CN106117470B - The synthetic method of polymer microballoon functional graphene oxide and its application of catalytic degradation organophosphor - Google Patents
The synthetic method of polymer microballoon functional graphene oxide and its application of catalytic degradation organophosphor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 230000015556 catabolic process 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 9
- 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 17
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 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
- 238000005406 washing Methods 0.000 claims description 4
- 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 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001059 synthetic polymer Polymers 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 230000000149 penetrating effect Effects 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 13
- 108090000790 Enzymes Proteins 0.000 abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 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
- 229940088598 enzyme Drugs 0.000 description 12
- 235000014304 histidine Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- 239000007853 buffer solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002411 histidines Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- -1 Graphite alkene Chemical class 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
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011701 zinc Substances 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
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000005949 Malathion Substances 0.000 description 1
- 206010058119 Neurogenic shock Diseases 0.000 description 1
- 206010033799 Paralysis 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
- 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
- 229940022698 acetylcholinesterase Drugs 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
- 125000003342 alkenyl group Chemical group 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
- 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
- 239000003575 carbonaceous material Substances 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
- 238000006555 catalytic 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
- 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
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 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
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 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
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 230000001272 neurogenic effect Effects 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of synthetic method of polymer microballoon functional graphene oxide and its application of catalytic degradation organophosphor, this method by 1 vinyl imidazole by cross-linker divinylbenzene covalence graft hydroxyethyl methacrylate functionalization surface of graphene oxide, polymer microballoon functional graphene oxide is successfully synthesized, effectively simulates the activated centre of organophosphor hydrolytic enzyme.Under the same conditions, the initial velocity of Inventive polymers microballoon functional graphene oxide catalytic degradation ethyl paraoxon improves 230 times relative to blank control, it is catalyzed the maximum initial velocity V of ethyl paraoxon hydrolysismaxFor 0.014mmol/Lmin, Michaelis constant KmFor 13.4mmol/L, and there is preferable recycling rate of waterused, hydrolysing activity only declines about 5.2% after reusing 5 times.Inventive polymers microballoon functional graphene oxide has potential application 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, and in particular to a kind of polymer microballoon functionalization oxidation
The synthetic method of graphene and its application of catalytic degradation organophosphor.
Background technology
Organophosphorus compounds is often widely used in insecticide, plasticizer, petroleum additive and chemical warfare poison
Agent, especially three ester of organic phosphoric acid, such as paraoxon, parathion, malathion, are applied to agriculture usually as crop protection agent
Industry field.But these materials have potential toxicity, can cause neurogenic shock, paralysis, shock and death.In chemical warfare
In be used as the compound of nerve gas, such as sarin, tabun and soman, fall within organophosphorus ester.These compounds suppress to participate in
The key enzyme of nerve signal --- acetylcholinesterase, and then cause neurogenic disease.Therefore, these organophosphorus compounds
Degraded be worldwide an important challenge, and much researchs are making great efforts to solve the problems, such as that this is important.
At present, the method for studying relatively broad degrading organic phosphor acid esters is enzymatic hydrolysis.Although natural organophosphor hydrolysis
Enzyme energy efficiently degrading organophosphorus, but its stability is poor, and be not easy to prepare, using being very restricted.Therefore, foundation
The structure and its degrading organic phosphor mechanism of natural organophosphor hydrolytic enzyme, design synthesize stable, efficient, inexpensive organophosphor hydrolysis mould
Intend the unremitting pursuit that enzyme is researcher.
Naturally isolated obtained organophosphor hydrolytic enzyme is dimer, and each monomer C-terminal has identical avtive spot, each
Contain 2 Zn in activated centre2+The distance between (α and β), two zinc ions areOne Zn2+(α) and two histidines
And the residue coordination of aspartic acid, another Zn2+The residue of (β) and two histidines are coordinated, the lysine and water of a carboxylation
Molecule (or hydroxide ion) by two zinc ion bridgings together, Zn2+(α) and OH-Distance beZn2+(β) and OH-
Distance be
Activated centre and Hydrolytic Mechanism according to natural organophosphor hydrolysis simulation enzyme, the research group where inventor is with 1-
Vinyl imidazole (1-VI) is function monomer, and methacrylic acid (MAA) is miscellaneous function monomer, the transition state analog of paraoxon
4- nitrobenzyls (D4NP) are template molecule, and having been synthesized by molecular imprinting technology design has organophosphor hydrolysis simulation enzymatic activity
Molecular blotting polymer microsphere.The paraoxon hydrolase activity and paraoxon of molecular blotting polymer microsphere prepared by this method are certainly
Hydrolyzing is compared, and hydrolysis efficiency maximum can improve 188 times, but this method preparation process is complicated, and needs to remove mould after having reacted
Plate molecule.
The content of the invention
A technical problem to be solved by this invention is to provide a kind of easy to operate, is capable of 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 above method synthesis
Graphite alkene provides a kind of new application.
Technical solution is made of following step used by solving above-mentioned technical problem：
1st, graphene oxide grafted methacrylic acid hydroxyl ethyl ester
By ultrasonic disperse after graphene oxide chloride in anhydrous n,N-Dimethylformamide, hydroxyethyl methacrylate is added
Ethyl ester, is added dropwise anhydrous triethylamine under nitrogen protection, and when back flow reaction 12~24 is small, product is done through methanol centrifuge washing, vacuum
It is dry, obtain the graphene oxide of vinyl functionalization.
2nd, synthetic polymer microballoon functional graphene oxide
It is 9 by the volume ratio that the graphene oxide of vinyl functionalization is added to acetonitrile and methanol:In 1 mixed liquor, room
Warm ultrasonic disperse is uniform, adds ZnCl2, methacrylic acid, 1- vinyl imidazoles, divinylbenzene, add under nitrogen protection
Azodiisobutyronitrile, then nitrogen protection, under room temperature, with wavelength be 365nm ultraviolet light 48~72 it is small when, and
And intermittent stirring in irradiation process；Centrifugation, obtained solid use ZnCl after methanol is washed, centrifuged after having irradiated2Methanol
Solution is incubated 20~40 minutes, and products therefrom is centrifuged, is dried in vacuo, and obtains polymer microballoon functionalization graphite oxide
Alkene.
In above-mentioned steps 1, the mass ratio of the graphene oxide and hydroxyethyl methacrylate, anhydrous triethylamine is 1:5
~10:1.5~3, the mass ratio of preferably graphene oxide and hydroxyethyl methacrylate, anhydrous triethylamine is 1:8:2.
In above-mentioned steps 2, graphene oxide, the ZnCl of the vinyl functionalization2, methacrylic acid, 1- vinyl miaows
Azoles, divinylbenzene, the mass ratio of azodiisobutyronitrile are 1:0.75~3:0.5~2:4~17:8.5~34:4~16, preferably
Graphene oxide, the ZnCl of vinyl functionalization2, methacrylic acid, 1- vinyl imidazoles, divinylbenzene, two isobutyl of azo
The mass ratio of nitrile is 1:1.5:1.0:8.5:17:8.
Application of the above-mentioned polymer microballoon functional graphene oxide in catalytic degradation organophosphor, specifically used method
For：Polymer microballoon functional graphene oxide is added in organic phosphorus solution to be hydrolyzed, shaken at room temperature can be catalyzed
Machine phosphorus hydrolyzes, and wherein the addition of polymer microballoon functional graphene oxide is adjusted according to the content and amount of hydrolysis of organophosphor.
Matrix of the present invention using graphene oxide as organophosphor hydrolysis simulation enzyme, is grafted methyl by graphene oxide first
Hydroxy-ethyl acrylate, obtains the graphene oxide of vinyl functionalization, then by the method for polymerization, with crosslinking agent divinyl
1- vinyl imidazoles polymerize by benzene jointly with the graphene oxide of vinyl functionalization, add ZnCl in the course of the polymerization process2With 1-
Vinyl imidazole is coordinated, and by 1- vinyl imidazoles covalence graft in the surface of graphene oxide of vinyl functionalization, is obtained new
Organophosphor hydrolysis simulation enzyme --- polymer microballoon functional graphene oxide.
Graphene oxide of the present invention has stable mechanical performance, excellent hydrophily, big specific surface area,
Above all its surface and edge contain more oxy radical, such as hydroxyl, carboxyl and epoxy group, can further functionalization, and
And since graphene oxide is rich in oxygen-containing functional group, there is the catalytic activity of hydrogen peroxide hydrolysis enzyme, can participate in building jointly
Enzyme active center, cooperates with 1- vinyl imidazole catalyzing hydrolysis paraoxon.Test result indicates that under the same conditions, the present invention is poly-
The initial velocity of compound microballoon functional graphene oxide catalytic degradation ethyl paraoxon improves 230 times relative to blank control,
It is catalyzed the maximum initial velocity V of ethyl paraoxon hydrolysismaxFor 0.014mmol/Lmin, Michaelis constant KmFor
13.4mmol/L, and there is preferable recycling rate of waterused, hydrolysing activity only declines about 5.2% after reusing 5 times.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
With potential application value.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene oxide for the vinyl functionalization that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope (SEM) photograph for the polymer microballoon functional graphene oxide that embodiment 1 obtains.
Fig. 3 is the scanning electron microscope (SEM) photograph for 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
(c), the infrared spectrogram of polymer microballoon functional graphene oxide (d).
Fig. 5 is graphene oxide (a), histidine functional graphene oxide (b), the graphene oxide (c) of carboxylated, second
The graphene oxide (d) of alkenyl functionalization, the Raman spectrogram of polymer microballoon functional graphene oxide (e).
Fig. 6 is the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon generation that embodiment 1 obtains
Uv absorption spectra of the p-nitrophenol at 400nm.
Fig. 7 is the dynamic of the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1~3 obtains
Force diagram figure.
Fig. 8 is the dynamic curve diagram of blank control group, experimental group and 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 for the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1 obtains
Using renderings.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, graphene oxide grafted methacrylic acid hydroxyl ethyl ester
Weigh 200mg graphene oxides (being purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) add 100mL go from
In sub- water, when ultrasonic disperse 1 is small, 12g NaOH are added, ultrasonic disperse 30 minutes, then adds 10g monoxones, ultrasonic disperse
2 it is small when, centrifuge, will centrifugation obtained solid with methanol wash centrifugation 3 times after, at 55 DEG C vacuum drying 12 it is small when, obtain
The graphene oxide of carboxylated；The graphene oxide of carboxylated is added in 20mL n,N-Dimethylformamide, ultrasonic disperse 30
Minute, 40mL thionyl chlorides are then added, when back flow reaction 24 is small, products therefrom is centrifuged, anhydrous tetrahydro furan washing 3
It is secondary, 55 DEG C vacuum drying 12 it is small when, obtain the graphene oxide of chloride；By the graphene oxide ultrasonic disperse of chloride in
In the anhydrous n,N-Dimethylformamide of 20mL, 1.6g hydroxyethyl methacrylates are added, 0.4g is slowly added dropwise under nitrogen protection
Anhydrous triethylamine, when back flow reaction 24 is small, product through methanol centrifuge washing, 55 DEG C vacuum drying 12 it is small when, obtain vinyl work(
The graphene oxide of energyization (see Fig. 1).
2nd, synthetic polymer microballoon functional graphene oxide
It is 9 by the volume ratio that the graphene oxide of 50mg vinyl functionalization is added to 40mL acetonitriles and methanol:1 mixing
In liquid, when room temperature ultrasound 1 is small, 0.075g ZnCl are added2, 0.050g methacrylic acids, 0.425g1- vinyl imidazoles,
0.850g divinylbenzenes, under nitrogen protection, add 0.400g azodiisobutyronitriles, then in nitrogen protection, room temperature condition
Under, with wavelength be 365nm ultraviolet light 48 it is small when, and intermittent stirring in irradiation process, centrifugation after having irradiated, institute
Solid centrifuges after methanol washs 3 times, then with 8mL 100mmol/L ZnCl2Methanol solution be incubated 30 minutes, from
The heart separates, and when 45 DEG C of vacuum drying 12 are small, obtains polymer microballoon functional graphene oxide (see Fig. 2).
Comparative example 1
0.1550g histidines are dissolved in 5mL deionized waters, add 0.0225g ZnCl2, after being stirred at room temperature 30 minutes
50mg graphene oxides are added, when ultrasonic disperse 1 is small, 5mL 200mmol/L NaOH aqueous solutions is added, reaction 24 is stirred at room temperature
Hour, centrifuge, centrifugation obtained solid is washed to solution with ethanol and is in neutrality, then with 100mmol/L ZnCl2First
Alcoholic solution is incubated 30 minutes, is centrifuged, and when 50 DEG C of vacuum drying 12 are small, obtains histidine functional graphene oxide (see figure
3)。
By Fig. 1~3 as it can be seen that after graphene oxide grafted methacrylic acid hydroxyl ethyl ester, smooth, even curface shows thick
Close and highly cross-linked form, shows that hydroxyethyl methacrylate has effectively been grafted to the surface of graphene oxide of chloride, into
One step is gathered 1- vinyl imidazoles and the graphene oxide of vinyl functionalization with divinylbenzene by the method for polymerization jointly
Close, form the microballoon that particle diameter is 2~3 μm in surface of graphene oxide, and microballoon is evenly distributed, that is, it is micro- to have obtained polymer
Ball functional graphene oxide；And the graphene oxide that histidine is grafted in comparative example 1 is that surface becomes coarse, out-of-flatness,
And thickness increase, does not form microballoon.
From fig. 4, it can be seen that curve c is in 1707cm-1The absworption peak at place is due to caused by the stretching vibration of C=C, and curve d
In 1707cm-1Locate no peak, illustrate the graphene oxide of vinyl functionalization by double bond covalence graft 1- vinyl imidazoles.
Meanwhile curve b and curve d are in 1370cm-1The weak absorbing peak at place is due to the stretching vibration peak of C-N.In conclusion successfully synthesize
Histidine functional graphene oxide and polymer microballoon functional graphene oxide.
As seen from Figure 5, in 1348cm-1And 1594cm-1Substantially there are two absworption peaks at place, is D peaks and G peaks respectively, D peaks are
By unordered sp3Caused by the carbon structure of hydridization, G peaks are by sp2The orderly kish shape structure that the carbon of hydridization produces causes
's.Graphene oxide, histidine functional graphene oxide, the graphene oxide of carboxylated, the oxidation stone of vinyl functionalization
The Raman spectral peaks intensity I of black alkene and polymer microballoon functional graphene oxide(D)/I(G)Respectively 0.593,0.602,
0.709、0.925、0.729.In general, unordered degree, that is, sp of carbon material3The carbon of hydridization is with I(D)/I(G)Increase and increase,
This further illustrates the graphene oxide for successfully synthesizing vinyl functionalization, and polymer microballoon functional graphene oxide
I(D)/I(G)Reduce on the contrary, be due to that polymer uniform is grafted on surface of graphene oxide, covered carbon signal.
Embodiment 2
In the step 2 of embodiment 1, the graphene oxide dosage of vinyl functionalization is reduced to 25mg, other steps
It is same as Example 1, obtain polymer microballoon functional graphene oxide.
Embodiment 3
In the step 2 of embodiment 1, the graphene oxide dosage of vinyl functionalization is increased into 100mg, other steps
It is same as Example 1, obtain polymer microballoon functional graphene oxide.
Embodiment 4
The polymer microballoon functional graphene oxide that embodiment 1~3 synthesizes answering in catalytic degradation ethyl paraoxon
With
2mg polymer microballoon functional graphene oxides are dispersed in 100 μ L acetonitriles, add 875 μ L20mmol/L pH
=9.0 Tris-HCl buffer solutions, ultrasonic disperse 30 minutes, then adds 25 μ L100mmol/L ethyl paraoxon acetonitrile solutions,
In 30 DEG C of vibrations, 50 μ L reaction solutions are taken different at the time of respectively, are diluted with 450 μ L deionized waters, and centrifugation, takes 450 μ of supernatant
L, with the absworption peak of paranitrophenol at ultraviolet-uisible spectrophotometer detection 400nm.Experimental result is shown in Fig. 6 and 7.
By Fig. 6 and 7 as it can be seen that the activity for the polymer microballoon functional graphene oxide catalytic degradation that embodiment 1~3 synthesizes
It is higher, with the extension of time, the amount of hydrolysis of ethyl paraoxon is quickly increasing, show Inventive polymers microballoon functionalization
Graphene oxide can effectively be catalyzed ethyl paraoxon hydrolysis, the polymer microballoon functionalization that wherein embodiment 1 synthesizes
The active highest of graphene oxide.
In order to prove beneficial effects of the present invention, inventor is according to the method for embodiment 4, the polymerization that embodiment 1 is synthesized
The histidine functional graphene oxide (contrast groups) that thing microballoon functional graphene oxide (experimental group) is obtained with comparative example 1 is urged
The activity for changing degraded ethyl paraoxon is compared, while does blank control test, and the result is shown in Fig. 8.As seen from the figure, in identical bar
Under part, histidine functional graphene oxide catalytic degradation ethyl paraoxon that comparative example 1 obtains it is active very poor, with blank pair
It is not much different according to group, and the polymer microballoon functional graphene oxide catalytic degradation ethyl paraoxon that embodiment 1 synthesizes is first
Speed improves 230 times relative to blank control group.Illustrate the polymer microballoon functional graphene oxide energy that the present invention synthesizes
Enough efficient catalytic degrading organic phosphors.
For the kinetic parameter of Study Polymer Melts microballoon functional graphene oxide hydrolyzing ethyl paraoxon, inventor will
2.0mg polymer microballoon functional graphene oxides are distributed in the Tris-HCl buffer solutions of 20mmol/L pH=9.0, then
The 100mmol/L ethyl paraoxon acetonitrile solutions of different volumes are added, the cumulative volume for 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, vibrated at 30 DEG C, respectively 0.5,2.5,
5th, 7.5,10,15,20,30,40,50,60 minutes when take 50 μ L mixed liquors, it is diluted with 450 μ L water, centrifugation (10000rpm,
1min), 450 μ L of supernatant liquid are taken in cuvette, then measure absorbance of the p-nitrophenol 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, VmaxRepresent the maximum initial velocity of reaction, [S] represents bottom
Thing concentration, KmIt is Michaelis constant, represents the affinity of substrate and enzyme, KmIt is worth smaller, affinity is higher, conversely, KmValue is bigger, parent
It is lower with power.In order to measure VmaxWith KmValue, the concentration range of ethyl paraoxon is confirmed as 1.0~7.5mmol/L.In pH
=9.0, under the conditions of polymer microballoon functional graphene oxide concentration is 2.0mg/mL, the functionalization oxidation of measure polymer microballoon
Graphene hydrolyzes anti-the ultraviolet-visible absorption spectroscopy of various concentrations ethyl paraoxon catalyzing hydrolysis so as to obtain 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 curves, such as Fig. 9.The intercept of curve and slope can obtain V from Fig. 9maxFor 0.014mmol/Lmin, KmFor 13.4mmol/
L。
For the reuse effect of Study Polymer Melts microballoon functional graphene oxide hydrolyzing ethyl paraoxon, inventor
2mg polymer microballoon functional graphene oxides are dispersed in 100 μ L acetonitriles, add 875 μ L20mmol/LpH=9.0's
Tris-HCl buffer solutions, ultrasonic disperse 30 minutes, then adds 25 μ L100mmol/L ethyl paraoxon acetonitrile solutions, at 30 DEG C
Vibration, reaction 5 it is small when after take 50 μ L reaction solutions, with 450 μ L deionized waters dilute, centrifugation, take 450 μ L of supernatant, with it is ultraviolet can
See the absworption peak of paranitrophenol at spectrophotometer detection 400nm.And centrifugation obtained solid is washed respectively with acetonitrile and ethanol
Afterwards, in 100mmol/L ZnCl2It is incubated 30 minutes, centrifuges in methanol solution, when 45 DEG C of vacuum drying 12 are small, obtained solid
Re-use, be repeated 5 times altogether.Reuse effect and see Figure 10.As seen from the figure, the polymer microballoon functionalization that the present invention synthesizes
Graphene oxide still keeps preferable degraded catalysis ethyl paraoxon activity when reusing, and is urged using degraded after 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 catalytic activity of preferable paraoxon.
Claims (5)
1. a kind of synthetic method of polymer microballoon functional graphene oxide, it is characterised in that it is made of following step：
(1) graphene oxide grafted methacrylic acid hydroxyl ethyl ester
By ultrasonic disperse after graphene oxide chloride in anhydrous n,N-Dimethylformamide, hydroxyethyl methacrylate second is added
Ester, is added dropwise anhydrous triethylamine under nitrogen protection, when back flow reaction 12~24 is small, product through methanol centrifuge washing, vacuum drying,
Obtain the graphene oxide of vinyl functionalization；
(2) synthetic polymer microballoon functional graphene oxide
It is 9 by the volume ratio that the graphene oxide of vinyl functionalization is added to acetonitrile and methanol:In 1 mixed liquor, room temperature surpasses
Sound is uniformly dispersed, and adds ZnCl2, methacrylic acid, 1- vinyl imidazoles, divinylbenzene, add azo under nitrogen protection
Bis-isobutyronitrile, then in nitrogen protection, under room temperature, with wavelength be 365nm ultraviolet light 48~72 it is small when, and shine
Intermittent stirring during penetrating；Centrifugation, obtained solid use ZnCl after methanol is washed, centrifuged after having irradiated2Methanol solution
It is incubated 20~40 minutes, products therefrom is centrifuged, is dried in vacuo, and obtains polymer microballoon functional graphene oxide；
Graphene oxide, the ZnCl of above-mentioned vinyl functionalization2, methacrylic acid, 1- vinyl imidazoles, divinylbenzene, azo
The mass ratio of bis-isobutyronitrile is 1:0.75~3:0.5~2:4~17:8.5~34:4~16.
2. the synthetic method of polymer microballoon functional graphene oxide according to claim 1, it is characterised in that：In step
Suddenly in (1), the mass ratio of the graphene oxide and hydroxyethyl methacrylate, anhydrous triethylamine is 1:5~10:1.5~3.
3. the synthetic method of polymer microballoon functional graphene oxide according to claim 1, it is characterised in that：In step
Suddenly in (1), the mass ratio of the graphene oxide and hydroxyethyl methacrylate, anhydrous triethylamine is 1:8:2.
4. the synthetic method of polymer microballoon functional graphene oxide according to claim 1, it is characterised in that：In step
Suddenly in (2), graphene oxide, the ZnCl of the vinyl functionalization2, methacrylic acid, 1- vinyl imidazoles, divinyl
Benzene, the mass ratio of azodiisobutyronitrile are 1:1.5:1:8.5:17:8.
5. polymer microballoon functional graphene oxide the answering in catalytic degradation organophosphor of the method synthesis of claim 1
With.
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