CN104083777B - Upper conversion composite nano materials and preparation method thereof, application - Google Patents
Upper conversion composite nano materials and preparation method thereof, application Download PDFInfo
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Abstract
The invention discloses composite nano materials and preparation method thereof, application are changed in one kind, the nano material is nucleocapsid structure, including synthesis Nd3+The nano-particle with heating effect of the 800nm laser excitations of doping, then in the nanoshells of external sheath up-conversion luminescence, it is middle that sealing coat can be added according to the difference of cladding material, and can be in the additional shell of luminescent layer to strengthen luminous intensity.The method for synthesizing this nano-particle is simple, it is easy to operate, and controllability is strong, and synthesizes the granule of different-grain diameter by controlling the consumption of raw material.The nano-particle of the method synthesis, the photo-thermal effect of material independence and up-conversion luminescence effect are integrated in one, and be can be applicable to and are prepared diagnosing tumour preparation, preparation temperature detection reagent, prepare tumor, bio-imaging.
Description
Technical field
The present invention relates to nano material preparation, nano biological photonic propulsion research field, more particularly to upper conversion composite Nano
Material and preparation method thereof, application.
Background technology
In recent years, up-conversion luminescence nanomaterial becomes the focus of research with its special performance and extensive purposes,
Solid State Laser, solaode, optical dynamic therapy, three dimensional display, especially as biomarker probe in terms of fluorescence imaging
There is very big potential using value.Compare with semiconductor-quantum-point with traditional organic dyestuff, up-conversion luminescence nanomaterial tool
There is special luminosity, two or more lower energy photons can be absorbed and a high-energy photon is radiated, typically by near-infrared
Light is converted into visible ray, and near infrared light have the advantages that depth penetration into tissue, organism is damaged it is little, without autofluorescence,
Simultaneously upper conversion nano granule avirulence itself, without photobleaching, be easily converted into biocompatibility.These advantages are all determined
Conversion nano material has good biologic applications value.
Traditional up-conversion nano material is with Yb mostly3+For sensitized ions, so laser of the exciting light for 980nm, and
Water has very strong absorption near 980nm.As organism all contains substantial amounts of moisture, so nano material is in biologic applications
The drawbacks of having certain.Find rare earth ion Nd within nearly 2 years3+Used as sensitizer, absorbing wavelength is 800nm, suction of the water to this wavelength
Receive very weak, and also have very big penetration depth in organism, therefore there can be good biologic applications.And due to Nd3+Than
Yb3+There is bigger absorption cross-section, therefore with Nd3+There is higher luminous efficiency as the nano-particle of sensitizer, can answer well
Use in bio-imaging.
At present, heating therapy history for a long time, and be just to rise in recent years with reference to the photo-thermal therapy method of nano material,
It is confined to the application of metal nano material, such as nanometer gold and nanometer silver.But metal nano material luminous effect while heating
Rate is low, is not suitable for while being lighted and being generated heat.Nearest report discovery, rare earth Nd3+The upper conversion nano granule of doping has
Good photo-thermal effect, under the laser excitation of near infrared light 800nm, the aqueous temperature of nano-particle can reach 50 DEG C with
On, and water hardly picks up the light of 800nm.General, when cellular environment temperature is increased to 45 DEG C, protein can degeneration and thin
Born of the same parents can be gradually weak, so as to irreversible infringement is caused to cell, cancerous cell is killed.And heat effect can also make cell simultaneously
Radiation to external world is more sensitive, therefore heat effect is also more efficient to radiation therapy.
According to statement above, how by Nd3+The luminous and heating effect of the upper conversion nano granule of doping combines,
There is great scientific meaning and social value to the early diagnosiss of the major diseases such as following cancer and tumor.
The content of the invention
Present invention is primarily targeted at overcoming the shortcoming and deficiency of prior art, there is provided composite Nano material is changed in one kind
Material, the material simultaneously have luminous and heating effect, can not only labelling cancerous cell can also carry out radiation therapy.
Further object is that providing the preparation method of above-mentioned upper conversion composite nano materials, the method is realized
Simply, it is easy to operate, controllability is strong, and the consumption that can pass through control raw material synthesizes the granule of different-grain diameter.
Further object is that provide it is above-mentioned it is upper conversion composite nano materials prepare diagnosing tumour preparation,
Preparation temperature detects reagent, is preparing tumor, the purposes in bio-imaging.
The purpose of the present invention is realized by following technical scheme：Composite nano materials are changed in one kind, body is nucleocapsid
Structure, kernel heating layer are doping Nd3+The nano-particle with heating effect, luminescent layer be up-conversion luminescence nanometer layer, it is interior
Nuclear heating layer is different with the excitation wavelength of luminescent layer.The excitation wavelength of kernel heating layer and luminescent layer is mixing by luminescent layer
Heteroion is determining.
Specifically, the kernel heating layer is NaYF4:Nd3+, excitation wavelength is 800nm, a diameter of 10-20nm；Described
Photosphere is NaYF4:Yb3+,Er3+/Tm3+, excitation wavelength is 980nm, and thickness is 5-15nm.
A kind of method for preparing above-mentioned upper conversion composite nano materials, including step：
(1) it is prepared into doping Nd3+The nano-particle with heating effect, preparation method is as follows：
(1-1) prepare a certain amount of rare earth chloride：A certain amount of yittrium oxide and Dineodymium trioxide are weighed respectively, add excess
Concentrated hydrochloric acid, dissolves in a heated condition, after being completely dissolved is evaporated solution, obtains rare earth chloride；
(1-2) prepare Oleic acid rare-earth salts presoma：Addition Oleic acid and 1- octadecylenes, heated under vacuum to 110 DEG C-
130 DEG C, kept for 30-50 minutes, obtain presoma, be cooled to 75 DEG C and react for next step；
(1-3) bath oiling prepares nano-particle：A certain amount of enuatrol and ammonium fluoride are added, is added under argon protective condition
Heat to 300 DEG C -320 DEG C, reaction keep 20 minutes 1 hour, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule, from
Repeat with washes of absolute alcohol several times, to obtain nano-particle, be dissolved in organic solvent, react for next step after the heart；
(2) luminescent layer is coated on the nano-particle of step (1-3) by chemical reaction, luminescent layer preparation method is such as
Under：
(2-1) prepare a certain amount of rare earth chloride：A certain amount of yittrium oxide, ytterbium oxide are weighed respectively, and it is a certain amount of
Erbia or Dithulium trioxide, add excessive concentrated hydrochloric acid, dissolve in a heated condition, solution is evaporated after being completely dissolved, obtain
To rare earth chloride；
(2-2) prepare Oleic acid rare-earth salts presoma：Oleic acid and 1- octadecylenes, heated under vacuum to 110 DEG C is added to protect
Hold 40 minutes, obtain presoma；It is cooled to 75 DEG C to react for next step；
(2-3) nano-particle of step (1-3) is added, the organic solvent of storage is evaporated；
(2-4) bath oiling prepares nano-particle：A certain amount of enuatrol and ammonium fluoride are added, is added under argon protective condition
Heat to 280 DEG C, reaction keep 40-50 minutes, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat after centrifugation
With washes of absolute alcohol several times, conversion composite nanometer particle is obtained, organic solvent is dissolved in.
Composite nano materials are changed in one kind, body is nucleocapsid structure, and kernel heating layer is doping Nd3+With heating effect
The nano-particle answered, intermediate layer are NaYF4Sealing coat, be coated on kernel heating layer；Luminescent layer is up-conversion luminescence nanometer
Layer, is the NaYF of doping with rare-earth ions4Nanometer layer, coats on the intermediate layer, the excitation wavelength of kernel heating layer and luminescent layer
It is identical.
Specifically, the kernel heating layer is NaYF4:Nd3+, excitation wavelength is 800nm, a diameter of 10-20nm；In described
Interbed is NaYF4Sealing coat, thickness is 5-10nm；Upper conversion nano layer NaYF of the luminescent layer for 800nm laser excitations4:
Nd3+, Yb3+,Er3+, thickness is 5-15nm.
A kind of method for preparing above-mentioned upper conversion composite nano materials, including step：
(1) kernel heating layer is prepared, step is as follows：
(1-1) a certain amount of yittrium oxide, Dineodymium trioxide are weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain dilute
Native chloride；
(1-2) a certain amount of Oleic acid, oleyl amine, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes,
Obtain presoma；It is cooled to 75 DEG C to react for next step；
(1-3) a certain amount of enuatrol and ammonium fluoride are added, 310 DEG C is heated under argon protective condition, reaction keeps
40-50 minutes, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol after centrifugation several times,
Nano-particle is obtained, organic solvent is dissolved in；
(2) it is NaYF to prepare intermediate layer4Sealing coat, step is as follows：
(2-1) a certain amount of yittrium oxide is weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain rare-earth chlorination
Thing；
(2-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtained
Presoma；It is cooled to 75 DEG C to react for next step；
(2-3) nano-particle in addition step (1-3), evaporates the organic solvent of storage；After add a certain amount of oil
Sour sodium and ammonium fluoride, are heated to 280 DEG C under argon protective condition, reaction keep 40-50 minutes, after be cooled to 75 DEG C, add
Dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol several times, to obtain composite nanometer particle, be dissolved in organic molten after centrifugation
Agent.
(3) luminescent layer is prepared, step is as follows：
(3-1) a certain amount of yittrium oxide, Dineodymium trioxide, ytterbium oxide, Erbia are weighed, excessive concentrated hydrochloric acid dissolving is added, after
Rotary evaporation obtains rare earth chloride；
(3-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtained
Presoma；It is cooled to 75 DEG C to react for next step；
(3-3) composite nanometer particle for adding step (2-3) to obtain, evaporates the organic solvent of storage.Add afterwards certain
The enuatrol and ammonium fluoride of amount, is heated to 280 DEG C under argon protective condition, reaction keep 40-50 minutes, after be cooled to 75
DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol several times, to obtain changing composite Nano after centrifugation
Grain, is dissolved in organic solvent.
Composite nano materials are changed in one kind, to be changed on above-mentioned and one is also coated on the outside of luminescent layer in composite nanometer particle
Doping Nd3+The nanometer layer for strengthening luminescent effect, this layer for luminescent layer shell.
Specifically, the kernel heating layer is NaYF4:Nd3+, a diameter of 10-20nm；The intermediate layer is NaYF4Every
Absciss layer, thickness are 5-10nm；Upper conversion nano layer NaYF of the luminescent layer for 800nm laser excitations4:Nd3+, Yb3+,Er3+,
Thickness is 5-15nm；The shell of the luminescent layer is NaYF4:Nd3+, thickness is 3-10nm.
A kind of method for preparing above-mentioned upper conversion composite nano materials, is combined in the preparation only upper conversion with intermediate layer and receives
On the basis of rice material, also including step：
(4) shell of luminescent layer is prepared, step is as follows：
(4-1) a certain amount of yittrium oxide, Dineodymium trioxide are weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain dilute
Native chloride；
(4-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtained
Presoma；It is cooled to 75 DEG C to react for next step；
(4-3) the upper conversion composite nanometer particle for adding step (3-3) to obtain, evaporates the organic solvent of storage；Afterwards plus
Enter a certain amount of enuatrol and ammonium fluoride, 280 DEG C are heated under argon protective condition, reaction is kept for 40-50 minutes, is cooled down afterwards
To 75 DEG C, dehydrated alcohol precipitated nanocrystals granule is added；Repeat with washes of absolute alcohol several times, to obtain final upper conversion after centrifugation
Composite nanometer particle, is dissolved in organic solvent.
The present invention compared with prior art, has the advantage that and beneficial effect：
1st, the present invention synthetic rare earth doped nano-particle of mature bath oiling, is lighted and heating effect is combined
Get up, the upper conversion composite nanometer particle that synthesis is obtained is not only heatable in the case of laser irradiation but also can light, and luminous effect
Rate is high, and fluorescence intensity is high, stable luminescence, and heating is rapid and can reach of a relatively high temperature, after surface modification, has very well
Biologic applications.
2nd, the method for synthesizing conversion composite nanometer particle on this of the invention is simple, it is easy to operate, controllability is strong, and by controlling
The consumption of raw material processed synthesizes the granule of different-grain diameter.
3rd, the upper conversion composite nanometer particle of present invention synthesis, by the photo-thermal effect of material independence and up-conversion luminescence effect
It is integrated in one, can be used for the medicament of the diseases such as treating cancer and tumor, have broad application prospects.
Description of the drawings
Structural representations of the Fig. 1 for the upper conversion composite nanometer particle in embodiment 1.
Fig. 2 be the upper conversion composite nanometer particle for preparing of embodiment 1 in aqueous, irradiated with the laser of 800nm
When, temperature versus time curve figure.
Structural representations of the Fig. 3 for the upper conversion composite nanometer particle in embodiment 2.
Fig. 4 is the transmission electron microscope picture of upper conversion composite nanometer particle prepared by embodiment 2.
Structural representations of the Fig. 5 for the upper conversion composite nanometer particle in embodiment 3.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
As shown in figure 1, the upper of the present embodiment synthesis changes composite nanometer particle into uniform mono-dispersed nano
Grain, size is 20-30nm.The kernel heating layer of nano-particle is NaYF4:90%Nd3+, excitation wavelength is 800nm.Outer layer lights
NaYF of the layer for 980nm laser excitations4:20%Yb3+, 2%Er3+.Its specific preparation method is as follows：
(1) 22.58mg yittrium oxide and 302.8mg Dineodymium trioxide are added in the round-bottomed flask of 100mL, add the concentrated hydrochloric acid of 2mL
Rotation after reaction is evaporated.
(2) Oleic acid 9mL, and 1- octadecylene 9mL are added.Agitating solution is placed in heating under vacuum and is kept for 40 points to 110 DEG C
Clock.
(3) and then cooling down to 75 DEG C, solid enuatrol 760mg and anhydrous ammonium fluoride 148mg is added.Then by solution
320 DEG C are heated to, are reacted 80 minutes.
(4) after being quickly cooled to 75 DEG C, add 9mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
Heart 4min.Nano-particle is once obtained with washes of absolute alcohol again, is dissolved in 4mL chloroforms.
(5) the yittrium oxide of 352.1mg, the ytterbium oxide of 157.6mg are added in the round-bottomed flask of 100mL, and adds 15.3mg
Erbia or 15.4mg Dithulium trioxide, add 5mL concentrated hydrochloric acid, be completely dissolved oxide, after reaction rotation be evaporated.
(6) add 12mL Oleic acid, and 12mL1- octadecylene agitating solutions heating under vacuum to be placed in 110 DEG C, kept for 40 points
Clock.
(7) 75 DEG C are cooled to afterwards, the nano-particle solution being stored in chloroform in being subsequently adding step (4), reduce pressure out dechlorination
It is imitative.Add 3040mg solids enuatrol and the anhydrous ammonium fluorides of 592mg.Then solution is heated to into 280 DEG C, is reacted 45 minutes.
(8) after being quickly cooled to 75 DEG C, add 20mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
The heart 4 minutes.Nano-particle is obtained once with washes of absolute alcohol again, dissolving is in organic solvent.
Good photo-thermal effect is had according to upper conversion nano granule prepared by said method, as shown in Fig. 2 near infrared light
Under the laser excitation of 800nm, at 3 minutes or so i.e. more than 50 DEG C, and corresponding, water is several for the upper conversion nano granule of the present embodiment
The light of 800nm is not absorbed, temperature increase is not obvious.Due to above-mentioned characteristic, thus can be used on prepare diagnosing tumour preparation,
Used in preparation temperature detection reagent, in preparation tumor.
Embodiment 2
The present embodiment in addition to following characteristics other structures with embodiment 1：As shown in figure 3, the upper conversion of the present embodiment synthesis
Composite nanometer particle is 4 Rotating fields, and ground floor kernel heating layer is NaYF4:90%Nd3+, the second layer is for preventing energy sudden
The sealing coat for going out, specially NaYF4, third layer luminescent layer is NaYF4:30%Nd3+, 0.5%Er3+, 1%Nd3+, and the 4th layer is sent out
The shell of photosphere is NaYF4:1%Nd3+, for strengthening luminous intensity.Its specific preparation method is as follows：
(1) 22.58mg yittrium oxide and 302.8mg Dineodymium trioxide are added in the round-bottomed flask of 100mL, add the concentrated hydrochloric acid of 2mL
Rotation after reaction is evaporated.
(2) Oleic acid 6.06mL, oleyl amine 4.82mL and 1- octadecylene 9mL are added.Agitating solution is placed in heating under vacuum extremely
110 DEG C are kept for 40 minutes.
(3) and then cooling down to 75 DEG C, solid enuatrol 760mg and anhydrous ammonium fluoride 148mg is added.Then by solution
310 DEG C are heated to, are reacted 50 minutes.
(4) after being quickly cooled to 75 DEG C, add 9mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
Heart 4min.Nano-particle is once obtained with washes of absolute alcohol again, is dissolved in 4mL chloroforms.
(5) 237.11mg yittrium oxide is added in the round-bottomed flask of 100mL, rotation after adding the concentrated hydrochloric acid reaction of 4mL is steamed
It is dry.
(6) Oleic acid 9mL, and 1- octadecylene 9mL are added.Agitating solution is placed in heating under vacuum and is kept for 40 points to 110 DEG C
Clock.
(7) 75 DEG C are cooled to afterwards, the nano-particle solution that (4) are stored in chloroform is subsequently adding, and reduce pressure away chloroform.Plus
Enter 874mg solids enuatrol and the anhydrous ammonium fluorides of 170.2mg.Then solution is heated to into 280 DEG C, is reacted 45 minutes.
(8) after being quickly cooled to 75 DEG C, add 20mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
The heart 4 minutes.Nano-particle is obtained once with washes of absolute alcohol again, dissolving is in organic solvent.
(9) the yittrium oxide of 773.4mg, the ytterbium oxide of 591mg, the Dineodymium trioxide of 16.8mg are added in the round-bottomed flask of 100mL
With the Erbia of 9.6mg, the concentrated hydrochloric acid of 5mL is added, oxide is completely dissolved, rotation after reaction is evaporated.
(10) Oleic acid 18mL, and 1- octadecylene 18mL are added.Agitating solution is placed in heating under vacuum and is kept for 40 points to 110 DEG C
Clock.
(11) 75 DEG C are cooled to afterwards, the nano-particle solution that (8) are stored in chloroform is subsequently adding, and reduce pressure away chloroform.Plus
Enter 3800mg solids enuatrol and the anhydrous ammonium fluorides of 740mg.Then solution is heated to into 280 DEG C, is reacted 45 minutes.
(12) after being quickly cooled to 75 DEG C, add 20mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
The heart 4 minutes.Nano-particle is obtained once with washes of absolute alcohol again, dissolving is in organic solvent.
(13) the yittrium oxide of 1806.6mg, and the Dineodymium trioxide of 672.8mg are added in the round-bottomed flask of 100mL, adds 8mL's
Concentrated hydrochloric acid, is completely dissolved oxide, and rotation after reaction is evaporated.
(14) Oleic acid 18mL, and 1- octadecylene 18mL are added.Agitating solution is placed in heating under vacuum and is kept for 40 points to 110 DEG C
Clock.
(15) 75 DEG C are cooled to afterwards, the nano-particle solution that (12) are stored in chloroform is subsequently adding, and reduce pressure away chloroform.Plus
Enter 7600mg solids enuatrol and the anhydrous ammonium fluorides of 1480mg.Then solution is heated to into 280 DEG C, is reacted 45 minutes.
(16) after being quickly cooled to 75 DEG C, add 20mL dehydrated alcohol precipitated nanocrystals granule, under the rotating speed of 7200rmp from
The heart 4 minutes.Nano-particle is obtained once with washes of absolute alcohol again, dissolving is in organic solvent.
Embodiment 3
The present embodiment in addition to following characteristics other structures with embodiment 1：As shown in figure 5, the upper conversion of the present embodiment synthesis
Composite nanometer particle is 3-tier architecture, and ground floor kernel heating layer is NaYF4:90%Nd3+, the second layer is for preventing energy sudden
The sealing coat for going out, specially NaYF4, third layer luminescent layer is NaYF4:30%Nd3+, 0.5%Er3+, 1%Nd3+.Which is specifically made
Preparation Method is identical with (1) of embodiment 2-(12).
Certainly the present invention does not limit the material and its exciting light of luminescent layer, as long as all feasible for effective up-conversion luminescence,
Therefore intermediate isolating layer is determined whether there are according to outer layer luminescent layer, therefore in size, also has little bit different, but generally all existed
More than 20nm and ensure its heating and luminous efficiency.But these corresponding changes should all belong to appended claims of the invention
Protection domain.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. composite nano materials are changed in one kind, it is characterised in that body is nucleocapsid structure, and kernel heating layer is NaYF4:90%
Nd3+, excitation wavelength is 800nm, luminescent layer for up-conversion luminescence nanometer layer, kernel heating layer and luminescent layer excitation wavelength not
Together, the luminescent layer is NaYF4:Yb3+,Er3+/Tm3+。
2. upper conversion composite nano materials according to claim 1, it is characterised in that the kernel heating layer is a diameter of
10-20nm；The luminescent layer excitation wavelength is 980nm, and thickness is 5-15nm.
3. the method for preparing the upper conversion composite nano materials described in claim 2, it is characterised in that comprise the following steps：
(1) it is prepared into doping Nd3+The nano-particle with heating effect, preparation method is as follows：
(1-1) prepare a certain amount of rare earth chloride：A certain amount of yittrium oxide and Dineodymium trioxide are weighed respectively, add excessive dense salt
Acid, dissolves in a heated condition, after being completely dissolved is evaporated solution, obtains rare earth chloride；
(1-2) prepare Oleic acid rare-earth salts presoma：Add Oleic acid and 1- octadecylenes, heated under vacuum to 110 DEG C -130 DEG C,
Kept for 30-50 minutes, obtain presoma, be cooled to 75 DEG C and react for next step；
(1-3) bath oiling prepares nano-particle：A certain amount of enuatrol and ammonium fluoride are added, is heated under argon protective condition
300 DEG C -320 DEG C, reaction keep 20 minutes 1 hour, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule, after centrifugation
Repeat with washes of absolute alcohol several times, to obtain nano-particle, be dissolved in organic solvent, react for next step；
(2) luminescent layer is coated on the nano-particle of step (1-3) by chemical reaction, luminescent layer preparation method is as follows：
(2-1) prepare a certain amount of rare earth chloride：A certain amount of yittrium oxide, ytterbium oxide, and a certain amount of oxygen are weighed respectively
Change erbium or Dithulium trioxide, add excessive concentrated hydrochloric acid, dissolve in a heated condition, solution is evaporated after being completely dissolved, obtain dilute
Native chloride；
(2-2) prepare Oleic acid rare-earth salts presoma：Oleic acid and 1- octadecylenes, heated under vacuum to 110 DEG C is added to keep 40
Minute, obtain presoma；It is cooled to 75 DEG C to react for next step；
(2-3) nano-particle of step (1-3) is added, the organic solvent of storage is evaporated；
(2-4) bath oiling prepares nano-particle：A certain amount of enuatrol and ammonium fluoride are added, is heated under argon protective condition
280 DEG C, reaction keep 40-50 minutes, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat to use nothing after centrifugation
Water-ethanol is cleaned several times, is obtained conversion composite nanometer particle, is dissolved in organic solvent.
4. composite nano materials are changed in one kind, it is characterised in that body is nucleocapsid structure, and kernel heating layer is NaYF4:90%
Nd3+, excitation wavelength is 800nm, and intermediate layer is NaYF4Sealing coat, be coated on kernel heating layer；Luminescent layer is sent out for upper conversion
Light nanometer layer NaYF4:Nd3+, Yb3+,Er3+, it is the NaYF of doping with rare-earth ions4Nanometer layer, coats on the intermediate layer, interior nuclear heating
Layer is identical with the excitation wavelength of luminescent layer.
5. upper conversion composite nano materials according to claim 4, it is characterised in that the kernel heating layer is a diameter of
10-20nm；The intermediate layer is NaYF4Sealing coat, thickness is 5-10nm；The luminescent layer is upper for 800nm laser excitations
Conversion nano layer NaYF4:Nd3+, Yb3+,Er3+, thickness is 5-15nm.
6. the method for preparing the upper conversion composite nano materials described in claim 5, it is characterised in that comprise the following steps：
(1) kernel heating layer is prepared, step is as follows：
(1-1) a certain amount of yittrium oxide, Dineodymium trioxide are weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain rare earth chlorine
Compound；
(1-2) a certain amount of Oleic acid, oleyl amine, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtained
Presoma；It is cooled to 75 DEG C to react for next step；
(1-3) a certain amount of enuatrol and ammonium fluoride are added, 310 DEG C is heated under argon protective condition, reaction keeps 40-50
Minute, after be cooled to 75 DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol several times, to obtain after centrifugation
Nano-particle, is dissolved in organic solvent；
(2) it is NaYF to prepare intermediate layer4Sealing coat, step is as follows：
(2-1) a certain amount of yittrium oxide is weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain rare earth chloride；
(2-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtains forerunner
Body；It is cooled to 75 DEG C to react for next step；
(2-3) nano-particle in addition step (1-3), evaporates the organic solvent of storage；After add a certain amount of enuatrol
And ammonium fluoride, 280 DEG C are heated under argon protective condition, reaction keep 40-50 minutes, after be cooled to 75 DEG C, add it is anhydrous
Ethanol precipitation nano-particle；Repeat with washes of absolute alcohol several times, to obtain composite nanometer particle, be dissolved in organic solvent after centrifugation；
(3) luminescent layer is prepared, step is as follows：
(3-1) a certain amount of yittrium oxide, Dineodymium trioxide, ytterbium oxide, Erbia are weighed, excessive concentrated hydrochloric acid dissolving is added, is rotated afterwards
Evaporation obtains rare earth chloride；
(3-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtains forerunner
Body；It is cooled to 75 DEG C to react for next step；
(3-3) composite nanometer particle for adding step (2-3) to obtain, evaporates the organic solvent of storage, adds afterwards a certain amount of
Enuatrol and ammonium fluoride, are heated to 280 DEG C under argon protective condition, reaction keep 40-50 minutes, after be cooled to 75 DEG C, plus
Enter dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol several times, to obtain conversion composite nanometer particle after centrifugation, it is molten
In organic solvent.
7. composite nano materials are changed in one kind, it is characterised in that change in composite nanometer particle on described in claim 4
A doping Nd is coated on the outside of luminescent layer also3+The nanometer layer for strengthening luminescent effect, this layer for luminescent layer shell.
8. upper conversion composite nano materials according to claim 7, it is characterised in that the kernel heating layer is NaYF4:
90%Nd3+, a diameter of 10-20nm；The intermediate layer is NaYF4Sealing coat, thickness is 5-10nm；The luminescent layer is
The upper conversion nano layer NaYF of 800nm laser excitations4:Nd3+, Yb3+,Er3+, thickness is 5-15nm；The shell of the luminescent layer is
NaYF4:Nd3+, thickness is 3-10nm.
9. the method for preparing the upper conversion composite nano materials described in claim 8, it is characterised in that described in claim 6
On the basis of preparation method, continue following steps：
(4) shell of luminescent layer is prepared, step is as follows：
(4-1) a certain amount of yittrium oxide, Dineodymium trioxide are weighed, adds excessive concentrated hydrochloric acid dissolving, rear rotary evaporation to obtain rare earth chlorine
Compound；
(4-2) a certain amount of Oleic acid, 1- octadecylenes are weighed, heated under vacuum to 110 DEG C is kept for 40 minutes, obtains forerunner
Body；It is cooled to 75 DEG C to react for next step；
(4-3) the upper conversion composite nanometer particle for adding step (3-3) to obtain, evaporates the organic solvent of storage；After add one
Quantitative enuatrol and ammonium fluoride, are heated to 280 DEG C under argon protective condition, reaction keep 40-50 minutes, after be cooled to 75
DEG C, add dehydrated alcohol precipitated nanocrystals granule；Repeat with washes of absolute alcohol several times, to obtain final upper conversion and be combined after centrifugation
Nano-particle, is dissolved in organic solvent.
10. upper conversion composite nano materials described in claim 1 or 4 or 7 are preparing diagnosing tumour preparation, are detecting in preparation temperature
Reagent, the purposes in tumor is prepared.
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