CN111307968B - Flower ball-shaped covalent organic framework material and preparation and application thereof - Google Patents
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Abstract
The invention relates to a flower ball-shaped covalent organic framework material and preparation and application thereof. The covalent organic framework material with good crystallinity and a nanosheet stacked flower-ball structure is prepared by taking tri (4-aminophenyl) amine and 1,3, 5-tri (4-formylphenyl) benzene as monomers and reacting at room temperature. The ball-flower covalent organic framework material is used as a solid phase extraction adsorbent, so that the separation and enrichment of quinolone antibiotics can be realized, the recycling performance is good, and the use cost is greatly reduced. The method for detecting the trace quinolone antibiotics in the complex samples such as the environmental water, the food and the like is combined with a high performance liquid chromatography tandem mass spectrometer, and has the advantages of high accuracy, good reproducibility, low detection limit and the like.
Description
Technical Field
The invention belongs to the field of covalent organic framework materials and analysis and detection, and particularly relates to a flower ball-shaped covalent organic framework material and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Quinolone antibiotics, as drugs for preventing and treating infectious diseases and antibacterial growth promoters, are widely used in medical treatment, livestock and aquatic animal breeding. However, improper or excessive use of such drugs results in excessive residues in environmental waters and foods, posing serious threats to ecosystem and human health. How to effectively detect quinolone antibiotics in complex samples remains a challenge in the field of analytical chemistry. Therefore, it is necessary to develop an efficient and sensitive assay for quinolone antibiotics.
Practical samples such as environmental water, food and the like have complex matrixes and low residual concentration of the quinolone antibiotics, and the quinolone antibiotics need to be separated and enriched by adopting a proper sample pretreatment technology. The Solid Phase Extraction (SPE) has the advantages of simple operation, high concentration factor, low organic solvent consumption and the like, and is an efficient and reliable sample pretreatment technology. The choice of adsorbent is one of the most important factors affecting the efficiency of solid phase extraction. Covalent Organic Frameworks (COFs) are crystalline organic porous materials formed by connecting light elements through covalent bonds, have the characteristics of high specific surface area, low density, good thermal stability, high orderliness and the like, show good application prospects in the fields of gas adsorption, heterogeneous catalysis, energy storage, sample pretreatment and the like, but the application of separating and enriching quinolone antibiotics by taking the COFs as a solid-phase extraction adsorbent is rarely reported.
The high-temperature solvothermal method is a classical synthesis method for preparing covalent organic framework materials, needs to be carried out in a sealed pressure-resistant pipe under inert atmosphere and high temperature and high pressure, and has the limitations of high energy consumption, complex operation, no contribution to large-scale production and the like. Therefore, the development of an effective and convenient method for synthesizing the covalent organic framework material is very necessary for popularizing and expanding the application of the covalent organic framework material. The room temperature method has the advantages of breaking through the bottleneck of high-temperature solvothermal synthesis, having great potential for large-scale and industrialized production, but the universal applicability of the method to monomers is yet to be explored.
Disclosure of Invention
In order to overcome the above or other potential problems, the present invention provides a flower-ball-shaped covalent organic framework material, and preparation and application thereof. The prepared spherical covalent organic framework material is used as a solid phase extraction column adsorbent, and high-sensitivity detection of trace quinolone antibiotics in environmental water and food is realized by combining a high performance liquid chromatography tandem mass spectrometry technology.
The first aspect of the present invention is: the feasibility of preparing the flower-ball-shaped covalent organic framework material with good crystallinity at room temperature by using tri (4-aminophenyl) amine (TAPA) and 1,3, 5-tri (4-formylphenyl) benzene as monomers (TFPB) is verified for the first time.
A second aspect of the present invention is: the flower-ball-shaped covalent organic framework material is found to be capable of providing various acting forces such as pi-pi action, hydrophobic action, hydrogen bond action and the like, and separating and enriching quinolone antibiotics in environment and food samples.
A third aspect of the present invention is: an analysis method for sensitively detecting quinolone antibiotics by using a ball-flower covalent organic framework material as a solid-phase extraction column adsorbent and combining a liquid chromatography-tandem mass spectrometer (LC-MS/MS) is constructed.
The invention has the beneficial effects that:
(1) the covalent organic framework material has good crystallization and a flower-ball-shaped structure stacked by nano sheets, and the preparation method is simple and mild.
(2) The research of the invention finds that the flower-ball-shaped covalent organic framework material as the solid-phase extraction column adsorbent has good adsorption property on quinolone antibiotics, can be repeatedly used and reduces the cost.
(3) The quinolone antibiotic detection method constructed by using the ball-flower covalent organic framework material as the solid-phase extraction column adsorbent and combining a liquid chromatography tandem mass spectrometer has good linear relation and higher sensitivity and repeatability, and is shown in table 1.
TABLE 1 Linear Range, correlation coefficient, detection limits, quantitation limits and precision of quinolone antibiotics
(4) The detection method provided by the invention is stable, reliable, simple and economical, is suitable for daily detection of trace carbostyril antibiotics in complex samples such as environmental water, food and the like, and has important production significance.
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The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the application, and the description of the exemplary embodiments and illustrations of the application are intended to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of a flower-like covalent organic framework material of example 1;
FIG. 2 is an X-ray diffraction pattern of the flower-like covalent organic framework material of example 1;
FIG. 3 is a Fourier transform infrared spectrum of the rosette-shaped covalent organic framework material of example 1;
FIG. 4 is a schematic diagram of the preparation of the flower-ball-shaped covalent organic framework material and its use as an adsorbent of a solid-phase extraction column for detecting quinolone antibiotics.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
A flower-ball-shaped covalent organic framework material is prepared by taking tri (4-aminophenyl) amine and 1,3, 5-tri (4-formylphenyl) benzene as monomers, taking mesitylene and 1, 4-dioxane as solvents and adopting a room-temperature method in the presence of acetic acid. According to the invention, the tri (4-aminophenyl) amine (TAPA) and the 1,3, 5-tri (4-formylphenyl) benzene are used as the monomers (TFPB) for the first time, and the flower-ball-shaped covalent organic framework material with good crystallinity is prepared by a room temperature method, so that the bottleneck of the conventional high-temperature solvothermal method synthesis is broken through, and a feasible basis is provided for large-scale and industrial production.
In some embodiments, the mesitylene to 1, 4-dioxane volume ratio is 1: 1-4.
in some embodiments, the molar concentration of acetic acid in the reaction system is 0.3-0.6 mol.L-1。
In some embodiments, the reaction temperature of the room temperature process is 25 ± 5 ℃ and the reaction time is 48-90 h.
The invention also provides a flower-ball-shaped covalent organic framework material prepared by any one of the methods.
Scanning electron microscope results show that the flower-sphere-shaped covalent organic framework material is uniform in size and regular in shape, and presents a flower-sphere-shaped structure assembled by nanosheets.
In X-ray diffraction data, the flower-ball-shaped covalent organic framework material has obvious diffraction peaks at 4.52 degrees, 7.72 degrees, 8.90 degrees, 12.05 degrees and 21.45 degrees of 2 theta.
The invention also provides application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics.
In some embodiments, the covalent organic framework material in the shape of a flower ball is used as an adsorbent of a solid phase extraction column, the column is packed in a dry method, after activation, a sample solution passes through the column, is eluted by an eluent, is blown by nitrogen, is redissolved, is filtered and then is transferred into a sample injection bottle, and is subjected to high performance liquid chromatography tandem mass spectrometry detection.
In some embodiments, the sample solution has a pH of between 3 and 9 and a sodium chloride content of between 0.1 and 0.8 mol.L-1To (c) to (d); the eluent was 5% ammonia-methanol.
In the present application, the detection conditions of hplc-tandem mass spectrometry are not particularly limited as long as they can ensure high sensitivity and reproducibility to quinolone antibiotics, and therefore, in some embodiments, the detection conditions of hplc-tandem mass spectrometry are preferably: the column was a 2.1mm X100 mm X2.5 μm Xbridge BEH C18 column temperature of 35 ℃; the mobile phase is 0.1% formic acid water (C) and acetonitrile (D); gradient condition is 0-4.0 min, 10-50% D; 4.0-4.1 min, 50-10% D; 4.1-6.0 min, 10% D. The mass spectrum monitoring mode is a multi-reaction monitoring mode MRM; the ion polarity is positive ion; the ion source temperature is 500 ℃; the electrospray voltage is 5500V to obtain better linear relation and sensitivity, improve detection efficiency.
In some embodiments, the quinolone antibiotic is cinoxacin, norfloxacin, ciprofloxacin, enrofloxacin, or gatifloxacin.
In some embodiments, the quinolone antibiotic is from tap water, spring water, chicken, or fish.
In some embodiments, mass spectrometry operating parameters for detecting parent ions, quantitative ions, qualitative ions, declustering voltage, and collision energy of five quinolone antibiotics are shown in table 2:
TABLE 2 parent ions, quantitative ions, qualitative ions, declustering voltage and collision energy of quinolone antibiotics
The present invention is described in further detail below with reference to specific examples, which should be construed as illustrative rather than restrictive.
Example 1. preparation of a flower-ball-shaped covalent organic framework material:
weighing 0.6mmol of tri (4-aminophenyl) amine and 0.6mmol of 1,3, 5-tri (4-formylphenyl) benzene in a three-neck flask, adding 6mL of mesitylene and 6mL of 1, 4-dioxane, performing ultrasonic treatment for 5min, adding 1.2mL of 6 mol. L-1Reacting with acetic acid at 25 ℃ for 72 hours, centrifuging, washing and drying to obtain the flower-ball-shaped covalent organic framework material. The scanning electron micrograph, the X-ray diffraction pattern and the Fourier transform infrared spectrogram are respectively shown as figure 1, figure 2 and figure 3.
Example 2. intercolumnar and intracolumn repeatability of a flowerlike covalent organic framework solid phase extraction column:
weighing the spherical covalent organic framework materials prepared in different batches (by adopting the method of example 1), filling the spherical covalent organic framework materials into a 6mL hollow column tube, and compacting a sieve plate to obtain six spherical covalent organic framework solid-phase extraction columns. Adjusting the concentration of sodium chloride in the ultrapure water to be 0.1 mol.L-11mL of 25. mu.g.L was added-1The quinolone antibiotics are mixed and loaded into a solid phase extraction column which is activated in advance after being mixed uniformly, elution is carried out by 5% ammonia water-methanol, elution liquid nitrogen is blown to be dry and is filtered through a 0.22 mu m filter membrane after redissolution, and detection is carried out by high performance liquid chromatography tandem mass spectrometry. The relative standard deviation is between 2.7% and 9.8%, which shows that the flower-ball-shaped covalent organic framework solid phase extraction column has good repeatability among columns.
The method of six repeated extractions is adopted, namely, a flower-ball-shaped covalent organic framework solid-phase extraction column is selected to evaluate the reusability of the flower-ball-shaped covalent organic framework solid-phase extraction column. The solid phase extraction column was washed with ultrapure water before the next extraction. The recovery of six replicates did not change significantly, with a relative standard deviation of between 3.3% and 12.0%. The method for regenerating the flower-ball-shaped covalent organic framework solid-phase extraction column is simple and good, and can be repeatedly used.
Example 3. floral ball covalent organic framework solid phase extraction column analysis of tap water samples:
filtering a tap water sample by a 0.45 microporous membrane, accurately measuring 500mL of tap water, and adjusting the concentration of sodium chloride to be 0.1 mol.L-1. By vacuumPump-driven tap water and spiked tap water were passed through a pre-activated, ball-flower covalent organic framework (using the method of example 1) solid phase extraction column, eluted with 5% ammonia-methanol, the eluted liquid nitrogen was blown dry, redissolved, passed through a 0.22 μm filter membrane, and HPLC tandem mass spectrometry detected. No quinolone antibiotic was detected in tap water. And (5) inspecting the accuracy of the method by adopting a standard adding recovery method. As shown in Table 3, the recovery rate of the quinolone antibiotics in the added standard tap water sample is between 85.2% and 103.5%, which shows that the method is accurate and reliable and can be used for analyzing trace quinolone antibiotics in the tap water sample.
Example 4. analysis of spring water samples with a flowered covalent organic framework solid phase extraction column:
filtering spring water with 0.45 microporous membrane, accurately measuring 500mL spring water, and adjusting sodium chloride concentration to 0.1 mol.L-1. Vacuum pump driven spring water and standard spring water pass through ball covalent organic frame (using example 1) solid phase extraction column, eluting with 5% ammonia-methanol, blowing eluting liquid nitrogen to dry, redissolving, passing through 0.22 μm filter membrane, and high performance liquid chromatography tandem mass spectrometry detection. No quinolone antibiotics were detected in the spring water. And (5) inspecting the accuracy of the method by adopting a standard adding recovery method. As shown in Table 3, the recovery rate of the quinolone antibiotics in the spring water is 85.9-107.6%, and the method is accurate and reliable and can be used for analyzing trace quinolone antibiotics in the spring water.
Example 5. floral sphere covalent organic framework solid phase extraction column analysis of chicken samples:
uniformly mashing a chicken sample by a high-speed tissue mashing machine, weighing 5.0g of the chicken sample, putting the chicken sample into a 50mL centrifuge tube, adding 15mL of 2% formic acid-acetonitrile solution (v/v), performing ultrasonic extraction for 15min, centrifuging, collecting supernatant into another clean 50mL centrifuge tube, adding 15mL of 2% formic acid-acetonitrile solution (v/v) into residues, repeatedly extracting once, centrifuging, combining the supernatants, and blowing nitrogen to dry.
Adding a solution containing 0.1 mol.L-1Sodium chloride dissolved in ultrapure water, vortexed and mixed, the sample was pumped by a vacuum pump through a ball-flower covalent organic framework (using the method of example 1) solid phase extraction column from 5% ammonia-AEluting with alcohol, blowing the elution liquid nitrogen to dry, redissolving, filtering with 0.22 μm filter membrane, and detecting with high performance liquid chromatography-tandem mass spectrometry. No quinolone antibiotics were detected in the chicken. And (5) inspecting the accuracy of the method by adopting a standard adding recovery method. As shown in Table 3, the recovery rate of the quinolone antibiotics in the labeled chicken is between 81.6 and 101.1 percent, which shows that the method is accurate and reliable and can be used for analyzing trace amount of quinolone antibiotics in chicken.
Example 6. floral sphere-like covalent organic framework solid phase extraction column analysis of fish samples:
uniformly mashing a fish sample by a high-speed tissue mashing machine, weighing 5.0g of the fish sample, placing the weighed fish sample in a 50mL centrifuge tube, adding 15mL of 2% formic acid-acetonitrile solution (v/v), performing ultrasonic extraction for 15min, centrifuging, collecting supernatant in another clean 50mL centrifuge tube, adding 15mL of 2% formic acid-acetonitrile solution (v/v) into residues, repeatedly extracting once, centrifuging, combining the supernatants, and blowing nitrogen to dry.
Adding a solution containing 0.1 mol.L-1Sodium chloride dissolved residues in ultrapure water, vortexed and mixed, the sample was driven by a vacuum pump to pass through a ball-flower covalent organic framework (using the method of example 1) solid phase extraction column, eluted with 5% ammonia-methanol, the eluted liquid nitrogen was blown dry, redissolved, passed through a 0.22 μm filter membrane and detected by hplc tandem mass spectrometry. No quinolone antibiotics were detected in the fish meat. And (5) inspecting the accuracy of the method by adopting a standard adding recovery method. As shown in Table 3, the recovery rate of the quinolone antibiotics in the labeled fish meat is between 80.0% and 99.9%, which shows that the method is accurate and reliable and can be used for analyzing trace amount of quinolone antibiotics in the fish meat.
TABLE 3 analysis results and standard recovery rates of tap water, spring water, chicken meat and fish meat
N.d., not detected; the labeled content is 10 ng.L-1(a),50ng·L-1(b),100ng·L-1(c),1ng·g-1(d),5ng·g-1(e),10ng·g-1(f)
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics is characterized in that the flower-ball-shaped covalent organic framework material is prepared by taking tri (4-aminophenyl) amine and 1,3, 5-tri (4-formylphenyl) benzene as monomers, taking mesitylene and 1, 4-dioxane as solvents and adopting a room temperature method in the presence of acetic acid;
the quinolone antibiotic is cinoxacin, norfloxacin, ciprofloxacin, enrofloxacin or gatifloxacin.
2. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 1, wherein the volume ratio of mesitylene to 1, 4-dioxane is 1: 1-4.
3. the application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 1, wherein the molar concentration of acetic acid in a reaction system is 0.3-0.6 mol-L-1。
4. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 1, wherein the reaction temperature of a room temperature method is 25 +/-5 ℃, and the reaction time is 48-90 h.
5. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 1, wherein the flower-ball-shaped covalent organic framework material is used as a solid phase extraction column adsorbent, a column is filled by a dry method, after activation, a sample solution passes through the column, is eluted by an eluent, is blown by nitrogen, is redissolved, is filtered and then is transferred into a sample feeding bottle, and high performance liquid chromatography tandem mass spectrometry detection is performed.
6. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 5, wherein the pH of the sample solution is 3-9, and the content of sodium chloride is 0.1-0.8 mol-L-1To (c) to (d); the eluent was 5% ammonia-methanol.
7. The application of the flower-ball-shaped covalent organic framework material in trace detection of quinolone antibiotics according to claim 5, wherein the conditions of high performance liquid chromatography tandem mass spectrometry detection are as follows: the column was a 2.1mm X100 mm X2.5 μm Xbridge BEH C18 column temperature of 35 ℃; the mobile phase is 0.1 percent formic acid water C and acetonitrile D; gradient condition is 0-4.0 min, 10-50% D, 4.0-4.1 min, 50-10% D; 4.1-6.0 min, 10% D; the mass spectrum monitoring mode is a multi-reaction monitoring mode MRM; the ion polarity is positive ion; the ion source temperature is 500 ℃; the electrospray voltage was 5500V.
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| CN113203819B (en) * | 2021-05-07 | 2022-08-12 | 山东大学 | Method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material |
| CN113201148A (en) * | 2021-06-11 | 2021-08-03 | 浙江树人学院（浙江树人大学） | Spiral infinite ordered growth COFs material and preparation method and application thereof |
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| CN113842901B (en) * | 2021-08-20 | 2023-07-25 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Sea urchin-shaped MOFs@COFs core-shell structure material and preparation method and application thereof |
| CN114689744B (en) * | 2022-03-21 | 2023-03-24 | 江南大学 | Application of functionalized three-dimensional covalent organic framework in detection of organophosphorus pesticide residues |
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