask. After 10 minutes of ultrasonic dispersion, 51mg of NOR and 68. Mu.L of MAA were added to the flask. The mixture was stirred at room temperature for 2 hours. After the reaction system was heated to 60 ℃, 400. Mu.L of EGDMA and 70mg of AIBN were added. The mixture was reacted at 60℃for 24 hours. After the reaction was completed, the precipitate was collected by centrifugation at 9000rpm and then washed with methanol/acetic acid (90:10, v/v) until the template was removed. Finally, the product was dried in vacuo at 60 ℃.
S2: establishing a norfloxacin liquid phase standard working curve: 215mg/L of norfloxacin standard solution was diluted to a series of concentrations of 43.0mg/L, 21.5mg/L, 14.3mg/L, 10.8mg/L, 5.4mg/L, 2.2mg/L, 1.1mg/L, 0.54mg/L, 0.27mg/L, 0.1mg/L, then mixed with the UIO-66@MIP prepared in step S1, respectively, and incubated on a shaker at 500rpm for 40 minutes, and the supernatant was removed by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; enriching the eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of the initial norfloxacin standard solution by using water, and detecting the obtained aqueous solution by using a high performance liquid chromatography; drawing a norfloxacin liquid phase standard working curve by using the peak area of the obtained data;
s3: detecting an actual water sample: 3ml of the actual water sample was taken into a centrifuge tube, and 10mg of UIO-66@MIP was added thereto. The mixture was incubated on a shaker at 500rpm for 40 minutes and the supernatant removed by centrifugation. Then 3ml of eluent (methanol/acetic acid=9:1) was added to the centrifuge tube and the eluent was collected after ultrasonic centrifugation. The eluent is enriched by a nitrogen blower and then is re-sized to 3ml by water. And detecting the obtained aqueous solution by using a high performance liquid chromatography, determining whether norfloxacin is contained or not by using dead time, substituting peak areas into a norfloxacin liquid phase standard working curve, and calculating to obtain the norfloxacin content in the actual water sample.
The liquid chromatography conditions in the above steps S2 and S3 are: in C 18 The column was stationary phase, 0.025mol/L phosphoric acid solution (pH adjusted to 3.0 with triethylamine) -acetonitrile (80:20) was used as mobile phase, the flow rate was set to 0.8ml, and the PDA detector wavelength was set to 277nm.
And (3) according to the norfloxacin liquid phase standard working curve obtained in the step S2, as shown in a figure 1, the HPLC chromatogram of the actual water sample in the step S3 is shown in a figure 2, and the peak area is substituted into the standard curve to calculate that the water sample contains 0.51mg/L norfloxacin.
Comparative example: synthesis of UiO-66@NIP
The detection method of UiO-66@NIP is basically the same as the preparation method of UiO-66@MIP in step S1 in example 1, except that NOR is not added in step S1 c.
Test example: characterization of the Structure of several materials obtained in example 1 and comparative example
Test example 1: infrared (FT-IR) characterization
FT-IR spectroscopy is used as a means of proving the composition of materials to help prove the success of the relevant material synthesis. As shown in FIG. 3, 3461cm -1 And 3351cm -1 The absorption at this point corresponds to symmetric and asymmetric N-H vibrations. N-H bending vibration and C-N stretching can be carried out at 1572cm -1 To 1385cm -1 Between which to find. With UiO-66-NH 2 UiO-66-M was at 1673cm compared to FT-IR spectrum of (C) -1 There is a new absorption peak due to the characteristic absorption peak of c=c, indicating successful synthesis of UiO-66-M. Due to the formation of the molecularly imprinted layer, uiOThe FT-IR spectrum of 66@MIP consists essentially of 2950cm -1 C-H absorption peak and 1716cm -1 C=O absorption peak composition, demonstrating that UiO-66-M and UiO-66@MIP have been successfully synthesized.
Test example 2: powder X-ray diffraction (PXRD) characterization
To demonstrate whether the material remained stable before and after modification and polymerization, for UiO-66-NH 2 Powder X-ray diffraction (PXRD) was performed for UiO-66-M and UiO-66@MIP. As shown in fig. 4, the black line peaks at 2θ=7.36, 8.48, 17.08, 22.25, and 33.12 ° correspond to the characteristic diffraction peaks of (110), (200), (022), (115), and (137) UiO-66s, respectively. UiO-66-NH 2 After reaction with methacrylic anhydride, the diffraction peak of UiO-66-M remained the same as that of the original UiO-66, indicating that the chemical reaction did not destroy the crystal structure. Due to the modification of the molecular imprinting, the XRD pattern of the UiO-66@MIP has a higher baseline, so that the obtained data is subjected to background subtraction and baseline correction. The obtained map peak is compared with the original UiO-66-NH 2 The peaks were identical, indicating that the original crystal structure was maintained even after polymerization.
Test example 3: thermogravimetric characterization
FIG. 5 is a thermogravimetric characterization of a material, uiO-66-NH 2 The mass reduction before 100 ℃ is attributed to the loss of solvent and moisture in the material, much like the thermogravimetric curve of UiO-66-M, and when the temperature is raised to about 270 ℃, the material begins to digest, generating CO, CO 2 Zirconium oxide. With respect to combustion residues, uiO-66-NH 2 Slightly higher than UiO-66-M, it can also be seen that the double bond modification was successful. The thermogravimetric curve of MIP@UiO-66 (same as UiO-66@MIP) is significantly different from the former two, and the combustion residues are much less, which proves that norfloxacin is successfully imprinted on UiO-66-NH 2 Is a surface of the substrate.
Test example 4: nitrogen adsorption and desorption experiment
Figures 6-7 show nitrogen adsorption and desorption experimental data of related materials. UiO-66-NH 2 Is typical of type I adsorption curves with UiO-66-M, demonstrating that they are microporous structures, where UiO-66-NH 2 The specific surface area of Langmuir reachesBy 943, comparing the pore volume distribution of the two, it can be seen that the pore diameter of UiO-66-M is slightly reduced, and the pore volume is smaller than that of the original UiO-66-NH 2 . UiO-66@mip is an IV-type adsorption curve, and the material also shows a new pore size due to imprinting of the molecularly imprinted layer.
Test example 5: scanning electron microscope characterization
FIGS. 8-11 are TEM images of several materials from which UiO-66-NH can be observed 2 Exhibiting a typical octahedral structure, about 100nm in size, consistent with the crystal structure synthesized by others. After reaction with methacrylic anhydride, the crystal structure of UiO-66-M was unchanged. This result corresponds to the previous XRD results. Due to the modification of the molecularly imprinted layer, uiO-66@mip was converted from the original octahedron into irregular spheres with a diameter of 250 nm.
Test example 1: proportion optimization test
The ratio of the functional monomer to the cross-linking agent plays an important role in the adsorption capacity of the molecularly imprinted material. In order to obtain a larger adsorption capacity of UiO-66@mip, the ratio of functional Monomer (MAA) to crosslinker (EGDMA) and the ratio of functional Monomer (MAA) to template (NOR) were optimized. When the ratio of MAA to EGDMA is studied, the molar ratio between MAA and NOR is fixed to be 5:1, the dosage of EGDMA is changed, and the rest synthesis process is kept unchanged according to S1c to synthesize UIO-66@MIP. As a result, as shown in FIGS. 12 to 13, if the ratio is too low, the imprinted polymer cannot be formed, and if the ratio is too high, the polymerization process becomes severe and the pores of the imprinted polymer are adversely affected. When the molar ratio of MAA to EGDMA is 1:2.5, the UiO-66@MIP has the optimal adsorption capacity. When the ratio of MAA to NOR was studied, the molar ratio of MAA to EGDMA was fixed at 1:2.5, and the amount of NOR was varied to synthesize UIO-66@MIP according to S1 c. When the amount of MAA is too small, it cannot be completely prepolymerized with a template, resulting in low adsorption capacity. And when MAA increases, it also results in more non-specific adsorption increase, which also affects the adsorption capacity of UiO-66@MIP. As can be seen from the graph, the UiO-66@MIP has better adsorption performance when the ratio of MAA to NOR is 5:1.
Test example 2: adsorption condition optimization test
As the external condition has a certain influence on the adsorption capacity of UiO-66@MIP, the test example focuses on researching the influence of the pH value on the adsorption capacity of UiO-66@MIP. Norfloxacin is a typical amphoteric compound, and therefore the pH has a great influence on the state of norfloxacin. The pKa1 and pKa2 of norfloxacin are 6.20 and 8.70, respectively. Norfloxacin exists mainly in an anionic form when the pH value is higher than 8.70, and exists in a cationic form when the pH value is lower than 6.20, namely, when the pH value of the solution is higher than 8.7 or lower than 6.2, electrostatic repulsion is generated between norfloxacin and a recognition site of molecular imprinting, so that interaction with UIO-66@MIP is hindered. In contrast, norfloxacin is in a neutral state when the pH is between 6.2 and 8.7, and therefore more easily interacts with the material via hydrogen bonding. The pH condition is the same as that of a daily water environment, and meets the application requirements in real life. As can be seen from FIG. 14, the adsorption capacity of UiO-66@MIP is strong in this pH range.
Test example 3: static adsorption experiments
NOR was prepared in standard solutions at concentrations of 10mg/L to 500 mg/L. The NOR standard solution was then added to the centrifuge tube and UiO-66@MIP and UiO-66@NIP were added, respectively. The mixture was incubated on a shaker at 500rpm for 24 hours. The supernatant was collected by centrifugation. The supernatant was examined at 277nm with an ultraviolet spectrophotometer and the concentration of NOR was calculated from the standard curve of NOR.
The adsorption capacities (Q, mg/g) of UiO-66@MIP and UiO-66@NIP were calculated by the following formulas, respectively:
Q＝(C 0 -C)*V/m
wherein C is 0 (mg/L) is the initial concentration of the NOR standard solution, C (mg/L) is the concentration of the solution after adsorption is completed, V (ml) is the volume of the NOR standard solution added, and m is the mass of UiO-66@MIP or UiO-66@NIP added.
The imprinting factor (α) and the selectivity factor (β) are important criteria for measuring the properties of molecularly imprinted polymers and non-molecularly imprinted polymers, and can be calculated by the following formula:
α＝Q MIP /Q NIP
β＝α 1 /α 2
wherein QMIP and QNIP are the adsorption capacities of UiO-66@MIP and UiO-66@NIP, respectively. Alpha 1 Is a selection factor of NOR, and alpha 2 Is a selection factor for other test targets.
The test example carries out static adsorption curve study on UiO-66@MIP and UiO-66@NIP at the concentration of norfloxacin of 0-450 mg/L. As shown in FIG. 15, the UiO-66@NIP adsorption capacity reached saturation at 200mg/L, and the saturated adsorption amount was about 25.9mg/g, because of the absence of blotting sites. In contrast, when the concentration of norfloxacin exceeds 300mg/L, the adsorption capacity of UiO-66@MIP gradually approaches equilibrium, and the imprinting sites on the UiO-66@MIP still reach saturation, and the saturated adsorption amount is about 53.1mg/g.
Scatchard's equation is an important criterion for evaluating static adsorption of UiO-66@MIP and UiO-66@NIP.
Q/C e ＝(Q m -Q)/K d
Wherein Q is m Represents the maximum adsorption capacity, K, of the material d Is dissociation constant, C e Is the equilibrium concentration of norfloxacin in the solution when adsorption is kept in equilibrium. FIG. 16 shows a Scatchard plot of UiO-66@MIP consisting of two different linear equations, illustrating that MIPs have two different binding sites. Compared to UiO-66@MIP, the Scatchard plot of UiO-66@NIP (FIG. 17) has only one straight line segment.
Test example 4: dynamic adsorption experiments
The UiO-66@mip was weighed into a centrifuge tube. Then 3ml of 150mg/L NOR solution was added thereto. The mixtures were incubated on a shaker at 500rpm for 1 min to 50 min, respectively. The supernatant was collected by centrifugation and detected by an ultraviolet spectrophotometer at 277nm.
The dynamic adsorption curves of UiO-66@MIP and UiO-66@NIP are shown in FIG. 18, and when the initial concentration of norfloxacin is 120mg/L, the UiO-66@MIP reaches adsorption equilibrium within 30 min. In contrast to UiO-66@MIP, uiO-66@NIP reaches an adsorption equilibrium, the adsorption capacity is lower than that of UiO-66@MIP, since there is no specific binding site.
Test example 5: selective adsorption experiments
2mL of NOR, CIP, SD and TC solutions at 200mg/L were mixed with UiO-66@MIP and UiO-66@NIP. All of these were incubated on a shaker at 500rpm for 60 minutes. After filtering off the precipitate, the clear liquid was collected for testing.
The selectivity of UiO-66@mip was evaluated by selecting Norfloxacin (NOR), its structural analog Ciprofloxacin (CIP) and other classes of antibiotic Sulfadiazine (SD) and Tetracycline (TC). As shown in FIG. 19, uiO-66@MIP shows an ultra-high selectivity in adsorbing other types of antibiotics. In contrast, uiO-66@nip showed significant non-specific adsorption to these antibiotics due to the lack of molecular imprinting recognition sites. However, due to the small structural differences between ciprofloxacin and norfloxacin, when UiO-66@mip interacts with ciprofloxacin, the binding sites are preferentially occupied, resulting in a higher adsorption capacity, but the adsorption capacity is still lower than for UiO-66@mip for norfloxacin. This result is consistent with the experimental results reported previously. In summary, the imprinting factor (. Alpha.) for UiO-66@MIP pairs NOR, CIP, SD and TC, respectively, was 2.09,1.86,0.94,1.07, while the selectivity factor (. Beta.) for UiO-66@NIP pairs CIP, SD and TC, respectively, was 1.12,2.22,1.95. In other words, the selectivity experiment proves that in UiO-66-NH 2 The surface creates molecularly imprinted sites.
Test example 6: reusability experiments with UiO-66@mip
The reusability of UiO-66@mip is an important indicator for measuring whether a material can be applied to actual detection. To evaluate reusability, uiO-66@mip was mixed with 3ml of norfloxacin solution at a concentration of 90mg/L for 30 minutes at 450 rpm. After adsorption, the supernatant was collected by a centrifuge and the concentration of residual norfloxacin in the solution was measured by an ultraviolet spectrophotometer. NOR on UiO-66@MIP was eluted using a methanol/acetic acid (90:10, v/v) solution. After the end, the above-mentioned process is repeated. As shown in FIG. 20, after 5 cycles, the UiO-66@MIP still maintains higher adsorption efficiency, and compared with the first time, the adsorption efficiency is reduced by only 12%. The results show that the material has excellent stability and reusability.
Effect comparative example: comparison of UiO-66@MIP with several existing adsorbent materials
TABLE 3 comparison of adsorption material effects
As shown in Table 3, according to the prior published document, compared with the prior several adsorption materials, the UiO-66@MIP adsorption capacity provided by the invention is obviously improved, the recovery rate is higher, and the comprehensive adsorption effect is excellent.
The invention is not limited to the use of the description and embodiments listed, which can be applied to various fields suitable for the invention, and further modifications and variations can be easily realized by those skilled in the art without departing from the spirit and the essence of the invention, but these corresponding modifications and variations shall fall within the scope of protection claimed by the invention.
The above description is only a few examples of the present invention and is not intended to limit the embodiments and the protection scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious changes made by the content of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A detection method of norfloxacin based on MOFs molecular imprinting polymer is characterized by comprising the following steps: the method comprises the following steps:
s1: MOFs molecular imprinting polymer UIO-66@MIP is prepared by adopting a surface imprinting method: preparation of UiO-66-NH 2 As a carrier for molecular imprinting, the reaction between anhydride and amino is carried out in UiO-66-NH 2 After grafting double bonds on the surface, imprinting NOR on the surface of MOFs through free radical polymerization to prepare UiO-66@MIP; the method comprises the following steps:
s1a: preparation of UiO-66-NH 2 As a carrier for molecular imprinting: zrCl is added to 4 And acetic acid was dissolved in DMF by ultrasonic wave for 5 min; 2-amino terephthalic acid was then dissolved in the solution and sonicated for a further 5 minutesAdding deionized water to the solution; zrCl 4 The ratio of acetic acid, DMF, 2-amino terephthalic acid and deionized water was 0.78g:5.55mL:80mL:0.58g:0.24mL; transferring the mixed solution into a polytetrafluoroethylene reactor, heating to 120 ℃ for 24 hours, and then cooling to room temperature; repeatedly washing the product with DMF and ethanol, and then drying in vacuum at 60 ℃;
s1b: the UiO-66-NH obtained in the step S1a 2 Dispersing in dichloromethane, ultrasonic treating for 20 min, adding methacrylic anhydride into the solution, and continuously reacting at 25 ℃ for 96 hours; after the reaction was completed, the precipitate was collected by centrifugation at 9000rpm and washed 3 times with methylene chloride; vacuum drying the product at 45 ℃ to obtain UIO-66-M; uiO-66-NH 2 The dosage ratio of dichloromethane to methacrylic anhydride is 1g to 15mL to 2.6mL;
s1c: mixing the UiO-66-M prepared in the step S1b with acetonitrile, performing ultrasonic dispersion for 10 minutes, adding NOR and MAA, and stirring the mixture at room temperature for 2 hours; after heating the mixture to 60 ℃, EGDMA and AIBN were added, with the ratio of UiO-66-M, acetonitrile, NOR, MAA, EGDMA and AIBN being 80mg:50mL:51 mg:68. Mu.L:400. Mu.L:70 mg; the mixture was reacted at 60℃for 24 hours; centrifuging at 9000rpm after the reaction is finished, collecting precipitate, and washing with an eluent until the template is removed; the eluent is methanol/acetic acid solution with the volume ratio of 9:1; finally, vacuum drying the product at 60 ℃ to obtain UIO-66@MIP;
s2: establishing a norfloxacin liquid phase standard working curve: mixing the norfloxacin standard solutions with serial concentrations with the UiO-66@mip prepared in the step S1 respectively, incubating the mixed solution on a shaker at 500rpm for 40 minutes, and removing the supernatant by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; enriching the eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of the initial norfloxacin standard solution by using water, and detecting the obtained aqueous solution by using a high performance liquid chromatography; drawing a norfloxacin liquid phase standard working curve by using the peak area of the obtained data;
s3: detecting an actual water sample: mixing the actual water sample with the UiO-66@MIP prepared in the step S1, incubating the mixture on a shaker for 40 minutes at 500rpm, and removing the supernatant by centrifugation; then adding eluent, and collecting the eluent after ultrasonic centrifugation; enriching eluent by a nitrogen blowing instrument, then re-sizing the eluent to the volume of an initial actual water sample by using water, detecting the obtained water solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, substituting peak areas into a norfloxacin liquid phase standard working curve, and calculating to obtain the norfloxacin content in the actual water sample;
the chromatographic conditions of the high performance liquid chromatography in the steps S2 and S3 are as follows: in C 18 The chromatographic column is a stationary phase, 0.025mol/L phosphoric acid solution-acetonitrile is used as a mobile phase, the flow rate is set to be 0.8ml, and the wavelength of the PDA detector is set to be 277nm; the volume ratio of the phosphoric acid solution to the acetonitrile is 80:20; the phosphoric acid solution was adjusted to pH 3.0 with triethylamine.
2. The method of claim 1, wherein: in the step S2, the dosage ratio of the norfloxacin standard solution to the UIO-66@MIP is 3mL:10mg; in the step S3, the dosage ratio of the actual water sample to the UIO-66@MIP is 3mL:10mg.
3. The method of claim 1, wherein: in the steps S2 and S3, the eluent is methanol/acetic acid solution with the volume ratio of 9:1, and the addition amount of the eluent is the same as the volume of the initial norfloxacin standard solution or the volume of the actual water sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111024140.9A CN113567594B (en) | 2021-09-02 | 2021-09-02 | Detection method of norfloxacin based on MOFs type molecularly imprinted polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111024140.9A CN113567594B (en) | 2021-09-02 | 2021-09-02 | Detection method of norfloxacin based on MOFs type molecularly imprinted polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113567594A CN113567594A (en) | 2021-10-29 |
| CN113567594B true CN113567594B (en) | 2023-06-27 |
Family
ID=78173450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111024140.9A Active CN113567594B (en) | 2021-09-02 | 2021-09-02 | Detection method of norfloxacin based on MOFs type molecularly imprinted polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113567594B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113055B (en) * | 2021-11-03 | 2024-01-30 | 湖南农业大学 | Method for detecting norfloxacin based on colorimetric chemical sensing technology |
| CN116574360B (en) * | 2023-07-12 | 2023-09-19 | 广州声博士声学技术有限公司 | Vibration and noise reduction material for carbon nano tube and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910836A (en) * | 2013-01-07 | 2014-07-09 | 中国药科大学 | Preparation method of magnetic carbon nano-tube surface molecular imprinting polymer for biological sample pretreatment |
| CN109813823A (en) * | 2019-04-04 | 2019-05-28 | 江苏省产品质量监督检验研究院 | The HPLC analytical method of metronidazole and Norfloxacin in a kind of toothpaste |
| CN110918073A (en) * | 2019-11-22 | 2020-03-27 | 山东农业大学 | Preparation method and application of magnetic MOF-based bisphenol A molecularly imprinted high-selectivity nanocomposite |
| CN111443152A (en) * | 2020-03-26 | 2020-07-24 | 中国检验检疫科学研究院 | Method and kit for detecting content of quinolone compounds |
| CN111624279A (en) * | 2020-05-22 | 2020-09-04 | 海南医学院 | Pretreatment method and quantitative detection method for quinolone antibiotics in biological sample |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070197548A1 (en) * | 2006-02-17 | 2007-08-23 | Murthy Yerramilli V S | Fluoroquinolone compositions |
| CN106799216A (en) * | 2017-02-20 | 2017-06-06 | 湖北省食品质量安全监督检验研究院 | A kind of preparation method of high selectivity carbostyril antibiotic molecularly imprinted polymer |
-
2021
- 2021-09-02 CN CN202111024140.9A patent/CN113567594B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910836A (en) * | 2013-01-07 | 2014-07-09 | 中国药科大学 | Preparation method of magnetic carbon nano-tube surface molecular imprinting polymer for biological sample pretreatment |
| CN109813823A (en) * | 2019-04-04 | 2019-05-28 | 江苏省产品质量监督检验研究院 | The HPLC analytical method of metronidazole and Norfloxacin in a kind of toothpaste |
| CN110918073A (en) * | 2019-11-22 | 2020-03-27 | 山东农业大学 | Preparation method and application of magnetic MOF-based bisphenol A molecularly imprinted high-selectivity nanocomposite |
| CN111443152A (en) * | 2020-03-26 | 2020-07-24 | 中国检验检疫科学研究院 | Method and kit for detecting content of quinolone compounds |
| CN111624279A (en) * | 2020-05-22 | 2020-09-04 | 海南医学院 | Pretreatment method and quantitative detection method for quinolone antibiotics in biological sample |
Non-Patent Citations (6)
| Title |
|---|
| Dual-template molecularly imprinted polymers for dispersive solid-phase extraction of fluoroquinolones in water samples coupled with high performance liquid chromatography;Lu Wenhui等;Analyst;第144卷;第1292-1302页 * |
| 分子印迹掺杂金属有机框架固相萃取-高效液相色谱-串联质谱法测定大米中10种磺酰脲类除草剂;朱旭冉;刘媛;韩正政;程铭;邢维海;张佳笑;杨立亭;王健;佘永新;;食品工业科技(第02期);第213-219、226页 * |
| 双模板印迹聚合物-分散固相萃取结合高效液相色谱测定水样中氟喹诺酮类抗生素残留;刘洁等;中国化学会第九届全国仪器分析及样品预处理学术研讨会论文集;第123-126页 * |
| 固相萃取/高效液相色谱法测定给水中的诺氟沙星;钭晨;江晨舟;薛罡;;中国给水排水(第24期);第82-85页 * |
| 磁分散固相萃取-高效液相色谱法测定牛奶中5种禁用喹诺酮类药物;刘艳丽;吴昊;杜晓慧;冯艺洋;赵雅妮;常银霞;;分析科学学报(第02期);第196-200页 * |
| 诺氟沙星磁分子印迹纳米粒子的制备及其富集分离;黄昭;李跑;曹亚男;李佳银;刘霞;;食品研究与开发(第18期);第52-57页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113567594A (en) | 2021-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113567594B (en) | Detection method of norfloxacin based on MOFs type molecularly imprinted polymer | |
| Jing et al. | Preparation of mixed-templates molecularly imprinted polymers and investigation of the recognition ability for tetracycline antibiotics | |
| Gao et al. | Selective extraction of sulfonamides from food by use of silica-coated molecularly imprinted polymer nanospheres | |
| Zhang et al. | Novel molecularly imprinted polymers based on multi-walled carbon nanotubes with binary functional monomer for the solid-phase extraction of erythromycin from chicken muscle | |
| Su et al. | HPLC determination of sulfamethazine in milk using surface-imprinted silica synthesized with iniferter technique | |
| Li et al. | Application of deep eutectic solvents in hybrid molecularly imprinted polymers and mesoporous siliceous material for solid-phase extraction of levofloxacin from green bean extract | |
| Gasparrini et al. | New hybrid polymeric liquid chromatography chiral stationary phase prepared by surface-initiated polymerization | |
| Liu et al. | Synthesis of core-shell molecularly imprinted polymers (MIP) for spiramycin I and their application in MIP chromatography | |
| Lv et al. | Grafting of norfloxacin imprinted polymeric membranes on silica surface for the selective solid-phase extraction of fluoroquinolones in fish samples | |
| Javanbakht et al. | Extraction and purification of penicillin G from fermentation broth by water-compatible molecularly imprinted polymers | |
| Sun et al. | A restricted access molecularly imprinted polymer coating on metal–organic frameworks for solid-phase extraction of ofloxacin and enrofloxacin from bovine serum | |
| CN111171212B (en) | Metal organic framework surface molecularly imprinted polymer and preparation method and application thereof | |
| Lv et al. | Adsorption-controlled preparation of molecularly imprinted hybrid composites for selective extraction of tetracycline residues from honey and milk | |
| Wu et al. | Binding characteristics of homogeneous molecularly imprinted polymers for acyclovir using an (acceptor–donor–donor)—(donor–acceptor–acceptor) hydrogen-bond strategy, and analytical applications for serum samples | |
| Zhao et al. | Novel metal-organic framework combining with restricted access molecularly imprinted nanomaterials for solid-phase extraction of gatifloxacin from bovine serum | |
| Zhou et al. | Preparation of surface molecularly imprinted polymer and its application for the selective extraction of teicoplanin from water | |
| Abdollahi et al. | Synthesis of a nano molecularly imprinted polymeric sorbent for solid phase extraction and determination of phenytoin in plasma, urine, and wastewater by HPLC | |
| Ma et al. | Preparation of pH-responsive stationary phase for reversed-phase liquid chromatography and hydrophilic interaction chromatography | |
| Lv et al. | Fast clean-up and selective enrichment of florfenicol in milk by restricted access media molecularly imprinted magnetic microspheres based on surface-initiated photoiniferter-mediated polymerization | |
| Roohi et al. | Thermo-responsive monolithic materials | |
| Guo et al. | Imprinted polymers with cyclodextrin pseudo-polyrotaxanes as pseudo-supports for protein recognition | |
| CN113603832B (en) | MOFs molecularly imprinted polymer for detecting norfloxacin and preparation method thereof | |
| CN113372525A (en) | Covalent organic framework material with molecular imprinting type and preparation method and application thereof | |
| Wei et al. | A core-shell spherical silica molecularly imprinted polymer for efficient selective recognition and adsorption of dichlorophen | |
| CN111269364B (en) | Temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on polysaccharose and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |