CN102391874A - NaYF4-based fluorescent nano particles with double effects and preparation method thereof - Google Patents
NaYF4-based fluorescent nano particles with double effects and preparation method thereof Download PDFInfo
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- CN102391874A CN102391874A CN2011102816059A CN201110281605A CN102391874A CN 102391874 A CN102391874 A CN 102391874A CN 2011102816059 A CN2011102816059 A CN 2011102816059A CN 201110281605 A CN201110281605 A CN 201110281605A CN 102391874 A CN102391874 A CN 102391874A
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Abstract
The invention relates to NaYF4-based fluorescent nano particles with double effects and a preparation method thereof. The NaYF4-based fluorescent nano particles at least comprise a kernel and a shell, wherein the kernel is NaYF4: Er/Yb/Gd or NaYF4: Er/Yb, and the shell is NaGdF4. By introducing different luminous ion pairs into different layers, the single-excitation multi-color luminescence function of the single fluorescent particles is realized, and the fluorescent particles have magnetic resonance imaging function; and meanwhile, by introducing a wrapping layer, surface defects of the particles are reduced, and the fluorescent strength of the particles is improved.
Description
Technical field
The present invention relates to the upconverting fluorescent material field, be specifically related to a kind of possess up-conversion fluorescence imaging and the double mode NaYF of nuclear magnetic resonance
4Base fluorescent nano particle and preparation method thereof.
Background technology
Early diagnosis of tumor presses for a kind of initiatively bioprobe of target of multiplex mode combination, efficient specificity that possesses.Fluorescence imaging and nuclear magnetic resonance at present is the diagnostic mode of tool potentiality.Research is expected to overcome the many weak points that exist in the present early diagnosis of cancer based on fluorescence/mr compound multi-mode probe, improves the diagnosis rate of clinical tumor.At present, the research emphasis of conventional fluorescent imaging field is based on the semiconductor-quantum-point that organic fluorescence is plain and contain heavy metal element.The former is not substituted by the latter because stability of photoluminescence is not good gradually.And the latter has also limited its further biologic applications because of the potential heavy metal toxicity.
Upconverting fluorescent material is one type of important rare earth (RE) luminescent material; It can convert the low frequency exciting light to high frequency emission light through multi-photon mechanism; Having near infrared excites; Emitted in ultraviolet-infrared the characteristics that wait multiband fluorescence has important use in fields such as solid statelaser, transmitter, solar cell and 3 D stereo demonstrations.
In recent years, the upconverting fluorescent material of nanoscale (upper conversion fluorescent nano particle) receives researchist's attention gradually in the application aspect the biomacromolecule detection as a kind of novel fluorescence affinity tag (probe).Than traditional fluorescent marker such as organic resorcinolphthalein and semiconductor-quantum-point etc., upper conversion fluorescent nano particle has as probe biomolecule that luminous intensity is high and stable, the tissue penetration degree of depth is big, background noise low and advantage such as the live body phototoxicity is low.For example, the exciting light of upper conversion fluorescent nano particle is a near infrared light, under this shooting conditions, can avoid the interference and the scattered light phenomenon of biological autofluorescence, thereby reduces detection background, improves signal to noise ratio.Therefore, upper conversion fluorescent nano particle all has extraordinary application prospect as fluorescent marker in biomacromolecule analysis and clinical medicine detection range.
In existing up-conversion fluorescence nano material, six side's phase NaYF
4Be the present best substrate material of luminescent properties in the report, through to NaYF
4In doping with rare-earth ions to (like Er
3+/ Yb
3+Tm
3+/ Yb
3+), can obtain the excellent fluorescent grain of luminescent properties.CN102140662 A discloses a kind of NaYF
4: Yb, Er upconverting fluorescent material and preparation method.Yet, nano NaY F
4Because the existence of surface imperfection, its luminous efficiency is starkly lower than body phase material usually, how to improve based on NaYF
4The luminescent properties of nano particle becomes an important subject of this area.
The foreign study personnel found to pass through to original luminous NaYF in 2009
4:Doped with rare-earth elements gadolinium ion in the Er/Yb nano particle, nano particle (Kumar, R.and Prasad, the P. N. that can realize having up-conversion fluorescence and nuclear magnetic resonance dual function smoothly
Adv. Funct. Mater. 2009,
19, 853.).Lanthanide rare gadolinium ion (Gd for example
3+) have half-full 4f layer electronics, be to use T the most widely at present
1-MRI radiography is used ion.The T of clinical use
1Mostly-MRI contrast medium is Gd
3+Complex compound, its longitudinal relaxation rate (
r 1) be 3.8 mM
-1s
-1About.Through to NaYF
4Doped with rare-earth elements Gd ion in the matrix can make material have T
1-MRI radiography function, yet, present Gd
3+Adulterated NaYF
4That has reported in the structure is the highest
r 1Value is merely 1.4 mM
-1s
-1(Park, Y. I. and Hyeon, T. Adv. Mater.
2009, 21,4467.), use the Gd agent well below clinical, therefore, demand urgently developing a kind of more efficiently based on NaYF
4Fluorescence/MR dual pattern nano biological molecular probe.
Summary of the invention
In the face of the problems referred to above that prior art exists, first aspect of the present invention provides a kind of NaYF with dual function
4The base fluorescent nano particle, said NaYF
4The base fluorescent nano particle comprises kernel and shell at least, and wherein said kernel is NaYF
4: Er/Yb/Gd or NaYF
4: Er/Yb, said shell are NaGdF
4
NaYF of the present invention
4The base fluorescent nano particle has nucleocapsid structure, and is right through introducing different light emitting ionics at different layers, realizes that the single of single fluorescent grain excites multicolor luminous function, and has nuclear magnetic resonance concurrently; Simultaneously, reduce the particulate surface imperfection, improved the particulate fluorescence intensity through introducing integument.
NaYF of the present invention
4The base fluorescent nano particle can comprise that also the middle layer forms three-decker, and said middle layer can be NaYF
4: Tm/Yb.
NaYF of the present invention
4In the base fluorescent nano particle, said shell NaGdF
4Mean thickness can be 0.2~4 nm, preferred 0.2~3.7 nm, more preferably 0.2~2.0 nm.Its corresponding longitudinal relaxation rate can be 1.18~6.18mM
-1S-
1, preferred 2.18 ~ 6.18mM
-1S-
1, more preferably 5.46 ~ 6.18mM
-1S-
1
Through optimizing outermost layer NaGdF
4Thickness, can improve up-conversion fluorescence particulate longitudinal relaxation rate, realize near in addition surpass the purpose of the longitudinal relaxation rate value of clinical Gd agent.Prepared particulate relaxation rate is up to 6.18 mM
-1s
-1, be 44 times of similar structures of document reported first.The maximum relaxation rate of single particle is 1.4 * 10
5MM
-1s
-1
On the other hand, the present invention provides a kind of preparation to have the NaYF of dual function
4The method of base fluorescent nano particle comprises: muriate, NaOH and the NH of the rare earth ion that said kernel is comprised
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed, and then cleans, is dispersed in the hexanaphthene kernel preparation process as kernel; And the muriate of the rare earth ion that said shell is comprised, cyclohexane solution, NaOH and the NH of the kernel that will coat
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed the shell preparation process of then cleaning, being dispersed in hexanaphthene.
Wherein, said kernel preparation process can comprise: the aqueous chloride solution of the rare earth ion that said kernel is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes; Add and be dispersed with NaOH and NH
4The methanol solution of F heats up and removes methyl alcohol; And 290~300 ℃ of thermolysiss after 1.5 hours, cooling, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, and centrifugal collection, products therefrom is dispersed in the hexanaphthene.
Said shell preparation process can comprise: the aqueous chloride solution of the rare earth ion that said shell is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes; Add the cyclohexane solution of the kernel that will coat, heat up and remove hexanaphthene; Add and be dispersed with NaOH and NH
4The methanol solution of F heats up and removes methyl alcohol; And 290~300 ℃ of thermolysiss after 1.5 hours, cooling, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, and centrifugal collection, products therefrom is dispersed in the hexanaphthene.
Method of the present invention can also comprise preparation middle layer NaYF
4: the Tm/Yb step: the muriate of the rare earth ion that said middle layer is comprised, cyclohexane solution, NaOH and the NH of the kernel that will coat
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed, and then cleans, is dispersed in the middle layer preparation of hexanaphthene.
Said middle layer preparation process comprises: the aqueous chloride solution of the rare earth ion that said middle layer is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes; Add the cyclohexane solution of the kernel that will coat, heat up and remove hexanaphthene; Add and be dispersed with NaOH and NH
4The methanol solution of F heats up and removes methyl alcohol; And 290~300 ℃ of thermolysiss after 1.5 hours, cooling, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, and centrifugal collection, products therefrom is dispersed in the hexanaphthene.
The employed raw material of the inventive method is inorganic salt, and the preparation process can not produce toxic gas.Prepared nano particle pattern is spherical, and the yardstick homogeneous is controlled, is six side's phase NaYF
4The NaYF that makes
4The base fluorescent nano particle has good up-conversion fluorescence emission and T
1-MRI weighting performance is expected in the early stage imaging of following tumour multi-mode, have a good application prospect.
Description of drawings
Figure 1A shows the NaYF of median size 18 nm of embodiment 1 preparation
4: Er/Yb/Gd low power TEM photo;
Figure 1B shows the NaYF of median size 18 nm of embodiment 1 preparation
4: Er/Yb/Gd high power TEM photo;
Fig. 2 A shows the NaYF of median size 22 nm of embodiment 2 preparations
4: Er/Yb/Gd NaYF
4: Tm/Yb low power TEM photo;
Fig. 2 B shows the NaYF of median size 26 nm of embodiment 2 preparations
4: Er/Yb/Gd NaYF
4: Tm/Yb high power TEM photo;
Fig. 3 A shows the NaYF of median size 26 nm of embodiment 3 preparations
4: Er/Yb/Gd NaYF
4: Tm/Yb NaGdF
4Low power TEM photo;
Fig. 3 B shows the NaYF of median size 26 nm of embodiment 3 preparations
4: Er/Yb/Gd NaYF
4: Tm/Yb NaGdF
4High power TEM photo;
Fig. 4 A shows the NaYF of the median size 24nm of embodiment 4 preparations
4: Er/Yb NaGdF
4Low power TEM photo;
Fig. 4 B shows the NaYF of median size 24 nm of embodiment 4 preparations
4: Er/Yb NaGdF
4High power TEM photo;
Fig. 5 A shows the NaYF of the median size 24.5nm of embodiment 5 preparations
4: Er/Yb NaGdF
4Low power TEM photo;
Fig. 5 B shows the NaYF of median size 24.5 nm of embodiment 5 preparations
4: Er/Yb NaGdF
4High power TEM photo;
Fig. 6 A shows the NaYF of the median size 25.8nm of embodiment 6 preparations
4: Er/Yb NaGdF
4Low power TEM photo;
Fig. 6 B shows the NaYF of median size 25.8 nm of embodiment 6 preparations
4: Er/Yb NaGdF
4High power TEM photo;
Fig. 7 A shows the NaYF of the median size 27.5nm of embodiment 7 preparations
4: Er/Yb NaGdF
4Low power TEM photo;
Fig. 7 b shows the NaYF of median size 27.5 nm of embodiment 7 preparations
4: Er/Yb NaGdF
4High power TEM photo;
Fig. 8 A illustrates the exemplary transmit spectrum of the nano particle of the present invention preparation, exciting light λ=980 nm wherein, and dotted line is NaYF
4: the fluorescence of Er/Yb/Gd, long and short dash line are NaYF
4: Er/Yb/GdNaYF
4: the fluorescence of Tm/Yb, solid line are NaYF
4: Er/Yb/Gd NaYF
4: Tm/Yb NaGdF
4Fluorescence;
Fig. 8 B illustrates the enlarged diagram of A part among Fig. 8 A;
Fig. 8 C illustrates the enlarged diagram of B part among Fig. 8 A;
Fig. 9 illustrates water-soluble NaYF
4: Er/Yb/Gd NaYF
4: Tm/Yb NaGdF
4The graphic representation of the longitudinal relaxation rate of nano particle, testing tool are clinical usefulness 3.0 T MRI;
Figure 10 illustrates water-soluble NaYF
4: Er/YbNaGdF
4The graphic representation of the longitudinal relaxation rate of (0.2 nm) nano particle, testing tool are clinical usefulness 3.0 T MRI;
Figure 11 illustrates water-soluble NaYF
4: Er/YbNaGdF
4The graphic representation of the longitudinal relaxation rate of (0.7 nm) nano particle, testing tool are clinical usefulness 3.0 T MRI;
Figure 12 illustrates water-soluble NaYF
4: Er/YbNaGdF
4The graphic representation of the longitudinal relaxation rate of (2.0 nm) nano particle, testing tool are clinical usefulness 3.0 T MRI;
Figure 13 illustrates water-soluble NaYF
4: Er/YbNaGdF
4The graphic representation of the longitudinal relaxation rate of (3.7 nm) nano particle, testing tool are clinical usefulness 3.0 T MRI.
Embodiment
With reference to Figure of description, and combine following embodiment to further specify the present invention, should be understood that Figure of description and following embodiment only are used to explain the present invention, and unrestricted the present invention.
The present invention is through nucleus assisting growth technology, and preparation has the upper conversion fluorescent nano particle of nucleocapsid structure, and it is right to introduce different light emitting ionics at the particulate different layers, below respectively with have three-decker and double-layer structure on the example that is prepared as describe.
One, the upper conversion fluorescent nano particle (NaYF that has three-decker
4: Er/YbGdNaYF
4: Tm/Yb NaGdF
4) preparation.
(1) kernel NaYF
4: the preparation of Er/YbGd
1) aqueous solution of rare earth chloride: take by weighing the muriate of an amount of yttrium (Y), ytterbium (Yb), erbium (Er) and gadolinium (Gd) respectively, subsequent use with deionized water dissolving.Rare earth chloride can adopt its hydrate commonly used separately (YCl for example here
36H
2O, YbCl
36H
2O, ErCl
36H
2O, GdCl
3XH
2O, the amount of the deionized water of employing can be dissolving said muriatic amount or excessive slightly.
2) in oleic acid and octadecylene mixed solution, add above-mentioned pre-configured aqueous solution of rare earth chloride, the oleic acid of employing and the volume ratio of octadecylene can be 1:2.Stirred about 1 hour under the room temperature.Logical argon gas certain hour (for example 5 minutes) then carries out removal process slowly to remove air.Dewater after the end, system temperature is raised to about 160 ℃ and is incubated certain hour, for example 60 minutes, obtains faint yellow clear liquor.Stop heating, system is cooled to room temperature (keeping logical argon gas therebetween) naturally.
3) take by weighing appropriate amount of NaOH and NH
4F is with an amount of methyl alcohol (for example 10mL) dissolving, ultra-sonic dispersion.Then it is added in the above-mentioned system carefully, stirred 2 hours under the room temperature; Then be warmed up to 80~100 ℃ and remove methyl alcohol, be incubated about 1 hour, finish up to the methyl alcohol removal.
4) after methyl alcohol had removed, system began to heat up, and at 290~300 ℃, condensing reflux kept 1.5 hours, reduced to room temperature then naturally with temperature-stable.
6) product cleaning: can carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, but repeated washing 4 times, final product disperses with cyclohexane solution, obtains colorless cleared solution.Product can be launched tangible green glow under the 980nm excitation light irradiation.
The preparation of (two) two layers of nucleocapsid structure: NaYF
4: Er/YbGdNaYF
4: Tm/Yb
1) aqueous solution of rare earth chloride: title takes by weighing an amount of yttrium (Y), ytterbium (Yb) respectively, reaches the muriate of thulium (Tm), and is subsequent use with deionized water dissolving.Rare earth chloride can adopt its hydrate commonly used separately, for example YCl here
36H
2O, YbCl
36H
2O, TmCl
36H
2O.The amount of the deionized water that adopts can be dissolving said muriatic amount or excessive slightly.
2) in oleic acid and octadecylene mixed solution, add above-mentioned pre-configured aqueous solution of rare earth chloride.The oleic acid that adopts and the volume ratio of octadecylene can be 1:2, stir about 1 hour under the room temperature.Logical argon gas certain hour (for example 5 minutes) then carries out removal process slowly to remove air.Dewater after the end, system temperature is raised to about 160 ℃, keeps certain hour, for example 60 minutes.Obtain faint yellow clear liquor.Stop heating, system is cooled to room temperature (keeping logical argon gas therebetween) naturally.
3) in system, add an amount of NaYF of preparation in advance
4: the Er/YbGd cyclohexane solution is as kernel.Stir after 30 minutes, be warming up to about 80 ℃ and remove cyclohexane solution;
4) take by weighing appropriate amount of NaOH and NH
4F uses an amount of dissolve with methanol, ultra-sonic dispersion.Then it is added in the above-mentioned system carefully, stirred about 2 hours under the room temperature; Be warmed up to 80~100 ℃ to remove methyl alcohol, kept about 1 hour, removed up to methyl alcohol.
5) after methyl alcohol had removed, system began to heat up, and at 290~300 ℃, condensing reflux kept 1.5 hours, reduced to room temperature then naturally with temperature-stable.
6) product cleaning: can carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, but repeated washing 4 times, final product disperses with cyclohexane solution, obtains colorless cleared solution.
(3) preparation of three-layer nuclear shell structure: NaYF
4: Er/YbGdNaYF
4: Tm/YbNaGdF
4
1) aqueous solution of rare earth chloride: take by weighing an amount of gadolinium muriate (GdCl for example
3XH
2O), subsequent use with the proper amount of deionized water dissolving.
) in oleic acid and octadecylene mixed solution, add above-mentioned pre-configured aqueous solution of rare earth chloride, stirred 1 hour under the room temperature.The oleic acid that adopts and the volume ratio of octadecylene can be 1:2.Logical argon gas certain hour (for example 5 minutes) then carries out removal process slowly to remove air.Dewater after the end, system temperature is raised to about 160 ℃, keeps certain hour, for example about 60 minutes.Obtain faint yellow clear liquor.Stop heating, system is cooled to room temperature (keeping logical argon gas therebetween) naturally.
3) in system, add an amount of NaYF of preparation in advance
4: Er/YbGdNaYF
4: the Tm/Yb cyclohexane solution is as kernel.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution;
4) take by weighing appropriate amount of NaOH and NH
4F uses an amount of dissolve with methanol, ultra-sonic dispersion.Then it is added in the above-mentioned system carefully, stirred 2 hours under the room temperature; Be warmed up to 80~100 ℃ to remove methyl alcohol, kept about 1 hour, removed up to methyl alcohol.
5) after methyl alcohol had removed, system began to heat up, and at 290~300 ℃, condensing reflux kept 1.5 hours, reduced to room temperature then naturally with temperature-stable.
6) product cleaning: can carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, but repeated washing 4 times, final product disperses with cyclohexane solution, obtains colorless cleared solution.
The NaYF that makes
4: Er/YbGdNaYF
4: Tm/YbNaGdF
4Exemplary transmit spectrum can be referring to accompanying drawing 8, its longitudinal relaxation rate can be referring to accompanying drawing 9.
The NaYF of embodiment 1 median size 18 nm
4: the preparation of Er/Yb/Gd:
Aqueous solution of rare earth chloride: the YCl that takes by weighing 1.3 mmol (394.368 mg) respectively
36H
2The YbCl of O, 0.36 mmol (139.4964 mg)
36H
2The ErCl of O, 0.04 mmol (15.2684 mg)
36H
2The GdCl of O and 0.3mmol (79.083)
3XH
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid, 30 mL octadecylenes add the pre-configured above-mentioned muriatic aqueous solution then, stir 1 hour under the room temperature.Logical argon gas 5 minutes is removed a bottle air, and system begins to carry out removal process slowly then.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating, let system be cooled to room temperature (keeping logical argon gas therebetween) naturally.
Take by weighing 200 mg NaOH, 296.3 mg NH
4F is with 10 mL dissolve with methanol, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, and kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, is kept 1.5 h.Naturally reduce to room temperature then.
Product cleaning: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10 mL, ultrasonic, add the alcohol of 15 mL then, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.980 nm laser irradiation product down can have been launched tangible green glow.
Making average size of products is 18nm, and its low power and high power TEM photo are respectively shown in Figure 1A, 1B.
Embodiment 2 (the NaYF4:Er/Yb/Gd NaYF4:Tm/Yb preparations of median size 22 nm):
On embodiment 1 basis, proceed following steps:
Aqueous solution of rare earth chloride: the YCl that takes by weighing 0.747 mmol (226.61 mg) respectively
36H
2The YbCl of O, 0.25 mmol (96.8725 mg)
36H
2The TmCl of O, 0.003mmol (0.8258 mg)
36H
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid and 30 mL octadecylenes, add pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed a bottle air, and system begins to carry out removal process slowly then.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating, let system be cooled to room temperature (keeping logical argon gas) naturally.
The NaYF that in system, adds embodiment 1 preparation of 1mmol
4: the Er/YbGd cyclohexane solution is as the kernel of growth.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution.
Prepare 100 mg NaOH, 148.15 mg NH
4F is with the dissolve with methanol of 10 mL, ultra-sonic dispersion.In the carefully adding system, stirred 2 hours under the room temperature then.After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, was kept 1.5 hours, reduces to room temperature then naturally.
Product cleaning: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min, centrifugal 10 minutes; The hexanaphthene that adds 5~10 mL then, and ultrasonic adds the alcohol of 15 mL, and ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, last product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 22nm, and its low power and high power TEM photo are respectively shown in Fig. 2 A, 2B.
Embodiment 3 (the NaYF of median size 26 nm
4: Er/Yb/Gd NaYF
4: Tm/Yb NaGdF
4Preparation):
On embodiment 2 bases, proceed following steps:
Aqueous solution of rare earth chloride: the GdCl that takes by weighing 1 mol (263.61 mg)
3XH
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid, 30 mL octadecylenes, add pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly then.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating, let system be cooled to room temperature (keeping logical argon gas) naturally.
The NaYF that in system, adds embodiment 2 preparations of 1 mmol
4: Er/YbGdNaYF
4: the Tm/Yb cyclohexane solution is as the kernel of growth.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution.
Prepare 100 mg NaOH, 148.15 mg NH
4F is with the dissolve with methanol of 10 mL, ultra-sonic dispersion.In the carefully adding system, stirred 2 hours under the room temperature then.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and final temp is stabilized in 290~300 ℃, keeps 1.5 hours.Naturally reduce to room temperature then.
Product cleaning: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10 mL, ultrasonic, add the alcohol of 15 mL, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 26nm, and its low power and high power TEM photo are respectively shown in Fig. 3 A, 3B.
Two, the conversion fluorescent nano particle (NaYF that has double-layer structure
4: preparation Er/Yb NaGdF).
(1) kernel NaYF
4: the preparation of Er/Yb
1) aqueous solution of rare earth chloride: take by weighing an amount of yttrium (Y), ytterbium (Yb), and the muriate of erbium (Er) respectively, subsequent use with deionized water dissolving.Rare earth chloride can adopt its hydrate commonly used separately, for example (YCl here
36H
2O, YbCl
36H
2O, ErCl
36H
2O.The amount of the deionized water that adopts can be dissolving said muriatic amount or excessive slightly.
2) in oleic acid and octadecylene mixed solution, add above-mentioned pre-configured aqueous solution of rare earth chloride, the oleic acid of employing and the volume ratio of octadecylene can be 1:2.Stirred about 1 hour under the room temperature.Logical argon gas certain hour (for example 5 minutes) then carries out removal process slowly to remove air.Dewater after the end, system temperature is raised to about 160 ℃ and is incubated certain hour, for example 60 minutes, obtains faint yellow clear liquor.Stop heating, system is cooled to room temperature (keeping logical argon gas therebetween) naturally.
3) take by weighing appropriate amount of NaOH and NH
4F is with an amount of methyl alcohol (for example 10mL) dissolving, ultra-sonic dispersion.Then it is added in the above-mentioned system carefully, stirred 2 hours under the room temperature; Be warmed up to 80~100 ℃ to remove methyl alcohol, be incubated about 1 hour, removed up to methyl alcohol.
4) after methyl alcohol had removed, system began to heat up, and at 290~300 ℃, condensing reflux kept 1.5 hours, reduced to room temperature then naturally with temperature-stable.
5) product cleaning: can carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, but repeated washing 4 times, final product disperses with cyclohexane solution, obtains colorless cleared solution.Product can be launched tangible green glow under the 980nm excitation light irradiation.
(2) two layers of nucleocapsid NaYF
4: Er/Yb NaGdF
4Preparation
1) aqueous solution of rare earth chloride: take by weighing an amount of gadolinium muriate (GdCl for example
3XH
2O), subsequent use with the proper amount of deionized water dissolving.
2) in oleic acid and octadecylene mixed solution, add above-mentioned pre-configured aqueous solution of rare earth chloride, stirred 1 hour under the room temperature.The oleic acid that adopts and the volume ratio of octadecylene can be 1:2.Logical argon gas certain hour (for example 5 minutes) then carries out removal process slowly to remove air.Dewater after the end, system temperature is raised to about 160 ℃, keeps certain hour, for example about 60 minutes.Obtain faint yellow clear liquor.Stop heating, system is cooled to room temperature (keeping logical argon gas therebetween) naturally.
3) in system, add an amount of NaYF of preparation in advance
4: the Er/Yb cyclohexane solution is as kernel.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution.
4) take by weighing appropriate amount of NaOH and NH
4F uses an amount of dissolve with methanol, ultra-sonic dispersion.Then it is added in the above-mentioned system carefully, stirred 2 hours under the room temperature; Be warmed up to 80~100 ℃ to remove methyl alcohol, kept about 1 hour, removed up to methyl alcohol; After methyl alcohol had removed, system began to heat up, and at 290~300 ℃, condensing reflux kept 1.5 hours, reduced to room temperature then naturally with temperature-stable.
5) product cleaning: can carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, but repeated washing 4 times, final product disperses with cyclohexane solution, obtains colorless cleared solution.
Embodiment 4 (the NaYF of median size 24 nm
4: Er/Yb NaGdF
4, preparation NaGdF
4Layer thickness is 0.2 nm):
The preparation of kernel: NaYF
4: Er/Yb
Aqueous solution of rare earth chloride: the YCl that takes by weighing 1.6 mmol (458.376 mg) respectively
36H
2The YbCl of O, 0.36 mmol (139.4964 mg)
36H
2The ErCl of O and 0.04 mmol (15.2684 mg)
36H
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid and 30 mL octadecylenes, add above-mentioned pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly then.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating, let system be cooled to room temperature (keeping logical argon gas) naturally.
Take by weighing 200 mg NaOH and 296.3mg NH
4F is with the dissolve with methanol of 10 mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, was kept 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10mL, ultrasonic, add the alcohol of 15 mL, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.980 nm laser irradiation product down can have been launched tangible green glow.
The preparation of two layers of nucleocapsid structure: NaYF
4: Er/YbNaGdF
4
Aqueous solution of rare earth chloride: take by weighing 0.337 mol GdCl
3XH
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid, 30 mL octadecylenes add pre-configured aqueous chloride solution then, stir 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
In system, add about 1 mmol NaYF of preparation in advance
4: the Er/Yb cyclohexane solution is as the kernel of growth.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution.
Take by weighing 33.7 mg NaOH and 49.92 mg NH4F, with the dissolve with methanol of 10 mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, and is kept 1.5h.Naturally reduce to room temperature.Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10 mL, ultrasonic, add the alcohol of 15 mL then, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, last product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 24 nm, and the mean thickness of shell is 0.2 nm, and its low power and high power TEM photo are respectively shown in Fig. 4 A, 4B; Its longitudinal relaxation rate can be referring to accompanying drawing 10.
Embodiment 5 (the NaYF of median size 24.5 nm
4: Er/Yb NaGdF
4Preparation, NaGdF
4Layer thickness is 0.7 nm):
The preparation of kernel: NaYF
4: Er/Yb
Aqueous solution of rare earth chloride: the YCl that takes by weighing 1.6 mmol (458.376 mg) respectively
36H
2The YbCl of O, 0.36 mmol (139.4964mg)
36H
2The ErCl of O and 0.04 mmol (15.2684 mg)
36H
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid, 30 mL octadecylenes add the above-mentioned in advance aqueous chloride solution that configures then, stir 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
Take by weighing 200 mg NaOH and 296.3 mg NH
4F is with the dissolve with methanol of 10 mL, ultra-sonic dispersion.In the carefully adding system, stirred 2 hours under the room temperature then.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, was kept 1.5 hours.Naturally reduce to room temperature then.
Product cleaning: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000r/min then, centrifugal 10 minutes; Add 5~10 mL hexanaphthenes, and ultrasonic, add the alcohol of 15 mL then, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, last product disperses with cyclohexane solution, obtains to be colorless cleared solution.980 nm laser irradiation product down can have been launched tangible green glow.
The preparation of two layers of nucleocapsid structure: NaYF
4: Er/Yb NaGdF
4:
Aqueous solution of rare earth chloride: take by weighing 0.08 mol GdCl
3XH
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid and 30 mL octadecylenes, add above-mentioned pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
In system, add about 1 mmol NaYF of preparation in advance
4: the Er/Yb cyclohexane solution is as the kernel of growth.Stir after 30 minutes, be warming up to 80 NaYF
4: Er/Yb removes cyclohexane solution.
Take by weighing 8 mg NaOH and 11.85 mg NH4F, with the dissolve with methanol of 10 mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, and was kept 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10 mL then, ultrasonic, add the alcohol of 15 mL then, ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, last product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 24.5 nm, and the mean thickness of shell is 0.7nm, and its low power and high power TEM photo are respectively shown in Fig. 5 A, 5B; Its longitudinal relaxation rate can be referring to accompanying drawing 11.
Embodiment 6 (the NaYF of median size 25.8 nm
4: Er/Yb NaGdF
4Preparation, NaGdF
4Layer thickness is 2.0 nm):
The preparation of kernel: NaYF
4: Er/Yb:
Aqueous solution of rare earth chloride: the YCl that takes by weighing 1.6 mmol (458.376 mg) respectively
36H
2The YbCl of O, 0.36 mmol (139.4964 mg)
36H
2The ErCl of O and 0.04 mmol (15.2684 mg)
36H
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid and 30 mL octadecylenes, add above-mentioned pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
Take by weighing 200 mg NaOH and 296.3 mg NH
4F is with 10 mL dissolve with methanol, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, was kept 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; The hexanaphthene that adds 5~10 mL then, and ultrasonic adds the alcohol of 15 mL, and ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.980 nm laser irradiation product down can have been launched tangible green glow.
Two layers of nucleocapsid structure NaGdF
4Preparation:
1) aqueous solution of rare earth chloride: take by weighing 0.02 mol GdCl
3XH
2The O powder, subsequent use with the 4mL deionized water dissolving.
In there-necked flask, add 15 mL oleic acid and 30mL octadecylene, add pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
In system, add above-mentioned about 1 mmol NaYF of preparation in advance
4: the Er/Yb cyclohexane solution is as the kernel of growth.After stirring 30 min, be warming up to 80 degree and remove cyclohexane solution.
Take by weighing 2 mg NaOH and 2.96 mg NH4F, with the dissolve with methanol of 10 mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and final temp is stabilized in 290~300 ℃, keeps 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add the absolute ethyl alcohol of 20 mL, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; The hexanaphthene that adds 5~10 mL then, and ultrasonic adds the alcohol of 15 mL, and ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 25.8 nm, and the mean thickness of shell is 2.0 nm, and its low power and high power TEM photo are respectively shown in Fig. 6 A, 6B; Its longitudinal relaxation rate can be referring to accompanying drawing 12.
Embodiment 7 (the NaYF of median size 27.5 nm
4: Er/Yb NaGdF
4Preparation, NaGdF
4Layer thickness is 3.7 nm):
The preparation of kernel: NaYF
4: Er/Yb
Aqueous solution of rare earth chloride: the YCl that takes by weighing 1.6 mmol (458.376 mg) respectively
36H
2The YbCl of O, 0.36 mmol (139.4964 mg)
36H
2The ErCl of O and 0.04 mmol (15.2684 mg)
36H
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid and 30 mL octadecylenes, add pre-configured aqueous chloride solution then, stirred 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
Take by weighing 200 mg NaOH and 296.3 mg NH
4F is with the dissolve with methanol of 10 mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and last temperature-stable at 290~300 ℃, was kept 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; Add the hexanaphthene of 5~10mL, ultrasonic, add the alcohol of 15mL, ultrasonic about 5 min, centrifugal collection then.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.980 nm laser irradiation product down can have been launched tangible green glow.
Two layers of nucleocapsid structure NaYF
4: Er/Yb NaGdF
4Preparation:
1) preparation of rare earth chloride: take by weighing 0.004 mol GdCl
3XH
2The O powder, subsequent use with 4 mL deionized water dissolvings.
In there-necked flask, add 15 mL oleic acid, 30 mL octadecylenes add pre-configured aqueous chloride solution then, stir 1 hour under the room temperature.Logical argon gas 5 minutes is removed the air in the bottle, and system begins to carry out removal process slowly then.Dewater finish after, system is raised to about 160 ℃, keeps 60 minutes.Obtain faint yellow clear liquor.Stop heating then, let system be cooled to room temperature (keeping logical argon gas) naturally.
In system, add about 1 mmol NaYF of preparation in advance
4: the Er/Yb cyclohexane solution is as the kernel of growth.Stir after 30 minutes, be warming up to 80 ℃ and remove cyclohexane solution.
Take by weighing 0.4 mg NaOH and 0.592 mg NH
4F is with the dissolve with methanol of 10mL, ultra-sonic dispersion.Then in the carefully adding system.Stirred 2 hours under the room temperature.
After 2 hours, system begins to get into except that the methyl alcohol link.Be warmed up to 80~100 ℃, kept 1 hour.Removed up to methyl alcohol.
After methyl alcohol has removed.Prolong is connected, and system begins to heat up, and final temp is stabilized in 290~300 ℃, keeps 1.5 hours.Naturally reduce to room temperature then.
Product cleaning process: at first in system, add 20 mL absolute ethyl alcohols, stirring at room 30 minutes.Use 10000 r/min then, centrifugal 10 minutes; The hexanaphthene that adds 5~10 mL, and ultrasonic adds the alcohol of 15 mL, and ultrasonic about 5 minutes, centrifugal collection.Repeated washing 4 times, final product disperses with cyclohexane solution, obtains to be colorless cleared solution.
Making average size of products is 27.5 nm, and the mean thickness of shell is 37nm, and its low power and high power TEM photo are respectively shown in Fig. 7 A, 7B; Its longitudinal relaxation rate can be referring to accompanying drawing 13.
The present invention preparation has the upper conversion fluorescent nano particle of nucleocapsid structure, and is right through introducing different light emitting ionics at different layers, and that can realize single fluorescent grain singlely excites multicolor luminous function; Simultaneously, reduce the particulate surface imperfection, improved the particulate fluorescence intensity through introducing integument.The second, through optimizing outermost layer NaGdF
4Thickness, improve up-conversion fluorescence particulate longitudinal relaxation rate, realize near in addition surpass the purpose of the longitudinal relaxation rate value of clinical Gd agent.Prepared particulate relaxation rate is up to 6.18 mM
-1s
-1, be 44 times of similar structures of document reported first.The maximum relaxation rate of single particle is 1.4 * 10
5MM
-1s
-1
Raw material used in the present invention is inorganic salt, and the preparation process can not produce toxic gas.Prepared nano particle pattern is spherical, and the yardstick homogeneous is controlled, is six side's phase NaYF
4This material has good up-conversion fluorescence emission and T
1-MRI weighting performance is expected in the early stage imaging of following tumour multi-mode, have a good application prospect.
Claims (13)
1. NaYF with dual function
4The base fluorescent nano particle is characterized in that said NaYF
4The base fluorescent nano particle comprises that at least kernel and shell are two-layer, and wherein said kernel is NaYF
4: Er/Yb/Gd or NaYF
4: Er/Yb, said shell are NaGdF
4
2. NaYF according to claim 1
4The base fluorescent nano particle is characterized in that said NaYF
4The base fluorescent nano particle also comprises the middle layer, and said middle layer is NaYF
4: Tm/Yb.
3. NaYF according to claim 1
4The base fluorescent nano particle is characterized in that said shell NaGdF
4Mean thickness be 0.2~4 nm.
4. NaYF according to claim 3
4The base fluorescent nano particle is characterized in that said shell NaGdF
4Mean thickness be 0.2~3.7 nm.
5. NaYF according to claim 4
4The base fluorescent nano particle is characterized in that said shell NaGdF
4Mean thickness be 0.2~2.0 nm.
6. NaYF according to claim 1
4The base fluorescent nano particle is characterized in that said NaYF
4The longitudinal relaxation rate of base fluorescent nano particle is 1.18~6.18mM
-1S-
1
7. NaYF according to claim 6
4The base fluorescent nano particle is characterized in that said NaYF
4The longitudinal relaxation rate of base fluorescent nano particle is 2.18 ~ 6.18mM
-1S-
1
8. NaYF according to claim 7
4The base fluorescent nano particle is characterized in that said NaYF
4The longitudinal relaxation rate of base fluorescent nano particle is 5.46 ~ 6.18mM
-1S-
1
9. one kind prepares the described NaYF with dual function of claim 1
4The method of base fluorescent nano particle is characterized in that, comprising:
Muriate, NaOH and the NH of the rare earth ion that said kernel is comprised
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed, and then cleans and be dispersed in the hexanaphthene kernel preparation process as kernel; And
The muriate of the rare earth ion that said shell is comprised, cyclohexane solution, NaOH and the NH of the kernel that will coat
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed, and then cleans and be dispersed in the shell preparation process of hexanaphthene.
10. method according to claim 9 is characterized in that, said kernel preparation process comprises:
The aqueous chloride solution of the rare earth ion that said kernel is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes;
Add and be dispersed with NaOH and NH
4The methanol solution of F then heats up and removes methyl alcohol; And
290~300 ℃ of thermolysiss after 1.5 hours, cooling, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively, centrifugal collection, and products therefrom is dispersed in the hexanaphthene.
11. method according to claim 9 is characterized in that, said shell preparation process comprises:
The aqueous chloride solution of the rare earth ion that said shell is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes;
Add the cyclohexane solution of the kernel that will coat, then heat up and remove hexanaphthene;
Add and be dispersed with NaOH and NH
4The methanol solution of F then heats up and removes methyl alcohol; And
, cool off, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively after 1.5 hours 290~300 ℃ of thermolysiss, centrifugal collection, products therefrom is dispersed in the hexanaphthene.
12. method according to claim 9 is characterized in that, said NaYF
4The base fluorescent nano particle also comprises the middle layer, and said middle layer is NaYF
4: Tm/Yb, said method also comprises:
The muriate of the rare earth ion that said middle layer is comprised, cyclohexane solution, NaOH and the NH of the kernel that will coat
4F elevated temperature heat in oleic acid and octadecylene mixed solution is decomposed, and then cleans, is dispersed in the middle layer preparation of hexanaphthene.
13. method according to claim 12 is characterized in that, said middle layer preparation process comprises:
The aqueous chloride solution of the rare earth ion that said middle layer is comprised adds in oleic acid and the octadecylene mixed solution, removes air and moisture, about 160 ℃, is incubated 60 minutes;
Add the cyclohexane solution of the kernel that will coat, then heat up and remove hexanaphthene;
Add and be dispersed with NaOH and NH
4The methanol solution of F then heats up and removes methyl alcohol; And
, cool off, carry out ultrasonic cleaning with absolute ethyl alcohol, hexanaphthene, alcohol successively after 1.5 hours 290~300 ℃ of thermolysiss, centrifugal collection, products therefrom is dispersed in the hexanaphthene.
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