CN102517020A - Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof - Google Patents
Superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material. The method comprises the following steps: 1) coating superparamagnetic Fe3O4 utilized as cores by utilizing silica, so as to synthesize nanometer magnetic silica spheres; 2) transferring up-conversion nanometer crystals from the organic phase to the water phase; 3) mixing the dispersions obtained in the previous two steps, adding water, ethanol, ammonia water and a silicon source, then using the magnetic silica spheres and the up-conversion nanometer crystals to perform electrostatic self-assembly under an alkaline condition so as to obtain a nanometer spherical material; and 4) removing a template agent to obtain the superparamagnetic fluorescent multifunctional mesoporous nanometer spherical material. The invention also discloses the material prepared by the method. The preparation technology is reasonable, controllable and efficient; the synthesized material is uniform in size and stable in structure; and the material has the advantages of stable up-conversion fluorescence, excellent superparamagnetism, larger specific surface area and the like, and can be used in biomedical fields such as magnetic resonance imaging, up-conversion fluorescence imaging, magnetic separation and targeted medicine carrying.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method and the material of the multi-functional meso-porous nano sphere material of a kind of ultra paramagnetic fluorescence.
Background technology
Fluorescent material, magneticsubstance and mesoporous material are the important application materials that biomedical sector launches deep layer research, and have a wide range of applications and prospect in directions such as immunoassay, pharmaceutical analysis, cellular segregation, living imaging and cancer cells physiotherapys.Along with the development of nanotechnology, the multifunctional nano probe with fluorescence and superparamagnetism ability, meso-hole structure characteristics receives unprecedented concern.Multi-functional meso-porous nano material has many advantages; On the one hand can mark biological tissue carry out the live body real-time monitored, on the other hand if this material can under the traction of external magnetic field, run to specific tumour cell through intravenous injection in vivo the time or cancer cells is regional.The more important thing is, if the load cancer therapy drug can discharge in specified tissue in its meso-hole structure, assisting down of RF magnetic field; The common kill cancer cell of magnetic heating physiotherapy and medicine; And normal cell is influenced less, reaches the purpose of non-diffusion treatment, thereby realizes better anticancer effect.
At present; The preparation method of magnetic nano-particle and the multi-functional meso-porous nano probe of fluorescent nano material bonded is varied; For example doping method, coupling method, entrapping method, microemulsion method, template, but the various complicacy of the general operation of aforesaid method, process are difficult to control, yield rate is low.Most methods all is after synthesising mesoporous structure both at home and abroad, again with magnetic nano-particle or fluorescent material load.In addition, difficult in the reaction process to the dispersed control of nanoparticle, thereby the pattern of multifunctional nano probe, stability etc. are influenced.
Summary of the invention
To above-mentioned deficiency, the object of the invention is, provides a kind of ME simple and easy, is easy to control and effectively guarantee the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence of quality product.
For realizing above-mentioned purpose, technical scheme provided by the present invention is:
The preparation method of the multi-functional meso-porous nano sphere material of a kind of ultra paramagnetic fluorescence, it may further comprise the steps:
(1) with ultra paramagnetic Fe
3O
4Nanometer ball coats it with silicon materials for nuclear, and synthetic mono-dispersed nano magnetic silicon ball with nucleocapsid structure is dispersed in this nano magnetic silicon ball in the ionized water, forms first dispersion liquid;
(2) will go up the conversion nano crystalline substance and be dispersed in the chloroform, form second dispersion liquid;
(3) the hexadecyl brometo de amonio is added in second dispersion liquid, and with first disperse liquid-phase mixing, add ionized water, ethanol, ammoniacal liquor and silicon source then successively, make nano magnetic silicon ball and last conversion nano crystalline substance be self-assembled into the nanometer spherical product;
(4) the nanometer spherical product is removed template hexadecyl brometo de amonio, make the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
Said step (1) specifically may further comprise the steps:
(1.1) preparation 48～52mg particle diameter is the water miscible ultra paramagnetic Fe of 100～200nm
3O
4Nanometer ball;
(1.2) preparation 80mL ethanol and 20mL deionized water mix this ethanol and de-ionized water, make first mixed solution;
(1.3) will surpass paramagnetic Fe
3O
4Nanometer ball is put into first mixed solution, and carries out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, makes second mixed solution;
(1.4) preparation 1mL ammoniacal liquor and 0.02～0.03g tetraethoxy add this ammoniacal liquor and tetraethoxy in second mixed solution, and at room temperature stirred 11～13 hours, make the 3rd mixed solution;
(1.5) the 3rd mixed solution dislocation centrifuge separator is carried out spinning and go out nano magnetic silicon ball, and this nano magnetic silicon ball is washed;
(1.6) preparation 10mL deionized water is dispersed in the nano magnetic silicon ball after the washing in this deionized water, makes first dispersion liquid.
Washing in the said step (1.5) comprise three times the washing and three ethanol wash.
Last conversion nano crystalline substance in the said step (2) is NaYF
4: Yb
3+/ Tm
3+Perhaps NaYF
4: Yb
3+/ Er
3+
Said step (2) specifically may further comprise the steps:
(2.1) the last conversion nano of preparation 1mL chloroform and 5～20mg is brilliant;
(2.2) the said conversion nano crystalline substance of going up is put into chloroform, and carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, make second dispersion liquid.
Silicon source in the said step (3) is a tetraethoxy.
Said step (3) specifically may further comprise the steps:
(3.1) preparation 0.1g hexadecyl brometo de amonio and 10mL deionized water are put into the 10mL deionized water with the hexadecyl brometo de amonio, carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance then; In the ultra-sonic dispersion process; Slowly add second dispersion liquid, make the 4th mixed solution, the 4th mixed solution is placed under 55～65 ℃ the environment; Stirred then 10～20 minutes, until guarantee that chloroform removes fully from mix;
(3.2) preparation 30mL deionized water, 30mL ethanol and 0.6mL ethanol add this deionized water, ethanol, ethanol and first dispersion liquid in the 4th mixed solution, stir 25～35 minutes, make the 5th mixed solution;
(3.3) preparation 0.06～0.20g tetraethoxy; This tetraethoxy added make the 6th mixed solution in the 5th mixed solution; The 6th mixed solution is placed on 28～32 ℃ down reaction 5～7 hours of environment, makes nano magnetic silicon ball and the brilliant fully self-assembly of last conversion nano in the 6th mixed solution to form the nanometer spherical product;
(3.4) the 6th mixed solution dislocation centrifuge separator is carried out spinning and go out the nanometer spherical products, use ethanol and deionized water repetitive scrubbing nanometer spherical product then.
Said step (4) specifically may further comprise the steps:
(4.1) acetone of preparation 50mL;
(4.2) the nanometer spherical product after will washing is put into acetone, forms the 7th mixed solution;
(4.3) the 7th mixed solution is placed under 75～85 ℃ the environment continuously stirring 45～55 hours;
(4.4) repeating step is (4.3) at least three times, until guaranteeing to remove template hexadecyl brometo de amonio fully, takes out the nanometer spherical product then;
(4.5) preparation ethanol washs the nanometer spherical product, and is dry then, makes the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
A kind of multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence that adopts the preceding method preparation.
Beneficial effect of the present invention is: the preparation technology of method provided by the invention is simple and easy, be easy to realize that production efficiency is high.The characteristics of the inventive method are to use " single stage method " self-assembling multifunctional meso-porous nano ball property material, simplify building-up process.Under ultrasonic heating condition, hydrophobic last conversion nano crystalline substance is transferred to aqueous phase from organic phase with tensio-active agent hexadecyl brometo de amonio (CTAB); The last conversion nano crystalline substance-CTAB micella that has the part positive charge that obtains, itself and Zata potential are negative magnetic silicon ball static self-assembly under alkaline condition.The further coordinated groups of unnecessary CTAB and tetraethoxy is dressed up the mesoporous lamella of short range order.
The inventive method specifically is a kind of monodispersed, multi-functional meso-porous nano material preparation method with superparamagnetism and up-conversion fluorescence performance, and its core characteristics are to adopt " single stage method " self-assembling multifunctional meso-porous nano ball property material, simplify building-up process.It is a nuclear with ultra paramagnetic Fe3O4 at first, with silicon-dioxide it is coated, synthetic mono-dispersed nano magnetic silicon ball with nucleocapsid structure; On the other hand, the brilliant ultrasonic heating of hydrophobic last conversion nano is transferred to water from organic phase in the middle of; Then the dispersion liquid with preceding two steps mixes, and adds entry, ethanol, ammoniacal liquor and silicon source, is self-assembled at the brilliant static of alkaline condition magnetic silicon ball and last conversion nano subsequently to be the nanometer spherical material; At last, remove template, promptly obtain the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
Preparing method provided by the invention has that technology is reasonable, easy to operate, easy control of structure, production efficiency is high, yield rate is high advantage; Adopt the multi-functional meso-porous nano sphere material of the ultra paramagnetic fluorescence of the inventive method synthetic size homogeneous, Stability Analysis of Structures; And have advantages such as up-conversion fluorescence is stable, superparamagnetism is excellent, specific surface area is bigger, can be applicable to biomedical sectors such as NMR imaging, up-conversion fluorescence imaging, magnetic resolution and target drug-carrying.
Below in conjunction with accompanying drawing and embodiment, the present invention is described further.
Description of drawings
Fig. 1 is the XRD photo of the embodiment of the invention 2 gained samples;
Fig. 2 is the magnetzation curve figure (VSM) of the embodiment of the invention 2 gained samples;
Fig. 3 is the fluorescence spectrum figure of the embodiment of the invention 2 gained samples under the 980nm LASER Light Source excites;
Fig. 4 is the nitrogen adsorption desorption isotherm and the graph of pore diameter distribution of the embodiment of the invention 2 gained samples.
Fig. 5 is transmission electron microscope (TEM) photo of the embodiment of the invention 3 gained samples;
Fig. 6 is high power transmission electron microscope (HRTEM) photo of the embodiment of the invention 3 gained samples;
Embodiment
Embodiment 1:
The preparation method of the multi-functional meso-porous nano sphere material of a kind of ultra paramagnetic fluorescence that present embodiment provides, it may further comprise the steps:
(1) with ultra paramagnetic Fe
3O
4Nanometer ball coats it with silicon materials for nuclear, and synthetic mono-dispersed nano magnetic silicon ball with nucleocapsid structure is dispersed in this nano magnetic silicon ball in the ionized water, forms first dispersion liquid;
(2) will go up the conversion nano crystalline substance and be dispersed in the chloroform, form second dispersion liquid;
(3) the hexadecyl brometo de amonio is added in second dispersion liquid, and with first disperse liquid-phase mixing, add ionized water, ethanol, ammoniacal liquor and silicon source then successively, make nano magnetic silicon ball and last conversion nano crystalline substance be self-assembled into the nanometer spherical product;
(4) the nanometer spherical product is removed template hexadecyl brometo de amonio, make the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
Said step (1) specifically may further comprise the steps:
(1.1) preparation 48～52mg particle diameter is the water miscible ultra paramagnetic Fe of 100～200nm
3O
4Nanometer ball;
(1.2) preparation 80mL ethanol and 20mL deionized water mix this ethanol and de-ionized water, make first mixed solution;
(1.3) will surpass paramagnetic Fe
3O
4Nanometer ball is put into first mixed solution, and carries out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, makes second mixed solution;
(1.4) preparation 1mL ammoniacal liquor and 0.02～0.03g tetraethoxy add this ammoniacal liquor and tetraethoxy in second mixed solution, and at room temperature stirred 11～13 hours, make the 3rd mixed solution;
(1.5) the 3rd mixed solution dislocation centrifuge separator is carried out spinning and go out nano magnetic silicon ball, and this nano magnetic silicon ball is washed;
(1.6) preparation 10mL deionized water is dispersed in the nano magnetic silicon ball after the washing in this deionized water, makes first dispersion liquid.
Washing in the said step (1.5) comprise three times the washing and three ethanol wash.
Last conversion nano crystalline substance in the said step (2) is NaYF
4: Yb
3+/ Tm
3+Perhaps NaYF
4: Yb
3+/ Er
3+
Said step (2) specifically may further comprise the steps:
(2.1) the last conversion nano of preparation 1mL chloroform and 5～20mg is brilliant;
(2.2) the said conversion nano crystalline substance of going up is put into chloroform, and carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, make second dispersion liquid.
Silicon source in the said step (3) is a tetraethoxy.
Said step (3) specifically may further comprise the steps:
(3.1) preparation 0.1g hexadecyl brometo de amonio and 10mL deionized water are put into the 10mL deionized water with the hexadecyl brometo de amonio, carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance then; In the ultra-sonic dispersion process; Slowly add second dispersion liquid, make the 4th mixed solution, the 4th mixed solution is placed under 55～65 ℃ the environment; Stirred then 10～20 minutes, until guarantee that chloroform removes fully from mix;
(3.2) preparation 30mL deionized water, 30mL ethanol and 0.6mL ethanol add this deionized water, ethanol, ethanol and first dispersion liquid in the 4th mixed solution, stir 25～35 minutes, make the 5th mixed solution;
(3.3) preparation 0.06～0.20g tetraethoxy; This tetraethoxy added make the 6th mixed solution in the 5th mixed solution; The 6th mixed solution is placed on 28～32 ℃ down reaction 5～7 hours of environment, makes nano magnetic silicon ball and the brilliant fully self-assembly of last conversion nano in the 6th mixed solution to form the nanometer spherical product;
(3.4) the 6th mixed solution dislocation centrifuge separator is carried out spinning and go out the nanometer spherical products, use ethanol and deionized water repetitive scrubbing nanometer spherical product then.
Said step (4) specifically may further comprise the steps:
(4.1) acetone of preparation 50mL;
(4.2) the nanometer spherical product after will washing is put into acetone, forms the 7th mixed solution;
(4.3) the 7th mixed solution is placed under 75～85 ℃ the environment continuously stirring 45～55 hours;
(4.4) repeating step is (4.3) at least three times, until guaranteeing to remove template hexadecyl brometo de amonio fully, takes out the nanometer spherical product then;
(4.5) preparation ethanol washs the nanometer spherical product, and is dry then, makes the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
A kind of multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence that adopts the preceding method preparation; Its size homogeneous, Stability Analysis of Structures; And have advantages such as up-conversion fluorescence is stable, superparamagnetism is excellent, specific surface area is bigger, can be applicable to biomedical sectors such as NMR imaging, up-conversion fluorescence imaging, magnetic resolution and target drug-carrying.
Embodiment 2:
The preparation method and the material of the multi-functional meso-porous nano sphere material of a kind of ultra paramagnetic fluorescence that present embodiment provides, itself and embodiment 1 are basic identical, and its difference is that its following concrete steps are different:
(1) preparation 50mg particle diameter is the water miscible ultra paramagnetic Fe of 100～200nm
3O
4Nanometer ball; Preparation 80mL ethanol and 20mL deionized water mix this ethanol and de-ionized water, make first mixed solution; To surpass paramagnetic Fe
3O
4Nanometer ball is put into first mixed solution, and carries out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, makes second mixed solution; Preparation 1mL ammoniacal liquor (28wt%) and 0.03g tetraethoxy add this ammoniacal liquor and tetraethoxy in second mixed solution, and at room temperature stirred 12 hours, make the 3rd mixed solution; The 3rd mixed solution dislocation centrifuge separator is carried out spinning goes out nano magnetic silicon ball, and to this nano magnetic silicon ball wash, ethanol wash each three times; Preparation 10mL deionized water is dispersed in the nano magnetic silicon ball after the washing in this deionized water, makes first dispersion liquid.Subsequent use.
(2) the hydrophobic last conversion nano crystalline substance of preparation 1mL chloroform and 5mg; The said conversion nano crystalline substance of going up is put into chloroform, and carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, make second dispersion liquid.
(3) preparation 0.1g hexadecyl brometo de amonio and 10mL deionized water are put into the 10mL deionized water with the hexadecyl brometo de amonio, carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance then; In the ultra-sonic dispersion process; Slowly add second dispersion liquid, make the 4th mixed solution, the 4th mixed solution is placed under 60 ℃ the environment; Stirred then 15 minutes, until guarantee that chloroform removes fully from mix; Preparation 30mL deionized water, 30mL ethanol and 0.6mL ethanol add this deionized water, ethanol, ethanol and first dispersion liquid in the 4th mixed solution, stir 30 minutes, make the 5th mixed solution; Preparation 0.06g tetraethoxy; This tetraethoxy added make the 6th mixed solution in the 5th mixed solution; The 6th mixed solution is placed on 30 ℃ down reaction 6 hours of environment, makes nano magnetic silicon ball and the brilliant fully self-assembly of last conversion nano in the 6th mixed solution to form the nanometer spherical product; The 6th mixed solution dislocation centrifuge separator is carried out spinning go out the nanometer spherical products, use ethanol and deionized water repetitive scrubbing nanometer spherical product then.
(4) acetone of preparation 50mL; The nanometer spherical product is put into acetone before will washing the back, forms the 7th mixed solution; The 7th mixed solution is placed under 80 ℃ the environment continuously stirring 48 hours; Repeat this whipping step three times,, take out the nanometer spherical product then until guaranteeing to remove template hexadecyl brometo de amonio fully; Preparation ethanol washs the nanometer spherical product, and is dry then, makes with Fe
3O
4Be embedded in the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence of mesoporous silicon oxide shell for conversion nano crystalline substance kernel, last.
Embodiment 3:
The preparation method and the material of the multi-functional meso-porous nano sphere material of a kind of ultra paramagnetic fluorescence that present embodiment provides, itself and embodiment 1 or 2 are basic identical, and its difference is that its following concrete steps are different:
(1) preparation 50mg particle diameter is the water miscible ultra paramagnetic Fe of 100～200nm
3O
4Nanometer ball; Preparation 80mL ethanol and 20mL deionized water mix this ethanol and de-ionized water, make first mixed solution; To surpass paramagnetic Fe
3O
4Nanometer ball is put into first mixed solution, and carries out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, makes second mixed solution; Preparation 1mL ammoniacal liquor (28wt%) and 0.2g tetraethoxy add this ammoniacal liquor and tetraethoxy in second mixed solution, and at room temperature stirred 12 hours, make the 3rd mixed solution; The 3rd mixed solution dislocation centrifuge separator is carried out spinning goes out nano magnetic silicon ball, and to this nano magnetic silicon ball wash, ethanol wash each three times; Preparation 10mL deionized water is dispersed in the nano magnetic silicon ball after the washing in this deionized water, makes first dispersion liquid.Subsequent use.
(2) the hydrophobic last conversion nano crystalline substance of preparation 1mL chloroform and 10mg; The said conversion nano crystalline substance of going up is put into chloroform, and carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, make second dispersion liquid.
(3) preparation 0.1g hexadecyl brometo de amonio and 10mL deionized water are put into the 10mL deionized water with the hexadecyl brometo de amonio, carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance then; In the ultra-sonic dispersion process; Slowly add second dispersion liquid, make the 4th mixed solution, the 4th mixed solution is placed under 60 ℃ the environment; Stirred then 15 minutes, until guarantee that chloroform removes fully from mix; Preparation 30mL deionized water, 30mL ethanol and 0.6mL ethanol add this deionized water, ethanol, ethanol and first dispersion liquid in the 4th mixed solution, stir 30 minutes, make the 5th mixed solution; The positive silicon of preparation 0.1g is joined ester; This tetraethoxy added make the 6th mixed solution in the 5th mixed solution; The 6th mixed solution is placed on 30 ℃ down reaction 6 hours of environment, makes nano magnetic silicon ball and the brilliant fully self-assembly of last conversion nano in the 6th mixed solution to form the nanometer spherical product; The 6th mixed solution dislocation centrifuge separator is carried out spinning go out the nanometer spherical products, use ethanol and deionized water repetitive scrubbing nanometer spherical product then.
(4) acetone of preparation 50mL; Nanometer spherical product after the washing is put into acetone, form the 7th mixed solution; The 7th mixed solution is placed under 80 ℃ the environment continuously stirring 48 hours; Repeat this whipping step three times,, take out the nanometer spherical product then until guaranteeing to remove template hexadecyl brometo de amonio fully; Preparation ethanol washs the nanometer spherical product, and is dry then, makes with Fe
3O
4Be embedded in the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence of mesoporous silicon oxide shell for conversion nano crystalline substance kernel, last.
Can find out through Fig. 1 to Fig. 6 (wherein the circular mark of Fig. 6 is that last conversion nano is brilliant):
Fig. 1 is the little angle XRD figure spectrum of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention, and its shell has order mesoporous structure.
Fig. 2 is the saturation magnetization curve spectrum of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention, and its saturation magnetization can reach～36emu/g.
Fig. 3 is the up-conversion fluorescence spectrum of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention, and it produces the near infrared light of wavelength 800nm under the laser excitation of wavelength 980nm.
Fig. 4 is the nitrogen adsorption desorption isotherm and the pore size distribution of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention, and visible its specific surface area and pore volume reach 135m respectively
2/ g and 0.18cm
3/ g, mean pore size is 5.4nm.
Fig. 5 is transmission electron microscope (TEM) picture of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention.
Fig. 6 can observe the conversion nano crystalline substance and successfully be modified at around the Fe3O4SiO2 for high power transmission electron microscope (HRTEM) picture of the multi-functional meso-porous nano sphere material that makes in the specific embodiment of the present invention.By above-mentioned visible; Come the multi-functional meso-porous nano sphere material of the ultra paramagnetic fluorescence of synthetic according to method provided by the present invention; Its size homogeneous, Stability Analysis of Structures; And have advantages such as up-conversion fluorescence is stable, superparamagnetism is excellent, specific surface area is bigger, can be applicable to biomedical sectors such as NMR imaging, up-conversion fluorescence imaging, magnetic resolution and target drug-carrying.
It is reasonable that the inventive method has technology, easy to operate, easy control of structure, and yield rate is high, and the advantage that production efficiency is high specifically is a kind of monodispersed, multi-functional meso-porous nano material preparation method with superparamagnetism and up-conversion fluorescence performance.Its core characteristics are to adopt " single stage method " self-assembling multifunctional meso-porous nano ball property material, simplify building-up process.Under ultrasonic heating condition, hydrophobic last conversion nano crystalline substance is transferred to aqueous phase from organic phase with tensio-active agent hexadecyl brometo de amonio (CTAB); The last conversion nano crystalline substance-CTAB micella that has the part positive charge that obtains, itself and Zata potential are negative magnetic silicon ball static self-assembly under alkaline condition.The further coordinated groups of unnecessary CTAB and tetraethoxy is dressed up the mesoporous lamella of short range order.Idiographic flow is to be nuclear with ultra paramagnetic Fe3O4, with silicon-dioxide it is coated, synthetic mono-dispersed nano magnetic silicon ball with nucleocapsid structure; On the other hand, the brilliant ultrasonic heating of hydrophobic last conversion nano is transferred to water from organic phase in the middle of; Then the dispersion liquid with preceding two steps mixes, and adds entry, ethanol, ammoniacal liquor and silicon source, is self-assembled at the brilliant static of alkaline condition magnetic silicon ball and last conversion nano subsequently to be the nanometer spherical material; At last, remove template, promptly obtain the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
Of the above embodiment of the present invention, adopt resulting other the preparation method and the meso-porous nano sphere material of meso-porous nano sphere material of method same or analogous, all in protection domain of the present invention with it.
Claims (9)
1. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence is characterized in that it may further comprise the steps:
(1) with ultra paramagnetic Fe
3O
4Nanometer ball coats it with silicon materials for nuclear, and synthetic mono-dispersed nano magnetic silicon ball with nucleocapsid structure is dispersed in this nano magnetic silicon ball in the ionized water, forms first dispersion liquid;
(2) will go up the conversion nano crystalline substance and be dispersed in the chloroform, form second dispersion liquid;
(3) the hexadecyl brometo de amonio is added in second dispersion liquid, and with first disperse liquid-phase mixing, add ionized water, ethanol, ammoniacal liquor and silicon source then successively, make nano magnetic silicon ball and last conversion nano crystalline substance be self-assembled into the nanometer spherical product;
(4) the nanometer spherical product is removed template hexadecyl brometo de amonio, make the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
2. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 1 is characterized in that said step (1) specifically may further comprise the steps:
(1.1) preparation 48～52mg particle diameter is the water miscible ultra paramagnetic Fe of 100～200nm
3O
4Nanometer ball;
(1.2) preparation 80mL ethanol and 20mL deionized water mix this ethanol and de-ionized water, make first mixed solution;
(1.3) will surpass paramagnetic Fe
3O
4Nanometer ball is put into first mixed solution, and carries out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, makes second mixed solution;
(1.4) preparation 1mL ammoniacal liquor and 0.02～0.03g tetraethoxy add this ammoniacal liquor and tetraethoxy in second mixed solution, and at room temperature stirred 11～13 hours, make the 3rd mixed solution;
(1.5) the 3rd mixed solution dislocation centrifuge separator is carried out spinning and go out nano magnetic silicon ball, and this nano magnetic silicon ball is washed;
(1.6) preparation 10mL deionized water is dispersed in the nano magnetic silicon ball after the washing in this deionized water, makes first dispersion liquid.
3. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 1 is characterized in that, the washing in the said step (1.5) comprise three times the washing and three ethanol wash.
4. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 3 is characterized in that, the last conversion nano crystalline substance in the said step (2) is NaYF
4: Yb
3+/ Tm
3+Perhaps NaYF
4: Yb
3+/ Er
3+
5. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 4 is characterized in that said step (2) specifically may further comprise the steps:
(2.1) the last conversion nano of preparation 1mL chloroform and 5～20mg is brilliant;
(2.2) the said conversion nano crystalline substance of going up is put into chloroform, and carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance, make second dispersion liquid.
6. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 4 is characterized in that the silicon source in the said step (3) is a tetraethoxy.
7. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 6 is characterized in that said step (3) specifically may further comprise the steps:
(3.1) preparation 0.1g hexadecyl brometo de amonio and 10mL deionized water are put into the 10mL deionized water with the hexadecyl brometo de amonio, carry out ultra-sonic dispersion on the dislocation ultra-sonic dispersion appearance then; In the ultra-sonic dispersion process; Slowly add second dispersion liquid, make the 4th mixed solution, the 4th mixed solution is placed under 55～65 ℃ the environment; Stirred then 10～20 minutes, until guarantee that chloroform removes fully from mix;
(3.2) preparation 30mL deionized water, 30mL ethanol and 0.6mL ethanol add this deionized water, ethanol, ethanol and first dispersion liquid in the 4th mixed solution, stir 25～35 minutes, make the 5th mixed solution;
(3.3) preparation 0.06～0.20g tetraethoxy; This tetraethoxy added make the 6th mixed solution in the 5th mixed solution; The 6th mixed solution is placed on 28～32 ℃ down reaction 5～7 hours of environment, makes nano magnetic silicon ball and the brilliant fully self-assembly of last conversion nano in the 6th mixed solution to form the nanometer spherical product;
(3.4) the 6th mixed solution dislocation centrifuge separator is carried out spinning and go out the nanometer spherical products, use ethanol and deionized water repetitive scrubbing nanometer spherical product then.
8. the preparation method of the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to claim 7 is characterized in that said step (4) specifically may further comprise the steps:
(4.1) acetone of preparation 50mL;
(4.2) the nanometer spherical product after will washing is put into acetone, forms the 7th mixed solution;
(4.3) the 7th mixed solution is placed under 75～85 ℃ the environment continuously stirring 45～55 hours;
(4.4) repeating step is (4.3) at least three times, until guaranteeing to remove template hexadecyl brometo de amonio fully, takes out the nanometer spherical product then;
(4.5) preparation ethanol washs the nanometer spherical product, and is dry then, makes the multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence.
9. multi-functional meso-porous nano sphere material of ultra paramagnetic fluorescence according to one of the said said method preparation of claim 1-7.
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| CN102936500A (en) * | 2012-12-10 | 2013-02-20 | 哈尔滨工程大学 | Core-shell-structure photomagnetic double-function nano composite material and preparation method thereof |
| CN103074066A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of multifunctional mesoporous directly-cladded fluorescence nano-bioprobe |
| CN103285791A (en) * | 2013-05-10 | 2013-09-11 | 深圳大学 | Magnetic mesoporous silica core-shell structure affinity microsphere based on metal ion modification as well as preparation method and application thereof |
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| DAN HU ET AL: "A facile method to synthesize superparamagnetic and up-conversion luminescent NaYF4:Yb, Er/Tm@SiO2@Fe3O4 nanocomposite particles and their bioapplication", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
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| CN102936500A (en) * | 2012-12-10 | 2013-02-20 | 哈尔滨工程大学 | Core-shell-structure photomagnetic double-function nano composite material and preparation method thereof |
| CN103074066A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of multifunctional mesoporous directly-cladded fluorescence nano-bioprobe |
| CN103074066B (en) * | 2013-01-10 | 2014-07-09 | 上海大学 | Preparation method of multifunctional mesoporous directly-cladded fluorescence nano-bioprobe |
| CN103285791A (en) * | 2013-05-10 | 2013-09-11 | 深圳大学 | Magnetic mesoporous silica core-shell structure affinity microsphere based on metal ion modification as well as preparation method and application thereof |
| CN103285791B (en) * | 2013-05-10 | 2016-03-16 | 深圳大学 | A kind of based on metal ion-modified magnetic mesoporous silicon dixoide nucleocapsid structure compatible micro balloons and its preparation method and application |
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| CN106221693B (en) * | 2016-07-26 | 2019-02-22 | 郑州轻工业学院 | A kind of preparation method of reusable nitrite anions sensing nano material |
| CN113035480A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院江西稀土研究院 | Magnetic refrigeration material and preparation method and application thereof |
| CN113035480B (en) * | 2021-02-26 | 2022-02-11 | 中国科学院江西稀土研究院 | Magnetic refrigeration material and preparation method and application thereof |
| CN115584259A (en) * | 2022-09-30 | 2023-01-10 | 中国科学技术大学 | Magnetic up-conversion latent fingerprint developer, preparation method thereof and latent fingerprint analysis method |
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