CN103804571B - A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof - Google Patents
A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof Download PDFInfo
- Publication number
- CN103804571B CN103804571B CN201310373052.9A CN201310373052A CN103804571B CN 103804571 B CN103804571 B CN 103804571B CN 201310373052 A CN201310373052 A CN 201310373052A CN 103804571 B CN103804571 B CN 103804571B
- Authority
- CN
- China
- Prior art keywords
- oleic acid
- metal ion
- ion
- temperature
- nanogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000005642 Oleic acid Substances 0.000 claims abstract description 70
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 31
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 30
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 30
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000013019 agitation Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 29
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 241000233803 Nypa Species 0.000 claims description 10
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000000274 adsorptive effect Effects 0.000 abstract description 5
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- -1 ion oleic acid compound Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000010926 purge Methods 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 239000000499 gel Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000006870 function Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 239000007863 gel particle Substances 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000002210 biocatalytic effect Effects 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000011557 critical solution Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical class O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229960001156 mitoxantrone Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention proposes a kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof.It is prepared by following preparation method: (1) prepares metallic print ion oleic acid compound；(2) by gained compound and Thermo-sensitive function monomer N N-isopropylacrylamide, crosslinking agent N, N ' methylene-bisacrylamide and nonionic emulsifier Qu Latong X 100, mix in aqueous, ultrasonically treated formation emulsion, magnetic agitation maintaining nitrogen purge, being added dropwise over initiator sodium peroxydisulfate, heating causes cross-linking polymerization；(3) metallic print ion in product is eluted, then dialyse purifying, freeze-drying.The novel metal ion blotting nanogel of the present invention has temperature and pH Lazer property, metallic print ion is had stable identity and adsorptive selectivity, adsorption/desorption additive process is reversible, controlled, and renewable, recycling, its preparation method is simple, operating condition is gentle.
Description
Technical field
The present invention relates to environmental functional technical field of polymer materials, be specifically related to a kind of hud typed temperature and pH Lazer
Property metal ion trace nanogel and preparation method thereof.
Background technology
Molecule (ion) imprinted polymer is the novel high polymer material that one is capable of identify that specific template molecule (ion).
This kind of imprinted polymer defines the sky matching with template molecule (ion) structure and can be combineding with each other in the course of the polymerization process
Cave, has special compatibility and identity by " memory effect " in hole to microsphere (ion), thus in enrichment point
From aspects such as, SPE, UF membrane, biology sensor and biological enzymes, there is important using value.Chinese patent
Application includes that CN102659971A, CN102304197A, CN102068968A, CN102824899A, CN102603965A report
Some metal ion imprinted polymers, as ion blotting bulk polymer, ion blotting microballoon, ion blotting integral post, from
Sub-trace interpenetration network hydrogel and Thermo-sensitive ion blotting gel.But, conventional ion imprinted polymer is generally by merit
Directly it is embedded in high molecular polymer after energy monomer (such as Isosorbide-5-Nitrae-dihydroxy anthraquinone) is compound with metal ion, its merit used
Can there is no crosslinkable functionality by monomer, it is impossible to by the polymer of cross-linking polymerization synthetic mesh structure, due to polymer orifices
The restriction of gap structure and diffusion inside effect has had a strong impact on the adsorption effect of imprinted polymer and has selected performance.On the other hand,
Traditional ion blotting gelatin polymer is the most unstable to compatibility and the adsorptive selectivity of metallic print ion, and it is with " mould
Plate trace " void structure and the validity of binding site easily disturbed by other metal ions and environmental condition, thus lead
Cause its selection hydraulic performance decline to metallic print ion, simultaneously as the rigid structure of macromolecular scaffold and physics and chemistry inertia, these
The binding site of gel macromolecule network is difficult to activation and regeneration, and the absorption of metallic print ion is the most inconvenient with elution process
Regulation and control.Although current published Thermo-sensitive ion blotting gel rubber material has certain ion identification ability and temperature is sensitive
Property, but gel polymeric network structure defective tightness, apparent yardstick (gel particle particle diameter is more than 100 microns) bigger than normal, only by it
Single Thermo-sensitive is difficult to the structure effect of metallic print ion binding site on Effective Regulation gel three-dimensional network, and polymerisation institute
The ligand monomer (such as chloromethylbenzene ethyl) used often has stronger toxicity, is not suitable for the most extensively applying.Therefore, anxious
Need to develop one can selective absorption special metal ion, again can by different approaches realize adsorption/desorption additive process reversible/
Controlled environmentally friendly ion blotting nanogel polymer.
Summary of the invention
It is an object of the invention to provide a kind of hud typed temperature-and pH-sensitivity metal ion trace nanogel
And preparation method thereof.The novel nano gel that the present invention provides is with Thermo-sensitive poly-N-isopropyl acrylamide as shell, and to hold concurrently
The compound that oleic acid and the metallic print ion of tool environmental organism security and pH sensitiveness is formed is core, its to trace metal from
Son has a stable selective absorption, and it is attached all can to control the adsorption/desorption of metallic print ion by regulation temperature or pH
Process, the simultaneously hud typed temperature of the present invention and the pH Lazer property renewable technique of nanogel is simple, it is effective to reuse.
The hud typed temperature of present invention offer and pH Lazer property metal ion trace nanogel, it is characterised in that by such as
Lower preparation method prepares:
(1) preparation of metallic print ion-oleic acid compound: by the metal salt solution containing imprinted templates and oleic acid, successively
Joining in water-ethanol-n-hexane mixed solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, is heated at reflux 1 ~ 4 hour；
After reaction terminates, take the oil phase of upper strata metal ion-oleic acid compound, first wash with water 1 ~ 3 time, then rotation boils off except n-hexane,
Products therefrom is metallic print ion-oleic acid compound；
(2) preparation of hud typed metal ion trace nanogel: by metallic print ion-oleic acid compound and Thermo-sensitive
Function monomer NIPA, crosslinking agent N, N '-methylene-bisacrylamide and nonionic emulsifier Qu Latong
X-100, adds deionized water mixing in there-necked flask, and ultrasonically treated 10 ~ 30 minutes, magnetic agitation formed emulsion, persistently leads to
Nitrogen, is added dropwise over initiator sodium peroxydisulfate, causes heat polymerization under constant temperature；
(3) metallic print ion wash-out: after (2) reaction terminates, product is first with under the nitric acid normal temperature of 0.5 ~ 2mol/L
Elute more than 2 hours, use instead in the NaOH of 0.1 ~ 1mol/L after wash-out and the acid solution of residual, then use deionized water dialysis 1 ~ 3 instead
My god, dialysis is after purification-40 ~-50 DEG C of freeze-dryings.
In described step (1), the mol ratio of described slaine and oleic acid is 1:2 ~ 3, the body of described water-ethanol-n-hexane
Long-pending ratio is 1 ~ 5:1 ~ 5:5 ~ 10, described slaine and the oleic acid total dosage in water-ethanol-n-hexane mixed solvent be 0.1 ~
1.5 mol/L, described in be heated at reflux condition at 60 ~ 70 DEG C 1 ~ 4 h；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl third in described step (2)
The mol ratio of acrylamide is 1:5 ~ 20, and both total dosages are 0.05 ~ 1 mol/L；
Optional, described crosslinking agent N, N '-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 0.5 ~ 10%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.05 ~ 0.5%, described initiator mistake
The weight/volume percent of sodium sulphate is 0.01 ~ 0.1%, and heat polymerization condition is under 65 ~ 75 DEG C of constant temperature 2 ~ 6 hours.
In described step (1), the mol ratio of slaine and oleic acid is 1:2, and the volume ratio of described water-ethanol-n-hexane is
3:4:7, described slaine and the oleic acid total dosage in water-ethanol-n-hexane mixed solvent is 0.1 ~ 0.5 mol/L；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl third in described step (2)
The mol ratio of acrylamide is 1:6.87, and both total dosages are 0.1 ~ 0.5 mol/L;
Optional, described crosslinking agent N, N '-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 3%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.1%, described initiator persulfuric acid
The weight/volume percent of sodium is 0.1%, and polymeric reaction condition is under 70 DEG C of constant temperature 4 ~ 6 hours.
Described metal ion is Cu2+, Fe2+, Au3+；
Optional, described slaine is chlorate, nitrate, sulfate, acetate, perchlorate.
The present invention also protects described hud typed temperature and the preparation method of pH Lazer property metal ion trace nanogel, its
It is characterised by, the preparation of (1) metallic print ion-oleic acid compound: by the metal salt solution containing imprinted templates and oleic acid, successively
Joining in water-ethanol-n-hexane mixed solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, is heated at reflux 1 ~ 4 h；Instead
After should terminating, take the oil phase of upper strata metal ion-oleic acid compound, first wash with water 1 ~ 3 time, then rotation boils off except n-hexane, institute
Obtain product and be metallic print ion-oleic acid compound；
(2) preparation of hud typed metal ion trace nanogel: by metallic print ion-oleic acid compound and Thermo-sensitive
Function monomer NIPA, crosslinking agent N, N '-methylene-bisacrylamide and nonionic emulsifier Qu Latong
X-100, adds deionized water mixing in there-necked flask, and ultrasonically treated 10 ~ 30 minutes, magnetic agitation formed emulsion, persistently leads to
Nitrogen, is added dropwise over initiator sodium peroxydisulfate, causes heat polymerization under constant temperature；
(3) metallic print ion wash-out: after (2) reaction terminates, product is first with under the nitric acid normal temperature of 0.5 ~ 2mol/L
Elute more than 2 hours, use instead in the NaOH of 0.1 ~ 1mol/L after wash-out and the acid solution of residual, then use deionized water dialysis 1 ~ 3 instead
My god, dialysis is after purification-40 ~-50 DEG C of freeze-dryings.
In described step (1), the mol ratio of described slaine and oleic acid is 1:2 ~ 3, the body of described water-ethanol-n-hexane
Long-pending ratio is 1 ~ 5:1 ~ 5:5 ~ 10, described slaine and the oleic acid total dosage in water-ethanol-n-hexane mixed solvent be 0.1 ~
1.5 mol/L, described in be heated at reflux condition at 60 ~ 70 DEG C 1 ~ 4 h；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl third in described step (2)
The mol ratio of acrylamide is 1:5 ~ 20, and both total dosages are 0.05 ~ 1 mol/L；
Optional, described crosslinking agent N, N '-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 0.5 ~ 10%.
Optional, the volume/volume percentage of described emulsifying agent Qu Latong-100 is 0.05 ~ 0.5%, described initiator mistake
The weight/volume percent of sodium sulphate is 0.01 ~ 0.1%, and heat polymerization condition is under 65 ~ 75 DEG C of constant temperature 2 ~ 6 hours.
In described step (1), the mol ratio of slaine and oleic acid is 1:2, and the volume ratio of described water-ethanol-n-hexane is
3:4:7, described slaine and the oleic acid total dosage in water-ethanol-n-hexane mixed solvent is 0.1 ~ 0.5 mol/L；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl third in described step (2)
The mol ratio of acrylamide is 1:6.87, and both total dosages are 0.1 ~ 0.5 mol/L;
Optional, described crosslinking agent N, N '-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 3%；
Optional, the volume/volume percentage of described emulsifying agent Qu Latong-100 is 0.1%, described initiator sodium peroxydisulfate
Weight/volume percent be 0.1%, polymeric reaction condition is under 70 DEG C of constant temperature 4 ~ 6 hours.
Described metal ion is Cu2+, Fe2+, Au3+；
Optional, described slaine is chlorate, nitrate, sulfate, acetate, perchlorate.
The present invention also protects described hud typed temperature and pH Lazer property metal ion trace nanogel for metal ion
Enrichment and the purposes of separation.
The present invention also protects described hud typed temperature and pH Lazer property metal ion trace nanogel in situ sampling
With the purposes polluting environmental dynamic monitor.
The invention provides different metal ion and (include Cu2+、Fe2+、Au3+) trace nanogel.By combining Thermo-sensitive
Monomer NIPA, uses molecular imprinting, in advance (templated metal ion is included Cu2+、Fe2+、Au3+) with
Oleic acid ligand forms compound, then is polymerized by one kettle way microemulsion radical crosslinking, synthetic kernel core-shell type nanometer gelatin polymer；
Meanwhile, use different metal ion as template, the core-shell type that specific objective metal ion is had recognition capability can be synthesized
Temperature and pH Lazer property metal ion trace nanogel.
Concrete synthetic schemes is as follows: 1) prepare the imprinted templates-oleic acid ligand compound of metal ion；Respectively by a certain amount of
Slaine and oleic acid (mol ratio is 1:2 ~ 3), add water-ethanol-n-hexane (volume ratio is 1 ~ 5:1 ~ 5:5 ~ 10) mixing
In solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, is heated at reflux 1 ~ 4 h at 60 ~ 70 DEG C；After reaction terminates, take
The oil phase of layer metal ion-oleic acid compound, first washes with water 3 times, then rotation boils off except n-hexane, and the product of gained is trace
Metal ion-oleic acid compound.2) divide and take above-mentioned metallic print ion-oleic acid compound after purification and Thermo-sensitive function monomer
NIPA (mol ratio is 1:5 ~ 20), adds deionized water mixing in there-necked flask, adds crosslinking agent N, N '-Asia
Bisacrylamide (accounts for temperature sensitive monomer proportion 0.5-10%), adds triton x-100 as emulsifying agent (volume/volume
Percentage is 0.05-0.5%), ultrasonic about 5-15 minute, magnetic agitation formed emulsion, after being continually fed into nitrogen 10-20min,
Being added dropwise over initiator sodium peroxydisulfate (weight/volume percent is 0.01 ~ 0.1%), 65 ~ 75 DEG C to add heat polymerization 2 ~ 6 little
Time；After reaction terminates, product first with wash-out more than 2 hours under the nitric acid normal temperature of 0.5 ~ 2mol/L, use 0.1 after wash-out instead ~
With the acid solution remained in the NaOH of 1mol/L, then using deionized water dialysis 3 days instead, dialysis purifies after being lyophilized, and products therefrom is
Ion blotting gelatin polymer.
By transmission electron microscope, dynamic light scattering particle size Distribution Analyzer and Fourier turn infrared
Instrument, has further characterized the pattern of the gelatin polymer of the present invention, particle size distribution and surface functionalities group thereof.Analysis result
Showing, prepared gel particle has spherical, core shell structure, gel particle average grain diameter between 100 ~ 900 nm, nanometer
It is cross-linked with each other between gel particle；Nanogel biocatalytic particle Surface testing includes carboxyl, amino to intended functional group.
Meanwhile, embodiments of the invention have investigated the selective absorption-solution of prepared copper ion trace nano-gel material
Adsorbing and adsorb-desorption test again, result of the test shows: the copper ion trace nanogel of the present invention is to trace metal
Ion Cu2+There is good selective absorption performance, its absorption-desorption is accompanied by and adsorb again-again desorption capacity to temperature and
PH has dependence；By changing temperature or pH, can effectively control metal biosorption/desorption process.
So, the hud typed metal ion trace nanogel of the present invention, have Thermo-sensitive, pH sensitiveness, metal ion concurrently
Identity and the feature such as adsorption/desorption additive process is controlled.
In step of the present invention (3), described metallic print ion wash-out time, first pass through nitric acid wash-out imprinted templates after again
With in NaOH and residual acid solution, make the macromolecule end of the chain/side chain end of ion blotting nanogel by-COOH type be converted into-
COONa type, is conducive to keeping conformation and the activity of metallic print ion binding site, thus improves nanogel of the present invention to print
The specific recognition of mark metal ion and selectivity.
Target metal ions and the oleic acid molecular having environmental organism security and pH sensitiveness concurrently are first formed multiple by the present invention
Compound, and in traditional imprinted polymer skeleton, introduce temperature-sensitive macromolecular monomer NIPA, simultaneously non-
Under the interface activation effect of ionic emulsifying agent triton x-100, by one kettle way microemulsion radical crosslinking polymerization synthetic kernel-
Shell mould temperature-and pH-sensitivity metal ion trace nanogel.
Hud typed temperature that the present invention is developed and pH Lazer property metal ion trace nanogel have temperature and pH is double
Weight sensitiveness, has good selective adsorption capacity, ionic radius phase identical especially for valence state to metallic print ion
Near non-metallic print ion can show specific selectivity absorption.Additionally, the imprinted material developed is embedded in film
After, compared with the blank lacquer of non-embedded material, the adsorption capacity of target metal ions is shown temperature for the former and pH is dual
Dependence, this explanation can effectively control this kind of imprinted polymer to specific gold by changing external environmental condition (such as temperature or pH)
Belong to the adsorption/desorption additive process of ion.Compared with traditional adsorbent, the novel metal ion imprinted polymer of the present invention has
There is temperature-and pH-sensitivity, target metal ions is had stable identity and adsorptive selectivity, desorption ability
By force, renewable, recycling, it is adaptable to Cu in aqueous environment2+、Fe2+、Au3+Enrichment, separation Deng metal ion.It is prepared
Method is simple, operating condition is gentle, energy consumption is low and environmental friendliness, therefore, and can be as diffusive gradients in thin-films in situ sampling device
The combination glue-line of middle metal ion, for polluting in situ sampling and the dynamic monitoring of special metal ion in environment.
Accompanying drawing explanation
Figure 1A is the TEM pattern of trace copper ion and the formed compound of oleic acid ligand；
Figure 1B is the composite particles particle diameter distribution of trace copper ion and oleic acid ligand；
Fig. 2 A is the TEM pattern of copper ion trace nanogel；
Fig. 2 B is the TEM pattern of copper ion trace nanogel after 1% phosphotungstic acid negative staining.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most from start to finish
Same or similar label represents same or similar element or has the element of same or like function.Below with reference to attached
The embodiment that figure describes is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.Embodiment
In unreceipted concrete technology or condition person, according to the technology described by the document in this area or condition or according to the description of product
Book is carried out.Agents useful for same or instrument unreceipted production firm person, be can by city available from conventional products.
Embodiment 1: the preparation of copper ion trace nanogel
The detailed preparation process of copper ion trace nanogel is as follows:
1) preparation of trace copper ion-oleic acid compound；Respectively by copper chloride and the oleic acid of 16mmol of 8mmol, successively
Adding in 15ml water-20ml ethanol-35ml n-hexane mixed solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, at 65 DEG C
Under be heated at reflux 1 ~ 4 h after；After reaction terminates, take the oil phase of upper strata copper ions-oleic acid compound, first wash with water 3 times, then revolve
Boiling off except n-hexane, the product of gained is trace copper ion-oleic acid compound, and wherein pattern is spherical particle (Figure 1A),
Grain average grain diameter about 150nm(Figure 1B)；
2) (dosage is respectively with Thermo-sensitive function monomer NIPA to take above-mentioned copper ion-oleic acid compound
For 3.2mmol and 22mmol), and the crosslinking agent N, N ' of 0.5mmol-methylene-bisacrylamide, add in there-necked flask
Ionized water mixing (liquor capacity is 45ml), adds the triton x-100 of 50 μ l as emulsifying agent, ultrasonic about 15 minutes, magnetic
Power stirring forms emulsion, after logical nitrogen 10-20min, is added dropwise over the 5ml aqueous solution containing 50mg sodium peroxydisulfate, and 70 DEG C add hot polymerization
Close reaction 4 hours；After reaction terminates, product is transferred completely into bag filter (MWCO:8000 ~ 14400), first with 0.5 ~
Elute more than 2 hours under the nitric acid normal temperature of 2mol/L, use instead in the NaOH of 0.1 ~ 1mol/L after wash-out and the acid solution of residual, then change
Dialysing 3 days by deionized water, finally-40 ~-50 DEG C of freeze-dryings, products therefrom is the polymerization of copper ion trace nanogel
Thing, as shown in Figure 2 A and 2B, prepared copper ion blot gel material is in rule spherical particle thing and has nanometer for its pattern
Size, has certain cross-linked network structure (Fig. 2 A) between nanogel biocatalytic particle, after processing by 1% phosphotungstic acid negative staining, trace is received
There is obvious nuclear structure (Fig. 2 B) in rice gel center.
By dynamic light scattering particle size distributional analysis and Fourier turn infrared, further characterize and developed
The particle size distribution of nano-gel material and surface functionalities group thereof.Analysis result shows, prepared trace nanogel
Material surface detects that intended functional group includes carboxyl, amino.Prepared nanogel biocatalytic particle has spherical, nucleocapsid knot
Structure, gel particle average grain diameter about 400nm.It is cross-linked with each other between nanogel biocatalytic particle, there is relatively lower critical solution temperature about 31
DEG C, also there is pH sensitiveness simultaneously, its phase in version pH is about about 5.5.
Embodiment 2: the preparation of ferrous ion trace nanogel
The preparation process of ferrous ion trace nanogel is as follows: the 1) preparation of trace ferrous ion-oleic acid compound；Point
Not by 8mmol iron ammonium sulfate and 16mmol oleic acid, successively adding in 15ml water-20ml ethanol-35ml mixed solvent, magnetic force stirs
Mix mixing and logical nitrogen removes oxygen, at 65 DEG C, be heated at reflux 1 ~ 4 h；After reaction terminates, take upper strata containing ferrous ion-oleic acid
The oil phase of compound, first washes with water 3 times, then rotation boils off except n-hexane, and the product of gained is trace ferrous ion-oleic acid and is combined
Thing.2) (dosage is respectively with Thermo-sensitive function monomer NIPA to take above-mentioned ferrous ion-oleic acid compound
3.2mmol and 22mmol)), and the crosslinking agent N, N ' of 0.5mmol-methylene-bisacrylamide, add in there-necked flask from
Sub-water mixing (liquor capacity is 45ml), adds the triton x-100 of 50 μ l as emulsifying agent, ultrasonic about 15 minutes, magnetic force
Stirring forms emulsion, after logical nitrogen 10-20min, is added dropwise over the 5ml aqueous solution containing 50mg sodium peroxydisulfate, and 70 DEG C add thermal polymerization
React at least 4 hours；After reaction terminates, product is transferred completely into bag filter (MWCO:8000 ~ 14400), first with 0.5
Elute more than 2 hours under the nitric acid normal temperature of ~ 2mol/L, use instead in the NaOH of 0.1 ~ 1mol/L after wash-out and the acid solution of residual, then
Using deionized water instead to dialyse 3 days, finally-40 ~-50 DEG C of freeze-dryings, obtained freeze-drying product is ferrous ion trace nanometer
Gelatin polymer.
Embodiment 3: the preparation of gold ion trace nanogel
The preparation process of gold ion trace nanogel is as follows: the 1) preparation of trace gold ion-oleic acid compound；Respectively will
1.6 mmol tetra chlorauric acids and 4.8 mmol oleic acid, successively add in 3ml water-4ml ethanol-7ml mixed solvent, and magnetic agitation is mixed
Even and logical nitrogen removes oxygen, is heated at reflux 1 ~ 4 h at 65 DEG C；After reaction terminates, take upper strata containing gold ion-oleic acid compound
Oil phase, first wash with water 3 times, then rotation boil off except n-hexane, the product of gained is trace gold ion-oleic acid compound.2) take
Above-mentioned gold ion-oleic acid compound and Thermo-sensitive function monomer NIPA (dosage be respectively 3.2mmol and
22mmol)), and the crosslinking agent N, N ' of 0.5mmol-methylene-bisacrylamide, in there-necked flask, add deionized water mixing
(liquor capacity is 45ml), adds the triton x-100 of 50 μ l as emulsifying agent, ultrasonic about 15 minutes, and magnetic agitation is formed
Emulsion, after logical nitrogen 10-20min, is added dropwise over the 5ml aqueous solution containing 50mg sodium peroxydisulfate, and 70 DEG C add heat polymerization at least 4
Hour；After reaction terminates, product is transferred completely into bag filter (MWCO:8000 ~ 14400), first with 0.5 ~ 2mol/L's
Elute more than 2 hours under nitric acid normal temperature, use instead in the NaOH of 0.1 ~ 1mol/L after wash-out and the acid solution of residual, then use deionization instead
Water is dialysed 3 days, and finally-40 ~-50 DEG C of freeze-dryings, obtained freeze-drying product is gold ion trace nanogel polymer.
Embodiment 4: the adsorptive selectivity test of copper ion trace nano-gel material
In order to investigate the adsorptive selectivity of prepared copper ion trace nano-gel material, selection valence state is identical, ion half
The Cu that footpath is close2+、Ni2+、Co2+And Mn2+As for examination metal ion.
First, the Cu of 0.01-2 mmol/L is prepared2+、Ni2+、Co2+、Mn2+Four metal ion species equivalent are mixed by stock solution
Close, filter through 0.45 micron membrane filter, regulate about pH6 with the NaOH of 0.1mol/L；By the copper ion trace prepared by embodiment 1
Nanogel polymer is put in metal ion mixed liquor by 1g/1000ml rate of charge.The 0.5th, 1,2,3,4,5,10,24h
Taking 0.5ml water sample respectively, be diluted to 5ml by deionized water and be acidified to pH < 2 with nitric acid, the water sample after acidifying is as to be measured
Liquid；In liquid to be measured, different metal ion concentration passes through Inductively coupled plasma optical emission spectrometer (Optima 7000 DV ICP-
OES, PerkinElmer) analysis.Experimental result is as follows:
By selecting coefficient k (k=QCu/ Qmetal, QCuFor the copper ion imprinted material unit adsorbance to copper ion,
QmetalFor the copper ion imprinted material unit adsorbance to other metal ion) calculate understand, copper ion trace nanogel material
Material is to Ni2+、Co2+And Mn2+The selection coefficient of three metal ion species is respectively 19.3,16.7,18.0.By contrast, commercial chelating
Resin (U.S.'s Bio-Rad Chelex-100 resin) is to Ni2+、Co2+And Mn2+The selection coefficient of three metal ion species is only respectively
1.0、1.3、0.9.Therefore, novel nano gel is to Cu2+、Ni2+、Co2+And Mn2+Four kinds have the strongest choosing for examination metal ion
Selecting property absorption property.
By the copper ion trace nano-gel material of embedding embodiment 1 gained in film, it was demonstrated that its adsorption effect is to temperature
Degree and pH all show dependence.Result of study shows, when solution is from higher temperature (the relatively lower critical solution temperature higher than gel
LCST, the LCST of copper ion blot gel is between 30 ~ 32 degree) it is transformed into lower temperature (< LCST), blot gel film pair
The adsorption capacity of copper significantly reduces；And when pH value of solution is reduced to reduced levels (less than 3.5) from higher level (more than 5.5), should
The adsorption capacity of copper is also remarkably decreased by blot gel film.Therefore, temperature and pH are had and depend on by copper ion trace nanogel
Rely property/sensitiveness, the enrichment/separation process of copper ion can be controlled by regulation temperature or pH.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to be interpreted as limitation of the present invention, those of ordinary skill in the art is without departing from the principle of the present invention and objective
In the case of above-described embodiment can be changed within the scope of the invention, revise, replace and modification.
Claims (10)
1. a hud typed temperature and pH Lazer property metal ion trace nanogel, it is characterised in that by following preparation method
Prepare:
(1) preparation of metallic print ion-oleic acid compound: by the metal salt solution containing imprinted templates and oleic acid, successively add
In water-ethanol-n-hexane mixed solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, is heated at reflux 1～4 hour；Reaction
After end, take the oil phase of upper strata metal ion-oleic acid compound, first wash with water 1～3 time, then rotation boils off except n-hexane, gained
Product is metallic print ion-oleic acid compound；
(2) preparation of hud typed metal ion trace nanogel: by metallic print ion-oleic acid compound and Thermo-sensitive function
Monomer NIPA, crosslinking agent N, N'-methylene-bisacrylamide and nonionic emulsifier Qu Latong X-
100, in there-necked flask, add deionized water mixing, ultrasonically treated 10～30 minutes, magnetic agitation formed emulsion, persistently leads to nitrogen
Gas, is added dropwise over initiator sodium peroxydisulfate, causes heat polymerization under constant temperature；
(3) metallic print ion wash-out: after (2) reaction terminates, product first elutes with under the nitric acid normal temperature of 0.5～2mo1/L
More than 2 hours, use instead in the NaOH of 0.l～lmol/L after wash-out and the acid solution of residual, then use deionized water dialysis 1～3 day instead,
Dialysis is after purification-40～-50 DEG C of freeze-dryings.
2. the hud typed temperature described in claim 1 and pH Lazer property metal ion trace nanogel, it is characterised in that described
In step (1), the mol ratio of described slaine and oleic acid is 1:2～3, and the volume ratio of described water-ethanol-n-hexane is 1～5:1
～total dosage that 5:5～10, described slaine and oleic acid are in water-ethanol-n-hexane mixed solvent is 0.1～1.5mol/
L, described in be heated at reflux condition at 60～70 DEG C 1～4h；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl acrylamide in described step (2)
The mol ratio of amine is 1:5～20, and both total dosages are 0.05～1mol/L；
Optional, described crosslinking agent N, N'-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 0.5～10%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.05～0.5%, described initiator over cure
The weight/volume percent of acid sodium is 0.01～0.1%, and described heat polymerization condition is 2～6 little under 65～75 DEG C of constant temperature
Time.
3. the hud typed temperature described in claim 2 and pH Lazer property metal ion trace nanogel, it is characterised in that described
In step (1), the mol ratio of slaine and oleic acid is 1:2, and the volume ratio of described water-ethanol-n-hexane is 4:3:7, described gold
Belong to salt and the oleic acid total dosage in water-ethanol-n-hexane mixed solvent is 0.1～0.5mol/L；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl acrylamide in described step (2)
The mol ratio of amine is 1:6.87, and both total dosages are 0.1～0.5mol/L；
Optional, described crosslinking agent N, N'-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 3%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.1%, described initiator sodium peroxydisulfate
Weight/volume percent is 0.1%, and polymeric reaction condition is under 70 DEG C of constant temperature 4～6 hours.
4. the arbitrary described hud typed temperature of claims 1 to 3 and pH Lazer property metal ion trace nanogel, its feature exists
In, described metal ion is Cu2+, Fe2+, Au3+；
Optional, described slaine is chlorate, nitrate, sulfate, acetate, perchlorate.
5. the hud typed temperature described in claim 1 and the preparation method of pH Lazer property metal ion trace nanogel, it is special
Levy and be, comprise the steps,
(1) preparation of metallic print ion-oleic acid compound: by the metal salt solution containing imprinted templates and oleic acid, successively add
In water-ethanol-n-hexane mixed solvent, magnetic agitation mixes and leads to nitrogen removes oxygen, is heated at reflux 1～4 hour: reaction
After end, take the oil phase of upper strata metal ion-oleic acid compound, first wash with water 1～3 time, then rotation boils off except n-hexane, gained
Product is metallic print ion-oleic acid compound；
(2) preparation of hud typed metal ion trace nanogel: by metallic print ion-oleic acid compound and Thermo-sensitive function
Monomer NIPA, crosslinking agent N, N'-methylene-bisacrylamide and nonionic emulsifier Qu Latong X-
100, in there-necked flask, add deionized water mixing, ultrasonically treated 10～30 minutes, magnetic agitation formed emulsion, persistently leads to nitrogen
Gas, is added dropwise over initiator sodium peroxydisulfate, causes heat polymerization under constant temperature；
(3) metallic print ion wash-out: after (2) reaction terminates, product first elutes with under the nitric acid normal temperature of 0.5～2mo1/L
More than 2 hours, use instead in the NaOH of 0.l-lmol/L after wash-out and the acid solution of residual, then use deionized water dialysis 1～3 day instead,
Dialysis is after purification-40～-50 DEG C of freeze-dryings.
6. the hud typed temperature described in claim 5 and the preparation method of pH Lazer property metal ion trace nanogel, it is special
Levying and be, in described step (1), the mol ratio of described slaine and oleic acid is 1:2～3, the body of described water-ethanol-n-hexane
Long-pending ratio is 1～5:l～5:5～10, and described slaine and the oleic acid total dosage in alcohol-water-n-hexane mixed solvent are
0.1～1.5mol/L, described in be heated at reflux condition at 60～70 DEG C 1～4h；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl acrylamide in described step (2)
The mol ratio of amine is 1:5～20, and both total dosages are 0.05～1mol/L；
Optional, described crosslinking agent N, N'-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 0.5～10%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.05～0.5%, described initiator over cure
The weight/volume percent of acid sodium is 0.01～0.1%, and heat polymerization condition is under 65～75 DEG C of constant temperature 2～6 hours.
7. the hud typed temperature described in claim 6 and the preparation method of pH Lazer property metal ion trace nanogel, it is special
Levying and be, in described step (1), the mol ratio of slaine and oleic acid is 1:2, and the volume ratio of described water-ethanol-n-hexane is 4:
3:7, described slaine and the oleic acid total dosage in alcohol-water-n-hexane mixed solvent is 0.1～0.5mol/L；
Optional, metallic print ion-oleic acid compound and Thermo-sensitive function monomer N-isopropyl acrylamide in described step (2)
The mol ratio of amine is 1:6.87, and both total dosages are 0.1～0.5mol/L；
Optional, described crosslinking agent N, N'-methylene-bisacrylamide accounts for temperature sensitive monomer weight proportion 3%；
Optional, the volume/volume percentage of described emulsifying agent triton x-100 is 0.1%, described initiator sodium peroxydisulfate
Weight/volume percent is 0.1%, and polymeric reaction condition is under 70 DEG C of constant temperature 4～6 hours.
8. the arbitrary described hud typed temperature of claim 5～7 and the preparation side of pH Lazer property metal ion trace nanogel
Method, it is characterised in that described metal ion is Cu2+, Fe2+, Au3+；
Optional, described slaine is chlorate, nitrate, sulfate, acetate, perchlorate.
9. hud typed temperature and pH Lazer property metal ion trace obtained by claim 1 or claim 5 preparation method are received
Rice gel is used for enrichment and the purposes of separation of metal ion.
10. hud typed temperature and pH Lazer property metal ion trace obtained by claim 1 or claim 5 preparation method are received
Rice gel is in situ sampling and the purposes of pollution environmental dynamic monitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310373052.9A CN103804571B (en) | 2013-08-26 | 2013-08-26 | A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310373052.9A CN103804571B (en) | 2013-08-26 | 2013-08-26 | A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103804571A CN103804571A (en) | 2014-05-21 |
| CN103804571B true CN103804571B (en) | 2016-08-31 |
Family
ID=50701999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310373052.9A Expired - Fee Related CN103804571B (en) | 2013-08-26 | 2013-08-26 | A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804571B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086688B (en) * | 2014-07-03 | 2017-01-11 | 江苏大学 | Method for preparing core-shell yeast/styrene molecularly-imprinted polymers through miniemulsion polymerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626611A (en) * | 2012-04-11 | 2012-08-08 | 哈尔滨工程大学 | Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance |
| CN102989429A (en) * | 2012-11-27 | 2013-03-27 | 中北大学 | Preparation method of cadmium ion surface imprint adsorbing material |
| CN103012677A (en) * | 2011-09-23 | 2013-04-03 | 中南大学 | Preparation method of ion imprinted hydroxamic acid chelate resin |
-
2013
- 2013-08-26 CN CN201310373052.9A patent/CN103804571B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012677A (en) * | 2011-09-23 | 2013-04-03 | 中南大学 | Preparation method of ion imprinted hydroxamic acid chelate resin |
| CN102626611A (en) * | 2012-04-11 | 2012-08-08 | 哈尔滨工程大学 | Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance |
| CN102989429A (en) * | 2012-11-27 | 2013-03-27 | 中北大学 | Preparation method of cadmium ion surface imprint adsorbing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804571A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zheng et al. | Magnetic nanocomposite hydrogel prepared by ZnO-initiated photopolymerization for La (III) adsorption | |
| CN102977288B (en) | Molecularly imprinted magnetic microsphere, preparation method and application thereof | |
| Dong et al. | Characterization and adsorption properties of a lanthanum-loaded magnetic cationic hydrogel composite for fluoride removal | |
| Rao et al. | Tailored materials for preconcentration or separation of metals by ion-imprinted polymers for solid-phase extraction (IIP-SPE) | |
| Shakerian et al. | Advanced polymeric materials: Synthesis and analytical application of ion imprinted polymers as selective sorbents for solid phase extraction of metal ions | |
| CN104592449B (en) | A kind of intelligent aqueous gel and preparation method and application | |
| CN102827321B (en) | Preparation method and application for magnetic molecularly imprinted polymers for selectively separating carbamazepine | |
| Xu et al. | Photonic and magnetic dual responsive molecularly imprinted polymers: preparation, recognition characteristics and properties as a novel sorbent for caffeine in complicated samples | |
| Rao et al. | Removal of natural organic matter by cationic hydrogel with magnetic properties | |
| Liu et al. | Thermal-responsive ion-imprinted polymer based on magnetic mesoporous silica SBA-15 for selective removal of Sr (II) from aqueous solution | |
| Liu et al. | Effect of anions on the polymerization and adsorption processes of Cu (II) ion-imprinted polymers | |
| Wang et al. | Selective adsorption of thiocyanate anions using straw supported ion imprinted polymer prepared by surface imprinting technique combined with RAFT polymerization | |
| Fereidoonipour et al. | Development of flow injection analysis-solid phase extraction based on ion imprinted polymeric nanoparticles as an efficient and selective technique for preconcentration of zinc ions from aqueous solution | |
| Zhang et al. | A Ce 3+-imprinted functionalized potassium tetratitanate whisker sorbent prepared by surface molecularly imprinting technique for selective separation and determination of Ce 3+ | |
| CN106622172A (en) | Preparation method of surface-functionalized, micron-sized, porous, paramagnetic and spherical resin particle | |
| Phutthawong et al. | Facile synthesis of magnetic molecularly imprinted polymers for caffeine via ultrasound-assisted precipitation polymerization | |
| Ali et al. | Synthesis of ion-imprinted polymers based on chitosan for high selectivity of La (III), Ce (III) and Sm (III) via solid phase extraction | |
| CN102489273B (en) | Preparation method of magnetic beads of dendritic molecular imprinting polymer on surface of estrogenic nano silica gel | |
| Kim et al. | Removal of Pb (II) ions from aqueous solutions using functionalized cryogels | |
| Zhang et al. | Magnetic Pb (II) ion-imprinted polymer prepared by surface imprinting technique and its adsorption properties | |
| CN107175086A (en) | The preparation method of ion blotting magnetite gathering material | |
| CN105688845A (en) | Microwave-assisted inverse emulsion preparing method and application of heavy metal ion imprinting material | |
| Zhu et al. | Preparation of surface-imprinted polymer magnetic nanoparticles with miniemulsion polymerization for recognition of salicylic acid | |
| Chen et al. | Syntheses of magnetic GO@ melamine formaldehyde resin for dyes adsorption | |
| Jiang et al. | Synthesis of Copper and Lead Ion Imprinted Polymer Submicron Spheres to Remove Cu 2+ and Pb 2+ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hu Chaohua Inventor after: Zhang Lei Inventor after: Zhang Youchi Inventor after: Luo Wensui Inventor before: Hu Chaohua Inventor before: Luo Wensui |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160831 |