CN113203819A - Method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material - Google Patents
Method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material Download PDFInfo
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Abstract
The invention belongs to the field of detection of environmental organic pollutants, and particularly relates to a method for separating and enriching glucocorticoid based on a hydroxylated covalent organic framework material. And the detection limit and the quantification limit of glucocorticoid are both lower by matching the extraction small column packing with a liquid chromatogram-tandem mass spectrum.
Description
Technical Field
The invention belongs to the field of detection of environmental organic pollutants, and particularly relates to a method for separating and enriching glucocorticoid based on a hydroxylated covalent organic framework material, which more particularly adopts the hydroxylated covalent organic framework material (TAPB-DHTA-COF) as a solid-phase extraction column filler and combines a liquid chromatography-tandem mass spectrometry technology to determine prednisone, prednisolone, hydrocortisone, betamethasone, flumethasone and triamcinolone acetonide in water.
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.
Glucocorticoids, also known as adrenocortical hormones, are anti-inflammatory and immunosuppressive agents that are widely used clinically, and are mainly used in the breeding industry to promote animal growth and increase protein conversion rates. With the development of intensive and industrial breeding modes, the demand of glucocorticoid in the aquatic and animal husbandry is continuously increased, and the use of high frequency and overdose is even abused, so that the glucocorticoid is accumulated in the environmental water body and is in a 'persistent' pollution state. Water quality monitoring is a foundation for well managing and protecting water resources, and has important practical significance for developing detection research of glucocorticoid in order to accurately reflect the water pollution degree.
Glucocorticoid detection methods include enzyme linked immunosorbent assay, liquid chromatography, gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, and the like. Wherein, the enzyme-linked immunosorbent assay is easy to generate cross reaction and false positive; the liquid chromatography has poor interference resistance and low sensitivity; gas chromatography-mass spectrometry requires a lengthy derivatization process. Liquid chromatography-tandem mass spectrometry methods do not require derivatization, and multiple reaction monitoring modes can provide lower detection limits and better selectivity. The matrix of the environmental water body is complex, the residual quantity of the glucocorticoid is mostly in trace or even ultra trace level, and in order to obtain reliable and sensitive monitoring data, a high-sensitivity detection technology is needed, and an efficient sample pretreatment technology is also needed to separate and enrich the glucocorticoid.
The solid phase extraction has the advantages of simple operation, high concentration factor, recyclable adsorbent, low organic solvent consumption and the like, and is widely used for pretreatment of organic compounds in water samples. The adsorption packing is the key to determine the efficiency of solid phase extraction.
However, the inventor researches and discovers that the adsorption efficiency of the conventional adsorption filler on glucocorticoid is limited, and although the prior art discloses that part of covalent organic framework materials are used for adsorbing and detecting estrogen, the adsorption effect, the detection limit and the quantitative limit effect are not ideal. The detection method of solid phase extraction-liquid chromatography-tandem mass spectrometry has higher requirements on the coordination of the types of extraction columns and the solid phase extraction-liquid chromatography-tandem mass spectrometry.
Disclosure of Invention
In order to solve the problems that the adsorption efficiency of conventional adsorption packing on glucocorticoid is limited and the detection limit and quantitative limit effects are not ideal in the prior art, the invention provides a method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework materials. Meanwhile, high-sensitivity detection of glucocorticoid is realized by combining a high performance liquid chromatography-mass spectrometer.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided the use of a hydroxylated covalent organic framework material as a glucocorticoid-rich material.
In a second aspect of the invention, a method for separating and enriching glucocorticoids based on a hydroxylated covalent organic framework material is provided, which comprises separating and enriching glucocorticoids in a sample by using the hydroxylated covalent organic framework material.
One or more embodiments of the present invention have the following advantageous effects:
1) the hydroxylated covalent organic framework material is firstly found to have better separation and enrichment effects on glucocorticoid and good reusability when being used as the solid phase extraction column filler, and the recovery rate is still kept above 85 percent after 5 times of recycling.
2) By optimizing the conditions of solid-phase extraction and liquid-mass detection, the detection limit of the glucocorticoid can reach the ng/L level, and the method has high sensitivity, wide linear range and strong practicability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a scanning electron micrograph of a hydroxylated covalent organic framework material of example 1 of the present invention.
FIG. 2 is a graph showing the effect of pH (a), ionic strength (b), eluent species (c) and volume (d) on solid phase extraction efficiency in example 2 of the present invention;
FIG. 3 is a MRM chromatogram of six glucocorticoids according to example 3 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
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 example embodiments according to the present disclosure. 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.
In order to solve the problems that the adsorption efficiency of a conventional adsorption filler to glucocorticoid is limited and the detection limit and the quantification limit effect are not ideal in the prior art, the invention provides a method for determining six glucocorticoids, namely prednisone, prednisolone, hydrocortisone, betamethasone, flumethasone and triamcinolone acetonide, in a water body by adopting a hydroxylated covalent organic framework material (TAPB-DHTA-COF) as a solid-phase extraction column filler and combining a liquid chromatography-tandem mass spectrometry technology. The detection method provided by the invention has the advantages of high sensitivity, wide linear range and strong practicability.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided the use of a hydroxylated covalent organic framework material as a glucocorticoid-rich material.
Experiments show that the hydroxylated covalent organic framework material has better adsorption or enrichment effect on six glucocorticoids, namely prednisone, prednisolone, hydrocortisone, betamethasone, flumethasone and triamcinolone acetonide.
The preparation method of the hydroxylated covalent organic framework material comprises the steps of taking 1,3, 5-tri (4-aminophenyl) benzene (TAPB) and 2, 5-dihydroxy terephthalaldehyde (DHTA) as monomers, adding a catalyst and a solvent, and synthesizing the hydroxylated covalent organic framework material by adopting a room-temperature solvent method.
The catalyst is acetic acid, and the solvent is acetonitrile.
Preferably, the molar ratio of the 1,3, 5-tris (4-aminophenyl) benzene to the 2, 5-dihydroxyterephthalaldehyde is 2:2 to 5, preferably 2: 3.
Preferably, the concentration of the 1,3, 5-tri (4-aminophenyl) benzene in the solvent is 4mmol/L, the concentration of the catalyst is 12mol/L, and the volume ratio of the solvent to the catalyst is 10: 1.
The solvent provides a certain reaction site for the reaction, the catalyst is used for catalytic reaction, the structure and the performance of the product are determined by the dosage and the concentration of the raw materials, the solvent and the catalyst.
Preferably, the solvent is added firstly, the catalyst is added after the ultrasonic treatment, and the mixture is kept standing for 72 hours at room temperature. The standing is to allow the product to grow into crystals and form a perfect structure.
Preferably, the reaction also comprises the steps of centrifugation, washing and drying after the reaction is finished.
The invention discovers for the first time that the specific hydroxylated covalent organic framework material has a better matching effect with the glucocorticoid when being used as the solid-phase extraction column packing, increases the adsorption effect of the glucocorticoid, has good reusability, and still keeps the recovery rate above 85 percent after the extraction column is recycled for 5 times.
In a second aspect of the invention, a method for separating and enriching glucocorticoids based on a hydroxylated covalent organic framework material is provided, which comprises separating and enriching glucocorticoids in a sample by using the hydroxylated covalent organic framework material.
The method comprises the steps of pretreatment of a sample to be detected, solid-phase extraction enrichment and detection of a liquid chromatography tandem mass spectrometry;
wherein the solid phase extraction adopts the hydroxylated covalent organic framework material to separate and enrich glucocorticoid in a sample.
The solid phase extraction is carried out by a solid phase extraction column, and the hydroxylated covalent organic framework material is used as a filler of the solid phase extraction column.
The preparation method of the solid phase extraction column comprises the following steps: weighing the hydroxylated covalent organic framework material, filling the material into a syringe type solid-phase extraction hollow column tube, and sealing two ends of the column tube by a sieve plate to obtain the solid-phase extraction column.
And the solid phase extraction column is activated by methanol and water respectively.
Preferably, the methanol and water are equal in volume;
preferably, the solid phase extraction column is activated in advance with 3.0mL of methanol and 3.0mL of water;
preferably, the pH and ionic strength of the loading solution of the solid phase extraction need not be adjusted.
Preferably, the sample loading speed of the solid phase extraction is 1-5 mL/min, and preferably 3 mL/min.
Preferably, the eluent for solid phase extraction is one or more of methanol, acetonitrile or acetone.
Preferably, the volume of the solid phase extraction eluent is 2.0-8.0 ml.
Preferably, the liquid chromatographic separation mobile phase is 0.1% formic acid aqueous solution and methanol; the flow rate of the mobile phase is 0.3 mL/min; the gradient elution procedure is 0-4.0 min, 50-90% methanol, 4.0-4.1 min, 90-50% methanol and 4.1-7.0 min, 50% methanol; the injection volume is 10. mu.L.
The mass spectrum detection conditions are as follows: electrospray ion source, positive ion mode; the ion source temperature is 400 ℃, and the accelerating voltage is 5500V.
The hydroxylation covalent organic framework material can have good selective adsorption to estrogen in a sample, the enriched sample has good purity, a clean detection background can be obtained through liquid-quality detection, and the detection accuracy is improved. By optimizing the solid-phase extraction and liquid-quality detection conditions, good detection sensitivity is realized, the detection limit can reach the ng/L level, the sensitivity is high, the linear range is wide, and the practicability is strong.
Based on the strong hydrogen bond action between hydroxyl and oxygen-containing groups of glucocorticoid, hydroxyl functionalized organic monomer 2, 5-dihydroxy terephthalaldehyde (DHTA) is used as a construction element, and a bottom-up construction strategy is adopted to prepare the hydroxylated covalent organic framework material, so that the hydroxylated covalent organic framework material is applied to glucocorticoid detection for the first time. Experimental results show that the hydroxylated covalent organic framework material has higher separation and enrichment efficiency in the pretreatment process of a sample of trace glucocorticoid and can be well recycled.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
EXAMPLE 1 preparation of a hydroxylated covalent organic framework solid phase extraction column
1,3, 5-tris (4-aminophenyl) benzene (0.2mmol) and 2, 5-dihydroxy terephthalaldehyde (0.3mmol) were weighed into a single-neck flask, 50mL of acetonitrile was added, sonication was carried out for 5 minutes, 5mL of 12mol/L acetic acid was added, stirring was carried out uniformly, and the mixture was allowed to stand at room temperature for 72 hours. Centrifuging, washing and drying to obtain powdery solid. The hydroxylated COF is spherical and uniform in particle size, and the scanning electron micrograph thereof is shown in figure 1.
Weighing 50mg of hydroxylated COF, transferring the hydroxylated COF into a 6mL syringe type solid phase extraction hollow tube, sealing two ends of a column tube by a sieve plate to prevent the filler from leaking outside, and compacting the sieve plate to obtain the solid phase extraction column.
Example 2 pretreatment conditions optimization based on hydroxylated COF solid phase extraction column:
in this example, the influence of parameters such as pH, ionic strength, eluent type and volume of a water sample on the separation and enrichment of glucocorticoid in a self-made solid phase extraction column is investigated. The specific operation is to adjust the pH of the water sample to 3.0, 5.0, 7.0, 9.0 or 11.0 respectively, the concentration of sodium chloride in the water sample is 0, 0.1, 0.2, 0.4 or 0.8mol/L respectively, the eluent is methanol, acetonitrile, acetone, ethyl acetate or n-hexane respectively, and the volume of the eluent is 2.0, 4.0, 6.0 or 8.0mL respectively.
The related optimization results are shown in figure 2, in the selected investigation range, the pH value, the ionic strength and the volume of the eluent of the water sample have no obvious influence on the recovery rate of the glucocorticoid, and the glucocorticoid can be effectively desorbed by adopting methanol, acetonitrile or acetone as the eluent.
Example 3 solid phase extraction-liquid chromatography-tandem mass spectrometry analysis procedure of glucocorticoid residual amount of water sample:
the hydroxylated COF solid phase extraction column was previously activated with 3.0mL of methanol and 3.0mL of water. The collected water sample is placed in a brown glass bottle, filtered by a glass fiber filter membrane and loaded to a home-made hydroxylation COF solid-phase extraction column, and the sampling rate is 3.0 mL/min. After completion of the loading, the column was eluted with 6.0mL of methanol. The elution liquid nitrogen was blown dry and redissolved with 1.0mL of methanol-water (50:50, V/V). And filtering the re-solution, transferring the re-solution to a sample injection bottle, and injecting the sample to a liquid chromatography-tandem mass spectrometry detection.
Wherein the liquid chromatography column is Waters Xbridge BEH C18(100mm × 2.1mm × 2.5 μm); the mobile phase is 0.1% formic acid water solution and methanol, the flow rate is 0.3mL/min, the gradient elution procedure is 0-4.0 min, 50-90% methanol, 4.0-4.1 min, 90-50% methanol and 4.1-7.0 min, 50% methanol; the injection volume is 10. mu.L.
Mass spectrum detection conditions: electrospray ion source, positive ion mode; the ion source temperature is 400 ℃, the acceleration voltage is 5500V, the gas curtain gas is 35psi, the atomization gas is 45psi, and the auxiliary gas is 50 psi. The detection was performed in the positive ion multiple reaction monitoring mode (MRM) and the glucocorticoid was quantitatively analyzed by external standard method, and the parameters of the multiple reaction monitoring mode are shown in Table 1.
The chromatographic test results are shown in fig. 3, and it can be seen that six glucocorticoids are completely eluted from the C18 column within seven minutes, and the peak shapes are good.
TABLE 1 relevant parameters for MRM model detection of six glucocorticoids
Example 4 reusability of hydroxylated COF solid phase extraction columns
The used hydroxylated COF solid phase extraction column was sealed with 3.0mL of methanol. The solid phase extraction column used in the 1 st elution was regenerated with 10mL of methanol, and after the regeneration was completed, the column was activated with 3.0mL of methanol and 3.0mL of water in this order, and a glucocorticoid solution of a fixed concentration was loaded, and the recovery rates were compared, and the results are shown in Table 2. After the extraction column is recycled for 5 times, the recovery rate is still kept above 85%.
TABLE 2 Recycling recovery data for hydroxylated solid phase extraction column
Example 5 determination of working curve related parameters for six glucocorticoids
Preparing standard solutions with the concentrations of 0.5, 1.0, 5.0, 10, 25, 50, 75 and 100 mu g/L, respectively diluting 1.0mL to 100mL to be used as a loading solution, carrying out separation and enrichment under the optimized solid phase extraction condition, and analyzing by liquid chromatography-tandem mass spectrometry. With a weight of 1/x2The linear range and the correlation coefficient are determined, and the method detection limit and the quantification limit are determined by the corresponding concentration when the signal-to-noise ratio is 3 and 10.
TABLE 3 Linear Range, correlation coefficient and method detection limits, quantitation limits for six glucocorticoids
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 changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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.
Claims (10)
1. An application of a hydroxylated covalent organic framework material as a glucocorticoid enrichment material.
2. Use of a hydroxylated covalent organic framework material according to claim 1 as a glucocorticoid enrichment material, characterized in that the glucocorticoid is selected from the group consisting of prednisone, prednisolone, hydrocortisone, betamethasone, flumethasone and triamcinolone acetonide.
3. Use of the hydroxylated covalent organic framework material according to claim 1 as a glucocorticoid enrichment material, characterized in that the hydroxylated covalent organic framework material is prepared by a method comprising: 1,3, 5-tri (4-aminophenyl) benzene and 2, 5-dihydroxy terephthalaldehyde are taken as monomers, a catalyst and a solvent are added, and a room-temperature solvent method is adopted to synthesize the hydroxylated covalent organic framework material.
4. Use of the hydroxylated covalent organic framework material of claim 3 as a glucocorticoid concentrating material, wherein the catalyst is acetic acid and the solvent is acetonitrile.
5. A method for the separation and enrichment of glucocorticoids on the basis of hydroxylated covalent organic framework material, characterized in that the method comprises separating and enriching glucocorticoids in a sample using hydroxylated covalent organic framework material.
6. The method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material according to claim 5, characterized in that the method comprises the steps of pre-treatment of a sample to be tested, solid phase extraction enrichment and detection by liquid chromatography tandem mass spectrometry;
wherein the solid phase extraction adopts the hydroxylated covalent organic framework material to separate and enrich glucocorticoid in a sample.
7. The method for separating and enriching glucocorticosteroids based on hydroxylated covalent organic framework materials according to claim 6, characterized in that solid phase extraction is carried out by means of a solid phase extraction column, the hydroxylated covalent organic framework materials being used as solid phase extraction cartridge packing;
preferably, the preparation method of the solid phase extraction column comprises the following steps: weighing the hydroxylated covalent organic framework material, filling the material into a syringe type solid-phase extraction hollow column tube, and sealing two ends of the column tube by a sieve plate to obtain the solid-phase extraction column.
8. The method for separating and enriching glucocorticoids according to claim 7, wherein the sample loading speed of the solid phase extraction is 1-5 mL/min, preferably 3 mL/min;
preferably, the solid phase extraction employs methanol as eluent.
9. The method for separating and enriching glucocorticoids according to claim 6, wherein the mobile phase of the liquid phase comprises formic acid solution and methanol, and the elution type comprises isocratic elution;
preferably, the mobile phase is 0.1% formic acid water solution and methanol, the flow rate is 0.3mL/min, the gradient elution procedure is 0-4.0 min, 50-90% methanol, 4.0-4.1 min, 90-50% methanol and 4.1-7.0 min, 50% methanol; the injection volume is 10. mu.L.
10. The method for separating and enriching glucocorticosteroids based on hydroxylated covalent organic framework materials according to claim 6, characterized in that the mass spectrometric detection conditions are: electrospray ion source, positive ion mode; the ion source temperature is 400 ℃, and the accelerating voltage is 5500V.
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