CN103224787B - Rear-earth-doped alkali earth metal fluoride nano material and its preparation and application - Google Patents
Rear-earth-doped alkali earth metal fluoride nano material and its preparation and application Download PDFInfo
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Abstract
The present invention discloses a kind of water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material with following component：xLn3+‑yNa+‑[1‑(x+y)]MF2, wherein Ln3+Selected from Ce3+、Yb3+、Er3+、Tm3+、Ho3+、Eu3+、Gd3+、Tb3+、Dy3+、Sm3+、Nd3+Or Pr3+In one kind or any a variety of；M is selected from Ca, Sr or Ba；0<X≤50 mol%, 0<The mol% of y≤50.The material has preferably water-soluble and luminescent properties, can be applied to the field such as biological detection and bio-imaging.
Description
Technical field
The present invention relates to a kind of rear-earth-doped inorganic nano material and its preparation and application, more particularly, to a kind of water-soluble
The synthesis of rear-earth-doped alkali earth metal fluoride nano fluorescent marker material and its biological detection with bio-imaging field
Application.
Background technology
Rear-earth-doped phosphor obtains extensive concern in recent years, and these materials are in some traditional fields such as mercury-free
Fluorescent lamp, flat-panel monitor, solid-state laser, optical storage, LED, solar cell etc., which all embody, greatly applies valency
Value, wherein application of the rear-earth-doped inorganic nano material most strikingly risen recently in terms of fluorescent biolabels.
With traditional fluorescence labeling material（Such as fluorescent dye and quantum dot）Compare, rear-earth-doped inorganic nano material has high chemistry
The comprehensive advantages such as stability, long fluorescence lifetime, hypotoxicity, tunable fluorescence emission wavelengths and bigger tissue penetration depths, it is
The fluorescent biolabels material of new generation generally having an optimistic view of at present.However, fluorescence labeling material to the size of nano particle, pattern,
Dispersiveness, water-soluble and biocompatibility etc. suffer from high requirement, the especially nanometer to monodispersed 10 below nm
Grain has special demand.Therefore, the small size for preparing uniform single dispersing, appearance and size, good water solubility and bio-compatible is received
Rice grain is such materials application in a premise of fluorescent biolabels.
In the material system reported at present, fluoride is due to high chemical stability, low phonon energy（300 -
500cm-1）, it is a kind of preferably rear-earth-doped host material.Wherein, alkali earth metal fluoride（CaF2、SrF2、BaF2）As height
The upper conversion of effect and down-conversion luminescent material, its biocompatibility is splendid, thus receives much concern.Synthesize single dispersing, pattern chi
Very little uniform alkaline earth fluoride nano granule mainly has two methods at present：Solvent heat and the side of trifluoroacetate thermal decomposition
Method（Bibliography：Li Yadong et al., Upconversion Luminescence of Monodisperse CaF2:
Yb3+/Er3+ Nanocrystals, J. Am. Chem. Soc., 131, 14200-14201 (2009); Yan
Chunhua et al., Uniform Alkaline Earth Fluoride Nanocrystals with Diverse
Shapes Grown from Thermolysis of Metal Trifluoroacetates in Hot Surfactant
Solutions, Cryst. Growth & Des., 9, 2013-2019 (2009)）.Solvent-thermal method needs special reaction
Device（Autoclave）, and the reaction time is longer（12-36 hours）, more consume energy；Other solvent-thermal method can not carry out core shell structure
Growth, this up-conversion luminescence for small nano particle is very unfavorable, and often particle is smaller, and the group on surface is to the upper of rare earth ion
It is more severe to change luminescence queenching, and it is a raising up-conversion luminescence well that a shell is coated on the basis of original core
Scheme, but the method for solvent heat can not also accomplish this point.The method of trifluoroacetate thermal decomposition can be released during the course of the reaction
The toxic gases such as hydrogen fluoride are released, this is all a kind of very big injury for human body and environment.Further, since rare earth ion exists
It is aliovalent doping in alkali earth metal fluoride, therefore carry out the rear-earth-doped of various concentrations to cause nanocrystalline pattern, size
Change a lot（Bibliography：Wang Yuansheng et al., Modifying the Size and Shape
of Monodisperse Bifunctional Alkaline-Earth Fluoride Nanocrystals through
Lanthanide Doping, J. Am. Chem. Soc., 132, 9976-9978 (2010)）.In view of the above-mentioned problems, this
Simple, green, environmentally friendly synthesis method is taken in invention, makees surfactant using oleic acid, sodium ion is as nucleator and electric charge
Compensation, the method being co-precipitated by high temperature have synthesized 10 below nm rear-earth-doped alkali earth metal fluoride and its nucleocapsid knot
Structure nano particle.The alkaline earth fluoride nano granule surface synthesized carries oily sulfonate groups, can be well dispersed in
In the non-polar organic solvents such as hexamethylene, chloroform, toluene；Due to the effect of sodium ion, pattern, the chi of obtained nano particle
It is very little big change not to occur with the species and concentration of doping with rare-earth ions, and the crystallization of nano particle is obtained for luminescent properties
Very big raising；Epitaxial growth is carried out on the basis of core, Core-shell Structure Nanoparticles can be made, so as to significantly increase upper conversion
It is luminous；The oleic acid of nano grain surface is exchanged using hydrophilic surfactant actives such as phosphoethanolamines, its surface modification can be made
Upper substantial amounts of amino or carboxyl functional group, so as to realize water solubility；Simultaneously can further conjugated biological molecules, applied to biology examine
The field such as survey and bio-imaging.
The content of the invention
It is an object of the invention to propose that a kind of be co-precipitated by high temperature is mixed with the step synthesizing water-solubility rare earth of ligand exchange two
The method of miscellaneous alkali earth metal fluoride nano fluorescent marker material.
The present invention adopts the following technical scheme that：
Water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material with following component：xLn3+-yNa+-[1-(x+
y)]MF2, wherein Ln3+Selected from Ce3+、Yb3+、Er3+、Tm3+、Ho3+、Eu3+、Gd3+、Tb3+、Dy3+、Sm3+、Nd3+Or Pr3+In one
Kind is any a variety of；M is selected from Ca, Sr or Ba；0<X≤50 mol%, 0<The mol% of y≤50.
The average-size of the material is less than 10 nm.
Described nano material is used for biological detection and bio-imaging.
The preparation method of described nano material, comprises the following steps：
(1) the rear-earth-doped alkaline earth fluoride nano granule of oil-soluble is prepared：With Alkaline Earth Metal Acetate and rare earth vinegar
Hydrochlorate is raw material, then adds oleic acid and octadecylene, is dissolved by heating under inert gas shielding, forms solution A, and be cooled to 70
Below DEG C；Sodium fluoride or ammonium fluoride are separately formed into solution B with sodium hydroxide dissolving in methyl alcohol, solution B is added in solution A
Formed mixed solution C, then heating exclude methanol, be warming up to 250-300 DEG C insulation a period of time after be down to room temperature, add acetone or
Ethanol precipitation is separated and washed, that is, obtains the rear-earth-doped alkaline earth fluoride nano granule of oil-soluble；
(2) step is utilized（1）Obtained nano particle prepares described water miscible rear-earth-doped alkali earth metal fluoride
Nano material.
In foregoing preparation process, the addition mole ratio of reactant（Relative to metal acetate salt total amount）For：
Alkaline Earth Metal Acetate：0.5~1；
Lanthanon acetate：0 ~0.5；
Sodium fluoride：1~3；
Ammonium fluoride：1~3；
Sodium hydroxide：0~3；
Oleic acid：3~10；
Octadecylene：0~20.
The present invention also provides the water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material with following component：xLn3+-
yNa+-[1-(x+y)]MF2, wherein Ln3+Selected from Ce3+、Yb3+、Er3+、Tm3+、Ho3+、Eu3+、Gd3+、Tb3+、Dy3+、Sm3+、Nd3+Or
Pr3+In one kind or any a variety of；M is selected from Ca, Sr or Ba； 0<X≤50 mol%, 0<The mol% of y≤50；The material is core
Shell structure.
The preparation method of described nano material, comprises the following steps：
(1) the rear-earth-doped alkaline earth fluoride nano granule kernel of oil-soluble is prepared：With Alkaline Earth Metal Acetate with it is dilute
Native acetate is raw material, then adds oleic acid and octadecylene, is dissolved by heating under inert gas shielding, forms solution A, and cool
To less than 70 DEG C；Sodium fluoride or ammonium fluoride are separately formed into solution B with sodium hydroxide dissolving in methyl alcohol, solution B added molten
Mixed solution C is formed in liquid A, then heating excludes methanol, is down to room temperature after being warming up to 250-300 DEG C of insulation a period of time, adds
Acetone or alcohol precipitation is separated and washed, and is then dissolved in 5-20 mL hexamethylenes, forms solution D；
(2) the rear-earth-doped alkali earth metal fluoride Core-shell Structure Nanoparticles of oil-soluble are prepared：With Alkaline Earth Metal Acetate
It is raw material with lanthanon acetate, then adds oleic acid and octadecylene, dissolved by heating under inert gas shielding, forms clear solution
E simultaneously cools, while will be such as step（1）The solution D is added in E side by side except hexamethylene is down to room temperature again, is separately dissolved ammonium fluoride
Clear solution F is formed in methyl alcohol, solution F is added mixed solution G is formed in solution E, and then heating excludes methanol, is warming up to
Room temperature is down to after 250-300 DEG C of insulation a period of time, adds acetone or alcohol precipitation to separate and wash, that is, obtains oil-soluble rare earth and mixes
Miscellaneous alkali earth metal fluoride Core-shell Structure Nanoparticles；
(3) step is utilized（2）Obtained nano particle prepares described water-solubility rare-earth adulterated alkaline-earth metal fluoride and received
Rice material, the material is core shell structure.
The sign of the nano material.Pass through X-ray powder diffraction（XRD）Detection shows the oil-soluble alkaline earth gold prepared
It is pure cube phase structure to belong to fluoride nano material.X-ray energy spectrum is analyzed（EDS）As a result contain in the material for confirming to synthesize
The Na and rare earth element for having Ca/Sr/Ba, F and being adulterated.Transmission electron microscope（TEM）What test display obtained is that average-size is 4
Nm extra small dispersed nano particle and the Core-shell Structure Nanoparticles that average-size is 6-10 nm.Fluorescence spectrum tests table
CaF that is bright, being dispersed in hexamethylene2:Ce/Tb/Na and CaF2:Eu/Na oil solubility nanometer particles are respectively provided with stronger seeing below and turned
Light is changed, and the doping of sodium ion significantly improves CaF2:Ce/Tb luminous has simultaneously elongated its fluorescence lifetime.Swash in 980 nm
Light excites down, the CaF being dispersed in hexamethylene2:Er/Yb/Na and CaF2:Tm/Yb/Na oil-soluble Core-shell Structure Nanoparticles are equal
With stronger visible up-conversion luminescence.The nano particle of the modified water-soluble nanoparticles in surface and Bioconjugation can be by red
Outside, thermogravimetric, ζ-potential etc. characterize.Thermogravimetric analysis（TGA）As a result oil solubility nanometer particle and phosphoethanolamine are shown（AEP）Bag
The water-soluble nanoparticles covered have visibly different weightless temperature scope, show that nano grain surface state becomes there occurs obvious
Change.FFIR（FTIR）Show, there is nano grain surface after ligand exchange apparent corresponds to phosphoric acid
The infrared vibration absworption peak of monoethanolamine：1078 cm-1Correspond to P-O vibration absorption peak；1642 cm-1Then correspond to-NH2
Vibration absorption peak, and corresponding to oleic acid long-chain-CH2- the cm of vibration absorption peak 2854 and 2924-1After ligand exchange
Intensity substantially weakens, and these results show that successfully phosphoethanolamine has been gone up in modification to nano grain surface；It is biotinylated to receive
Rice grain is in 1678 cm-1There is obvious amido link vibration peak in place, shows that nano grain surface is connected to biotin molecule.
ζ-potential shows that after ligand exchange nano particle carries+46.8 mV positive potential, it was demonstrated that phosphoethanolamine can wrap well
Overlay on nano grain surface；Biotinylation and coupling urokinase amino end segment（ATF）After albumen, ζ-potential of nano particle
It is changed into+24.5 mV and+9.4 mV respectively, nano grain surface can be successfully incorporated in by indicating biotin and ATF albumen.
The biological detection application of the nano material can pass through the out-phase time-resolved fluorescence of biomolecule（TRPL）Detect and equal
Phase time-resolved fluorescence resonant energy transfer（TR-FRET）Detection proves；TRPL testing results show, biomolecule to be detected
（Such as affinity prime）It is in proportionate relationship in the fluorescence signal of finite concentration scope and nano material；TR-FRET testing result tables
It is bright, biomolecule to be detected（Such as affinity prime and ATF albumen）Respectively in finite concentration scope and fluorescein and nano material
The ratio of fluorescence signal intensity be in proportionate relationship.Bio-imaging application is then proved by the targeted imaging of tumour cell；Carefully
Born of the same parents' imaging results show, in urokinase receptor（uPAR）The human lung adenocarcinoma cell H1299 of height expression, due to the nano material pair
The specific recognition of tumour cell, the fluorescence signal of the nano material can be observed；And the people of the uPAR low expressions in control
In embryo lung fibroblast HELF, due in the absence of specific recognition, therefore the nano material can not be seen in such cell
In it is luminous.
Water-solubility rare-earth adulterated alkaline-earth metal fluoride and its core-shell structured nanomaterials are prepared for by the present invention, prepared
Process is simple, synthesis condition is easily controlled, is reproducible.The preparation of oil-soluble nano particle of the present invention with showing both at home and abroad at present
Some solvent heats are compared with trifluoroacetate thermally decomposes two methods, more energy efficient, environmentally friendly and simple to operate, the nanometer of preparation
Grain dispersiveness is more preferable, particle diameter more uniform, controllable, can be coupled using the modified amino in surface or carboxyl with various biomolecule,
Further apply the fields such as biological detection and bio-imaging.
Brief description of the drawings
Following doped samples are molar percentage.
Accompanying drawing 1: (a) CaF2、(b) CaF2: 5%Eu, 5%Na、(c) CaF2:5%Ce, 5%Tb, 10%Na and (d)
CaF2:The X-ray powder diffraction figure of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is MiniFlex2, producer
For Rigaku, copper target radiation wavelength is the nm of λ=0.154187.
Accompanying drawing 2: CaF2The transmission electron microscope picture of nano particle.INSTRUMENT MODEL is JEM-2010, producer JEOL.
Accompanying drawing 3: CaF2:The transmission electron microscope picture of 5%Eu, 5%Na nano particle.INSTRUMENT MODEL is JEM-2010, and producer is
JEOL。
Accompanying drawing 4: CaF2:The transmission electron microscope picture of 5%Ce, 5%Tb, 10%Na nano particle.INSTRUMENT MODEL is JEM-
2010, producer JEOL.
Accompanying drawing 5: CaF2:The transmission electron microscope picture of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is JEM-
2010, producer JEOL.
Accompanying drawing 6: SrF2:The X-ray powder diffraction figure of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is
MiniFlex2, producer Rigaku, copper target radiation wavelength are the nm of λ=0.154187.
Accompanying drawing 7: BaF2:The X-ray powder diffraction figure of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is
MiniFlex2, producer Rigaku, copper target radiation wavelength are the nm of λ=0.154187.
Accompanying drawing 8: SrF2:(a) transmission electron microscope picture and (b) high-resolution of 0.5%Er, 18%Yb, 18%Na nano particle are saturating
Penetrate electron microscope.INSTRUMENT MODEL is JEM-2010, producer JEOL.
Accompanying drawing 9: BaF2:(a) transmission electron microscope picture and (b) high-resolution of 0.5%Er, 18%Yb, 18%Na nano particle are saturating
Penetrate electron microscope.INSTRUMENT MODEL is JEM-2010, producer JEOL.
Accompanying drawing 10： (a) CaF2:0.5%Er, 18%Yb, 18%Na kernel and (b) CaF2: 0.5%Er, 18%Yb,
18%Na@CaF2(c) CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2@CaF2And (d) CaF2: 0.5%Er,18%Yb,
18%Na@CaF2@CaF2@CaF2The X-ray powder diffraction figure of Core-shell Structure Nanoparticles.INSTRUMENT MODEL is MiniFlex2, producer
For Rigaku, copper target radiation wavelength is the nm of λ=0.154187.
Accompanying drawing 11： CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2The transmission electron microscope of individual layer Core-shell Structure Nanoparticles
Figure.INSTRUMENT MODEL is JEM-2010, producer JEOL.
Accompanying drawing 12： CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2@CaF2The transmission of double-deck Core-shell Structure Nanoparticles
Electron microscope.INSTRUMENT MODEL is JEM-2010, producer JEOL.
Accompanying drawing 13：CaF2:The X-ray energy spectrum analysis chart of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is
JSM-6700F, producer JEOL.
Accompanying drawing 14：SrF2:The X-ray energy spectrum analysis chart of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is
JSM-6700F, producer JEOL.
Accompanying drawing 15：BaF2:The X-ray energy spectrum analysis chart of 0.5%Er, 18%Yb, 18%Na nano particle.INSTRUMENT MODEL is
JSM-6700F, producer JEOL.
Accompanying drawing 16: CaF2:The lower conversion of 5%Eu, 5%Na nano particle excites and launching light spectrogram.INSTRUMENT MODEL is
FLS920, producer Edinburgh, excitation source are xenon lamp.
Accompanying drawing 17: CaF2:The lower conversion of 5%Ce, 5%Tb, 10%Na nano particle excites and launching light spectrogram.Instrument
Model FLS920, producer Edinburgh, excitation source are xenon lamp.
Accompanying drawing 18: CaF2:5%Ce, 5%Tb and CaF2:The launching light spectrogram of 5%Ce, 5%Tb, 10%Na nano particle.
INSTRUMENT MODEL is FLS920, and producer Edinburgh, excitation source is xenon lamp.
Accompanying drawing 19: CaF2:5%Ce, 5%Tb and CaF2:The fluorescence decay of 5%Ce, 5%Tb, 10%Na nano particle is bent
Line.INSTRUMENT MODEL is FLS920, and producer Edinburgh, excitation source is xenon lamp.
Accompanying drawing 20: CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2The Up-conversion emission light of Core-shell Structure Nanoparticles
Spectrogram（Excitation wavelength is 980 nm）.INSTRUMENT MODEL is FSP920-C, and producer Edinburgh, excitation source is 980-nm half
Conductor laser.
Accompanying drawing 21: CaF2: 0.5%Tm, 18%Yb, 18%Na@CaF2The Up-conversion emission light of Core-shell Structure Nanoparticles
Spectrogram（Excitation wavelength is 980 nm）.INSTRUMENT MODEL is FSP920-C, and producer Edinburgh, excitation source is 980-nm half
Conductor laser.
Accompanying drawing 22：Oil-soluble and water-soluble CaF2The thermogravimetric curve of Nanoparticles Nanoparticles, INSTRUMENT MODEL STA449C
, producer Netzsch.
Accompanying drawing 23：Oil-soluble, water solubility and biotinylation CaF2The FFIR of nano particle, instrument type
Number be 750, producer Magna.
Accompanying drawing 24：Water-soluble, biotinylation and coupling ATF PROTEIN Cs aF2ζ-potential of nano particle, INSTRUMENT MODEL are
Nano ZS ZEN3600, producer Malvern.
Accompanying drawing 25：Biotinylated CaF2:Ce, Tb, Na nano material are to affinity prime（avidin）Out-phase TRPL
Detection：(a) TRPL detection principle diagrams；(b) TRPL spectrum；(c) standard curve.INSTRUMENT MODEL is Synergy 4, and producer is
BioTek。
Accompanying drawing 26：The CaF of biotinylation and coupling ATF2:Ce, Tb, Na nano material swash to affinity prime and urine respectively
Enzyme acceptor（suPAR）Homogeneous TR-FRET detection：(a) TR-FRET detection principle diagrams；(b) TR-FRET of Avidin is detected
Spectrum；(c) standard curve of Avidin is detected；(d) the TR-FRET spectrum of urokinase receptor are detected；(e) urokinase is detected
The standard curve of acceptor.INSTRUMENT MODEL is Synergy 4, producer BioTek.
Accompanying drawing 27：It is coupled ATF CaF2:Targeted imaging of Ce, Tb, the Na nano material to tumour cell：(a) uPAR is high
The human lung adenocarcinoma cell H1299 of expression imaging schematic diagram；(b) the human embryonic lung fibroblasts HELF of uPAR low expressions into
As schematic diagram.INSTRUMENT MODEL is FV1000, producer Olympus.
Embodiment
The preparation of water-solubility rare-earth adulterated alkaline-earth metal fluoride and its core-shell structured nanomaterials provided by the present invention
Method, its substantive features and Preliminary Applications can further be embodied by following examples.（Following doped samples are
Molar percentage）
Example 1：CaF2:The preparation of 5%Eu, 5%Na nano material.
Weigh 0.167 g Ca (CH3COO)2·H2O and 0.02g Eu (CH3COO)3·4H2O, then add 5 mL oleic acid
With 15 mL octadecylenes, logical nitrogen is heated to 160 °C and is incubated 30 minutes, forms clear solution A, be down to room temperature；Separately by 0.084
g NH4F and 0.084 g NaOH is dissolved in formation clear solution B in 10 mL methanol, solution B is added mixing is formed in solution A
Solution C, be then heated to 60 °C and be incubated 30 minutes exclude methanol, be warming up to 280 °C insulation 1 hour after be down to room temperature, add
Enter 30 mL acetone precipitations and separate and wash the oil-soluble CaF for producing that average-size is 4 nm2:5%Eu, 5%Na nano particle.
Oil solubility nanometer particle is dispersed in 10 mL hexamethylenes, adds 10 mL thereto dissolved with the two of 30 mg tetrafluoro boric acid nitrous
Chloromethanes solution, hybrid reaction are centrifuged after 30 minutes, and obtained precipitation is dispersed in 10 mL dimethylformamides again, added
Enter 0.1 g phosphoethanolamines stirring reaction after 30 minutes, centrifugation is precipitated, and is alternately washed several times with dimethylformamide and water
It can obtain the water-soluble CaF that average-size is 4 nm2:5%Eu, 5%Na nano material.
Example 2：CaF2:The preparation of 5%Ce, 5%Tb, 10%Na nano material.With 0.158 g Ca (CH3COO)2·
H2O、0.02g Ce(CH3COO)3·4H2O and 0.02g Tb (CH3COO)3·4H2O is raw material, synthesis step such as example 1, finally
The water-soluble CaF that average-size is 4nm is made2:5%Ce, 5%Tb, 10%Na nano material.
Example 3：CaF2:The preparation of 0.5%Er, 18%Yb, 18%Na nano particle.With 0.144 g Ca (CH3COO)2·
H2O、0.002g Er(CH3COO)3·4H2O and 0.076g Yb (CH3COO)3·4H2O is raw material, synthesis step such as example 1, most
The water-soluble CaF that obtained average-size is 4nm eventually2:0.5%Er, 18%Yb, 18%Na nano material.
Example 4：CaF2:The preparation of 0.5%Tm, 50%Yb, 50%Na nano material.With 0.0872 g Ca
(CH3COO)2·H2O、0.002g Tm(CH3COO)3·4H2O and 0.211g Yb (CH3COO)3·4H2O is raw material, synthesis step
Such as example 1, the water-soluble CaF that final obtained average-size is 4nm2:0.5%Tm, 18%Yb, 50%Na nano material.
Example 5：SrF2:The preparation of 0.5%Er, 18%Yb, 18%Na nano material.With 0.168 g Sr (CH3COO)2·
0.5 H2O、0.002g Er(CH3COO)3·4H2O and 0.076g Yb (CH3COO)3·4H2O is raw material, synthesis step such as example
1, the water-soluble SrF that final obtained average-size is 4nm2:0.5%Er, 18%Yb, 18%Na nano material.
Example 6：BaF2:The preparation of 0.5%Er, 18%Yb, 18%Na nano material.Weigh 0.208 g Ba
(CH3COO)2、0.002g Er(CH3COO)3·4H2O and 0.076g Yb (CH3COO)3·4H2O, 20 mL oleic acid are then added,
Logical nitrogen is heated to 240 °C and is incubated 1 hour, forms clear solution A, is down to room temperature；Separately by 0.084 g NH4F and 0.084
G NaOH are dissolved in formation clear solution B in 10 mL methanol, and solution B is added in solution A and forms mixed solution C, is then heated
To 60 °C and it is incubated 30 minutes and excludes methanol, is down to room temperature after being warming up to 280 °C of insulations 1 hour, adds 30 mL acetone precipitations
Separate and wash the oil-soluble BaF for producing that average-size is 8 nm2:0.5%Er, 18%Yb, 18%Na nano particle.Oil is molten
Property nano particle is dispersed in 10 mL hexamethylenes, adds dichloromethane of 10 mL dissolved with 25 mg tetrafluoro boric acid nitrous thereto
Solution, hybrid reaction are centrifuged after 30 minutes, and obtained precipitation is dispersed in 10 mL dimethylformamides again, add 0.1 g
After phosphoethanolamine stirring reaction 30 minutes, centrifugation is precipitated, and with dimethylformamide and water, alternately washing can obtain several times
To the water-soluble BaF that average-size is 8 nm2:0.5%Er, 18%Yb, 18%Na nano material.
Example 7: CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2The preparation of core-shell structured nanomaterials.First, strictly according to the facts
Example 3 prepares CaF2:0.5%Er, 18%Yb, 18%Na oil solubility nanometer particle, and take half to be dissolved in 10 mL hexamethylenes and formed
Clear solution A；Then, 0.176 g Ca (CH are weighed3COO)2·H2O, 5 mL oleic acid and 15 mL octadecylenes are then added, lead to nitrogen
Gas is heated to 160 °C and is incubated 30 minutes, forms clear solution B, is down to 80 °C；A is added in B and forms mixed solution C,
30 minutes are incubated under 80 °C and excludes hexamethylene, is down to room temperature；Separately by 0.084 g NH4F is dissolved in 10 mL methanol and formed thoroughly
Bright solution D, solution D is added mixed solution E is formed in solution C, be then heated to 60 °C and be incubated 30 minutes exclusion methanol,
Room temperature is down to after being warming up to 280 °C of insulations 1 hour, is added 30 mL acetone precipitations and is separated and wash that to produce average-size be 7 nm
Oil-soluble CaF2: 0.5%Er, 18%Yb@CaF2Core-shell Structure Nanoparticles.Oil solubility nanometer particle is dispersed in 10 mL rings
In hexane, add dichloromethane solutions of 10 mL dissolved with 20 mg tetrafluoro boric acid nitrous thereto, hybrid reaction after 30 minutes from
The heart, obtained precipitation is dispersed in 10 mL dimethylformamides again, adds 0.1 g phosphoethanolamines stirring reaction 30 and divide
Zhong Hou, centrifugation are precipitated, and it is the water-soluble of 7 nm that with dimethylformamide and water, alternately washing can obtain average-size several times
Property CaF2: 0.5%Er, 18%Yb, 18%Na@CaF2Core-shell structured nanomaterials.
Example 8: CaF2:The out-phase TRPL detections of 5%Ce, 5%Tb, 10%Na nano material.Detecting step is as follows：It is first
First, the 100 μ L to be detected various concentrations affinity prime being dissolved in coating buffer is added in high close plate and under 4 °C
After being incubated an evening, phosphate buffer is used（PBST）Washing three times；Then, 100 μ L confining liquids are added and under 37 °C toward hole
After being incubated 2 hours, confining liquid is outwelled；Then toward adding 100 μ L in hole（50 μg/mL）Described biotinylated nano material
And be incubated 2 hours under 37 °C, after washing three times with PBST, the detection time resolved fluorometric signal in fluorescence plate reader.Due to
The specific binding of affinity prime and biotin so that the nanometer with affinity prime respective amount is combined on high close plate
Grain, the concentration of affinity prime is quantified by the fluorescence intensity of nano particle.Testing result shows that affinity prime is in 0.1-
The fluorescence signal intensity of 20 nanomolar concentration ranges and nano particle is linear, it was demonstrated that the nano material can be used for micro-
Measure the out-phase TRPL detections of biomolecule.
Example 9: CaF2:The homogeneous TR-FRET detections of 5%Ce, 5%Tb, 10%Na nano material.Detecting step is as follows：
First, will be dissolved with 1 mg urokinase receptors（suPAR）500 μ L carbonate buffer solutions and the isothiocyanic acid dissolved with 0.2 mg it is glimmering
Light element（FITC）100 μ L dimethyl sulfoxides（DMSO）Buffer solution is sufficiently mixed, and is reacted a night in 4 °C of lower lucifuges, then 4 °C
Lower dialysis 48 hours so that FITC and suPAR is coupled together and removes unnecessary FITC；100 μ L various concentrations are connected with FITC
SuPAR solution add 96 hole microwell plates in, be subsequently added into 100 μ L（50 μg/mL）Described coupling ATF nano material,
And half an hour is incubated under 37 °C, the then detection time resolved fluorometric signal in fluorescence plate reader.Due to ATF's and suPAR
Specific binding, the nano material that furthered and FITC distance so that nano particle transfers energy to FITC and is allowed to
Launch fluorescence；FITC is relevant with the suPAR concentration added with the relative intensity of the nano material fluorescence signal, therefore can determine
Amount analysis suPAR concentration.TR-FRET testing results show, suPAR albumen in 0.3-800 nanomolar concentration ranges and FITC and
The relative intensity of the nano material fluorescence signal is in proportionate relationship, it was demonstrated that the nano material can be used for micro biomolecule
Homogeneous TR-FRET detection.
Example 10: CaF2:The tumour cell targeted imaging of 5%Ce, 5%Tb, 10%Na nano material.Experimental procedure is such as
Under：First, respectively by the human embryonic lung fibroblasts of human lung adenocarcinoma cell H1299 and the uPAR low expression of the high expression of uPAR
HELF is added in culture plate and with after being cultivated 24 hours under 37 °C of nutrient solution, uses phosphate buffer（PBS）Washing is several times；
Then add under 37 °C of the nutrient solution containing the upper ATF nano materials of coupling described in 500 μ g/mL and be incubated 2 hours, then washed with PBS
Wash the nano particle for removing be not attached to cell for several times；Then, add DAPI dyes core 5 minutes, and washed for several times with PBS；Finally,
Targets identification situation of the nano material to tumour cell is observed using confocal fluorescence microscopy.Cell imaging result shows,
In the human lung adenocarcinoma cell H1299 of the high expression of uPAR, due to ATF and uPAR specific binding, stronger institute can be observed
State the luminous of nano material；And in the human embryonic lung fibroblasts HELF of uPAR low expressions, due to lacking this specific binding,
The luminous of nano material can not be monitored.These results indicate that the nano material can be used by being coupled specific biomolecule
In cancer target bio-imaging.
Claims (7)
1. a kind of water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material, the nano material have following component：xLn3+-
yNa+-[1-(x+y)]MF2, wherein Ln3+Selected from Ce3+、Yb3+、Er3+、Tm3+、Ho3+、Eu3+、Gd3+、Tb3+、Dy3+、Sm3+、Nd3+Or
Pr3+In one kind or any a variety of；M is selected from Ca, Sr or Ba；0<X≤50mol%, 0<Y≤50mol%；The nano material table
The oleic acid in face is exchanged by phosphoethanolamine.
2. nano material according to claim 1, it is characterised in that：The average-size of the nano material is less than 10nm.
3. the preparation method of the nano material described in claim 1 or 2, comprises the following steps：
(1) the rear-earth-doped alkaline earth fluoride nano granule of oil-soluble is prepared：With Alkaline Earth Metal Acetate and lanthanon acetate
For raw material, then add oleic acid and octadecylene, dissolved by heating under inert gas shielding, form solution A, and be cooled to 70 DEG C with
Under；Sodium fluoride dissolving is separately formed into solution B in methyl alcohol, or ammonium fluoride and sodium hydroxide dissolving are formed into solution in methyl alcohol
B；Will solution B add solution A in form mixed solution C, then heating exclude methanol, be warming up to 250-300 DEG C insulation one section when
Between after be down to room temperature, add acetone or alcohol precipitation separate and wash, that is, obtain the rear-earth-doped alkali earth metal fluoride of oil-soluble receive
Rice grain；
(2) nano particle produced using step (1) prepares described water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material
Material, it is the oleic acid for the nano grain surface produced using phosphoethanolamine exchange step (1), it is described water-soluble dilute so as to prepare
Native adulterated alkaline-earth metal fluoride nano material.
4. preparation method according to claim 3, it is characterised in that：Relative to Alkaline Earth Metal Acetate total amount, artificial oil
Dissolubility nano particle process introduces sodium ion and the addition mole ratio of reactant is：
Alkaline Earth Metal Acetate：1；
Lanthanon acetate：0~0.5 and be 0；
If sodium ion, sodium fluoride are introduced with sodium fluoride：1~3；If introducing sodium ion with ammonium fluoride and sodium hydroxide, it is fluorinated
Ammonium：1~3 and sodium hydroxide：0~3 and be 0；
Oleic acid：3~10；
Octadecylene：0~20 and be 0.
5. a kind of water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material, the material is core shell structure；With following component：
xLn3+-yNa+-[1-(x+y)]MF2, wherein Ln3+Selected from Ce3+、Yb3+、Er3+、Tm3+、Ho3+、Eu3+、Gd3+、Tb3+、Dy3+、Sm3+、
Nd3+Or Pr3+In one kind or any a variety of；M is selected from Ca, Sr or Ba；0<X≤50mol%, 0<Y≤50mol%；The nanometer
The oleic acid of material surface is exchanged by phosphoethanolamine.
6. the preparation method of the nano material described in claim 5, comprises the following steps：
(1) the rear-earth-doped alkaline earth fluoride nano granule kernel of oil-soluble is prepared：With Alkaline Earth Metal Acetate and rare earth vinegar
Hydrochlorate is raw material, then adds oleic acid and octadecylene, is dissolved by heating under inert gas shielding, forms solution A, and be cooled to 70
Below DEG C；Sodium fluoride dissolving is separately formed into solution B in methyl alcohol, or ammonium fluoride and sodium hydroxide dissolving are formed in methyl alcohol
Solution B；Solution B is added in solution A and forms mixed solution C, then heating excludes methanol, is warming up to 250-300 DEG C of insulation one
Room temperature is down to after the section time, adds acetone or alcohol precipitation to separate and wash, is then dissolved in 5-20mL hexamethylenes, form solution
D；
(2) the rear-earth-doped alkali earth metal fluoride Core-shell Structure Nanoparticles of oil-soluble are prepared：With Alkaline Earth Metal Acetate with it is dilute
Native acetate is raw material, then adds oleic acid and octadecylene, is dissolved by heating under inert gas shielding, forms clear solution E simultaneously
Cooling, while will be added such as step (1) solution D in E side by side except hexamethylene is down to room temperature again, ammonium fluoride is separately dissolved in first
Clear solution F is formed in alcohol, solution F is added mixed solution G is formed in solution E, then heating excludes methanol, is warming up to 250-
Room temperature is down to after 300 DEG C of insulation a period of times, adds acetone or alcohol precipitation to separate and wash, that is, obtains the rear-earth-doped alkali of oil-soluble
Earth metal fluoride core-shell structure nano particle；
(3) nano particle produced using step (2) prepares described water-solubility rare-earth adulterated alkaline-earth metal fluoride nano material
Material, it is the oleic acid on the shell surface for the nano particle produced using phosphoethanolamine exchange step (2), it is described water-soluble so as to prepare
The rear-earth-doped alkali earth metal fluoride nano material of property, the material is core shell structure.
7. the nano material described in claim 1 or 2 or 5 is being prepared in reagent of the biological detection with bio-imaging
Purposes, the biological detection are glimmering including out-phase time-resolved fluorescence (TRPL) detection, homogeneous phase time discrimination with bio-imaging
Photoresonance energy transmission (TR-FRET) detection, out-phase up-conversion fluorescence (UCL) detection and homogeneous up-conversion fluorescence resonance energy pass
Pass (UC-FRET) detection and cancer target bio-imaging.
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| CN105969347A (en) * | 2016-05-31 | 2016-09-28 | 吉林大学 | Method for acquiring up-conversion white light |
| ES2648639B2 (en) * | 2016-06-30 | 2018-09-06 | Universitat De València | Luminescent upconversion materials and their preparation method |
| CN110272732B (en) * | 2018-03-14 | 2020-10-02 | 中国科学院福建物质结构研究所 | Transition metal ion luminescence-based nano material, preparation method and application thereof |
| CN108469445B (en) * | 2018-03-29 | 2020-09-01 | 福州大学 | Kit for detecting content of cancer antigen in blood without background based on lanthanide fluorescent nanoparticles excited by X-rays and preparation method thereof |
| CN110592678B (en) * | 2019-09-26 | 2020-12-01 | 中国科学院长春光学精密机械与物理研究所 | Method for regulating and controlling surface microstructure of nano crystal with unchanged particle size |
| CN111071991B (en) * | 2020-01-03 | 2021-07-20 | 大连民族大学 | Environment-friendly fluoride nano-material large-scale preparation method |
| JP7085773B2 (en) * | 2020-01-03 | 2022-06-17 | 大連民族大学 | How to scale up environmentally friendly fluoride nanomaterials |
| CN115197703B (en) * | 2021-04-14 | 2024-07-09 | 中国科学院化学研究所 | Method for preparing lanthanum-based rare earth nano particles with assistance of alkali |
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