CN103865538A - Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof - Google Patents
Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof Download PDFInfo
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- CN103865538A CN103865538A CN201410059634.4A CN201410059634A CN103865538A CN 103865538 A CN103865538 A CN 103865538A CN 201410059634 A CN201410059634 A CN 201410059634A CN 103865538 A CN103865538 A CN 103865538A
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Abstract
The invention belongs to the technical field of nanometer biological materials, and particularly relates to an 800nm excitation-based up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and a synthesis method thereof. The synthetic up/down conversion dual-mode fluorescent nanomaterial for Nd<3+>sensitization designed by the invention has a multi-layer core-shell structure, and comprises a down conversion luminous layer, an up conversion luminous layer, an isolation layer and a passivation layer. Different layers of the material synergistically play respective different roles, and meanwhile, the dual-mode fluorescent probe with up conversion fluorescence and down conversion fluorescence is finally achieved under an 800nm of excitation light with a low-heat effect. The up conversion excitation light is expanded to about 800nm from 980nm by Nd<3+>, Yb<3+> and Er<3+>-doped NaGdF4:Nd, Yb, Er up conversion layer due to introduction of Nd<3+>, and the fluorescent process from a near infrared light to a visible light is achieved. The process meets the requirements of an in-vitro fluorescent probe. In addition, the typical down conversion fluorescence from the near infrared light to a far infrared light is also achieved in one nanoparticle due to the synergistic effect of the NaGdF4:Nd core.
Description
Technical field
The invention belongs to nano meter biomaterial technical field, be specifically related to a kind of Nd
3+up/down conversion bimodulus fluorescent nano material and the synthetic method thereof of sensitization.
Background technology
Along with the fast development of nanotechnology, various high-quality rear-earth-doped upper conversion fluorescent nano particles are synthesized out, and the various fields that are successfully applied to (especially life science).Compare with traditional biomarker (as organic dye and quantum dot etc.), up-conversion fluorescence nano material has a lot of advantages, such as high chemical stability, hypotoxicity, high signal to noise ratio etc.Researcher is verified, no matter be for external application or for the application of live body, " infrared window " is all even more important.Because near infrared light possesses following advantage: can effectively reduce biological background fluorescence, the injury of smaller object, the deep tissue penetration degree of depth and low scattering of light.For external fluorescence imaging (such as cell imaging), have that near infrared excites, VISIBLE LIGHT EMISSION is optimal selection.Can effectively reduce background fluorescence and the injury to object because near infrared excites, the more important thing is that the emission energy of visible ray is very beneficial for naked eyes or microscopical observation (the most of equipment of microscope is all to have visible light-responded Si-CCD camera at present).For the application of live body, near infrared is optimal selection near infrared fluorescence because for tissue penetrate and pass near infrared light there is the high tissue penetration degree of depth, the advantages such as high s/n ratio.Down-conversion fluorescent has high luminous efficiency in addition, is more conducive to the imaging of dark tissue.Up to the present, there have been a variety of fluorescent nano materials based on rare earth ion doped to be synthesized out, comprising upper conversion fluorescent nano particle and lower conversion nano particle.All the time, all two fields in being parallel to each other of up-conversion nano material and lower conversion nano material.Realize under single exciting light, possess near infrared simultaneously and for us, still there is certain challenge to visible up-conversion fluorescence and near infrared to the bimodulus fluorescent nano material of near infrared down-conversion fluorescent.But the exploitation of this material for above-mentioned external-all there is very large meaning live body double-mode imaging.In addition, because most of upconverting fluorescent material all adopts Yb
3+as sensitized ions, so for traditional up-conversion fluorescence nano material, most of Yb that adopts
3+980 corresponding nm laser are as excitation light source.But from the scope of " the biological window of near infrared ", this excitation light source is not obviously within the scope of this.Wherein topmost reason is in biological tissue that moisture is for the absorption of 980 nm exciting lights.This absorption not only can reduce the launching efficiency of exciting light, the most important thing is that the exciting light that water absorbs can convert a large amount of heat to, thereby further causes the damage of checking matter or burn.From the scope of " near infrared biological window ", 800 ~ 900 nm and the checking matter minimum that influences each other, is therefore the selection of people's the best.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology 800 nm simple, that can be used in vitro and living imaging to excite Nd
3+up/down conversion bimodulus fluorescent nano material and the synthetic method thereof of sensitization.
800 nm provided by the invention excite Nd
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is a kind of nano material of core@shell 1@shell 2@shell 3 structures, comprises lower conversion luminescence layer, up-conversion luminescence layer, four parts of sealing coat and passivation layer.Wherein, lower conversion luminescence layer, for absorbing the exciting light of specific wavelength, is launched the down-conversion fluorescent of high quantum production rate; Up-conversion luminescence layer, for absorbing the exciting light of specific wavelength, is launched up-conversion fluorescence; Sealing coat, for the isolation of up-conversion luminescence layer and lower conversion luminescence layer, is avoided influencing each other between two luminescent layers; Passivation layer, for strengthening stability of photoluminescence and the luminous efficiency of nano particle, reduces the impact of external environment on up/down conversion fluorescence.Double mode fluorescence imaging nano material provided by the invention, will be for later providing a kind of brand-new thinking based on structure design regulation and control fluorescence excitation and transmitting site, thereby provide a strong instrument and platform for its application in various fields.
Core@shell 1@shell 2@shell 3 structures involved in the present invention comprise following several structure formation: lower conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2@passivation layer shells 3; Conversion luminescence layer shell 2@passivation layer shells 3 under up-conversion luminescence core@sealing coat shell 1@; Lower conversion luminescence core@up-conversion luminescence layer shell 1@passivation layer shell 2; Conversion luminescence layer shell 1@passivation layer shell 2 under up-conversion luminescence core@; Conversion luminescence layer shell 1 under up-conversion luminescence core@; Lower conversion luminescence core@up-conversion luminescence layer shell 1.
In the present invention, described lower conversion luminescence layer comprises matrix and luminescence center; Wherein, substrate material is selected from: fluorochemical, oxide compound, oxysulfide, halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9; Luminescence center is Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+in one or several; The molar content of luminescence center is 0.01% ~ 50%; This lower conversion luminescence layer can be under the exciting of certain wavelength, and for example 800 nm exciting lights, launch corresponding down-conversion fluorescent.
In the present invention, described up-conversion luminescence layer comprises matrix, sensitivity speck and luminescence center; Wherein, substrate material comprises: fluorochemical, oxide compound, oxysulfide, halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9; Sensitivity speck is Nd
3+, Yb
3+in a kind of or two kinds; The molar content of sensitivity speck is 0.01% ~ 60%; Luminescence center is Er
3+, Tm
3+, Ho
3+in one or several; The molar content of luminescence center is 0.01% ~ 10%; This up-conversion luminescence layer can be under the exciting of certain wavelength, and for example 980 nm or 800 nm exciting lights, launch corresponding up-conversion fluorescence.
In the present invention, described sealing coat and passivation layer form by substrate material; Substrate material comprises: fluorochemical, oxide compound, oxysulfide, halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9.
The invention provides above-mentioned 800 nm and excite Nd
3+the synthetic method of the up/down conversion bimodulus fluorescent nano material of sensitization, concrete steps are as follows:
(1) preparation of shell presoma:
The preparation of a, earth solution presoma: the salt of rare earth is dissolved in the middle of high boiling solvent under vacuum condition; Wherein, the salt of rare earth is selected from: muriate, nitrate, acetate, oxide compound, trifluoroacetate, acetylacetonate; The rare earth element comprising is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; High boiling solvent is: one or several in oleic acid, stearic acid, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, octadecylene, whiteruss, sweet oil; Solvent temperature is 20-150 degree Celsius, and preferably temperature is 100-140 degree Celsius; The concentration of final gained solution be 0.01 mol/L to 5 mol/L, preferred concentration is 0.1-2 mol/L;
The preparation process of b, sodium trifluoroacetate/potassium/lithium/barium solution is: by sodium trifluoroacetate/potassium/lithium/barium salt, i.e. sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or trifluoroacetic acid barium, is dissolved in high boiling solvent; High boiling solvent is: one or several in oleic acid, stearic acid, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, octadecylene, whiteruss, sweet oil; Solvent temperature is 20-150 degree Celsius, and preferably temperature is 30-80 degree Celsius; The concentration of final gained solution be 0.01 mol/L to 5 mol/L, preferred concentration is 0.4-3 mol/L.
(2) lower conversion or upper conversion nano nucleus synthetic: adopting oleic acid, oily ammonia, trioctylphosphine, octadecylene, whiteruss is high-temperature solvent, rare earths material employing rare earth chloride, rare earth trifluoroacetate, rare earth nitrate, or lanthanon acetate; Reactant should comprise one or several in Neutral ammonium fluoride, Sodium Fluoride, lithium fluoride, Potassium monofluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide; Under 200-320 degrees Celsius, nitrogen atmosphere, react, obtain dispersed and homogeneity upper conversion or lower conversion nano nucleus preferably.
(3) core shell 1 structure nano crystalline substance is synthetic: nanocrystalline as core taking what prepare in previous step, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, and introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution be 10:1 to 1:10, preferred proportion is that 2:1 is to 1:2.
(4) core shell 1 shell 2 structure nano crystalline substances is synthetic: taking the core shell 1 structure nano crystalline substance prepared in previous step as core, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution be 10:1 to 1:10, preferred proportion is that 2:1 is to 1:2.
(5) core shell 1 shell 2 shell 3 nano-crystal with core-shell structure is synthetic: taking the core shell 1 shell 2 structure nano crystalline substances prepared in previous step as core, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution be 10:1 to 1:10, preferred proportion is that 2:1 is to 1:2.
Between core@shell 1@shell 2@shell 3 different layers of synthesized of the present invention, work in coordination with and bring into play different separately effects, finally realized under low thermal effect 800 nm exciting lights, possess the bimodulus fluorescent probe of upper conversion and down-conversion fluorescent simultaneously.Nd
3+, Yb
3+, Er
3+the NaGdF of three doping
4: Nd, Yb, the upper conversion layer of Er is due to Nd
3+introducing the exciting light of upper conversion has been extended to 800 about nm from 980 nm, realized the fluorescence process of near infrared (800 nm) to visible ray (540 nm).This process has met the requirement of external fluorescent probe above-mentioned completely.In addition due to NaGdF
4: the synergy of Nd core, typical near infrared (800 nm) is also realized to the down-conversion fluorescent of near infrared (860-895 nm) simultaneously in a nano particle.Due to low heat effect, the dark advantage such as the tissue penetration degree of depth, high luminous efficiency, this material also can be employed in the middle of live body whole body imaging field simultaneously.The design of the double mode fluorescence imaging in the present invention is synthetic will be for provide a kind of brand-new thinking based on structure design regulation and control fluorescence excitation and transmitting site later, thereby provide a strong instrument and platform for its application in various fields.
Brief description of the drawings
Fig. 1. Nd
3+the structural representation of the up/down conversion bimodulus fluorescent nano material of sensitization.
Fig. 2. prepared NaGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaYF
4the transmission electron microscope photo of lower conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2@passivation layer shell 3 structure nano crystalline substances.
Fig. 3. prepared NaGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaYF
4angle of elevation annular details in a play not acted out on stage, but told through dialogues-scanning transmission electron microscope image of lower conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2@passivation layer shell 3 structure nano crystalline substances.
Fig. 4. prepared NaGdF
4: conversion luminescence core, NaGdF under Nd
4: Nd@NaYF
4lower conversion luminescence core@sealing coat shell 1, NaGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2, NaGdF under Er
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaYF
4the lower conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2 fluorescence spectrum figures of@passivation layer shell 3 structure nano crystalline substances under 800 nm near infrared lights excite.
Embodiment
The invention is further illustrated by the following examples.
embodiment 1:naGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaYF
4the upper conversion of lower conversion core@sealing coat shell 1@shell 2@protective layer shell 3 800 nm excite Nd
3+the up/down conversion bimodulus fluorescent nano material preparation of sensitization.Concrete steps are as follows:
(1) preparation of shell presoma.
Y-OA(0.1 M) the preparation of presoma: getting tri-mouthfuls of round-bottomed flasks of 50 mL is reaction vessel, adds successively 2.5 mmol YCl
3, 10 mL oleic acid (OA), 15 mL octadecylenes (ODE).Under vacuum and magnetic agitation condition, be heated to 140 degrees Celsius and keep 1 hour, finally obtain the Y-OA(0.1 M of clear) presoma.
Gd-OA(0.10 M), Nd-OA(0.10 M), Yb-OA(0.10 M) and, Er-OA(0.10 M), and Tm-OA(0.10 M) preparation of presoma: Gd-OA, Nd-OA, Yb-OA, Er-OA, the preparation of the preparation of going before Tm-OA and above-mentioned Y-OA presoma is similar, by the YCl in above-mentioned
3replace with respectively GdCl
3, NdCl
3, YbCl
3, ErCl
3, TmCl
3.
The preparation of Na-TFA-OA presoma: getting tri-mouthfuls of round-bottomed flasks of 25 mL is reaction vessel, adds 4 mmol sodium trifluoroacetates and 10 mL oleic acid successively, and under vacuum and agitation condition, room temperature is dissolved, and obtains the Na-TFA-OA precursor solution of water white transparency clarification.
(2) NaGdF
4: under Nd, change nanocrystalline the synthesizing of core.
Getting tri-mouthfuls of round-bottomed flasks of 50 mL is reaction vessel, first adds 0.95 mmol GdCl
3, 0.05 mmol NdCl
3; Add subsequently 4 mL oleic acid (OA), 15 mL octadecylenes (ODE).Said mixture is heated with stirring to 140
oc, vacuum hydro-extraction deoxidation 60 minutes, finally obtains transparent mixed solution.Be cooled to after room temperature until this clear solution, by 2.5 mmol NaOH and 4 mmol NH
4f is dissolved in 10 mL methanol solutions and mixes and to inject above-mentioned reaction soln and react.After continuously stirring 20 minutes, by reactant under high-purity argon gas protection with 10
oCthe speed of/min is warming up to 290 degrees Celsius and insulation reaction 100 minutes.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(3) NaGdF
4: Nd@NaYF
4synthesizing of lower conversion core@sealing coat nano-crystal with core-shell structure.
Get the above-mentioned purification liquid of 3.5 mL (~ 2.5 mmlol) in 4 mL oleic acid (OA), 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then in reaction flask, alternately drip 1 mL Y-OA presoma and 0.5 mL Na-TFA-OA presoma.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(4) NaGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, changes the synthetic of the upper conversion layer nano-crystal with core-shell structure of core@sealing coat@under Er.
By the NaGdF of gained in upper step
4: Nd@NaYF
4lower conversion core@sealing coat nano-crystal with core-shell structure is in 4 mL oleic acid (OA), and 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then to alternately dripping 1 mL Gd-Nd-Yb-Er-OA presoma (by Gd-OA, Nd-OA, Yb-OA, Er-OA presoma mixes according to a certain percentage) and 0.5 mL Na-TFA-OA presoma in reaction flask.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(5) NaGdF
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaGdF
4synthesizing of the upper conversion layer@passivation layer nano-crystal with core-shell structure of lower conversion core@sealing coat@.
By the NaGdF of gained in upper step
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, changes the upper conversion layer nano-crystal with core-shell structure of core@sealing coat@in 4 mL oleic acid (OA) under Er, and 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then in reaction flask, alternately drip 1 mL Y-OA presoma and 0.5 mL Na-TFA-OA presoma.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in hexanaphthene for subsequent use.
Prepared NaGdF in this example
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaGdF
4the upper conversion layer@passivation layer nano-crystal with core-shell structure of lower conversion core@sealing coat@is under the exciting of 800 nm near infrared lights, so because the existence of upper conversion layer can be sent green and the red upper conversion visible ray of 550 nm left and right and 650 nm left and right; So can send again the lower conversion near infrared light of 860 ~ 895 nm simultaneously due to the existence of lower conversion layer.
embodiment 2:naYF
4: Nd, Yb, Tm@NaYF
4@NaYF
4: Nd@NaYF
4under upper conversion core@sealing coat shell 1@, change shell 2@protective layer shell 3 800 nm and excite Nd
3+the up/down conversion bimodulus fluorescent nano material preparation of sensitization.Concrete steps are as follows:
(1) preparation of shell presoma.
Y-OA(0.1 M) the preparation of presoma: getting tri-mouthfuls of round-bottomed flasks of 50 mL is reaction vessel, adds successively 2.5 mmol YCl
3, 10 mL oleic acid (OA), 15 mL octadecylenes (ODE).Under vacuum and magnetic agitation condition, be heated to 140 degrees Celsius and keep 1 hour, finally obtain the Y-OA(0.1 M of clear) presoma.
Gd-OA(0.10 M), Nd-OA(0.10 M), Yb-OA(0.10 M) and, Er-OA(0.10 M), and Tm-OA(0.10 M) preparation of presoma: Gd-OA, Nd-OA, Yb-OA, Er-OA, the preparation of the preparation of going before Tm-OA and above-mentioned Y-OA presoma is similar, by the YCl in above-mentioned
3replace with respectively GdCl
3, NdCl
3, YbCl
3, ErCl
3, TmCl
3.
The preparation of Na-TFA-OA presoma: getting tri-mouthfuls of round-bottomed flasks of 25 mL is reaction vessel, adds 4 mmol sodium trifluoroacetates and 10 mL oleic acid successively, and under vacuum and agitation condition, room temperature is dissolved, and obtains the Na-TFA-OA precursor solution of water white transparency clarification.
(2) NaYF
4: Nd, Yb, what the upper conversion of Tm core was nanocrystalline synthesizes.
Getting tri-mouthfuls of round-bottomed flasks of 50 mL is reaction vessel, first adds 0.79 mmol YCl
3, 0.005 mmol NdCl
3, 0.2 mmol YbCl
3, 0.005 mmol TmCl
3; Add subsequently 4 mL oleic acid (OA), 15 mL octadecylenes (ODE).Said mixture is heated with stirring to 140
oc, vacuum hydro-extraction deoxidation 60 minutes, finally obtains transparent mixed solution.Be cooled to after room temperature until this clear solution, by 2.5 mmol NaOH and 4 mmol NH
4f is dissolved in 10 mL methanol solutions and mixes and to inject above-mentioned reaction soln and react.After continuously stirring 20 minutes, by reactant under high-purity argon gas protection with 10
oCthe speed of/min is warming up to 290 degrees Celsius and insulation reaction 100 minutes.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(3) NaYF
4: Nd, Yb, Tm@NaYF
4synthesizing of upper conversion core@sealing coat nano-crystal with core-shell structure.
Get the above-mentioned purification liquid of 3.5 mL (~ 2.5 mmlol) in 4 mL oleic acid (OA), 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then in reaction flask, alternately drip 1 mL Y-OA presoma and 0.5 mL Na-TFA-OA presoma.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(4) NaYF
4: Nd, Yb, Tm@NaYF
4@NaYF
4: under the upper conversion of Nd core@sealing coat@, conversion layer nano-crystal with core-shell structure is synthetic.
By the NaYF of gained in upper step
4: Nd, Yb, Tm@NaYF
4upper conversion core@sealing coat nano-crystal with core-shell structure is in 4 mL oleic acid (OA), and 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then in reaction flask, alternately drip 1 mL Y-Nd-OA presoma (Y-OA and Nd-OA presoma are mixed according to a certain percentage) and 0.5 mL Na-TFA-OA presoma.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in 15 mL hexanaphthenes for subsequent use.
(5) NaYF
4: Nd, Yb, Tm@NaYF
4@NaYF
4: Nd@NaYF
4under upper conversion core@sealing coat@, conversion layer@passivation layer nano-crystal with core-shell structure is synthetic.
By the NaYF of gained in upper step
4: Nd, Yb, Tm@NaYF
4@NaYF
4: under the upper conversion of Nd core@sealing coat@, conversion layer nano-crystal with core-shell structure is in 4 mL oleic acid (OA), and 6 mL octadecylenes (ODE) are mixed and heated to 70 degrees Celsius, keep removing for 30 minutes hexanaphthene and the oxygen in reaction system under vacuum condition.Then by reaction system with 20
oCthe speed of/min is warming up to 280 degrees Celsius.Then in reaction flask, alternately drip 1 mL Y-OA presoma and 0.5 mL Na-TFA-OA presoma.Be 15 minutes each interval time dripping.Dripping number of times can adjust according to the needs of shell thickness.After question response finishes, reaction mother liquor is cooled to 50
oCafter add ethanol to make product Precipitation from solution, centrifugal subsequently, obtain product after using dehydrated alcohol repetitive scrubbing 3-5 time, and product be dissolved in hexanaphthene for subsequent use.
Prepared NaYF in this example
4: Nd, Yb, Tm@NaYF
4@NaYF
4: Nd@NaYF
4under upper conversion core@sealing coat@, conversion layer@passivation layer nano-crystal with core-shell structure is under the exciting of 800 nm near infrared lights, so because the existence of upper conversion layer can be sent the 450 blue upper conversion visible rays in nm left and right; So can send again the lower conversion near infrared light of 860 ~ 895 nm simultaneously due to the existence of lower conversion layer.
embodiment 3:prepared NaGdF in example 1
4: Nd@NaYF
4@NaGdF
4: Nd, Yb, Er@NaGdF
4the upper conversion layer@passivation layer nano-crystal with core-shell structure of lower conversion core@sealing coat@be have hydrophobic surperficial, by parents' molecule to its modification can by nanocrystalline gained become water-soluble, thereby make it have better biocompatibility.Gained water-solubility nanocrystalline and cell are hatched to cultivation, nano particle is gulped down and is entered cell by Inner, utilize this nanocrystallinely to have green and red visible ray up-conversion fluorescence and a near infrared down-conversion fluorescent, we can carry out multimodal imaging to cell simultaneously.In addition, obtained water-soluble upper conversion nano crystalline substance is arrived by tail vein injection in the body of mouse, we just can utilize the near infrared down-conversion fluorescent of nano particle to carry out living imaging.Because the excitation light source of the lower conversion near-infrared fluorescent of this nano particle is also in infrared window, so adopt the living imaging that this nano particle carries out just to have better signal to noise ratio.
Claims (6)
1. a Nd
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that: be the up/down conversion bimodulus fluorescent nano material that 800 nm of core@shell 1@shell 2@shell 3 structures excite; Comprise following four integral parts: lower conversion luminescence layer, up-conversion luminescence layer, sealing coat and passivation layer;
Wherein, described core@shell 1@shell 2@shell 3 structures comprise following several structure: lower conversion luminescence core@sealing coat shell 1@up-conversion luminescence layer shell 2@passivation layer shells 3; Conversion luminescence layer shell 2@passivation layer shells 3 under up-conversion luminescence core@sealing coat shell 1@; Lower conversion luminescence core@up-conversion luminescence layer shell 1@passivation layer shell 2; Conversion luminescence layer shell 1@passivation layer shell 2 under up-conversion luminescence core@; Conversion luminescence layer shell 1 under up-conversion luminescence core@; Lower conversion luminescence core@up-conversion luminescence layer shell 1.
2. Nd according to claim 1
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that described lower conversion luminescence layer comprises matrix and luminescence center; Wherein, substrate material is: fluorochemical, oxide compound,, oxysulfide or halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9; Luminescence center is Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+in one or several; The molar content of luminescence center is 0.01% ~ 50%; This lower conversion luminescence layer can, under the exciting of certain wavelength, be launched corresponding down-conversion fluorescent.
3. Nd according to claim 1
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that described up-conversion luminescence layer comprises matrix, sensitivity speck and luminescence center three parts; Wherein, substrate material is: fluorochemical, oxide compound, oxysulfide or halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9; Sensitivity speck is Nd
3+, Yb
3+in a kind of or two kinds; The molar content of sensitivity speck is 0.01% ~ 60%; Luminescence center is Er
3+, Tm
3+, Ho
3+in one or several; The molar content of luminescence center is 0.01% ~ 10%; This up-conversion luminescence layer can, under the exciting of certain wavelength, be launched corresponding up-conversion fluorescence.
4. Nd according to claim 1
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that described sealing coat is made up of substrate material; This substrate material is: fluorochemical, oxide compound, oxysulfide or halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9.
5. Nd according to claim 1
3+the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that described passivation layer is made up of substrate material; This substrate material is: fluorochemical, oxide compound, oxysulfide or halogenide; Fluorochemical is: CaF
2, BaF
2, LaF
3, YF
3, ZnF
2, NaYF
4, LiYF
4, KYF
4, BaYF
4, NaGdF
4or NaLuF
4; Oxide compound is: La
2o
3, Y
2o
3, Gd
2o
3or Lu
2o
3; Oxysulfide is Y
2o
2s, CaS
2or La
2s
3; Halogenide is Cs
3lu
2br
9.
6. Nd according to claim 1
3+the synthetic method of the up/down conversion bimodulus fluorescent nano material of sensitization, is characterized in that concrete steps are as follows:
(1) preparation of shell presoma:
The preparation of a, earth solution presoma: the salt of rare earth is dissolved in the middle of high boiling solvent under vacuum condition; Wherein, the salt of rare earth is selected from: muriate, nitrate, acetate, oxide compound, trifluoroacetate, acetylacetonate; The rare earth element comprising is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; High boiling solvent is: one or several in oleic acid, stearic acid, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, octadecylene, whiteruss, sweet oil; Solvent temperature is 20-150 degree Celsius; The concentration of final gained solution is that 0.01 mol/L is to 5 mol/L;
The preparation of b, sodium trifluoroacetate/potassium/lithium/barium solution: by sodium trifluoroacetate/potassium/lithium/barium salt, i.e. sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or trifluoroacetic acid barium, is dissolved in high boiling solvent; High boiling solvent is: one or several in oleic acid, stearic acid, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, octadecylene, whiteruss, sweet oil; Solvent temperature is 20-150 degree Celsius; The concentration of final gained solution is that 0.01 mol/L is to 5 mol/L;
(2) lower conversion or upper conversion nano nucleus synthetic: adopting oleic acid, oily ammonia, trioctylphosphine, octadecylene, whiteruss is high-temperature solvent, rare earths material employing rare earth chloride, rare earth trifluoroacetate, rare earth nitrate, or lanthanon acetate; Reactant also should comprise one or several in Neutral ammonium fluoride, Sodium Fluoride, lithium fluoride, Potassium monofluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide; Under 200-320 degree Celsius, nitrogen atmosphere, react, obtain dispersed and homogeneity upper conversion or lower conversion nano nucleus preferably;
(3) core shell 1 structure nano crystalline substance is synthetic: nanocrystalline as core taking what prepare in previous step, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, and introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution is that 10:1 is to 1:10;
(3) core shell 1 shell 2 structure nano crystalline substances is synthetic: taking the core shell 1 structure nano crystalline substance prepared in previous step as core, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution is that 10:1 is to 1:10;
(4) core shell 1 shell 2 shell 3 nano-crystal with core-shell structure is synthetic: taking the core shell 1 shell 2 structure nano crystalline substances prepared in previous step as core, under hot conditions, according to the composition needs of shell, alternately introduce continuously shell precursor solution, introducing mode is for dripping, and temperature is 150-340 degree Celsius; Each volume ratio of introducing high boiling point earth solution and sodium trifluoroacetate/potassium/lithium/barium solution is that 10:1 is to 1:10.
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Application publication date: 20140618 |