CN102085381B - Ferroferric oxide-silicon dioxide-thymine nanoparticles and preparation method and application thereof - Google Patents

Ferroferric oxide-silicon dioxide-thymine nanoparticles and preparation method and application thereof Download PDF

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CN102085381B
CN102085381B CN2011100266533A CN201110026653A CN102085381B CN 102085381 B CN102085381 B CN 102085381B CN 2011100266533 A CN2011100266533 A CN 2011100266533A CN 201110026653 A CN201110026653 A CN 201110026653A CN 102085381 B CN102085381 B CN 102085381B
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nanoparticle
thymus pyrimidine
silicon dioxide
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amino
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CN102085381A (en
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杨仕平
田志卿
杨红
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Shanghai Normal University
University of Shanghai for Science and Technology
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Abstract

The invention relates to the field of magnetic resonance contrast agents and nuclear magnetic resonance sensors and discloses ferroferric oxide-silicon dioxide-thymine nanoparticles which have water solubility, good monodispersity and superparamagnetism, and the average particle size is 10-20nm. The preparation method comprises the steps of preparing the Fe3O4 nanoparticles by high-temperature pyrolysis, wrapping silicon dioxide, connecting with amino groups, and further connecting with thymine. The nanoparticles can be used for preparing the magnetic resonance contrast agents and preparing the nuclear magnetic resonance sensors for detecting mercury ions.

Description

A kind of ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanoparticle
Technical field
The present invention relates to magnetic resonance contrast agent and nmr sensor field, be specially a kind of ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanoparticle.
Background technology
It is main because two reasons why nuclear magnetic resonance, NMR becomes one of current popular main detection method: (1) MRI (NMR-imaging, or magnetic imaging) can provide spatial resolution clearly, can access the details of physiological tissue and organ; (2) be the research means of a kind of nothing injury (noninvasive).MRI can realize pair cell or tissue " noninvasive ", 3D imaging clearly, in physics, chemistry, biology and clinical medicine domain, is bringing into play important effect.It can be used to observe little structure and character to molecule, arrives living animal and even people's anatomical structure and function greatly.Exactly because also be with a wide range of applications and prospect, nuclear magnetic resonance technique is obtaining development at full speed over nearly 50 years.At present, mostly contrast agent with the metal ion of paramagnetism or superparamagnetism (for example: gadolinium) or magnetic nano-particle (for example: Fe 3O 4) be magnetic core, contrast agent can strengthen the NMR signal of proton, changes the relaxation rate (relaxationrates) of proton.After these contrast agent are modified, produced nmr sensor (MRsensor).
Magnetic Nano material receives people's attention owing to its distinctive physics and chemical property; Have a wide range of applications in machinery, electricity, optics, magnetics, chemistry and biology field; Particularly in recent years, the research of the contrast agent emphasis paid close attention to of people especially.At present, mostly contrast agent with the metal ion of paramagnetism or superparamagnetism (for example: gadolinium) or magnetic nano-particle (for example: Fe 3O 4) be magnetic core, contrast agent can strengthen the NMR signal of proton, changes the relaxation rate (relaxation rates) of proton.These contrast agent are carried out having amplified out a kind of new pick off after the finishing---nmr sensor (MR sensor).
Emily L.Que and Christopher J.Chang have synthesized a kind of novel nmr sensor that can carry out living imaging.This pick off is the coordination compound that is formed by gadolinium and part thereof, experiment showed, that it can carry out specificity with copper ion and combine, and under the copper ion existence condition, it can improve 41% relaxation rate.We just can reach the purpose of identification copper ion through the detection to relaxation rate, so can it be used as the magnetic resonance sensors of copper ion.Its minimum detectable level can reach the micromole.People such as Tatjana Atanasijevic and Maxim Shusteff have synthesized a kind of nmr sensor that can the sensing calcium ion.This resonance sensor is a magnetic core with the ferric oxide nano particles of superparamagnetism, the finishing calmodulin.In the presence of calcium ion, the T of surrounding 2Relaxation rate becomes original 5 times, and its LDL can reach nanomole, and is highly sensitive.At present nmr sensor is except the sensing metal ion, can also sensing pH, biomacromolecules such as temperature and DNA.
Nmr sensor mainly is divided into two types: a kind of is that metal ion contrast agent by paramagnetism or superparamagnetism constitutes, as: gadolinium, manganese etc.; Another kind is to be made up of magnetic nanoparticle contrast agent, like the oxide of ferrum.At present; The nmr sensor that is made up of the metal ion contrast agent mainly is positioned at metal circumnuclear boundary water molecule number or the hydration number (directly and the quantity of the hydrone of metallic ion coordination) at coordination compound center through change; The relaxation rate of ambient water molecule or proton is changed, and for example: people such as Xiao-an Zhang and Katherine S.Lovejoy synthesized a kind of zinc ion pick off with magneto-optic double-function in 2007.Because the magnetic property of magnetic nano-particle between single dispersed and polymeric form is very different, the difference of relaxation rate is very big.A kind of pick off often earlier carries out functionalization in the magnetic nano particle sub-surface after the institute; Cause nanoparticle between monomer and polymeric form, to change through targeting or other means then; And then cause that the hydrone on every side or the relaxation rate of proton change, and make us can detect target substance.For example: people such as Mehmet Veysel Yigit and Debapriya Mazumdar have synthesized the contrast agent of a kind of " intelligence ", and it is a nuclear with the ferrum oxide of superparamagnetism, finishing the α of human body-thrombin albumen is fit (aptamer).This pick off can be reunited by the induced nano particle in the presence of α-thrombin is proteic, makes the relaxation rate of surrounding become big, therefore can be used as the proteic pick off of α-thrombin and uses.All right other metal ion of sensing of nmr imaging technique, protein, enzyme, DNA and intermolecular interaction; And strong help can be provided for the detection of early stage disease; As a kind of noinvasive, quick, reliable detection means, application is arranged all in a lot of fields.Simultaneously, the NMR-imaging sensing technology as a kind of cry new, develop detection method faster, aspect a lot of, all also need further grope and study.
Hydrargyrum all exists great threat to plant and human beings'health, and it is a kind of highly toxic global environmental contaminants, and scientists is found Hg 2+Can match the coordination compound T-Hg of formation with thymus pyrimidine (T) in the DNA (DNA) 2+-T structural property is highly stable, and it is to Hg 2+The selectivity recognition function that height is arranged, so this discovery is for Hg 2+The research of detection technique has great help.Adopt the report of magnetic nano-particle detection mercury ion actually rare at present.
Summary of the invention
The present invention aims to provide a kind of ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanoparticle.
The present invention also provides above-mentioned nanometer particle process method.
Another object of the present invention is above-mentioned nanoparticle is used to prepare magnetic resonance contrast agent.
The present invention also is used to prepare the nmr sensor that detects mercury ion with above-mentioned nanoparticle.
This ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanoparticle (Fe 3O 4SiO 2-T), having water solublity, monodispersity is good, and the material pattern is spherical in shape, has superparamagnetism, and mean diameter is at 10～20nm.This nanoparticle can be used for preparing the nmr sensor of magnetic resonance contrast agent and preparation detection mercury ion.
Method for preparing may further comprise the steps:
(1) high temperature pyrolytic cracking (HTP) prepares Fe 3O 4Nanoparticle: acetyl acetone ferrum mixes with oleyl amine and phenylate, is heated to 170～190 ℃ of insulation reaction 20～60min under nitrogen or the inert gas shielding; Be warming up to 290～320 ℃ of insulation reaction 30～120min again,, wash centrifugally, get deposition with alcohol deposition; The mol ratio of acetyl acetone ferrum and oleyl amine is 1: 1～1: 3, with the molal volume ratio of phenylate be 1: 3～10mol/L;
Described non-functionalized silicon source is positive tetraethyl orthosilicate, tetramethoxy-silicane or vinyltrimethoxy silane; The described functionalized silicon source that has amino is 3-aminopropyl silane, γ-An Jibingjisanyiyangjiguiwan or 3-sulfydryl propyl trimethoxy silicane; Described organic solvent is preferably cyclohexane extraction;
(2) wrap up silicon dioxide and be connected amino: Fe 3O 4Nanoparticle and α-(4-nonyl phenyl)-ω-hydroxyl-gather (oxidation-1,2-joins ethane) is dispersed in the organic solvent Fe 3O 4Nanoparticle concentration is 2～4mg/ml, and the concentration of α-(4-nonyl phenyl)-ω-hydroxyl-gather (oxidation-1,2-joins ethane) is 0.05～0.1g/ml;
Adding ammonia adjusting pH value is 7.5～8.0, adds non-functionalized silicon source and has amino functionalized silicon source, and both weight ratios are 5～10, reaction 24～96hr; With alcohol deposition, wash centrifugally, get deposition, obtain Fe 3O 4SiO 2-NH 2Nanoparticle; Organic solvent is preferably N, dinethylformamide;
(3) connect thymus pyrimidine: with thymus pyrimidine, condensing agent and bridging agent are dissolved in anhydrous organic solvent, and lucifuge activation 1～3hr under nitrogen or inert gas shielding adds step (2) gained Fe 3O 4SiO 2-NH 2Nanoparticle; Reaction 10～24hr under nitrogen or inert gas shielding; Washing centrifuging and taking deposition;
Said thymus pyrimidine and condensing agent and bridging agent mol ratio are 1: (2～3): (3～5);
Said thymus pyrimidine and Fe 3O 4SiO 2-NH 2Mol ratio amino in the nanoparticle is 200～500: 1; Bridging agent is preferably N-hydroxy-succinamide; Condensing agent is preferably 1-ethyl-(3-dimethyl aminopropyl) phosphinylidyne diimmonium salt hydrochlorate.
In the preparation process steps (1), be solvent with the phenylate, oleyl amine not only is a solvent but also be surfactant and Reducing agent; Obtain oil-soluble Fe with high temperature pyrolysis acetyl acetone ferrum 3O 4Magnetic nano-particle; With Fe 3O 4Magnetic nano-particle is for nuclear, at Fe 3O 4Magnetic nano-particle finishing oleyl amine enables to be dissolved in the organic solvent; Nitrogen-atoms in the oleyl amine and Fe coordination obtain oil loving alkane chain nanoparticle outwardly, and the nanoparticle (normal hexane etc.) in nonpolar reagent of this moment has good dispersibility, but does not possess bio-compatibility.
Use non-functionalized silicon source (like positive tetraethyl orthosilicate) then and have amino functionalized silicon source (like 3-aminopropyl-triethoxysilane) and wrap silicon and amidized modification, promptly in bag silicon, modify amino.After parcel silicon dioxide and amination, the silicon shell can be protected magnetic core, provides amino simultaneously, makes material have water solublity and good dispersibility, and is that next step modification is provided convenience; Amino can further be reacted with thymus pyrimidine.Saturated magnetization rate before the bag silicon is higher, and the saturated magnetization rate behind the bag silicon is lower.
Next carry to modify and go up thymus pyrimidine, water miscible Fe 3O 4SiO 2-NH 2Nanoparticle must be under anhydrous condition, to carry out in the process of carrying out the finishing thymus pyrimidine, and the coating material thymus pyrimidine needs excessively, so just can guarantee that coating material can not be hydrolyzed and modification thymus pyrimidine that can be as much as possible.Because thymus pyrimidine ability and Hg 2+Carry out specificity and combine, the material that obtains through finishing promptly can be used as Fe 3O 4SiO 2-T nanometer nuclear magnetic resonance, NMR mercury ion sensor material.
Through the identification ability of thymus pyrimidine for mercury ion, carry out the targeting experiment of hydrargyrum, induce ferriferrous oxide nano-particle to carry out self assembly.In this process, the self assembly meeting of ferriferrous oxide nano-particle changes the relaxation rate of ambient water proton, and this change can be detected by NMR, thereby detects the sensing effect of material to hydrargyrum.
The method for preparing response time of the present invention is short, and raw material is easy to get, and economy is easy to operate.This invention provides a kind of new prospect---mercury ion magnetic resonance sensors for the application of nano magnetic resonance imaging contrast agent material, and reference value is provided for the clinical experiment of human body.
Description of drawings
Fig. 1 is the prepared Fe of embodiment 1 3O 4The transmission electron microscope picture of nanoparticle.
Fig. 2 is the prepared Fe of embodiment 2 3O 4SiO 2-NH 2The transmission electron microscope picture of nanoparticle.
Fig. 3 is the prepared Fe of embodiment 4 3O 4SiO 2The transmission electron microscope picture of-T nanoparticle.
Fig. 4 is the prepared Fe of embodiment 1 3O 4The electronogram of nanoparticle.
Fig. 5 is the prepared Fe of embodiment 1,2 and 4 3O 4Nanoparticle (a), Fe 3O 4SiO 2-NH 2Nanoparticle (b) and Fe 3O 4SiO 2X-ray diffraction (XRD) spectrogram of-T nanoparticle (c).
Fig. 6 is the prepared Fe of embodiment 1,2 and 4 3O 4Nanoparticle (a), Fe 3O 4SiO 2-NH 2Nanoparticle (b) and Fe 3O 4SiO 2The infrared spectrum of-T nanoparticle (c).
Fig. 7 is embodiment 1 and 2 prepared Fe 3O 4Nanoparticle (a), Fe 3O 4SiO 2-NH 2Nanoparticle (b) and hysteresis curve figure.
Fig. 8 is the prepared Fe of embodiment 1,2 and 4 3O 4Nanoparticle (a), Fe 3O 4SiO 2-NH 2Nanoparticle (b) and Fe 3O 4SiO 2The thermal multigraph of-T nanoparticle (c).
Fig. 9 is the Fe among the embodiment 5 3O 4SiO 2The transverse and longitudinal relaxation rate (r of-T magnetic nano-particle 2).Fe 3O 4SiO 2The r of-T magnetic nano-particle 2Be 175.5mM -1s -1
Figure 10 is the Fe among the embodiment 6 3O 4SiO 2-T magnetic nano-particle is at μ M, 10 μ M, 20 μ M, 30 μ M, 40 μ M and 50 μ M Hg 2+The Hepes buffer in Δ T 2Value.
Figure 11 is the Fe among embodiment 7 and the embodiment 8 3O 4SiO 2In the Hepes buffer of-T magnetic nano-particle, add other metal ion K respectively +, Na +, Ca 2+, Co 2+, Cu 2+, Ni 2+, Mg 2+, Pb 2+And Zn 2+(50 μ M) and these metal ions and Hg 2+Caused Δ T during the mixed solution of (each 50 μ M) 2Value.
Figure 12 is the Fe among embodiment 7 and the embodiment 8 3O 4SiO 2In the Hepes buffer of-T magnetic nano-particle, add other metal cations Fe respectively 3+, Mn 2+(50 μ M) and these metal ions and Hg 2+Caused Δ T during the mixed solution of (each 50 μ M) 2Value.
The specific embodiment
Embodiment 1 synthetic Fe 3O 4Nanoparticle:
Get acetyl acetone ferrum (1.060g, 3mmol), phenylate (15mL) and oleyl amine (15mL; 6mmol) mix, under nitrogen protection, be heated to 180 ℃ (nitrogen can replace with noble gases such as helium), reaction is 30 minutes under this temperature; Be warming up to 300 ℃ again, reaction is 1 hour under this temperature.The product that obtains is centrifugal with absolute ethanol washing, and vacuum drying obtains Fe 3O 4Magnetic nano-particle.The Electronic Speculum transmission plot is as shown in Figure 1, Fe 3O 4Magnetic nano-particle dispersibility in normal hexane organic solvents such as (or) cyclohexane extraction is better, and average-size approximately is 8.25nm, belong in the size range of superparamagnetism, and the size homogeneous, and have good monodispersity.Electronogram is as shown in Figure 4.
Embodiment 2 synthetic Fe 3O 4SiO 2-NH 2Nanoparticle (wrap silicon and be connected amino):
Get the Fe that embodiment 1 obtains 3O 4Nanoparticle 10mg, cyclohexane extraction 35ml and α-(4-nonyl phenyl)-ω-hydroxyl-gather (oxidation-1,2-joins ethane) (being Igepal CO-520) 2.0g (4.64mol) mixes, and stirs; Add 0.35ml 25wt% ammonia and transfer pH value 7.5～8.0, (content is 98wt%, 33mg), stirs 24～48 hours to add the positive tetraethyl orthosilicate of 0.2mL (186mg) and 0.035ml 3-aminopropyl-triethoxysilane again.
Add the 50mL dehydrated alcohol, the centrifugal Fe that obtains 3O 4SiO 2Nanoparticle; The Electronic Speculum transmission plot is as shown in Figure 2, the particle size homogeneous, and have good monodispersity.
Embodiment 3 measures amino density
Get the Fe that embodiment 2 obtains 3O 4SiO 2-NH 2(60mg 0.2mol) is dissolved in the anhydrous N of 5mL to nanoparticle 26mg and chloro-carbonic acid-9-fluorenyl methyl ester (Fmoc-Cl), and dinethylformamide (DMF) is at N 2Protection is reacted more than 12 hours down.With the centrifugal postlyophilization of absolute methanol.The dry nanoparticle of crossing is about 20mg.Add 1.5mL dry DMF and 0.5mL piperidines, ultrasonic 30min.Centrifugal then 15min gets deposition, obtains with amino nanoparticle (Fe 3O 4SiO 2-NH 2Nanoparticle).Get clear liquid and survey ultraviolet, obtain Fe through calculating 3O 4SiO 2The amino quantity of nanoparticle surface; Through detecting amino density is 1.35*10 -4Mol/g.
Embodiment 4 synthetic Fe 3O 4SiO 2-T nanoparticle (connecing thymus pyrimidine):
Get N-hydroxy-succinamide 0.87mmol (100mg) and 1-ethyl-(3-dimethyl aminopropyl) phosphinylidyne diimmonium salt hydrochlorate 0.58mmol (111mg); Be dissolved in the anhydrous N of 10ml; Dinethylformamide (DMF); Add 50mg thymus pyrimidine (0.27mmol), under nitrogen protection, lucifuge activation 1～3 hour.Add the prepared Fe of 60mg embodiment 2 3O 4SiO 2-NH 2Nanoparticle (contains 8.1*10 -3Mmol is amino), reaction is 12～24 hours under nitrogen protection.Use absolute ethanol washing, centrifugal, get deposition, obtain connecting the Fe of thymus pyrimidine 3O 4SiO 2-T nanoparticle; Figure is as shown in Figure 2 in the Electronic Speculum projection, and particle can be dissolved in the dehydrated alcohol (perhaps water, alcoholic acid aqueous solution), and nanoparticle is circular, and the size homogeneous about about 18nm, less than 20nm, and has good monodispersity greatly.
X-ray diffraction (XRD) spectrogram of embodiment 1,2,4 products obtained therefroms is obtained by the test of DMAX 2000X-x ray diffractometer x respectively shown in curve a, b and the c of Fig. 5, this diffractometer be the Cu/K alpha radiation (λ=0.15405nm) (and 40kV, 40mA).Having the Figure further illustrates embodiment 1 prepared magnetic nano-particle is the Fe of face-centered cubic type (the card sequence number 65-3107 of JCPDS) 3O 4Nanocrystal; 22 to 28 ° is SiO 2Signal peak, the magnetic nano-particle of embodiment 2 prepared parcel silicon dioxide also is the face-centered cubic type; Embodiment 4 further modifies the crystal formation that also can not influence nanoparticle.
The infrared spectrum of embodiment 1,2,4 products obtained therefroms is shown in curve a, b and the c of Fig. 6: among the curve a, and 3427cm -1The place is the water peak, because this peak broad, so all it covers the amino of oleyl amine characteristic peak herein; 2924cm -1And 2848cm -1The place is the C-H stretching vibration peak, and this is to be caused by the long hydrocarbon chain on the oleyl amine; 1625cm -1The place is the C=C stretching vibration; 1565cm -1The place is-NH 2Bending vibration.590cm -1The place is the characteristic peak of Fe-O.Among the curve b, 1639cm -1The place is-NH 2Bending vibration; 1116cm -1And 1050cm -1Go out to be respectively the stretching vibration of Si-O-Si and Si-O-C; 842cm -1Stretching vibration for Si-O-Si and Si-C.Among the curve c, 3435cm -1Be water peak, 3148cm -1It is the C-H stretching vibration of alkene on N-H stretching vibration or the thymus pyrimidine on the amide; 1626cm -1For-NH 2The bending vibration peak; 1381cm -1Bending vibration peak for C-H; All the other are the characteristic peak of C-H, from infared spectrum, can judge Fe basically 3O 4Nanoparticle surface has been wrapped silicon and has been connected thymus pyrimidine.
The magnetic of embodiment 1,2 products obtained therefroms returns and stagnates line chart shown in the curve a of Fig. 8, b: from hysteresis curve figure, can find out that embodiment 1 and 2 obtained nanoparticles are superparamagnetism, Fe 3O 4The saturation magnetization of nanoparticle is 45.2emu/g to the maximum; All can cause its saturation magnetization to weaken after the bag silicon, but can not influence the superparamagnetism of material.
The thermal multigraph of embodiment 1,2,4 products obtained therefroms is shown in curve a, b and the c of Fig. 8: from thermal multigraph, can find out Fe 3O 4, Fe 3O 4SiO 2And Fe 3O 4SiO 2The content of organics of-T nanoparticle surface is about 12%, 34% and 43% respectively.
Embodiment 5
With Fe 3O 4SiO 2-T adds the Hepes buffer solution (Fe content 20mM) of pH=7.4, surveys T 2Value is also passed through the ICP match, obtains r 2=175.46mM -1S -1, as shown in Figure 9.Because r 2Numerical value is bigger, and Fe is described 3O 4SiO 2-T nanoparticle is a kind of magnetic resonance material, has very strong relaxation ability, proves that this material is suitable as T 2Contrast agent, and can obtain good effect.
Embodiment 6
At the Fe that contains 0.02mM Fe 3O 4SiO 2Add Hg respectively in the Hepes buffer solution (pH=7.2) of-T nanoparticle 2+, make Hg 2+Concentration is respectively 0 μ mol/L, 10 μ mol/L, 20 μ mol/L, 30 μ mol/L, 40 μ mol/L and 50 μ mol/L, detects by the caused Δ T of the mercury ion of variable concentrations 2Value changes; Shown in the result as shown in the figure 10.As can be seen from the figure: along with Hg 2+The increase of concentration, Δ T 2It is big that value becomes gradually; Work as Hg 2+When being 50 μ M, Δ T 2Value is about 60ms.Hg 2+LDL be about 20 μ M.
Embodiment 7
Containing Fe 3O 4SiO 2Add other metal ion K respectively in the Hepes buffer solution (pH value is about 7.2) of-T nanoparticle (Fe content 0.02mmol/L) +, Na +, Ca 2+, Co 2+, Cu 2+, Ni 2+, Mg 2+, Pb 2+, Zn 2+, Fe 3+And Mn 2+(concentration 50 μ mol/L) are relatively by the caused Δ T of other metal ion 2Value changes, and detects this magnetic resonance contrast agent sensor material to Hg 2+Selectivity.Result such as Figure 11 and shown in Figure 12.
Embodiment 8
Containing Fe 3O 4SiO 2(Hg in the Hepes buffer solution of-T nanoparticle (Fe content 0.02mmol/L) 2+ Ion concentration 50 μ mol/L, pH value is about 7.2) add 50 other metal ions of μ M respectively, compare Δ T 2Value changes, detect this magnetic resonance contrast agent sensor material under the condition that other metal ion exists to Hg 2+Selectivity and sensitivity.Result such as Figure 11 and shown in Figure 12.
From figure, can know: Fe 3O 4SiO 2-T magnetic nano-particle is to Hg 2+Selectivity and sensitivity are preferably arranged, be not easy to receive the influence and the interference of other metal ion, but Fe 3+And Mn 2+Existence can have a strong impact on Fe 3O 4SiO 2-T nmr sensor is to Hg 2+The sensing effect.

Claims (4)

1. ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanometer particle process method is characterized in that, may further comprise the steps:
(1) high temperature pyrolytic cracking (HTP) prepares Fe 3O 4Nanoparticle: acetyl acetone ferrum mixes with oleyl amine and phenylate, is heated to 170～190 ℃ of insulation reaction 20～60min under nitrogen or the inert gas shielding; Be warming up to 290～320 ℃ of insulation reaction 30～120min again,, wash centrifugally, get deposition with alcohol deposition; The mol ratio of acetyl acetone ferrum and oleyl amine is 1: 1～1: 3, with the molal volume ratio of phenylate be 1: 3～10mol/L;
(2) wrap up silicon dioxide and be connected amino: Fe 3O 4Nanoparticle and α-(4-nonyl phenyl)-ω-hydroxyl-gather (oxidation-1,2-joins ethane) is dispersed in the organic solvent Fe 3O 4Nanoparticle concentration is 2～4mg/ml, and the concentration of α-(4-nonyl phenyl)-ω-hydroxyl-gather (oxidation-1,2-joins ethane) is 0.05～0.1g/ml;
Adding ammonia adjusting pH value is 7.5～8.0, adds non-functionalized silicon source and has amino functionalized silicon source, and both weight ratios are 5～10, reaction 24～96hr; With alcohol deposition, wash centrifugally, get deposition, obtain Fe 3O 4SiO 2-NH 2Nanoparticle;
Described non-functionalized silicon source is positive tetraethyl orthosilicate, tetramethoxy-silicane or vinyltrimethoxy silane; The described functionalized silicon source that has amino is 3-aminopropyl silane, γ-An Jibingjisanyiyangjiguiwan or 3-sulfydryl propyl trimethoxy silicane; Described organic solvent is a cyclohexane extraction;
(3) connect thymus pyrimidine: with thymus pyrimidine, condensing agent and bridging agent are dissolved in anhydrous organic solvent, and lucifuge activation 1～3hr under nitrogen or inert gas shielding adds step (2) gained Fe 3O 4SiO 2-NH 2Nanoparticle; Reaction 10～24hr under nitrogen or inert gas shielding; Washing centrifuging and taking deposition;
Said thymus pyrimidine and condensing agent and bridging agent mol ratio are 1: (2～3): (3～5);
Said thymus pyrimidine and Fe 3O 4SiO 2-NH 2Mol ratio amino in the nanoparticle is 200～500: 1;
Described organic solvent is N, dinethylformamide; Said bridging agent is a N-hydroxy-succinamide; Condensing agent is 1-ethyl-(3-dimethyl aminopropyl) phosphinylidyne diimmonium salt hydrochlorate.
2. ferroso-ferric oxide-silicon dioxide-thymus pyrimidine nanoparticle is characterized in that having water solublity, and mean diameter is at 10～20nm, through the said method preparation of claim 1.
3. the application of the said ferroso-ferric oxide-silicon dioxide of claim 2-thymus pyrimidine nanoparticle aspect the preparation magnetic resonance contrast agent.
4. the application of the said ferroso-ferric oxide-silicon dioxide of claim 2-thymus pyrimidine nanoparticle aspect the nmr sensor of preparation detection mercury ion.
CN2011100266533A 2011-01-25 2011-01-25 Ferroferric oxide-silicon dioxide-thymine nanoparticles and preparation method and application thereof Expired - Fee Related CN102085381B (en)

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郑浩然 等.核壳结构Fe3O4@SiO2复合纳米粒子的制备.《化学研究与应用》.2010,第22卷(第5期),587-591.
郑浩然 等.核壳结构Fe3O4SiO2复合纳米粒子的制备.《化学研究与应用》.2010,第22卷(第5期),587-591. *

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