CN114471495A - Covalent organic framework surface functionalized solid phase extraction monolithic column - Google Patents

Covalent organic framework surface functionalized solid phase extraction monolithic column Download PDF

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CN114471495A
CN114471495A CN202210053288.3A CN202210053288A CN114471495A CN 114471495 A CN114471495 A CN 114471495A CN 202210053288 A CN202210053288 A CN 202210053288A CN 114471495 A CN114471495 A CN 114471495A
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organic framework
monolithic column
covalent organic
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CN114471495B (en
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王家斌
孙健
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Fuzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • B01D15/203—Equilibration or regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • B01D15/206—Packing or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres

Abstract

The invention discloses a Covalent Organic Framework (COF) surface functionalized solid-phase extraction monolithic column, which takes a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) monolithic column as a matrix monolithic column, and takes alkaline p-phenylenediamine solution as a functionalizing agent to functionalize the surface of the poly (p-phenylenediamine) fiber; and then, filling the reaction liquid for preparing the imine COF into the monolithic column, taking the poly-p-phenylenediamine fiber as a binding site, and generating COF microspheres on the surface of the monolithic column in situ through Schiff base reaction to prepare the COF microsphere. The invention utilizes a large amount of amino groups on the surface of the poly-p-phenylenediamine fiber to improve the surface coverage rate of COF, can be applied to solid phase (micro) extraction to realize enrichment extraction of medium polarity and nonpolar analysis objects, provides a new way for introducing COF into a monolithic column, and has the advantages of simple and convenient process, easy operation, no need of expensive instruments, easy popularization and wide application range of analysis objects.

Description

Covalent organic framework surface functionalized solid phase extraction monolithic column
Technical Field
The invention belongs to the field of monolithic column preparation, and particularly relates to a covalent organic framework surface functionalized solid phase extraction monolithic column.
Background
The monolithic column is also called a continuous bed, and is a continuous column bed with a porous structure prepared by an in-situ polymerization method in a tube. The monolithic column has a unique network space structure, has the advantages of good permeability, high mass transfer speed, strong mechanical stability, easy chemical modification, good biocompatibility and the like, and is widely applied to the fields of chromatographic separation, sample pretreatment and the like.
Covalent Organic Frameworks (COFs) are novel porous crystalline organic polymers formed by completely covalently connecting light elements, have the advantages of low skeleton density, large specific surface area, high porosity, controllable pore size, functional structure and the like, and are the leading edge of research in the field of material science in recent years. At present, most methods for introducing the covalent organic framework into the monolithic column are physical doping, and no report of the covalent organic framework surface functionalized monolithic column exists. The invention is based on a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column with active epoxy groups on the surface, uses alkaline p-phenylenediamine solution as a functionalization reagent, and realizes the functionalization of the poly-p-phenylenediamine fibers on the surface of the matrix monolithic column through ring-opening reaction and self-polymerization reaction of the p-phenylenediamine which are synchronously generated; and then, filling the reaction solution for preparing the imine COF into the monolithic column, taking the poly-p-phenylenediamine fiber as a binding site, and carrying out Schiff base reaction to generate COF microspheres on the surface of the monolithic column in situ so as to prepare the COF surface functionalized monolithic column. The invention provides a new way for introducing the covalent organic framework into the monolithic column.
Disclosure of Invention
The invention aims to provide a covalent organic framework surface functionalized solid phase extraction monolithic column. The method takes a Poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (Poly (GMA-co-EDMA)) monolithic column as a matrix monolithic column and uses alkaline p-phenylenediamine solution as a functional reagent. Under alkaline conditions, the amino group of p-phenylenediamine can open the epoxy group on the surface of the monolithic column of the matrix and is connected with the matrix through epoxy ring-opening reaction, and meanwhile, oxygen free radical formed by ring opening can initiate the oxidative self-polymerization of the p-phenylenediamine, so that a layer of poly-p-phenylenediamine (PPDA) fiber is formed on the surface of the monolithic column of the matrix. The surface of the poly-p-phenylenediamine fiber contains a large number of amino groups, so that a large number of action sites are provided for the functionalization of the COF on the surface of the monolithic column, and the surface functionalization of the COF is very favorable. And then, filling the mixed solution of the reaction solution for preparing the imine COF and the acetic acid aqueous solution into the monolithic column, taking the PPDA fiber as a binding site, forming chemical linkage between the COF microspheres and the PPDA fiber by utilizing a large amount of amino groups on the surface of the PPDA fiber, and carrying out Schiff base reaction to generate the COF microspheres on the surface of the monolithic column in situ so as to prepare the COF surface functionalized monolithic column. Due to pi-pi stacking effect and hydrophobic interaction between the COF surface functionalized monolithic column and medium polarity and nonpolar analysis objects (such as benzodiazepine compounds), the monolithic column can realize online enrichment and detection of trace medium polarity and nonpolar analysis objects in complex actual samples.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a covalent organic framework surface functionalized solid phase extraction monolithic column, which is prepared by taking a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) monolithic column as a matrix monolithic column, using an alkaline p-phenylenediamine solution as a functionalizing reagent to functionalize poly-p-phenylenediamine fiber on the surface of the monolithic column, filling the monolithic column with a mixed solution of a reaction liquid of an imine covalent organic framework and an acetic acid aqueous solution, and taking the poly-p-phenylenediamine fiber as a binding site to generate covalent organic framework microspheres on the surface of the monolithic column in situ.
Wherein the alkaline p-phenylenediamine solution used as the functionalizing agent is a p-phenylenediamine methanol solution with the concentration of 0.5-3 mol/L, and the alkaline p-phenylenediamine solution contains 0.1-0.5 mol/L of sodium hydroxide.
The imine covalent organic framework is obtained by reacting an amino ligand and an aldehyde ligand, wherein the amino ligand is 1,3, 5-tri (4-aminophenyl) benzene, and the aldehyde ligand is any one of terephthalaldehyde, 2, 5-divinyl-1, 4-benzenedicarboxaldehyde, 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde or 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde.
The invention also provides a preparation method of the covalent organic framework surface functionalized solid phase micro-extraction monolithic column, which comprises the following steps:
1) preparation of poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column: firstly, washing a stainless steel hollow column tube for chromatography for 20 minutes by using methanol, and putting the stainless steel hollow column tube into a 60 ℃ oven for drying for later use; preparing a filler of the matrix monolithic column, wherein the filler consists of 300 mg of glycidyl methacrylate, 100 mg of ethylene glycol dimethacrylate, 480 mg of 1, 4-butanediol, 120 mg of N, N-dimethylformamide and 1.2 mg of azobisisobutyronitrile, uniformly mixing by using a vortex mixer, and performing ultrasonic treatment for 15 minutes; injecting the prepared filler into the stainless steel hollow column tube by using an injector, and putting the stainless steel hollow column tube into a water bath at 60 ℃ for reaction for 24 hours; after the reaction is finished, using methanol as a mobile phase, and washing the stainless steel column for about 1 hour by using a liquid chromatography pump to remove residual pore-foaming agent, unreacted monomers and some oligomers generated by the reaction in the bed layer, thereby obtaining the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column;
2) surface functionalization of poly-p-phenylenediamine fibers: preparing 0.5-3 mol/L alkaline p-phenylenediamine methanol solution (containing 0.1-0.5 mol/L sodium hydroxide), injecting the solution into a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column through a micro injection pump, fully injecting and sealing, and reacting at normal temperature for 24-72 hours; after the reaction is finished, firstly, methanol is used as a mobile phase, a liquid chromatographic pump is used for washing the stainless steel column for about 1-2 hours, and then acetonitrile is used for washing for about 1-2 hours, so that the surface functionalization of the poly-p-phenylenediamine fiber of the matrix monolithic column is finished;
3) preparing a covalent organic framework surface functionalized solid phase extraction monolithic column: taking 0.04 mmol of amino ligand and 0.06 mmol of aldehyde ligand, adding into 5 mL of acetonitrile to prepare covalent organic framework reaction liquid; respectively placing the covalent organic framework reaction solution, 12 mol/L acetic acid aqueous solution and the substrate monolithic column with the surface functionalized into a refrigerator for precooling for 2 hours at 4 ℃, then adding 1.0 mL of the covalent organic framework reaction solution into 30-100 mu L of 12 mol/L acetic acid aqueous solution, uniformly mixing by shaking, injecting the mixture into the substrate monolithic column with the surface functionalized by using a micro-injection pump, and after filling and sealing, placing the substrate monolithic column with the surface functionalized into a 50-80 ℃ water bath for reaction; taking out the column after 1 hour, naturally cooling for about 10 minutes, injecting the mixed solution of the covalent organic framework reaction solution and the acetic acid aqueous solution again from the opposite direction according to the method, filling the solution into the solution, sealing, and then putting the solution into a water bath at 50-80 ℃ for reaction again; repeating the above operation for 3 times; after the last injection is finished, placing the stainless steel column in a water bath at 50-80 ℃ for reaction for 12 hours to ensure that the stainless steel column fully reacts; and after the reaction is finished, washing the stainless steel column for about 2 hours by using acetonitrile as a mobile phase and using a liquid chromatographic pump to obtain the covalent organic framework surface functionalized solid phase extraction monolithic column.
The invention also provides application of the covalent organic framework surface functionalized solid phase micro-extraction monolithic column in enriching and extracting medium-polarity and non-polarity analysis objects.
The invention has the following remarkable advantages:
1) the invention skillfully utilizes a large amount of amino on the surface of the poly-p-phenylenediamine fiber and provides a large amount of reaction sites for the surface functionalization of the covalent organic framework, thereby improving the surface coverage rate of the covalent organic framework and realizing the preparation of the solid-phase microextraction monolithic column with the surface functionalization of the covalent organic framework.
2) In other previous work reporting physical doping of monolithic columns using covalent organic frameworks, the vast majority of COFs were embedded in the monolithic column matrix, resulting in COF performance that was not adequately demonstrated. The COF surface functionalization method provided by the invention can ensure that the COF is on the surface of the integral column, and is beneficial to fully exerting the unique performance of the COF.
3) According to the method, the generation rate of COF is reduced by low temperature and reduction of the amount of the catalyst, so that enough time for filling COF reaction liquid into a column is reserved; the reaction temperature is raised to reduce the particle diameter of the generated COF particles, thereby preventing the COF from blocking the through holes of the substrate material.
4) The invention has simple process, easy operation and no need of expensive instruments.
Drawings
FIG. 1 is a scanning electron microscope image (10000 times magnification) of three monolithic columns during preparation and the corresponding EDAX energy spectrum. Wherein a and d are poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic columns, b and e are poly-p-phenylenediamine fiber surface functionalized monolithic columns, and c and f are covalent organic framework surface functionalized monolithic columns.
FIG. 2 is a Fourier transform infrared spectrum of three monoliths during preparation. Wherein, a is a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column, b is a poly-p-phenylenediamine fiber surface functionalized monolithic column, and c is a covalent organic framework surface functionalized monolithic column.
FIG. 3 is a high performance liquid chromatogram. Wherein a is a chromatographic separation chart for directly detecting a mixture of 6 benzodiazepine novel drugs by using high performance liquid chromatography; b, taking the monolithic column with the functionalized surface of the poly-p-phenylenediamine fiber as a solid phase microextraction monolithic column, constructing an in-tube solid phase microextraction-high performance liquid chromatography online combined system, and detecting a chromatographic separation chart of a 6 benzodiazepine drug mixture; c, constructing an in-tube solid phase microextraction-high performance liquid chromatography on-line combined system by using the covalent organic framework surface functionalized monolithic column as a solid phase microextraction monolithic column, and detecting a chromatographic separation chart of a 6 benzodiazepine novel drug mixture. Sample concentration: 100 ng/mL. Peak identification: 1, nitrazepam; 2, estazolam; 3, oxazepam; 4, triazolam; 5, diazepam; 6, flunitrazepam.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The embodiment provides a preparation method of a covalent organic framework surface functionalized solid phase extraction monolithic column, which specifically comprises the following steps:
1) preparation of poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column: firstly, a stainless steel hollow column tube with the length of 33 mm and the inner diameter of 2.1 mm is washed by methanol for 20 minutes and then is put into a 60 ℃ oven for drying for later use; the preparation filler of the matrix monolithic column consists of 300 mg of glycidyl methacrylate, 100 mg of ethylene glycol dimethacrylate, 480 mg of 1, 4-butanediol, 120 mg of N, N-dimethylformamide and 1.2 mg of azobisisobutyronitrile, and after the mixture is uniformly mixed by a vortex mixer, the mixture is subjected to ultrasonic treatment for 15 minutes at room temperature (the ultrasonic frequency is 40 kHz, and the ultrasonic power is 100W); injecting the prepared filler into the stainless steel column by using an injector, and putting the stainless steel column into a water bath at 60 ℃ for reaction for 24 hours; after the reaction is finished, using methanol as a mobile phase, and washing the stainless steel column for about 1 hour by using a liquid chromatography pump to remove residual pore-foaming agent, unreacted monomers and some oligomers generated by the reaction in the bed layer, thereby obtaining the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column;
table 1 partial schemes selected for the preparative procedures
Figure 344335DEST_PATH_IMAGE001
2) Surface functionalization of poly-p-phenylenediamine fibers: weighing corresponding p-phenylenediamine and sodium hydroxide according to the table 1, adding 20 mL of methanol, uniformly oscillating by using a vortex mixer, and performing ultrasonic treatment at room temperature for about 20 minutes (the ultrasonic frequency is 40 kHz, and the ultrasonic power is 100W) to obtain the alkaline p-phenylenediamine methanol solution with the corresponding concentration. Injecting alkaline p-phenylenediamine methanol solution into a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column through a micro-injection pump, and reacting at normal temperature after full injection and sealing, wherein the corresponding reaction time is shown in table 1; after the reaction is finished, firstly, methanol is used as a mobile phase, a liquid chromatographic pump is used for washing the stainless steel column for about 2 hours, and then acetonitrile is used for washing for about 2 hours, so that the surface functionalization of the poly-p-phenylenediamine fiber of the matrix monolithic column is finished;
3) preparing a covalent organic framework surface functionalized solid phase extraction monolithic column: 14.06 mg of 1,3, 5-tris (4-aminophenyl) benzene (TAPB) and 11.17 mg of 2, 5-divinyl-1, 4-benzenedicarboxaldehyde (DVA) were added to 5 mL of acetonitrile to prepare a covalent organic framework reaction solution; respectively placing the covalent organic framework reaction liquid, 12 mol/L acetic acid aqueous solution and the substrate monolithic column with surface functionalization completed in the step 2) into a refrigerator for precooling for 2 hours at 4 ℃, then taking 1.0 mL of the covalent organic framework reaction liquid, adding a corresponding amount of 12 mol/L acetic acid aqueous solution according to the table 1, shaking and uniformly mixing, injecting the covalent organic framework reaction liquid into the substrate monolithic column with surface functionalization completed by using a micro-injection pump, fully injecting and sealing, and then placing into a water bath for reaction, wherein the water bath temperature is shown in the table 1; taking out the column after 1 hour, naturally cooling for about 10 minutes, injecting the mixed solution of the covalent organic framework reaction solution and the acetic acid aqueous solution again from the opposite direction according to the method, filling the solution into the water bath for reaction after sealing; repeating the above operation 3 times; after the last injection, the stainless steel column is placed in the water bath for reaction for 12 hours, so that the stainless steel column is fully reacted; and after the reaction is finished, washing the stainless steel column for about 2 hours by using acetonitrile as a mobile phase and using a liquid chromatography pump to obtain the covalent organic framework surface functionalized solid phase extraction monolithic column.
Application example 1
According to the specific embodiment and scheme B in Table 1, a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column, a poly-p-phenylenediamine fiber surface functionalized monolithic column and a covalent organic framework surface functionalized monolithic column are prepared, and scanning electron microscope test and energy spectrum analysis are respectively carried out. As shown in FIGS. 1a-c, the surface of the monolithic column (a) of the matrix has an irregular blocky structure; the surface of the monolithic column (b) is provided with slender filaments after the surface of the poly-p-phenylenediamine fiber is functionalized, and the poly-p-phenylenediamine fibers are generated by the self-polymerization reaction of the p-phenylenediamine on the surface of the monolithic column of the matrix under the alkaline condition, so that the successful functionalization of the surface of the matrix by the poly-p-phenylenediamine fibers is proved; the surface of the covalent organic framework surface functionalized monolithic column (c) is covered with a large amount of spheroidal polymers with the particle size of about 600 nm, which shows that the covalent organic framework microspheres almost completely cover the surface of the monolithic column through the combination of the poly-p-phenylenediamine fibers.
As shown in FIGS. 1d-f, the matrix monolith (d) showed only two elements of C, O (the appearance of Au element is caused by gold spraying); the signal of N element is also added in the integral column (e) after the surface of the poly-p-phenylenediamine fiber is functionalized, thereby further proving that the surface of the substrate is successfully derived by the poly-p-phenylenediamine fiber, wherein the Na element is generated because residual NaOH in the sample is not completely removed; the signal of the C element is obviously enhanced in the covalent organic framework surface functionalized monolithic column (f), which is because the high carbon content covalent organic framework functionalization improves the total carbon element content of the monolithic column.
Application example 2
According to the specific embodiment and scheme A in Table 1, a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column, a poly-p-phenylenediamine fiber surface functionalized monolithic column and a covalent organic framework surface functionalized monolithic column are prepared, and Fourier transform infrared spectroscopy tests are respectively carried out. As shown in FIG. 2, the infrared spectrum (a) of the monolithic column for the matrix was 1050 cm-1The absorption peak appeared at the position is attributed to the stretching vibration of the C-O-C bond in the epoxy group, and is at 901 cm-1The absorption peak is attributed to the vibration of an epoxy group ring, which proves the successful synthesis of the matrix material, and the infrared spectrum (b, c) of the monolithic column after the two-step functionalization does not have the two absorption peaks, which indicates that the epoxy groups almost completely participate in the functionalization reaction; the infrared spectrum (b) of the monolithic column after the surface functionalization of the poly-p-phenylenediamine fiber is 1607 cm-1The absorption peak is attributed to the N-H stretching vibration of the aromatic amine, but the absorption peak hardly appears in the infrared spectrum (c) of the covalent organic framework surface functionalized monolithic column, because the aromatic amine on the poly-p-phenylenediamine fiber almost completely participates in the functionalization of the covalent organic framework; the infrared spectrum (b) of the monolithic column after the surface functionalization of the poly-p-phenylenediamine fiber and the infrared spectrum (c) of the covalent organic framework surface functionalized monolithic column are 1527 cm-1The absorption peak is attributed to the stretching vibration of C = C on the benzene ring, which proves that the poly-p-phenylenediamine fiber and the covalent organic framework are successfully introduced into the matrix monolithic column.
Application example 3
Preparing a surface functionalized monolithic column of poly-p-phenylenediamine fibers and a surface functionalized solid-phase microextraction monolithic column of a covalent organic framework according to the specific embodiment and scheme F In Table 1, taking the two monolithic columns as the solid-phase microextraction monolithic columns, combining an In-tube solid-phase microextraction-high performance liquid chromatography (In-tube SPME-HPLC) combined system (patent number: CN 107290455B), constructing an In-tube solid-phase microextraction-high performance liquid chromatography online combined system, and inspecting the solid-phase microextraction of 6 benzodiazepine drug mixtures (nitrazepam, estazolam, oxazepam, triazolam, diazepam and flunitrazepam) of 100 ng/mL, and directly comparing the solid-phase microextraction with a high performance liquid chromatography detection method.
The specific separation conditions are as follows: sample carrying liquid composition: acetonitrile/water =10%/90% (v/v); sample solvent: acetonitrile/water =10%/90% (v/v); sample introduction flow rate: 0.05 mL/min; sample introduction volume: 500 mu L of the solution; the eluent composition is as follows: acetonitrile/0.1% trifluoroacetic acid =60%/40% (v/v); elution flow rate: 0.1 mL/min; elution volume: 250 mu L; separating a mobile phase: acetonitrile/0.1% trifluoroacetic acid =60%/40% (v/v); separation flow rate: 1.0 mL/min; temperature of the column oven: 40 ℃; detection wavelength: 229 nm.
As shown in FIG. 3, when the detection was performed directly by HPLC (curve a), the detection intensities of the 6 substances were all low; when the monolithic column with functionalized poly-p-phenylenediamine fiber surface is used as a solid phase micro extraction monolithic column (curve b), the detection peak intensity is enhanced to a certain extent, but the interference peak is also enhanced to a certain extent, which shows that the poly-p-phenylenediamine fiber has certain enrichment to the benzodiazepine compounds, but the enrichment capacity is not outstanding due to the strong polarity of a large amount of amino groups on the surface of the poly-p-phenylenediamine fiber; when the covalent organic framework surface functionalized monolithic column is used as a solid phase micro-extraction monolithic column (curve c), the detection intensity is further enhanced, and the interference peak intensity is lower, which shows that the covalent organic framework shows obvious enrichment capacity to benzodiazepine compounds, and in addition, the covalent organic framework also shows excellent purification capacity.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (5)

1. A covalent organic framework surface functionalized solid phase extraction monolithic column is characterized in that: the integral column is characterized in that a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) integral column is used as a matrix integral column, alkaline p-phenylenediamine solution is used as a functionalization reagent to functionalize poly-p-phenylenediamine fiber on the surface of the integral column, then mixed liquid of reaction liquid of an imine covalent organic framework and acetic acid aqueous solution is filled in the integral column, poly-p-phenylenediamine fiber is used as a binding site, covalent organic framework microspheres are generated on the surface of the integral column in situ, and the covalent organic framework surface functionalized integral column is prepared.
2. The covalent organic framework surface functionalized solid phase extraction monolithic column of claim 1, wherein: the alkaline p-phenylenediamine solution used as the functionalizing agent is a p-phenylenediamine methanol solution of 0.5-3 mol/L, and the alkaline p-phenylenediamine solution contains 0.1-0.5 mol/L of sodium hydroxide.
3. The covalent organic framework surface functionalized solid phase extraction monolithic column of claim 1, wherein: the imine covalent organic framework is obtained by reacting an amino ligand and an aldehyde ligand, wherein the amino ligand is 1,3, 5-tri (4-aminophenyl) benzene, and the aldehyde ligand is any one of terephthalaldehyde, 2, 5-divinyl-1, 4-benzenedicarboxaldehyde, 2, 5-dihydroxy-1, 4-benzenedicarboxaldehyde or 2, 5-dimethoxy-1, 4-benzenedicarboxaldehyde.
4. A method of preparing a covalent organic framework surface functionalized solid phase extraction monolithic column of claim 1, wherein: the preparation process comprises the following steps:
1) preparation of poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column: firstly, washing a stainless steel hollow column tube for chromatography for 20 minutes by using methanol, and putting the stainless steel hollow column tube into a 60 ℃ oven for drying for later use; preparing a filler for the matrix monolithic column, wherein the filler consists of 300 mg of glycidyl methacrylate, 100 mg of ethylene glycol dimethacrylate, 480 mg of 1, 4-butanediol, 120 mg of N, N-dimethylformamide and 1.2 mg of azobisisobutyronitrile, uniformly mixing the components by using a vortex mixer, performing ultrasonic treatment for 15 minutes, injecting the prepared filler into the stainless steel hollow column tube by using an injector, and placing the stainless steel hollow column tube into a water bath at 60 ℃ for reaction for 24 hours; after the reaction is finished, using methanol as a mobile phase, and washing the stainless steel column for about 1 hour by using a liquid chromatography pump to remove residual pore-foaming agent, unreacted monomers and some oligomers generated by the reaction in the bed layer, thereby obtaining the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) matrix monolithic column;
2) surface functionalization of poly-p-phenylenediamine fibers: preparing alkaline p-phenylenediamine solution, injecting the solution into a poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) substrate monolithic column through a micro-injection pump, fully injecting and sealing, and reacting at normal temperature for 24-72 hours; after the reaction is finished, firstly, methanol is used as a mobile phase, a liquid chromatographic pump is used for washing the stainless steel column for about 1-2 hours, and then the mobile phase is replaced by acetonitrile for washing for about 1-2 hours, so that the surface functionalization of the poly-p-phenylenediamine fiber of the matrix monolithic column is finished;
3) preparing a covalent organic framework surface functionalized solid phase extraction monolithic column: taking 0.04 mmol of amino ligand and 0.06 mmol of aldehyde ligand, adding into 5 mL of acetonitrile to prepare covalent organic framework reaction liquid; respectively placing the prepared covalent organic framework reaction liquid, 12 mol/L acetic acid aqueous solution and the substrate monolithic column with the surface functionalized at 4 ℃ for precooling for 2 hours, then adding 1.0 mL of the covalent organic framework reaction liquid into 30-100 mu L of 12 mol/L acetic acid aqueous solution, uniformly mixing by shaking, injecting the mixture into the substrate monolithic column with the surface functionalized by using a micro-injection pump, filling and sealing, and then placing the mixture into a water bath with 50-80 ℃ for reaction; taking out the column after 1 hour, naturally cooling for about 10 minutes, injecting the mixed solution of the covalent organic framework reaction solution and the acetic acid aqueous solution again from the opposite direction according to the method, filling the solution into the solution, sealing, and then putting the solution into a water bath at 50-80 ℃ for reaction again; repeating the above operation for 3 times; after the last injection is finished, placing the stainless steel column in a water bath at 50-80 ℃ for reaction for 12 hours to ensure that the stainless steel column fully reacts; and after the reaction is finished, washing the stainless steel column for about 2 hours by using acetonitrile as a mobile phase and using a liquid chromatography pump to obtain the covalent organic framework surface functionalized solid phase extraction monolithic column.
5. Use of the covalent organic framework surface functionalized solid phase extraction monolithic column of claim 1, wherein: the covalent organic framework surface functionalized solid phase extraction monolithic column is applied to enrichment extraction of medium polarity and nonpolar analysis objects.
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