CN106117470A - The synthetic method of polymer microballoon functional graphene oxide and the application of catalytic degradation organophosphor thereof - Google Patents
The synthetic method of polymer microballoon functional graphene oxide and the application of catalytic degradation organophosphor thereof Download PDFInfo
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- CN106117470A CN106117470A CN201610496830.7A CN201610496830A CN106117470A CN 106117470 A CN106117470 A CN 106117470A CN 201610496830 A CN201610496830 A CN 201610496830A CN 106117470 A CN106117470 A CN 106117470A
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- graphene oxide
- polymer microballoon
- functional graphene
- synthetic method
- organophosphor
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 114
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 230000015556 catabolic process Effects 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 30
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011592 zinc chloride Substances 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001059 synthetic polymer Polymers 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- 230000003760 hair shine Effects 0.000 claims 1
- 230000012447 hatching Effects 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229960004623 paraoxon Drugs 0.000 abstract description 30
- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 abstract description 29
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 15
- 102000004190 Enzymes Human genes 0.000 abstract description 11
- 108090000790 Enzymes Proteins 0.000 abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 230000003592 biomimetic effect Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004971 Cross linker Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 12
- 229940088598 enzyme Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- 101001099451 Alteromonas sp Xaa-Pro dipeptidase Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000005949 Malathion Substances 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 206010058119 Neurogenic shock Diseases 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- GRXKLBBBQUKJJZ-UHFFFAOYSA-N Soman Chemical compound CC(C)(C)C(C)OP(C)(F)=O GRXKLBBBQUKJJZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PJVJTCIRVMBVIA-JTQLQIEISA-N [dimethylamino(ethoxy)phosphoryl]formonitrile Chemical compound CCO[P@@](=O)(C#N)N(C)C PJVJTCIRVMBVIA-JTQLQIEISA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000006872 enzymatic polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229960000453 malathion Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000003958 nerve gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
Abstract
The invention discloses synthetic method and the application of catalytic degradation organophosphor thereof of a kind of polymer microballoon functional graphene oxide, 1 vinyl imidazole is passed through the cross-linker divinylbenzene covalence graft surface of graphene oxide in hydroxyethyl methylacrylate functionalization by the method, successfully synthesize polymer microballoon functional graphene oxide, effectively simulate the active center of organophosphor hydrolytic enzyme.Under the same conditions, the initial velocity of Inventive polymers microsphere functional graphene oxide catalytic degradation ethyl paraoxon improves 230 times relative to blank, the maximum initial velocity V of its catalysis ethyl paraoxon hydrolysismaxFor 0.014mmol/L min, Michaelis constant KmFor 13.4mmol/L, and having preferable recycling rate of waterused, after reusing 5 times, hydrolysing activity only declines about 5.2%.Inventive polymers microsphere functional graphene oxide has potential using value in terms of the structure of degrading organic phosphor poisonous substance and detection organic phosphates biomimetic sensor.
Description
Technical field
The invention belongs to the degradation technique field of organic phosphorus compound, be specifically related to a kind of polymer microballoon functionalization oxidation
The synthetic method of Graphene and the application of catalytic degradation organophosphor thereof.
Background technology
Organophosphorus compounds is often widely used in insecticide, plasticizer, petroleum additive and chemical warfare poison
Agent, especially organic phosphoric acid three ester, such as paraoxon, parathion, Malathion etc., be applied to agriculture usually used as crop protection agent
Industry field.But these materials have potential toxicity, neurogenic shock can be caused, benumb, suffer a shock and dead.In chemical warfare
In be used as the compound of nerve gas, such as sarin, tabun and soman, fall within organophosphorus ester.The suppression of these compounds participates in
The key enzyme acetylcholinesterase of nerve signal, and then cause nervous system disease.Therefore, these organophosphorus compoundss
Degraded be worldwide an important challenge, and much research solves this important problem making great efforts.
At present, the method studying relatively broad degrading organic phosphor acid esters is enzymatic hydrolysis.Although natural organophosphor hydrolyzes
Enzyme energy efficiently degrading organophosphorus, but its less stable, and it is difficult to preparation, application is very restricted.Therefore, foundation
The structure of natural organophosphor hydrolytic enzyme and degrading organic phosphor mechanism thereof, design synthesizing stable, efficient, inexpensive organophosphor hydrolysis mould
Intend the unremitting pursuit that enzyme is researcher.
The naturally isolated organophosphor hydrolytic enzyme obtained is dimer, and each monomer C-terminal has identical avtive spot, each
2 Zn are contained in active center2+(α and β), the distance between two zinc ioies isOne Zn2+(α) with two histidine
And the residue coordination of aspartic acid, another Zn2+(β) residue with two histidine is coordinated, the lysine of a carboxylation and water
Molecule (or hydroxide ion) by two zinc ion bridgings together, Zn2+(α) and OH-Distance beZn2+(β) and OH-
Distance be
According to active center and the Hydrolytic Mechanism of natural organophosphor hydrolysis simulation enzyme, the research group at inventor place is with 1-
Vinyl imidazole (1-VI) is function monomer, and methacrylic acid (MAA) is miscellaneous function monomer, the transition state analogs of paraoxon
4-nitrobenzyl (D4NP) is template molecule, has been synthesized by molecular imprinting design and has had organophosphor hydrolysis simulation enzymatic activity
Molecular blotting polymer microsphere.The paraoxon hydrolase activity of molecular blotting polymer microsphere prepared by the method is with paraoxon certainly
Hydrolyzing is compared, and hydrolysis efficiency maximum can improve 188 times, but the method preparation process is complicated, and needs after having reacted to remove mould
Plate molecule.
Summary of the invention
A technical problem to be solved by this invention is to provide a kind of simple to operate, it is possible to efficiently degrading organophosphorus
The synthetic method of polymer microballoon functional graphene oxide.
Another technical problem to be solved by this invention is the polymer microballoon functionalization oxygen for said method synthesis
Functionalized graphene provides a kind of new application.
Solve the technical scheme that above-mentioned technical problem used to be made up of following step:
1, graphene oxide grafted methacrylic acid hydroxyl ethyl ester
By ultrasonic disperse after graphene oxide chloride in anhydrous DMF, add hydroxyethyl methacrylate
Ethyl ester, drips anhydrous triethylamine, back flow reaction 12～24 hours under nitrogen protection, and product is done through methanol centrifuge washing, vacuum
Dry, obtain the graphene oxide of vinyl functionalization.
2, synthetic polymer microsphere functional graphene oxide
The graphene oxide of vinyl functionalization is joined in the mixed liquor that volume ratio is 9:1 of acetonitrile and methanol, room
Temperature ultrasonic disperse is uniform, adds ZnCl2, methacrylic acid, 1-vinyl imidazole, divinylbenzene, add under nitrogen protection
Azodiisobutyronitrile, then under nitrogen protection, room temperature condition, irradiates 48～72 hours with the ultraviolet light that wavelength is 365nm, and
And intermittent stirring in irradiation process；Having irradiated rear centrifugation, gained solid, after methanol washing, being centrifuged, uses ZnCl2Methanol
Solution hatches 20～40 minutes, and products therefrom is performing centrifugal separation on, is vacuum dried, and obtains polymer microballoon functionalization graphite oxide
Alkene.
In above-mentioned steps 1, described graphene oxide is 1:5 with hydroxyethyl methylacrylate, the mass ratio of anhydrous triethylamine
～10:1.5～3, preferential oxidation Graphene is 1:8:2 with hydroxyethyl methylacrylate, the mass ratio of anhydrous triethylamine.
In above-mentioned steps 2, the graphene oxide of described vinyl functionalization, ZnCl2, methacrylic acid, 1-vinyl miaow
Azoles, divinylbenzene, the mass ratio of azodiisobutyronitrile are 1:0.75～3:0.5～2:4～17:8.5～34:4～16, preferably
The graphene oxide of vinyl functionalization, ZnCl2, methacrylic acid, 1-vinyl imidazole, divinylbenzene, azo two isobutyl
The mass ratio of nitrile is 1:1.5:1.0:8.5:17:8.
The application in catalytic degradation organophosphor of the above-mentioned polymer microballoon functional graphene oxide, specifically used method
For: polymer microballoon functional graphene oxide being joined in organophosphor solution to be hydrolyzed, shaken at room temperature can be catalyzed
Machine phosphorus hydrolyzes, and wherein the addition of polymer microballoon functional graphene oxide adjusts according to content and the amount of hydrolysis of organophosphor.
Graphene oxide, using graphene oxide as the substrate of organophosphor hydrolysis simulation enzyme, is first grafted methyl by the present invention
2-(Acryloyloxy)ethanol, obtains the graphene oxide of vinyl functionalization, then by the method for polymerization, uses cross-linking agent divinyl
The graphene oxide of 1-vinyl imidazole with vinyl functionalization is polymerized by benzene jointly, adds ZnCl in the course of the polymerization process2With 1-
Vinyl imidazole is coordinated, and by 1-vinyl imidazole covalence graft in the surface of graphene oxide of vinyl functionalization, obtains novel
Organophosphor hydrolysis simulation enzymatic polymerization thing microsphere functional graphene oxide.
Graphene oxide of the present invention has stable mechanical performance, excellent hydrophilic, big specific surface area,
The most important thing is that its surface and edge contain more oxy radical, such as hydroxyl, carboxyl and epoxy radicals, can functionalization further, and
And owing to graphene oxide is rich in oxygen-containing functional group, there is the catalysis activity of hydrogen peroxide hydrolysis enzyme, can jointly participate in building
Enzyme active center, collaborative 1-vinyl imidazole catalyzing hydrolysis paraoxon.Test result indicate that, under the same conditions, the present invention gathers
The initial velocity of compound microsphere functional graphene oxide catalytic degradation ethyl paraoxon improves 230 times relative to blank,
The maximum initial velocity V of its catalysis ethyl paraoxon hydrolysismaxFor 0.014mmol/L min, Michaelis constant KmFor
13.4mmol/L, and there is preferable recycling rate of waterused, after reusing 5 times, hydrolysing activity only declines about 5.2%.The present invention
Polymer microballoon functional graphene oxide is in terms of the structure of degrading organic phosphor poisonous substance and detection organic phosphates biomimetic sensor
There is potential using value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene oxide of the vinyl functionalization that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph of the polymer microballoon functional graphene oxide that embodiment 1 obtains.
Fig. 3 is the scanning electron microscope (SEM) photograph of the histidine functional graphene oxide that comparative example 1 obtains.
Fig. 4 is graphene oxide (a), histidine functional graphene oxide (b), the graphene oxide of vinyl functionalization
The infrared spectrogram of (c), polymer microballoon functional graphene oxide (d).
Fig. 5 is graphene oxide (a), histidine functional graphene oxide (b), carboxylated graphene oxide (c), second
The graphene oxide (d) of thiazolinyl functionalization, the Raman spectrogram of polymer microballoon functional graphene oxide (e).
Fig. 6 is that the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1 obtains generates
Paranitrophenol uv absorption spectra at 400nm.
Fig. 7 is the dynamic of the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that obtains of embodiment 1～3
Force diagram figure.
Fig. 8 is blank group, experimental group and the kinetic curve figure of contrast groups catalytic degradation ethyl paraoxon.
Fig. 9 is the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1 obtains
Lineweaver-Burk schemes.
Figure 10 is the repetition of the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1 obtains
Using effect figure.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1, graphene oxide grafted methacrylic acid hydroxyl ethyl ester
Weigh 200mg graphene oxide (purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) add 100mL go from
In sub-water, ultrasonic disperse 1 hour, add 12g NaOH, ultrasonic disperse 30 minutes, be subsequently adding 10g monoxone, ultrasonic disperse
2 hours, centrifugation, after centrifugal 3 times of centrifugal gained solids with methanol washing, it is vacuum dried 12 hours at 55 DEG C, obtains
Carboxylated graphene oxide；Carboxylated graphene oxide is added in 20mL DMF, ultrasonic disperse 30
Minute, it being subsequently adding 40mL thionyl chloride, back flow reaction 24 hours, products therefrom is performing centrifugal separation on, anhydrous tetrahydro furan washing 3
Secondary, 55 DEG C be vacuum dried 12 hours, obtain the graphene oxide of chloride；By the graphene oxide ultrasonic disperse of chloride in
In the anhydrous DMF of 20mL, add 1.6g hydroxyethyl methylacrylate, be slowly added dropwise 0.4g under nitrogen protection
Anhydrous triethylamine, back flow reaction 24 hours, product through methanol centrifuge washing, 55 DEG C be vacuum dried 12 hours, obtain vinyl merit
The graphene oxide (see Fig. 1) of energyization.
2, synthetic polymer microsphere functional graphene oxide
The graphene oxide of 50mg vinyl functionalization is joined the mixing that volume ratio is 9:1 of 40mL acetonitrile and methanol
In liquid, ultrasonic 1 hour of room temperature, add 0.075g ZnCl2, 0.050g methacrylic acid, 0.425g1-vinyl imidazole,
0.850g divinylbenzene, under nitrogen protection, adds 0.400g azodiisobutyronitrile, then at nitrogen protection, room temperature condition
Under, irradiate 48 hours with the ultraviolet light that wavelength is 365nm, and intermittent stirring in irradiation process, irradiate rear centrifugation, institute
Solid washs centrifugation after 3 times through methanol, then with 8mL 100mmol/L ZnCl2Methanol solution hatch 30 minutes, from
The heart separates, and 45 DEG C are vacuum dried 12 hours, obtain polymer microballoon functional graphene oxide (see Fig. 2).
Comparative example 1
0.1550g histidine is dissolved in 5mL deionized water, adds 0.0225g ZnCl2, after being stirred at room temperature 30 minutes
Add 50mg graphene oxide, ultrasonic disperse 1 hour, add 5mL 200mmol/L NaOH aqueous solution, reaction 24 is stirred at room temperature
Hour, centrifugation, it is neutrality by centrifugal gained solid washing with alcohol to solution, then uses 100mmol/L ZnCl2First
Alcoholic solution is hatched 30 minutes, centrifugation, and 50 DEG C are vacuum dried 12 hours, obtain histidine functional graphene oxide (see figure
3)。
From Fig. 1～3, after graphene oxide grafted methacrylic acid hydroxyl ethyl ester, smooth, even curface presents thick
Close and highly cross-linked form, shows that hydroxyethyl methylacrylate has effectively been grafted to the surface of graphene oxide of chloride, enters
The graphene oxide of 1-vinyl imidazole with vinyl functionalization, by the method for polymerization, is jointly gathered by one step by divinylbenzene
Close, define, in surface of graphene oxide, the microsphere that particle diameter is 2～3 μm, and microsphere is evenly distributed, and has i.e. obtained polymer micro-
Ball functional graphene oxide；And the graphene oxide being grafted histidine in comparative example 1 is surface becomes coarse, out-of-flatness,
And thickness increases, and does not forms microsphere.
From fig. 4, it can be seen that curve c is at 1707cm-1The absworption peak at place is owing to the stretching vibration of C=C causes, and curve d
At 1707cm-1Place does not has peak, illustrates that the graphene oxide of vinyl functionalization passes through double bond covalence graft 1-vinyl imidazole.
Meanwhile, curve b and curve d is at 1370cm-1The weak absorbing peak at place is the stretching vibration peak due to C-N.In sum, successfully synthesize
Histidine functional graphene oxide and polymer microballoon functional graphene oxide.
As seen from Figure 5, at 1348cm-1And 1594cm-1Substantially there are two absworption peaks at place, is D peak and G peak respectively, and D peak is
By unordered sp3The carbon structure of hydridization causes, and G peak is by sp2The orderly kish shape structure that the carbon of hydridization produces causes
's.Graphene oxide, histidine functional graphene oxide, carboxylated graphene oxide, the oxidation stone of vinyl functionalization
Ink alkene and Raman spectral peaks intensity I of polymer microballoon functional graphene oxide(D)/I(G)Be respectively 0.593,0.602,
0.709、0.925、0.729.It is said that in general, the unordered degree i.e. sp of material with carbon element3The carbon of hydridization is with I(D)/I(G)Increase and increase,
This further illustrates the graphene oxide successfully synthesizing vinyl functionalization, and polymer microballoon functional graphene oxide
I(D)/I(G)Reduce on the contrary, be owing to polymer uniform is grafted on surface of graphene oxide, hidden carbon signal.
Embodiment 2
In the step 2 of embodiment 1, the graphene oxide consumption of vinyl functionalization is reduced to 25mg, other steps
Same as in Example 1, obtain polymer microballoon functional graphene oxide.
Embodiment 3
In the step 2 of embodiment 1, the graphene oxide consumption of vinyl functionalization is increased to 100mg, other steps
Same as in Example 1, obtain polymer microballoon functional graphene oxide.
Embodiment 4
The polymer microballoon functional graphene oxide of embodiment 1～3 synthesis answering in catalytic degradation ethyl paraoxon
With
2mg polymer microballoon functional graphene oxide is dispersed in 100 μ L acetonitriles, adds 875 μ L20mmol/L pH
The Tris-HCl buffer of=9.0, ultrasonic disperse 30 minutes, it is subsequently adding 25 μ L100mmol/L ethyl paraoxon acetonitrile solutions,
30 DEG C of vibrations, take 50 μ L reactant liquors in the different moment respectively, with 450 μ L deionized water dilutions, centrifugal, take supernatant 450 μ
L, detects the absworption peak of paranitrophenol at 400nm with ultraviolet-uisible spectrophotometer.Experimental result is shown in Fig. 6 and 7.
From Fig. 6 and 7, the activity of the polymer microballoon functional graphene oxide catalytic degradation of embodiment 1～3 synthesis
The highest, prolongation over time, the amount of hydrolysis of ethyl paraoxon is quickly increasing, is showing Inventive polymers microsphere functionalization
Graphene oxide can be catalyzed ethyl paraoxon hydrolysis, wherein the polymer microballoon functionalization of embodiment 1 synthesis effectively
The activity of graphene oxide is the highest.
In order to prove beneficial effects of the present invention, inventor is according to the method for embodiment 4, polymerization embodiment 1 synthesized
The histidine functional graphene oxide (contrast groups) that thing microsphere functional graphene oxide (experimental group) and comparative example 1 obtain is urged
The activity changing degraded ethyl paraoxon compares, and does blank test simultaneously, and result is shown in Fig. 8.As seen from the figure, at identical bar
Under part, the activity of the histidine functional graphene oxide catalytic degradation ethyl paraoxon that comparative example 1 obtains is very poor, right with blank
It is more or less the same according to group, and at the beginning of the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon of embodiment 1 synthesis
Speed improves 230 times relative to blank group.The polymer microballoon functional graphene oxide energy that the present invention synthesizes is described
Enough efficient catalytic degrading organic phosphors.
For the kinetic parameter of Study Polymer Melts microsphere functional graphene oxide hydrolyzing ethyl paraoxon, inventor will
2.0mg polymer microballoon functional graphene oxide is distributed in the Tris-HCl buffer of 20mmol/L pH=9.0, then
Adding the 100mmol/L ethyl paraoxon acetonitrile solution of different volumes, the cumulative volume making reaction system is 1mL, ethyl paraoxon
Ultimate density be respectively 1.0,1.25,1.65,2.5,5.0 and 7.5mmol/L, vibrate at 30 DEG C, respectively 0.5,2.5,
5,7.5,10,15,20,30,40,50,60 minutes time take 50 μ L mixed liquors, with 450 μ L water by dilution, centrifugal (10000rpm,
1min), take 450 μ L of supernatant liquid in cuvette, then measure paranitrophenol absorbance at 400nm.
The Hydrolytic catalyzing of polymer is evaluated with Michaelis-Menten enzyme kinetics model.Michaelis-Menton kinetics side
Formula: V0=Vmax[S]/(Km+ [S]), V0Represent the initial velocity of reaction, VmaxRepresenting the maximum initial velocity of reaction, [S] represents the end
Substrate concentration, KmIt is Michaelis constant, represents the affinity of substrate and enzyme, KmBeing worth the least, affinity is the highest, otherwise, KmIt is worth the biggest, parent
The lowest with power.In order to measure VmaxWith KmValue, the concentration range of ethyl paraoxon is confirmed as 1.0～7.5mmol/L.At pH
=9.0, under the conditions of polymer microballoon functional graphene oxide concentration is 2.0mg/mL, measure the oxidation of polymer microballoon functionalization
The Graphene ultraviolet-visible absorption spectroscopy to variable concentrations ethyl paraoxon catalyzing hydrolysis, thus it is anti-to obtain the hydrolysis of ethyl paraoxon
The initial velocity V answered0, with the 1/V reciprocal of initial velocity of reaction0Map with the inverse 1/ [S] of concentration of substrate, Lineweaver-can be obtained
Burk curve, such as Fig. 9.From Fig. 9, intercept and the slope of curve can obtain VmaxFor 0.014mmol/L min, KmFor 13.4mmol/
L。
Effect, inventor is reused for Study Polymer Melts microsphere functional graphene oxide hydrolyzing ethyl paraoxon
2mg polymer microballoon functional graphene oxide is dispersed in 100 μ L acetonitriles, adds 875 μ L20mmol/LpH=9.0's
Tris-HCl buffer, ultrasonic disperse 30 minutes, it is subsequently adding 25 μ L100mmol/L ethyl paraoxon acetonitrile solutions, at 30 DEG C
Vibration, takes 50 μ L reactant liquors after reacting 5 hours, with 450 μ L deionized water dilutions, centrifugal, takes supernatant 450 μ L, can by ultraviolet
See the absworption peak of paranitrophenol at spectrophotometer detection 400nm.And centrifugal gained solid acetonitrile and ethanol are washed respectively
After, at 100mmol/L ZnCl2Hatching in methanol solution 30 minutes, centrifugation, 45 DEG C are vacuum dried 12 hours, gained solid
Repeat use, be repeated 5 times altogether.Reuse effect and see Figure 10.As seen from the figure, the polymer microballoon functionalization of present invention synthesis
Graphene oxide still keeps preferably degraded catalysis ethyl paraoxon activity when reusing, and degrades and urge after using the 5th
Change activity and only decline about 5.2%, illustrate that the polymer microballoon functional graphene oxide that the present invention synthesizes can regenerate, and still
Keep the degraded catalysis activity of preferable paraoxon.
Claims (6)
1. the synthetic method of a polymer microballoon functional graphene oxide, it is characterised in that it is made up of following step:
(1) graphene oxide grafted methacrylic acid hydroxyl ethyl ester
By ultrasonic disperse after graphene oxide chloride in anhydrous DMF, add hydroxyethyl methacrylate second
Ester, drips anhydrous triethylamine under nitrogen protection, back flow reaction 12～24 hours, product through methanol centrifuge washing, vacuum drying,
Obtain the graphene oxide of vinyl functionalization；
(2) synthetic polymer microsphere functional graphene oxide
Being joined by the graphene oxide of vinyl functionalization in the mixed liquor that volume ratio is 9:1 of acetonitrile and methanol, room temperature surpasses
Sound is uniformly dispersed, and adds ZnCl2, methacrylic acid, 1-vinyl imidazole, divinylbenzene, add azo under nitrogen protection
Bis-isobutyronitrile, then under nitrogen protection, room temperature condition, irradiates 48～72 hours with the ultraviolet light that wavelength is 365nm, and shines
It is emitted through intermittent stirring in journey；Having irradiated rear centrifugation, gained solid, after methanol washing, being centrifuged, uses ZnCl2Methanol solution
Hatching 20～40 minutes, products therefrom is performing centrifugal separation on, is vacuum dried, and obtains polymer microballoon functional graphene oxide.
The synthetic method of polymer microballoon functional graphene oxide the most according to claim 1, it is characterised in that: in step
Suddenly, in (1), described graphene oxide is 1:5～10:1.5～3 with hydroxyethyl methylacrylate, the mass ratio of anhydrous triethylamine.
The synthetic method of polymer microballoon functional graphene oxide the most according to claim 1, it is characterised in that: in step
Suddenly, in (1), described graphene oxide is 1:8:2 with hydroxyethyl methylacrylate, the mass ratio of anhydrous triethylamine.
The synthetic method of polymer microballoon functional graphene oxide the most according to claim 1, it is characterised in that: in step
Suddenly in (2), the graphene oxide of described vinyl functionalization, ZnCl2, methacrylic acid, 1-vinyl imidazole, divinyl
Benzene, the mass ratio of azodiisobutyronitrile are 1:0.75～3:0.5～2:4～17:8.5～34:4～16.
The synthetic method of polymer microballoon functional graphene oxide the most according to claim 1, it is characterised in that: in step
Suddenly in (2), the graphene oxide of described vinyl functionalization, ZnCl2, methacrylic acid, 1-vinyl imidazole, divinyl
Benzene, the mass ratio of azodiisobutyronitrile are 1:1.5:1:8.5:17:8.
6. polymer microballoon functional graphene oxide the answering in catalytic degradation organophosphor of the method synthesis of claim 1
With.
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| CN107537565A (en) * | 2016-06-29 | 2018-01-05 | 中国科学院大连化学物理研究所 | Cross linked amphoteric polymeric supported precious metal catalyst and preparation and alcohol method for oxidation |
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