CN102516822A - 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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- CN102516822A CN102516822A CN2011103452581A CN201110345258A CN102516822A CN 102516822 A CN102516822 A CN 102516822A CN 2011103452581 A CN2011103452581 A CN 2011103452581A CN 201110345258 A CN201110345258 A CN 201110345258A CN 102516822 A CN102516822 A CN 102516822A
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- amino
- nanoparticle
- quinoline
- chloracetyl
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 37
- 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 claims abstract description 23
- 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
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 239000002245 particle Substances 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
- 150000005012 8-aminoquinolines Chemical class 0.000 claims description 9
- -1 amino silicane Chemical compound 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 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
- 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
- 238000005303 weighing Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 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
- 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
- 239000000047 product Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
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- 239000003054 catalyst Substances 0.000 description 3
- 239000008187 granular material Substances 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
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Soft Magnetic Materials (AREA)
- Catalysts (AREA)
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 particularly relates to and a kind ofly with synthetic 8-chloro acetylamino quinoline ferriferrous oxide nano-particle is carried out the method for the control of finishing and particle diameter thereof, and is applied to Cu
2+Enrichment and detection.
Background technology
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 owing to having.Synthetic and modification about the magnetic ferroferric oxide particle in recent years causes people's extensive concern.Be in the Chinese patent of CN 101554574A for example at publication number; Use amino silicane coupling agent that the superparamagnetism ferroferric oxide nano granules that glucose coats is carried out finishing, utilize high-hydrophilic, the aqueous phase stable dispersion property of ferroferric oxide nano granules, reduce the reticuloendothelial system phagocytic amount; Prolong cycling time in the blood; Can combine with monoclonal antibody easily simultaneously body not to be caused toxic side effect, good biocompatibility to improve initiatively target property; The preparation method is simple, has a good application prospect at diagnosing early malignant tumor and magnetic target therapy field.Publication number is the Chinese patent of CN 101139409A; Disclose a kind of functionalized macromolecular magnetic carrier, become nucleocapsid structure with macromolecular compound coated ferroferric oxide magnetic particle core group, surface bond has hydroxyl and amido; Successfully carrier is modified through epoxidation and functional amido reaction; Can be applicable to handle heavy metal-containing waste water, dyeing waste water, respond well, aspect wastewater treatment, good prospects for application is arranged.Publication number is the Chinese patent of CN 1805086A, discloses a kind of preparation method of silane coupledization magnetic ferroferric oxide nanometer matrix material, through divalent iron salt and trivalent iron salt are dissolved in the water; Under protection of inert gas, drip alkaline solution to alkalescence, the heated and stirred reaction makes nano ferriferrous oxide granule, adds dispersion solvent and silane coupling reagent then; Heated and stirred makes the magnetic ferroferric oxide nanometer matrix material of silane coupledization; And it is technological that they are applied to the lasting pollutent residue detection of environment, and this technology detecting method is accurate, favorable reproducibility; The recyclable recycling of material, step is simple.Z 250 adopts chemical coprecipitation to synthesize usually, but Z 250 is oxidized easily, therefore needs it is modified, and makes it existence stable in the air, and unrestricted when using.Existing surface modification method comprises physical adsorption; Surface deposition; Electrostatic interaction and Van der Waals force etc., these methods all can not make the ferriferrous oxide nanometer material surface have different reactive functional mostly, though perhaps have surface reaction activity functional group; But a little less than interacting with nano-material surface, be unfavorable for 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 is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
In the formula: R
2Be CH
2R
3Be H, CH
3, CH
2CH
3Or SH; N=1-3.
This nanoparticle has enrichment and detects Cu among the present invention
2+Ability.
Another purpose of the present invention is to provide a kind of to Cu
2+Surface-functionalized Fe with enrichment detection effect
3O
4Nanometer particle process method, this method is coupled at Fe with the method for chemical covalent coupling with synthetic 8-aminoquinoline derivatives molecular chemistry
3O
4Nanoparticle surface, and according to surface molecular structure and Cu
2+Between specificity contact be used for enrichment and detect Cu
2+
The surface-functionalized Fe of the present invention
3O
4Nanoparticle obtains through following steps:
1, magnetic Fe
3O
4The preparation of nanoparticle
Take by weighing FeCl
24H
2O 0.2-20 g, FeCl
36H
2O 0.54-54 g, 1:2-3 puts into reaction flask by mass ratio, be dissolved in the 50-300 ml zero(ppm) water, under the condition of nitrogen protection with the speed Dropwise 5 .5-100 ml ammoniacal liquor of constant pressure funnel with 1-10 ml/min; Heating in water bath is to 40-90 ℃, stirring reaction 1-6 h, and reaction finishes; Naturally cooling 20-60 min uses zero(ppm) water, absolute ethyl alcohol successively; Toluene washs respectively 3 times, and vacuum-drying 1-24 h makes 0.696-69.6 g magnetic Fe
3O
4Nanoparticle;
2,8-chloracetyl amino quinoline derivatives is synthetic
Get the 0.095-9.5g 8-aminoquinoline derivatives in flask, add 0.1-10 ml triethylamine, add 5-500 ml dichloromethane solution again, keep 30-60 min down at 0 ℃; Add 0.06-6 ml chloroacetyl chloride then, airtight normal temperature lucifuge lower magnetic force stirring reaction 1-48 h, the evaporation of final reaction liquid removes desolvates, and 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 with prepared magnetic Fe in the step 1
3O
4Nanoparticle 0.2-20g is dispersed in the 50-200ml toluene solution, adds amino silicane coupling agent 0.5-50 ml, under the nitrogen protection condition; Heating in water bath 30-90 ℃; Stirring reaction 1-12 h, magnetic separated after reaction was accomplished, and washed with acetonitrile; And it is dispersed in the acetonitrile, make the ferriferrous oxide nano-particle of amino silicane coupling agent finishing;
3.2 getting the ferriferrous oxide nano-particle 0.2-20 g of amino silicane coupling agent finishing is dispersed in the 50-200ml acetonitrile solution; Add catalyzer 0.02-2 g under the nitrogen protection condition; Stirring and evenly mixing adds prepared 8-chloro acetylamino quinoline 0.03-5g in the step 2, the airtight heating in water bath 40-90 of lucifuge ℃ again; Stirring reaction 1-24 h; Use zero(ppm) water at last respectively, absolute ethyl 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, the 8-amino-2-mercapto phenyl formic quinoline.
Among the present invention 8-chloracetyl amino quinoline derivatives product is carried out using behind the purifying, purifying adopts the 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 a γ-An Jibingjisanyiyangjiguiwan; Gamma-amino propyl trimethoxy silicane ammonia; Gamma-amino propyl group tripropoxy silane, a kind of in beta-aminoethyl triethoxyl silane, the alpha-amino group Union carbide A-162.
Catalyzer described in the present invention is K
2CO
3Or Na
2CO
3
Reaction reagent used among the present invention is all bought from market, and purity is CP, perhaps the above reagent of CP.
The present invention is used for the surface-functionalized ferriferrous oxide nano-particle of 8-chloro acetylamino quinoline that makes enrichment and detects solution Cu
2+, concrete operations are following:
Prepare 1 mmol/L Cu
2+With 0.1 mmol/LCu
2+The aqueous solution with prepared surface-functionalized ferriferrous oxide nano-particle, joins 2 ml, 1 mmol/L (63.5ppm) Cu respectively
2+With 2 ml, 0.1 mmol/L (6.35ppm) Cu
2+In the aqueous solution, vibration absorption 1-24 h, first magnetic separates, and then spinning goes out supernatant liquid, detects supernatant liquid with atomic absorption, 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 %.The result shows, surface-functionalized Fe
3O
4Nanoparticle is to Cu
2+Good inrichment is arranged.
Surface-functionalized Fe through this method preparation
3O
4Nanoparticle is to Cu
2+Have stronger bioaccumulation efficiency, can be used for purification of waste water processing, effective enrichment target heavy metal ion or trace heavy metal Cu
2+Fields such as ion detection, and method is simple to operate, and accumulation rate is high, is easy to realize.
Description of drawings
Fig. 1 is that the inventive method prepares surface-functionalized Fe
3O
4The nanoparticle principle schematic;
Fig. 2 is the surface-functionalized Fe that utilizes the inventive method preparation
3O
4Nanoparticle is to Cu
2+Inrichment effect synoptic diagram.
R among the figure
1Be CH
3Or C
2H
5R
2Be CH
2R
3Be H, CH
3, CH
2CH
3Or SH; N=1-3.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain, but protection scope of the present invention is not limited to said content.
Embodiment 1: this surface-functionalized Fe
3O
4Nanometer particle process method may further comprise the 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 zero(ppm) water, under the condition of nitrogen protection, with the speed Dropwise 55 ml ammoniacal liquor of constant pressure funnel with 5 ml/min; 65 ℃ of stirring reaction 2h of heating in water bath stop heating, naturally cooling 30 min; Use zero(ppm) water respectively, absolute ethyl 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, add 50 ml dichloromethane solutions again, keep 30 min down at 0 ℃; The chloroacetyl chloride that adds 0.6 ml then; The airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 40 h, reaction back decompression rotary evaporation obtains thick product, thick product through column chromatography separate (petrol ether/ethyl acetate=3:1) purify 8-chloro acetylamino quinoline 0.4 g; 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 the 150 ml toluene solutions, adds 5 ml γ-An Jibingjisanyiyangjiguiwans then, under 80 ℃ of nitrogen protection conditions, and stirring reaction 12 h, magnetic separates then, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing that makes is dispersed in it in 100ml acetonitrile after acetonitrile washs three times, adds 0.2 g catalyzer K under the nitrogen protection condition
2CO
3, stirring and evenly mixing adds 8-chloro acetylamino quinoline 0.4g then, 40 ℃ of the airtight heating in water bath of lucifuge, and stirring reaction 24 h use zero(ppm) water successively, and absolute ethyl 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 is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
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 the solution
2+, concrete operations are following:
Prepare 1 mmol/L (63.5ppm) Cu
2+With 0.1 mmol/L (6.35ppm) Cu
2+The aqueous solution joins 2 ml, 1 mmol/L Cu respectively with 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.Spinning is got supernatant liquid and is done the atomic absorption detection, and the result is as shown in Figure 2, and surface-functionalized ferriferrous oxide nano-particle is to 2ml 1 mmol/L Cu
2+Adsorption efficiency reaches 57.48 %, to 2 ml, 0.1 mmol/LCu
2+Adsorption efficiency reaches 91.56 %.
The used reaction reagent of present embodiment is commercially available AR.
Embodiment 2: this surface-functionalized Fe
3O
4Nanometer particle process method may further comprise the 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 zero(ppm) water, under the condition of nitrogen protection, with the speed Dropwise 5 .5 ml ammoniacal liquor of constant pressure funnel with 1ml/min; 40 ℃ of stirring reaction 6h of heating in water bath stop heating, naturally cooling 20 min; Use zero(ppm) water respectively, absolute ethyl 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, add the 5ml dichloromethane solution again, keep 10min down at 0 ℃; The chloroacetyl chloride that adds 0.06 ml then, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 1 h, decompression rotary evaporation in reaction back 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 the 50 ml toluene solutions, adds 0.55ml beta-aminoethyl triethoxyl silane then, under 30 ℃ of nitrogen protection conditions, and stirring reaction 2 h, magnetic separates then, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing that makes is dispersed in it in 50ml acetonitrile after acetonitrile washs three times, adds 0.02 g catalyzer K under the nitrogen protection condition
2CO
3, stirring and evenly mixing adds 8-chloracetyl amino-2-ethyl quinoline 0.04g then; 60 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 12 h use zero(ppm) water successively; Absolute ethyl 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 is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
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 the solution
2+, concrete operations are following:
Prepare 1 mmol/L Cu
2+With 0.1 mmol/LCu
2+The aqueous solution joins 2 ml, 1 mmol/L Cu respectively with 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.Spinning 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
4Nanometer particle process method may further comprise the 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 zero(ppm) water, under the condition of nitrogen protection, drips 100 ml ammoniacal liquor with constant pressure funnel with the speed of 10 ml/min; 90 ℃ of stirring reaction 1h of heating in water bath stop heating, naturally cooling 60 min; Use zero(ppm) water respectively, absolute ethyl 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 quinoline in round-bottomed flask, add 10 ml triethylamines, add the 500ml dichloromethane solution again, keep 60 min down at 0 ℃; The chloroacetyl chloride that adds 6 ml then, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 48 h, reaction back decompression rotary evaporation, column chromatography separate (petrol ether/ethyl acetate=3:1) purify 8-chloro acetylamino-2-toluquinoline 4 g.
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 the 200 ml toluene solutions, adds 50ml gamma-amino propyl trimethoxy silicane then, under 90 ℃ of nitrogen protection conditions, and stirring reaction 10 h, magnetic separates then, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing that makes is dispersed in it in acetonitrile after acetonitrile washs three times, adds 2g catalyst n a under the nitrogen protection condition
2CO
3, stirring and evenly mixing adds 8-chloro acetylamino-2-toluquinoline 4 g then; 90 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 1 h uses zero(ppm) water successively; Absolute ethyl 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 is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
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 the solution
2+, concrete operations are following:
Prepare 1 mmol/L Cu
2+With 0.1 mmol/LCu
2+The aqueous solution joins 2 ml, 1 mmol/L Cu respectively with 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.Spinning 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
4Nanometer particle process method may further comprise the 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 zero(ppm) water, under the condition of nitrogen protection, drips 45 ml ammoniacal liquor with constant pressure funnel with the speed of 5 ml/min; 60 ℃ of stirring reaction 2h of heating in water bath stop heating, naturally cooling 35 min; Use zero(ppm) water respectively, absolute ethyl 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, add the 250ml dichloromethane solution again, keep 40 min down at 0 ℃; The chloroacetyl chloride that adds 4 ml then, the airtight lucifuge condition of normal temperature lower magnetic force stirring reaction 35 h, reaction back decompression rotary evaporation, column chromatography separate (petrol ether/ethyl acetate=3:1) purify 8-chloro acetylamino-2-mercaptoquinoline 2.1g.
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 the 200 ml toluene solutions, adds 25ml alpha-amino group Union carbide A-162 then, under 70 ℃ of nitrogen protection conditions, and stirring reaction 11 h, magnetic separates then, makes the ferriferrous oxide nano-particle of amido functional group finishing.The ferriferrous oxide nano-particle of the amido functional group finishing that makes is dispersed in it in acetonitrile after acetonitrile washs three times, adds 1g catalyst n a under the nitrogen protection condition
2CO
3, stirring and evenly mixing adds 8-chloro acetylamino-2-mercaptoquinoline 2.1 g then; 70 ℃ of the airtight heating in water bath of lucifuge, stirring reaction 2 h use zero(ppm) water successively; Absolute ethyl 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 is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
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 the solution
2+, concrete operations are following:
Prepare 1 mmol/L Cu
2+With 0.1 mmol/LCu
2+The aqueous solution joins 2 ml, 1 mmol/L Cu respectively with 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.Spinning 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. surface-functionalized Fe
3O
4Nanoparticle is characterized in that: be the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3O
4Nanoparticle is at Fe
3O
4The nanoparticle surface coupling has 8-ammonia ethanoyl quinoline molecule, and its chemical structural formula is:
R in the formula
2Be CH
2R
3Be H, CH
3, CH
2CH
3Or SH; N=1-3.
2. by the described surface-functionalized Fe of claim 1
3O
4Nanoparticle is characterized in that: this nanoparticle has enrichment and detects Cu
2+Ability.
3. surface-functionalized Fe
3O
4Nanometer particle process method is characterized in that: may further comprise the steps:
(1) magnetic Fe
3O
4The preparation of nanoparticle
Take by weighing FeCl
24H
2O 0.2-20 g, FeCl
36H
2O 0.54-54 g, 1:2-3 puts into reaction flask by mass ratio, be dissolved in the 50-300 ml zero(ppm) water, under the condition of nitrogen protection with the speed Dropwise 5 .5-100 ml ammoniacal liquor of constant pressure funnel with 1-10 ml/min; Heating in water bath is to 40-90 ℃, stirring reaction 1-6 h, and reaction finishes; Naturally cooling 20-60 min uses zero(ppm) water, absolute ethyl alcohol successively; Toluene washs respectively 3 times, and vacuum-drying 1-24 h makes magnetic Fe
3O
4Nanoparticle;
(2) 8-chloracetyl amino quinoline derivatives is synthetic
Get the 0.095-9.5g 8-aminoquinoline derivatives, join in the 0.1-10 ml triethylamine and dissolve, add 5-500 ml dichloromethane solution again, keep 10-60 min down at 0 ℃; Add 0.06-6 ml chloroacetyl chloride then, lucifuge magnetic agitation reaction 1-48 h under the normal temperature air tight condition, the evaporation of final reaction liquid removes desolvates, and obtains 8-chloracetyl amino quinoline derivatives product;
(3) preparation of the surface-functionalized ferriferrous oxide nano-particle of 8-chloracetyl amino quinoline derivatives
3.1) get 0.2-20 g magnetic Fe
3O
4Nanoparticle is dispersed in the 50-200 ml toluene solution; Add amino silicane coupling agent 0.5-50 ml, under the nitrogen protection condition, heating in water bath 30-90 ℃; Stirring reaction 1-12 h; Magnetic separated after reaction was accomplished, and was dispersed in the acetonitrile with the acetonitrile washing and with it, made the Fe of amino silicane coupling agent finishing
3O
4Nanoparticle;
3.2) the ferriferrous oxide nano-particle 0.2-20g that gets the amino silicane coupling agent finishing is dispersed in the 50-200 ml acetonitrile solution; Under the nitrogen protection condition; Add catalyzer 0.02-2 g, stirring and evenly mixing adds 8-chloro acetylamino quinoline 0.03-5g again; The airtight heating in water bath 40-90 of lucifuge ℃, stirring reaction continues 1-24 h; Use zero(ppm) water at last successively, absolute ethyl alcohol is respectively washed 3 times, obtains the surface-functionalized Fe of 8-chloracetyl amino quinoline derivatives
3O
4Nanoparticle.
4. by the described surface-functionalized Fe of claim 3
3O
4Nanometer particle process method is characterized in that: 8-aminoquinoline derivatives is a kind of in 8-quinolylamine, 8-amino-2-methyl quinoline, 8-amino-2-ethyl quinoline, the 8-amino-2-mercapto phenyl formic quinoline.
5. by the described surface-functionalized Fe of claim 3
3O
4Nanometer particle process method is characterized in that: 8-chloracetyl amino quinoline derivatives product is carried out using behind the purifying, and purifying adopts rotary evaporation and column chromatography purification purifying.
6. by the described surface-functionalized Fe of claim 3
3O
4Nanometer particle process method; It is characterized in that: amino silicane coupling agent is a γ-An Jibingjisanyiyangjiguiwan; Gamma-amino propyl trimethoxy silicane ammonia, gamma-amino propyl group tripropoxy silane, a kind of in beta-aminoethyl triethoxyl silane, the alpha-amino group Union carbide A-162.
7. by the described surface-functionalized Fe of claim 3
3O
4Nanometer particle process method is characterized in that: catalyzer is K
2CO
3Or Na
2CO
3
8. by claim 1 or 3 described surface-functionalized Fe
3O
4Nanoparticle is characterized in that: this surface-functionalized ferriferrous oxide nano-particle is at enrichment and detection Cu
2+In application.
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| CN109879327A (en) * | 2019-01-25 | 2019-06-14 | 重庆科技学院 | It is a kind of to prepare Fe using metal oxide oxidation catalyst3O4Method |
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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 |
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| CN114314795A (en) * | 2021-12-24 | 2022-04-12 | 王晶晶 | Method for degrading organic pollutants by activating persulfate through supported alumina particles |
| 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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