CN102898461A - Method for preparing fluorescent and magnetic resonance dual-functional nanometer super-paramagnetic particles for detecting life system - Google Patents
Method for preparing fluorescent and magnetic resonance dual-functional nanometer super-paramagnetic particles for detecting life system Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- ILSCGIHFKLZTME-UHFFFAOYSA-N 2-chloro-n-quinolin-8-ylacetamide Chemical compound C1=CN=C2C(NC(=O)CCl)=CC=CC2=C1 ILSCGIHFKLZTME-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
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- 230000005298 paramagnetic effect Effects 0.000 claims description 21
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- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
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- 238000012986 modification Methods 0.000 claims description 6
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 claims description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 8
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Abstract
The invention relates to a method for preparing fluorescent and magnetic resonance dual-functional nanometer super-paramagnetic particles for detecting a life system. The method comprises the following steps of: preparing Fe3O4 nanoparticles, preparing 8-[(chloracetyl)amino]quinoline, and preparing QTEPA (N-(8-quinolone)-2-[3-(triethoxysilicyl)-alanyl]acetamide); and modifying Fe3O4 nanoparticles by using QTEPA to obtain the nanometer super-paramagnetic particles. In the method, fluorescent molecules are modified onto the surfaces of the nanometer super-paramagnetic particles through silicon dioxide, so that the fluorescent molecules are concentrated on the surfaces of the particles, the fluorescent identifying actions of the fluorescent molecules on metal zinc ions are enhanced, the detection lower limit of zinc ion concentration is lowered, and the feedback functions of the fluorescent molecules on zinc ions to be detected are enhanced; on the other hand, the nanoparticles have high dispersibility in an aqueous solution, so that the application limit of the fluorescent molecules due to poor water solubility is reduced and even eliminated; and meanwhile, the nanoparticles have high superparamagnetism, so that the nanoparticles can be taken as a proper T2 magnetic resonance contrast agent.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer ultra paramagnetic particle, particularly a kind of preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system.
Background technology
Zinc is a kind of important micro elements needed by human, is distributed widely in the cell and body fluid of human body.At present, the known Zn that comprises at active centre place
2+Enzyme outnumber 1000 kinds, approximately had 5000 kinds of protein to contain Zn in 2007 in the cited 40000 kinds of protein structures of Brookhaven Protein Data Bank (PDB)
2+Zn in the organism
2+Generation important in inhibiting all of detection analysis, genetic expression synthetic to research protein structure and function, DNA and RNA, metabolism and nerve degenerative diseases (such as Alzheimer's disease etc.).Yet, Zn
2+Be not free d track and unpaired electron, can not show performance spectrum or magnetic signal, give the Zn in the human body
2+Research brings certain difficulty.With respect to other common analytical procedures, Induced Fluorescence Microscopy is Zn in the detection of biological body
2+One of the most effective means.The zinc ion fluorescent technology is convenient and swift, highly sensitive and selectivity is good and the aspect advantage such as real-time in-situ detection is outstanding.Coming the mark biomolecules with fluorescence labels is one of important means that is used in the biological and medical field high-sensitivity detection target biological molecules.The molecule organic dye has been widely used in the life sciences such as diagnostics and molecular imaging as biological fluorescent labeling.Yet most of organic fluorescence probes are to photo-labile, and fluorescence spectrum is wider, are subject to the interference of the fluorescent signal background of sample own.Have specifically, high-sensitive probe molecule becomes the major objective of research.Nano-probe technology such as inorganic light-emitting quantum dot (luminescent quantum dots) and fluorescence nano emulsion microballoon (fluorescent latex nanoparticles) have overcome some shortcomings of organic dye.But the inorganic light-emitting quantum dot is because it is water-soluble relatively poor, and viscosity is large, and quantum yield is lower, and contains poisonous cadmium metal compound, thereby is subject to certain restrictions in fields such as biomedicines.Therefore, the Nano microsphere of organic molecule modification and the inorganic nanometer microballoon take silicon-dioxide as representative etc. have become one of study hotspot of namo fluorescence probe as the matrix of load fluorescence molecule.The above-mentioned matrix of these nanometers can realize higher mark rate, greatly improved sensitivity for analysis, but the overwhelming majority is inorganic or the organic polymer Nano microsphere needs to introduce the higher functional group of reactive behavior before mark fluorescent molecule and biomolecules, along with the development of nanotechnology, the binding of fluorescent probe molecule and nano material has caused widely interest of chemist.2008, Bonancchi etc. studies have shown that, nanotechnology is attached in the fluorescent probe technique, had significantly improved many organic molecule fluorescent probes and had detected limitation.In traditional fluorescence chemical sensor, acceptor has affected the character of single covalent coupling fluorophor on the identification of target.And suitable organic molecule is modified at nano oxidized silicon face thick and fast, and so that the fluorescence recognition reaction no longer limits to " original position ", can transmit excitation energy to binding site by more widely " fluorescence group network ", thus so that fluorescence intensity multiplication.The people such as Teolato are also by studies have shown that, by with the organic fluorescence molecular modification to silica sphere, not only keep the recognition function of this organic fluorescence molecule for original ion, and be not subjected to deliquescent restriction, this probe can be used for living things system.This organic fluorescence molecule also increases greatly for the sensitivity that detects thing simultaneously, has reduced the detection lower limit for particle to be detected.
On the other hand, work as magnetic Fe
3O
4Nanoparticle diameter (Fe during less than certain critical size
3O
4＜30 nm), produce superparamagnetism, namely have in magnetic field than ferromagnetism, magnetic does not disappear very soon when having magnetic field, so that nanoparticle can be by permanent magnetization in magnetic field.And because this nanoparticle has the easily characteristics such as functionalization of good superparamagnetism and surface, in recent years, the research of superparamagnetic nanoparticle has been caused people's extensive concern.With Fe
3O
4Be the magnetic Nano material of representative, after modifying through various functional groups, with its special nano effect, superparamagnetism, accurately targeting and extremely low side effect, be widely used in the fields such as cellular segregation, targeted drug, nuclear-magnetism contrast medium.The functionalized nano compound ion that integrates fluorescence/magnetic all has many reports in fields such as biology, medical science and environment.The present invention has prepared and has been used for the difunctional nanometer ultra paramagnetic particle of fluorescence-magnetic resonance radiography that the life system detects, when utilizing magnetic resonance radiography instrument location focus, concentrate on privileged site by externally-applied magnetic field directional guide magnetic detection reagent, such as neural system such as brains, then by fluorescence develop spike and sign.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency, a kind of preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system is provided.
The technical scheme that realizes the object of the invention is: a kind of preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system; Comprise step 1: Fe
3O
4The preparation of nanoparticle; Step 2: the preparation of 8-[(chloracetyl) amino] quinoline; Step 3: prepare the N-(8-quinoline with 8-[(chloracetyl) amino] quinoline)-and the 2-[3-(triethoxysilyl) the-third amino] ethanamide (QTEPA); Step 4: QTEPA is modified Fe by St ber method
3O
4Nanoparticle obtains the difunctional nanometer ultra paramagnetic particle of product.
The preparation method of the above-mentioned difunctional nanometer ultra paramagnetic particle of fluorescence, mr that is used for the detection of life system, step 1 is: with ferric chloride hexahydrate, Iron dichloride tetrahydrate, diethylene glycol join in the reaction vessel successively; With dissolution of sodium hydroxide in Diethylene Glycol, then this sodium hydroxide solution is joined in the previous reaction container, mix, mixing solutions is heated to 190 ~ 210 ℃, kept 2 hours, then cool to room temperature, product is separated by externally-applied magnetic field, wash respectively six times with ethanol and intermediate water, filter and obtain product, be dispersed in the intermediate water it stand-by.
The preparation method of the above-mentioned difunctional nanometer ultra paramagnetic particle of fluorescence, mr that is used for the detection of life system; step 2 is: with the 8-quinolylamine; the 2-chloroacetyl chloride; pyridine joins in the methylene dichloride successively; keep 0 ℃ two hours, reaction solution is reduced pressure away, with product with methylene dichloride as eluent; column chromatography for separation obtains 8-[(chloracetyl) amino] quinoline, is " I " among Fig. 1.
The preparation method of the above-mentioned difunctional nanometer ultra paramagnetic particle of fluorescence, mr that is used for the detection of life system; step 3 is: with (3-aminopropyl) triethoxyl silane; 8-[(chloracetyl) amino] quinoline, Anhydrous potassium carbonate joins in the anhydrous acetonitrile simultaneously, obtains mixture; this mixture was refluxed 3 hours; filter, again filter after filtrate is left standstill more than 12 hours, obtain filtrate; behind the low pressure rotary evaporation, obtain yellow oil and be QTEPA, be " II " among Fig. 1.
The preparation method of the above-mentioned difunctional nanometer ultra paramagnetic particle of fluorescence, mr that is used for the detection of life system, step 4 is: with the Fe of step 1 preparation
3O
4Nanoparticle is distributed in the solvent, puts into reaction vessel, allows system be uniformly dispersed in ultrasonic 30 minutes, slowly join tetraethoxysilane in the dispersion system afterwards, continued ultrasonic 1 hour, and made the dispersion system temperature maintain 45 ~ 50 ℃, obtain the reaction product system.Again the reaction product system is separated by externally-applied magnetic field, with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly, obtain primary product respectively; Getting dried primary product again is dispersed in and is placed in the solvent in another reaction vessel, ultrasonic 30 minutes, then the QTEPA that step 3 is obtained joins in the reaction vessel, continue to keep 45 ~ 50 ℃ ultrasonic 2 hours, isolate product by externally-applied magnetic field, more respectively with after ethanol and the intermediate water washing repeatedly, room temperature vacuum-drying, obtain the difunctional nanometer ultra paramagnetic particle of final product, be expressed as Fe
3O
4@SiO
2-QTEPA.
The preparation method of the above-mentioned difunctional nanometer ultra paramagnetic particle of fluorescence, mr that is used for the detection of life system, the Fe of described step 1 preparation
3O
4Nanoparticle is distributed in the solvent and gets dried primary product and again is dispersed in the solvent, and described solvent is the mixed solvent of ethanol and pure and mild intermediate water.
The present invention utilizes fluorescence molecule in the modification of super-paramagnetism nano silica sphere, obtain having the super-paramagnetism nano matrix material to the metallic zinc ion identification, realize that this material is to the fluorescence identification of metallic zinc ion and easily separation in externally-applied magnetic field, utilize simultaneously the superparamagnetism of particle, this material can simultaneously as T2 type magnetic resonance contrast agent, further be able to successful Application in biomass cells.
The present invention has positive effect: the research purpose of (1) this project is exactly the research in conjunction with this two aspect, on the basis of fluorescence organic molecule to zine ion identification, realizes that the fluorescence organic molecule coats superparamagnetism Fe
3O
4Particle.Utilize intensive at silica sphere of fluorescence molecule, thereby enlarged the fluorescence recognition reaction to the metallic zinc ion, thereby the detection lower limit that has reduced zinc ion concentration strengthens fluorescence molecule to the retroactive effect of ion to be detected, namely strengthens sensitivity; On the other hand, utilize this nanoparticle good dispersiveness in the aqueous solution, reduce even eliminate the application limitation of fluorescence molecule, as: solubleness is difficult to separate etc.To reach the practical ranges that enlarges some fluorescence molecule, make it to be used for the vitro detection of cell zine ion, finally realize the application in the organism.(2) because the superparamagnetism that has of this ion, utilize the externally-applied magnetic field can the target target and be conducive to separate, also can be used as the magnetic resonance contrast agent of T2 type simultaneously.(3) utilize simultaneously the characteristics of the nano material of superparamagnetism, in externally-applied magnetic field, reach the separation to magnetic nanoparticle, realize efficiently nondestructive testing of sample.Then this matrix material is applied in the cells in vitro experiment, by Induced Fluorescence Microscopy, realizes diagnosis and explanation to relative disease.The final interior fluoroscopic examination application of cell paste that realizes this material.
Description of drawings
Content of the present invention is easier to be expressly understood in order to make, and the below is according to specific embodiment and by reference to the accompanying drawings, and the present invention is further detailed explanation, wherein
Fig. 1 is that the preparation method reacts schematic diagram;
Fig. 2 is the nuclear-magnetism H spectrum of QTEPA;
Fig. 3 is Fe
3O
4And Fe
3O
4@SiO
2The stereoscan photograph of-QTEPA;
Fig. 4 is Fe
3O
4And Fe
3O
4@SiO
2The x-ray powder crystallogram of-QTEPA;
Fig. 5 is Fe
3O
4And Fe
3O
4@SiO
2The infrared spectrogram of-QTEPA;
Fig. 6 is under room temperature (298.5K), Fe
3O
4And Fe
3O
4@SiO
2The magnetic hysteresis loop of-QTEPA nanoparticle;
Fig. 7 is under externally-applied magnetic field exists, and the magnetic nano-particle (left side) of favorable dispersity is gathered near photo on the bottle wall of externally-applied magnetic field originally;
Fig. 8 is the as a result figure of the nuclear magnetic resonance experiment of cell;
A is difunctional Fe among Fig. 9
3O
4@SiO
2The fluorescence emission spectrum of-QTEPA in zine ion adding situation;
Figure 10 is the fluorescence co-focusing figure as a result of cell.
Embodiment
Fig. 1 is concrete reactions steps schematic diagram.
(1) step 1: magnetic nano-particle Fe
3O
4Preparation
270mg ferric chloride hexahydrate (FeCl
36H
2O, 1mmol), 99.4mg Iron dichloride tetrahydrate (FeCl
24H
2O, 99.4mg, 0.5mmol) and 20g diethylene glycol (DEG) join successively in the three-necked bottle of nitrogen protection, 160mg(4mmol) NaOH is dissolved in the 10g Diethylene Glycol and joins in the above-mentioned three-necked bottle.Mixing solutions be heated to 190 ~ 210 ℃ two hours, stopped heating, cool to room temperature, product separates by externally-applied magnetic field, washs respectively six times to remove unnecessary DEG and some other material with ethanol and intermediate water.At last, product is dispersed in the 10mL intermediate water stand-by.
(2) step 2: " I " i.e. be synthesizing of 8-[(chloracetyl) amino] quinoline (I)
1.15g(8mmol) 8-quinolylamine and 1.25g(11.2mmol), 2-chloroacetyl chloride and 890mg pyridine (11.2mmol) join in the 50mL methylene dichloride successively, keep 0 ℃ two hours.The reaction solution decompression is removed, and as eluent, column chromatography for separation obtains I to product with methylene dichloride.
(3) step 3: " II " is the N-(8-quinoline)-the 2-[3-(triethoxysilyl) the-third amino] ethanamide (QTEPA) synthetic
2.5 the mmol(3-aminopropyl) triethoxyl silane (APTES), 2.27mmolI and 4.305 mmol Anhydrous potassium carbonates join in the 40mL anhydrous acetonitrile.Mixture refluxed 3 hours, filtered, and again filtered after filtrate is spent the night, and obtained filtrate low pressure rotary evaporation and obtained yellow oil (II).
(4) step 4: the preparation of 8-aminoquinoline derivatives modified magnetic nano particles
The ready Fe in 200 μ L fronts
3O
4Nanoparticle is distributed in the mixed solvent of 50 mL ethanol and 10 mL intermediate waters, allows system be uniformly dispersed in ultrasonic 30 minutes.0.1mL tetraethoxysilane (TEOS) slowly joins in the dispersion liquid afterwards, continues ultrasonic 1 hour.System temperature maintains 45 ~ 50 ℃.Reaction product is separated by externally-applied magnetic field, respectively with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly.Get in the mixed solvent that the dried product of 20mg is distributed to 50 mL ethanol and 10 mL intermediate waters again ultrasonic 30 minutes, 30 mg QTEPA(II then) join in the reaction flask, continue to keep 45 ~ 50 ℃ ultrasonic 2 hours.Reaction product is separated by externally-applied magnetic field, with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly, obtains product Fe respectively
3O
4@SiO
2-QTEPA.
(1) step 1: the preparation of magnetic nano-particle Fe3O4
270mg ferric chloride hexahydrate (FeCl
36H
2O, 1mmol), 99.4mg Iron dichloride tetrahydrate (FeCl
24H
2O, 99.4mg, 0.5mmol) and 20g diethylene glycol (DEG) join successively in the three-necked bottle of nitrogen protection, 160mg(4mmol) NaOH is dissolved in the 10g Diethylene Glycol and joins in the above-mentioned three-necked bottle.Mixing solutions be heated to 190 ℃ two hours, stopped heating, cool to room temperature, product separates by externally-applied magnetic field, washs respectively six times to remove unnecessary DEG and some other material with ethanol and intermediate water.At last, product is dispersed in the 10mL intermediate water stand-by.
(2) step 2: " I " i.e. be synthesizing of 8-[(chloracetyl) amino] quinoline (I)
1.15g(8mmol) 8-quinolylamine and 1.25g(11.2mmol), 2-chloroacetyl chloride and 890mg pyridine (11.2mmol) join in the 50mL methylene dichloride successively, keep 0 ℃ two hours.The reaction solution decompression is removed, and as eluent, column chromatography for separation obtains I to product with methylene dichloride.
(3) step 3: " II " is the N-(8-quinoline)-the 2-[3-(triethoxysilyl) the-third amino] ethanamide (QTEPA) synthetic
2.5 the mmol(3-aminopropyl) triethoxyl silane (APTES), 2.27mmolI and 4.305 mmol Anhydrous potassium carbonates join in the 40mL anhydrous acetonitrile.Mixture refluxed 3 hours, filtered, and again filtered after filtrate is spent the night, and obtained filtrate low pressure rotary evaporation and obtained yellow oil (II).
(4) step 4: the preparation of 8-aminoquinoline derivatives modified magnetic nano particles
The ready Fe in 200 μ L fronts
3O
4Nanoparticle is distributed in the mixed solvent of 50 mL ethanol and 10 mL intermediate waters, allows system be uniformly dispersed in ultrasonic 30 minutes.0.1mL tetraethoxysilane (TEOS) slowly joins in the dispersion liquid afterwards, continues ultrasonic 1 hour.System temperature maintains 45 ~ 50 ℃.Reaction product is separated by externally-applied magnetic field, respectively with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly.Get in the mixed solvent that the dried product of 20mg is distributed to 50 mL ethanol and 10 mL intermediate waters again ultrasonic 30 minutes, 30 mg QTEPA(II then) join in the reaction flask, continue to keep 45 ~ 50 ℃ ultrasonic 2 hours.Reaction product is separated by externally-applied magnetic field, with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly, obtains product Fe respectively
3O
4@SiO
2-QTEPA.
Embodiment 3
(1) step 1: magnetic nano-particle Fe
3O
4Preparation
270mg ferric chloride hexahydrate (FeCl
36H
2O, 1mmol), 99.4mg Iron dichloride tetrahydrate (FeCl
24H
2O, 99.4mg, 0.5mmol) and 20g diethylene glycol (DEG) join successively in the three-necked bottle of nitrogen protection, 160mg(4mmol) NaOH is dissolved in the 10g Diethylene Glycol and joins in the above-mentioned three-necked bottle.Mixing solutions is heated to, 190 ~ 210 ℃ two hours, stopped heating, cool to room temperature, product separates by externally-applied magnetic field, washs respectively six times to remove unnecessary DEG and some other material with ethanol and intermediate water.At last, product is dispersed in the 10mL intermediate water stand-by.
(2) step 2: " I " i.e. be synthesizing of 8-[(chloracetyl) amino] quinoline (I)
1.15g(8mmol) 8-quinolylamine and 1.25g(11.2mmol), 2-chloroacetyl chloride and 890mg pyridine (11.2mmol) join in the 50mL methylene dichloride successively, keep 0 ℃ two hours.The reaction solution decompression is removed, and as eluent, column chromatography for separation obtains I to product with methylene dichloride.
(3) step 3: " II " is the N-(8-quinoline)-the 2-[3-(triethoxysilyl) the-third amino] ethanamide (QTEPA) synthetic
2.5 the mmol(3-aminopropyl) triethoxyl silane (APTES), 2.27mmolI and 4.305 mmol Anhydrous potassium carbonates join in the 40mL anhydrous acetonitrile.Mixture refluxed 3 hours, filtered, and again filtered after filtrate is spent the night, and obtained filtrate low pressure rotary evaporation and obtained yellow oil (II).
(4) step 4: the preparation of 8-aminoquinoline derivatives modified magnetic nano particles
The ready Fe in 200 μ L fronts
3O
4Nanoparticle is distributed in the mixed solvent of 50 mL ethanol and 10 mL intermediate waters, allows system be uniformly dispersed in ultrasonic 30 minutes.0.1mL tetraethoxysilane (TEOS) slowly joins in the dispersion liquid afterwards, continues ultrasonic 1 hour.System temperature maintains 48 ℃.Reaction product is separated by externally-applied magnetic field, respectively with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly.Get in the mixed solvent that the dried product of 20mg is distributed to 50 mL ethanol and 10 mL intermediate waters again ultrasonic 30 minutes, 30 mg QTEPA(II then) join in the reaction flask, continue to keep 45 ~ 50 ℃ ultrasonic 2 hours.Reaction product is separated by externally-applied magnetic field, with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly, obtains product Fe respectively
3O
4@SiO
2-QTEPA.
The routine of product dual-function nano particle characterizes in the present embodiment 1:
Fig. 2 is the nucleus magnetic hydrogen spectrum of compound Q TEPA II, and the result of integral result and II coincide.
1H-NMR?(500?MHz,?CDCl3):?δ?(ppm):?0.83(t,?J?=?15.00?Hz,?2H,?Si-CH2*CH2CH2N),?1.23?(t,?J?=?15.00?Hz,?9H,?Si-(OCH2CH3*)3,?1.76?(tt,?J?=?30.00,?6.70?Hz,?2H,?Si-CH2CH2*CH2N?),?2.78?(t,?J?=15.00?Hz,?2H,?Si-CH2CH2CH2*N),?3.57?(s,?2H,?(CO)CH2*NH),?3.83(q,?J?=?20.00?Hz,?6H,?Si-(OCH2*CH3)3),?H-Quinoline:?7.45-7.56?(m,?3H),?8.17?(dd,?1H),?8.85?(dd,?1H),?8.89?(dd,?1H),11.47?(s,?1H,?(CO)CH2NH*)
Fig. 3 is Fe among the embodiment 1
3O
4And Fe
3O
4The stereoscan photograph of@SiO-QTEPA has shown magnetic Nano Fe among the figure
3O
4And Fe
3O
4@SiO
2The diameter dimension of-QTEPA is respectively about 7nm and 20nm, and size distribution is even, favorable dispersity.Can observe the nucleocapsid structure of Fe3O4@SiO2-QTEPA from transmission electron microscope photo, also the Z 250 of proof is wrapped wherein simultaneously.A more than ferriferrous oxide nano-particle is covered by in the same nucleocapsid structure in the coating process.
Fig. 4 is Fe among the embodiment 1
3O
4And Fe
3O
4@SiO
2The x-ray powder crystallogram of-QTEPA, the top line is Fe in two line segments
3O
4Diffraction angle, the below line is the diffraction angle of Fe3O4@SiO2-QTEPA, as can be seen from the figure all there is Fe in two lines
3O
4 Characteristic diffraction peak 2 θ of crystal are 30.1o, 35.5o, and 43.1o, 53.6o, 57.2o and 62.7o illustrate in the nanoparticle of really modifying and have really wrapped up Fe
3O
4
Fig. 5 is Fe among the embodiment 1
3O
4@SiO
2And Fe
3O
4@SiO
2The infrared spectrogram of-QTEPA can be confirmed from infrared spectrum, and QTEPA successfully modifies Fe
3O
4@SiO
2The surface.3410.37cm-1 broad peak be surface-OH peak; 1643.33 the peak of cm-1 represents the flexural vibration of O-H; 1103.04 the spike of locating is the vibration of Si-O-Si; The demonstration of Si-OH shuttle belt is positioned at 802-950cm-1.With Fe
3O
4@SiO
2Infrared spectrum relatively, the N-H vibration appears at 3402 cm-1 to be followed-broad peak of OH and particle surface water; 1531.4 cm-1 is the flexible peak of the C=C of aromatic ring; Carbonyl peak appears at 1662.3cm-1; Group peak between between 1325-1478cm-1 and the C-H stretching vibration of aliphatic hydrocarbon coincide.The infrared fine modification of these data declarations II is to the magnetic nano particle sub-surface.
Fig. 6 be among the embodiment 1 under room temperature (298.5K), Fe
3O
4And Fe
3O
4@SiO
2The magnetic hysteresis loop of-QTEPA nanoparticle, B-H loop does not all appear in two kinds of particles, illustrates that these two kinds of particles show as superparamagnetism at ambient temperature.Because Fe
3O
4The silicon-dioxide of external parcel, the particle saturation magnetization of QTEPA parcel is less than pure Fe
3O
4At room temperature, Fe
3O
4And Fe
3O
4@SiO
2The saturation magnetization of-QTEPA is 13emu/g, and the Fe of unmodified
3O
4Saturation magnetization be 69emu/g.
Fig. 7 is under externally-applied magnetic field exists among the embodiment 1, and the magnetic nano-particle (left side) of favorable dispersity is gathered near photo on the bottle wall of externally-applied magnetic field originally.Illustrate that this particle can remove easily by externally-applied magnetic field.
Fig. 8 is the as a result figure of the nuclear magnetic resonance experiment of cell among the embodiment 1
We use the Fe that contains different concns
3O
4@SiO
2The buffered soln of-QTEPA was hatched respectively the MCF-7 cell 3 hours, then washed unnecessary nanoparticle off with PBS, and cell is done nuclear magnetic resonance experiment after disperseing with damping fluid PBS.The result shows along with the increasing of the nanoparticle concentration that is used for hatching, namely contained Fe
3O
4Amount increase, the nuclear magnetic signal color of cell is more and more darker among the figure.Experimental result shows Fe
3O
4@SiO
2-QTEPA can pass through cytolemma, and also is well based on Fe
3O
4T2 type mri contrast agent, our cell experiment is also laid a good foundation for further experimentation on animals.
A is embodiment 1 difunctional Fe among Fig. 9
3O
4@SiO
2The fluorescence emission spectrum of-QTEPA in zine ion adding situation excites with 372nm, along with the adding of zine ion, Fe
3O
4@SiO
2The fluorescence intensity of the dispersion liquid of-QTEPA in damping fluid strengthens gradually.The magnetic nano-particle that the QTEPA modified is described has good recognition function to zine ion.Other metal ions are such as Ag
+, Cd
2+, Co
2+, Cr
3+, Cu
2+, Fe
2+, Fe
3+, Hg
2+, Mn
2+, Ni
2+And Pb
2+Add respectively and do not cause that the considerable change of dispersion liquid fluorescence intensity sees b among Fig. 9, illustrate that this magnetic nano-particle not only has good recognition reaction and with respect to other metal ions good selectivity arranged zine ion.
Figure 10 is the fluorescence co-focusing experiment of embodiment 1 cell
We with on the MCF-7 cell with containing Fe
3O
4@SiO
2The dispersion liquid hatching of-QTEPA is hatched 4h under 37 ℃ of temperature, wash away unnecessary Fe with the PBS damping fluid
3O
4@SiO
2-QTEPA nanoparticle.Then add Zn
2+, continue hatching 20 minutes.The fluorescence co-focusing that cell under the different incubation conditions carries out is taken pictures.Figure 10 is the photo result of fluorescence co-focusing.From figure, can be clearly seen that, only use Fe
3O
4@SiO
2The cell fluorescence intensity of-QTEPA hatching relatively a little less than, add Zn
2+After, the fluorescence intensity in the cell obviously strengthens.This bifunctional nanoparticle of these presentation of results can have the potential application of further biology.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. preparation method who is used for the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that the life system detects; It is characterized in that: comprise step 1: preparation Fe
3O
4Nanoparticle; Step 2: preparation 8-[(chloracetyl) amino] quinoline; Step 3: prepare the N-(8-quinoline with 8-[(chloracetyl) amino] quinoline)-and the 2-[3-(triethoxysilyl) the-third amino] ethanamide; Step 4: use the N-(8-quinoline)-and the 2-[3-(triethoxysilyl) the-third amino] ethanamide modification Fe
3O
4Nanoparticle obtains the difunctional nanometer ultra paramagnetic particle of product.
2. the preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system according to claim 1, it is characterized in that: step 1 is: with ferric chloride hexahydrate, Iron dichloride tetrahydrate, diethylene glycol join in the reaction vessel successively; With dissolution of sodium hydroxide in Diethylene Glycol, then this sodium hydroxide solution is joined in the previous reaction container, mix, mixing solutions is heated to 190 ~ 210 ℃, kept 2 hours, then cool to room temperature, product is separated by externally-applied magnetic field, wash respectively six times with ethanol and intermediate water, filter and obtain product, be dispersed in the intermediate water it stand-by.
3. the preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system according to claim 1; it is characterized in that: step 2 is: with the 8-quinolylamine; the 2-chloroacetyl chloride; pyridine joins in the methylene dichloride successively; keep 0 ℃ two hours; reaction solution is reduced pressure away, use methylene dichloride as eluent product, column chromatography for separation obtains 8-[(chloracetyl) amino] quinoline.
4. the fluorescence that detects for the life system according to claim 1; the preparation method of the difunctional nanometer ultra paramagnetic particle of mr; it is characterized in that: step 3 is: with (3-aminopropyl) triethoxyl silane; 8-[(chloracetyl) amino] quinoline; Anhydrous potassium carbonate joins in the anhydrous acetonitrile simultaneously; obtain mixture; this mixture was refluxed 3 hours; filter; after leaving standstill more than 12 hours, filtrate again filters; obtain filtrate, behind the low pressure rotary evaporation, obtain yellow oil and be the N-(8-quinoline)-the 2-[3-(triethoxysilyl) the-third amino] ethanamide.
5. the preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system according to claim 1, it is characterized in that: step 4 is: with the Fe of step 1 preparation
3O
4Nanoparticle is distributed in the solvent, puts into reaction vessel, allows system be uniformly dispersed in ultrasonic 30 minutes, slowly join tetraethoxysilane in the dispersion system afterwards, continued ultrasonic 1 hour, and made the dispersion system temperature maintain 45 ~ 50 ℃, obtain the reaction product system; Again the reaction product system is separated by externally-applied magnetic field, with room temperature vacuum-drying after ethanol and the intermediate water washing repeatedly, obtain primary product respectively; Getting dried primary product again is dispersed in and is placed in the solvent in another reaction vessel, ultrasonic 30 minutes, then the N-(8-quinoline that step 3 is obtained)-and the 2-[3-(triethoxysilyl) the-third amino] ethanamide joins in the reaction vessel, continue to keep 45 ~ 50 ℃ ultrasonic 2 hours, isolate product by externally-applied magnetic field, respectively with after ethanol and the intermediate water washing repeatedly, room temperature vacuum-drying obtains the difunctional nanometer ultra paramagnetic particle of product final product again.
6. the preparation method of the difunctional nanometer ultra paramagnetic particle of fluorescence, mr that detects for the life system according to claim 5 is characterized in that: the Fe of described step 1 preparation
3O
4Nanoparticle is distributed in the solvent and gets dried primary product and again is dispersed in the solvent, and described solvent is the mixed solvent of ethanol and intermediate water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483612A (en) * | 2013-05-22 | 2014-01-01 | 黄淮学院 | Fluorescent silicon nanoparticle modified optical fiber and preparation method thereof |
| CN107228848A (en) * | 2017-06-16 | 2017-10-03 | 上海市第十人民医院 | Wide fluorescence spectrum and MRI slur is as functional microsphere spike mescenchymal stem cell and application |
| CN108250141A (en) * | 2017-10-16 | 2018-07-06 | 华南师范大学 | Methyl-P-tyrosine modifies N-（8- quinolyls）Acetamide compound, synthetic method and application |
| CN108358978A (en) * | 2018-03-20 | 2018-08-03 | 四川农业大学 | A kind of enhancement magnetic targeted cell fluorescence nano-probe and preparation method thereof |
| CN110724518A (en) * | 2019-10-21 | 2020-01-24 | 福建医科大学 | Fe applicable to dual-mode imaging system3O4Construction of @ CuInS2 core-shell structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070148095A1 (en) * | 2005-12-23 | 2007-06-28 | Industrial Technology Research Institute | Fluorescent magnetic nanoparticles with specific targeting functions |
| CN101923932A (en) * | 2009-06-09 | 2010-12-22 | 南京大学 | Multifunctional double-layer core-shell structure magnetic nano particle, preparation method and application thereof |
| CN102516822A (en) * | 2011-11-04 | 2012-06-27 | 昆明理工大学 | Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof |
-
2012
- 2012-10-25 CN CN2012104138384A patent/CN102898461A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070148095A1 (en) * | 2005-12-23 | 2007-06-28 | Industrial Technology Research Institute | Fluorescent magnetic nanoparticles with specific targeting functions |
| CN101923932A (en) * | 2009-06-09 | 2010-12-22 | 南京大学 | Multifunctional double-layer core-shell structure magnetic nano particle, preparation method and application thereof |
| CN102516822A (en) * | 2011-11-04 | 2012-06-27 | 昆明理工大学 | Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| SHIVA K. RASTOGI等，: "8-Aminoquinoline Functionalized Silica Nanoparticles: A Fluorescent Nanosensor for Detection of Divalent Zinc in Aqueous and in Yeast Cell Suspension", 《ACS APPL. MATER. INTERFACES》, vol. 3, 21 April 2011 (2011-04-21) * |
| 张文莉等，: "Fe3O4@SiO2@An磁性纳米荧光粒子的制备及对锌离子的识别", 《光谱实验室》, vol. 29, no. 1, 31 January 2012 (2012-01-31) * |
| 邱琳等,: "蒽衍生物自组装膜的制备及其对金属离子的识别作用", 《无机化学学报》, vol. 22, no. 10, 31 October 2006 (2006-10-31), pages 1745 - 1749 * |
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| CN103483612A (en) * | 2013-05-22 | 2014-01-01 | 黄淮学院 | Fluorescent silicon nanoparticle modified optical fiber and preparation method thereof |
| CN103483612B (en) * | 2013-05-22 | 2015-07-15 | 黄淮学院 | Fluorescent silicon nanoparticle modified optical fiber and preparation method thereof |
| CN107228848A (en) * | 2017-06-16 | 2017-10-03 | 上海市第十人民医院 | Wide fluorescence spectrum and MRI slur is as functional microsphere spike mescenchymal stem cell and application |
| CN108250141A (en) * | 2017-10-16 | 2018-07-06 | 华南师范大学 | Methyl-P-tyrosine modifies N-（8- quinolyls）Acetamide compound, synthetic method and application |
| CN108250141B (en) * | 2017-10-16 | 2021-04-20 | 华南师范大学 | Tyrosine methyl ester modified N- (8-quinolyl) acetamide compound, and synthesis method and application thereof |
| CN108358978A (en) * | 2018-03-20 | 2018-08-03 | 四川农业大学 | A kind of enhancement magnetic targeted cell fluorescence nano-probe and preparation method thereof |
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