CN113567594A - 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 PDF

Info

Publication number
CN113567594A
CN113567594A CN202111024140.9A CN202111024140A CN113567594A CN 113567594 A CN113567594 A CN 113567594A CN 202111024140 A CN202111024140 A CN 202111024140A CN 113567594 A CN113567594 A CN 113567594A
Authority
CN
China
Prior art keywords
uio
norfloxacin
mip
eluent
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.)
Granted
Application number
CN202111024140.9A
Other languages
Chinese (zh)
Other versions
CN113567594B (en
Inventor
黄泽宇
许泽彬
刘婉琼
林立斌
梁晓琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foshan Sanshui Foshui Water Supply Co ltd
Original Assignee
Foshan Sanshui Foshui Water Supply Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Foshan Sanshui Foshui Water Supply Co ltd filed Critical Foshan Sanshui Foshui Water Supply Co ltd
Priority to CN202111024140.9A priority Critical patent/CN113567594B/en
Publication of CN113567594A publication Critical patent/CN113567594A/en
Application granted granted Critical
Publication of CN113567594B publication Critical patent/CN113567594B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Library & Information Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a method for detecting norfloxacin based on MOFs (metal-organic frameworks) molecularly imprinted polymers, which comprises the following steps of: s1: preparing MOFs type molecularly imprinted polymer UiO-66@ MIP; s2: establishing a norfloxacin liquid phase standard working curve: s3: and (3) actual water sample detection: mixing the actual water sample with UiO-66@ MIP prepared in step S1 and incubating at 500rpm on a shaker for 40 minutes, and removing the supernatant by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; and enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial actual water sample volume by using water again, detecting the obtained aqueous solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, and substituting the peak area into a norfloxacin liquid phase standard working curve to calculate the content of the norfloxacin in the actual water sample. The detection method effectively reduces the detection cost and operation difficulty of norfloxacin, and simultaneously improves the detection efficiency.

Description

Detection method of norfloxacin based on MOFs type molecularly imprinted polymer
Technical Field
The invention belongs to the field of antibiotic detection, and particularly relates to a method for detecting norfloxacin based on MOFs type molecularly imprinted polymers.
Background
Norfloxacin (NOR) is one of quinolone antibiotics, and is widely used in human and animal products for disease treatment and control as a broad-spectrum, inexpensive antibiotic. According to incomplete statistics, the usage amount of antibiotics in China exceeds 50% of the total usage amount in the world, thereby causing a plurality of problems. Since it is only partially metabolized, a large amount of antibiotics are discharged to the environment with feces and urine, and therefore, it is not uncommon to detect antibiotics in lakes and rivers. And long-term drinking of water containing antibiotics can cause the reduction of human immunity, the imbalance of intestinal flora, even carcinogenesis and teratogenesis. Therefore, the development of a low-cost, simple and efficient norfloxacin separation and detection method is urgent. Currently, Solid Phase Extraction (SPE) or QuEChERS is widely used for extracting norfloxacin from water, but has the problems of high cost, low adsorption capacity, no selectivity and the like. Therefore, these methods still have 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. Due to low cost, high stability and high selectivity, molecular imprinting is a common method for improving material selectivity. The high-selectivity polymer needs to be attached to a 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 been the focus of much research. Due to the large accessible surface area, uniform and adjustable pore size, chemical modularity, fluorescence and catalytic activity, MOFs and composite materials thereof are widely applied to the fields of separation, enrichment, analysis and detection. In these fields, however, the properties exhibited by MOFs are well documented as having the potential to be combined with molecular imprinting.
Disclosure of Invention
An object of the present invention is to provide a method for detecting norfloxacin based on MOFs type molecularly imprinted polymer, which can realize low-cost, simple and efficient qualitative and quantitative detection of norfloxacin by preparing the MOFs type molecularly imprinted polymer UiO-66@ MIP with high adsorption capacity, high selectivity and high stability and applying the same in norfloxacin adsorption detection.
In order to achieve the above object, the present invention provides a method for detecting norfloxacin based on MOFs type molecularly imprinted polymers, which is characterized in that: the method comprises the following steps:
s1: preparing MOFs type molecularly imprinted polymer UiO-66@ MIP: preparation of UiO-66-NH2As a carrier for molecular imprinting, by the reaction of acid anhydride and amino group, in UiO-66-NH2After double bonds are grafted on the surface, NOR is imprinted on the surface of MOFs through free radical polymerization to prepare UiO-66@ MIP;
s2: establishing a norfloxacin liquid phase standard working curve: mixing norfloxacin standard solutions with a series of concentrations with the UiO-66@ MIP prepared in step S1, respectively, incubating at 500rpm for 40 minutes on a shaker, and removing the supernatant by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial norfloxacin standard solution volume by using water again, 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: and (3) actual water sample detection: mixing the actual water sample with UiO-66@ MIP prepared in step S1 and incubating at 500rpm on a shaker for 40 minutes, and removing the supernatant by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; and enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial actual water sample volume by using water again, detecting the obtained aqueous solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, and substituting the peak area into a norfloxacin liquid phase standard working curve to calculate the content of the norfloxacin in the actual water sample.
Compared with the prior art, the method combines the molecular imprinting technology with MOFs, and selects the UiO-66-NH with high stability2As a carrier for molecular imprinting, by the reaction of acid anhydride and amino group, in UiO-66-NH2After surface grafting of double bonds, 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, and is used for separating and detecting norfloxacin, so that the detection cost and the operation difficulty are effectively reduced, and the detection efficiency is improved.
Preferably, in step S2, the ratio of the norfloxacin standard solution to the UiO-66@ MIP is 3mL:10 mg; in step S3, the ratio of the actual water sample to UiO-66@ MIP is 3mL to 10 mg.
Preferably, the chromatographic conditions of the high performance liquid chromatography in steps S2 and S3 are: with C18The 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 277 nm; adjusting the pH value of the phosphoric acid solution to 3.0 by using triethylamine; the volume ratio of the phosphoric acid solution to the acetonitrile is 80: 20.
Preferably, in steps S2 and S3, the eluent is a 9:1 methanol/acetic acid solution, and the amount of the eluent added is the same as the volume of the initial norfloxacin standard solution or the volume of the actual water sample.
Preferably, step S1 includes the steps of:
s1 a: preparation of UiO-66-NH2As a carrier for molecular imprinting;
s1 b: the UiO-66-NH prepared in the step S1a2Dispersing in dichloromethane, carrying out ultrasonic treatment for 20 minutes, adding methacrylic anhydride into the solution, and continuously reacting for 96 hours at 25 ℃; after the reaction is finished, centrifuging at 9000rpm, collecting the precipitate, and washing with dichloromethane for 3 times; vacuum drying the product at 45 deg.C to obtain UiO-66-M;
s1 c: mixing the UiO-66-M prepared in the step S1b with acetonitrile, ultrasonically dispersing for 10 minutes, adding NOR and MAA, and stirring the mixture for 2 hours at room temperature; heating the mixture to 60 ℃, adding EGDMA and AIBN, and reacting the mixture at 60 ℃ for 24 hours; after the reaction is finished, centrifuging at 9000rpm to collect precipitates, and then washing by using an eluant until the template is removed; and finally, drying the product at 60 ℃ in vacuum to obtain the UiO-66@ MIP.
Preferably, in step S1b, UiO-66-NH2The ratio of the amount of methylene chloride to the amount of methacrylic anhydride was 1g:15mL:2.6 mL.
Preferably, in step S1c, UiO-66-M, acetonitrile, NOR, MAA, EGDMA and AIBN are used in a ratio of 80mg:50mL:51mg:68 μ L:400 μ L:70 mg.
Preferably, step S1a includes the steps of: reacting ZrCl4And acetic acid was dissolved in DMF by ultrasonic waves for 5 minutes; dissolving 2-amino terephthalic acid in the solution, carrying out ultrasonic treatment for 5 minutes, and adding deionized water into the solution; transferring the mixed solution into a polytetrafluoroethylene reactor, heating to 120 ℃, keeping for 24 hours, and then cooling to room temperature; the product was washed repeatedly with DMF and ethanol and then dried under vacuum at 60 ℃.
Preferably, in step S1a, ZrCl4The ratio of the amounts of acetic acid, DMF, 2-aminoterephthalic acid and deionized water was 0.78g:5.55mL:80mL:0.58g:0.24 mL.
Preferably, the eluent in step S1a is a 9:1 volume ratio methanol/acetic acid solution.
Preferably, the concentration of the standard solution of series norfloxacin 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 graph of HPLC chromatograms of an actual water sample and a UiO-66@ MIP adsorption elution solution in an effect test example
FIG. 3 shows UiO-66-NH prepared in example 12Infrared characterization of UiO-66-M and UiO-66@ MIP
FIG. 4 shows UiO-66-NH prepared in example 12XRD profiles of UiO-66-M and UiO-66@ MIP
FIG. 5 shows UiO-66-NH prepared in example 12Thermogravimetric characterization of UiO-66-M and UiO-66@ MIP
FIG. 6 shows UiO-66-NH prepared in example 12Nitrogen adsorption and desorption curve and aperture distribution diagram with UiO-66-M
FIG. 7 is a graph showing the nitrogen desorption curve and the pore size distribution of UiO-66@ MIP prepared in example 1
FIG. 8 shows UiO-66-NH prepared in example 12TEM image of
FIG. 9 is a TEM image of UiO-66-M obtained in example 1
FIG. 10 is a TEM image of 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 of the effect of the ratio of functional monomer to crosslinker in UiO-66@ MIP on adsorption capacity
FIG. 14 is a bar graph of the effect of pH on adsorption capacity under adsorption conditions
FIG. 15 is a graph showing the static adsorption profiles 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 prepared in example 1
FIG. 17 is a Scatchard plot of UiO-66@ NIP prepared by a comparative example
FIG. 18 is a graph showing the dynamic adsorption profiles of UiO-66@ MIP prepared in example 1 and UiO-66@ NIP prepared in comparative example
FIG. 19 is a bar graph of the results of the selectivity test of UiO-66@ MIP prepared in example 1 versus UiO-66@ NIP prepared in the comparative example
FIG. 20 is a histogram of the reusability test of UiO-66@ MIP prepared in example 1
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative of the present invention only, and are not intended to limit the scope of the present invention.
The instruments used in the following examples, test examples and test examples are shown in Table 1, and the reagents are shown in Table 2.
TABLE 1 Experimental instruments
Figure BDA0003242735530000041
Figure BDA0003242735530000051
TABLE 2 Experimental reagent Table
Figure BDA0003242735530000052
Example 1: method for detecting norfloxacin in actual water sample
Detecting norfloxacin in an actual water sample according to the following steps:
s1: the MOFs type molecularly imprinted polymer UiO-66@ MIP is prepared according to the following steps:
s1 a: preparation of UiO-66-NH2As a carrier for molecular imprinting: 0.78g of ZrCl4And 5.55mL of acetic acid was dissolved in 80mL of DMF by sonication for 5 minutes. Then, 0.58g of 2-amino terephthalic acid was dissolved in the solution. After another 5 minutes of sonication, 0.24mL of 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 washed repeatedly with DMF and ethanol and then dried under vacuum at 60 ℃.
S1 b: by means of acidsReaction of anhydrides and amino groups in UiO-66-NH2Grafting double bonds on the surface to synthesize UiO-66-M: 1g of UiO-66-NH prepared in step S1a2Dispersed in 15mL dichloromethane. After 20 minutes of sonication, 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 ℃.
S1 c: imprinting NOR on the surface of UiO-66-M by radical polymerization, to synthesize UiO-66@ MIP: 80mg of UiO-66-M and 50mL of acetonitrile were charged to a 100mL flask. After 10 minutes of sonication, 51mg NOR and 68. mu.L 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 under vacuum at 60 ℃.
S2: establishing a norfloxacin liquid phase standard working curve: 215mg/L norfloxacin standard solution is 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 respectively mixed with the UiO-66@ MIP prepared in the step S1 and incubated at 500rpm on a shaker for 40 minutes, and the supernatant is removed by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial norfloxacin standard solution volume by using water again, 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: and (3) actual water sample detection: 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 the 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 blowing instrument and then is added with water to reach the constant volume of 3 ml. And detecting the obtained aqueous solution by a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, and substituting the peak area into a norfloxacin liquid phase standard working curve to calculate the content of norfloxacin in the actual water sample.
The liquid chromatography conditions in the above steps S2 and S3 were: with C18The column was stationary and the mobile phase was 0.8ml in 0.025mol/L phosphoric acid solution (pH adjusted to 3.0 with triethylamine) -acetonitrile (80:20), and the wavelength of the PDA detector was set at 277 nm.
The norfloxacin liquid phase standard working curve obtained in the step S2 is shown in fig. 1, the HPLC chromatogram of the actual water sample in the step S3 is shown in fig. 2, and the peak area is substituted into the standard curve to calculate the norfloxacin content in the water sample of 0.51 mg/L.
Comparative example: synthesis of UiO-66@ NIP
The detection method of UiO-66@ NIP is substantially 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: structural characterization of several materials from example 1 and comparative examples
Test example 1: infrared (FT-IR) characterization
FT-IR spectroscopy is used as a means of demonstrating the composition of materials to help demonstrate the success of the synthesis of the relevant materials. 3461cm as shown in FIG. 3-1And 3351cm-1The absorption corresponds to symmetric and asymmetric N-H vibration. The N-H bending vibration and the C-N stretching can be 1572cm-1To 1385cm-1Are found in (a). With UiO-66-NH2Compared with the FT-IR spectrum of the product, UiO-66-M is 1673cm-1There was a new absorption peak due to the characteristic absorption peak of C ═ C, indicating the successful synthesis of UiO-66-M. Due to the formation of the molecularly imprinted layer, the FT-IR spectrum of UiO-66@ MIP mainly consists of 2950cm-1C-H absorption Peak and 1716cm-1C ═ 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 remains stable before and after modification and polymerization, it is stable to UiO-66-NH2Powder X-ray diffraction (PXRD) was performed for UiO-66-M and UiO-66@ MIP. As shown in the figure4, the black line peaks at 2 θ ═ 7.36, 8.48, 17.08, 22.25, and 33.12 ° correspond to the characteristic diffraction peaks of UiO-66s for (110), (200), (022), (115), and (137), respectively. UiO-66-NH2After reaction with methacrylic anhydride, the diffraction peak of UiO-66-M was consistent with that of the original UiO-66, indicating that the chemical reaction did not destroy its crystal structure. Due to the modification of molecular imprinting, the XRD pattern of UiO-66@ MIP has a higher baseline, so that the obtained data are subjected to background subtraction and baseline correction. The obtained pattern peak is compared with the original UiO-66-NH2The peaks are the same, indicating that the original crystal structure is maintained even after polymerization.
Test example 3: thermogravimetric characterization
FIG. 5 is a thermogravimetric characterization of the material, UiO-66-NH2Approximately similar to the thermogravimetric curve of UiO-66-M, the mass reduction before 100 ℃ is attributed to the loss of solvent and moisture in the material, which begins to be digested to CO, when the temperature rises to around 270 ℃2And zirconia. In terms of combustion residues, UiO-66-NH2Slightly above 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 obviously different from that of the former two, and the combustion residue is much less, which proves that norfloxacin is successfully imprinted into UiO-66-NH2Of (2) is provided.
Test example 4: nitrogen adsorption and desorption experiment
FIGS. 6 to 7 show experimental data of nitrogen adsorption and desorption of relevant materials. UiO-66-NH2Typical type I adsorption curves are compared with UiO-66-M, which proves that the adsorption curves are microporous structures, wherein UiO-66-NH2The Langmuir specific surface area of 943, and a comparison of the pore volume distributions shows that the pore diameter of UiO-66-M is slightly reduced and the pore volume is smaller than that of the original UiO-66-NH2. The UiO-66@ MIP is a type IV adsorption curve, and the material has a new pore size due to imprinting of a molecular imprinting layer.
Test example 5: characterization of scanning Electron microscope
FIGS. 8 to 11 are TEM images of several materials from which UiO-66-NH can be observed2Presents a typical octahedral structure with a size of about 100nm, consistent with the crystal structure synthesized by others. The crystal structure of UiO-66-M did not change after reaction with methacrylic anhydride. This result corresponds to the previous XRD results. Due to the modification of the molecularly imprinted layer, UiO-66@ MIP is converted from an original octahedron into an irregular sphere with a diameter of 250 nm.
Test example 1: ratio 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. To obtain a UiO-66@ MIP with a larger adsorption capacity, the ratio of functional Monomer (MAA) to cross-linker (EGDMA) and the ratio of functional Monomer (MAA) to template (NOR) were optimized. In discussing the ratio of MAA to EGDMA, the molar ratio between MAA and NOR was fixed at 5:1, the amount of EGDMA was varied, and the remaining synthesis was 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 vigorous and side effects are generated on the pores of the imprinted polymer. UiO-66@ MIP possesses the best adsorption capacity when the molar ratio of MAA to EGDMA is 1: 2.5. In studying the ratio of MAA to NOR, 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, complete prepolymerization with the template is not possible, resulting in a low adsorption capacity. When the MAA increases, it also leads to more non-specific adsorption, which also affects the adsorption capacity of UiO-66@ MIP. As can be seen from the figure, UiO-66@ MIP has better adsorption performance when the ratio of MAA to NOR is 5: 1.
Test example 2: adsorption condition optimization test
Since the external conditions have a certain influence on the adsorption capacity of the UiO-66@ MIP, the experimental example focuses on the influence of the pH value on the adsorption capacity of the UiO-66@ MIP. Norfloxacin is a typical amphoteric compound, and thus pH has a great influence on the state of norfloxacin. Norfloxacin has pKa1 and pKa2 of 6.20 and 8.70, respectively. Norfloxacin exists primarily in anionic form at pH greater than 8.70 and in cationic form at pH less than 6.20, i.e., norfloxacin and recognition sites of the molecular imprint would electrostatically repel and hinder its interaction with UiO-66@ MIP at pH greater than 8.7 or less than 6.2 in solution. In contrast, norfloxacin is in a neutral state when the pH is between 6.2 and 8.7, and therefore interacts more easily with the material through hydrogen bonds. The pH condition is the same as the daily water environment, and the application requirements in real life are met. As can be seen from FIG. 14, the adsorption capacity of UiO-66@ MIP is stronger in this pH range.
Test example 3: static adsorption experiment
NOR was prepared in standard solutions at concentrations of 10mg/L to 500 mg/L. Then adding the NOR standard solution into a centrifuge tube, and respectively adding the UiO-66@ MIP and the UiO-66@ NIP. The mixture was incubated on a shaker at 500rpm for 24 hours. The supernatant was collected by centrifugation. The supernatant was examined with an ultraviolet spectrophotometer at 277nm 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 respectively calculated by the following formulas:
Q＝(C0-C)*V/m
wherein C is0(mg/L) is the initial concentration of the NOR standard solution, C (mg/L) is the concentration of the solution after completion of adsorption, V (ml) is the volume of the NOR standard solution added, and m is the mass to which UiO-66@ MIP or UiO-66@ NIP is added.
The imprinting factor (α) and the selectivity factor (β) are important criteria for measuring the performance of molecularly imprinted polymers and non-molecularly imprinted polymers, which can be calculated by the following formula:
α＝QMIP/QNIP
β＝α1/α2
wherein QMIPP and QNIP are the adsorption capacities of UiO-66@ MIP and UiO-66@ NIP, respectively. Alpha is alpha1Is a selection factor of NOR, and alpha2Is a selection factor for other test objectives.
In this test example, a static adsorption curve study was conducted on UiO-66@ MIP and UiO-66@ NIP at norfloxacin concentrations of 0 to 450 mg/L. As shown in FIG. 15, due to the absence of the imprinted sites, the UiO-66@ NIP adsorption capacity reached saturation at 200mg/L, and the saturated adsorption capacity was about 25.9 mg/g. In contrast, when norfloxacin concentration exceeded 300mg/L, the adsorption capacity of UiO-66@ MIP gradually approached equilibrium, and the imprinted sites on UiO-66@ MIP were still saturated, with a saturated adsorption of about 53.1 mg/g.
The Scatchard equation is an important criterion for evaluating the static adsorption of UiO-66@ MIP and UiO-66@ NIP.
Q/Ce＝(Qm-Q)/Kd
Wherein QmDenotes the maximum adsorption capacity, K, of the materialdIs the dissociation constant, CeIs the equilibrium concentration of norfloxacin in the solution at equilibrium for adsorption. FIG. 16 shows a Scatchard plot of UiO-66@ MIP consisting of two different linear equations, illustrating that the MIP has two different binding sites. The Scatchard plot (FIG. 17) for the UiO-66@ NIP has only one straight line segment compared to the UiO-66@ MIP.
Test example 4: dynamic adsorption experiment
The UiO-66@ MIP was weighed into a centrifuge tube. Then 3ml of 150mg/L NOR solution was added thereto. The mixture was incubated on a shaker at 500rpm for 1 to 50 minutes, respectively. The supernatant was collected by centrifugation and detected by UV spectrophotometer at 277 nm.
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 the adsorption equilibrium at 30 min. Compared with UiO-66@ MIP, UiO-66@ NIP achieves adsorption equilibrium, and the adsorption capacity is lower than that of UiO-66@ MIP, because specific binding sites are not available.
Test example 5: selective adsorption experiment
2mL of NOR, CIP, SD and TC solutions at a concentration of 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, a clear liquid was collected for testing.
The selectivity of UiO-66@ MIP was evaluated by selecting the antibiotic Sulfadiazine (SD) and Tetracycline (TC) in combination with Norfloxacin (NOR), its structural analog Ciprofloxacin (CIP) and other classes. As shown in FIG. 19, UiO-66@ MIP shows an ultra-high selectivity in adsorbing other types of antibiotics. In contrast, UiO-66@ NIP is for thisSome antibiotics exhibit significant non-specific adsorption due to the lack of molecularly imprinted recognition sites. However, due to the small difference in the structures of ciprofloxacin and norfloxacin, when the UiO-66@ MIP interacts with ciprofloxacin, it preferentially occupies the binding site, resulting in a higher adsorption capacity, but the adsorption capacity is still lower than for the norfloxacin UiO-66@ MIP. The results are consistent with the experimental results reported previously. As mentioned above, UiO-66@ MIP has imprinting factors (. alpha.) of 2.09,1.86, 0.94,1.07 for NOR, CIP, SD and TC, respectively, while UiO-66@ NIP has selectivity factors (. beta.) of 1.12,2.22,1.95 for CIP, SD and TC, respectively. In other words, the selectivity experiments demonstrated in UiO-66-NH2The surface creates molecularly imprinted sites.
Test example 6: reusability experiment of UiO-66@ MIP
The reusability of UiO-66@ MIP is an important index for measuring whether the material can be applied to practical detection. To evaluate reusability, UiO-66@ MIP was mixed with 3ml norfloxacin solution at 90mg/L for 30 minutes at 450 rpm. After adsorption, the supernatant was collected by a centrifuge, and the concentration of norfloxacin remaining in the solution was measured by an ultraviolet spectrophotometer. The NOR on the UiO-66@ MIP was eluted using a methanol/acetic acid (90:10, v/v) solution. After completion, the above process is repeated. As shown in fig. 20, after 5 cycles, the UiO-66@ MIP still maintained a high adsorption efficiency, which was only a 12% reduction compared to the first. The results show that the material has excellent stability and reusability.
Comparative effect example: comparison of UiO-66@ MIP with several existing adsorption materials
TABLE 3 comparison of the effectiveness of the adsorption Material
Figure BDA0003242735530000101
Figure BDA0003242735530000111
As shown in Table 3, according to the existing published literature data, compared with the existing several adsorbing materials, the UiO-66@ MIP adsorbing capacity provided by the invention is obviously improved, the recovery rate is higher, and the comprehensive adsorbing effect is excellent.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
The above description is only a partial example of the present invention, and does not limit the embodiments and the protection scope of the present invention, therefore, it should be recognized that the present invention is covered by the protection scope of the present invention by the equivalent substitution and obvious change made by the description of the present invention for those skilled in the art.

Claims (10)

1. A method for detecting norfloxacin based on MOFs type molecularly imprinted polymers is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing MOFs type molecularly imprinted polymer UiO-66@ MIP: preparation of UiO-66-NH2As a carrier for molecular imprinting, by the reaction of acid anhydride and amino group, in UiO-66-NH2After double bonds are grafted on the surface, NOR is imprinted on the surface of MOFs through free radical polymerization to prepare UiO-66@ MIP;
s2: establishing a norfloxacin liquid phase standard working curve: mixing norfloxacin standard solutions with a series of concentrations with the UiO-66@ MIP prepared in step S1, respectively, incubating at 500rpm for 40 minutes on a shaker, and removing the supernatant by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial norfloxacin standard solution volume by using water again, 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: and (3) actual water sample detection: mixing the actual water sample with UiO-66@ MIP prepared in step S1 and incubating at 500rpm on a shaker for 40 minutes, and removing the supernatant by centrifugation; then adding an eluent, carrying out ultrasonic centrifugation, and collecting the eluent; and enriching the eluent by a nitrogen blowing instrument, then fixing the volume to the initial actual water sample volume by using water again, detecting the obtained aqueous solution by using a high performance liquid chromatography, determining whether norfloxacin is contained by using dead time, and substituting the peak area into a norfloxacin liquid phase standard working curve to calculate the content of the norfloxacin in the actual water sample.
2. The detection method according to claim 1, characterized in that: in step S2, the dosage ratio of the norfloxacin standard solution to the UiO-66@ MIP is 3mL to 10 mg; in step S3, the ratio of the actual water sample to UiO-66@ MIP is 3mL to 10 mg.
3. The detection method according to claim 1, characterized in that: the chromatographic conditions of the high performance liquid chromatography in steps S2 and S3 are: with C18The 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 277 nm; adjusting the pH value of the phosphoric acid solution to 3.0 by using triethylamine; the volume ratio of the phosphoric acid solution to the acetonitrile is 80: 20.
4. The detection method according to claim 1, characterized in that: 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.
5. The detection method according to claim 1, characterized in that: step S1 includes the following steps:
s1 a: preparation of UiO-66-NH2As a carrier for molecular imprinting;
s1 b: the UiO-66-NH prepared in the step S1a2Dispersing in dichloromethane, carrying out ultrasonic treatment for 20 minutes, adding methacrylic anhydride into the solution, and continuously reacting for 96 hours at 25 ℃; after the reaction is finished, centrifuging at 9000rpm, collecting the precipitate, and washing with dichloromethane for 3 times; vacuum drying the product at 45 deg.C to obtain UiO-66-M;
s1 c: mixing the UiO-66-M prepared in the step S1b with acetonitrile, ultrasonically dispersing for 10 minutes, adding NOR and MAA, and stirring the mixture for 2 hours at room temperature; heating the mixture to 60 ℃, adding EGDMA and AIBN, and reacting the mixture at 60 ℃ for 24 hours; after the reaction is finished, centrifuging at 9000rpm to collect precipitates, and then washing by using an eluant until the template is removed; and finally, drying the product at 60 ℃ in vacuum to obtain the UiO-66@ MIP.
6. The detection method according to claim 5, characterized in that: in step S1b, UiO-66-NH2The ratio of the amount of methylene chloride to the amount of methacrylic anhydride was 1g:15mL:2.6 mL.
7. The detection method according to claim 5, characterized in that: in step S1c, UiO-66-M, acetonitrile, NOR, MAA, EGDMA and AIBN were used in a ratio of 80mg:50mL:51mg: 68. mu.L: 400. mu.L: 70 mg.
8. The detection method according to claim 5, characterized in that: step S1a includes the following steps: reacting ZrCl4And acetic acid was dissolved in DMF by ultrasonic waves for 5 minutes; dissolving 2-amino terephthalic acid in the solution, carrying out ultrasonic treatment for 5 minutes, and adding deionized water into the solution; transferring the mixed solution into a polytetrafluoroethylene reactor, heating to 120 ℃, keeping for 24 hours, and then cooling to room temperature; the product was washed repeatedly with DMF and ethanol and then dried under vacuum at 60 ℃.
9. The detection method according to claim 8, characterized in that: in step S1a, ZrCl4The ratio of the amounts of acetic acid, DMF, 2-aminoterephthalic acid and deionized water was 0.78g:5.55mL:80mL:0.58g:0.24 mL.
10. The detection method according to claim 8, characterized in that: the eluent in step S1a was a 9:1 volume ratio methanol/acetic acid solution.
CN202111024140.9A 2021-09-02 2021-09-02 Detection method of norfloxacin based on MOFs type molecularly imprinted polymer Active CN113567594B (en)

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 true CN113567594A (en) 2021-10-29
CN113567594B 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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114113055A (en) * 2021-11-03 2022-03-01 湖南农业大学 Method for detecting norfloxacin based on colorimetric chemical sensing technology
CN116574360A (en) * 2023-07-12 2023-08-11 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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070197548A1 (en) * 2006-02-17 2007-08-23 Murthy Yerramilli V S Fluoroquinolone compositions
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
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
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070197548A1 (en) * 2006-02-17 2007-08-23 Murthy Yerramilli V S Fluoroquinolone compositions
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
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
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 (22)

* Cited by examiner, † Cited by third party
Title
LU WENHUI等: "Dual-template molecularly imprinted polymers for dispersive solid-phase extraction of fluoroquinolones in water samples coupled with high performance liquid chromatography", 《ANALYST》 *
LU WENHUI等: "Dual-template molecularly imprinted polymers for dispersive solid-phase extraction of fluoroquinolones in water samples coupled with high performance liquid chromatography", 《ANALYST》, vol. 144, 4 December 2018 (2018-12-04), pages 1292 - 1302 *
LU WENHUI等: "Dual-template molecularly imprinted polymers for dispersive solid-phase extraction of fluoroquinolones in water samples coupled with high performance liquid chromatography", ANALYST, vol. 144, pages 1292 - 1302 *
RAN YU等: "Quantification of ultratrace levels of fluoroquinolones in wastewater by molecularly imprinted solid phase extraction and liquid chromatography triple quadrupole mass", 《ENVIRONMENTALTECHNOLOGY & INNOVATION》 *
RAN YU等: "Quantification of ultratrace levels of fluoroquinolones in wastewater by molecularly imprinted solid phase extraction and liquid chromatography triple quadrupole mass", 《ENVIRONMENTALTECHNOLOGY & INNOVATION》, vol. 19, 31 August 2020 (2020-08-31), pages 1 - 11 *
YI ZHANG等: "Preparation of porous magnetic molecularly imprinted polymers for fast and specifically extracting trace norfloxacin residue in pork liver", 《JOURNAL OF SEPARATION SCIENCE》 *
YI ZHANG等: "Preparation of porous magnetic molecularly imprinted polymers for fast and specifically extracting trace norfloxacin residue in pork liver", 《JOURNAL OF SEPARATION SCIENCE》, no. 2, 21 October 2019 (2019-10-21), pages 478 - 485 *
刘洁等: "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", 《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》 *
刘洁等: "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", 《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》, 24 June 2017 (2017-06-24), pages 123 - 126 *
刘洁等: "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", 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, pages 123 - 126 *
刘艳丽;吴昊;杜晓慧;冯艺洋;赵雅妮;常银霞;: "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", 分析科学学报, no. 02, pages 196 - 200 *
刘艳丽等: "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", 《分析科学学报》 *
刘艳丽等: "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", 《分析科学学报》, no. 02, 17 April 2018 (2018-04-17), pages 196 - 200 *
朱旭冉;刘媛;韩正政;程铭;邢维海;张佳笑;杨立亭;王健;佘永新;: "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", 食品工业科技, no. 02, pages 213 - 219 *
朱旭冉等: "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", 《食品工业科技》 *
朱旭冉等: "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", 《食品工业科技》, no. 02, 26 July 2019 (2019-07-26), pages 213 - 219 *
钭晨;江晨舟;薛罡;: "固相萃取/高效液相色谱法测定给水中的诺氟沙星", 中国给水排水, no. 24, pages 82 - 85 *
钭晨等: "固相萃取/高效液相色谱法测定给水中的诺氟沙星", 《中国给水排水》 *
钭晨等: "固相萃取/高效液相色谱法测定给水中的诺氟沙星", 《中国给水排水》, no. 24, 17 December 2009 (2009-12-17), pages 82 - 85 *
黄昭;李跑;曹亚男;李佳银;刘霞;: "诺氟沙星磁分子印迹纳米粒子的制备及其富集分离", 食品研究与开发, no. 18, pages 52 - 57 *
黄昭等: "诺氟沙星磁分子印迹纳米粒子的制备及其富集分离", 《食品研究与开发》 *
黄昭等: "诺氟沙星磁分子印迹纳米粒子的制备及其富集分离", 《食品研究与开发》, no. 18, 8 September 2020 (2020-09-08), pages 52 - 57 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114113055A (en) * 2021-11-03 2022-03-01 湖南农业大学 Method for detecting norfloxacin based on colorimetric chemical sensing technology
CN114113055B (en) * 2021-11-03 2024-01-30 湖南农业大学 Method for detecting norfloxacin based on colorimetric chemical sensing technology
CN116574360A (en) * 2023-07-12 2023-08-11 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
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

Also Published As

Publication number Publication date
CN113567594B (en) 2023-06-27

Similar Documents

Publication Publication Date Title
CN113567594B (en) Detection method of norfloxacin based on MOFs type molecularly imprinted polymer
Gao et al. Selective extraction of sulfonamides from food by use of silica-coated molecularly imprinted polymer nanospheres
Jing et al. Preparation of mixed-templates molecularly imprinted polymers and investigation of the recognition ability for tetracycline antibiotics
Xu et al. Photonic and magnetic dual responsive molecularly imprinted polymers: preparation, recognition characteristics and properties as a novel sorbent for caffeine in complicated samples
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
CN111171212B (en) Metal organic framework surface molecularly imprinted polymer and preparation method and application thereof
Javanbakht et al. Extraction and purification of penicillin G from fermentation broth by water-compatible molecularly imprinted polymers
Tan et al. Development of surface imprinted core–shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion
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
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. Recognition and selective extraction of poly-γ-glutamic acid based on molecular imprinting technology
Dhal et al. Surface grafting of functional polymers to macroporous poly (trimethylolpropane trimethacrylate)
Jiang et al. Synthesis of Copper and Lead Ion Imprinted Polymer Submicron Spheres to Remove Cu 2+ and Pb 2+
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
CN113603832B (en) MOFs molecularly imprinted polymer for detecting norfloxacin and preparation method thereof
Guo et al. Imprinted polymers with cyclodextrin pseudo-polyrotaxanes as pseudo-supports for protein recognition
Cui et al. Cellulose-incorporated imprinted materials with amphiphilic crosslinking structure for selective adsorption of bisphenol A
CN117101616A (en) Molecularly imprinted polymer adsorption material based on metal-organic framework, and preparation method and application thereof
CN111909311A (en) Zearalenone functionalized graphene surface molecularly imprinted material and preparation method 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