CN111621018A - Boron affinity molecular imprinting mesoporous polymer based on Mn-doped ZnS quantum dots and preparation method and application thereof - Google Patents
Boron affinity molecular imprinting mesoporous polymer based on Mn-doped ZnS quantum dots and preparation method and application thereof Download PDFInfo
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- CN111621018A CN111621018A CN202010506090.7A CN202010506090A CN111621018A CN 111621018 A CN111621018 A CN 111621018A CN 202010506090 A CN202010506090 A CN 202010506090A CN 111621018 A CN111621018 A CN 111621018A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 48
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SQVRNKJHWKZAKO-UHFFFAOYSA-N beta-N-Acetyl-D-neuraminic acid Natural products CC(=O)NC1C(O)CC(O)(C(O)=O)OC1C(O)C(O)CO SQVRNKJHWKZAKO-UHFFFAOYSA-N 0.000 claims abstract description 95
- SQVRNKJHWKZAKO-OQPLDHBCSA-N sialic acid Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@](O)(C(O)=O)OC1[C@H](O)[C@H](O)CO SQVRNKJHWKZAKO-OQPLDHBCSA-N 0.000 claims abstract description 94
- 239000000178 monomer Substances 0.000 claims abstract description 43
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 62
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- AUVSUPMVIZXUOG-UHFFFAOYSA-N (4-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(S)C=C1 AUVSUPMVIZXUOG-UHFFFAOYSA-N 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
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- 238000007664 blowing Methods 0.000 claims description 3
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- 239000012535 impurity Substances 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 abstract description 73
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000004005 microsphere Substances 0.000 description 27
- 239000011148 porous material Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
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- 238000012512 characterization method Methods 0.000 description 9
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- 239000000523 sample Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000012650 click reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
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- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012525 sialic acid detection Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- SQVRNKJHWKZAKO-PFQGKNLYSA-N N-acetyl-beta-neuraminic acid Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@](O)(C(O)=O)O[C@H]1[C@H](O)[C@H](O)CO SQVRNKJHWKZAKO-PFQGKNLYSA-N 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a boron affinity molecular imprinting mesoporous polymer based on Mn-doped ZnS quantum dots, which comprises a boric acid functionalized siloxane monomer and Mn-doped ZnS quantum dots modified by 3-mercaptopropionic acid, wherein the boric acid functionalized siloxane monomer is provided with a cavity formed by sialic acid. The invention also discloses a preparation method and application thereof, and a method for detecting sialic acid. The molecularly imprinted polymer provided by the invention has specific recognition capability on sialic acid, has good adsorption performance, and can accurately, sensitively and effectively detect sialic acid.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a boron affinity molecular imprinting mesoporous polymer based on Mn-doped ZnS quantum dots, and a preparation method and application thereof.
Background
Sialic Acid (SA), also known as N-acetylneuraminic acid, is a naturally occurring 9-carbon monosaccharide derivative. Sialic acid is usually present in the form of oligosaccharides, glycoproteins or glycolipids, the main food sources of which are breast milk, milk powder and cow milk. It has been shown that sialic acid may be involved in cell differentiation, proliferation and canceration, and may also be an important causative factor in bacterial and viral infections, and is closely related to human health and disease. The existing methods for detecting sialic acid include spectroscopic analysis, liquid chromatography, gas chromatography, amperometry, electrophoresis and the like. The above methods require precise instruments, expensive reagents and specialized operating techniques. There is a need to establish a simple, fast and low cost detection method.
The molecular imprinting technique is a technique of polymerizing a certain template molecule and a monomer having an appropriate functional group in different ways to prepare a polymer that is perfectly matched with the certain molecule in spatial structure and binding site and can specifically recognize the template molecule, and the prepared macromolecular compound is called a Molecularly Imprinted Polymer (MIP). The imprinting sites in the molecularly imprinted polymer have a memory function, can selectively adsorb template molecules, and realizes the separation and purification processes of the template molecules. The prepared molecularly imprinted polymer has the characteristics of acid and alkali resistance, high temperature, high pressure, long service life, easiness in storage, low cost and the like, is widely applied to aspects of solid-phase extraction, catalysis, organic synthesis and the like, and is a reliable means for solving the problem of high-selectivity identification of specific target molecules in complex systems such as environment, biology and the like.
Disclosure of Invention
The invention aims to overcome the defects of long determination time, complex pretreatment and low determination accuracy of the traditional determination method, and aims to prepare a molecularly imprinted material capable of accurately and efficiently identifying sialic acid, and apply the molecularly imprinted material to analysis, detection, separation and purification of sialic acid.
The invention also aims to provide a preparation method of the molecular imprinting material.
It is a further object of the present invention to provide a method for detecting sialic acid.
In order to achieve the above object, the present invention provides a boron affinity molecularly imprinted mesoporous polymer based on Mn-doped ZnS quantum dots, which comprises a boronic acid functionalized siloxane monomer having a hole formed by sialic acid thereon and a Mn-doped ZnS quantum dot modified with 3-mercaptopropionic acid.
The invention also provides a preparation method of the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots, which comprises the following steps:
step 1: synthesizing a boric acid functionalized siloxane monomer;
step 2: synthesizing Mn-doped ZnS quantum dots modified by 3-mercaptopropionic acid;
and step 3: synthesizing the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots.
According to the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots, the Mn-doped ZnS quantum dots are used as signal elements, sialic acid is used as template molecules, a boric acid functionalized siloxane monomer with sialic acid recognition capability is synthesized based on sulfydryl-alkenyl click reaction and used as a functional monomer, and the molecular imprinting polymer with a highly ordered mesoporous structure is synthesized by a one-step hydrothermal method.
Preferably, the step 1 is as follows: adding 248.35 mu L of silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane into 0.1540g of 4-mercaptophenylboronic acid, adding 5mL of methanol to dissolve the silane coupling agent, dropwise adding triethylamine to enable the pH value of the solution to be 8, introducing nitrogen, heating in a water bath, enabling the solution to be 60 ℃, stirring to react for 2 hours, and after the reaction is finished, carrying out nitrogen blowing concentration on the solution until solid is separated out to obtain the boric acid functionalized siloxane monomer.
Preferably, the step 2 is as follows: fully mixing 50mL of 0.04 mol/L3-mercaptopropionic acid, 1mL of 0.01mol/L manganese chloride solution and 2.5mL of 0.1mol/L zinc sulfide solution, dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of the solution to 10, stirring uniformly at room temperature, introducing nitrogen to saturate for 30min, and ensuring that the stabilizing agents of 3-mercaptopropionic acid and Zn are2+、Mn2+Fully complexing, then injecting 2.5mL of 0.1mol/L sodium sulfide solution under the condition of air isolation, continuing to react for 20min at room temperature to obtain a 3-mercaptopropionic acid modified Mn doped ZnS quantum dot solution, then exposing to the air, aging for 4h at 50 ℃, using equal volume of absolute ethyl alcohol to enable quantum dots to settle, centrifuging, and decanting a supernatant to obtain the 3-mercaptopropionic acid modified Mn doped ZnS quantum dot.
Preferably, the step 3 is as follows: dissolving 0.0310g of template molecule sialic acid in 5mL of methanol solution, adding 2mL of aqueous solution containing 0.2mmol of boric acid functional siloxane monomer, magnetically stirring at room temperature for 2h to form a template molecule and functional monomer mixed solution, adding 100mL of deionized water into 0.2g of surfactant cetyl trimethyl ammonium bromide to dissolve the solution, dropwise adding 2mol/L of sodium hydroxide solution to adjust the pH of the solution to 10, magnetically stirring, heating to 80 ℃, dropwise adding 1mL of cross-linking agent tetraethyl silicate, the template molecule and functional monomer mixed solution and 2mL of 3-mercaptopropionic acid modified Mn doped ZnS quantum dot solution, continuing to react at 80 ℃ for 72h, cooling the solution to room temperature after the reaction is finished, centrifuging, removing supernatant, adding ethanol, ultrasonically cleaning, removing unreacted impurities, centrifuging, discarding supernatant, and (2) vacuum drying at 40 ℃, then taking 85% v/v acetonitrile/water solution as an eluent, ultrasonically cleaning, centrifuging, discarding the supernatant, removing sialic acid and a surfactant CTAB in the compound, and vacuum drying at 40 ℃ for 24h to obtain a solid product, namely the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots.
The invention also provides application of the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots to sialic acid detection.
The invention also provides a method for detecting sialic acid, comprising the steps of: and mixing the aqueous solution of the boron affinity molecular imprinting mesoporous polymer with sialic acid, and comparing the change of fluorescence intensity before and after mixing.
The preparation method combines the advantages of high selectivity and specificity of a molecular imprinting technology, high specific surface area of a mesoporous material, excellent optical performance of quantum dots and the like, selects Mn-doped ZnS quantum dots as signal elements, takes cis-dihydroxy compound sialic acid as template molecules, synthesizes boric acid functionalized siloxane monomers (KH-4-MAPB) with sialic acid recognition capacity as functional monomers based on sulfydryl-alkenyl click reaction, synthesizes a molecular imprinting polymer with a highly ordered mesoporous structure by adopting a one-step hydrothermal method, and researches the structure and the fluorescence performance of the prepared fluorescent molecular imprinting polymer.
In particular, the Mn-doped ZnS quantum dot with good luminescence effect and stable property is synthesized by taking MPA as a stabilizer and adopting a coprecipitation method in a water phase, and has strong orange fluorescence emission. Based on sulfydryl-alkenyl click reaction, a silane coupling agent KH-570 and 4-sulfydryl phenylboronic acid are combined to react to generate a boric acid functionalized siloxane monomer, the boric acid functionalized siloxane monomer is used as a functional monomer, a one-step hydrothermal method is adopted, the boric acid functionalized siloxane monomer reacts with template molecule sialic acid, Mn-doped ZnS quantum dots, a structure directing agent CTAB and a cross-linking agent TEOS together, methanol is used as a solvent, the boric acid affinity molecularly imprinted mesoporous polymer based on the Mn-doped ZnS quantum dots is synthesized, and the boric acid affinity molecularly imprinted mesoporous polymer is used as a fluorescence sensor to characterize the structure and fluorescence performance.
The structure and the morphology of the molecularly imprinted polymer are characterized by Fourier transform infrared spectroscopy (FT-IR), small-angle X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TGA) and nitrogen adsorption-desorption experiments, and the experimental results show that the prepared molecularly imprinted polymer has a highly ordered mesoporous structure and a large number of imprinted holes, so that the specific selectivity of the molecularly imprinted polymer is ensured.
Through fluorescence spectrum, equilibrium adsorption kinetics experiments and the exploration of imprinting performance under different pH conditions, the fluorescence performance of the molecularly imprinted polymer is characterized and analyzed, and experimental results show that when template molecule sialic acid is captured by the molecularly imprinted polymer, fluorescence quenching is successfully caused, and the sialic acid concentration is 1.25-100 × 10-2The fluorescence quenching degree of the molecularly imprinted polymer at the time of mu g/L shows a good linear relationship with sialic acid. The molecularly imprinted polymer has higher recognition capability on sialic acid.
In conclusion, the molecularly imprinted polymer provided by the invention has specific recognition capability on sialic acid, has good adsorption performance, and has good application prospect in the fields of sialic acid detection, separation and purification.
Drawings
FIG. 1 is a schematic diagram of the synthesis of boronic acid functionalized siloxane monomers.
FIG. 2 is a schematic diagram of a preparation process of sialic acid imprinted mesoporous silica Microspheres (MIPs).
FIG. 3 is a Fourier infrared absorption spectrum of a boronic acid functionalized siloxane monomer.
Fig. 4 is a fourier infrared absorption spectrum of sialic acid imprinted mesoporous silica Microspheres (MIPs) before and after elution.
Fig. 5 is a fourier infrared absorption spectrum of sialic acid imprinted mesoporous silica Microspheres (MIP) and non-imprinted mesoporous silica microspheres (NIP).
Figure 6 is a small angle XRD diffractogram of sialic acid imprinted mesoporous silica Microspheres (MIPs).
Fig. 7 is a TEM image of sialic acid imprinted mesoporous silica Microspheres (MIPs).
FIG. 8 is a thermogravimetric analysis curve of MCM-41 and sialic acid imprinted mesoporous silica Microspheres (MIPs).
Fig. 9 is a nitrogen adsorption-desorption curve of sialic acid imprinted mesoporous silica Microspheres (MIPs).
Fig. 10 is a pore size distribution of sialic acid imprinted mesoporous silica Microspheres (MIPs).
FIG. 11 is fluorescence emission spectra of sialic acid imprinted mesoporous silica Microspheres (MIPs) at different concentrations of sialic acid.
FIG. 12 is a fluorescence emission spectrum of non-imprinted mesoporous silica microspheres (NIPs) at different concentrations of sialic acid.
FIG. 13 shows fluorescence quenching values (F) of sialic acid imprinted mesoporous silica Microspheres (MIP) system0/F-1) is plotted linearly against sialic acid concentration.
FIG. 14 shows fluorescence quenching values (F) of non-imprinted mesoporous silica microspheres (NIP) system0/F-1) is plotted linearly against sialic acid concentration.
Fig. 15 is a graph showing the dynamic adsorption of sialic acid by sialic acid imprinted mesoporous silica Microspheres (MIPs) and non-imprinted mesoporous silica microspheres (NIPs).
FIG. 16 shows the effect of solution pH on sialic acid assay on sialic acid imprinted mesoporous silica Microspheres (MIP) and non-imprinted mesoporous silica microspheres (NIP).
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative of the present invention only, and are not intended to limit the scope of the present invention.
Example 1: synthesis of boronic acid functionalized siloxane monomer (KH-4-MAPB)
0.1540g of 4-mercaptophenylboronic acid (4-MAPB) was weighed into a 10mL round-bottomed flask, 248.35. mu.L of 3- (methacryloyloxy) propyltrimethoxysilane (KH-570) as a silane coupling agent was added, and 5mL of methanol was added thereto and dissolved. Triethylamine was added dropwise to bring the pH of the solution to about 8. Introducing nitrogen, heating in water bath at 60 deg.C, and stirring for 2 hr. After the reaction is finished, the solution is concentrated by blowing nitrogen until a small amount of solid is separated out to obtain boric acid functionalized siloxane monomer (KH-4-MAPB), and the boric acid functionalized siloxane monomer is stored in a refrigerator at 4 ℃ for later use.
FIG. 1 is a schematic diagram of the synthesis of boronic acid functionalized siloxane monomers.
Example 2: synthesis of Mn-doped ZnS quantum dot modified by 3-mercaptopropionic acid
50mL of 0.04mol/L flask is added into a 250mL three-neck flask in sequence3-mercaptopropionic acid (MPA), 1mL of a 0.01mol/L manganese chloride solution and 2.5mL of a 0.1mol/L zinc sulfide solution, the three solutions being mixed thoroughly. Dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of the solution to 10, magnetically stirring the solution at room temperature, introducing nitrogen to saturate the solution for 30min, and ensuring that the stabilizing agents 3-mercaptopropionic acid and Zn are added2+、Mn2+And (4) fully complexing. Then 2.5mL of 0.1mol/L sodium sulfide solution was injected with a syringe under air exclusion. And continuously reacting for 20min at room temperature to obtain the Mn-doped ZnS quantum dot solution modified by 3-mercaptopropionic acid. Followed by exposure to air and aging at 50 ℃ for 4 h. The quantum dots were allowed to settle using an equal volume of absolute ethanol, centrifuged at high speed, and the supernatant decanted, repeated several times. Storing at 4 deg.C in dark for use.
Example 3: synthesis of molecular imprinting mesoporous Microsphere (MIP) with mesoporous structure
0.0310g (0.1mmol) of template molecule Sialic Acid (SA) is added to a 10mL centrifuge tube, dissolved in 5mL methanol, and 2mL (0.2mmol) of a solution of functional monomer KH-4-MAPB is added, and the mixture is magnetically stirred at room temperature for 2h to form a mixed solution of template molecule and functional monomer. 0.2g of cetyltrimethylammonium bromide (CTAB), a surfactant, was weighed into a 250mL round-bottomed flask, dissolved by adding 100mL of deionized water, and then 2mol/L sodium hydroxide solution was added dropwise to bring the pH of the solution to 10. Magnetically stirring and heating to 80 ℃. 1mL of cross-linking agent tetraethyl silicate (TEOS), template molecule and functional monomer mixed solution and 2mL of Mn-doped ZnS quantum dot solution modified by 3-mercaptopropionic acid are added dropwise in sequence by using a constant-pressure dropping funnel. The mixed solution is reacted for 72 hours at 80 ℃. After the reaction was completed, the solution was cooled to room temperature, centrifuged, and the supernatant was removed. Adding ethanol, ultrasonic cleaning, removing unreacted impurities, centrifuging, discarding supernatant, and repeating for several times. Drying under vacuum at 40 deg.C.
Ultrasonic cleaning with 85% acetonitrile/water (v/v) solution as eluent, centrifuging, discarding supernatant, removing sialic acid and surfactant CTAB in the complex, and repeating for several times. And (3) drying the mixture for 24 hours in vacuum at the temperature of 40 ℃ to obtain a solid sample, namely the sialic acid imprinted mesoporous silica Microsphere (MIP).
Fig. 2 shows a schematic diagram of a process for preparing a molecularly imprinted Microsphere (MIP) having a mesoporous structure.
The synthesis method of the non-imprinted mesoporous silica microspheres (NIP) is the same as the method, but the template molecule sialic acid is not added.
Experimental example 1: structural characterization of functional monomer and molecularly imprinted microsphere
1. Fourier Infrared Spectroscopy (FT-IR) characterization of boronic acid functionalized siloxane monomers
To determine whether the functional monomer was successfully synthesized, a Fourier transform infrared spectrometer was used to synthesize KH-4-MAPB at 4000-500 cm-1And scanning to obtain an infrared spectrogram. And (3) analyzing characteristic absorption peaks of O-H, C-H, C-O, C-O, Si-O and the like to confirm the existence of corresponding functional groups, and further judging whether the composition of the functional monomer meets the requirements.
FIG. 3 shows the Fourier IR absorption spectrum of the boric acid functionalized siloxane monomer KH-4-MAPB. As can be seen in FIG. 3, 3448cm-1The peak at the position represents O-H stretching vibration, 3090cm-1To 3010cm-1The peak at the position represents the unsaturated C-H stretching vibration, 2982cm-1To 2887cm-1The peak of the region represents a saturated C-H stretching vibration, 1718cm-1The peak of position is caused by C-O stretching vibration, 1590cm-1The peak of the position is caused by the C-C stretching vibration of the benzene ring, 1322cm-1The peak at the position is caused by C-O stretching vibration at-C-O-C-, 1117cm-1Peak at position of 818cm, antisymmetric stretching vibration of Si-O-Si-1The peak at the position is shown as the characteristic absorption peak for the para-disubstituted benzene ring. Meanwhile, S-H is 2590cm-1To 2550cm-1The characteristic absorption peaks of the regions disappear. This indicates that the boronic acid functionalized siloxane monomer, KH-4-MAPB, has been successfully synthesized.
2. Fourier Infrared Spectroscopy (FT-IR) characterization of molecularly imprinted microspheres
To confirm whether the preparation of the sialic acid imprinted mesoporous silica Microspheres (MIPs) and non-imprinted mesoporous silica microspheres (NIPs) in example 3 was successful, dried 100mg of potassium bromide, 1mg of the MIPs before elution, the MIPs after elution, and the NIPs were weighed, and the powders were sufficiently pulverizedGrinding, mixing, tabletting, and making into tablet with Fourier infrared converter at 4000-500 cm-1Scanning to obtain an infrared spectrogram. The characterization is carried out by analyzing characteristic absorption peaks of C-O, Si-O-Si, Si-O and the like.
Fig. 4 is a fourier infrared absorption spectrum of a boron-affinity molecularly imprinted mesoporous polymer based on Mn-doped ZnS quantum dots Before elution (beform) and After elution (After). As can be seen from the figure, the difference in the IR spectra of MIP before and after elution is mainly 3000cm-1To 2800cm-1The region in which the non-eluted MIPs show two sharp peaks, characteristic absorption peaks for methyl and methylene groups. In the synthesis of molecular imprinted polymer reaction, using surfactant CTAB as structure guide agent, therefore judge 3000cm-1To 2800cm-1The peaks in the region are characteristic peaks of CTAB. The peaks of the eluted MIP in the region are not sharp, which indicates that the surfactant CTAB is eluted cleanly.
Fig. 5 is a fourier infrared absorption spectrum of sialic acid imprinted mesoporous silica Microspheres (MIP) and non-imprinted mesoporous silica microspheres (NIP). 1038cm can be seen from the figure-1A strong vibration absorption peak appears at the position, which is caused by the antisymmetric vibration extension of Si-O-Si, and compared with the infrared absorption spectrogram of KH-4-MAPB, the Si-O-Si displacement is probably caused by the fact that the molecularly imprinted polymer is wrapped on the surface of the quantum dot. At 965cm-1And 790cm-1The positions of the three characteristic absorption peaks are respectively a Si-O-H stretching vibration absorption peak and a Si-O bending vibration peak, and the appearance of the three characteristic absorption peaks indicates that the molecular imprinting mesoporous silica microspheres taking the silicon-based material as the main component are successfully coated on the surfaces of the quantum dots to finish the silanization process. 2938cm-1To 2926cm-1The peak of the region is caused by C-H stretching vibration, which shows that TEOS is successfully grafted on the surface of the quantum dot, and proves that the molecular imprinting polymer is successfully coated on the surface of the MPA modified quantum dot.
3. Small angle X-ray diffraction (XRD) characterization
The pore channels of the mesoporous material are often arranged periodically. Information about the periodicity of the mesoporous structure can thus be derived by means of X-ray diffraction. The main three diffraction peaks of the mesoporous structure appear in a low-angle range (0-10 degrees). For example, MCM-4l has an X-ray diffraction peak corresponding to the (100) crystal plane of the hexagonal phase and two diffraction peaks corresponding to the (110) and (200) crystal planes, respectively. Taking a proper amount of MIP sample, grinding the MIP sample into powder, placing the powder on a special glass plate, flattening the powder, and then placing the powder into an instrument for scanning and determination.
Scanning in a low-angle range (0-10 ℃) by using an X-ray diffractometer to obtain an MIP small-angle XRD pattern. As shown in fig. 6, it is a small angle XRD diffractogram of the sialic acid imprinted mesoporous silica microsphere. From the figure, three distinct characteristic peaks can be seen, representing three crystal planes (100), (110) and (200), respectively, with corresponding lattice spacings of 4.41, 3.83, 2.25 nm. In the MCM-41 ordered mesoporous material, the lattice spacing of a hexagonal unit cell is usually 4.5nm, so that MIP can be proved to keep the mesoporous structure of the typical MCM-41.
4. Transmission Electron Microscopy (TEM) characterization
An electron microscope is an important means for representing the nano mesoporous material, and a morphology diagram of a mesoporous material pore channel structure can be observed through an electron microscope diagram. Dissolving a small amount of MIP in water, dispersing the MIP uniformly by utilizing ultrasound, then sucking a small amount of solution from the MIP by using a micro-pipette gun, dripping the solution on the surface of a copper mesh special for a transmission electron microscope, drying the copper mesh in a drying oven at the temperature of 40 ℃ for 24 hours, and then putting the copper mesh into an instrument for observation.
FIG. 7 is a TEM image of sialic acid imprinted mesoporous silica Microspheres (MIP). As can be seen from the figure, the pore channel structure arrangement of the synthesized MIP is compact and regular, which basically conforms to the structure of the MCM-41 mesoporous material and is consistent with the result of the previous XRD. Since ultrasonic cleaning is used in the elution process, the shape regularity of a part of the polymer is destroyed.
5. Thermogravimetric analysis (TGA) characterization
Thermogravimetric analysis is carried out on MIP and MCM-41, the change of the mass of the mesoporous material along with the temperature rise is measured, the structure and the relevant properties of the prepared fluorescent imprinting mesoporous microsphere are discussed, and whether the functional monomer is combined on the mesoporous microsphere is proved. 2-3mg of pure MCM-41 and MIP samples were weighed separately on a balance and carefully placed in a special crucible and measured after setting the instrument parameters.
FIG. 8 shows the thermogravimetric analysis curves of MCM-41 and sialic acid imprinted mesoporous silica Microspheres (MIPs). It is obvious from the figure that the weight loss rate of MIP is much larger than that of MCM-41, mainly because the molecularly imprinted polymer in MIP is decomposed after being heated. This result indicates successful synthesis of molecularly imprinted polymers.
6. Characterization of Nitrogen adsorption-desorption
The adsorption performance of the mesoporous material can be characterized by a nitrogen adsorption experiment, and the specific surface area, the pore volume and the pore size distribution of the mesoporous material are measured. After a proper amount of MIP solid sample is put into a vacuum drying oven for drying for a certain time, 0.1g of MIP solid sample is quickly weighed and carefully poured into a dry professional tube by means of a paper groove, and then the MIP solid sample is put into a nitrogen adsorption instrument for testing.
The surface area and pore volume of the MIP were 1850m, respectively, according to the Brunauer-Emmett-Teller (BET) method2G and 1.46cm3The MIP has a large internal space, which is shown to facilitate the distribution of the imprinted sites. Fig. 9 shows a curve of type IV, which indicates that the nitrogen adsorption-desorption isotherm of MIP belongs to the nitrogen adsorption-desorption isotherm typical of mesoporous materials. As can be seen from FIG. 10, the pore size of MIP is mainly concentrated between 2.9-3.4nm, and the distribution of pore size peak is concentrated and sharp, reflecting that the pore size distribution of MIP is uniform and concentrated. The average pore size of the MIP obtained by the Barrett-Joyner-Halenda (BJH) method was 3.1nm, which is consistent with a small angle XRD characterization.
Experimental example 2: fluorescence performance research of molecularly imprinted microspheres
1. Drawing of standard curve
Accurately weighing 100mg of sialic acid, dissolving in 10mL of deionized water to prepare 10 mug/L sialic acid standard solution, storing at 4 ℃ in a dark place, respectively taking a certain amount of MIP and NIP nanoparticles, preparing 5 mug/L solution by using the deionized water, ultrasonically dispersing for 5min, putting a certain amount of the sialic acid standard solution and 200 mug of MIP or NIP solution in a 4mL centrifuge tube, supplementing the volume to 4mL by using a phosphate buffer solution with the pH value of 7, and preparing to obtain final concentrations of 0, 1.25, 2.50, 5.00, 12.50, 25.00, 37.50, 50.00, 75.00, 100.00 × 10-2μ g/L of standard solution. Dispersing for 10min by ultrasonic wave. Separating the fluorescenceThe parameters of the spectrophotometer F-4600 are set as follows: the excitation wavelength is 287nm, the scanning range is 500-700nm, the grating slits are all 10.0nm, and the excitation voltage is 400V. Each sample was assayed in 3 replicates and averaged.
The results are shown in FIGS. 11 and 12. When sialic acid is added into the solution, emission spectra of the MIP and the NIP are obviously changed, the fluorescence intensity of the MIP and the NIP is weakened along with the increase of the concentration of the added sialic acid, and compared with the NIP, the fluorescence intensity of the MIP is more greatly quenched. In the MIP imprinting process, free radical substitution reaction occurs between the functional monomer KH-4-MAPB and sialic acid, which belongs to covalent bonds, and after the template molecule sialic acid is eluted, a large number of combined cavities complementary to the spatial structure, size, shape and covalent bonding of sialic acid molecules are formed in the molecularly imprinted microspheres. Sialic acid is specifically combined in the MIP due to the existence of imprinting holes, Mn-doped ZnS quantum dots exist in the MIP, and charge transfer occurs between the quantum dots and the sialic acid, so that the Mn-doped ZnS quantum dots have obvious fluorescence quenching. The combination between the NIP and the sialic acid mainly depends on physical adsorption, namely nonspecific adsorption, the adsorption of the NIP to the sialic acid reaches a saturated state in a short time, the number of successfully adsorbed sialic acid molecules is limited, and the fluorescence quenching degree of the Mn-doped ZnS quantum dots is low.
In this detection system, the standard curve equation can be expressed according to the Stem-Volmer equation:
F0/F-1＝KSV[CSA]
wherein, F0Is the fluorescence intensity of the solution without added sialic acid, i.e. blank conditions, and F is the fluorescence intensity of the solution with added sialic acid in the amount, i.e. in the presence of quencher. KSVIs the quenching constant. CSAIs the sialic acid concentration, i.e., the quencher concentration, in units of × 10-2mu.g/L. Obtaining a standard curve according to the above equation, and obtaining a ratio K of the slopes of the standard curve obtained by MIP and NIPSV(MIP)/KSV(NIP)The imprinting factor IF is used for measuring the imprinting effect of the imprinted polymer.
As shown in fig. 13, the concentration is 1.25-100 × 10-2Degree of fluorescence quenching of MIP (. mu.g/L) (F)0the/F-1) shows good linear relation to sialic acid, the correlation coefficient is 0.9946, and the Stem-Volmer equation is F0/F-1＝0.0215[CSA]+0.0241，[CSA]Is the concentration of sialic acid (× 10)-2μg/L)，KSV(MIP)Is 0.0215. As shown in FIG. 14, the fluorescence quenching degree (F) of NIP was observed in the same concentration range0the/F-1) also shows good linear relation to sialic acid, the correlation coefficient is 0.9964, and the Stem-Volmer equation is F0/F-1＝0.0088[CSA]+0.0432，[CSA]Is the concentration of sialic acid (× 10)-2μg/L)，KSV(NIP)Is 0.0088. The imprinting factor IF, i.e. KSV(MIP)/KSV(NIP)And was 2.44. The MIP has better specificity recognition capability on sialic acid.
2. Equilibrium adsorption kinetics experiment
To a 4mL centrifuge tube was added 50. mu.L of a 10. mu.g/L sialic acid standard solution, 100. mu.L of a 5. mu.g/L MIP solution, and the volume was made up to 4mL with a pH 7 phosphate buffer. The shaking speed is 150 rpm at room temperature using a constant temperature culture shaker, i.e. a shaking table, and the shaking time is 0, 5, 10, 15, 20, 30, 40, 50, 60 min. The parameters of the spectrofluorometer F-4600 were set to: the excitation wavelength is 287nm, the scanning range is 500-700nm, the grating slits are all 10.0nm, and the excitation voltage is 400V. Each sample was assayed in 3 replicates and averaged. The same method is also used for measuring the fluorescence intensity of the NIP at different times, and the adsorption kinetics of the MIP and the NIP are explored.
Figure 15 is a graph of adsorption kinetics of MIPs and NIPs for sialic acid. As can be seen from the figure, the fluorescence intensity of MIP is rapidly reduced within 0-20min after adding sialic acid, and gradually reduced within the rest 40min, and then stabilized within about 30min, and the change is not obvious, which indicates that the adsorption equilibrium time of MIP is 30 min. To explore the effect of non-specific adsorption on the preparation of MIPs, equilibrium adsorption kinetics experiments were performed on NIP under the same experimental conditions. As can be seen from the figure, the fluorescence intensity of the NIP is rapidly reduced within 0-10min, the reduction amplitude is gradually reduced, the stability is kept at about 30min, the change is not obvious, and the absence of a specific recognition site between the sialic acid and the NIP is proved. The combination mode of the NIP and the sialic acid is physical adsorption, which belongs to nonspecific adsorption, so that the fluorescence intensity is rapidly reduced, and when the nonspecific adsorption reaches the balance, the fluorescence intensity of the NIP tends to be stable. And a large number of specifically adsorbed imprinted cavities exist in the MIP, so that the action time of the MIP with sialic acid is prolonged, and the fluorescence intensity is not changed after complete adsorption. The experimental results show that the response time of MIP is 15 min.
3. Effect of solution pH on MIP determination of sialic acid
A citric acid-sodium citrate buffer solution (50mmol/L) having a pH of 3, 4, and 5 was prepared using citric acid and sodium citrate, and a phosphate buffer solution (50mmol/L) having a pH of 6, 7, and 8 was prepared using sodium dihydrogen phosphate and disodium hydrogen phosphate. 100 μ L of 10 μ g/L sialic acid standard solution, 100 μ L of 5 μ g/L MIP or NIP solution were placed in 4mL centrifuge tubes, and the volume was made up to 4mL with buffer solutions of different pH. The mixture was incubated at room temperature using a constant temperature incubator, i.e., shaker, with a shaking speed of 150 rpm for 30 min. The parameters of the spectrofluorometer F-4600 were set to: the excitation wavelength is 287nm, the scanning range is 500-700nm, the grating slits are all 10.0nm, and the excitation voltage is 400V. The fluorescence intensity of different samples was measured, 3 replicates of each sample were taken and averaged.
The fluorescence intensity measured at a constant pH with the aid of a solution without added sialic acid as a control was recorded as F0The fluorescence intensity of the sample solution was measured and recorded as F. The change in fluorescence intensity and ability to recognize sialic acid of MIP or NIP solution is expressed by the following formula:
ΔF＝F0-F
IF’＝ΔFMIP-ΔFNIP
as shown in FIG. 16, the change in fluorescence intensity of MIP and NIP before and after addition of sialic acid to solutions of different pH was explored. As can be seen, the blotting factor IF' increases and then decreases with increasing pH of the solution, reaching a maximum at pH 7. When the pH is within the range of 3 to 5, the imprinting factor is small, probably because the Mn-doped ZnS quantum dots change the internal structure of the mesoporous microsphere under the condition of low pH, the covalent bonding of the functional monomer and sialic acid is easy to break, and the fluorescence intensity is low. And in the range of pH 6 to 7, the quantum dot crystal structure is stable, the covalent bonding of the functional monomer and the sialic acid cis-diol is tight, the fluorescence intensity is obviously enhanced, and the imprinting factor is gradually increased. When the pH is too high, part of the structure of the quantum dot is destroyed, and the fluorescence intensity is reduced. The results showed that the blotting factor was maximal at pH 7.
Claims (7)
1. A boron-affinity molecularly imprinted mesoporous polymer based on Mn-doped ZnS quantum dots comprises a boric acid functionalized siloxane monomer and 3-mercaptopropionic acid modified Mn-doped ZnS quantum dots, wherein the boric acid functionalized siloxane monomer is provided with a cavity formed by sialic acid.
2. The preparation method of the boron-compatible molecularly imprinted mesoporous polymer according to claim 1, comprising the steps of:
step 1: synthesizing a boric acid functionalized siloxane monomer;
step 2: synthesizing Mn-doped ZnS quantum dots modified by 3-mercaptopropionic acid;
and step 3: synthesizing the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots.
3. The method according to claim 2, wherein step 1 is specifically as follows: adding 248.35 mu L of silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane into 0.1540g of 4-mercaptophenylboronic acid, adding 5mL of methanol to dissolve the silane coupling agent, dropwise adding triethylamine to enable the pH value of the solution to be 8, introducing nitrogen, heating in a water bath, enabling the solution to be 60 ℃, stirring to react for 2 hours, and after the reaction is finished, carrying out nitrogen blowing concentration on the solution until solid is separated out to obtain the boric acid functionalized siloxane monomer.
4. The method according to claim 2, wherein step 2 is specifically as follows: fully mixing 50mL of 0.04 mol/L3-mercaptopropionic acid, 1mL of 0.01mol/L manganese chloride solution and 2.5mL of 0.1mol/L zinc sulfide solution, and dropwise adding 2mol/L sodium hydroxide solution to adjust the pH of the solutionStirring at room temperature to 10 deg.C, introducing nitrogen to saturate for 30min to ensure that stabilizer 3-mercaptopropionic acid and Zn2+、Mn2+Fully complexing, then injecting 2.5mL of 0.1mol/L sodium sulfide solution under the condition of air isolation, continuing to react for 20min at room temperature to obtain a 3-mercaptopropionic acid modified Mn doped ZnS quantum dot solution, then exposing to the air, aging for 4h at 50 ℃, using equal volume of absolute ethyl alcohol to enable quantum dots to settle, centrifuging, and decanting a supernatant to obtain the 3-mercaptopropionic acid modified Mn doped ZnS quantum dot.
5. The method according to claim 2, wherein step 3 is specifically as follows: dissolving 0.0310g of template molecule sialic acid in 5mL of methanol, adding 2mL of aqueous solution containing 0.2mmol of boric acid functional siloxane monomer, magnetically stirring at room temperature for 2h to form a template molecule and functional monomer mixed solution, adding 100mL of deionized water into 0.2g of surfactant cetyl trimethyl ammonium bromide to dissolve the solution, dropwise adding 2mol/L of sodium hydroxide solution to adjust the pH of the solution to 10, magnetically stirring, heating to 80 ℃, dropwise adding 1mL of cross-linking agent tetraethoxysilane, the template molecule and functional monomer mixed solution and 2mL of 3-mercaptopropionic acid modified Mn doped ZnS quantum dot solution, continuing to react at 80 ℃ for 72h, cooling the solution to room temperature after the reaction is finished, centrifuging, removing supernatant, adding ethanol, ultrasonically cleaning, removing unreacted impurities, centrifuging, discarding supernatant, and (2) vacuum drying at 40 ℃, then taking 85% v/v acetonitrile/water solution as an eluent, ultrasonically cleaning, centrifuging, discarding the supernatant, removing sialic acid and a surfactant CTAB in the compound, and vacuum drying at 40 ℃ for 24h to obtain a solid product, namely the boron affinity molecular imprinting mesoporous polymer based on the Mn-doped ZnS quantum dots.
6. Use of the boron affinity molecularly imprinted mesoporous polymer according to claim 1 for detecting sialic acid.
7. A method for detecting sialic acid, comprising the steps of: mixing the aqueous solution of the boron-compatible molecularly imprinted mesoporous polymer according to claim 1 with sialic acid, and comparing the change in fluorescence intensity before and after mixing.
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