CN115301216B - High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof - Google Patents
High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof Download PDFInfo
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- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 229910001385 heavy metal Inorganic materials 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 4
- LUGMCBPXVLNBJX-UHFFFAOYSA-N C(C)O.C(=C)[Si](OC)(OC)OC Chemical compound C(C)O.C(=C)[Si](OC)(OC)OC LUGMCBPXVLNBJX-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000005350 fused silica glass Substances 0.000 claims description 4
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 2
- NNTSNLLUPOATCC-UHFFFAOYSA-N 2,3-dimethylterephthalaldehyde Chemical compound CC1=C(C)C(C=O)=CC=C1C=O NNTSNLLUPOATCC-UHFFFAOYSA-N 0.000 claims description 2
- LXIGMDZIEMIPTI-UHFFFAOYSA-N 2,5-bis(prop-2-ynoxy)terephthalaldehyde Chemical compound O=CC1=CC(OCC#C)=C(C=O)C=C1OCC#C LXIGMDZIEMIPTI-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- WERKSKAQRVDLDW-ANOHMWSOSA-N [(2s,3r,4r,5r)-2,3,4,5,6-pentahydroxyhexyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO WERKSKAQRVDLDW-ANOHMWSOSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- -1 cadmium (Cd) Chemical class 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
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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
- B01D15/206—Packing or coating
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3287—Layers in the form of a liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/84—Capillaries
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a high internal phase emulsion polymerization hierarchical porous capillary monolithic column, a preparation method and application thereof, wherein the method comprises the following steps: activating the capillary tube to obtain a pre-activated capillary tube; uniformly mixing glycidyl methacrylate, p-divinylbenzene and toluene to obtain a continuous phase; adding water into anhydrous calcium chloride and potassium peroxodisulfate to carry out ultrasonic dissolution to obtain an internal phase; adding the continuous phase into a surfactant span80, adding the internal phase and the COF-SH under stirring, and stirring to obtain a high internal phase emulsion; and injecting the high internal phase emulsion into the preactivated capillary, sealing two ends of the preactivated capillary, heating at 58-66 ℃ for reaction, and cleaning to obtain the COF-SH loaded hierarchical porous monolithic column. The monolithic column has the advantages of hierarchical porous structure, large specific surface area, high COF-SH accessibility, simple preparation, good reproducibility and large adsorption capacity.
Description
Technical Field
The invention relates to the technical field of separation and analysis detection, in particular to a high internal phase emulsion polymerization hierarchical porous capillary monolithic column, a preparation method and application thereof.
Background
Heavy Metal (HMs) is a group of heavy metals with density of more than 5g cm -3 The elements of (a) include metals such As cadmium (Cd), mercury (Hg), lead (Pb) and the like and metalloid arsenic (As), have the characteristics of high stability, dissolution in atmospheric water and being capable of being absorbed by soil and organisms, and after being released into the environment, the elements are bioaccumulated along a food chain, so that the accumulation of heavy metals in human tissues and organs is aggravated. The concentration of heavy metals in blood and urine can reflect the level of heavy metal exposure, and thus, monitoring the blood and urineHeavy metal levels are of great importance for health risk assessment.
Inductively coupled plasma mass spectrometry (ICP-MS) has the advantages of high sensitivity, wide dynamic range, simultaneous detection capability of multiple elements/isotopes and the like, and has become a powerful means for quantitative analysis of trace elements, however, the direct application of the inductively coupled plasma mass spectrometry (ICP-MS) to analysis of trace elements in biological samples has the problems of insufficient instrument sensitivity, serious matrix effect, multi-atom interference, large sample consumption and the like. Therefore, a miniaturized sample pretreatment strategy is needed to achieve the effects of low sample consumption, high enrichment factor and matrix removal, and a high-sensitivity and high-accuracy analysis method for trace heavy metal elements in biological samples is established.
Capillary micro-extraction has the advantages of simplicity, rapidness, low sample consumption, solvent-free extraction and the like, and has become an emerging direction for miniaturized pre-enrichment of trace analytes. Among them, capillary microextraction based on polymer monolithic columns has the advantages of simple preparation, various selectable monomers, easy modification and the like, and has been widely used for analysis of trace elements. Based on the selective affinity capability between heavy metal and sulfhydryl, the sulfhydryl functional monolithic column prepared by one-step synthesis or post-modification can effectively enrich target heavy metal ions, the extraction performance of the monolithic column is mainly determined by the quantity of modified sulfhydryl groups and accessibility of sulfhydryl sites mediated by pore structures, and the monolithic column of the polymer prepared by free radical polymerization still has the defects of small specific surface area, uneven pore structures and less micropore quantity. The hierarchical porous structure can be obtained by incorporating porous framework materials such as covalent organic framework materials (COFs) having large specific surface areas and ordered microporous structures into the overall structure, and incorporating uniformly well-defined micropores and mesopores into known macropores. This three-mode integration of pores with micropores-mesopores-macropores helps to promote interfacial transport and efficient mass transfer kinetics.
COF is a novel porous material composed of light elements (N, O, B, C, H and Si) and connected by covalent bonds, has the advantages of large surface area, good chemical stability, low density, adjustable pore diameter and the like, and can avoid the problem of poor acid-base stability under the condition of maintaining a hierarchical porous structure when preparing a COF composite polymer monolithic column. However, due to van der Waals force, electrostatic force and the like on the surface of the COF, the COF is easy to agglomerate and settle in the prepolymerization liquid of free radical polymerization, and is uneven in dispersion, so that the preparation of a subsequent monolithic column is affected. Current solutions include vinyl functionalization, prolonged ultrasonic dispersion, and in situ surface modification, however, the above approach is only applicable to specific COFs containing vinyl groups or small particle sizes.
Therefore, there is a need to develop a simple and versatile method for preparing COF composite type hierarchical porous monolithic columns.
Disclosure of Invention
The invention aims to provide a high internal phase emulsion polymerization hierarchical porous capillary monolithic column, a preparation method and application thereof, and the monolithic column has the advantages of hierarchical porous structure, large specific surface area, simple preparation, good reproducibility and large adsorption capacity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention there is provided a method of preparing a high internal phase emulsion polymerization hierarchical porous capillary monolith, the method comprising:
activating the capillary tube to obtain a pre-activated capillary tube;
dispersing COF in DMF solution, adding 1, 2-ethanedithiol, heating to 58-62 ℃ under nitrogen protection, adding initiator AIBN, heating to 78-82 ℃ for reaction, cleaning and freeze-drying after the reaction is completed to obtain orange solid COF-SH;
uniformly mixing glycidyl methacrylate, p-divinylbenzene and toluene to obtain a continuous phase;
adding water into anhydrous calcium chloride and potassium peroxodisulfate to carry out ultrasonic dissolution to obtain an internal phase;
adding the continuous phase into a surfactant span80, adding the internal phase and the COF-SH under stirring, and stirring to obtain a high internal phase emulsion;
and injecting the high internal phase emulsion into the preactivated capillary, sealing two ends of the preactivated capillary, heating at 58-62 ℃ for reaction, and cleaning to obtain the COF-SH loaded hierarchical porous monolithic column.
Further, the activating the capillary tube to obtain a pre-activated capillary tube comprises:
washing fused quartz capillary with ethanol, water and NaOH solution sequentially, washing with HCl solution, washing with ethanol after water is washed to neutrality, filling capillary with 50% (v/v) vinyl trimethoxy silane ethanol solution, sealing both ends, heating at 68-72deg.C for 10-14 hr, washing with ethanol, and washing with N 2 Drying for standby to obtain the preactivated capillary.
Further, the mass volume ratio of the COF to the DMF solution is (8-10) mg/mL, and the volume ratio of the DMF solution to the 1, 2-ethanedithiol is (4-6): 2.
further, the mass ratio of the initiator to the COF is 2: (8-10).
Further, the volume ratio of the glycidyl methacrylate to the p-divinylbenzene to the toluene is 1: (1.5-2): (1-2.5).
Further, the mass ratio of the anhydrous calcium chloride to the potassium peroxodisulfate is 1: (1-2).
Further, the High Internal Phase Emulsion (HIPE) consists of a continuous phase, a surfactant span80 and an internal phase, wherein the volume ratio of the continuous phase, the surfactant span80 and the internal phase is (1-10): (1-2): (30-50) the mass concentration of COF-SH in the HIPE was (10-30) mg/mL.
In a second aspect of the invention there is provided a high internal phase emulsion polymerization fractionation porous capillary monolith obtained by the method described.
In a third aspect of the invention, the application of the high internal phase emulsion polymerization hierarchical porous capillary monolithic column in enriching and detecting heavy metal elements in a sample is provided.
The high internal phase emulsion polymerization grading porous capillary monolithic column is used for online combination analysis with inductively coupled plasma mass spectrometry (ICP-MS), so that online analysis of Cd, hg, pb and other heavy metal elements in human serum and urine is realized.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) In the preparation method of the high internal phase emulsion polymerization grading porous capillary monolithic column, COF particles can be quickly adsorbed to the oil-water interface of emulsion liquid drops, so that the problems that COF is easy to settle in a prepolymer liquid and a complex dispersion solvent system is optimized in the preparation of the COF composite monolithic column can be avoided, modification of the COF is not needed, the preparation method has the advantages of simplicity in operation and easiness in popularization, and the COF adsorbed on the pore wall of a poly (HIPE) polymer has higher accessibility (95%), thereby being beneficial to fully playing the advantage of rich micropore structures of the COF.
(2) The poly (COF-SH-HIPE) monolithic column prepared by the COF-SH with rich sulfhydryl and thioether groups and large specific surface area is selected, has the advantages of hierarchical porous structure, large specific surface area, simple preparation, good reproducibility and large adsorption capacity, and is combined with ICP-MS on line to construct a novel method for analyzing trace heavy metals in biological samples. The established method has the advantages of small sample consumption, low detection limit, strong interference resistance and the like, and is successfully applied to the determination of trace heavy metals in urine samples and serum of healthy people.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the principle of synthesis of the model materials COF-SH and poly (COF-SH-HIPE) monolithic columns prepared in example 1.
FIG. 2 is an X-ray diffraction (XRD) pattern of the model material COF-SH prepared in example 1.
FIG. 3 is an infrared spectrum (IR) diagram of the COF, COF-SH, poly (COF-SH-HIPE) monolith prepared in example 1.
FIG. 4 is an X-ray diffraction (XRD) pattern of poly (COF-SH-HIPE) and poly (HIPE) monolithic capillaries prepared in example 1.
FIG. 5 is a Scanning Electron Microscope (SEM) image of the relevant monolithic column prepared in example 1; wherein FIGS. 5a, 5b, 5c, 5d, 5e, 5f are electron micrographs at 200nm, 500 μm, 200 μm, 20 μm, 5 μm, respectively.
FIG. 6 is a nitrogen adsorption/desorption isotherm (6 a), pore size distribution map (6 b) and thermogravimetric analysis (6 c) of the relevant monolithic column prepared in example 1.
FIG. 7 is an X-ray diffraction (XRD) pattern of poly (COF-SH-HIPE) prepared in example 1, immersed in various solutions for 24 hours.
FIG. 8 is a photograph of the stability of HIPE with other COFs prepared in example 1.
Fig. 9 is a Scanning Electron Microscope (SEM) image of other COF composite monoliths prepared in example 1.
Fig. 10 is an X-ray diffraction (XRD) pattern of other COF composite monoliths prepared in example 1.
FIG. 11 is an optimized graph of pH of a sample solution of poly (COF-SH-HIPE) monolithic column prepared in example 1.
FIG. 12 is an optimized graph of thiourea concentration in a poly (COF-SH-HIPE) monolith eluent prepared in example 1.
FIG. 13 shows HNO in the poly (COF-SH-HIPE) monolith eluent prepared in example 1 3 Optimization graph of concentration.
FIG. 14 is an optimized graph of sample injection flow rate for a poly (COF-SH-HIPE) monolith prepared in example 1.
FIG. 15 is an optimized plot of the elution volume of a poly (COF-SH-HIPE) monolith prepared in example 1.
FIG. 16 is an optimized plot of sample injection volume for a poly (COF-SH-HIPE) monolith prepared in example 1.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, etc., used in the present invention are commercially available or may be obtained by existing methods.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for preparing a high internal phase emulsion polymerization hierarchical porous capillary monolith, the method comprising:
s1, activating a capillary to obtain a pre-activated capillary;
the step S1 specifically includes:
washing fused quartz capillary with ethanol, water and NaOH solution sequentially, washing with HCl solution, washing with ethanol after water is washed to neutrality, filling capillary with 50% (v/v) vinyl trimethoxy silane ethanol solution, sealing both ends, heating at 68-72deg.C for 10-14 hr, washing with ethanol, and washing with N 2 Drying for standby to obtain the preactivated capillary.
S2, dispersing the COF in a DMF solution, then adding 1, 2-ethanedithiol, heating to 58-62 ℃ under the protection of nitrogen, adding an initiator AIBN, heating to 78-82 ℃ for reaction, and cleaning and freeze-drying after the reaction is finished to obtain orange solid COF-SH;
in the step S2 of the above-mentioned process,
the mass volume ratio of the COF to the DMF solution is (8-10) mg/ml, and the volume ratio of the DMF solution to the 1, 2-ethanedithiol is (4-6): 2.
the mass ratio of the initiator to the COF is 2: (8-10).
If the material adding proportion is not proper, the material adding proportion is not in the range, and the sulfhydryl modification of the COF is adversely affected;
s3, uniformly mixing Glycidyl Methacrylate (GMA), p-Divinylbenzene (DVB) and toluene to obtain a continuous phase; the volume ratio of the glycidyl methacrylate to the p-divinylbenzene to the toluene is 1: (1.5-2): (1-2.5).
Adding water into anhydrous calcium chloride and potassium peroxodisulfate to carry out ultrasonic dissolution to obtain an internal phase; the mass ratio of the anhydrous calcium chloride to the potassium peroxodisulfate is 1: (1-2).
Adding the continuous phase into a surfactant span80, adding the internal phase and the COF-SH under stirring, and stirring to obtain a high internal phase emulsion;
the volume ratio of the continuous phase, the surfactant span80 and the internal phase is (1-10): (1-2): (30-50),
the mass-volume ratio of the COF-SH to the COF-SH is (10-30) mg/mL.
The mass ratio, or the volume ratio, is not within the range, and a stable emulsion cannot be formed, adversely affecting the permeability of the whole column.
Preferably, the volume ratio of GMA, DVB, toluene, surfactant span80, internal phase is 20:35:40:23:810. namely, the C9 monolith in Experimental example 2.
S4, injecting the high internal phase emulsion into the preactivated capillary, sealing two ends of the preactivated capillary, and then heating at 58-62 ℃ for reaction and cleaning to obtain the COF-SH loaded hierarchical porous monolithic column.
The principle of the invention is as follows: a strategy for preparing the COF composite polymer monolithic column is constructed by adopting a surfactant sorbitol monooleate (span 80) and a COF particle bistable high internal phase water-in-oil emulsion polymerization method. The COF particles can be quickly adsorbed to the oil-water interface of the emulsion liquid drops, so that the problems that the COF is easy to settle in a prepolymer liquid and the complex dispersion solvent system optimization process are solved when the COF composite monolithic column is prepared, the COF adsorbed on the pore wall of a poly (HIPE) polymer has higher accessibility, and the advantage of rich micropore structures of the COF is fully exerted. And a poly (COF-SH-HIPE) monolithic column prepared from the COF-SH with rich mercapto and thioether groups and large specific surface area is selected, so that the adsorption sites on the surface of the monolithic column are remarkably increased, and the anti-interference capability and adsorption capacity of the monolithic column are improved.
According to another exemplary embodiment of the present invention, there is provided a high internal phase emulsion polymerization graded porous capillary monolith obtained by the method.
According to another exemplary embodiment of the present invention, there is provided the use of the high internal phase emulsion polymerization fractionation porous capillary monolith in the enrichment and detection of heavy metal elements in a sample.
Based on the good adsorption capacity of the high internal phase emulsion polymerization grading porous capillary monolithic column to heavy metal elements, the invention provides a novel method for analyzing heavy metal elements in complex matrix samples by combining the high internal phase emulsion polymerization grading porous capillary monolithic column with inductively coupled plasma mass spectrometry, and the method can realize on-line analysis of Cd, hg and Pb elements in human urine and serum (after digestion). The established method has the advantages of small sample consumption, low detection limit, strong interference resistance and the like, and is successfully applied to the determination of trace heavy metals in urine samples and serum of healthy people.
A high internal phase emulsion polymerization fractionation porous capillary monolith of the present application, and methods of making and using the same, are described in detail below in conjunction with the examples, comparative examples, and experimental data.
Example 1 high internal phase emulsion polymerization fractionation porous capillary monolith and method of making the same
(1) The pre-activation process of the capillary: fused silica capillary (20 cm. Times.530 μm) was used, and the capillary was washed with ethanol and water sequentially for 10min,1mol L -1 Washing with NaOH solution for 10h and 1mol L -1 Washing with HCl solution for 4 hr, washing with ethanol for 1 hr, filling capillary with 50% (v/v) vinyl trimethoxy silane ethanol solution, sealing two ends, heating at 70deg.C for 12 hr, washing with ethanol, and washing with N 2 Blow-drying for standby;
(2) Synthesis of COF-SH: 1,3, 5-tris (4-aminophenyl) benzene (TAPB, 56mg,0.16 mmol), dimethyl terephthalaldehyde (DMTA, 23mg,0.12 mmol) and 2, 5-bis (2-propynyloxy) terephthalaldehyde (BPTA, 29mg,0.12 mmol) were sonicated in 20mL acetonitrile and 1.6mL 12mol L was added -1 After acetic acid solution is mixed for 1min by vortex, standing at room temperature for reaction for 3d, respectively washing with THF and methanol for 3 times, and drying at 60 ℃ to obtain 90mg yellow solid COF, and the yield is 83.3%.90mg of COF is dispersed inAdding 4mL of 1, 2-ethanedithiol into 10mL of DMF solution, heating to 60 ℃ under the protection of nitrogen, adding 20mg of initiator AIBN, heating to 80 ℃, reacting for 5 hours, respectively cleaning with DMF and ethanol for 3 times, and freeze-drying to obtain orange solid COF-SH;
(3) preparation of poly (COF-SH-HIPE) monolith: the different proportions of emulsion polymerization were optimized to achieve the preparation of high internal phase emulsion polymerization monoliths with high COF loading and good permeability using COF particles and surfactant span80 (hlb=4.2) as double emulsion droplet stabilizers. A certain amount of Glycidyl Methacrylate (GMA), p-Divinylbenzene (DVB) and toluene are uniformly mixed to obtain a continuous phase. Anhydrous calcium chloride (72 mg,1%, w/w) and potassium peroxodisulfate (72 mg,1%, w/w) are added into 7.2g of water, the mixture is an internal phase after ultrasonic dissolution, 90 mu L of continuous phase is taken out in a 5mL glass bottle, a certain amount of surfactant span80 is added, 500 mu L of internal phase is added under stirring at 1500rpm, a certain amount of material is added, the rest of internal phase is added, stirring is carried out for 40min at 2500rpm, the obtained High Internal Phase Emulsion (HIPE) is injected into a capillary tube, two ends are sealed and heated at 60 ℃ for reaction for 4h, acetonitrile and water are used for washing after the mixture is taken out, and a graded porous monolithic column with a COF-SH load, which is called a poly (COF-SH-HIPE) monolithic column for short, is obtained.
Comparative example 1
In this comparative example 1, the control monolith, i.e., the non-COF loaded monolith poly (HIPE), was prepared in the same manner as in example 1 except that COF-SH was not added.
Experimental example 1 characterization of the poly (COF-SH-HIPE) monolith obtained in example 1
1. The COF material before modification and the COF-SH material after modification by the firing reaction were characterized by XRD, and the results are shown in fig. 2. As can be seen from fig. 2, diffraction peaks at 2.7, 4.8, 5.6, 7.2, 9.7 and 25.2 ° correspond to (100), (110), (200), (210), (220) and (001) crystal planes, respectively, illustrating successful synthesis of COF. The decrease in the diffraction peak intensity of the mercapto-modified COF characteristic is because the decreased intensity does not reflect the deterioration of crystallinity of the COF backbone itself due to the amorphous nature of the chains attached to the pore walls.
2. For example 1The prepared COF, COF-SH and poly (COF-SH-HIPE) monoliths were infrared characterized and the results are shown in FIG. 3. As can be seen from FIG. 3, 3294 and 2123cm are clearly observed in COF -1 The characteristic absorption peak at the position is a stretching vibration peak of C.ident.C, 1620cm -1 The stretching vibration peak of C=N is observed, when the stretching vibration peak is subjected to click reaction, the alkynyl vibration peak is obviously weakened, and the stretching vibration peak of C=N is observed on a poly (COF-SH-HIPE) monolithic column, so that the COF-SH is successfully introduced into the monolithic column framework.
3. The poly (COF-SH-HIPE) and the poly (HIPE) monolithic column structure of comparative example 1 were characterized by XRD, and the results are shown in FIG. 4. As can be seen from FIG. 4, the poly (HIPE) monolith had one broad peak at only 20℃indicating that the poly (HIPE) monolith was amorphous in structure; poly (COF-SH-HIPE) monoliths were consistent with COF-SH at Jiang Yanshe peaks of 2.7, 4.8, 5.6, 7.2, 9.7 and 25.2℃in addition to the characteristic diffraction peaks with amorphous structure at 20℃indicating successful preparation of poly (COF-SH-HIPE) monoliths.
4. The morphology of the COF, COF-SH and poly (COF-SH-HIPE) monolithic column cross section synthesized at room temperature was characterized by SEM, and as can be seen from fig. 5, the synthesized COF is uniformly spherical, has a rough surface and a particle size of about 400nm, and the morphology of the COF-SH after thiol modification is not significantly changed, is uniformly spherical, and has reduced surface roughness. The monolithic bed was tightly bonded to the inner walls of the capillaries, the bed contained a pore window structure characteristic of a high internal phase emulsion polymerized monolithic material, and semi-embedded COF-SH material was observed on the pore walls, indicating successful fabrication of poly (COF-SH-HIPE) monolithic columns.
5. Characterization of specific surface area, pore size distribution and accessibility of micropores of the synthesized COF-SH, poly (COF-SH-HIPE) and poly (HIPE) monoliths by means of nitrogen adsorption experiment and thermogravimetric analysis experiment (FIG. 6) shows that specific surface areas of the COF-SH, poly (COF-SH-HIPE) and poly (HIPE) monoliths are 858, 377 and 159m, respectively 2 g -1 Pore volumes of 0.42, 0.34 and 0.29cm, respectively 3 g -1 . As can be seen from the pore size distribution, the prepared COF-SH has micro-mesopores of 1.5 and 2.7nm, and also shows COF-SH in a poly (COF-SH-HIPE) monolithic columnIn addition to the characteristic pore size of poly (HIPE) at 20, 37, 50, 68 and 86nm, which is generated during emulsion droplet polymerization, in combination with the pore size of about 1 μm in FIG. 5e, shows that the prepared material has a multi-scale distributed hierarchical porous structure, which helps to facilitate the mass transfer process of extraction. The micropore accessibility of COF-SH in poly (COF-SH-HIPE) was 95% calculated from the thermal weight loss maps of the three materials and the following formula.
Accessibility＝S meartured /S estimated (2)
Wherein S is estimated Is calculated as the weighted sum of the mass percent of COF-SH in a poly (COF-SH-HIPE) monolithic column and the mass percent of poly (HIPE) polymer and the respective specific surface area, S meartured Is a poly (COF-SH-HIPE) monolithic column through N 2 Specific surface area measured by adsorption experiments.
6. Characterization of the thiol content of the prepared poly (COF-SH-HIPE) monolith by UV-Vis spectra and DTNB color reaction revealed that the thiol content of the poly (COF-SH-HIPE) monolith was 0.0064. Mu. Mol cm -1 。
7. To examine the chemical stability of the prepared poly (COF-SH-HIPE) monolith, 10mg of the poly (COF-SH-HIPE) monolith was immersed in 1mol L, respectively -1 HCl、2mol L -1 NaOH and 0.5mol L -1 HNO 3 After 24h of 4% (w/w) thiourea solution, the structural stability was investigated by XRD characterization. As can be seen from FIG. 7, the material maintains its original crystalline structure in strong acid, strong base and desorbent, demonstrating that the poly (COF-SH-HIPE) monolith has good chemical stability.
Experimental example 2 Effect of different Synthesis conditions on high internal phase emulsion polymerization fractionation porous monolithic column poly (COF-SH-HIPE)
Firstly, COF-SH is selected as a model material, and the feasibility of preparing the COF composite monolithic column by high internal phase emulsion polymerization is explored. The preparation of high internal phase emulsion polymerization monoliths with high COF loading and good permeability was investigated using COF particles and surfactant span80 (hlb=4.2) as double emulsion droplet stabilizers, optimizing the different proportions of emulsion polymerization to achieve high internal phase emulsion polymerization monoliths with high COF loading and good permeability, see table 1.
TABLE 1 optimization of HIPEs compositions
As can be seen from table 1, as the COF content increases (C1-2), the permeability of the monolith decreases significantly; as the internal phase increases, the permeability of the monolith increases, and when the internal phase exceeds 90%, stable emulsions (C3, C5) cannot be formed, so the internal phase is preferably 74% to 90% by volume of the total HIPE; increasing the amount of surfactant (C2, C4) helps to improve the permeability of the monolith; increasing the toluene content in the continuous phase, the permeability of the continuous phase is obviously increased (C6-8), reducing the amount of the cross-linking agent DVB is beneficial to improving the permeability (C8-9) of the monolithic column, and finally, C9 is selected as the synthesis proportion of the monolithic column.
Experimental example 3, universality of emulsion polymerization synthetic COF composite hierarchical porous monolithic column
Preparation of other COF composite monoliths (poly (COF-OMe-HIPE), poly (COF-F-HIPE), poly (CTF-1-HIPE)). 200. Mu.L of GMA, 350. Mu.L of DVB and 400. Mu.L of toluene are uniformly mixed, 90. Mu.L of the mixed solution is taken, 22.5. Mu.L of spn80 is added, 500. Mu.L of aqueous phase solution is added under stirring at 1500rpm, 20mg of COF-OMe, 20mg of COF-F and 30mg of CTF-1 material are respectively added, 130. Mu.L of aqueous phase solution (wherein CTF-1 is added into 230. Mu.L of aqueous phase solution) is continuously added, stirring at 2500rpm is carried out for 40min, heating reaction is carried out at 60 ℃ for 4h after sealing the two ends, and acetonitrile and water are used for washing after taking out, thus obtaining poly (COF-OMe-HIPE), poly (COF-HIPE) and poly (CTF-1-HIPE) monolithic columns.
1. As shown in FIG. 8, the COF materials in the different COF materials and span80 stabilized HIPE were uniformly dispersed, and after 2 days of standing, the HIPE did not change significantly, indicating good stability of the HIPE. In the COF composite poly (HIPE) integral material obtained by heating to initiate polymerization, no obvious shrinkage occurs, and the COF in the material is uniformly dispersed and no obvious precipitation exists. This benefits from the HIPE's ability to demulsify or precipitate (because the droplets are tightly packed together, they cannot move up or down, macroscopically assume a semi-solid gel state), and the COF particles can be rapidly adsorbed to the oil-water interface of the emulsified droplets, blocking their precipitation in the prepolymer liquid.
2. HIPE with different COF stability is injected into a capillary monolithic column, heated and polymerized, washed by acetonitrile and water, dried and characterized by SEM. As shown in fig. 9 (d-f), all three columns exhibited pore window structures unique to the high internal phase emulsion polymerization columns, and embedded COF/POF materials could be observed on the pore walls, indicating successful synthesis of the five composite columns.
3. XRD characterization was performed on COF materials and COF composite pillars, and as shown in fig. 10, the crystalline structure of the corresponding COF was shown in each of the COF composite pillars.
The above results demonstrate the versatility of the established Pickering and surfactant bistable HIPE process in preparing COF composite monoliths. Compared with the COF composite monolithic column prepared by free radical polymerization, the method can avoid the problem of uneven COF dispersion caused by easy sedimentation due to poor dispersion of the COF in the prepolymerization liquid in the preparation process of the COF composite monolithic column, does not need to carry out complex dispersion solvent screening and long-time ultrasonic dispersion according to different COFs, and has the advantages of simplicity, rapidness and easy popularization. On the other hand, the span80 is introduced into the water-in-oil HIPE as a co-stabilizer, the COF does not need hydrophilic modification, and the polymerized integral material has better structural mechanical property and does not shrink obviously.
Experimental example 4 optimization of extraction conditions for a Poly (COF-SH-HIPE) monolith
1. Firstly, optimizing the extraction conditions of a poly (COF-SH-HIPE) monolithic column, as shown in fig. 11-16, adopting a single variable method to optimize the extraction conditions one by one, and finally determining the optimal conditions that the pH value of a sample solution is 5 and the loading flow rate is 50 mu L min -1 The sample volume was 0.5mL and the eluent was 0.5mol L of 4% (w/v) thiourea -1 The volume of nitric acid solution, eluent was 50 μl.
2. The effect of common interfering ions (as in table 2) on extraction and detection was examined under optimal conditions.
TABLE 2 tolerant concentration of coexisting ions for use in extraction experiments with poly (COF-SH-HIPE) monoliths
The results in Table 2 show that the method has strong matrix interference resistance and matrix separation capability when carrying out actual sample analysis, and can be used for analyzing trace heavy metal elements in human urine and serum.
3. Reproducibility of the preparation and lifetime of poly (COF-SH-HIPE) monoliths were examined. And 5 monolithic columns in the same batch and 5 monolithic columns in different batches are prepared in total according to the fact that the capillary monolithic columns formed by heating polymerization in the same batch are in the same batch, so as to evaluate the preparation reproducibility. Under the optimal condition, the concentration of the target heavy metal ions is selected to be 2 mu g L -1 The reproducibility of the preparation, expressed as recovery Relative Standard Deviation (RSD), was examined and is shown in table 3.
TABLE 3 reproducibility of preparation of poly (COF-SH-HIPE) monoliths
As shown by the results in Table 3, the batch reproducibility was 2.6 to 4.6%, the batch reproducibility was 5.5 to 10.2%, and the production reproducibility was good. The poly (COF-SH-HIPE) monolith was subjected to extraction analysis of the target element under optimal conditions and regeneration of the column material with 50 μl DTT and 100 μl aqueous solution. On the premise of ensuring quantitative recovery, the same monolithic column can be used for more than 30 times.
4. To examine the adsorption capacity of the poly (COF-SH-HIPE) monolith, the target ion concentration was 1mg L -1 Sequentially flowing through a 2cm long poly (COF-SH-HIPE) monolithic column, taking 1mL of effluent liquid, and measuring and examining the adsorption capacity of the monolithic column to target ions by ICP-MS. The results indicate that poly (COF-SH-HIPE)) The adsorption capacities of the monolithic column for Cd, hg and Pb are 66, 688 and 172 mu g m respectively -1 。
5. For the analytical performance of the method, it is shown in Table 4.
TABLE 4 Performance of CME-ICP-MS analysis of target ions
As can be seen from Table 4, under the optimal experimental conditions, the detection limits of the method on Cd, hg and Pb are 6.1,44.0 and 28.5ng L respectively -1 The relative standard deviation is 4.9-9.2%.
6. The method is used for analyzing urine and serum of healthy people, and the accuracy of the method is verified through a labeled recovery experiment, and the result is shown in table 5.
TABLE 5 detection results and labeled recovery results of target elements in urine and serum of healthy people
As shown in Table 5, three heavy metals in urine and blood are detected, the labeled recovery rate is between 81.5 and 109%, and the labeled recovery rate is good, so that the method can be used for analyzing trace heavy metal elements in complex biological samples.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. A method for preparing a high internal phase emulsion polymerization graded porous capillary monolith, the method comprising:
activating the capillary tube to obtain a pre-activated capillary tube;
56mg of 1,3, 5-tris (4-aminophenyl) benzene, 23mg dimethyl terephthalaldehyde and 29mg of 2, 5-bis (2-propynyloxy) terephthalaldehyde were sonicated in 20mL acetonitrile solution and 1.6mL, 12 mol.L were added -1 Mixing acetic acid solution by vortex for 1min, standing at room temperature for reaction 3d, respectively washing 3 times by THF and methanol, and drying at 60 ℃ to obtain 90mg yellow solid COF;
dispersing the COF in DMF solution, then adding 1, 2-ethanedithiol, heating to 58-62 ℃ under the protection of nitrogen, adding initiator AIBN, heating to 78-82 ℃ for reaction, and cleaning and freeze-drying after the reaction is finished to obtain orange solid COF-SH; the mass volume ratio of the COF to the DMF solution is (8-10) mg/mL, and the volume ratio of the DMF solution to the 1, 2-ethanedithiol is (4-6): 2; the mass ratio of the initiator to the COF is 2: (8-10);
uniformly mixing glycidyl methacrylate, p-divinylbenzene and toluene to obtain a continuous phase; adding water into anhydrous calcium chloride and potassium peroxodisulfate to carry out ultrasonic dissolution to obtain an internal phase; adding the continuous phase into a surfactant span80, adding the internal phase and the COF-SH under stirring, and stirring to obtain a high internal phase emulsion; the volume ratio of the glycidyl methacrylate to the p-divinylbenzene to the toluene is 1: (1.5-2): (1-2.5); the mass ratio of the anhydrous calcium chloride to the potassium peroxodisulfate is 1: (1-2); the high internal phase emulsion HIPE consists of a continuous phase, a surfactant span80 and an internal phase, wherein the volume ratio of the continuous phase to the surfactant span80 to the internal phase is (1-10): (1-2): (30-50) the mass concentration of COF-SH in the HIPE is (10-30) mg/mL;
and injecting the high internal phase emulsion into the preactivated capillary, sealing two ends of the preactivated capillary, heating at 58-62 ℃ for reaction, and cleaning to obtain the COF-SH loaded hierarchical porous monolithic column.
2. The method of preparing a high internal phase emulsion polymerization hierarchical porous capillary monolith according to claim 1, wherein said activating the capillary to obtain a pre-activated capillary comprises:
washing fused quartz capillary with ethanol, water and NaOH solution sequentially, washing with HCl solution, washing with ethanol after water is washed to neutrality, filling capillary with 50% v/v vinyl trimethoxy silane ethanol solution, sealing two ends, heating at 68-72deg.C for 10-14h, washing with ethanol, and washing with N 2 Drying for standby to obtain the preactivated capillary.
3. A high internal phase emulsion polymerization fractionation porous capillary monolith prepared by the method of any one of claims 1-2.
4. Use of the high internal phase emulsion polymerization fractionation porous capillary monolith of claim 3 for enriching and detecting heavy metal elements in a sample.
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