CN109718745A - A kind of Ianus type magnetic blotting nanometer sheet and its preparation method and application - Google Patents
A kind of Ianus type magnetic blotting nanometer sheet and its preparation method and application Download PDFInfo
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- CN109718745A CN109718745A CN201910072483.9A CN201910072483A CN109718745A CN 109718745 A CN109718745 A CN 109718745A CN 201910072483 A CN201910072483 A CN 201910072483A CN 109718745 A CN109718745 A CN 109718745A
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- janus
- nanometer sheet
- ianus
- molecularly imprinted
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003463 adsorbent Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- -1 3- dimethylamino-propyl Chemical group 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical class ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000008236 heating water Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 239000005642 Oleic acid Substances 0.000 abstract description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000002525 ultrasonication Methods 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 230000005661 hydrophobic surface Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 239000006249 magnetic particle Substances 0.000 description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CKTSBUTUHBMZGZ-SHYZEUOFSA-N 2'‐deoxycytidine Chemical compound O=C1N=C(N)C=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 CKTSBUTUHBMZGZ-SHYZEUOFSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- DEVYBOZJYUYBMC-KVVVOXFISA-N iron;(z)-octadec-9-enoic acid Chemical compound [Fe].CCCCCCCC\C=C/CCCCCCCC(O)=O DEVYBOZJYUYBMC-KVVVOXFISA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- YKBGVTZYEHREMT-KVQBGUIXSA-N 2'-deoxyguanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@H]1C[C@H](O)[C@@H](CO)O1 YKBGVTZYEHREMT-KVQBGUIXSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- 239000002126 C01EB10 - Adenosine Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229960005305 adenosine Drugs 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002777 nucleoside Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- JDXQWYKOKYUQDN-UHFFFAOYSA-N 3-hydroxypyrrolidine-2,5-dione Chemical class OC1CC(=O)NC1=O JDXQWYKOKYUQDN-UHFFFAOYSA-N 0.000 description 1
- 208000030507 AIDS Diseases 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of magnetic molecularly imprinted nanometer sheets of Ianus type and its preparation method and application, belong to functional material technical field.Janus hollow microsphere has been made by sol-gal process in the present invention, ultrasonication obtain containing amino, while the Janus nanometer sheet containing chlorine element；Then using surface chlorine element as the initiator of atom transfer radical polymerization, dA is template molecule, 5-(2- methoxy-ethylene base) -2'- BrdU be function monomer, Janus nanometer sheet hydrophobic surface be grafted dA molecularly imprinted polymer；Again by the bonding action between amino and carboxyl, by the Fe of Coated with Oleic Acid3O4Particle is integrated on the water-wetted surface of Janus, prepares the magnetic molecularly imprinted nanometer sheet adsorbent of Janus type, and obtained material is used for the adsorbing separation of dA.The trace adsorbent material that the present invention constructs has good, the advantage of large amount of adsorption and quick separating to object dA of selectivity.
Description
Technical field
The present invention relates to a kind of magnetic molecularly imprinted nanometer sheets of Ianus type and its preparation method and application, belong to functionality
Field of material technology.
Background technique
2'- desoxyadenossine (dA) is genomic medicine and gene as one of the purines nucleosides with good physiological activity
The important raw material of engineering research.In addition, dA has good physiological activity, it is many antiviral and antitumors and anti-AIDS
The generally acknowledged good intermediate of drug, therefore have extremely widespread demand on the market.Currently, the acquisition methods of common dA have synthesis
Method, crystallisation and absorption method, but the by-product of synthetic method is more, and the concentration of product is low；Crystallisation energy consumption is high, generating rate compared with
Slowly；Absorption method has the advantages that recovery rate is high and easily operates continuously to dA micro in product, but the selectivity of common adsorbents, suction
Attached capacity and mass transfer rate still need to be further increased.Therefore according to dA molecular structure the characteristics of, from dA and adsorbent adsorption potential
The interaction of point is set out, and is studied new adsorbent and is used to obtain high-purity dA of crucial importance.
Molecularly imprinted polymer (MIPs), commonly referred to as synthetic antibody analogies can carry out specificity point to target molecule
Son identification.Compared with natural antibody, MIPs is more stable, be content with very little it is widely applied requirement and also it is cheap.It is surface imprinted
Polymer (SMIPs) is polymeric adsorbant molecular engram recognition site constructed in host surface, shows high combination
Ability, rapid mass transfer and fast binding kinetics.So far, a variety of silica-base materials prepare SMIPs frequently as host material,
The silicon-based substrate being related to is mostly spherical or tubular structure, such as silica, zeolite, kaolin, molecular sieve, halloysite nanotubes
Deng.Nanometer sheet has higher specific surface area, and has differentiation directionality due to their higher aspect ratios, can be real
Existing multiple functions act on same nanometer sheet matrix.
It is magnetic molecularly imprinted polymer using the compound imprinted polymer that supperparamagnetic particles are matrix preparation
(MMIPs).The identification of object and the magnetic response quick separating of adsorbent can be achieved at the same time in MMIPs, effectively prevents by numerous
Trivial centrifugation, standing, filtering and etc. material is separated with mother liquor.Currently, existing research is using the modified SiO of magnetic-particle2It receives
Rice piece prepares MMIPs, but the introducing of magnetic particle can cover imprinted sites and generate uneven distribution, to reduce in conjunction with holding
Amount.Meanwhile the introducing of trace polymerization nitride layer easily leads to saturation magnetization reduction, and the MMIPs after multiple adsorption-desorption cycle
The magnetic-particle of leakage reversible can not restore.
Summary of the invention
The present invention be solve functional site present in existing MMIPs compound adsorbent it is Chong Die with region, it is selectively low and
One of technical bottlenecks such as inferior separating effect provide a kind of preparation method of Janus type magnetic blotting nanometer sheet adsorbent, and real
The Selective Separation of dA is showed.
The present invention passes through sol-gal process first and Janus hollow microsphere has been made, and is contained on one side by ultrasonication
Amino (hydrophilic), another side contain the Janus nanometer sheet of chlorine element (hydrophobic)；Then using surface chlorine element as atom transfer freedom
Base polymerize the initiator of (ATRP), and dA forms hydrogen bond with dA and have the 5-(2- methoxyl group of preferable matching as template molecule
Vinyl) -2'- BrdU (AcrU) is as function monomer, in Janus nanometer sheet hydrophobic surface grafting dA molecular engram
Polymer (Janus-MIPs)；Again by the bonding action between amino and carboxyl, by the Fe of Coated with Oleic Acid3O4Particle is integrated to
On the water-wetted surface of Janus, it is prepared for the magnetic molecularly imprinted nanometer sheet adsorbent (Janus-MMIPs) of Janus type, and will obtain
Material be applied to aqueous solution in dA efficient selective absorption and separate.
To achieve the purpose that above-mentioned technology, the technical solution adopted by the present invention is that:
The present invention provides a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent (Janus-MMIPs) of Ianus type,
Described method includes following steps:
(1) carboxy-modified Fe3O4The preparation of particle:
0.2 mol/L aqueous solution sodium oleate is mixed according to a certain percentage with 0.2 mol/L ferric chloride in aqueous solution.Filter to obtain brown
Oleic acid iron complex makes its dispersion with n-hexane, then is washed with distilled water, dry in drier.It is at room temperature that this is compound
Object is added in the 20mL ethyl alcohol containing a certain amount of oleic acid.Mixture is transferred in autoclave and is heated to 180 DEG C and keeps 5
Hour.After having reacted, with the Fe of ethanol washing black oil acid blocked3O4Nano particle (Fe3O4NPs it) and with magnet separates.It will
Product is redispersed in toluene with the concentration of 10 mg/mL.
Wherein the volume ratio of the aqueous solution sodium oleate and ferric chloride in aqueous solution is 1 mL:1-2 mL, the ethyl alcohol
In the amount of oleic acid that the contains concentration that is be 10-15 %.
(2) preparation of Janus nanometer sheet:
It regard a certain amount of HSMA and water as continuous phase in beaker, adjusts pH to 3-4 with HCl solution.Take a certain amount of solid stone
A certain amount of 3- aminopropyl triethoxysilane (APTES) and a certain amount of 3- chloropropyl triethoxysilane is added in wax
(CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) is used as dispersed phase, in high-speed stirred by dispersed phase after 70 heating water baths
It is added dropwise in continuous phase, stirs 5 min, mixture reacts 12 h at 70 DEG C.Then, it is collected by centrifugation, washes away oily phase, surpass
Sound is broken, obtains Janus nanometer sheet, is dried in vacuo.
(3) preparation of Janus molecularly imprinted polymer (Janus-MIPs):
Firstly, by 2'- desoxyadenossine (dA), 5-(2- methoxy-ethylene base) -2'- BrdU (AcrU) be dissolved in dimethyl sulfoxide and
In the mixed liquor of acetonitrile, room temperature leads to 30 min of nitrogen, is protected from light 1.5 h of self assembly；Add ethylene glycol dimethacrylate
(EGDMA) and Janus nanometer sheet N, N, N are added, after 30 DEG C of 0.5 h of stirring, N, N- pentamethyl-diethylenetriamine (PMDEIA),
Copper chloride (CuCl2) and ascorbic acid (VC), mixed solution persistently stir and at 70 DEG C after 12 h of heating in water bath for reaction,
Product is collected by centrifugation, then Janus-MIPs is washed using methanol/hydrochloric acid mixed solution as eluant, eluent (7: 3, V: V)
Purifying, to remove unreacted template molecule and organic solvent, finally, 45oMake the Janus-MIPs dry 24 of purifying under C
h。
The 2'- desoxyadenossine and 5-(2- methoxy-ethylene base) -2'- BrdU mass ratio are as follows: 1: 4-5；Institute
The dosage for stating the mixed liquor of 2'- desoxyadenossine and dimethyl sulfoxide and acetonitrile is 1 g: 200-250 mL；
The volume ratio of dimethyl sulfoxide and acetonitrile in the mixed liquor of the dimethyl sulfoxide and acetonitrile are as follows: 1:3-4；
The logical nitrogen time is 30min, and the self assembly time is 1.5h；
The dosage of the 2'- desoxyadenossine, Janus nanometer sheet and ethylene glycol dimethacrylate is 1g:2-3g:10-12mL；
The N, N, N, N, N- pentamethyl-diethylenetriamine, copper chloride, ascorbic acid dosage be 1.0mL:0.2-0.3g:
0.08-0.1g。
(4) preparation of magnetic Ianus type bifunctional molecule trace adsorbent (Janus-MMIPS):
By Fe3O4NPs is dissolved in ultrasonic disperse in methanol, then (1- (3- dimethylamino-propyl) -3- ethyl is added in mixed solution
Carbodiimide hydrochloride) (EDC), N- hydroxysuccinimides (NHS), it is uniformly mixed, ultrasound is anti-after adding Janus-MIPs
20 min are answered, are collected by centrifugation, 12 h are then dried in vacuo at 45 DEG C.
The Janus-MIPs and Fe3O4The mass ratio of NPs is 1: 0.1-0.15；
The Fe3O4NPs, N- hydroxysuccinimides and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
Mass ratio is 1:1.5-3: 1.5-3.
Compared with prior art, beneficial effects of the present invention embody as follows:
The present invention improves the special knowledge of imprinted layer to form hydrogen bond with preferable matching AcrU as function monomer with dA
Other property, while Janus nano material is prepared for using sol-gel method, and using the dual character of Janus nanometer sheet to magnetic point
It has been carried out from functional area and dA molecular recognition function region individually designed, has effectively prevented interacting for two kinds of functions.From
And the magnetic molecular engram adsorbent material of tool is constructed, have selectivity good, the large amount of adsorption to object dA and quickly point
From advantage.
Detailed description of the invention
Fig. 1 be the Janus nanometer sheet (a) prepared in embodiment 1, Janus-MIPs nanometer sheet (b) and (c) and
The scanning electron microscope (SEM) photograph of Janus-MMIPs nanometer sheet (d).
Fig. 2 is Janus nanometer sheet (a), the Janus-MIPs nanometer sheet (b), Janus-MMIPs (c) prepared in embodiment 1
And Fe3O4(d) infrared spectrum.
Fig. 3 is that Janus nanometer sheet, Janus-MIPs nanometer sheet, the X-ray of Janus-MMIPs prepared in embodiment 1 is spread out
Penetrate the energy spectrum diagram of (XRD).
Fig. 4 is the Janus nanometer sheet, Janus-MIPs nanometer sheet, the thermogravimetric of Janus-MMIPs point prepared in embodiment 1
Analyse (TGA) curve.
Fig. 5 is the Fe prepared in embodiment 13O4The hysteresis loop of NPs and Janus-MMIPs.
Fig. 6 is that the Janus-MMIPs and Janus-MNIPs of preparation adsorb the dynamics data and model of dA in 298 K
Matched curve.
Fig. 7 is that the Janus-MMIPs and Janus-MNIPs of preparation adsorb the equilibrium data of dA in 298 K and model is intended
Close curve.
Fig. 8 is the one pack system absorption result to dA, dG, AMP, dC of the Janus-MMIPs and Janus-MNIPs of preparation.
Specific embodiment
Preferably to make those skilled in the art understand that technical solution of the present invention, combined with specific embodiments below and attached drawing
To technical solution of the present invention further instruction.
Recognition performance evaluation carries out by the following method in the specific embodiment of the invention:
It is completed using Staticadsorption experiment: the certain density dA solution of 5 mL is added in centrifuge tube, be added a certain amount of
Janus-MMIPs adsorbent is placed in 25 DEG C of constant temperature waters and stands several hours, and dA content is divided with UV, visible light after absorption
Photometric determination, and adsorption capacity is calculated according to result；The dA solution that 5 mL initial concentrations are 300 μm of ol/L is added to
In centrifuge tube, a certain amount of Janus-MMIPs adsorbent is added, is taken out under certain time gradient respectively, and according to result meter
Adsorption capacity is calculated, for participating in the dynamic performance of research Janus-MMIPs adsorbent.Select several structures similar with property
Nucleoside compound, such as 2- deoxyguanosine (dG), 2- deoxycytidine (dC) and 5 '-monophosphates-adenosine (AMP) etc. as choosing
Selecting property adsorbate participates in the recognition performance of research adsorbent.
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
(1) carboxy-modified Fe3O4The preparation of particle
0.2 mol/L aqueous solution sodium oleate, 100 mL is mixed with the 0.2 mol/L ferric chloride in aqueous solution of 100 mL.It filters
Brown oleic acid iron complex makes its dispersion with n-hexane, then is washed with distilled water three times, dry in drier.At room temperature
The compound is added in the 20.0 mL ethyl alcohol containing 10% oleic acid.Mixture is transferred in autoclave and is heated to 180
DEG C keep 5 hours.After having reacted, with the Fe of ethanol washing black oil acid blocked3O4Nano particle (Fe3O4NPs) and magnet is used
Separation.Product is redispersed in toluene with 10 mg/mL concentration.
(2) preparation of Janus nanometer sheet
It regard a certain amount of 10 wt%HSMA and water as continuous phase in beaker, adjusts pH to 3-4 with the HCl solution of 2 mol/L.It takes
A certain amount of 3- aminopropyl triethoxysilane (APTES) and a certain amount of 3- chloropropyl three is added in a certain amount of solid paraffin
Ethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) are used as dispersed phase, 12000 after 70 DEG C of heating water baths
Dispersed phase is added dropwise in continuous phase the high-speed stirred of rpm, stirs 5 min, and mixture reacts 12 h at 70 DEG C.Then,
It is collected by centrifugation, washs ultrasonication three times with ethyl alcohol, n-hexane, obtain Janus nanometer sheet, be then dried in vacuo at 45 DEG C
12 h。
(3) preparation of Janus molecularly imprinted polymer (Janus-MIPs)
Firstly, by the 5-(2- methoxy-ethylene base of the 2'- desoxyadenossine (dA) of 0.1 g and 0.45 g) -2'- BrdU
(AcrU) it is dissolved in the dimethyl sulfoxide of 5 mL and the acetonitrile mixture of 15 mL, room temperature leads to 30 min of nitrogen, is protected from light self assembly 1.5
h；Add the ethylene glycol dimethacrylate (EGDMA) of 1.12 mL and the Janus nanometer sheet of 0.2 g, 30 DEG C of stirrings 0.5
After h, the N, N, N of 0.1 mL, N, the copper chloride (CuCl of N- pentamethyl-diethylenetriamine (PMDEIA), 0.03 g is added2) and
The ascorbic acid (VC) of 0.01 g, mixed solution are persistently stirred and at 70 DEG C after 12 h of heating in water bath for reaction, are collected by centrifugation
Product then washs Janus-MIPs using methanol/hydrochloric acid mixed solution as eluant, eluent (7: 3, V: V) and purifies, with
Unreacted template molecule and organic solvent are removed, finally, making dry 24 h of the Janus-MIPs of purifying at 45 DEG C.
(4) preparation of magnetic Ianus type bifunctional molecule trace adsorbent (Janus-MMIPS)
By the Fe of 0.0025 g3O4NPs is dissolved in ultrasonic disperse in 20 mL methanol, then is added 0.0041 g's in mixed solution
(1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride) of N- hydroxysuccinimides (NHS) and 0.0041 g
(EDC), it is uniformly mixed, adds 20 min of ultrasonic reaction after the Janus-MIPs of 0.02 g, be collected by centrifugation, then at 45 DEG C
It is dried in vacuo 12 h.
Fig. 1 be the Janus nanometer sheet (a) prepared in the embodiment, Janus-MIPs nanometer sheet (b) and (c) and
The scanning electron microscope (SEM) photograph of Janus-MMIPs nanometer sheet (d).Show that molecularly imprinted polymer is successfully prepared from figure, while can see
Magnetic particle is obviously connected in the other side of nanometer sheet out, shows that magnetic molecularly imprinted polymer is successfully prepared.
Fig. 2 is Janus nanometer sheet (a), the Janus-MIPs nanometer sheet (b), Janus-MMIPs prepared in the embodiment
(c) and Fe3O4(d) infrared spectrum.The 3200-3500 cm in a, b, c-1With 2918 cm-1There is broad absorption band, it is believed that
It is the stretching vibration of the N-H and O-H key of material, in 1715 cm-1The peak at place is considered the characteristic peak of amido bond, and in 701cm-1
There is appearance at place, it is believed that and it is the characteristic peak of C-Cl key, 509 cm in c and d-1Locate appearance, it is Fe that this is corresponding3O4Feature
Peak, magnetic molecularly imprinted polymer indicated above are successfully prepared.
Fig. 3 is Janus nanometer sheet, Janus-MIPs nanometer sheet, the X-ray of Janus-MMIPs prepared in the embodiment
The energy spectrum diagram of diffraction (XRD), there are Fe by Janus-MMIPs in figure3O4Structure, with Fe3O4Peak having the same is located at 30.2 °,
It is 35.6 °, 43.4 °, 50.1 °, 54.1 °, 57.3 ° and 62.6 °, corresponding with its index (111), (220), (311), (400),
(422), (511), (440) and (511).Show to be successfully prepared magnetic polymer.
Fig. 4 is the Janus nanometer sheet, Janus-MIPs nanometer sheet, the thermogravimetric of Janus-MMIPs point prepared in the embodiment
(TGA) curve is analysed, Janus-MMIPs final low about 16 % of heat loss ratio Janus-MIPs, this is mainly due to Janus-
Magnetic particle in MIPS surface modification, the i.e. Fe of Janus-MIPs surface modification3O4Amount be about 16%.And Janus-MIPs is most
Whole low about 12 % of heat loss ratio Janus nanometer sheet, there is one on the surface of the heat loss proof Janus-MIPs in this stage
The imprinted layer of layer dA.
Fig. 5 is the Fe prepared in the embodiment3O4The hysteresis loop of NPs and Janus-MMIPs, two curves do not lag
Phenomenon, Fe3O4NPs and Janus-MMIPs is superparamagnetism, Fe3O4The saturation that NPs and Janus-MMIPs are obtained at room temperature
The intensity of magnetization (Ms) value is respectively 49.71 emu/g and 12.23 emu/g, shows that Janus-MMIPs comes with enough magnetic force
Meet the needs of Magneto separate.
Embodiment 2:
(1) carboxy-modified Fe3O4The preparation of particle
0.2 mol/L aqueous solution sodium oleate, 100 mL is mixed with the 0.2 mol/L ferric chloride in aqueous solution of 150 mL.It filters
Brown oleic acid iron complex makes its dispersion with n-hexane, then is washed with distilled water three times, dry in drier.At room temperature
The compound is added in the 20.0 mL ethyl alcohol containing 12.5% oleic acid.Mixture is transferred in autoclave and is heated to
180 DEG C are kept for 5 hours.After having reacted, with the Fe of ethanol washing black oil acid blocked3O4Nano particle (Fe3O4NPs it) is used in combination
Magnet separation.Product is redispersed in toluene with 10 mg/mL concentration.
(2) preparation of Janus nanometer sheet
It regard a certain amount of 10 wt%HSMA and water as continuous phase in beaker, adjusts pH to 3-4 with the HCl solution of 2 mol/L.It takes
A certain amount of 3- aminopropyl triethoxysilane (APTES) and a certain amount of 3- chloropropyl three is added in a certain amount of solid paraffin
Ethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) are used as dispersed phase, 12000 after 70 DEG C of heating water baths
Dispersed phase is added dropwise in continuous phase the high-speed stirred of rpm, stirs 5 min, and mixture reacts 12 h at 70 DEG C.Then,
It is collected by centrifugation, washs ultrasonication three times with ethyl alcohol, n-hexane, obtain Janus nanometer sheet, be then dried in vacuo at 45 DEG C
12 h。
(3) preparation of Janus molecularly imprinted polymer (Janus-MIPs)
Firstly, by the 5-(2- methoxy-ethylene base of the 2'- desoxyadenossine (dA) of 0.1 g and 0.40 g) -2'- BrdU
(AcrU) it is dissolved in the dimethyl sulfoxide of 5 mL and the acetonitrile mixture of 17.5 mL, room temperature leads to 30 min of nitrogen, is protected from light self assembly
1.5 h；Add the ethylene glycol dimethacrylate (EGDMA) of 1 mL and the Janus nanometer sheet of 0.2 g, 30 DEG C of stirrings 0.5
After h, the N, N, N of 0.10 mL, N, the copper chloride (CuCl of N- pentamethyl-diethylenetriamine (PMDEIA), 0.02 g is added2) and
The ascorbic acid (VC) of 0.008 g, mixed solution are persistently stirred and at 70 DEG C after 12 h of heating in water bath for reaction, are collected by centrifugation
Product then washs Janus-MIPs using methanol/hydrochloric acid mixed solution as eluant, eluent (7: 3, V: V) and purifies, with
Unreacted template molecule and organic solvent are removed, finally, making dry 24 h of the Janus-MIPs of purifying at 45 DEG C.
(4) preparation of magnetic Ianus type bifunctional molecule trace adsorbent (Janus-MMIPS):
By the Fe of 0.002 g3O4NPs is dissolved in ultrasonic disperse in 20 mL methanol, then the N- of 0.003 g is added in mixed solution
(1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride) of hydroxysuccinimides (NHS) and 0.003 g
(EDC), it is uniformly mixed, adds 20 min of ultrasonic reaction after the Janus-MIPs of 0.02 g, be collected by centrifugation, then at 45 DEG C
It is dried in vacuo 12 h.
Embodiment 3:
(1) carboxy-modified Fe3O4The preparation of particle
0.2 mol/L aqueous solution sodium oleate, 100 mL is mixed with the 0.2 mol/L ferric chloride in aqueous solution of 200 mL.It filters
Brown oleic acid iron complex makes its dispersion with n-hexane, then is washed with distilled water three times, dry in drier.At room temperature
The compound is added in the 20.0 mL ethyl alcohol containing 15% oleic acid.Mixture is transferred in autoclave and is heated to 180
DEG C keep 5 hours.After having reacted, with the Fe of ethanol washing black oil acid blocked3O4Nano particle (Fe3O4NPs) and magnet is used
Separation.Product is redispersed in toluene with 10 mg/mL concentration.
(2) preparation of Janus nanometer sheet
It regard a certain amount of 10 wt % HSMA and water as continuous phase in beaker, adjusts pH to 3-4 with the HCl solution of 2 mol/L.
A certain amount of solid paraffin is taken, a certain amount of 3- aminopropyl triethoxysilane (APTES) and a certain amount of 3- chloropropyl is added
Triethoxysilane (CPTES) and a certain amount of tetraethyl orthosilicate (TEOS) are used as dispersed phase, after 70 DEG C of heating water baths
Dispersed phase is added dropwise in continuous phase the high-speed stirred of 12000 rpm, stirs 5 min, and mixture reacts 12 h at 70 DEG C.
Then, it is collected by centrifugation, washs ultrasonication three times with ethyl alcohol, n-hexane, obtain Janus nanometer sheet, then the vacuum at 45 DEG C
Dry 12 h.
(3) preparation of Janus molecularly imprinted polymer (Janus-MIPs)
Firstly, by the 5-(2- methoxy-ethylene base of the 2'- desoxyadenossine (dA) of 0.1 g and 0.5 g) -2'- BrdU
(AcrU) it is dissolved in the dimethyl sulfoxide of 5 mL and the acetonitrile mixture of 20 mL, room temperature leads to 30 min of nitrogen, is protected from light self assembly 1.5
h；Add the ethylene glycol dimethacrylate (EGDMA) of 1.2 mL and the Janus nanometer sheet of 0.2 g, 30 DEG C of 0.5 h of stirring
Afterwards, the N, N, N of 0.10 mL, N, the copper chloride (CuCl of N- pentamethyl-diethylenetriamine (PMDEIA), 0.025 g is added2) and
The ascorbic acid (VC) of 0.008 g, mixed solution are persistently stirred and at 70 DEG C after 12 h of heating in water bath for reaction, are collected by centrifugation
Product then washs Janus-MIPs using methanol/hydrochloric acid mixed solution as eluant, eluent (7: 3, V: V) and purifies, with
Unreacted template molecule and organic solvent are removed, finally, making dry 24 h of the Janus-MIPs of purifying at 45 DEG C.
(4) preparation of magnetic Ianus type bifunctional molecule trace adsorbent (Janus-MMIPS)
By the Fe of 0.003 g3O4NPs is dissolved in ultrasonic disperse in 20 mL methanol, then the N- hydroxyl of 0.009g is added in mixed solution
(1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride) (EDC) of base amber Asia amide (NHS) and 0.009 g,
It is uniformly mixed, adds 20 min of ultrasonic reaction after the Janus-MIPs of 0.02 g, be collected by centrifugation, then vacuum is dry at 45 DEG C
Dry 12 h.
Test example 1:
Taking 5 mL initial concentrations is that the dA solution of 300 μm of ol/L is added separately in centrifuge tube, is separately added into 5 mg embodiments 1
The Janus-MMIPs adsorbent of middle preparation takes out when 10,20,30,60,120,240,360,480 min respectively；It is logical
Magnet is crossed to separate trace adsorbent and solution.DA concentration in filtrate is by ultraviolet specrophotometer under the wavelength of 259 nm
Measurement is calculated, Fig. 6 has been obtained according to result, Fig. 6 is the Janus-MMIPs prepared in embodiment 1 and Janus-MNIPs 298
The dynamics data and models fitting curve of dA are adsorbed when K, while calculating the time for reaching adsorption equilibrium；The result shows that most
The adsorption capacity of first 60 min, Janus-MMIPs and Janus-MNIPs quickly increase, and pattern of descriptive parts molecule can be easily
Diffuse into adsorbent.And the adsorption efficiency of Janus-MMIPs is obviously faster than Janus-MNIPs, holds to the absorption of dA
Amount is also bigger than Janus-MNIPs, illustrates the imprinted sites for having a large amount of skies on the surface Janus-MMIPs.After quick adsorption, by
In the decline of dA concentration and the reduction of binding site quantity, the rate of adsorption sharply declines and reaches balance in 2.0 h.
Test example 2:
Taking 5 mL initial concentrations is respectively the dA solution of 50,100,150,200,300,500,700,900,1000 μm of ol/L
It is added in centrifuge tube, is separately added into the Janus-MMIPs adsorbent prepared in 5 mg embodiments 1, test fluid is placed on 25 DEG C
Water-bath in stand 10 h after, trace adsorbent and solution are separated by magnet, unadsorbed dA molecular concentration is used respectively
Ultraviolet-uisible spectrophotometer measures under the wavelength of 259 nm, obtains Fig. 7 according to result, Fig. 7 is Janus- in embodiment 1
MMIPs and Janus-MNIPs adsorbs the equilibrium data and models fitting curve of dA in 298 K, meet Langmuir and
Freundlich Adsorption Model, while calculating adsorption capacity.The result shows that under the conditions of 25 DEG C, when reaching adsorption equilibrium
Janus-MMIPs is 61.22 μm of ol/g to the maximum adsorption capacity of dA, and Janus-MNIPs is to dA's when reaching adsorption equilibrium
Maximum adsorption capacity is 42.36 μm of ol/g respectively, at the same temperature the maximum adsorption of Janus-MMIPs ratio Janus-MNIPs
Amount wants high, it was demonstrated that Janus-MMIPs is the adsorbent of effectively identification dA a kind of.
Test example 3:
Select 2- deoxyguanosine (dG), 2- deoxycytidine (dC) and 5 '-monophosphates-adenosine (AMP) alternatively property adsorbate pair
According to, the solution of three of the above compound is prepared respectively, concentration is 700 μm of ol/L, take 5 mL to be added in centrifuge tube respectively, then
It is separately added into the trace adsorbent prepared in 5 mg embodiments 1 and non-trace adsorbent, the water-bath that test fluid is placed on 25 DEG C is shaken
Swing in device after 10 h, separated trace adsorbent and solution by magnet, unadsorbed dA molecular concentration use respectively it is ultraviolet can
See that spectrophotometer measures under the wavelength of 259 nm, and Fig. 8 is obtained according to result.The result shows that Janus-MMIPs is to four kinds
The adsorbance of compound follows the sequence of dA ﹥ dG ﹥ AMP ﹥ dC, it can therefore be concluded that the surface of Janus-MMIPs exists and dA shape
The consistent imprinted sites of shape size make Janus-MMIPs have absorption specificity well to dA.
Claims (10)
1. a kind of magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type, the adsorbent has superparamagnetism, the material tool
There is hydrophilic and hydrophobic dual character.
2. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type described in claim 1, the method
Include the following steps:
(1) carboxy-modified Fe is prepared3O4Particle；
(2) Janus nanometer sheet is prepared；
(3) Janus molecularly imprinted polymer is prepared:
Firstly, by 2'- desoxyadenossine, 5-(2- methoxy-ethylene base) -2'- BrdU is dissolved in the mixing of dimethyl sulfoxide and acetonitrile
In liquid, after room temperature leads to nitrogen, it is protected from light self assembly；Ethylene glycol dimethacrylate and Janus nanometer sheet are added, is stirred and evenly mixed
Afterwards, N, N, N is added, N, N- pentamethyl-diethylenetriamine, copper chloride and ascorbic acid, mixed solution persistently stirs and heating water bath
After reaction, product is collected by centrifugation, then Janus-MIPs is washed using methanol/hydrochloric acid mixed solution as eluant, eluent and is purified,
To remove unreacted template molecule and organic solvent, desciccate；
(4) magnetic Ianus type bifunctional molecule trace adsorbent is prepared:
By Fe3O4NPs is dissolved in ultrasonic disperse in methanol, then 1- (3- dimethylamino-propyl) -3- ethyl carbon is added in mixed solution
Diimmonium salt hydrochlorate, N- hydroxysuccinimides are uniformly mixed, add ultrasonic reaction after Janus-MIPs, be collected by centrifugation, so
After be dried in vacuo.
3. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is, 2'- desoxyadenossine described in step (3) and 5-(2- methoxy-ethylene base) mass ratio of -2'- BrdU are as follows: 1:
4-5。
4. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is that 2'- desoxyadenossine described in step (3) is 1 g: 200-250 with the dosage of dimethyl sulfoxide and the mixed liquor of acetonitrile
mL；
The volume ratio of dimethyl sulfoxide and acetonitrile in the mixed liquor of the dimethyl sulfoxide and acetonitrile are as follows: 1:3-4；
The logical nitrogen time is 30min, and the self assembly time is 1.5h.
5. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is that the dosage of 2'- desoxyadenossine, Janus nanometer sheet and ethylene glycol dimethacrylate described in step (3) is 1 g:
2-3 g:10-12mL；
After the addition ethylene glycol dimethacrylate and Janus nanometer sheet, stirring condition is 30 DEG C of 0.5 h of stirring.
6. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is, N described in step (3), N, N, N, N- pentamethyl-diethylenetriamine, copper chloride, ascorbic acid dosage be 1.0mL:
0.2-0.3g:0.08-0.1g；
The heating in water bath for reaction condition is 12 h of heating in water bath for reaction at 70 DEG C.
7. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is, Janus-MIPs and Fe described in step (4)3O4The mass ratio of NPs is 1: 0.1-0.15.
8. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is, Fe described in step (4)3O4NPs, N- hydroxysuccinimides and 1- (3- dimethylamino-propyl) -3- ethyl carbon two are sub-
The mass ratio of amine hydrochlorate is 1:1.5-3: 1.5-3.
9. a kind of preparation method of the magnetic molecularly imprinted nanometer sheet adsorbent of Ianus type according to claim 2, special
Sign is, ultrasonic reaction 30min described in step (4).
10. the suction that the magnetic molecularly imprinted nanometer sheet adsorbent of a kind of Ianus type described in claim 1 is used for 2'- desoxyadenossine
Fufen from.
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