CN101670107A - Multifunctional nuclear shell structure drug carrier material and preparation method thereof - Google Patents
Multifunctional nuclear shell structure drug carrier material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multifunctional nuclear shell structure drug carrier material and a preparation method thereof; the preparation method comprises the following steps: step one, adopting a solvent-thermal method for preparing monodispersed ferroferric oxide magnetic nanoparticles with grain diameter of about 60nm as ferromagnetic nuclear material of the nuclear shell structure; step two, adopting a sol-gel method for cladding an imporous silicon dioxide layer and a meso-porous layer outside ferromagnetic nucleus in sequence; step three, adopting the sol-gel method for loading a layer ofup-conversion fluorescent material NaYF4: Yb, Er on the material obtained in the step two, wherein the molar concentration of Yb occupies 17% of Y concentration, and the molar concentration of Er occupies 3% of Y concentration. In the invention, an inertia SiO2 layer is designed between the magnetic nucleus and post-functionalized rare earth luminescent material for separating magnetic material from a rare earth luminescent layer so as to prevent fluorescent quenching; up-conversion fluorescent powder with higher fluorescent efficiency is used as fluorescent material; and the sol-gel method with mild reaction condition and uniform dispersion is adopted for forming the nuclear shell structure.
Description
(1) technical field
What the present invention relates to is a kind of nuclear shell structure drug carrier material.The invention still further relates to a kind of preparation method of nuclear shell structure drug carrier material.
(2) background technology
The nucleocapsid structure material can well be brought into play shell material and nuclear material sharpest edges separately.Nuclear material is after coating extra shell, still keep its inherent characteristic, simultaneously surfaces characteristic such as its surface charge density, functional, reactive, biocompatibility, stability and dispersibility are subjected to the adjustment and the optimization of shell material, may therefore produce many new characteristics, so nm-class core-and-shell particles all have great development potentiality and using value at aspects such as catalyst, optics, electromagnetism, biology, medical science and high-performance mechanical materials.In conjunction with the core-shell structure ordered mesoporous material of magnetic, fluorescence because its magnetic, fluorescence, hypotoxicity, excellent biological compatibility and character such as mesoporous obtain broad research in curing, bio-separation and the medicament slow release field of diseases analysis, enzyme.
Up to now, some bibliographical informations magnetisable material for nuclear, silicon dioxide is the multifunctional composite of the core-shell structure of shell.Some fluorescent materials such as organic dyestuff, CdSe/ZnS quantum dot functionalization are subsequently finally made the core-shell structure material that possesses magnetic, fluorescence and order mesoporous multi-functional character in a part surperficial or the formation shell.But organic dyestuff has the shortcoming of fluorescence decay and cancellation as fluorescent material, and quantum dot is owing to use Cd
2+And Pb
2+Etc. heavy metal and seriously limited its application, the especially application of human experimentation at biomedical sector.Recently, along with the research of upconverting fluorescent material wins initial success, the report of magnetic of being applied to and fluorescent material has been arranged.Yet, possess highly active functionalization material requirements at biological field and possess some unique character, have good disperse properties or the like as regular spherical morphology, slick surface, little particle size distribution, big specific surface (be used for drug molecule, enzyme and proteinic support and solidify), big magnetic intensity (in order to enough field signals to be provided) and at solution.Therefore, a kind of like this multifunction material with uniqueness of above-mentioned character of design preparation has a good application prospect at biomedical sector.
La rear earth ion doped inorganic nanocrystal is because the succedaneum that its stable optical property, high chemistry and characteristics such as photochemical stability and hypotoxicity have become organic dyestuff and quantum dot.The upconverting fluorescent material of the nanoscale of mentioning before especially, it was subjected to the attention of research worker as a kind of novel fluorescence label in recent years gradually in the application aspect the biomacromolecule detection, and relevant report is increasing.Compare with quantum dot etc. with conventional fluorescent label such as organic dyestuff, the up-conversion fluorescence nano material have that toxicity is low, chemical stability good, luminous intensity is high and stable and
Advantages such as displacement is big.In addition, the exciting light of up-conversion fluorescence nano material is an infrared light, can avoid the interference and the scattered light phenomenon of biological sample autofluorescence under this shooting condition, thereby reduces detection background, improves signal to noise ratio.Therefore, the up-conversion fluorescence nano material all has extraordinary application prospect as fluorescent marker in biomacromolecule analysis and clinical medicine detection range.Yet the inorganic rare earth luminescent material produces the fluorescent quenching effect and has limited the application of rare earth luminescent material as multi-functional optomagnetic material owing to contacting with magnetic material.
(3) summary of the invention
The object of the present invention is to provide that a kind of purity height, particle diameter are little, the multifunctional nuclear shell structure drug carrier material of good dispersion, good crystalline; The present invention also aims to provide a kind of when reducing the material particle size size and improving dispersion of materials, can improve the preparation method of the multifunctional nuclear shell structure drug carrier material of application powers such as its magnetic, fluorescence detectability and absorption.
The object of the present invention is achieved like this:
The chemical expression of multifunctional nuclear shell structure drug carrier material of the present invention is:
Fe
3O
4@nSiO
2@mSiO
2@NaYF
4:Yb，Er
NSiO wherein
2Represent the atresia silicon dioxide layer; MSiO
2Represent the meso-porous titanium dioxide silicon layer; NaYF
4: Yb, Er are the up-conversion fluorescence bisque of outermost layer load, and wherein the molar concentration of Yb accounts for 17% of Y concentration, and the molar concentration of Er accounts for 3% of Y concentration.
The preparation method of multifunctional nuclear shell structure drug carrier material of the present invention is: the first step adopts a solvent-thermal method preparation grain 60nm, the monodispersed ferroferric oxide magnetic nano-particles ferromagnetism nuclear material as nucleocapsid structure; Second step adopted sol-gel process to coat one deck atresia silicon dioxide layer and one deck meso-porous titanium dioxide silicon layer successively outside ferromagnetism nuclear; The 3rd step adopted sol-gel process to go on foot load one deck upconverting fluorescent material NaYF on the material that obtains second once more
4: Yb, Er, wherein the molar concentration of Yb accounts for 17% of Y concentration, and the molar concentration of Er accounts for 3% of Y concentration.
(1) described employing solvent-thermal method prepares the ferromagnetism nuclear material and is: with 1g FeCl
36H
2200 ℃ of reaction kettle for reaction 12 hours, 80 ℃ of dryings were also ground preparation Fe behind O, 20mL ethylene glycol, 3g anhydrous sodium acetate and the 10mL ethylenediamine uniform mixing
3O
4Nanoparticle.
(2) described employing sol-gel process coats one deck atresia silicon dioxide layer and one deck meso-porous titanium dioxide silicon layer is successively in that ferromagnetism nuclear is outer: adopt modification
Sol-gel process, Fe
3O
4Spheroidal particle is with dehydrated alcohol supersound process 20 minutes, these through the particle of supersound process with deionized water wash after with ultra-sonic dispersion in the mixed solution of forming by ethanol, deionized water and ammonia; Again will with Fe
3O
4Mass ratio be that 3: 10 ethyl orthosilicate (TEOS) slowly is added drop-wise in the top mixed solution and at room temperature stirred the product called after Fe of preparation 6 hours
3O
4@nSiO
2Then, adopt the Fe of sol-gel process with cetyl trimethyl ammonium bromide (CTAB) as organic formwork agent in above-mentioned preparation
3O
4@nSiO
2The surface forms outer meso-porous titanium dioxide silicon layer; Adopt circumfluence method to remove organic formwork again, the microsphere of preparation is called Fe
3O
4@nSiO
2@mSiO
2
(3) described employing sol-gel process goes on foot load one deck upconverting fluorescent material NaYF on the material that obtains second
4: Yb, Er is: adopt the Pechini sol-gel process with NaYF
4: Yb, the Er luminescent powder is deposited on the mesoporous silicon oxide; The molar concentration of Yb accounts for 17% of Y concentration in the luminescent powder, and the molar concentration of Er accounts for 3% of Y concentration; With NaF and Fe
3O
4@nSiO
2@mSiO
2Microsphere by mass ratio be 21: 1 ultra-sonic dispersion in deionized water, obtain finely dispersed mixture; Measure the YCl that concentration is 0.2mol/L respectively by stoichiometric proportion again
3, YbCl
3, ErCl
3Become mixed solution with the EDTA solution allocation; The mixed solution for preparing is added to rapidly in the uniform mixture of ultra-sonic dispersion, and the final mixture that obtains is stirring reaction 4h at room temperature; With high-intensity magnetic field reacted product is separated at last, and also dry with deionized water wash; That obtain is the multifunctional material microsphere Fe of not roasting
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er; The multifunctional material microsphere Fe of roasting not
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er put into the chamber type electric resistance furnace roasting, have just obtained multi-functional nuclear shell structure nano microsphere Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er.
The present invention is directed to the defective that the magnetic described in the background technology, fluorescence and mesoporous nucleocapsid structure material exist, proposed: 1. between the rare earth luminescent material of magnetic core and back functionalization, design one deck inertia SiO
2Layer separates magnetic material and rare earth luminous layer to prevent fluorescent quenching; 2. adopt the higher up-conversion phosphor of fluorescence efficiency as luminescent material; 3. adopt reaction condition gentleness, finely dispersed sol-gel process to form nucleocapsid structure.Although Chinese scholars is done a lot of work to the prescription and the applied research of the nucleocapsid structure material of functionalization,, preparation and correlation theory with medicine slow/controlled release carrier material of ferromagnetism, up-conversion fluorescence and mesoporous property still belong to blank.
The atresia silicon dioxide inert layer that coats earlier outside magnetic core can separate magnetic material and rare earth luminous layer to prevent fluorescent quenching.In addition, the infrared upconverting fluorescent material NaYF of load to visible waveband
4: Yb, Er have given the stronger fluorescence of material, stability, colour-fast and be not subject to performances such as environment (as buffer agent pH value or analysis temperature) influence.
The present invention adopts solvent-thermal method to prepare Fe
3O
4Nanoparticle.This method has two characteristics, and the one, higher reaction temperature (130～250 ℃) helps the raising of magnetic property; The 2nd, in closed container, carry out, the generation relatively high pressure (0.3～4MPa), avoid component volatilization, help improving degree of purity of production.Have also simultaneously that raw material is easy to get, advantage such as particle purity height, particle diameter are little, good dispersion, good crystalline.The present invention adopts two step sol-gel processes that magnetic nano-particle is carried out mesoporous and NaYF
4: Yb, the Er fluorescence coating coats, this method than other method have the reaction condition gentleness, be uniformly dispersed even can reach " molecule is compound " level, can prepare purity height, particle size distribution is even, chemism is big one pack system or multicomponent molecular level mixture at low temperatures, and can prepare the advantages such as product that traditional method can not or be difficult to make.
(4) description of drawings
(a) and (b), (c), (d) are respectively Fe among Fig. 1
3O
4Nanoparticle, Fe
3O
4@nSiO
2@mSiO
2Microsphere, Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er (not roasting) and Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the XRD spectra of Er microsphere.
Fig. 2 (a) and Fig. 2 (b) are Fe
3O
4The SEM figure of nanoparticle; Fig. 2 (c) and Fig. 2 (d) are Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the SEM figure of Er microsphere.
Fig. 3 (a) and Fig. 3 (c) are respectively Fe
3O
4The TEM of nanoparticle and HRTEM figure; Fig. 3 (b) and Fig. 3 (d, e) are respectively Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the TEM of Er microsphere and HRTEM figure.
Fig. 4 (a) is Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the total spectrogram of the XPS of Er microsphere; Fig. 4 (b), Fig. 4 (c), Fig. 4 (d), Fig. 4 (e) and Fig. 4 (f) are the partial enlarged drawings of Fig. 4 (a).
Fig. 5 is respectively Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the emission spectra of Er microsphere.
Fig. 6 (a), Fig. 6 (b) and Fig. 6 (c) are respectively Fe
3O
4Nanoparticle, Fe
3O
4@nSiO
2@mSiO
2Microsphere and Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the hysteresis curve figure of Er microsphere; Fig. 6 (d) is Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the magnetic separation process diagrammatic sketch of Er microsphere.
(5) specific embodiment
For example the present invention is done in more detail below and describes:
Implementation process 1:Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er microsphere synthetic
1. Fe
3O
4The preparation of nanoparticle
Adopt solvent-thermal method, earlier with 1g FeCl
36H
2O, 20mL ethylene glycol, 3g anhydrous sodium acetate and 10mL ethylenediamine mix and strong agitation 30min, form clear solution.Then gained solution is transferred to the politef of sealing and done in the stainless steel cauldron of liner, react 12h down at 200 ℃.Naturally cool to room temperature after the reaction.With product water and absolute ethanol washing several, just obtained Fe at 80 ℃ of dry 12h and grind into powder at last
3O
4Nanoparticle.
2. Fe
3O
4@nSiO
2The preparation of magnetic microsphere
The Fe of core-shell structure
3O
4@nSiO
2Microsphere adopts modification
The sol-gel process preparation.Typical preparation process is as follows: the Fe that 0.10g prepares above
3O
4Nanoparticle dehydrated alcohol supersound process 20min.These through the particle of supersound process with deionized water wash after with ultra-sonic dispersion in the mixed solution of forming by the ammonia of 80mL ethanol, 20mL deionized water and 1mL 28%.Again 0.03g ethyl orthosilicate (TEOS) slowly is added drop-wise to and also at room temperature stirs 6h in the top mixed solution.Reaction back centrifugalize, and, just obtained coating one deck atresia SiO with deionized water and absolute ethanol washing several
2The magnetic core-shell structure nanometer particle, we are expressed as Fe
3O
4@nSiO
2, above-mentioned coating process weighs twice.
3. Fe
3O
4@nSiO
2@mSiO
2The preparation of magnetic and mesoporous nuclear shell structure nano microsphere
The Fe that 2. step is prepared
3O
4@nSiO
2Particle is distributed in the mixed solution that is dissolved with 0.3g cetyl trimethyl ammonium bromide (CTAB), 80mL deionized water, 1.0mL strong aqua ammonia and 60mL dehydrated alcohol.After this mixed solution stirs 30min, under high degree of agitation, add 0.40g tetraethoxysilance (TEOS).System reaction 6h, the product that obtains separates through high-intensity magnetic field, separates with deionized water wash several reuse centrifuge with dehydrated alcohol.Last 80 ℃ of dry 12h grind, and the product that obtains is at Fe
3O
4@nSiO
2The magnetic microsphere surface has coated mesoporous SiO
2Magnetic and mesoporous nuclear shell structure nano microsphere.Above-mentioned coating process repeats twice.Used template CTAB because formation is mesoporous, and the template CTAB in mesoporous does not remove as yet, is with us this product to be expressed as Fe
3O
4@nSiO
2@mSiO
2-CTAB.
Adopt circumfluence method to remove above-mentioned product (Fe
3O
4@nSiO
2@mSiO
2-CTAB) residual template CTAB in the mesopore orbit.Detailed process is as follows: (1) is with 0.6g Fe
3O
4@nSiO
2@mSiO
2-CTAB sample and 120mL acetone join in the there-necked flask, and there-necked flask is placed 75 ℃ of oily territories (dimethicone) backflow 48h; (2) sample after will refluxing separates the back with washing with acetone once with high-intensity magnetic field, adds 120mL acetone backflow 48h again; (3) repeating step (2) once with washing with acetone twice, is put in the cold drying case dryly the sample that obtains, just having obtained removing the magnetic and the mesoporous nuclear shell structure nano microsphere of template through grinding again, is expressed as Fe
3O
4@nSiO
2@mSiO
2
4. Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, the preparation of Er microsphere
The preparation of employing sol-gel process, concrete experimental procedure is as follows: with 2.1g NaF and 0.100gFe
3O
4@nSiO
2@mSiO
2Microsphere ultrasonic (45min) is distributed in the 120mL deionized water, obtains finely dispersed mixture.Measure the YCl that concentration is 0.2mol/L more respectively
3, YbCl
3, ErCl
3Be configured to mixed solution with each 16mL of EDTA, 3.4mL, 0.6mL and 20mL.The mixed solution for preparing is added to rapidly in the mixture of ultrasonic 45min, and the final mixture that obtains is stirring reaction 4h at room temperature.With high-intensity magnetic field reacted product is separated at last, and with deionized water wash once, be put into dry 12h in the cold drying case.What obtain is the multifunctional material microsphere of not roasting, is expressed as Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er (not roasting), above-mentioned coating process repeats twice.
Above-mentioned sample is put into the chamber type electric resistance furnace roasting.Roasting is from room temperature, is warmed up to 400 ℃ with the speed program of 20 ℃/min, and at 400 ℃ of roasting 5h, naturally cools to room temperature again, and the grind into powder sample has just obtained the nuclear shell structure nano microsphere of multi-functional (magnetic, mesoporous and fluorescence), is expressed as follows: Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er.
Claims (6)
1, a kind of multifunctional nuclear shell structure drug carrier material is characterized in that: its chemical expression is:
Fe
3O
4@nSiO
2@mSiO
2@NaYF
4:Yb，Er
NSiO wherein
2Represent the atresia silicon dioxide layer; MSiO
2Represent the meso-porous titanium dioxide silicon layer; NaYF
4: Yb, Er are the up-conversion fluorescence bisque of outermost layer load, and wherein the molar concentration of Yb accounts for 17% of Y concentration, and the molar concentration of Er accounts for 3% of Y concentration.
2, a kind of preparation method of multifunctional nuclear shell structure drug carrier material is characterized in that: the first step adopts a solvent-thermal method preparation grain 60nm, the monodispersed ferroferric oxide magnetic nano-particles ferromagnetism nuclear material as nucleocapsid structure; Second step adopted sol-gel process to coat one deck atresia silicon dioxide layer and one deck meso-porous titanium dioxide silicon layer successively outside ferromagnetism nuclear; The 3rd step adopted sol-gel process to go on foot load one deck upconverting fluorescent material NaYF on the material that obtains second once more
4: Yb, Er, wherein the molar concentration of Yb accounts for 17% of Y concentration, and the molar concentration of Er accounts for 3% of Y concentration.
3, the preparation method of multifunctional nuclear shell structure drug carrier material according to claim 2 is characterized in that: described employing solvent-thermal method prepares the ferromagnetism nuclear material and is: with 1g FeCl
36H
2200 ℃ of reaction kettle for reaction 12 hours, 80 ℃ of dryings were also ground preparation Fe behind O, 20mL ethylene glycol, 3g anhydrous sodium acetate and the 10mL ethylenediamine uniform mixing
3O
4Nanoparticle.
4, according to the preparation method of claim 2 or 3 described multifunctional nuclear shell structure drug carrier materials, it is characterized in that: described employing sol-gel process coats one deck atresia silicon dioxide layer successively outside ferromagnetism nuclear and one deck meso-porous titanium dioxide silicon layer is: adopt and modify
Sol-gel process, Fe
3O
4Spheroidal particle is with dehydrated alcohol supersound process 20 minutes, these through the particle of supersound process with deionized water wash after with ultra-sonic dispersion in the mixed solution of forming by ethanol, deionized water and ammonia; Again will with Fe
3O
4Mass ratio be that 3: 10 ethyl orthosilicate slowly is added drop-wise in the top mixed solution and at room temperature stirred the product called after Fe of preparation 6 hours
3O
4@nSiO
2Then, adopt the Fe of sol-gel process with cetyl trimethyl ammonium bromide as organic formwork agent in above-mentioned preparation
3O
4@nSiO
2The surface forms outer meso-porous titanium dioxide silicon layer; Adopt circumfluence method to remove organic formwork again, the microsphere of preparation is called Fe
3O
4@nSiO
2@mSiO
2
5, according to the preparation method of claim 2 or 3 described multifunctional nuclear shell structure drug carrier materials, it is characterized in that: described employing sol-gel process goes on foot load one deck upconverting fluorescent material NaYF on the material that obtains second
4: Yb, Er is: adopt the Pechini sol-gel process with NaYF
4: Yb, the Er luminescent powder is deposited on the mesoporous silicon oxide; The molar concentration of Yb accounts for 17% of Y concentration in the luminescent powder, and the molar concentration of Er accounts for 3% of Y concentration; With NaF and Fe
3O
4@nSiO
2@mSiO
2Microsphere by mass ratio be 21: 1 ultra-sonic dispersion in deionized water, obtain finely dispersed mixture; Measure the YCl that concentration is 0.2mol/L respectively by stoichiometric proportion again
3, YbCl
3, ErCl
3Become mixed solution with the EDTA solution allocation; The mixed solution for preparing is added to rapidly in the uniform mixture of ultra-sonic dispersion, and the final mixture that obtains is stirring reaction 4h at room temperature; With high-intensity magnetic field reacted product is separated at last, and also dry with deionized water wash; That obtain is the multifunctional material microsphere Fe of not roasting
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er; The multifunctional material microsphere Fe of roasting not
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er put into the chamber type electric resistance furnace roasting, have just obtained multi-functional nuclear shell structure nano microsphere Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er.
6, the preparation method of multifunctional nuclear shell structure drug carrier material according to claim 4 is characterized in that: described employing sol-gel process goes on foot load one deck upconverting fluorescent material NaYF on the material that obtains second
4: Yb, Er is: adopt the Pechini sol-gel process with NaYF
4: Yb, the Er luminescent powder is deposited on the mesoporous silicon oxide; The molar concentration of Yb accounts for 17% of Y concentration in the luminescent powder, and the molar concentration of Er accounts for 3% of Y concentration; With NaF and Fe
3O
4@nSiO
2@mSiO
2Microsphere by mass ratio be 21: 1 ultra-sonic dispersion in deionized water, obtain finely dispersed mixture; Measure the YCl that concentration is 0.2mol/L respectively by stoichiometric proportion again
3, YbCl
3, ErCl
3Become mixed solution with the EDTA solution allocation; The mixed solution for preparing is added to rapidly in the uniform mixture of ultra-sonic dispersion, and the final mixture that obtains is stirring reaction 4h at room temperature; With high-intensity magnetic field reacted product is separated at last, and also dry with deionized water wash; That obtain is the multifunctional material microsphere Fe of not roasting
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er; The multifunctional material microsphere Fe of roasting not
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er put into the chamber type electric resistance furnace roasting, have just obtained multi-functional nuclear shell structure nano microsphere Fe
3O
4@nSiO
2@mSiO
2@NaYF
4: Yb, Er.
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