CN117101616A - Molecularly imprinted polymer adsorption material based on metal-organic framework, and preparation method and application thereof - Google Patents
Molecularly imprinted polymer adsorption material based on metal-organic framework, and preparation method and application thereof Download PDFInfo
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- CN117101616A CN117101616A CN202310872333.2A CN202310872333A CN117101616A CN 117101616 A CN117101616 A CN 117101616A CN 202310872333 A CN202310872333 A CN 202310872333A CN 117101616 A CN117101616 A CN 117101616A
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- adsorption material
- organic framework
- material based
- metal
- molecularly imprinted
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims description 26
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000002077 nanosphere Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 127
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 240000002791 Brassica napus Species 0.000 description 14
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000013207 UiO-66 Substances 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 230000005540 biological transmission Effects 0.000 description 4
- QAIPRVGONGVQAS-DUXPYHPUSA-N caffeic acid Natural products OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 2
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 241000143432 Daldinia concentrica Species 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 239000012917 MOF crystal Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 240000007651 Rubus glaucus Species 0.000 description 2
- 235000011034 Rubus glaucus Nutrition 0.000 description 2
- 235000009122 Rubus idaeus Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000004883 caffeic acid Nutrition 0.000 description 2
- 229940074360 caffeic acid Drugs 0.000 description 2
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 2
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000007965 phenolic acids Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
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- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- -1 zirconium ions Chemical class 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 235000019779 Rapeseed Meal Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009830 antibody antigen interaction Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000899 pressurised-fluid extraction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000004456 rapeseed meal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01J20/22—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
-
- 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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Abstract
The invention discloses a molecular imprinting polymer adsorption material based on a metal organic framework, and a preparation method and application thereof. According to the invention, the carbohydrate and the acrylic acid are subjected to hydrothermal reaction to obtain the nano carbon sphere, then the MOF material is constructed on the surface of the nano carbon sphere in situ, and the MOF material is further grafted on the surface of the nano carbon sphere in situ to serve as a carrier, so that the obtained adsorption material has higher specific surface area and large adsorption capacity, has higher selective recognition capability and stronger adsorption capability on target molecules, and can be used for selective recognition and extraction separation of the target molecules.
Description
Technical Field
The invention relates to an adsorption material, in particular to a molecular imprinting polymer adsorption material based on a metal organic framework, a preparation method thereof and application of the adsorption material as an adsorption material for extracting template molecules (such as sinapic acid), and belongs to the technical field of functional materials.
Background
Sinapic acid, also known as 4-hydroxy-3, 5-dimethoxy cinnamic acid, belongs to phenolic acid active substances and is widely found in nature. Sinapic acid has a plurality of biological activities such as good free radical scavenging ability, antioxidation, blood sugar reduction, anti-tumor, organism immunity improvement and the like, and has been paid more attention in recent years. Sinapic acid is mainly distributed in various foods such as oil crops, grains, spices, fruits and the like, and the content of sinapic acid in rapeseeds is particularly rich. Rapeseed cake is a byproduct of rapeseed oil extraction, contains a large amount of sinapic acid, and is a great waste of precious resources if discarded directly.
However, the rapeseed cake has complex components, various active ingredients and low content, and brings great difficulty to separation and extraction of the active ingredients. The current method for extracting phenolic acid active ingredients from rapeseed cakes mainly comprises two major methods, namely a solvent extraction method (organic solvent extraction, pressurized liquid extraction, supercritical fluid extraction and the like) and an adsorption method (biomass adsorbent, hollow fiber membrane adsorption, macroporous resin adsorption, bentonite adsorption, volcanic soil adsorption and the like). Although these methods have achieved good extraction results in terms of extracting phenolic acid-like active ingredients, they have the common disadvantage of lacking selectivity for a certain active ingredient during the extraction process, thus limiting the further use of the extracted active ingredient.
The molecular imprinting technology introduces recognition sites of target molecules into a polymer material through simulating antibody-antigen interaction, and prepares a molecular imprinting polymer which is matched with the target molecules in shape, size, charge and functional group distribution, so as to realize specific recognition and adsorption of the target molecules. With the intensive research, in recent years, molecular imprinting technology has been applied to the selective extraction of bioactive components, but has some disadvantages. For example, the molecularly imprinted polymer prepared by the traditional technology has poor selectivity, low adsorption capacity, slow adsorption rate, large interference by a matrix when applied to a practical complex sample, and the like.
Document (R.T.Til, M.Alizadeh-Khaledabad, R.Mohammadi, S.Pirsa, L.D.Wilson, molecular imprinted polymers for the controlled uptake of si)napic acid from aqueous media, food Function,2020,11,895-906.) discloses that a imprinted polymer of sinapic acid was prepared using co-precipitation polymerization and used to extract sinapic acid from rapeseed cake, with a maximum adsorption of 161. Mu. Mol g of sinapic acid -1 . Literature (R.Zhu, M.Lai, M.Zhu, H.Liang, Q.Zhou, R.Li, W.Zhang, H.Ye, A functional ratio fluorescence sensor platform based on the graphene/Mn-ZnS quantum dots loaded with molecularly imprinted polymer for selective and visual detection sinapic acid, spectrochimica Acta Part A,2021,244,118845) discloses the adoption of graphene and Mn-ZnS quantum dots as carriers, and the visual detection of sinapic acid is realized by introducing a ratio fluorescence sensing technology. Literature (Y.Sun, C.Yao, J.Zeng, Y.Zhang, Y.Zhang, eco-friendly deep eutectic solvents skeleton patterned molecularly imprinted polymers for the separation of sinapic acid from agricultural wastes, colloids and Surfaces A: physicochemical and Engineering Aspects,2022,640,128441.) and (Y.Sun, Y.Zhang, Y.Hou, H.Gong, Y.Pang, X.Ge, M.Li, molecularly imprinted polymers based on calcined rape pollen and deep eutectic solvents for efficient sinapic acid extraction from rapeseed meal extract, food Chemistry,2023,416,135811.) respectively use hydroxyapatite and pollen as carriers, and a surface molecular imprinting technique is used to prepare a imprinted polymer of sinapic acid, so that selective adsorption of sinapic acid in rapeseed cakes is realized. However, these imprinted polymers have a limited number of imprinted sites, and have low equilibrium adsorption of sinapic acid and low selectivity.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide a molecular imprinting polymer adsorption material based on a metal organic framework, which has the characteristics of large specific surface area, high adsorption capacity and strong selective recognition and extraction capability for target small molecules.
The second aim of the invention is to provide a preparation method of the molecular imprinting polymer adsorption material based on the metal-organic framework, which is simple to operate, low in cost, mild in condition and beneficial to mass production and application.
A third object of the present invention is to provide an application of a molecularly imprinted polymer adsorption material based on a metal organic framework, which can obtain adsorption materials with completely different molecular imprinting through different template molecules, endow the adsorption materials with high selective recognition and strong adsorption capacity, can be used for efficiently and selectively extracting and enriching template molecules in complex systems, such as adsorption materials obtained by taking sinapic acid as the template molecules, and has an adsorption amount of up to 141.3mg g for sinapic acid -1 The selectivity is good (IF=3.29), the adsorption is fast (10 min), and the purpose of efficiently and selectively extracting and enriching sinapic acid can be achieved.
In order to achieve the technical aim, the invention provides a preparation method of a molecular imprinting polymer adsorption material based on a metal-organic framework, which comprises the following steps:
1) Carrying out hydrothermal reaction I on saccharides and acrylic acid to obtain a nano carbon sphere;
2) Carrying out hydrothermal reaction II on the nano carbon spheres, zirconium salt and 2-amino terephthalic acid to obtain an amino modified MOF@nano carbon sphere carrier;
3) Carrying out amidation reaction on the amino modified MOF@carbon nanosphere carrier and methacrylic anhydride to obtain a double-bond modified MOF@carbon nanosphere carrier;
4) And (3) performing free radical polymerization on the MOF@nanocarbon ball carrier modified by the double bond, a template molecule, an alkene polymerization monomer, a cross-linking agent and an initiator, and eluting the template molecule to obtain the modified MOF@nanocarbon ball carrier.
According to the preparation method of the molecular engram polymer adsorption material based on the metal organic framework, saccharides and acrylic acid are used as raw materials, and the nano carbon spheres are synthesized through a hydrothermal method, so that the surfaces of the nano carbon spheres are rich in carboxyl groups due to the fact that the acrylic acid is introduced into the raw materials, the carboxyl groups can induce the MOF material to be generated on the surfaces of the nano carbon spheres in situ, so that the MOF material can be uniformly dispersed and stably loaded, the technical problem that the MOF material is easy to agglomerate in the use process is well solved, double bonds are further introduced into the MOF material, the double bonds can be used for grafting polymers, and therefore the molecular engram polymer with a three-dimensional structure is constructed on the surfaces of the MOF material in situ, the loading stability of the molecular engram polymer can be improved, meanwhile, the molecular engram active sites of the molecular engram polymer are fully exposed on the surfaces of the MOF material taking the nano carbon spheres as a supporting body, the adsorption selectivity and the adsorption capacity of the molecular engram polymer can be greatly improved, the whole adsorption material has large specific surface area, multiple active sites, large adsorption energy and selective recognition capacity and strong adsorption capacity to target molecules.
The molecular engram polymer adsorption material based on the metal organic framework uses the nano carbon spheres as a support of the MOF material, and further uses the MOF material to load the molecular engram polymer. Although the MOF material has the characteristics of large specific surface area, adjustable functional groups and good adsorption performance, and can be used as a carrier for molecular imprinting polymers, the nano MOF material is easy to cause serious agglomeration, so that imprinting sites of the molecular imprinting polymers are covered in the adsorption material. The nano carbon spheres are used as a support, particularly the nano carbon spheres with carboxyl modified surfaces can induce MOF crystals to uniformly distribute and grow on the surface of the support in situ, so that agglomeration behavior in the subsequent use process can be well avoided, the advantages of high specific surface area and porosity of the MOF material are better exerted, the characteristics can endow the subsequently prepared molecularly imprinted polymer with high-content imprinting sites and stronger imprinting effect, and the adsorption capacity and selectivity of the imprinted polymer to target molecules are improved. The MOF material generated on the surface of the carbon nano particle in situ is in a raspberry shape, and the MOF material is used as a porous carrier to load a molecularly imprinted polymer, so that the specific recognition and adsorption performance of the MOF material on target molecules can be enhanced.
As a preferable embodiment, the mass ratio of the saccharide to the acrylic acid is 50 (0.2 to 3). In the process of preparing the nano carbon sphere, a proper amount of acrylic acid is introduced to enable the surface of the nano carbon sphere to be rich in-COOH, and the-COOH on the surface of the nano carbon sphere can coordinate zirconium ions, so that MOF material nano particles are induced to be generated on the surface of the nano carbon sphere in situ and uniformly distributed on the surface of the nano carbon sphere. If acrylic acid is not added or the addition amount of acrylic acid is too small, the surface of the nano carbon sphere is smooth, but the content of-COOH is extremely low, and after a proper amount of acrylic acid is added, the particle surface is not smooth, and is in a raspberry-shaped structure, the effect is more obvious along with the increase of the amount of acrylic acid, when the addition amount of acrylic acid reaches 1wt%, part of the nano carbon sphere is in a raspberry shape, the surface of part of the nano carbon sphere is smooth, and when the amount of acrylic acid is increased to more than 5wt%, the nano carbon sphere is in a micron-sized aggregate, so that the mass ratio of sugar to acrylic acid is more preferably 50:0.5-1.5. The saccharide is preferably glucose.
As a preferred embodiment, the hydrothermal reaction I conditions are: the hydrothermal reaction conditions are as follows: the temperature is 160-200 ℃ and the time is 2-5 hours. In the preferred temperature range, the size of the nanocarbon balls gradually increases as the hydrothermal reaction time increases, and the diameter of the carbon balls is about 250nm when the time is 5 hours, and the diameter of the resulting carbon balls is about 500nm when the reaction time is prolonged to 8 hours.
As a preferable scheme, the molar ratio of the nano carbon spheres to the zirconium salt and the 2-amino terephthalic acid is 0.3-0.5 g, 1-2 mM, 2-3 mM. The zirconium salt may be a conventional water-soluble zirconium salt such as zirconium chloride. The ratio of the nano carbon spheres needs to be controlled in a proper range, so that the generated MOF material is difficult to disperse and load when the ratio of the nano carbon spheres is too low, and the amount of the MOF material deposited on the surfaces of the nano carbon spheres is too small when the ratio of the nano carbon spheres is too high.
As a preferred embodiment, the hydrothermal reaction II conditions are: the temperature is 120-150 ℃ and the time is 15-30 hours. The MOF material can be generated on the surface of the nano carbon sphere in situ through hydrothermal reaction, so that the uniform distribution and stable load of the MOF material on the surface of the nano carbon sphere are realized.
As a preferred embodiment, the template molecule is a phenolic small molecule compound, such as sinapic acid.
As a preferable embodiment, the vinyl polymer monomer is at least one of methacrylic acid, acrylic acid, acrylamide, N-isopropylacrylamide, 4-vinylpyridine and 2-vinylpyridine. The preferred vinyl polymeric monomers each contain polar groups which are incorporated to facilitate incorporation of small phenolic compounds and the like by complexation. A further preferred ethylenically polymeric monomer is methacrylic acid.
As a preferable scheme, the cross-linking agent is at least one of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and divinylbenzene. The loading stability of the molecularly imprinted polymer can be improved and a three-dimensional structure can be constructed by introducing a cross-linking agent.
As a preferred embodiment, the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
As a preferable scheme, the dosage ratio of the MOF@nanocarbon ball carrier modified by double bonds to the template molecule, the vinyl polymer monomer and the crosslinking agent is 0.2-0.6 g/1 mmol/5-10 mmol/5-15 mmol.
As a preferred embodiment, the conditions for the radical polymerization are: under the protection atmosphere, the reaction is carried out for 15 to 25 hours at the temperature of 60 to 70 ℃.
As a preferred embodiment, the eluting solution used for eluting the template molecule is acetic acid and methanol according to the volume ratio=1: (4-19).
The invention also provides a molecular imprinting polymer adsorption material based on the metal-organic framework, which is obtained by the preparation method.
The invention also provides application of the molecular imprinting polymer adsorption material based on the metal-organic framework, which is applied as an adsorption material for extracting template molecules. For example, the adsorption material prepared by taking the sinapic acid as a template molecule has higher selective recognition capability and strong selective adsorption capability on the sinapic acid, can be used for adsorption separation and detection of the sinapic acid in rapeseed cakes, and shows excellent separation and detection performance.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) According to the molecular engram polymer adsorption material based on the metal organic framework, composite particles of MOF materials are generated on the surfaces of the nano carbon spheres in situ and used as carriers, the technical problem that the MOF material nano particles are used as carriers singly and are easy to agglomerate is solved, and the composite particles have the advantages of being high in specific surface area, developed in pore structure, not easy to agglomerate and the like.
2) The molecular engram polymer adsorption material based on the metal organic framework has a molecular engram polymer layer modified on the surface, has high selective recognition and strong adsorption capacity on target molecules, for example, the adsorption material prepared by taking sinapic acid as a template molecule has high adsorption capacity (141.3 mg/g) on sinapic acid, has good selectivity (IF=3.29), is fast to adsorb (10 min), can efficiently and selectively extract and enrich the sinapic acid, is particularly suitable for carrying out adsorption separation and detection on the sinapic acid in rapeseed cakes, and shows excellent separation and detection performances.
3) According to the molecular engram polymer adsorption material based on the metal organic framework, double bonds are introduced into the MOF material, and the molecular engram polymer can be grafted through chemical bonding, so that the stability of the adsorption material is greatly improved.
4) The molecular imprinting polymer adsorption material based on the metal organic framework takes the nano carbon spheres rich in carboxyl as a support body, can induce MOF crystals to be uniformly distributed and grow on the surface of the support body in situ, can well avoid agglomeration in the subsequent use process, better plays the advantages of the MOF material in terms of high specific surface area and porosity, can endow the molecular imprinting polymer prepared subsequently with high-content imprinting sites and stronger imprinting effect, and improves the adsorption capacity and selectivity of the imprinting polymer to target molecules.
5) The preparation method of the molecular engram polymer adsorption material based on the metal organic framework has the advantages of simple operation, low cost and mild condition, and is beneficial to large-scale production and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments will be briefly described below. The drawings in the following description are only examples of embodiments of the present invention and other drawings may be made from these drawings by those of ordinary skill in the art without undue burden.
FIG. 1 is a flow chart of the preparation of BC@UiO-66@MIPs according to the invention and a flow chart for selectively recognizing and adsorbing sinapic acid from rapeseed cakes.
FIG. 2 is a photograph of a sample of pressed rapeseed cake and the chemical structural formula of sinapic acid.
Fig. 3 is a scanning electron microscope picture (a) and a transmission electron microscope picture (b) of the carbon nanoball Barecarbon (BC) prepared in example 1.
FIG. 4 is a scanning electron microscope picture (a) and a transmission electron microscope picture (b) of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1.
FIG. 5 is an infrared spectrum analysis chart of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1. FIG. 6 is a graph showing the adsorption capacity of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1 against sinapic acid and its structural analogues.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
Example 1
Preparing carbon nanospheres: glucose (2.0 g) is dissolved in deionized water (25.0 mL), acrylic acid (0.04 g) is added, the mixture is transferred into a reaction kettle with a tetrafluoroethylene lining after being uniformly mixed, the mixture is heated for 5h at 190 ℃, and after being cooled to room temperature, the product is washed by deionized water and ethanol, so that black carbon nanosphere carbon (BC) is obtained.
Preparation of MOF composite particles: synthesizing MOF composite particles on the surface of the carbon nanospheres by adopting a hydrothermal method, namely: firstly, uniformly dispersing carbon nanospheres (0.40 g) into N, N-Dimethylformamide (DMF) (40.0 mL) by ultrasonic, and sequentially adding ZrCl under magnetic stirring 4 (1.5 mM) and 2-amino terephthalic acid NH 2 BDC (2.0 mM), after being uniformly mixed, is transferred into a reaction kettle with a tetrafluoroethylene lining, heated for 24 hours at 120 ℃, naturally cooled, and then washed alternately with DMF and ethanol, so as to obtain MOF composite nano particles, which are named BC@UiO-66.
Surface modification of BC@UiO-66: to impart higher polymerization ability to bc@uio-66, methacrylic anhydride is used to introduce an unsaturated bond (carbon-carbon double bond) in an alkaline environment. To this end, BC@UiO-66 (0.60 g) was sonicated into chloroform (50 mL), methacrylic anhydride (10.0 mM) and triethylamine (4.0 mM) were added with stirring, refluxed for 24h at 60 ℃, naturally cooled, washed with chloroform and ethanol, and dried under vacuum at 60 ℃, the product designated BC@UiO-66-C=C.
Preparation of bc@uio-66-c=c as support bc@uio-66@mips: carrier bc@uio-66-c=c (140.0 mg) and template molecule sinapic acid (0.24 mmol) were added to a mixture of acetonitrile and methanol (40 ml, v: v=4:1), sonicated for 10min, and stirred at room temperature for 4h for pre-assembly. MAA (1.92 mmol), HEMA (1.92 mmol) and initiator AIBN (35.0 mg) were then added in this order, the reaction flask was sealed and then purged with nitrogen 3 times to remove oxygen from the system, and the mixture was heated and stirred at 65℃for 20 hours to effect polymerization. And (3) eluting the template molecules by using methanol-acetic acid (V: V=85:15) after cooling until no sinapic acid is detected in the eluent, washing residual acetic acid by using methanol, and drying in vacuum at 65 ℃ to obtain the sinapic acid imprinted MIPs, which are abbreviated as BC@UiO-66@MIPs.
As a control, non-imprinted polymers BC@UiO-66@NIPs were prepared simultaneously, and the preparation method was the same as that of BC@UiO-66@MIPs except that no sinapic acid was added.
In order to highlight the excellent properties of BC@UiO-66@MIPs, while preparing UiO-66@MIPs using only UiO-66 as a support material, the preparation method can be referred to as BC@UiO-66@MIPs (except that BC is not used).
The preparation flow of BC@UiO-66@MIPs and the flow for selectively identifying and adsorbing sinapic acid from rapeseed cakes are shown in the figure 1.
In order to study the adsorption performance of the prepared BC@UiO-66@MIPs on sinapic acid, a kinetic adsorption experiment and a static adsorption experiment are carried out. BC@UiO-66@MIPs or BC@UiO-66@NIPs were added to 10.0mL of the sinapic acid solution and shaken at a constant temperature of 30℃in a shaker. After the completion of the adsorption, the mixture was centrifuged by a high-speed centrifuge (9000 rpm,5 min), and filtered through a 0.45 μm nitrocellulose membrane. Each set of experiments was performed three times, averaged, and the adsorption amount Q was calculated according to equation 1 e (mg g -1 ). Wherein C is 0 And C e The initial concentration of sinapic acid and the concentration at which adsorption equilibrium is reached (mg mL) -1 ) V is the volume of the sinapic acid solution (10.0 mL) and m is the mass of the adsorbent (10.0 mg).
Q e ＝(C 0 -C e ) V/m equation 1
Kinetic adsorption experiments: setting different adsorption time intervals (2-40 min), and setting initial concentration of sinapic acid to 1.6mg mL -1 The adsorption quantity Q at the adsorption time t is calculated according to the formula 2 t (mg g -1 ). Wherein C is 0 And C t The initial concentration of sinapic acid and the concentration at time t (mg mL -1 ) V is the volume of the sinapic acid solution (10.0 mL) and m is the mass of the adsorbent (10.0 mg).
Q t ＝(C 0 -C t ) V/m equation 2
Isotherm adsorption experiments: the initial concentration of sinapic acid was set to: 0.20,0.40,0.60,0.80,1.0,1.2,1.4,1.6,1.8,2.0,2.5,3.0mg mL -1 The adsorption time was set to 10min.
To study the selectivity of BC@UiO-66@MIPs to sinapic acid, a selective adsorption experiment was performed: and (3) selecting coumaric acid, vanilloid, trans-cinnamic acid, trans-ferulic acid and caffeic acid which have similar structures to sinapic acid as control substances, and carrying out an adsorption experiment.
Study of the reusability properties of BC@UiO-66@MIPs: the bc@uio-66@mips after adsorbing sinapic acid were subjected to desorption by shaking in an eluent (acetic acid: methanol=85:15, volume ratio), and after centrifugal separation and drying, the adsorbent material was reused for the adsorption of sinapic acid, and the adsorption amount was calculated by using formula 1.
Adsorbing and extracting sinapic acid in the rapeseed cakes: firstly, the rapeseed cakes are pretreated, ground into powder, sieved and dried for 1 day at 80 ℃. The resulting powder (5.0 g) was mixed with NaOH solution (3.0M, 100 ml), magnetically stirred at 70 ℃ for 5h, cooled to room temperature, centrifuged (7000 rpm/min,5 min) to separate the mixture, and the supernatant was adjusted to ph=10.0 with HCl solution (3.0M), filtered and subjected to adsorption experiments. BC@UiO-66@MIPs or BC@UiO-66@NIPs (10.0 mg) were added to an alkaline extract (10.0 mL), the mixture was centrifuged (9000 rpm,5 min) after completion of adsorption in a water bath at 30℃in a shaker, and the supernatant was analyzed by High Performance Liquid Chromatography (HPLC) after filtration through a microporous filter membrane (13 mm. Times.0.45 μm). Chromatographic column conditions: the mobile phase composition for the column Thermo scientificC (250×4.6 mm) was as follows: and (3) solution A: 0.2% phosphoric acid solution; and (2) liquid B: methanol; and C, liquid: acetonitrile.
FIG. 2 is a photograph (a) of a sample of pressed rapeseed cake and chemical structural formula (b) of sinapic acid.
FIG. 3 is a scanning electron microscope photograph (a) and a transmission electron microscope photograph (b) of the carbon nanosphere Bare Carbon (BC) prepared in example 1, from which it can be seen that the carbon nanospheres have a uniform particle size of about 200 to 300nm and a smooth surface.
FIG. 4 is a scanning electron microscope picture (a) and a transmission electron microscope picture (b) of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1. BC@UiO-66@MIPs prepared by taking BC@UiO-66 as a framework show good dispersibility, and the porous structure and the high specific surface area of the BC@UiO-66@MIPs are ensured. In addition, the BC@UiO-66@MIPs are rough and uneven in surface, and the thickness of the polymerized imprinting layer is about 20nm, so that recognition and combination of imprinting sites on target molecules in a later adsorption experiment are facilitated, and the adsorption quantity and mass transfer efficiency can be further improved.
FIG. 5 is an infrared spectrum analysis chart of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1. BC is 600-3200 cm due to stretching vibration of-O-COOH and-C=C on the aromatic ring -1 、1709cm -1 And 1655cm -1 And the like exhibit typical absorption peaks. Stretching vibration of the organic ligand to make BC@UiO-66 at 1437cm -1 And 1387cm -1 There is an additional absorption peak for UiO-66. At 750-400 cm -1 Where metallic nuclei Zr appear 2+ The absorption peak of the asymmetric tensile vibration of the ion indicates that bc@uio-66 conforming particles have been successfully prepared. BC@UiO-66-C=C at 1660cm -1 There is a significantly enhanced peak indicating that the surface has been successfully incorporated with vinyl groups. BC@UiO-66@MIPs and UiO-66@MIPs at 2979cm -1 、1730cm -1 、1442cm -1 And 1392cm -1 There appear new absorption peaks derived from the-CH-and-C=O groups of MAA, HEMA and EGDMA, indicating successful synthesisThe blotting material is formed.
FIG. 6 is a graph of adsorption capacity of the molecularly imprinted polymer BC@UiO-66@MIPs prepared in example 1 against sinapic acid and its structural analogs (coumaric acid, vanillic acid, trans-cinnamic acid, trans-ferulic acid and caffeic acid). When the adsorption equilibrium is reached, the adsorption amounts of BC@UiO-66@MIPs to the analytes are 141.3, 76.6, 62.4, 70.4, 57.9, 65.3mg g, respectively -1 . Since the imprinting sites on BC@UiO-66@MIPs are only matched and complementary to sinapic acid, and cannot be effectively identified and combined with other molecules, the adsorption amount of sinapic acid is far higher than that of other molecules. Since UiO-66@MIPs prepared by using only UiO-66@MIPs as a framework have the phenomenon of large-scale agglomeration, a large amount of imprinting is shielded, and a target molecule is difficult to contact with the imprinting, the adsorption amount of the UiO-66@MIPs to sinapic acid is 54.3mg g -1 Far lower than BC@UiO-66@MIPs (141.3 mg g- 1 )。
Example 2
Preparing carbon nanospheres: glucose (1.5 g) is dissolved in deionized water, acrylic acid (0.04 g) is added, the mixture is transferred into a reaction kettle with a tetrafluoroethylene lining after being uniformly mixed, the mixture is heated for 8 hours at 190 ℃, and after being cooled to room temperature, the product is washed by the deionized water and ethanol, so that black carbon nanosphere (BC) is obtained.
Preparation of MOF composite particles: firstly, uniformly dispersing carbon nanospheres (0.650 g) into N, N-Dimethylformamide (DMF) by ultrasonic, and sequentially adding ZrCl under magnetic stirring 4 (2.05 mM) and 2-amino terephthalic acid NH 2 BDC (3.0 mM), after being uniformly mixed, is transferred into a reaction kettle with a tetrafluoroethylene lining, heated for 18 hours at 120 ℃, naturally cooled, and then washed alternately with DMF and ethanol, so as to obtain MOF composite nano particles, which are named BC@UiO-66.
Surface modification of BC@UiO-66: to impart higher polymerization ability to bc@uio-66, methacrylic anhydride is used to introduce an unsaturated bond (carbon-carbon double bond) in an alkaline environment. To this end, BC@UiO-66 (0.8 g) was sonicated into acetone (60 mL), methacrylic anhydride (12.0 mM) and triethylamine (6.5 mM) were added with stirring, refluxed for 18h at 60 ℃, naturally cooled, washed with chloroform and ethanol, and dried under vacuum at 60 ℃, the product designated BC@UiO-66-C=C.
Preparation of bc@uio-66-c=c as support bc@uio-66@mips: the carrier bc@uio-66-c=c (120.0 mg) and the template molecule sinapic acid (0.50 mmol) were added to acetone (60 mL), sonicated for 15min, and stirred at room temperature for 5h for preassembly. Then, 4-vinylpyridine (2.50 mmol), EGDMA (5.50 mmol) and AIBN (50.0 mg) were successively added thereto, and after the reaction flask was sealed, the mixture was purged with nitrogen gas 3 times to remove oxygen from the system, and the mixture was heated at 60℃and stirred for 24 hours to effect polymerization. After cooling, eluting the template molecules with methanol-acetic acid (V: v=90:10) until no sinapic acid is detected in the eluent, washing the residual acetic acid with methanol, and vacuum drying at 60 ℃ to obtain sinapic acid imprinted MIPs, abbreviated as bc@uio-66@mips.
As a control, non-imprinted polymers BC@UiO-66@NIPs were prepared simultaneously, and the preparation method was the same as that of BC@UiO-66@MIPs except that no sinapic acid was added.
The BC nanoparticles prepared in example 2 had a diameter of about 500nm, and the maximum equilibrium adsorption of sinapic acid by BC@UiO-66@MIPs and BC@UiO-66@NIPs were 110.9mg g, respectively -1 And 36.8mg g -1 Slightly lower than the BC@UiO-66@MIPs of example 1 (141.3 mg g) -1 ) This is because the BC particle size obtained in example 2 is large, the BC@UiO-66@MIPs are also large in particle size, the specific surface area of the imprinting material is reduced, and the density of imprinting sites is also reduced. The blotting factor IF was 3.01, slightly lower than the IF value of example 1 (3.29), and 15min was required to reach adsorption equilibrium.
Example 3
Preparing carbon nanospheres: glucose (2.5 g) is dissolved in deionized water, acrylic acid (0.15 g) is added, the mixture is transferred into a reaction kettle with a tetrafluoroethylene lining after being uniformly mixed, the mixture is heated for 4 hours at 180 ℃, and after being cooled to room temperature, the product is washed by the deionized water and ethanol, and then black carbon nanosphere carbon (BC) is obtained.
Preparation of MOF composite particles: firstly, uniformly dispersing carbon nanospheres (0.80 g) into N, N-Dimethylformamide (DMF) by ultrasonic, and sequentially adding ZrCl under magnetic stirring 4 (2.8 mM) and 2-amino terephthalic acid NH 2 BDC (6.0 mM), after mixing well, transferred to a reaction vessel with tetrafluoroethylene lining, heated at 130 DEG CAnd (3) after 20h, naturally cooling, washing with DMF and ethanol alternately to obtain MOF composite nano particles, which are marked as BC@UiO-66.
Surface modification of BC@UiO-66: to impart higher polymerization ability to bc@uio-66, methacrylic anhydride is used to introduce an unsaturated bond (carbon-carbon double bond) in an alkaline environment. To this end, bc@uio-66 (1.0 g) was sonicated into acetonitrile (70 mL), methacrylic anhydride (15.0 mM) and triethylamine (8.0 mM) were added with stirring, refluxed for 18h at 60 ℃, naturally cooled, washed with acetonitrile and ethanol, and dried in vacuo at 50 ℃, the product was designated bc@uio-66-c=c.
Preparation of bc@uio-66-c=c as support bc@uio-66@mips: carrier bc@uio-66-c=c (80.0 mg) and template molecule sinapic acid (0.40 mmol) were added to acetonitrile (50 mL), sonicated for 153min, and stirred at room temperature for 4h for preassembly. Then, acrylic acid (2.00 mmol), EGDMA (4.0 mmol) and azobisisoheptonitrile (40.0 mg) were added in this order, and after the reaction flask was sealed, the system was purged with nitrogen gas 3 times to remove oxygen therefrom, and the mixture was heated at 60℃and stirred for 18 hours to effect polymerization. And (3) eluting the template molecules by using methanol-acetic acid (V: V=92:8) after cooling until no sinapic acid is detected in the eluent, washing the residual acetic acid by using ethanol, and drying in vacuum at 60 ℃ to obtain the sinapic acid imprinted MIPs, which are abbreviated as BC@UiO-66@MIPs.
As a control, non-imprinted polymers BC@UiO-66@NIPs were prepared simultaneously, and the preparation method was the same as that of BC@UiO-66@MIPs except that no sinapic acid was added.
The BC nanoparticles prepared in example 3 had slightly roughened surfaces, were in the form of small particle aggregates with a diameter of 1 μm, and had maximum equilibrium adsorption of sinapic acid of 1. Mu.m, BC@UiO-66@MIPs and BC@UiO-66@NIPs, respectively, of 91.1mg g -1 And 29.3mg g -1 Are lower than the BC@UiO-66@MIPs of example 1 (141.3 mg g) -1 ) This is because the BC particle size obtained in example 3 is larger, the BC@UiO-66@MIPs particle size is also much larger than the BC@UiO-66@MIPs in example 1, the specific surface area of the imprinting material is reduced, and the density of imprinting sites is also greatly reduced. The blotting factor IF was 3.11, which was close to the IF value of example 1 (3.29), and it took 15min to reach adsorption equilibrium, slightly higher than 10min of example 1.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and the technical solution according to the present invention and the inventive concept thereof are equally exchanged or changed, and should be covered in the scope of the present invention.
Claims (10)
1. A preparation method of a molecular imprinting polymer adsorption material based on a metal organic framework is characterized by comprising the following steps of: the method comprises the following steps:
1) Carrying out hydrothermal reaction I on saccharides and acrylic acid to obtain a nano carbon sphere;
2) Carrying out hydrothermal reaction II on the nano carbon spheres, zirconium salt and 2-amino terephthalic acid to obtain an amino modified MOF@nano carbon sphere carrier;
3) Carrying out amidation reaction on the amino modified MOF@carbon nanosphere carrier and methacrylic anhydride to obtain a double-bond modified MOF@carbon nanosphere carrier;
4) And (3) performing free radical polymerization on the MOF@nanocarbon ball carrier modified by the double bond, a template molecule, an alkene polymerization monomer, a cross-linking agent and an initiator, and eluting the template molecule to obtain the modified MOF@nanocarbon ball carrier.
2. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework, according to claim 1, is characterized in that: the mass ratio of the saccharide to the acrylic acid is 50 (0.2-3).
3. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework according to claim 1 or 2, wherein the method comprises the following steps of: the conditions of the hydrothermal reaction I are as follows: the temperature is 160-200 ℃ and the time is 2-5 hours.
4. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework, according to claim 1, is characterized in that: the dosage ratio of the nano carbon sphere to the zirconium salt to the 2-amino terephthalic acid is 0.3-0.5 g:1-2 mM:2-3 mM.
5. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework according to claim 1 or 4, wherein the method comprises the following steps of: the conditions of the hydrothermal reaction II are as follows: the temperature is 120-150 ℃ and the time is 15-30 hours.
6. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework, according to claim 1, is characterized in that:
the template molecule is a phenolic micromolecular compound;
the vinyl polymer monomer is at least one of methacrylic acid, acrylic acid, acrylamide, N-isopropyl acrylamide, 4-vinyl pyridine and 2-vinyl pyridine;
the cross-linking agent is at least one of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and divinylbenzene; the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
7. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework according to claim 1 or 6, wherein the method comprises the following steps of: the dosage ratio of the MOF@nanocarbon ball carrier modified by double bonds to the template molecule, the vinyl polymer monomer and the cross-linking agent is 0.2-0.6 g:1 mmol:5-10 mmol:5-15 mmol.
8. The method for preparing the molecularly imprinted polymer adsorption material based on the metal-organic framework, according to claim 1, is characterized in that: the conditions of the free radical polymerization are as follows: under the protection atmosphere, the reaction is carried out for 15 to 25 hours at the temperature of 60 to 70 ℃.
9. A molecularly imprinted polymer adsorption material based on a metal-organic framework, which is characterized in that: obtained by the production process according to any one of claims 1 to 8.
10. Use of a molecularly imprinted polymer adsorption material based on a metal-organic framework according to claim 9, wherein: as an adsorption material for extracting template molecules.
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| CN117534058B (en) * | 2024-01-04 | 2024-03-29 | 内蒙古大学 | High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof |
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