CN102936500A - Core-shell-structure photomagnetic double-function nano composite material and preparation method thereof - Google Patents
Core-shell-structure photomagnetic double-function nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a core-shell-structure photomagnetic double-function nano composite material and a preparation method thereof. The preparation method comprises the following steps: preparing an NaGdF4:Yb,Tm upconversion fluorescent nanocrystal nuclear material by high-temperature pyrolysis; coating an active upconversion fluorescent layer made of the same material on the surface of the NaGdF4:Yb,Tm upconversion fluorescent nanocrystal nuclear material by high-temperature pyrolysis; and coating an Fe3O4 magnetic shell on the surface of the core-shell structure by high-temperature pyrolysis to obtain the NaGdF4:Yb,Tm@NaGdF4:Yb,Tm@Fe3O4 core-shell-structure photomagnetic double-function nano composite material. The composite material provided by the invention has strong upconversion luminescence property and magnetic properties; and the middle active fluorescent layer enhances the fluorescence intensity, inhibits the quenching effect between the nuclear material and the strong-magnetism shell material, and improves the fluorescence of the finally prepared photomagnetic double-function composite material of which the particle size is only 20nm or so.
Description
Technical field
What the present invention relates to is a kind of nucleocapsid structure multifunctional nanocomposites, the present invention also relates to a kind of preparation method of nucleocapsid structure multifunctional nanocomposites.
Background technology
In more than ten years in the past, multifunctional nanocomposites with unique magnetic and photoluminescent property has received very big concern, because this material is extensive in the biomedical sector application prospect, such as slow releasing carrier of medication, diagnositc analysis, magnetic response imaging, bioseparation and fluorescence labels.Wherein, traditional fluorescent material is mainly semiconductor nano and organic dye molecule.Yet, develop in recent ten years rapidly Study of Nanoscale Rare Earth Luminescent Materials because of excellent properties such as its larger Stokes shift, narrow emmission spectrum, long fluorescence lifetime, high chemistry/photochemical stability, hypotoxicity and low photobleachings, become in biologic applications and have more promising luminescent material.
The main synthetic method of nano material has solid phase method, the hot method of hydrothermal/solvent, sol-gel method, coprecipitation method and high temperature pyrolytic cracking (HTP).Wherein, high temperature pyrolytic cracking (HTP) is shown one's talent in recent years and has been obtained widely research, because the product of the method preparation is that to have a high-crystallinity, narrow particle size distribution, size nanocrystalline at the high quality of a few nanometer to tens nanometers.In the research to high temperature pyrolytic cracking (HTP), main organometallic precursor comprises trifluoroacetate, oleate, acetylacetonate and acetate at present.Most study is trifluoroacetate at present, explains the fluoride gas that is placed with poison yet trifluoroacetate drives body heat, limits greatly its development and application; The product of acetylacetonate or the preparation of acetate presoma is dispersed and homogeneity is relatively poor.And the oleate presoma has been avoided above-mentioned shortcoming, is a kind of very promising By Means of Pyrolyzed Precursor.
In addition, high temperature pyrolytic cracking (HTP) develops into today, no longer only limited to prepare the pure material of single structure, and beginning develops to the high-performance with nucleocapsid/satellite structure/multifunctional nanocomposites, the nanocrystalline composite material that especially has magnetic and fluorescence property has caused investigator's interest.Yet, at present high temperature pyrolytic cracking (HTP) prepare such material report seldom, major cause be the luminous intensity of the standby optomagnetic functional materials of this legal system or/and magnetic is very weak, be difficult in vivo detect.Up to now, unique one routine fluorescence property and magnetic all stronger nano composite material be the composite material of core-shell structure (up-conversion phosphor coats the oxide compound of iron) of professor Li Fuyou of Fudan University preparation.Yet the suitability of the method, material and structure is very poor, be only applicable in the example that Prof Lee provides, and definite they uses is the hot method of high-temperature solvent.In our common high temperature pyrolytic cracking (HTP), the optomagnetic performance of said structure is then very low; In addition, this material only provides the T2 pattern of magnetic response imaging contrast agent.
To sum up, the scheme or the route that be of universal significance, applicable different high temperature pyrolytic cracking (HTP)s prepare the optomagnetic function nano matrix material of high-performance were not also reported.
Summary of the invention
The object of the present invention is to provide a kind of optomagnetic difunctional nano composite material of nucleocapsid structure that has simultaneously strong up-conversion fluorescence performance and magnetic property.The present invention also aims to provide the preparation method of the optomagnetic difunctional nano composite material of nucleocapsid structure of a kind of magnetic that can improve matrix material and fluorescence property.
The object of the present invention is achieved like this:
Formation and the chemical expression of the optomagnetic difunctional nano composite material of nucleocapsid structure of the present invention are: NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Wherein, "@" expression coats.
The preparation method of the optomagnetic difunctional nano composite material of nucleocapsid structure of the present invention is:
1. adopt high temperature pyrolytic cracking (HTP) to prepare NaGdF
4: Yb, Tm up-conversion fluorescence nano-crystal nuclear matter;
2. adopt high temperature pyrolytic cracking (HTP) at NaGdF
4: Yb, the surface of Tm up-conversion fluorescence nano-crystal nuclear matter coats one deck with activity of materials up-conversion fluorescence layer;
The nucleocapsid structure surface of 3. continuing to adopt high temperature pyrolytic cracking (HTP) to obtain in the upper step coats one deck Fe
3O
4Magnetic crust.
Described employing high temperature pyrolytic cracking (HTP) prepares NaGdF
4: Yb, the method for Tm up-conversion fluorescence nano-crystal nuclear matter is: taking by weighing total amount is that 0.8～1.2mmol stoichiometric ratio is the rare earth oleate Gd (C of 80:17:3
18H
33O
2)
3, Yb (C
18H
33O
2)
3And Tm (C
18H
33O
2)
3Place container, add 0.16～0.25g NaF, 12～18mL oleic acid and 12～18mL octadecylene, be warming up to 100 ° of C and logical N
2Gas 30min is at N
2To be warming up to 280 ° of C under the gas protection, and be incubated 1～5h, after reaction finishes; naturally cooling treats that temperature is reduced to 70 ° of C, adds ethanol and makes the product precipitation; use ethanol and hexanaphthene washed twice, product is stored in the 5mL hexanaphthene, namely obtains the NaGdF of Yb and Tm codoped again
4The nanocrystal material is expressed as NaGdF
4: Yb, Tm.
Described employing high temperature pyrolytic cracking (HTP) is at NaGdF
4: Yb, the surface of Tm up-conversion fluorescence nano-crystal nuclear matter coats one deck and with the method for activity of materials up-conversion fluorescence layer is: be the rare earth oleate Gd (C of 80:17:3 with 0.16～0.25g NaF and 0.8～1.2mmol stoichiometric ratio
18H
33O
2)
3, Yb (C
18H
33O
2)
3, Tm (C
18H
33O
2)
3Add in 12～18mL oleic acid and the 12～18mL octadecylene, be warming up to 100 ° of C, slowly drip the NaGdF that is stored in the hexanaphthene
4: Yb, Tm nanocrystal material, 100 ° of C insulation 30min remove hexanaphthene, at the logical N of 100 ° of C
2Behind the gas 30min, be warming up to 320 ° of C, and insulation 20min～1h, after reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation, used ethanol and hexanaphthene washed twice again, the product that obtains is stored in the 5mL hexanaphthene and is NaGdF
4: Yb, Tm coats NaGdF
4: Yb, the core-shell structured nanomaterials of Tm is expressed as NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm.
Coat one deck Fe
3O
4The method of magnetic crust is: with 3～5mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 25～35mL octadecylene, be warming up to 100 ° of C, slowly drip the NaGdF that is stored in the hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, the Tm core-shell structured nanomaterials, 100 ° of C insulation 30min remove hexanaphthene, logical N
2Be warming up to 320 ° of C behind the gas 30min, and insulation 20min-1h, after reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation, used ethanol and hexanaphthene washed twice again, namely obtained nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Optomagnetic difunctional nano composite material.
The present invention at first adopt high temperature pyrolytic cracking (HTP) prepare particle diameter evenly, the NaGdF of favorable dispersity
4: Yb, Tm up-conversion fluorescence nano-crystal nuclear matter; Adopt again high temperature pyrolytic cracking (HTP) to coat one deck with activity of materials up-conversion fluorescence layer on the surface of nuclear matter, to improve fluorescence property; The nucleocapsid structure surface of continuing at last to adopt high temperature pyrolytic cracking (HTP) to obtain in the upper step coats one deck Fe
3O
4Magnetic crust.The matrix material of this scheme preparation has strong up-conversion luminescence performance and magnetic property simultaneously, because the design of middle active fluoro layer improves fluorescence intensity on the one hand, suppress on the other hand the quenching effect between nuclear matter and ferromagnetism shell material, strengthen the fluorescence property of the optomagnetic difunctional matrix material that finally obtains, and particle diameter only has about 20nm.
The present invention adopts high temperature pyrolytic cracking (HTP) to prepare NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.This method has two characteristics, and the one, middle activity has improved the fluorescence property of matrix material greatly with the design of material up-conversion fluorescence layer, and does not affect the magnetic property of material; The 2nd, product good crystallinity, the purity of high temperature pyrolytic cracking (HTP) preparation is high, size distribution evenly and only has about 20nm; The 3rd, can not produce toxic products, environmental protection in the oleate By Means of Pyrolyzed Precursor itself that adopts and the reaction process.This method is that design route has all characteristics such as even environmental protection of product purity height, size distribution than other method, the most important thing is, activity is extensive with the design applicability of material up-conversion fluorescence layer in the middle of this route, can overcome the low shortcoming of fluorescence/magnetic intensity of the optomagnetic difunctional matrix material for preparing in the traditional method.
Description of drawings
Fig. 1 is NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4(@represents to coat) synthetic route chart.
Fig. 2 (a)-Fig. 2 (b) is the product pattern of embodiment (), and wherein Fig. 2 (a) is NaGdF
4: Yb, Tm@Fe
3O
4The TEM photo of sample; Fig. 2 (b) is NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4The TEM photo of sample.
Fig. 3 is the product magnetic result of embodiment (), is NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4The magnetic hysteresis loop figure of sample.
Fig. 4 is the product fluorescence result of embodiment (), is NaGdF
4: Yb, Tm@Fe
3O
4(dotted line) and NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4(solid line) upper inversion spectrum figure.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention and effect are further described.But employed concrete grammar, prescription and explanation are not limitation of the present invention.
Embodiment (one):
(1) the warm solution of first mining height prepares up-conversion fluorescence NaGdF
4: Yb, Tm nanocrystal material.At first, taking by weighing total amount is that the 1mmol stoichiometric ratio is the rare earth oleate Gd (C of 80:17:3
18H
33O
2)
3, Yb (C
18H
33O
2)
3And Tm (C
18H
33O
2)
3, place there-necked flask.Add again 0.21g NaF, 15mL oleic acid and 15mL octadecylene.Be warming up to 100 ° of C and logical N
2Gas 30min.At N
2The gas protection is lower to be warming up to 280 ° of C with system, and insulation 2.5h.After reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation.Use again ethanol and hexanaphthene washed twice.Product is stored in the 5mL hexanaphthene, namely obtains the NaGdF of Yb and Tm codoped
4(be expressed as NaGdF
4: Yb, Tm) the nanocrystal material.
(2) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm nano material.Concrete experimental procedure is as follows: be the rare earth oleate Gd (C of 80:17:3 with 0.21g NaF and 1mmol stoichiometric ratio
18H
33O
2)
3, Yb (C
18H
33O
2)
3, Tm (C
18H
33O
2)
3Add in 15mL oleic acid and the 15mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm nanocrystal material, 100 ° of C insulation 30min remove hexanaphthene.At the logical N of 100 ° of C
2Behind the gas 30min, system is warming up to 320 ° of C, and insulation and insulation 30min.Precipitation is identical with the upper step with washing step, and the product that obtains is stored in the 5mL hexanaphthene and is NaGdF
4: Yb, Tm coats NaGdF
4: Yb, Tm (is expressed as NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm) core-shell structured nanomaterials.
(3) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.Concrete experimental procedure is as follows: with 4.56mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 28.9mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, Tm nanocrystal material.0.5h remove hexanaphthene.Logical N
2Gas 30min also is warming up to 320 ° of C, and insulation 0.5h.Washing step namely obtains nucleocapsid structure NaGdF with upper identical
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.
(4) nucleocapsid structure NaGdF
4: Yb, Tm@Fe
3O
4Change composite manufacture on (with comparing) magnetic
Concrete steps are as follows: with 4.56mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 28.9mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm nanocrystal material.100 ° of C insulation 30min remove hexanaphthene.Logical N
2Be warming up to 320 ° of C behind the gas 30min, and insulation 30min.Washing step namely obtains nucleocapsid structure NaGdF with upper identical
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.
Embodiment (two):
(1) the warm solution of first mining height prepares up-conversion fluorescence NaGdF
4: Yb, Tm nanocrystal material.At first, taking by weighing total amount is that the 0.8mmol stoichiometric ratio is the rare earth oleate Gd (C of 80:17:3
18H
33O
2)
3, Yb (C
18H
33O
2)
3And Tm (C
18H
33O
2)
3, place there-necked flask.Add again 0.16g NaF, 12mL oleic acid and 12mL octadecylene.Be warming up to 100 ° of C and logical N
2Gas 30min.At N
2The gas protection is lower to be warming up to 280 ° of C with system, and insulation 1h.After reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation.Use again ethanol and hexanaphthene washed twice.Product is stored in the 5mL hexanaphthene, namely obtains NaGdF
4: Yb, Tm nanocrystal material.
(2) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm nano material.Concrete experimental procedure is as follows: be the rare earth oleate Gd (C of 80:17:3 with 0.16g NaF and 0.8mmol stoichiometric ratio
18H
33O
2)
3, Yb (C
18H
33O
2)
3, Tm (C
18H
33O
2)
3Add in 12mL oleic acid and the 12mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm nanocrystal material, 100 ° of C insulation 30min remove hexanaphthene.At the logical N of 100 ° of C
2Behind the gas 30min, system is warming up to 320 ° of C, and insulation and insulation 20min.Precipitation is identical with the upper step with washing step, and the product that obtains is stored in the 5mL hexanaphthene and is NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm core-shell structured nanomaterials.
(3) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.Concrete experimental procedure is as follows: with 3mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 25mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, Tm nanocrystal material.0.5h remove hexanaphthene.Logical N
2Gas 30min also is warming up to 320 ° of C, and insulation 20min.Washing step namely obtains nucleocapsid structure NaGdF with upper identical
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.
Embodiment (three):
(1) the warm solution of first mining height prepares up-conversion fluorescence NaGdF
4: Yb, Tm nanocrystal material.At first, taking by weighing total amount is that the 1.2mmol stoichiometric ratio is the rare earth oleate Gd (C of 80:17:3
18H
33O
2)
3, Yb (C
18H
33O
2)
3And Tm (C
18H
33O
2)
3, place there-necked flask.Add again 0.25g NaF, 18mL oleic acid and 18mL octadecylene.Be warming up to 100 ° of C and logical N
2Gas 30min.At N
2The gas protection is lower to be warming up to 280 ° of C with system, and insulation 5h.After reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation.Use again ethanol and hexanaphthene washed twice.Product is stored in the 5mL hexanaphthene, namely obtains NaGdF
4: Yb, Tm nanocrystal material.
(2) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm nano material.Concrete experimental procedure is as follows: be the rare earth oleate Gd (C of 80:17:3 with 0.25g NaF and 1.2mmol stoichiometric ratio
18H
33O
2)
3, Yb (C
18H
33O
2)
3, Tm (C
18H
33O
2)
3Add in 18mL oleic acid and the 18mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm nanocrystal material, 100 ° of C insulation 30min remove hexanaphthene.At the logical N of 100 ° of C
2Behind the gas 30min, system is warming up to 320 ° of C, and insulation and insulation 5h.Precipitation is identical with the upper step with washing step, and the product that obtains is stored in the 5mL hexanaphthene and is NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm core-shell structured nanomaterials.
(3) the warm solution of mining height prepares nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.Concrete experimental procedure is as follows: with 5mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 35mL octadecylene, be warming up to 100 ° of C.What slowly dripped that the upper step obtains is stored in NaGdF in the 5mL hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, Tm nanocrystal material.0.5h remove hexanaphthene.Logical N
2Gas 30min also is warming up to 320 ° of C, and insulation 1h.Washing step namely obtains nucleocapsid structure NaGdF with upper identical
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Change matrix material on the magnetic.
Claims (6)
1. the optomagnetic difunctional nano composite material of nucleocapsid structure is characterized in that formation and chemical expression are: NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Wherein, "@" expression coats.
2. the preparation method of the optomagnetic difunctional nano composite material of nucleocapsid structure claimed in claim 1 is characterized in that:
1. adopt high temperature pyrolytic cracking (HTP) to prepare NaGdF
4: Yb, Tm up-conversion fluorescence nano-crystal nuclear matter;
2. adopt high temperature pyrolytic cracking (HTP) at NaGdF
4: Yb, the surface of Tm up-conversion fluorescence nano-crystal nuclear matter coats one deck with activity of materials up-conversion fluorescence layer;
The nucleocapsid structure surface of 3. continuing to adopt high temperature pyrolytic cracking (HTP) to obtain in the upper step coats one deck Fe
3O
4Magnetic crust.
3. the preparation method of the optomagnetic difunctional nano composite material of nucleocapsid structure according to claim 2 is characterized in that described employing high temperature pyrolytic cracking (HTP) prepares NaGdF
4: Yb, the method for Tm up-conversion fluorescence nano-crystal nuclear matter is: taking by weighing total amount is that 0.8～1.2mmol stoichiometric ratio is the rare earth oleate Gd (C of 80:17:3
18H
33O
2)
3, Yb (C
18H
33O
2)
3And Tm (C
18H
33O
2)
3Place container, add 0.16～0.25g NaF, 12～18mL oleic acid and 12～18mL octadecylene, be warming up to 100 ° of C and logical N
2Gas 30min is at N
2To be warming up to 280 ° of C under the gas protection, and be incubated 1～5h, after reaction finishes; naturally cooling treats that temperature is reduced to 70 ° of C, adds ethanol and makes the product precipitation; use ethanol and hexanaphthene washed twice, product is stored in the 5mL hexanaphthene, namely obtains the NaGdF of Yb and Tm codoped again
4The nanocrystal material is expressed as NaGdF
4: Yb, Tm.
4. according to claim 2 or the preparation method of the optomagnetic difunctional nano composite material of 3 described nucleocapsid structures, it is characterized in that described employing high temperature pyrolytic cracking (HTP) is at NaGdF
4: Yb, the surface of Tm up-conversion fluorescence nano-crystal nuclear matter coats one deck and with the method for activity of materials up-conversion fluorescence layer is: be the rare earth oleate Gd (C of 80:17:3 with 0.16～0.25g NaF and 0.8～1.2mmol stoichiometric ratio
18H
33O
2)
3, Yb (C
18H
33O
2)
3, Tm (C
18H
33O
2)
3Add in 12～18mL oleic acid and the 12～18mL octadecylene, be warming up to 100 ° of C, slowly drip the NaGdF that is stored in the hexanaphthene
4: Yb, Tm nanocrystal material, 100 ° of C insulation 30min remove hexanaphthene, at the logical N of 100 ° of C
2Behind the gas 30min, be warming up to 320 ° of C, and insulation 20min～1h, after reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation, used ethanol and hexanaphthene washed twice again, the product that obtains is stored in the 5mL hexanaphthene and is NaGdF
4: Yb, Tm coats NaGdF
4: Yb, the core-shell structured nanomaterials of Tm is expressed as NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm.
5. according to claim 2 or the preparation method of the optomagnetic difunctional nano composite material of 3 described nucleocapsid structures, it is characterized in that coating one deck Fe
3O
4The method of magnetic crust is: with 3～5mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 25～35mL octadecylene, be warming up to 100 ° of C, slowly drip the NaGdF that is stored in the hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, the Tm core-shell structured nanomaterials, 100 ° of C insulation 30min remove hexanaphthene, logical N
2Be warming up to 320 ° of C behind the gas 30min, and insulation 20min-1h, after reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation, used ethanol and hexanaphthene washed twice again, namely obtained nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Optomagnetic difunctional nano composite material.
6. the preparation method of the optomagnetic difunctional nano composite material of nucleocapsid structure according to claim 4 is characterized in that coating one deck Fe
3O
4The method of magnetic crust is: with 3～5mmol Fe (C
18H
33O
2)
3Add in 0.72mL oleic acid and the 25～35mL octadecylene, be warming up to 100 ° of C, slowly drip the NaGdF that is stored in the hexanaphthene
4: Yb, Tm@NaGdF
4: Yb, the Tm core-shell structured nanomaterials, 100 ° of C insulation 30min remove hexanaphthene, logical N
2Be warming up to 320 ° of C behind the gas 30min, and insulation 20min-1h, after reaction finished, naturally cooling treated that temperature is reduced to 70 ° of C, added ethanol and made the product precipitation, used ethanol and hexanaphthene washed twice again, namely obtained nucleocapsid structure NaGdF
4: Yb, Tm@NaGdF
4: Yb, Tm@Fe
3O
4Optomagnetic difunctional nano composite material.
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| CN103771541A (en) * | 2014-01-13 | 2014-05-07 | 哈尔滨工程大学 | Preparation method for preparing magnetic nano-composite material by using high-temperature pyrolysis method |
| CN104342155A (en) * | 2014-10-13 | 2015-02-11 | 江南大学 | Preparation method of pyramid assembly structure simultaneously having fluorescent, magnetic and chiral signals |
| CN104498038A (en) * | 2014-12-25 | 2015-04-08 | 哈尔滨工程大学 | Rare-earth up-conversion luminescent core-shell nano-luminescence material and preparation method thereof |
| CN105001867A (en) * | 2015-07-29 | 2015-10-28 | 武汉理工大学 | Multi-color tunable luminous KYF4 up-converting luminescence material and preparation method thereof |
| CN105214099A (en) * | 2015-10-21 | 2016-01-06 | 哈尔滨工程大学 | A kind of nano composite material and preparation method being applied to optical dynamic therapy |
| CN105295892A (en) * | 2015-11-24 | 2016-02-03 | 西南民族大学 | Preparation method of core-shell structured magnetic up-conversion luminescence bifunctional nano-particles |
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| CN106318392A (en) * | 2015-06-26 | 2017-01-11 | 东北林业大学 | Rare earth nano-material with both up/down conversion fluorescence and photothermal properties |
| CN106479484A (en) * | 2016-09-26 | 2017-03-08 | 上海科润光电技术有限公司 | A kind of composite preparation process of the immune magnetic Nano up-conversion luminescent material with nucleocapsid structure |
| CN107523289A (en) * | 2017-09-05 | 2017-12-29 | 哈尔滨工程大学 | A kind of dye sensitization rare earth up-conversion and preparation method thereof |
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| CN105214099A (en) * | 2015-10-21 | 2016-01-06 | 哈尔滨工程大学 | A kind of nano composite material and preparation method being applied to optical dynamic therapy |
| CN105214099B (en) * | 2015-10-21 | 2017-11-28 | 哈尔滨工程大学 | A kind of nano composite material and preparation method applied to optical dynamic therapy |
| CN105295892A (en) * | 2015-11-24 | 2016-02-03 | 西南民族大学 | Preparation method of core-shell structured magnetic up-conversion luminescence bifunctional nano-particles |
| CN105623663A (en) * | 2016-01-04 | 2016-06-01 | 哈尔滨工程大学 | Red up-conversion luminous nano-carrier and preparation method |
| CN106479484A (en) * | 2016-09-26 | 2017-03-08 | 上海科润光电技术有限公司 | A kind of composite preparation process of the immune magnetic Nano up-conversion luminescent material with nucleocapsid structure |
| CN107523289A (en) * | 2017-09-05 | 2017-12-29 | 哈尔滨工程大学 | A kind of dye sensitization rare earth up-conversion and preparation method thereof |
| CN110964510A (en) * | 2019-11-14 | 2020-04-07 | 上海大学 | Magnetic/up-conversion luminescence water-soluble nano material, preparation method and application thereof |
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