CN113624866A - CNT@COFTHB-TAPBAdsorbent and application thereof in online solid-phase extraction and mass spectrum combined device - Google Patents
CNT@COFTHB-TAPBAdsorbent and application thereof in online solid-phase extraction and mass spectrum combined device Download PDFInfo
- Publication number
- CN113624866A CN113624866A CN202110850532.4A CN202110850532A CN113624866A CN 113624866 A CN113624866 A CN 113624866A CN 202110850532 A CN202110850532 A CN 202110850532A CN 113624866 A CN113624866 A CN 113624866A
- Authority
- CN
- China
- Prior art keywords
- thb
- adsorbent
- cof
- tapb
- phase extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to the technical field of analysis and detection, in particular to a Chip On Film (COF) based on carbon nanotube @ COFTHB‑TAPBAn on-line solid phase extraction and mass spectrum combined device of an adsorbent and application thereof. The adsorbent is formed by forming a covalent organic framework COF on the surface of an aminated carbon nanotube in a covalent bond modeTHB‑TAPBThe layers are made. The adsorbent has a hydrophobic surface, crystallinity, porosity, a large specific surface area, a pi-pi conjugated system and hydrogen bond sites, and can realize high-selectivity adsorption on sterol hormones. And filling the adsorbent into a stainless steel hollow column to prepare a solid phase extraction small column for detecting the sterol hormone by using a device combining online solid phase extraction and high-resolution mass spectrometry. The detection method has the advantages of high extraction efficiency, short time and the like, and is suitable for sterol kinase in complex biological samplesHigh sensitivity and quick detection of the element.
Description
Technical Field
The invention relates to the technical field of analysis and detection, and particularly relates to a CNT @ COFTHB-TAPB adsorbent and application thereof in an online solid-phase extraction and mass spectrum combined device.
Background
Steroid hormones are derivatives of cyclopentanoperhydrophenanthrene. All four types of steroid hormones are lipophilic, low molecular weight and biologically active compounds. Although sterols have been banned by the European Union (EU) for meat production since 1981, they are still used in animal husbandry to promote growth and reduce morbidity. Excessive and illegal use can lead to accumulation of sterol hormones and their metabolites in animals and interference with the human endocrine system through the food chain. They are reported to have potential toxicity and carcinogenicity to human health, and may even cause serious diseases such as breast, uterine and prostate cancer. With the growing public concern and the need for legislative strategies, there is a need to develop rapid assays with high sensitivity and specificity for the detection of steroid hormones in biological matrices.
Since the first proposal in 1959, immunoassay has long been the traditional technique for the detection of steroid hormones due to its sensitivity, cost and simplicity. However, problems with specificity, reproducibility, false positives, and cross-reactivity with glucocorticoids limit their use.
Patent No. cn201110373574.x discloses a method for measuring the content of active substance beta-sitosterol in supercritical extract of pollen pini, and the sterol component is analyzed and measured by gas chromatography-mass spectrometry and high performance liquid chromatography. Determining that the main component of sterols in the supercritical extract of the pine pollen is beta-sitosterol by gas chromatography-mass spectrometry; extracting by a saponification method; and (3) measuring the content of the beta-sitosterol by using a high performance liquid chromatography. The invention only analyzes the sitosterol by gas chromatography-mass spectrometry.
So far, based on CNT @ COFTHB-TAPBThe technology of on-line solid phase extraction of the adsorbent and high-resolution mass spectrometry is not used for detection of sterol hormones.
Disclosure of Invention
In view of the above, the present invention is directed to a CNT @ COFTHB-TAPBThe adsorbent is formed by forming a covalent organic framework COF on the surface of the aminated carbon nanotube in a covalent bond modeTHB-TAPBThe layers are made. CNT @ COFTHB-TAPBThe adsorbent has carbon nanotubes andthe complex properties of the organic framework, such as hydrophobic surface, good crystallinity, porosity, large specific surface area, pi-pi conjugated system and hydrogen bond sites, can realize high selective adsorption on sterol hormones.
As an emerging class of porous materials, Covalent Organic Frameworks (COFs) have good stability and crystallinity, large specific surface area, high porosity and controllable structures. Carbon Nanotubes (CNTs) are another porous adsorbent that can adsorb many compounds, but they tend to aggregate in closed circuits and cause high back pressure. Functionalization of carbon Nanotubes (NH) by COFs with amino groups2-CNTs) will improve the extraction efficiency and overcome the aggregation of CNTs.
The CNT @ COFTHB-TAPBThe preparation method of the adsorbent comprises the following steps:
(1) mixing the aminated carbon nanotube, dimethyl sulfoxide and a solvent a to form a homogeneous liquid a;
(2) mixing 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene with the homogeneous solution to obtain a homogeneous solution b;
(3) mixing the 1, 3, 5-tri (4-aminophenyl) benzene and the homogeneous liquid b to obtain a homogeneous liquid c;
(4) mixing 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene and 1, 3, 5-tri (4-aminophenyl) benzene with the homogeneous liquid c, and sealing to react to generate CNT @ COFTHB-TAPBAn adsorbent.
The solvent a is selected from one or more of mesitylene, ethanol or 1,4 dioxane.
Preferably, in step (3), a catalytic amount of acetic acid is added; and/or in step (4), adding a catalytic amount of acetic acid again before the sealing reaction. More preferably, the amount of acetic acid used relative to the ligand is 0.5-2 mL/mmol. The concentration of the acetic acid can be adjusted according to actual conditions, and the preferred concentration of the acetic acid in the invention is 3mol/mL or 6 mol/mL.
Preferably, in the step (2) and the step (3), the molar ratio of the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene to the 1, 3, 5-TRIS (4-aminophenyl) benzene is 1: 1; in the step (4), the molar ratio of the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene to the 1, 3, 5-TRIS (4-aminophenyl) benzene is 1: 1.
Preferably, the mass ratio of the aminated carbon nanotube to the total 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene is 0.5-3: 1, more preferably 1.5: 1. the amount of 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene as a whole refers to the total mass of 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene in step (2) and step (4).
Preferably, the molar ratio of the 1, 3, 5-TRIS (3 '-formyl-4' -hydroxyphenyl) benzene to the 1, 3, 5-TRIS (4-aminophenyl) benzene in step (2) and step (3) is 1: 1; and the molar ratio of the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene to the 1, 3, 5-TRIS (4-aminophenyl) benzene in the step (4) is 1: 1.
Preferably, the molar ratio of 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene in step (2) to 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene in step (4) is from 1:4 to 1:10, more preferably 1: 4.
Preferably, the mixture is filtered, washed with N, N-dimethylformamide and methanol, soxhlet extracted with methanol and filtered to give a solid, which is freeze-dried to give CNT @ COFTHB-TAPBAn adsorbent powder.
In certain embodiments, the CNT @ COFTHB-TAPBThe preparation method of the adsorbent comprises the following steps:
(1) adding 33-200mg of aminated carbon nanotube, 2-8mL of dimethyl sulfoxide and 0.5-2mL of mesitylene into 30mL of glass sealed tube, and stirring the suspension at room temperature for 6-42 hours to form homogeneous liquid;
(2) adding 13.1mg of ligand 1, 3, 5-TRIS (3 '-formyl-4' -hydroxybenzene) benzene (THB) into the homogeneous liquid, performing ultrasonic treatment for 1-5 minutes, and stirring at room temperature for 0.5-2 hours to obtain THB modified carbon nanotube homogeneous liquid;
(3) adding 10.5 mg ligand 1, 3, 5-tri (4-aminophenyl) benzene (TAPB) and 10-50 μ L acetic acid into the THB modified carbon nanotube homogeneous solution respectively under stirring, performing ultrasonic treatment for 1-5 min, and stirring at room temperature for 0.5-2 hr to obtain micro COFTHB-TAPBGrain-modified carbon nanotube homogeneous solution;
(4) 52.5mg of ligand THB and 42.1mg of ligand TAPB were added to the above-mentioned minimal COF under stirringTHB-TAPSubjecting the crystal-modified carbon nanotube homogeneous solution to ultrasonic treatment for 1-5 min, adding 50-200 μ L of acetic acid under stirring, sealing the reaction flask, and reacting at 90-120 deg.C for 12-72 hr to obtain black CNT @ COFTHB-TAPBA crude product;
(5) CNT @ COF as defined aboveTHB-TAPBFiltering the crude product, washing with 5-30mL of N, N-dimethylformamide and 5-30mL of methanol respectively, performing Soxhlet extraction with appropriate amount of methanol at 100 ℃ for 12-24 hours, filtering, and freeze-drying the solid for 12-24 hours to obtain CNT @ COFTHB-TAPBAnd (3) powder.
Preferably, the amount of the aminated carbon nanotube in the step (1) is 100 mg.
Preferably, the amounts of acetic acid of the steps (3) and (4) are 30 μ L and 120 μ L, respectively.
The invention aims to further provide a Chip On Film (COF) based on CNT @ COFTHB-TAPBThe device is used for detecting a plurality of sterol hormones in a biological matrix. Biological sample matrices are relatively complex and require sample pre-treatment to decontaminate and enrich for analytes prior to mass spectrometry. An effective method for improving the pretreatment efficiency of a solid phase extraction material with specificity and high efficiency is developed. Covalent Organic Frameworks (COFs) have good stability and crystallinity, large specific surface area, high porosity and a controllable structure. While Carbon Nanotubes (CNTs) are another porous adsorbent that can adsorb many compounds, they tend to aggregate in closed circuits and cause high back pressure. Functionalization of carbon Nanotubes (NH) by COFs with amino groups2-CNTs) will improve the extraction efficiency and overcome the aggregation of CNTs.
In particular, compounds having a structure similar to that of sterols can also be detected using detection methods based on the device, such as vitamin D.
The detection method comprises the following steps: detecting using a solid phase extraction and mass spectrometry apparatus, the solid phase extraction and mass spectrometry apparatus comprising: a solid phase extraction column, a sample injector, a binary pump system, a sample quantitative ring,A sample injection six-way valve (V1), a solid phase extraction small column, a switching six-way valve (V2), a flow pipeline and a mass spectrometer; the solid phase extraction column is connected between the sample injection six-way valve (V1) and the switching six-way valve (V2), the binary pump system is connected with the sample injection six-way valve (V1), and the switching six-way valve (V2) is connected with the mass spectrometer; the solid phase extraction cartridge comprises the CNT @ COF of any one of claims 1 to 6THB-TAPBThe adsorbent is used as a solid phase; the detection method comprises the following steps:
(1) in the sample loading state, a sample extracting solution is loaded in the sample quantifying ring;
(2) in a loading state, the binary pump system pumps 0-10% of methanol and/or acetonitrile solvent at the flow rate of 0.1-1mL/min, so that the sample in the quantitative ring is automatically loaded on the solid phase extraction small column;
(3) in a loading state, the binary pump system pumps 0-20% methanol and/or acetonitrile solvent at a flow rate of 1-2mL/min to clean the sample matrix and impurities loaded on the solid phase extraction column;
(4) in a loading state, the binary pump system pumps 50-100% methanol and/or acetonitrile solvent at a flow rate of 0.3-0.8mL/min to elute a sample retained in the solid phase extraction cartridge;
(5) and (5) carrying out mass spectrum detection on the eluted sample.
The solid phase extraction column is connected between a sample injection six-way valve (V1) and a switching six-way valve (V2), the binary pump system is connected with the sample injection six-way valve (V1), the switching six-way valve (V2) is connected with a mass spectrometer, and samples sequentially pass through a sample injector, a sample quantitative ring, the sample injection six-way valve (V1), the solid phase extraction column, the switching six-way valve (V2) and the mass spectrometer in the online solid phase extraction and high-resolution liquid mass spectrometry device.
In particular, mass spectrometry-based methods have been used as an alternative to immunoassays because of their higher specificity and sensitivity, and can provide analyte structural information. The high-resolution mass spectrum has high mass precision, high mass resolution and rapid polarity switching performance, and has become an important technology for sterol hormone detection. The combination of solid phase extraction and high resolution mass spectrometry can further simplify the analysis steps and improve the analysis efficiency.
Preferably, the mass spectrometer is a high resolution mass spectrometer. More preferably, the mass spectrometric detection is performed on-line.
Further, after mass spectrum detection, continuously (6) pumping 80-100% methanol or acetonitrile solvent by a binary pump system at the flow rate of 0.3-0.8mL/min under the loading state, and cleaning the strong retention impurities adsorbed on the extraction small column; then continuing (7) under the loading condition, the binary pump system pumps 0-20% methanol or acetonitrile solvent at a flow rate of 1-2mL/min to equilibrate the extraction cartridge for use in the next analysis.
Preferably, the CNT @ COFTHB-TAPBThe loading of the adsorbent is 3-100mg, more preferably 5 mg.
Preferably, the loading amount of the step (1) is 500. mu.L.
Preferably, the flow rate of the binary pump system in the step (2) is 0.3mL/min, and the loading solvent is 0% methanol or acetonitrile.
Preferably, the flow rate of the binary pump system in the step (3) is 1.5mL/min, and the cleaning solvent is 10% methanol or acetonitrile.
Preferably, the flow rate of the binary pump system in the step (4) is 0.5mL/min, and the elution solvent is 98% methanol or acetonitrile.
Preferably, the flow rate of the binary pump system in the step (6) is 0.5mL/min, and the cleaning solvent is 98% methanol or acetonitrile.
Preferably, the flow rate of the binary pump system in the step (7) is 1.5mL/min, and the elution solvent is 0% methanol or acetonitrile.
In certain embodiments, the detection method comprises the following steps:
(1) in the sample loading state, 250-;
(2) in a loading state, a binary pump system pumps 0-10% of methanol or acetonitrile solvent at the flow rate of 0.1-1mL/min, so that a sample in a quantitative ring is automatically loaded on a solid phase extraction column;
(3) under the loading state, a binary pump system pumps 0-20% methanol or acetonitrile solvent at the flow rate of 1-2mL/min to clean the substrate and impurities adsorbed on the solid phase extraction small column;
(4) under the loading state, a binary pump system pumps 50-100% of methanol or acetonitrile solvent at the flow rate of 0.3-0.8mL/min, and samples remained in the extraction small column are eluted;
(5) directly carrying out online high-resolution mass spectrometry detection on the eluted sample;
(6) under the loading state, a binary pump system pumps 80-100% methanol or acetonitrile solvent at the flow rate of 0.3-0.8mL/min to clean the strong retention impurities adsorbed on the extraction small column;
(7) in the loaded state, the binary pump system pumps 0-20% methanol or acetonitrile solvent at a flow rate of 1-2mL/min to equilibrate the extraction cartridge for use in the next analysis.
Furthermore, the on-line solid-phase extraction and high-resolution liquid mass spectrometry combined device also carries out automatic control on the external automatic valve switching device and the solid-phase extraction and high-resolution liquid mass spectrometry combined device through a single chip microcomputer control system, thereby realizing the on-line extraction, cleaning, elution and mass spectrometry detection of the sample.
The invention has the beneficial effects that
The invention provides CNT @ COFTHB-TAPBThe adsorbent has the composite performance of the carbon nano tube and the covalent organic framework, such as hydrophobic surface, good crystallinity, porosity, large specific surface area, pi-pi conjugated system and hydrogen bond sites, and can realize high-selectivity adsorption on sterol hormones.
The on-line solid phase extraction and high-resolution liquid mass spectrometry combined device provided by the invention automatically controls the external automatic valve switching device and the high-resolution mass spectrometer through the single chip microcomputer control system, so that the on-line extraction, cleaning, elution and mass spectrometry detection of a sample are realized, the pretreatment efficiency of the sample is greatly improved, the analysis time is reduced, and the on-line solid phase extraction and high-resolution liquid mass spectrometry combined device can be used for simultaneously detecting multiple sterol hormones in a biological matrix.
The method for detecting the sterol hormones provided by the invention greatly improves the detection sensitivity and the analysis speed of the sample, and is suitable for high-sensitivity and rapid detection of the sterol hormones in a complex biological sample.
Drawings
FIG. 1 is a schematic diagram of a device combining online solid-phase extraction and high-resolution mass spectrometry for simultaneously detecting multiple steroid hormones in a biological matrix.
FIG. 2 is based on CNT @ COFTHB-TAPBThe device combining online solid-phase extraction of the adsorbent and high-resolution mass spectrometry is used for extracting an ion flow diagram for detecting 16 sterol hormones in pork.
FIG. 3 is CNT @ COFTHB-TAPBAnd comparing the recovery rate of the sterol hormones in the pork by the adsorbent with that of other adsorbents.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
In the embodiment of the invention, a schematic diagram of an online solid-phase extraction and high-resolution mass spectrometry device is shown in fig. 1, and the online solid-phase extraction and high-resolution mass spectrometry device comprises a sample injector, a binary pump system, a sample quantification ring, a sample injection six-way valve (V1), a solid-phase extraction small column, a switching six-way valve (V2), a flow pipeline and a high-resolution mass spectrometer, wherein the solid-phase extraction small column is connected between the sample injection six-way valve (V1) and the switching six-way valve (V2), the binary pump system is connected with the sample injection six-way valve (V1), the switching six-way valve (V2) is connected with the high-resolution mass spectrometer, a sample in the online solid-phase extraction and high-resolution mass spectrometry device sequentially passes through the sample injector, the sample quantification ring, the sample injection six-way valve (V1), the solid-phase extraction small column, the switching six-way valve (V2) and the high-resolution mass spectrometer, and the online solid-phase extraction and high-resolution mass spectrometry device is automatically controlled by a singlechip control system.
In the embodiment of the invention, the step of detecting the sterol hormones in pork by using a device combining online solid-phase extraction and high-resolution mass spectrometry comprises the following steps: in a sample loading state, 250 mu L of sample extracting solution is loaded in a sample quantifying ring by an injector, in the loading state, pure water is pumped for 1 minute at the flow rate of 0.3mL/min, so that the sample in the quantifying ring is automatically loaded to the solid phase extraction small column, the pure water is pumped for 2 minutes at the flow rate of 1.5mL/min, the substrate and impurities adsorbed on the solid phase extraction small column are cleaned, 98% methanol or acetonitrile solvent is pumped for 6 minutes at the flow rate of 0.5mL/min, the sample remained in the extraction small column is eluted, the eluted sample is directly subjected to online high-resolution mass spectrometry, 100% methanol or acetonitrile solvent is pumped at the flow rate of 0.5mL/min, the strong retention impurities adsorbed on the extraction small column are cleaned, and the pure water is pumped for 2 minutes at the flow rate of 1.5mL/min, and the extraction small column is balanced.
In the examples of the present invention, the recovery rate of each type of analyte is S/S0(ii) a S is the peak area detected after the labeled pork sample is subjected to the online solid phase extraction, S0Is the peak area of the solvent spiked sample that was not detected by the on-line solid phase extraction. The average recovery per class is the sum of the recoveries of each analyte in the class and/or the total number of analytes in the class.
Example 1 CNT @ COFTHB-TAPBPreparation of the adsorbent a
100mg of aminated carbon nanotube was mixed with 4mL of dimethyl sulfoxide and 1mL of mesitylene, and the mixture was put into a 30mL glass-sealed tube, and the suspension was stirred at room temperature for 12 hours to form a homogeneous solution. Adding 13.1mg of ligand 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene (THB), carrying out ultrasonic treatment for 1 minute, and stirring at room temperature for 1 hour to obtain the THB modified carbon nanotube homogeneous solution. Adding 10.5 mg ligand 1, 3, 5-tri (4-aminophenyl) benzene (TAPB) and 30 μ L acetic acid respectively under stirring, ultrasonic treating for 1 min, and stirring at room temperature for 1 hr to obtain micro COFTHB-TAPBAnd (3) grain-modified carbon nanotube homogeneous liquid. Adding 52.5mg of ligand THB and 42.1mg of ligand TAPB under stirring, performing ultrasonic treatment for 1 minute, adding 120 μ L of acetic acid, sealing the reaction flask, and reacting at 120 ℃ for 72 hours to obtain black CNT @ COFTHB-TAPBAnd (5) crude product. CNT @ COFTHB-TAPBFiltering the crude product, washing with 10mL of N, N-dimethylformamide and 10mL of methanol respectively, performing Soxhlet extraction with appropriate amount of methanol at 100 deg.C for 12 hr, filtering, and freeze-drying the solid for 12 hr to obtain CNT @ COFTHB-TAPBAnd (3) powder.
Example 2 CNT @ COFTHB-TAPBPreparation of the adsorbent b
80mg of aminated carbon nanotube was mixed with 4mL of dimethyl sulfoxide and 1mL of mesitylene and added to 30mL of glassIn the glass-sealed tube, the suspension was stirred at room temperature for 12 hours to form a homogeneous liquid. Adding 13.1mg of ligand 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene (THB), carrying out ultrasonic treatment for 1 minute, and stirring at room temperature for 1 hour to obtain the THB modified carbon nanotube homogeneous solution. Adding 10.5 mg ligand 1, 3, 5-tri (4-aminophenyl) benzene (TAPB) and 30 μ L acetic acid respectively under stirring, ultrasonic treating for 1 min, and stirring at room temperature for 1 hr to obtain micro COFTHB-TAPBAnd (3) grain-modified carbon nanotube homogeneous liquid. Adding 52.5mg of ligand THB and 42.1mg of ligand TAPB under stirring, performing ultrasonic treatment for 1 minute, adding 120 μ L of acetic acid, sealing the reaction flask, and reacting at 120 ℃ for 72 hours to obtain black CNT @ COFTHB-TAPBAnd (5) crude product. CNT @ COFTHB-TAPBFiltering the crude product, washing with 10mL of N, N-dimethylformamide and 10mL of methanol respectively, performing Soxhlet extraction with appropriate amount of methanol at 100 deg.C for 12 hr, filtering, and freeze-drying the solid for 12 hr to obtain CNT @ COFTHB-TAPBAnd (3) powder.
Example 3 contains CNT @ COFTHB-TAPBDevice for detecting sterol hormones in pork by combining online solid-phase extraction and high-resolution mass spectrometry of adsorbent
(1) 5mg CNT @ COF prepared in example 1THB-TAPBThe adsorbent is filled into a stainless steel hollow column of a solid phase extraction small column to prepare the adsorbent containing CNT @ COFTHB-TAPBAnd (3) a solid phase extraction column of the adsorbent.
(2) 2.0. + -. 0.01g of a sample of pork blank, 10.89mL MeOH/H2O (v/v,1/4) and 110. mu.L of the standard working solution were added to a 50mL centrifuge tube. After vortexing for 5 minutes, it was centrifuged at 9,500rpm for 5 minutes. 10mL of the supernatant was near dry at 45 ℃ with nitrogen, then 1mL MeOH/H2And (8) re-dissolving O (v/v,1/19) to prepare a pork sample extracting solution.
(3) Injecting 250 mu L of pork sample extracting solution into a sample quantitative ring, and using an optimized CNT @ COF-based sampleTHB-TAPBThe method combining the on-line solid phase extraction of the adsorbent and the high-resolution mass spectrometry is used for simultaneously detecting the sterol hormones in 16 parts of pork, and the flow diagram of the detected extracted ion flow is shown in figure 2.
Comparative example 1 detection of sterol hormones in pork by on-line solid phase extraction with other adsorbents and high resolution mass spectrometry
(1) 5mg CNT @ COFTHB-TAPBAdsorbent, 5mg COP adsorbent, 5mg CNT-NH2And respectively filling the adsorbent, the 5mg CNT-COOH adsorbent and the 5mg C18 adsorbent into a stainless steel hollow column of the solid phase extraction column to prepare the solid phase extraction column containing different adsorbents.
(2) The pork extraction is detected by respectively using 6 prepared solid phase extraction small columns and using a device combining online solid phase extraction and high-resolution mass spectrometry, and the device contains CNT @ COFTHB-TAPBThe results of the average recovery rates of sterol hormones such as glucocorticoids, androgens, progestogens and estogens in pork using solid phase extraction columns containing adsorbents and solid phase extraction columns containing other adsorbents are shown in fig. 3, and the results of the average recovery rates of sterol hormones such as glucocorticoids, androgens, progestogens and estogens in pork are obtained by using solid phase extraction columns containing CNTs @ COFTHB-TAPBWhen the online solid-phase extraction and high-resolution mass spectrometry of the solid-phase extraction column of the adsorbent are used for detection, the highest average recovery rate of the four sterol hormones is 82% -98%.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1.CNT@COFTHB-TAPBThe adsorbent is characterized in that the preparation method comprises the following steps:
(1) mixing the aminated carbon nanotube, dimethyl sulfoxide and a solvent a to form a homogeneous liquid a;
(2) mixing 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene with the homogeneous solution to obtain a homogeneous solution b;
(3) mixing 1, 3, 5-tri (4-aminophenyl) benzene with the homogeneous liquid b to obtain a homogeneous liquid c;
(4) mixing 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene, 1, 3, 5-TRIS (4-aminophenyl) benzene and the homogeneous liquid cEncapsulation reaction to CNT @ COFTHB-TAPBAn adsorbent.
The solvent a is selected from one or more of mesitylene, ethanol or 1, 4-dioxane.
2. The CNT @ COF of claim 1THB-TAPBThe adsorbent is characterized in that the mass ratio of the aminated carbon nanotube to the total 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene is 0.5-3: 1.
3. the CNT @ COF of claim 1THB-TAPBThe adsorbent is characterized in that in the step (3), a catalytic amount of acetic acid is added; and/or in step (4), adding a catalytic amount of acetic acid before the sealing reaction.
4. The CNT @ COF of claim 1THB-TAPBThe adsorbent is characterized in that in the step (2) and the step (3), the molar ratio of the 1, 3, 5-TRIS (3 '-formyl-4' -hydroxybenzene) benzene to the 1, 3, 5-tri (4-aminophenyl) benzene is 1: 1; in the step (4), the molar ratio of the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene to the 1, 3, 5-TRIS (4-aminophenyl) benzene is 1: 1.
5. The CNT @ COF of claim 1THB-TAPBThe adsorbent is characterized in that the molar ratio of the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene in the step (2) to the 1, 3, 5-TRIS (3 '-aldehyde-4' -hydroxybenzene) benzene in the step (4) is 1:4-1: 10.
6. CNT @ COF according to any of claims 1-5THB-TAPBAdsorbent, characterized in that the CNT @ COFTHB-TAPBFiltering the adsorbent, washing with N, N-dimethylformamide and methanol, performing Soxhlet extraction with methanol, filtering to obtain solid, and freeze-drying the solid to obtain CNT @ COFTHB-TAPBAn adsorbent powder.
7. A method for detecting a steroid hormone, characterized in thatThe detection method comprises the following steps of detecting by using a solid phase extraction and mass spectrometry device, wherein the solid phase extraction and mass spectrometry device comprises: the device comprises a solid phase extraction column, a sample injector, a binary pump system, a sample quantification ring, a sample injection six-way valve (V1), a solid phase extraction column, a switching six-way valve (V2), a flow pipeline and a mass spectrometer; the solid phase extraction column is connected between the sample injection six-way valve (V1) and the switching six-way valve (V2), the binary pump system is connected with the sample injection six-way valve (V1), and the switching six-way valve (V2) is connected with the mass spectrometer; the solid phase extraction cartridge comprises the CNT @ COF of any one of claims 1 to 6THB-TAPBThe adsorbent is used as a solid phase; the detection method comprises the following steps:
(1) in the sample loading state, a sample extracting solution is loaded in the sample quantifying ring;
(2) in a loading state, the binary pump system pumps 0-10% of methanol and/or acetonitrile solvent at the flow rate of 0.1-1mL/min, so that the sample in the quantitative ring is automatically loaded on the solid phase extraction small column;
(3) in a loading state, the binary pump system pumps 0-20% methanol and/or acetonitrile solvent at a flow rate of 1-2mL/min to clean the sample matrix and impurities loaded on the solid phase extraction column;
(4) in a loading state, the binary pump system pumps 50-100% methanol and/or acetonitrile solvent at a flow rate of 0.3-0.8mL/min to elute a sample retained in the solid phase extraction cartridge;
(5) and (5) carrying out mass spectrum detection on the eluted sample.
8. The detection method according to claim 7, wherein said CNT @ COFTHB-TAPBThe filling amount of the adsorbent is 3-100 mg.
9. The detection method according to claim 7, wherein the device for solid phase extraction and mass spectrometry is automatically controlled by a single-chip microcomputer control system.
10. The CNT @ COF of any of claims 1-6THB-TAPBThe application of the adsorbent in extracting/detecting sterol hormones and analogues thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110850532.4A CN113624866B (en) | 2021-07-27 | 2021-07-27 | CNT@COF THB-TAPB Adsorbent and application thereof in online solid-phase extraction and mass spectrum combined device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110850532.4A CN113624866B (en) | 2021-07-27 | 2021-07-27 | CNT@COF THB-TAPB Adsorbent and application thereof in online solid-phase extraction and mass spectrum combined device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113624866A true CN113624866A (en) | 2021-11-09 |
| CN113624866B CN113624866B (en) | 2023-09-01 |
Family
ID=78381098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110850532.4A Active CN113624866B (en) | 2021-07-27 | 2021-07-27 | CNT@COF THB-TAPB Adsorbent and application thereof in online solid-phase extraction and mass spectrum combined device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113624866B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115290778A (en) * | 2022-07-27 | 2022-11-04 | 山东省分析测试中心 | Method for analyzing and identifying trace glucocorticoid in environmental water body |
| CN115290778B (en) * | 2022-07-27 | 2024-05-31 | 山东省分析测试中心 | Analysis and identification method for trace glucocorticoid in environmental water body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| CN110240705A (en) * | 2019-05-10 | 2019-09-17 | 山东省分析测试中心 | A kind of preparation method and applications of richness nitrogen covalent organic framework material |
| 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 |
| CN113075309A (en) * | 2021-03-12 | 2021-07-06 | 江南大学 | Membrane-protected solid-phase microextraction device and application thereof in detection of estradiol in milk |
-
2021
- 2021-07-27 CN CN202110850532.4A patent/CN113624866B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| CN110240705A (en) * | 2019-05-10 | 2019-09-17 | 山东省分析测试中心 | A kind of preparation method and applications of richness nitrogen covalent organic framework material |
| 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 |
| CN113075309A (en) * | 2021-03-12 | 2021-07-06 | 江南大学 | Membrane-protected solid-phase microextraction device and application thereof in detection of estradiol in milk |
Non-Patent Citations (3)
| Title |
|---|
| XING HAN 等: "Chiral Covalent Organic Frameworks with High Chemical Stability for Heterogeneous Asymmetric Catalysis", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| YUFENG SUN 等: "Three-dimensional electrochemical sensor with covalent organic framework decorated carbon nanotubes signal amplification for the detection of furazolidone", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 明美廷 等: "共价有机骨架材料在样品前处理中的应用", 《分析仪器》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115290778A (en) * | 2022-07-27 | 2022-11-04 | 山东省分析测试中心 | Method for analyzing and identifying trace glucocorticoid in environmental water body |
| CN115290778B (en) * | 2022-07-27 | 2024-05-31 | 山东省分析测试中心 | Analysis and identification method for trace glucocorticoid in environmental water body |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113624866B (en) | 2023-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Determination of tetracyclines in food samples by molecularly imprinted monolithic column coupling with high performance liquid chromatography | |
| Sánchez-González et al. | Porous membrane-protected molecularly imprinted polymer micro-solid-phase extraction for analysis of urinary cocaine and its metabolites using liquid chromatography–Tandem mass spectrometry | |
| Jimmy et al. | β-Cyclodextrin epichlorohydrin copolymer as a solid-phase extraction adsorbent for aromatic compounds in water samples | |
| Wang et al. | Construction of uniformly sized pseudo template imprinted polymers coupled with HPLC–UV for the selective extraction and determination of trace estrogens in chicken tissue samples | |
| CN107262078B (en) | Graphene/silica gel solid phase extraction material and application thereof | |
| Zeng et al. | Molecularly imprinted polymer for selective extraction and simultaneous determination of four tropane alkaloids from Przewalskia tangutica Maxim. fruit extracts using LC-MS/MS | |
| CN114674961A (en) | Kit for synchronously detecting 17 steroid hormones in serum without derivatization and application thereof | |
| Zhang et al. | Development of an aptamer-functionalized capillary monolithic column for the highly-selective and highly-efficient recognition of patulin | |
| Hsieh et al. | Determination of eight penicillin antibiotics in pharmaceuticals, milk and porcine tissues by nano-liquid chromatography | |
| Yang et al. | Study on the molecularly imprinted polymers with methyl-testosterone as the template | |
| CN108623834B (en) | Method for detecting triazine herbicide residue in agricultural products by molecular imprinting-dispersive solid-phase extraction | |
| CN112782328A (en) | Method and kit for detecting catecholamine and metabolites thereof in urine and application of kit | |
| CN113203819B (en) | Method for separating and enriching glucocorticoid based on hydroxylated covalent organic framework material | |
| CN106868622B (en) | Nanofiber capable of being used for detecting tetracycline and preparation and application thereof | |
| CN114324658B (en) | Method for detecting melamine by combining dispersion solid phase extraction and high performance liquid chromatography | |
| Herráez-Hernández et al. | Chiral separation of ephedrines by liquid chromatography using β-cyclodextrins | |
| Tan et al. | Highly sensitive determination of amanita toxins in biological samples using β-cyclodextrin collaborated molecularly imprinted polymers coupled with ultra-high performance liquid chromatography tandem mass spectrometry | |
| Yang et al. | Porous capillary monolithic column coupled with ultrahigh performance liquid chromatography-tandem mass spectrometry for fast and effective separation and determination of estrogens | |
| CN113624866B (en) | CNT@COF THB-TAPB Adsorbent and application thereof in online solid-phase extraction and mass spectrum combined device | |
| Su et al. | Evaluation of diazepam-molecularly imprinted microspheres for the separation of diazepam and its main metabolite from body fluid samples | |
| Zhou et al. | Determination of azithromycin residue in pork using a molecularly imprinted monolithic microcolumn coupled to liquid chromatography with tandem mass spectrometry | |
| Hansson et al. | Sertoli cell function in the androgen insensitive (TFM) rat | |
| Xiao et al. | Sulfonate-bonded covalent organic polymer as mixed-mode sorbent for on-line solid-phase extraction of ß2-receptor agonists | |
| CN113624893B (en) | Cis-trans monodiunsaturated fatty acid methyl ester on-line solid-phase extraction-high performance liquid chromatography combined detection method | |
| CN113929842A (en) | Beauverine magnetic molecularly imprinted material and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |