CN102516822B - Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof - Google Patents
Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof Download PDFInfo
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- CN102516822B CN102516822B CN201110345258.1A CN201110345258A CN102516822B CN 102516822 B CN102516822 B CN 102516822B CN 201110345258 A CN201110345258 A CN 201110345258A CN 102516822 B CN102516822 B CN 102516822B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000008878 coupling Effects 0.000 claims abstract description 9
- 238000010168 coupling process Methods 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- JCRFIMFHWUDIFY-UHFFFAOYSA-N 1-(2-aminoquinolin-8-yl)-2-chloroethanone Chemical compound C1=CC=C(C(=O)CCl)C2=NC(N)=CC=C21 JCRFIMFHWUDIFY-UHFFFAOYSA-N 0.000 claims description 11
- -1 amino silicane Chemical compound 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 150000005012 8-aminoquinolines Chemical class 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- UCCQXCFFHYCLEC-UHFFFAOYSA-N 1-quinolin-2-ylethanone Chemical compound C1=CC=CC2=NC(C(=O)C)=CC=C21 UCCQXCFFHYCLEC-UHFFFAOYSA-N 0.000 claims description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- NXXWVJFQPYIXRH-UHFFFAOYSA-N 2-ethylquinolin-8-amine Chemical compound CCc1ccc2cccc(N)c2n1 NXXWVJFQPYIXRH-UHFFFAOYSA-N 0.000 claims description 3
- JHIAOWGCGNMQKA-UHFFFAOYSA-N 2-methyl-8-quinolinamine Chemical compound C1=CC=C(N)C2=NC(C)=CC=C21 JHIAOWGCGNMQKA-UHFFFAOYSA-N 0.000 claims description 3
- BHWUCEATHBXPOV-UHFFFAOYSA-N 2-triethoxysilylethanamine Chemical compound CCO[Si](CCN)(OCC)OCC BHWUCEATHBXPOV-UHFFFAOYSA-N 0.000 claims description 3
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 claims description 2
- FWLQTOSQDYKDHG-UHFFFAOYSA-N CCCCCCCC[ClH]CCCCCCCNC1=NC2=CC=CC=C2C=C1 Chemical compound CCCCCCCC[ClH]CCCCCCCNC1=NC2=CC=CC=C2C=C1 FWLQTOSQDYKDHG-UHFFFAOYSA-N 0.000 claims 6
- 238000013019 agitation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- QHUJOBSPMFNIHY-UHFFFAOYSA-N C(CCCCCC[ClH]CCCCCCCC)C=1C(=NC2=CC=CC=C2C=1)N Chemical class C(CCCCCC[ClH]CCCCCCCC)C=1C(=NC2=CC=CC=C2C=1)N QHUJOBSPMFNIHY-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000243 solution Substances 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 45
- 125000003368 amide group Chemical group 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 150000005010 aminoquinolines Chemical class 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LHZUOKZVTOBRRI-UHFFFAOYSA-N CCCCCCCC[ClH]CCCCCCCC(C1=CC=CC=C1N=C1CC)=C1N Chemical compound CCCCCCCC[ClH]CCCCCCCC(C1=CC=CC=C1N=C1CC)=C1N LHZUOKZVTOBRRI-UHFFFAOYSA-N 0.000 description 2
- UCAAPFACRRIOSD-UHFFFAOYSA-N ClC=1C=CC=C2C=C(C(=NC12)S)NC(C)=O Chemical compound ClC=1C=CC=C2C=C(C(=NC12)S)NC(C)=O UCAAPFACRRIOSD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 241000399119 Spio Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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Abstract
The invention discloses surface-functionalized Fe3O4 nanoparticles and a preparation method thereof, and a method for applying the nanoparticles to enrich and detect Cu<2+>. The method comprises the steps of: carrying out surface modification on ferroferric oxide nanoparticles through chemical covalent coupling by adopting a chemosynthetic 8-chloracetyl aminoquinoline derivative, treating Cu<2+> aqueous solutions of different concentrations by utilizing surface-functionalized magnetic ferroferric oxide nanoparticles, and then detecting the enriching and adsorbing effect by atomic absorption. The detection result shows that the surface-functionalized Fe3O4 nanoparticles have very strong enriching action on trace Cu<2+>, and the enriching capability is 10-15 times that of surface-unfunctionalized Fe3O4 nanoparticles. The surface-functionalized Fe3O4 nanoparticles prepared by the preparation method have the characteristics of good enriching effect and high adsorption efficiency to Cu<2+>, simplicity and convenience in operation and easiness in analysis; and by utilizing the method, trace Cu<2+> in the solution can be effectively enriched and detected.
Description
Technical field
The present invention relates to a kind of surface-functionalized Fe
3o
4nanoparticle and its preparation method and application, particularly relates to the synthetic 8-chloro acetylamino quinoline of a kind of use and ferriferrous oxide nano-particle is carried out to the method for the control of finishing and particle diameter thereof, and be applied to Cu
2+enrichment and detection.
Background technology
Owing to having, magnetic and raw material are easy to get ferriferrous oxide nano-particle, cheap magnetic recording material, immobilized enzyme, immunodiagnosis, targeted drug, support of the catalyst, magnetic microsphere and the bioprobe etc. of being widely used as.Synthetic and modification about magnetic ferroferric oxide particle in recent years causes people's extensive concern.At publication number, be for example in the Chinese patent of CN 101554574A, use amino silicane coupling agent to carry out finishing to the coated SPIO nano particle of glucose, utilize the high-hydrophilic of ferroferric oxide nano granules, Investigation of stabilized dispersion of nano in water, reduce reticuloendothelial system phagocytic amount, extend cycling time in blood, can be combined easily to improve initiatively targeting with monoclonal antibody, body is not caused to toxic side effect simultaneously, good biocompatibility, preparation method is simple, at diagnosing early malignant tumor and magnetic target therapy field, have a good application prospect.Publication number is the Chinese patent of CN 101139409A, a kind of functionalized macromolecular magnetic carrier is disclosed, with macromolecular compound coated ferroferric oxide magnetic particle core composition nucleocapsid structure, surface bond has hydroxyl and amido, by epoxidation and functional amido reaction, successfully carrier is modified, can be applicable to process heavy metal-containing waste water, dyeing waste water, respond well, aspect wastewater treatment, there is good application prospect.Publication number is the Chinese patent of CN 1805086A, a kind of preparation method of silane coupledization magnetic ferroferric oxide nanometer matrix material is disclosed, by divalent iron salt and trivalent iron salt are dissolved in the water, under protection of inert gas, drip alkaline solution to alkalescence, heated and stirred reaction makes nano ferriferrous oxide granule, then add dispersion solvent and silane coupling reagent, heated and stirred makes the magnetic ferroferric oxide nanometer matrix material of silane coupledization, and they are applied to the lasting pollutent residue detection of environment technology, this technology detecting method is accurate, favorable reproducibility, the recyclable recycling of material, step is simple.Z 250 adopts chemical coprecipitation to synthesize conventionally, but Z 250 is easily oxidized, therefore need modify it, makes it existence stable in the air, and unrestricted when application.Existing surface modification method comprises physical adsorption, surface deposition, electrostatic interaction and Van der Waals force etc., these methods all can not make ferriferrous oxide nanometer material surface have different reactive functional mostly, though or there is surface reaction activity functional group, but and a little less than nano-material surface interaction, be unfavorable for the further finishing of nano material and application.
Summary of the invention
The object of the present invention is to provide a kind of surface-functionalized Fe
3o
4nanoparticle is the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
In formula: R
2for CH
2; R
3for H, CH
3, CH
2cH
3or SH; N=1-3.
In the present invention, this nanoparticle has enrichment and detects Cu
2+ability.
Another object of the present invention is to provide a kind of to Cu
2+the surface-functionalized Fe with enrichment detection effect
3o
4the preparation method of nanoparticle, the method is coupled at Fe by the method for chemical covalent coupling by synthetic 8-aminoquinoline derivatives molecular chemistry
3o
4nanoparticle surface, and according to surface molecule structure and Cu
2+between specificity contact for enrichment with detect Cu
2+.
The surface-functionalized Fe of the present invention
3o
4nanoparticle obtains by following steps:
1, magnetic Fe
3o
4the preparation of nanoparticle
Take FeCl
24H
2o 0.2-20 g, FeCl
36H
2o 0.54-54 g, 1:2-3 puts into reaction flask in mass ratio, is dissolved in 50-300 ml distilled water; under the condition of nitrogen protection, use constant pressure funnel to drip 5.5-100 ml ammoniacal liquor with the speed of 1-10 ml/min; heating in water bath is to 40-90 ℃, and stirring reaction 1-6 h, reacts complete; naturally cooling 20-60 min; use successively distilled water, dehydrated alcohol, toluene washs respectively 3 times; vacuum-drying 1-24 h, makes 0.696-69.6 g magnetic Fe
3o
4nanoparticle;
2,8-chloracetyl amino quinoline derivatives is synthetic
Get 0.095-9.5g 8-aminoquinoline derivatives in flask, add 0.1-10 ml triethylamine, then add 5-500 ml dichloromethane solution, at 0 ℃, keep 30-60 min; Then add 0.06-6 ml chloroacetyl chloride, airtight normal temperature lucifuge lower magnetic force stirring reaction 1-48 h, the evaporation of final reaction liquid, except desolventizing, obtains 8-chloracetyl amino quinoline derivatives product;
3, the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloracetyl amino quinoline derivatives
3o
4-QTPA) preparation
3.1 by prepared magnetic Fe in step 1
3o
4nanoparticle 0.2-20g is dispersed in 50-200ml toluene solution, add amino silicane coupling agent 0.5-50 ml, under nitrogen protection condition, heating in water bath 30-90 ℃, stirring reaction 1-12 h, has reacted rear magnetic separation, with acetonitrile, washs, and be dispersed in acetonitrile, make the ferriferrous oxide nano-particle of amino silicane coupling agent finishing;
The 3.2 ferriferrous oxide nano-particle 0.2-20 g that get amino silicane coupling agent finishing are dispersed in 50-200ml acetonitrile solution; under nitrogen protection condition, add catalyzer 0.02-2 g; stirring and evenly mixing; add again prepared 8-chloro acetylamino quinoline 0.03-5g in step 2; the airtight heating in water bath 40-90 ℃ of lucifuge; stirring reaction 1-24 h; finally use respectively distilled water; dehydrated alcohol is respectively washed 3 times, makes the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloro acetylamino quinoline
3o
4-QTPA).
8-aminoquinoline derivatives described in the present invention is a kind of in 8-quinolylamine, 8-amino-2-methyl quinoline, 8-amino-2-ethyl quinoline, 8-amino-2-mercapto phenyl formic quinoline.
In the present invention, 8-chloracetyl amino quinoline derivatives product is carried out using after purifying, purifying adopts column chromatography purifying technique after adopting rotary evaporation to purify again, and productive rate is 20-80%.
Amino silicane coupling agent described in the present invention is γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane ammonia, gamma-amino propyl group tripropoxy silane, a kind of in beta-aminoethyl triethoxyl silane, alpha-amino group Union carbide A-162.
Catalyzer described in the present invention is K
2cO
3or Na
2cO
3.
In the present invention, reaction reagent used is all bought from the market, and purity is chemical pure, or reagent more than chemical pure.
The present invention by the surface-functionalized ferriferrous oxide nano-particle of 8-chloro acetylamino quinoline making for enrichment with detect solution Cu
2+, concrete operations are as follows:
Prepare 1 mmol/L Cu
2+with 0.1 mmol/LCu
2+the aqueous solution, by prepared surface-functionalized ferriferrous oxide nano-particle, joins respectively 2 ml 1 mmol/L(63.5ppm) Cu
2+with 2 ml 0.1 mmol/L(6.35ppm) Cu
2+in the aqueous solution, vibration absorption 1-24 h, first magnetic is separated, and then centrifugation goes out supernatant liquid, by atomic absorption, detects supernatant liquid, and surface-functionalized ferriferrous oxide nano-particle is to 2 ml 1mmol/L Cu
2+adsorption efficiency reach 50-70 %, to 2 ml 0.1 mmol/LCu
2+adsorption efficiency reach 90-99 %.Result shows, surface-functionalized Fe
3o
4nanoparticle is to Cu
2+there is good inrichment.
The surface-functionalized Fe preparing by the method
3o
4nanoparticle is to Cu
2+there is stronger bioaccumulation efficiency, can be used for purification of waste water processing, effective enrichment target heavy metal ion or trace heavy metal Cu
2+the fields such as ion detection, and method is simple to operate, and accumulation rate is high, is easy to realize.
Accompanying drawing explanation
Fig. 1 is that the inventive method is prepared surface-functionalized Fe
3o
4nanoparticle principle schematic;
Fig. 2 is the surface-functionalized Fe that utilizes the inventive method to prepare
3o
4nanoparticle is to Cu
2+inrichment effect schematic diagram.
R in figure
1for CH
3or C
2h
5; R
2for CH
2; R
3for H, CH
3, CH
2cH
3or SH; N=1-3.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1: this surface-functionalized Fe
3o
4the preparation method of nanoparticle comprises the following steps:
1, the preparation of magnetic ferroferric oxide nano-particles
Get 2.0244 g FeCl
24H
2o and 5.3904 g FeCl
36H
2o is dissolved in 150 ml distilled water; under the condition of nitrogen protection; by constant pressure funnel, with the speed of 5 ml/min, drip 55 ml ammoniacal liquor, 65 ℃ of stirring reaction 2h of heating in water bath, stop heating; naturally cooling 30 min; use respectively distilled water, dehydrated alcohol, toluene wash 3 times; vacuum-drying 12 h, make the uniform magnetic Fe of size distribution
3o
4nanoparticle.
2,8-chloracetyl amino quinoline derivatives is synthetic
Get 0.95 g 8-quinolylamine in round-bottomed flask, add 1 ml triethylamine, then add 50 ml dichloromethane solutions, at 0 ℃, keep 30 min; Then the chloroacetyl chloride that adds 0.6 ml, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 40 h, after reaction, decompression rotary evaporation obtains thick product, and thick product is through column chromatography separated (petrol ether/ethyl acetate=3:1) 8-chloro acetylamino quinoline 0.4 g that purifies to obtain, productive rate 48 %
1h-NMR: δ ppm (CDCl3,400 MHz) 7.7 (m, 1H), 10.7 (s, 1H, (CO) NH-quinoline), 8.4 (m, 1H), 8.6 (m, 1H), 8.9 (m, 1H), 4.5 (s, 2H, (CO) CH
2cl).
3, the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloracetyl amino quinoline derivatives
3o
4-QTPA) preparation
Get 2 g magnetic Fe
3o
4nanoparticle is dispersed in 150 ml toluene solutions, then adds 5 ml γ aminopropyltriethoxy silanes, under 80 ℃ of nitrogen protection conditions, and stirring reaction 12 h, then magnetic is separated, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing making is dispersed in 100ml acetonitrile after acetonitrile washs three times, under nitrogen protection condition, is added 0.2 g catalyzer K
2cO
3, stirring and evenly mixing, then adds 8-chloro acetylamino quinoline 0.4g, 40 ℃ of the airtight heating in water bath of lucifuge, and stirring reaction 24 h, use distilled water successively, and dehydrated alcohol is washed 3 times, makes the surface-functionalized ferriferrous oxide nano-particle of 8-chloracetyl amino quinoline derivatives.
The surface-functionalized Fe that present method obtains
3o
4nanoparticle is the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
, R in formula
2for CH
2; R
3for H; N=3.
This nanoparticle has enrichment and detects Cu
2+ability.
The surface-functionalized ferriferrous oxide nano-particle of this 8-chloro acetylamino quinoline can be used for enrichment and detects Cu in solution
2+, concrete operations are as follows:
Prepare 1 mmol/L(63.5ppm) Cu
2+with 0.1 mmol/L(6.35ppm) Cu
2+the aqueous solution, joins respectively 2 ml 1 mmol/L Cu by the surface-functionalized ferriferrous oxide nano-particle 2g of 8-aminoquinoline derivatives
2+with 2 ml 0.1 mmol/LCu
2+in the aqueous solution, vibration absorption 24 h.Centrifugation is got supernatant liquid and is done atomic absorption detection, and as shown in Figure 2, surface-functionalized ferriferrous oxide nano-particle is to 2ml 1 mmol/L Cu for result
2+adsorption efficiency reaches 57.48 %, to 2 ml 0.1 mmol/LCu
2+adsorption efficiency reaches 91.56 %.
The present embodiment reaction reagent used is commercially available analytical reagent.
Embodiment 2: this surface-functionalized Fe
3o
4the preparation method of nanoparticle comprises the following steps:
1, the preparation of magnetic ferroferric oxide nano-particles
Get 0.2 g FeCl
24H
2o and 0.54g FeCl
36H
2o is dissolved in 50 ml distilled water; under the condition of nitrogen protection; by constant pressure funnel, with the speed of 1ml/min, drip 5.5 ml ammoniacal liquor, 40 ℃ of stirring reaction 6h of heating in water bath, stop heating; naturally cooling 20 min; use respectively distilled water, dehydrated alcohol, toluene wash 3 times; vacuum-drying 1 h, makes the uniform magnetic Fe of size distribution
3o
4nanoparticle.
2,8-chloracetyl amino quinoline derivatives is synthetic
Get 0.095 g 8-amino-2-ethyl quinoline in round-bottomed flask, add 0.1 ml triethylamine, then add 5ml dichloromethane solution, at 0 ℃, keep 10min; Then the chloroacetyl chloride that adds 0.06 ml, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 1 h, after reaction, decompression rotary evaporation obtains 0.04 g 8-chloracetyl amino-2-ethyl quinoline product.
3, the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloracetyl amino quinoline derivatives
3o
4-QTPA) preparation
Get 0.2 g Fe
3o
4nanoparticle is dispersed in 50 ml toluene solutions, then adds 0.55ml beta-aminoethyl triethoxyl silane, under 30 ℃ of nitrogen protection conditions, and stirring reaction 2 h, then magnetic is separated, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing making is dispersed in 50ml acetonitrile after acetonitrile washs three times, under nitrogen protection condition, is added 0.02 g catalyzer K
2cO
3, stirring and evenly mixing, then adds 8-chloracetyl amino-2-ethyl quinoline 0.04g; 60 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 12 h, use distilled water successively; dehydrated alcohol is washed 3 times, makes the surface-functionalized ferriferrous oxide nano-particle of 8-chloracetyl amino quinoline derivatives.
The surface-functionalized Fe that present method obtains
3o
4nanoparticle is the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
, R in formula
2for CH
2; R
3for CH
2cH
3; N=2.
This nanoparticle has enrichment and detects Cu
2+ability.
The surface-functionalized ferriferrous oxide nano-particle of this 8-chloro acetylamino quinoline can be used for enrichment and detects Cu in solution
2+, concrete operations are as follows:
Prepare 1 mmol/L Cu
2+with 0.1 mmol/LCu
2+the aqueous solution, joins respectively 2 ml 1 mmol/L Cu by the surface-functionalized ferriferrous oxide nano-particle 0.2g of 8-aminoquinoline derivatives
2+with 2 ml 0.1 mmol/LCu
2+in the aqueous solution, vibration absorption 1 h.Centrifugation is got supernatant liquid and is made atomic absorption and detect, and the surface-functionalized ferriferrous oxide nano-particle of result is to 2 ml 1 mmol/L Cu
2+adsorption efficiency reaches 51.01 %, to 2 ml 0.1 mmol/LCu
2+adsorption efficiency reaches 90.1 %.
Embodiment 3: this surface-functionalized Fe
3o
4the preparation method of nanoparticle comprises the following steps:
1, the preparation of magnetic ferroferric oxide nano-particles
Get 20g FeCl
24H
2o and 54g FeCl
36H
2o is dissolved in 300 ml distilled water; under the condition of nitrogen protection; by constant pressure funnel, with the speed of 10 ml/min, drip 100 ml ammoniacal liquor, 90 ℃ of stirring reaction 1h of heating in water bath, stop heating; naturally cooling 60 min; use respectively distilled water, dehydrated alcohol, toluene wash 3 times; vacuum-drying 24 h, make the uniform magnetic Fe of size distribution
3o
4nanoparticle.
2,8-chloracetyl amino quinoline derivatives is synthetic
Get 9.5 g 8-amino-2-methyl quinolines in round-bottomed flask, add 10 ml triethylamines, then add 500ml dichloromethane solution, at 0 ℃, keep 60 min; Then the chloroacetyl chloride that adds 6 ml, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 48 h, decompression rotary evaporation after reaction, column chromatography separated (petrol ether/ethyl acetate=3:1) 8-chloro acetylamino-2-toluquinoline 4 g that purify to obtain.
3, the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloracetyl amino quinoline derivatives
3o
4-QTPA) preparation
Get 20g Fe
3o
4nanoparticle is dispersed in 200 ml toluene solutions, then adds 50ml gamma-amino propyl trimethoxy silicane, under 90 ℃ of nitrogen protection conditions, and stirring reaction 10 h, then magnetic is separated, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing making is dispersed in acetonitrile after acetonitrile washs three times, under nitrogen protection condition, is added 2g catalyst n a
2cO
3, stirring and evenly mixing, then adds 8-chloro acetylamino-2-toluquinoline 4 g; 90 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 1 h, uses distilled water successively; dehydrated alcohol is washed 3 times, makes the surface-functionalized ferriferrous oxide nano-particle of 8-chloracetyl amino quinoline derivatives.
The surface-functionalized Fe that present method obtains
3o
4nanoparticle is the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
, R in formula
2for CH
2; R
3for CH
3; N=3.
This nanoparticle has enrichment and detects Cu
2+ability.
The surface-functionalized ferriferrous oxide nano-particle of this 8-chloro acetylamino quinoline can be used for enrichment and detects Cu in solution
2+, concrete operations are as follows:
Prepare 1 mmol/L Cu
2+with 0.1 mmol/LCu
2+the aqueous solution, joins respectively 2 ml 1 mmol/L Cu by the surface-functionalized ferriferrous oxide nano-particle 2g of 8-aminoquinoline derivatives
2+with 2 ml 0.1 mmol/LCu
2+in the aqueous solution, vibration absorption 20h.Centrifugation is got supernatant liquid and is made atomic absorption and detect, and the surface-functionalized ferriferrous oxide nano-particle of result is to 2 ml 1 mmol/L Cu
2+adsorption efficiency reaches 65.4 %, to 2 ml 0.1 mmol/LCu
2+adsorption efficiency reaches 96.1%.
Embodiment 4: this surface-functionalized Fe
3o
4the preparation method of nanoparticle comprises the following steps:
1, the preparation of magnetic ferroferric oxide nano-particles
Get 10g FeCl
24H
2o and 20g FeCl
36H
2o is dissolved in 200 ml distilled water; under the condition of nitrogen protection; by constant pressure funnel, with the speed of 5 ml/min, drip 45 ml ammoniacal liquor, 60 ℃ of stirring reaction 2h of heating in water bath, stop heating; naturally cooling 35 min; use respectively distilled water, dehydrated alcohol, toluene wash 3 times; vacuum-drying 20 h, make the uniform magnetic Fe of size distribution
3o
4nanoparticle.
2,8-chloracetyl amino quinoline derivatives is synthetic
Get 5 g 8-amino-2-mercapto phenyl formic quinoline in round-bottomed flask, add 5 ml triethylamines, then add 250ml dichloromethane solution, at 0 ℃, keep 40 min; Then the chloroacetyl chloride that adds 4 ml, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 35 h, decompression rotary evaporation after reaction, column chromatography separated (petrol ether/ethyl acetate=3:1) 8-chloro acetylamino-2-mercaptoquinoline 2.1g that purifies to obtain.
3, the surface-functionalized ferriferrous oxide nano-particle (Fe of 8-chloracetyl amino quinoline derivatives
3o
4-QTPA) preparation
Get 10g Fe
3o
4nanoparticle is dispersed in 200 ml toluene solutions, then adds 25ml alpha-amino group Union carbide A-162, under 70 ℃ of nitrogen protection conditions, and stirring reaction 11 h, then magnetic is separated, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing making is dispersed in acetonitrile after acetonitrile washs three times, under nitrogen protection condition, is added 1g catalyst n a
2cO
3, stirring and evenly mixing, then adds 8-chloro acetylamino-2-mercaptoquinoline 2.1 g; 70 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 2 h, use distilled water successively; dehydrated alcohol is washed 3 times, makes the surface-functionalized ferriferrous oxide nano-particle of 8-chloracetyl amino quinoline derivatives.
The surface-functionalized Fe that present method obtains
3o
4nanoparticle is the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
, R in formula
2for CH
2; R
3for SH; N=1.
This nanoparticle has enrichment and detects Cu
2+ability.
The surface-functionalized ferriferrous oxide nano-particle of this 8-chloro acetylamino quinoline can be used for enrichment and detects Cu in solution
2+, concrete operations are as follows:
Prepare 1 mmol/L Cu
2+with 0.1 mmol/LCu
2+the aqueous solution, joins respectively 2 ml 1 mmol/L Cu by the surface-functionalized ferriferrous oxide nano-particle 2g of 8-aminoquinoline derivatives
2+with 2 ml 0.1 mmol/LCu
2+in the aqueous solution, vibration absorption 15h.Centrifugation is got supernatant liquid and is made atomic absorption and detect, and the surface-functionalized ferriferrous oxide nano-particle of result is to 2 ml 1 mmol/L Cu
2+adsorption efficiency reaches 60.4 %, to 2 ml 0.1 mmol/LCu
2+adsorption efficiency reaches 95.1%.
Claims (8)
1. a surface-functionalized Fe
3o
4nanoparticle, is characterized in that: be the surface-functionalized Fe of 8-chloracetyl quinolylamine and derivative thereof
3o
4nanoparticle, at Fe
3o
4nanoparticle surface coupling has 8-ammonia ethanoyl quinoline and its derivates molecule, and its chemical structural formula is:
R in formula
2for CH
2; R
3for H, CH
3, CH
2cH
3or SH; N=1-3.
2. by surface-functionalized Fe claimed in claim 1
3o
4nanoparticle, is characterized in that: this nanoparticle has enrichment and detects Cu
2+ability.
3. a surface-functionalized Fe
3o
4the preparation method of nanoparticle, is characterized in that: comprise the following steps:
(1) magnetic Fe
3o
4the preparation of nanoparticle
Take FeCl
24H
2o 0.2-20 g, FeCl
36H
2o 0.54-54 g, 1:2-3 puts into reaction flask in mass ratio, is dissolved in 50-300 ml distilled water; under the condition of nitrogen protection, use constant pressure funnel to drip 5.5-100 ml ammoniacal liquor with the speed of 1-10 ml/min; heating in water bath is to 40-90 ℃, and stirring reaction 1-6 h, reacts complete; naturally cooling 20-60 min; use successively distilled water, dehydrated alcohol, toluene washs respectively 3 times; vacuum-drying 1-24 h, makes magnetic Fe
3o
4nanoparticle;
(2) 8-chloracetyl quinolylamine and derivative thereof is synthetic
Get 0.095-9.5g 8-quinolylamine and derivative thereof, join in 0.1-10 ml triethylamine and dissolve, then add 5-500 ml dichloromethane solution, at 0 ℃, keep 10-60 min; Then add 0.06-6 ml chloroacetyl chloride, lucifuge magnetic agitation reaction 1-48 h under normal temperature air tight condition, the evaporation of final reaction liquid, except desolventizing, obtains 8-chloracetyl quinolylamine and derivative product thereof;
(3) preparation of 8-chloracetyl quinolylamine and the surface-functionalized ferriferrous oxide nano-particle of derivative thereof
3.1) get 0.2-20 g magnetic Fe
3o
4nanoparticle is dispersed in 50-200 ml toluene solution; add amino silicane coupling agent 0.5-50 ml; under nitrogen protection condition; heating in water bath 30-90 ℃; stirring reaction 1-12 h; react rear magnetic separated, with acetonitrile, washed and be dispersed in acetonitrile, made the Fe of amino silicane coupling agent finishing
3o
4nanoparticle;
3.2) the ferriferrous oxide nano-particle 0.2-20g that gets amino silicane coupling agent finishing is dispersed in 50-200 ml acetonitrile solution, under nitrogen protection condition, add catalyzer 0.02-2 g, stirring and evenly mixing, add again 8-chloro acetylamino quinoline and its derivates 0.03-5g, the airtight heating in water bath 40-90 ℃ of lucifuge, stirring reaction continues 1-24 h; Finally use successively distilled water, dehydrated alcohol is respectively washed 3 times, obtains the surface-functionalized Fe of 8-chloracetyl quinolylamine and derivative thereof
3o
4nanoparticle.
4. by surface-functionalized Fe claimed in claim 3
3o
4the preparation method of nanoparticle, is characterized in that: 8-aminoquinoline derivatives is a kind of in 8-amino-2-methyl quinoline, 8-amino-2-ethyl quinoline, 8-amino-2-mercapto phenyl formic quinoline.
5. by surface-functionalized Fe claimed in claim 3
3o
4the preparation method of nanoparticle, is characterized in that: 8-chloracetyl quinolylamine and derivative product thereof are carried out using after purifying, and purifying adopts rotary evaporation and column chromatography purification purifying.
6. by surface-functionalized Fe claimed in claim 3
3o
4the preparation method of nanoparticle, it is characterized in that: amino silicane coupling agent is γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane ammonia, gamma-amino propyl group tripropoxy silane, a kind of in beta-aminoethyl triethoxyl silane, alpha-amino group Union carbide A-162.
7. by surface-functionalized Fe claimed in claim 3
3o
4the preparation method of nanoparticle, is characterized in that: catalyzer is K
2cO
3or Na
2cO
3.
8. surface-functionalized Fe claimed in claim 1
3o
4nanoparticle is in enrichment and detect Cu
2+in application.
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| CN102898461A (en) * | 2012-10-25 | 2013-01-30 | 南京大学 | Method for preparing fluorescent and magnetic resonance dual-functional nanometer super-paramagnetic particles for detecting life system |
| CN106807335A (en) * | 2015-11-27 | 2017-06-09 | 武汉中地金盾环境科技有限公司 | Magnetic retention polyamino adsorbent particulate material, preparation method and applications |
| CN107381749B (en) * | 2017-08-29 | 2020-11-27 | 南京华淳环保股份有限公司 | Magnetic flocculant and preparation method and application thereof |
| CN109879327B (en) * | 2019-01-25 | 2021-09-10 | 重庆科技学院 | Preparation of Fe by using metal oxide as catalyst3O4Method (2) |
| CN113019334B (en) * | 2021-03-11 | 2022-09-23 | 东北林业大学 | Preparation of modified lignin magnetic composite material and method for removing dye in wastewater by using modified lignin magnetic composite material |
| CN114314795B (en) * | 2021-12-24 | 2023-10-31 | 王晶晶 | Method for degrading organic pollutants by activating persulfate through supported alumina particles |
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