CN113842901B - Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof - Google Patents
Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113842901B CN113842901B CN202110964773.1A CN202110964773A CN113842901B CN 113842901 B CN113842901 B CN 113842901B CN 202110964773 A CN202110964773 A CN 202110964773A CN 113842901 B CN113842901 B CN 113842901B
- Authority
- CN
- China
- Prior art keywords
- cofs
- mofs
- core
- sea urchin
- shaped
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
-
- 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 sea urchin-shaped MOFs@COFs core-shell structure material and a preparation method and application thereof, and relates to the technical field of synthetic materials. The sea urchin-shaped MOFs@COFs core-shell structure material comprises NH 2 MIL-125 (Ti) and COFs; the COFs have an imine bond connection structure of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine as structural units. The material is presented as NH 2 The sea urchin-like morphology with MIL-125 (Ti) nano-wafer as a core and COFs nano-wire as a shell can be used as an adsorbent and an auxiliary matrix to effectively enrich fluoroquinolone antibiotics in complex environment and biological liquid samples, and then the fluoroquinolone antibiotics are analyzed by surface auxiliary laser desorption plasma mass spectrometry, so that the sea urchin-like morphology has high analysis speed and high sensitivity.
Description
Technical Field
The invention relates to the technical field of synthetic materials, in particular to a sea urchin-shaped MOFs@COFs core-shell structure material and a preparation method and application thereof.
Background
Antibiotics are chemical substances which can interfere the development function of living cells of pathogens, save lives of countless people since being discovered, and are widely applied to the fields of disease control, agricultural production and the like nowadays. However, as global climate changes, population increases and thus demand for animal proteins increases, the total amount of antibiotics consumed increases year by year and abuse occurs. A large number of artificially synthesized antibiotics flow into the environment through excretion and cultivation wastewater, so that resistance genes are accumulated continuously, and 'super bacteria' frequently appear, thereby seriously threatening human health. In order to be public health safe and better understand the effect of antibiotics on natural water environments and human health, it is necessary to monitor the composition and content of antibiotics in the environment and organisms.
The conventional antibiotic detection methods include liquid chromatography, enzyme-linked immunosorbent assay, capillary electrophoresis and the like. However, due to the complex environment and biological medium composition and the low content of antibiotics therein, conventional liquid chromatography and capillary electrophoresis require a complex and time-consuming sample pretreatment process for analysis of such substances, which reduces the analysis efficiency. Although the ELISA method simplifies the pretreatment steps of the sample, the detection specificity is strong due to the principle, and the detection of various antibiotics is difficult. Therefore, there is a need to develop new analytical methods to enable rapid, accurate and sensitive analysis of trace antibiotics in complex environments and biological samples.
Matrix-assisted laser desorption ionization mass spectrometry (Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry, MALDI MS) is a method for desorbing and ionizing sample molecules suspended therein by utilizing Matrix absorption and transmission laser energy and then detecting the sample molecules in a mass spectrometer, and has the characteristics of strong sample substrate tolerance, simplicity and convenience in operation, rapidness, high flux and the like, and can simultaneously analyze various targets. However, in the analysis of small molecule compounds, conventional small molecule auxiliary matrices can create serious interference around the target ion to mass-to-core ratio, which is detrimental to the analysis of micro and trace components. In order to increase the sensitivity of the analysis, on the one hand, the target must be enriched, and on the other hand, a novel matrix must be developed to reduce the interference to the target. Surface-assisted laser desorption Ionization (SALDI) adopts non-crystallization and non-volatilization inorganic materials as matrixes, but does not cause background pollution, but lacks selectivity when analyzing specific compounds, trace components to be detected need to be enriched in advance by other methods, and the analysis speed and operability are reduced. To solve this problem, a new SALDI matrix material that integrates the separation and enrichment functions and the auxiliary ionization functions must be developed.
To date, numerous new porous materials such as zeolites, carbon nanotubes, molecularly imprinted polymers, metal oxides and hydroxides, metal Organic Frameworks (MOFs), and Covalent Organic Frameworks (COFs) have been successfully used for selective enrichment of targets in complex matrices. MOFs and COFs are porous crystalline materials, wherein MOFs have adjustable metal nodes and easily modifiable organic linking ligands, and frames of different sizes and structures can be obtained. At the same time, the existence of the metal clusters promotes the migration of electrons and energy in the structure. Therefore, MOFs are widely used in the fields of adsorption, separation, catalysis, and sensing. The COFs are formed by covalent connection of pure organic ligands, and the material has the characteristics of light weight and easy modification. By selection and adjustment of the ligands, structures of different pore sizes and functions can be obtained. While large conjugated structures also help to broaden the light absorption range of the material and the transfer of electrons and energy. In addition, covalent bonds also impart excellent chemical stability to COFs. There have been increasing applications of COFs for adsorption, separation, catalysis, sensing. There are still few cases where the two materials are combined to achieve a particular application, compared to the range of applications for each of the two materials. Whether MOFs or COFs, applications in the field of SALDI MS analysis remain to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a sea urchin-shaped MOFs@COFs core-shell structure material for selectively enriching fluoroquinolone antibiotics, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: sea urchin-shaped MOFs@COFs core-shell structure material containing NH 2 MIL-125 (Ti) and COFs; the COFs have an imine bond connection structure of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine as structural units.
MOFs and COFs have large specific surface area and high porosity, the sea urchin-shaped morphology further improves the specific surface area of the material, and active functional groups on the ligand can realize the complex environment and the selective enrichment of trace fluoroquinolone antibiotics in biological liquid samples. The material with the absorbed target object is further loaded on a commercial MALDI target board, and the COFs are excited by the energy of laser to effectively transfer the absorbed energy to the absorbed target object by utilizing the light absorption property of the COFs, the electron and energy transfer property of MOFs and the synergistic effect of the two, so that the latter is excited and ionized.
Preferably, the material is present as NH 2 -sea urchin-like morphology with MILs-125 (Ti) nanosheets as core and COFs nanowires as shell.
Preferably, the NH 2 MIL-125 (Ti) and COFs are connected with an imine bond.
In the invention, due to the heterojunction formed by covalent bond connection of MOFs and COFs and the existence of redox active metal clusters in the MOFs, photo-generated electrons and holes are effectively separated and transferred, and possible molecular-ion reaction in the ionization process of the target is promoted, so that ionization of the target is facilitated. The prepared sea urchin-shaped MOFs@COFs core-shell structure material has high selectivity and high enrichment capacity on fluoroquinolone antibiotics, can be directly used as a SALDI matrix to carry out mass spectrometry on the target after enriching the target, and realizes rapid, sensitive and high-flux analysis on trace fluoroquinolone antibiotics in complex environment and biological liquid samples.
Meanwhile, the invention also provides a preparation method of the sea urchin-shaped MOFs@COFs core-shell structure material, which comprises the following steps:
(1) Adding 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde into a solvent, and obtaining a solution A after complete dissolution;
(2) NH is added to 2 MIL-125 (Ti) is added into the solution A, and solution B is obtained after uniform dispersion;
(3) Adding acetic acid aqueous solution into the solution B, uniformly mixing, and performing ultrasonic treatment for 20-60 min to obtain suspension C;
(4) Adding 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine into a solvent, and obtaining a solution D after complete dissolution;
(5) Adding an acetic acid aqueous solution into the suspension C, and uniformly mixing to obtain a suspension E;
(6) Adding the solution D into the suspension E, uniformly mixing, carrying out ultrasonic treatment for 20-60 min, and standing for 24-36 h;
(7) And separating and purifying to obtain the sea urchin-shaped MOFs@COFs core-shell structure material.
Preferably, the solvent in the step (1) and the step (4) is a mixed solution of N, N-dimethylacetamide, acetonitrile and o-dichlorobenzene; in the steps (1) - (4), ultrasonic dissolution, dispersion or mixing are carried out at 15-35 ℃; in the step (3) and the step (5), the concentration of acetic acid in the acetic acid aqueous solution is 11-13 mol/L.
The invention is determined by experiments, and the sea urchin-shaped MOFs@COFs core-shell structure material can be synthesized by taking a mixed solution of N, N-dimethylacetamide, acetonitrile and o-dichlorobenzene as a solvent. In addition, the purpose of the present invention is to add the aqueous acetic acid solution in two times during the preparation process in order to make the reaction proceed more sufficiently.
Preferably, in the solvent, the volume ratio of the N, N-dimethylacetamide to the acetonitrile to the o-dichlorobenzene is N, N-dimethylacetamide to acetonitrile to o-dichlorobenzene=1:3-5:9-11; the amount of acetic acid and NH in step (3) 2 The molar ratio of the amount of MIL-125 (Ti) is 270-300:1; the amount of acetic acid and NH in step (5) 2 The molar ratio of the amount of MIL-125 (Ti) is 370-400:1.
Preferably, the 2,3,5, 6-tetrafluoro-p-dibenzoyl aldehyde and NH 2 The molar ratio of MIL-125 (Ti) to 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 2,3,5, 6-tetrafluoro-p-dibenzoyl-NH 2 MILs-125 (Ti) 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine=3:0.8-1.2:0.8-1.2.
Preferably, the separation and purification method in the step (7) is as follows: centrifuging to obtain precipitate, washing with N, N-dimethylacetamide, tetrahydrofuran and acetone, and vacuum drying at 100-130 deg.c.
In addition, the invention also discloses application of the sea urchin-shaped MOFs@COFs core-shell structure material in selective enrichment of fluoroquinolone antibiotics in environmental and biological liquid samples. The application method comprises the following steps:
(1) Filtering the environmental and/or biological fluid sample, and collecting the filtrate;
(2) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in filtrate, and enriching fluoroquinolone antibiotics in the filtrate on the sea urchin-shaped MOFs@COFs core-shell structure materials;
(3) The supernatant was removed by centrifugation and the solid was collected.
Preferably, the filtration in step (1) is performed using an aqueous microporous filter membrane having a pore size of 0.22 μm.
In addition, the invention also discloses application of the sea urchin-shaped MOFs@COFs core-shell structure material in qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental and biological liquid samples.
Preferably, the application comprises the steps of:
(1) Filtering the environmental and/or biological fluid sample, and collecting the filtrate;
(2) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in filtrate, and enriching fluoroquinolone antibiotics in the filtrate on the sea urchin-shaped MOFs@COFs core-shell structure materials;
(3) The supernatant was removed by centrifugation and the solid was collected.
(4) Adding the collected solid into a desorption solvent to obtain a suspension;
(5) Adding the suspension into blank sample loading points of a stainless steel target plate for a matrix-assisted laser desorption ionization source, and baking until the solvent is completely volatilized to form a layer of solid film;
(6) Loading the target plate into a mass spectrometer, and analyzing a sample by using a surface-assisted laser desorption ionization mass spectrum;
the desorption solvent is a mixed solvent of methanol, water and trifluoroacetic acid.
Preferably, the application may also use another method, including the following steps:
(1) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in a desorption solvent to obtain a suspension;
(2) Adding the suspension into blank sample loading points of a stainless steel target plate for a matrix-assisted laser desorption ionization source, and baking until the solvent is completely volatilized to form a layer of solid film;
(3) Filtering the environmental and/or biological fluid sample, and collecting the filtrate;
(4) Loading filtrate on the solid film, and baking until the solvent is completely volatilized to form a layer of solid film;
(5) Loading the target plate into a mass spectrometer, and analyzing a sample by using a surface-assisted laser desorption ionization mass spectrum;
the desorption solvent is a mixed solvent of methanol, water and trifluoroacetic acid.
Preferably, the baking is performed by using an infrared lamp in the two methods; the volume ratio of methanol to water to trifluoroacetic acid in the desorption solvent is methanol to water to trifluoroacetic acid=75-85:18-22:0.1. The material may be more fully dispersed when the composition of the desorbing solvent meets the above-described limitations.
Compared with the prior art, the invention has the beneficial effects that: the sea urchin-shaped MOFs@COFs core-shell structure material has a disc-shaped NH with the diameter of 1-2 mu m and the thickness of 400-500 nm 2 -MILs-125 (Ti) core and COFs nanowire shell with diameter 80-100 nm and length 200-300 nm. The sea urchin-shaped MOFs@COFs core-shell structure material can be used as an enrichment material of fluoroquinolone antibiotics, and the fluoroquinolone antibiotics are selectively adsorbed through size selection effect, hydrophobic interaction, electrostatic interaction, fluorine-fluorine bond interaction and hydrogen bond interaction. In addition, the sea urchin-shaped MOFs@COFs core-shell structure material can be used as a SALDI matrix material, and laser desorption ionization of an analyte is realized through efficient absorption and transmission of laser energy by a COFs shell layer and effective separation and transmission of photo-generated electrons and holes by metal clusters in MOFs-COFs heterojunction and MOFs, so that rapid, sensitive and high-flux qualitative and quantitative analysis is performed on the target object through a mass spectrometry means.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the sea urchin-shaped MOFs@COFs core-shell structure material of example 1;
FIG. 2 is an X-ray powder diffraction pattern of the sea urchin-shaped MOFs@COFs core-shell structured material of example 1;
FIG. 3 is a scanning electron microscope image of the sea urchin-shaped MOFs@COFs core-shell structure material of example 1;
FIG. 4 is a schematic diagram showing the application of the sea urchin-shaped MOFs@COFs core-shell structured material described in example 4 in qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental and biological fluid samples;
fig. 5 is a physical diagram of the core-shell structure material of the sea urchin-shaped mofs@cofs of example 1 after enrichment of fluoroquinolone antibiotics to be tested, and then loading the material on a stainless steel target plate for a matrix-assisted laser desorption ionization source;
FIG. 6 is a mass spectrum of the core-shell structured material of sea urchin-shaped MOFs@COFs of example 1 as an adsorbent and an auxiliary ionization matrix for enriching and analyzing fluoroquinolone antibiotics in an environmental water sample and a labeled milk sample;
FIG. 7 is a schematic diagram showing the application of the sea urchin-shaped MOFs@COFs core-shell structured material described in example 5 to qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental and biological fluid samples;
FIG. 8 is a mass spectrum obtained when the core-shell structure material of sea urchin-shaped MOFs@COFs as a SALDI matrix was analyzed by different methods with fluoroquinolone antibiotics in labeled pure water.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
Example 1
Fig. 1 is a schematic diagram of a synthesis process of the sea urchin-shaped mofs@cofs core-shell structure material according to the embodiment, specifically as follows:
(1) Weighing 6.2mg (0.03 mmol) of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde in a 10mL glass bottle, adding 0.14mL of N, N-dimethylacetamide, carrying out ultrasonic treatment until reactants are completely dissolved, sequentially adding 0.6mL of acetonitrile and 1.4mL of o-dichlorobenzene, fully and uniformly mixing to obtain a clear and transparent solution, and marking the clear and transparent solution as a solution A;
(2) 10.0mg (0.01 mmol) of fresh NH 2 Adding MIL-125 (Ti) powder into the solution A, and performing ultrasonic dispersion to obtainSolution B;
(3) Adding 0.24mL of acetic acid aqueous solution with the concentration of 12mol/L as a catalyst for reaction into the solution B, fully mixing uniformly, and performing ultrasonic treatment at room temperature for 30min to enable NH 2 Condensation of the amino groups of MIL-125 (Ti) with the aldehyde groups of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde, bonding the latter to NH 2 -MIL-125 (Ti), obtaining suspension C after the reaction is completed;
(4) 3.5mg (0.01 mmol) of 2,4,6- (4-aminophenyl) -1,3, 5-triazine was put in a 10mL glass bottle, followed by sequentially adding 0.14mL of N, N-dimethylacetamide, 0.6mL of acetonitrile and 1.4mL of o-dichlorobenzene to dissolve the materials, thereby obtaining a solution D;
(5) Adding 0.32mL of acetic acid aqueous solution with the concentration of 12mol/L into the suspension C, and uniformly mixing to obtain a suspension E;
(6) Adding the solution D into the suspension E, performing ultrasonic treatment at room temperature for 30min, and standing at room temperature for 30h, wherein yellow precipitate is continuously separated out in the process;
(7) Transferring the system into a glass centrifuge tube, centrifuging to remove supernatant, washing the precipitate with N, N-dimethylacetamide, tetrahydrofuran and acetone respectively, and vacuum drying at 120 ℃ for 12 hours to obtain 15.8mg of earthy yellow powdery solid, namely the sea urchin-shaped MOFs@COFs core-shell structure material in the embodiment, wherein the yield is 80%.
The structure and morphology of the sea urchin-shaped MOFs@COFs core-shell structure material of example 1 are characterized, wherein an X-ray powder diffraction diagram is shown in FIG. 2, and a scanning electron microscope diagram is shown in FIG. 3. As can be seen from the figure, the sea urchin-shaped MOFs@COFs core-shell structure material has a disc-shaped NH with the diameter of 1-2 mu m and the thickness of 400-500 nm 2 -MILs-125 (Ti) core and COFs nanowire shell with diameter 80-100 nm and length 200-300 nm.
The COFs in the sea urchin-shaped MOFs@COFs core-shell structure material in this embodiment hasHas good enrichment effect on fluoroquinolone antibiotics, and can be used for preparing fluoroquinolone antibiotics through size selection effect, hydrophobic interaction, electrostatic interaction, fluorine-fluorine bond interaction and hydrogen bond interactionSelective adsorption is performed. The COFs shell layer can efficiently absorb and transfer laser energy, and metal clusters in MOFs-COFs heterojunction and MOFs can effectively separate and transfer photogenerated electrons and holes, so that laser desorption ionization of analytes is realized.
Example 2
The preparation method of the sea urchin-shaped MOFs@COFs core-shell structure material comprises the following steps of:
(1) Weighing 6.2mg (0.03 mmol) of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde in a 10mL glass bottle, adding 0.12mL of N, N-dimethylacetamide, carrying out ultrasonic treatment until reactants are completely dissolved, sequentially adding 0.6mL of acetonitrile and 1.32mL of o-dichlorobenzene, fully and uniformly mixing to obtain a clear and transparent solution, and marking the clear and transparent solution as a solution A;
(2) 10.0mg (0.01 mmol) of fresh NH 2 Adding MIL-125 (Ti) powder into the solution A, and performing ultrasonic dispersion to obtain a solution B;
(3) Adding 0.23mL of acetic acid aqueous solution with the concentration of 12mol/L as a catalyst for reaction into the solution B, fully mixing uniformly, and performing ultrasonic treatment at room temperature for 30min to enable NH 2 Condensation of the amino groups of MIL-125 (Ti) with the aldehyde groups of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde, bonding the latter to NH 2 -MIL-125 (Ti), obtaining suspension C after the reaction is completed;
(4) 3.5mg (0.01 mmol) of 2,4,6- (4-aminophenyl) -1,3, 5-triazine was put in a 10mL glass bottle, followed by sequentially adding 0.12mL of N, N-dimethylacetamide, 0.6mL of acetonitrile and 1.32mL of o-dichlorobenzene to dissolve the materials, thereby obtaining a solution D;
(5) Adding 0.33mL of acetic acid aqueous solution with the concentration of 12mol/L into the suspension C, and uniformly mixing to obtain a suspension E;
(6) Adding the solution D into the suspension E, performing ultrasonic treatment at room temperature for 30min, and standing at room temperature for 24h, wherein yellow precipitate is continuously separated out in the process;
(7) Transferring the system into a glass centrifuge tube, centrifuging to remove supernatant, washing the precipitate with N, N-dimethylacetamide, tetrahydrofuran and acetone respectively, and vacuum drying at 100deg.C for 12h to obtain 15.0mg of turquoise powder solid, which is the sea urchin-shaped MOFs@COFs core-shell structure material in the embodiment, with a yield of 76%.
The structure and morphology of the sea urchin-shaped MOFs@COFs core-shell structure material in this embodiment are the same as those in embodiment 1.
Example 3
The preparation method of the sea urchin-shaped MOFs@COFs core-shell structure material comprises the following steps of:
(1) Weighing 6.2mg (0.03 mmol) of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde in a 10mL glass bottle, adding 0.15mL of N, N-dimethylacetamide, carrying out ultrasonic treatment until reactants are completely dissolved, sequentially adding 0.45mL of acetonitrile and 1.35mL of o-dichlorobenzene, fully and uniformly mixing to obtain a clear and transparent solution, and marking the clear and transparent solution as a solution A;
(2) 10.0mg (0.01 mmol) of fresh NH 2 Adding MIL-125 (Ti) powder into the solution A, and performing ultrasonic dispersion to obtain a solution B;
(3) Adding 0.25mL of acetic acid aqueous solution with the concentration of 12mol/L as a catalyst for reaction into the solution B, fully mixing uniformly, and performing ultrasonic treatment at room temperature for 30min to enable NH 2 Condensation of the amino groups of MIL-125 (Ti) with the aldehyde groups of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde, bonding the latter to NH 2 -MIL-125 (Ti), obtaining suspension C after the reaction is completed;
(4) 3.5mg (0.01 mmol) of 2,4,6- (4-aminophenyl) -1,3, 5-triazine was put in a 10mL glass bottle, followed by sequentially adding 0.15mL of N, N-dimethylacetamide, 0.45mL of acetonitrile and 1.35mL of o-dichlorobenzene to dissolve them, to obtain a solution D;
(5) Adding 0.31mL of acetic acid aqueous solution with the concentration of 12mol/L into the suspension C, and uniformly mixing to obtain a suspension E;
(6) Adding the solution D into the suspension E, performing ultrasonic treatment at room temperature for 30min, and standing at room temperature for 36h, wherein yellow precipitate is continuously separated out in the process;
(7) Transferring the system into a glass centrifuge tube, centrifuging to remove supernatant, washing the precipitate with N, N-dimethylacetamide, tetrahydrofuran and acetone respectively, and vacuum drying at 120 ℃ for 12 hours to obtain 14.9mg of earthy yellow powdery solid, namely the sea urchin-shaped MOFs@COFs core-shell structure material in the embodiment, wherein the yield is 76%.
The structure and morphology of the sea urchin-shaped MOFs@COFs core-shell structure material in this embodiment are the same as those in embodiment 1.
Example 4
An example of application of the sea urchin-shaped MOFs@COFs core-shell structure material in qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental and biological liquid samples is shown in FIG. 4, wherein the application is schematically shown in the following steps:
(1) Filtering the sample solution with a microporous filter membrane of 0.22 mu m to obtain filtrate;
(2) Adding the sea urchin-shaped MOFs@COFs core-shell structure material described in the embodiment 1 into filtrate to enrich fluoroquinolone antibiotics in the material;
(3) Centrifuging to remove supernatant, and collecting solid;
(4) Placing the solid in a desorption solvent for dispersion to obtain uniform suspension;
(5) 2.0 mu L of the suspension is loaded in a blank sample loading point of a stainless steel target plate (MTP 384target plate ground steel BC commercial stainless steel target plate manufactured by Bruker Daltonics corporation) for a commercial matrix assisted laser desorption ionization source, and is baked by an infrared lamp until the solvent is completely volatilized, so that a layer of solid film is formed, as shown in figure 5;
(6) Loading the target plate into a mass spectrometer, and analyzing the sample by using a surface-assisted laser desorption ionization source mass spectrum.
Taking pure water as a matrix, and respectively adding 4 representative fluoroquinolone antibiotics with concentration ranging from 0.1 to 250 mug/L as sample solutions: enoxacin (ENX), ciprofloxacin (CFX), enrofloxacin (EFX) and Ofloxacin (OFX) to establish qualitative and quantitative analysis methods of surface-assisted laser desorption ionization source mass spectrometry of fluoroquinolones.
The concentration of the sea urchin-shaped MOFs@COFs core-shell structure material in the step (2) in the filtrate is 0.1-0.5 mg/mL, and the concentration of the solid in the step (4) in the desorption solvent is 0.1-0.5 mg/mL; the desorption solvent is a mixed solution of methanol, water and trifluoroacetic acid in the volume ratio of methanol to water to trifluoroacetic acid=80:20:0.1.
Table 1 is a table of results of analysis of fluoroquinolone antibiotics based on the linear equation, linear range, detection limit, quantitative limit, reproducibility and recovery rate of sea urchin-shaped MOFs@COFs core-shell structure materials and surface-assisted laser desorption ionization mass spectrometry.
TABLE 1
As can be seen from Table 1, the sensitivity of the method of the present invention is high, and the minimum detection limit and the quantification limit are 0.11 to 0.14. Mu.g/L and 0.34 to 0.48. Mu.g/L, respectively (determined by the target analyte concentrations corresponding to the mass spectrum peak signal-to-noise ratios of 3 and 10). The linear relation is good, and the correlation coefficient (r) is not lower than 0.992. In the reproducibility experiment, 3 parallel experiments are adopted, under the same condition, the sea urchin-shaped MOFs@COFs core-shell structure material is used for extracting and analyzing water samples with the concentrations of ENX, CFX, EFX and OFX of 20 mug/L, and the result shows that the RSD is between 6.1 and 11.4%, so that the method has better reproducibility and stability.
FIG. 6 is a mass spectrum of the core-shell structured material of sea urchin-shaped MOFs@COFs of example 1 as an adsorbent and an auxiliary ionization matrix for enriching and analyzing fluoroquinolone antibiotics in an environmental water sample and a labeled milk sample. In the recovery rate experiment, adopting a milk standard adding mode, adding the four antibiotics with the concentration of 20 mug/L into milk without ENX, CFX, EFX and OFX, and then extracting and analyzing the content of the antibiotics by the method; the results show that the recovery rate of the fluoroquinolone antibiotics in the milk is 74.5-108.5%. In addition, as can be seen from FIG. 6, in a lake (environment) water sample, only EFX was detected, the concentration was 1.1. Mu.g/L, the signal to noise ratio was 18.1, and then, a standard recovery experiment was performed using EFX of 20. Mu.g/L, and the recovery rate was 89.2 to 103.6%. The above results indicate that the method has good accuracy in the analysis of actual complex samples.
Example 5
An embodiment of the application of the sea urchin-shaped MOFs@COFs core-shell structure material in qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental and biological liquid samples is shown in fig. 7, wherein the application is schematically shown in the specification, and the specific application method is as follows:
(1) Dispersing the sea urchin-shaped MOFs@COFs core-shell structure material described in the embodiment 1 in a desorption solvent to obtain a uniform suspension; the desorption solvent is a mixed solution of methanol, water and trifluoroacetic acid in a volume ratio of methanol to water to trifluoroacetic acid=80:20:0.1; the concentration of the sea urchin-shaped MOFs@COFs core-shell structure material in the desorption solvent is 0.1-0.5 mg/mL;
(2) 2.0 mu L of the suspension is loaded in a blank sample loading point of a stainless steel target plate (MTP 384target plate ground steel BC commercial stainless steel target plate manufactured by Bruker Daltonics corporation) for a commercial matrix assisted laser desorption ionization source, and is baked by an infrared lamp until the solvent is completely volatilized, so that a layer of solid film is formed;
(3) Loading 2.0 mu L of sample solution to be tested on the prepared solid film, and baking by an infrared lamp until the solvent is completely volatilized;
(4) Loading the target plate into a mass spectrometer, and analyzing the sample by using a surface-assisted laser desorption ionization source mass spectrum.
ENX, CFX, EFX and OFX, both having a concentration of 250. Mu.g/L, were added to pure water as sample solutions and analyzed, and the results were shown in FIG. 8, and ENX, CFX, EFX and OFX were successfully detected with signal-to-noise ratios of 9.0, 7.5, 13.9 and 9.2, respectively. The sea urchin-shaped MOFs@COFs core-shell structure material is not used, other conditions are kept for a certain time, and the sample solution to be measured is directly loaded in a blank sample loading point of a stainless steel target plate for a commercial matrix-assisted laser desorption ionization source, so that any sample signal cannot be detected. The results show that the sea urchin-shaped MOFs@COFs core-shell structure material developed by the invention can be used as an auxiliary matrix to effectively promote ionization of a sample. As can be seen from FIG. 8, the results obtained by directly loading samples on the sea urchin-shaped MOFs@COFs core-shell structure material and performing mass spectrometry are compared with the results obtained by performing enrichment and then loading on the target object by using the sea urchin-shaped MOFs@COFs core-shell structure material under the same condition, and the target object signals in the sea urchin-shaped MOFs@COFs core-shell structure material are found to be obviously amplified, so that the developed sea urchin-shaped MOFs@COFs core-shell structure material has good adsorption effect on the to-be-detected object.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (12)
1. The application of the sea urchin-shaped MOFs@COFs core-shell structure material in the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample is characterized by comprising the following steps:
(1) Filtering an environmental liquid sample, and collecting filtrate;
(2) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in filtrate, and enriching fluoroquinolone antibiotics in the filtrate on the sea urchin-shaped MOFs@COFs core-shell structure materials;
(3) Centrifuging to remove supernatant, and collecting solid;
the sea urchin-shaped MOFs@COFs core-shell structure material comprises NH 2 MIL-125 (Ti) and COFs; the COFs have an imine bond connection structure of 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine as structural units.
2. The use of a sea urchin-shaped mofs@cofs core-shell structured material according to claim 1 for the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample, wherein the sea urchin-shaped mofs@cofs core-shell structured material is represented by NH 2 -sea urchin-like morphology with MILs-125 (Ti) nanosheets as core and COFs nanowires as shell.
3. The fluoroquinolone based on sea urchin-shaped MOFs@COFs core-shell structured material as claimed in claim 1 in an environmental liquid sampleUse of selective enrichment of antibiotics, characterized in that the NH 2 MIL-125 (Ti) and COFs are connected with an imine bond.
4. The use of the sea urchin-shaped mofs@cofs core-shell structured material according to claim 1 for the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample, wherein the preparation method of the sea urchin-shaped mofs@cofs core-shell structured material comprises the following steps:
(1) Adding 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde into a solvent, and obtaining a solution A after complete dissolution;
(2) NH is added to 2 MIL-125 (Ti) is added into the solution A, and solution B is obtained after uniform dispersion;
(3) Adding an acetic acid aqueous solution into the solution B, uniformly mixing, and performing ultrasonic treatment for 20-60 min to obtain a suspension C;
(4) Adding 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine into a solvent, and obtaining a solution D after complete dissolution;
(5) Adding an acetic acid aqueous solution into the suspension C, and uniformly mixing to obtain a suspension E;
(6) Adding the solution D into the suspension E, uniformly mixing, carrying out ultrasonic treatment for 20-60 min, and standing for 24-36 h;
(7) And separating and purifying to obtain the sea urchin-shaped MOFs@COFs core-shell structure material.
5. The use of the sea urchin-shaped mofs@cofs core-shell structured material according to claim 4 for the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample, wherein the solvent in step (1) and step (4) is a mixed solution of N, N-dimethylacetamide, acetonitrile and o-dichlorobenzene; the steps (1) - (4) are dissolved, dispersed or mixed by ultrasonic at 15-35 ℃; in the step (3) and the step (5), the concentration of acetic acid in the acetic acid aqueous solution is 11-13 mol/L.
6. The application of the sea urchin-shaped MOFs@COFs core-shell structure material in the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample according to claim 5, wherein the volume ratio of N, N-dimethylacetamide, acetonitrile and o-dichlorobenzene in the solvent is N, N-dimethylacetamide to acetonitrile to o-dichlorobenzene=1:3-5:9-11.
7. The use of the sea urchin-shaped MOFs@COFs core-shell structured material according to claim 4 for the selective enrichment of fluoroquinolone antibiotics in environmental body samples, wherein the 2,3,5, 6-tetrafluoro-p-dibenzoaldehyde, NH 2 The molar ratio of MIL-125 (Ti) to 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 2,3,5, 6-tetrafluoro-p-dibenzoyl-NH 2 MILs-125 (Ti) 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine=3:0.8-1.2:0.8-1.2.
8. The use of the sea urchin-shaped mofs@cofs core-shell structured material according to claim 4 for the selective enrichment of fluoroquinolone antibiotics in an environmental liquid sample, wherein the separation and purification method in the step (7) is as follows: and (3) centrifuging to obtain a precipitate, washing with N, N-dimethylacetamide, tetrahydrofuran and acetone respectively, and vacuum drying at 100-130 ℃.
9. The application of the sea urchin-shaped MOFs@COFs core-shell structure material in qualitative and quantitative analysis of fluoroquinolone antibiotics in environmental liquid samples, which is characterized in that the sea urchin-shaped MOFs@COFs core-shell structure material is the sea urchin-shaped MOFs@COFs core-shell structure material in the application of any one of claims 1-3.
10. The use according to claim 9, comprising the steps of:
(1) Filtering an environmental liquid sample, and collecting filtrate;
(2) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in filtrate, and enriching fluoroquinolone antibiotics in the filtrate on the sea urchin-shaped MOFs@COFs core-shell structure materials;
(3) Centrifuging to remove supernatant, and collecting solid;
(4) Adding the collected solid into a desorption solvent to obtain a suspension;
(5) Adding the suspension into blank sample loading points of a stainless steel target plate for a matrix-assisted laser desorption ionization source, and baking until the solvent is completely volatilized to form a layer of solid film;
(6) Loading the target plate into a mass spectrometer, and analyzing a sample by using a surface-assisted laser desorption ionization mass spectrum;
the desorption solvent is a mixed solvent of methanol, water and trifluoroacetic acid.
11. The use according to claim 9, comprising the steps of:
(1) Dispersing sea urchin-shaped MOFs@COFs core-shell structure materials in a desorption solvent to obtain a suspension;
(2) Adding the suspension into blank sample loading points of a stainless steel target plate for a matrix-assisted laser desorption ionization source, and baking until the solvent is completely volatilized to form a layer of solid film;
(3) Filtering an environmental liquid sample, and collecting filtrate;
(4) Loading filtrate on the solid film, and baking until the solvent is completely volatilized;
(5) Loading the target plate into a mass spectrometer, and analyzing a sample by using a surface-assisted laser desorption ionization mass spectrum;
the desorption solvent is a mixed solvent of methanol, water and trifluoroacetic acid.
12. The use according to any one of claims 10 to 11, wherein the baking in step (2) is performed using an infrared lamp; the volume ratio of methanol to water to trifluoroacetic acid in the desorption solvent is methanol to water to trifluoroacetic acid=75-85:18-22:0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110964773.1A CN113842901B (en) | 2021-08-20 | 2021-08-20 | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110964773.1A CN113842901B (en) | 2021-08-20 | 2021-08-20 | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113842901A CN113842901A (en) | 2021-12-28 |
| CN113842901B true CN113842901B (en) | 2023-07-25 |
Family
ID=78975842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110964773.1A Active CN113842901B (en) | 2021-08-20 | 2021-08-20 | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113842901B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160181B (en) * | 2021-12-15 | 2023-02-28 | 昆明理工大学 | Core-shell catalyst for removing organic sulfur, preparation method and application thereof |
| CN114405481A (en) * | 2022-01-24 | 2022-04-29 | 福州大学 | Preparation method of copper-based-covalent organic framework composite core-shell adsorbent for adsorbing rifamycin sodium |
| CN114471730A (en) * | 2022-02-25 | 2022-05-13 | 武汉工程大学 | NH2-MIL-101(Fe) @ SNW-1 composite catalyst and preparation method and application thereof |
| CN114713286B (en) * | 2022-04-12 | 2023-06-20 | 中南大学 | Ti-MOFs@COFs hybrid material with stable core-shell structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111307968A (en) * | 2020-02-24 | 2020-06-19 | 山东省分析测试中心 | Flower ball-shaped covalent organic framework material and preparation and application thereof |
| CN111604039A (en) * | 2020-05-26 | 2020-09-01 | 首都师范大学 | Three-dimensional covalent organic framework material, open-tube capillary electrochromatography column and preparation method |
| CN112316929A (en) * | 2020-08-28 | 2021-02-05 | 广东省测试分析研究所（中国广州分析测试中心） | Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3801880A1 (en) * | 2018-03-14 | 2021-04-14 | Desiccant Rotors International Private Ltd. | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
-
2021
- 2021-08-20 CN CN202110964773.1A patent/CN113842901B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111307968A (en) * | 2020-02-24 | 2020-06-19 | 山东省分析测试中心 | Flower ball-shaped covalent organic framework material and preparation and application thereof |
| CN111604039A (en) * | 2020-05-26 | 2020-09-01 | 首都师范大学 | Three-dimensional covalent organic framework material, open-tube capillary electrochromatography column and preparation method |
| CN112316929A (en) * | 2020-08-28 | 2021-02-05 | 广东省测试分析研究所（中国广州分析测试中心） | Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Construction of Core−Shell MOFs@COF Hybrids as a Platform for the Removal of UO22+ and Eu3+ Ions from Solution;Xin Zhong et al.;《ACS Appl. Mater. Interfaces》;第13卷;13883-13895 * |
| Core−Shell MOF@COF Motif Hybridization: Selectively Functionalized Precursors for Titanium Dioxide Nanoparticle-Embedded Nitrogen-Rich Carbon Architectures with Superior Capacitive Deionization Performance;Xiaohong Liu et al.;《Chem. Mater.》;第33卷;1657-1666 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113842901A (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113842901B (en) | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof | |
| Gao et al. | Development and application of vortex-assisted membrane extraction based on metal–organic framework mixed-matrix membrane for the analysis of estrogens in human urine | |
| Wang et al. | Covalent-organic frameworks as adsorbent and matrix of SALDI-TOF MS for the enrichment and rapid determination of fluorochemicals | |
| Huang et al. | Porous organic polymers with different pore structures for sensitive solid-phase microextraction of environmental organic pollutants | |
| CN102928488B (en) | Method for detecting phenol compounds in water body environment through enzyme electrochemical biosensor | |
| WO2021103429A1 (en) | Method for analyzing and detecting four sulfonamide antibiotics in environmental water sample | |
| CN111307968A (en) | Flower ball-shaped covalent organic framework material and preparation and application thereof | |
| CN112588265B (en) | Solid-phase microextraction film for enriching hydroxyl polycyclic aromatic hydrocarbon and preparation and application thereof | |
| Peng et al. | A regenerable sorbent composed of a zeolite imidazolate framework (ZIF-8), Fe 3 O 4 and graphene oxide for enrichment of atorvastatin and simvastatin prior to their determination by HPLC | |
| CN109331795A (en) | A kind of magnetic nanometer composite material and its preparation and application | |
| Lu et al. | Rapid isolation and determination of bisphenol A in complicated matrices by magnetic molecularly imprinted electrochemical sensing | |
| CN113209947B (en) | Phenylboronic acid functionalized Ti 3 C 2 T x Magnetic composite material and preparation method and application thereof | |
| Wang et al. | Using activated attapulgite as sorbent for solid-phase extraction of melamine in milk formula samples | |
| CN111257464A (en) | Method for quantitatively determining micro-plastic in water environment | |
| Feng et al. | Boronic acid grafted metal-organic framework for selective enrichment of cis-diol-containing compounds | |
| Yin et al. | Preparation of porous carbon-based molecularly imprinted polymers for separation of triazine herbicides in corn | |
| CN113203819B (en) | Method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material | |
| Han et al. | A novel covalent organic framework with abundant NOO and NNO sites for detection and removal of Zn2+, Cd2+, Pb2+, Cu2+, and Hg2+ | |
| CN111239314B (en) | Separation and analysis method of chitin oligosaccharide | |
| Tang et al. | Surface molecularly imprinted-based matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for highly selective and sensitive direct analysis of paraquat in complicated samples | |
| CN110672763A (en) | Application of porous imine chain covalent organic framework material in estrogen detection | |
| Hong et al. | Evaluation of a porous imine-based covalent organic framework for solid-phase extraction of nitroimidazoles | |
| CN114354582B (en) | Preparation method of dual-signal amplification electrochemiluminescence aptamer sensor and Pb detection method thereof 2+ Applications of (2) | |
| CN114904492B (en) | Polymer composite microsphere for extracting and purifying diquat metabolite in blood plasma, preparation method, kit and extraction method | |
| CN114113394B (en) | Magnetic microsphere for extracting and purifying paraquat metabolite, preparation method, kit and extraction method |
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 |