CN110205126A - The fluorescent material and preparation method and application of fluorescent material, glucan package - Google Patents
The fluorescent material and preparation method and application of fluorescent material, glucan package Download PDFInfo
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- CN110205126A CN110205126A CN201910649257.2A CN201910649257A CN110205126A CN 110205126 A CN110205126 A CN 110205126A CN 201910649257 A CN201910649257 A CN 201910649257A CN 110205126 A CN110205126 A CN 110205126A
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- apatite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
- G01N21/6458—Fluorescence microscopy
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Abstract
The fluorescent material and preparation method and application wrapped up the present invention provides fluorescent material, glucan, belongs to fluorescent material field.The present invention passes through the ion Ba of different radii2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The mode of doping, ion doping are mainly displacement doping, substitute Ca in original rare earth apatite fluorescent material2+Position so that electron transition probability changes, and then improve fluorescence intensity to change the local crystalline field symmetry of former nano material.
Description
Technical field
The present invention relates to fluorescent material technical field more particularly to the fluorescent materials of a kind of fluorescent material, glucan package
And preparation method and application.
Background technique
With the rapid development of nano science and nanotechnology, Study of Nanoscale Rare Earth Luminescent Materials has become scientist and studies extensively
Hot topic, be especially applied to biomedical novel light-emitting nano material and attract wide attention.For traditional phosphor
Material, rare earth up-conversion use near-infrared laser as excitaton source, and tissue penetration is strong.However, rare earth is mixed at this stage
The lower fluorescence intensity of miscellaneous fluorescent nano material is still one of the key technique problem faced on bio-imaging.On apatite
Conversion nano material has good photochemical stability, long fluorescence lifetime, emission spectrum bandwidth and biocompatibility.Existing one
A little research teams are changed and improve the fluorescence intensity of apatite nano material to the content of rare earth ion, but it is as fluorescence
The fluorescence intensity of probe is still lower, is unfavorable for bio-imaging.
Summary of the invention
In consideration of it, the purpose of the present invention is to provide a kind of fluorescent material, the fluorescent material of glucan package and preparation sides
Method and application.The fluorescence intensity of fluorescent material provided by the invention is high, and being conducive to enhancing can bio-imaging.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of fluorescent material, the fluorescent material is that ion doping enhancing can bio-imaging rare earth phosphorus ash
Stone fluorescent material, the ion include Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+, the rare earth apatite fluorescent material includes dilute
Soil doping fluor-apatite nano material or rear-earth-doped hydroxyapatite nanoparticle.
Preferably, the mole of the fluorescent material intermediate ion accounts for ion and Ca2+Mole summation 0~35%.
Preferably, when the rare earth apatite fluorescent material is rare earth apatite upconverting fluorescent material, the rare earth
Rare earth element in apatite upconverting fluorescent material includes the mischmetal of ytterbium and holmium, the mischmetal of ytterbium and erbium or ytterbium and thulium
Mischmetal, when the rare earth apatite fluorescent material is rare earth apatite downconversion fluorescent material, rare earth phosphorus ash
Rare earth element in stone downconversion fluorescent material is terbium or europium.
Preferably, when the rare earth apatite fluorescent material includes ytterbium, the ytterbium is in the rare earth apatite fluorescent material
A mole doping percentage composition in material is 0~60%, mole of the holmium, erbium or thulium in the rare earth apatite fluorescent material
Doping percentage composition independently is 0~5%.
The present invention also provides the preparation methods of the fluorescent material described in above-mentioned technical proposal, when the rare earth apatite is glimmering
When luminescent material is rear-earth-doped fluor-apatite nano material, comprising the following steps:
Octadecylamine, oleic acid and ethyl alcohol are mixed, mixed solution is obtained；
The mixed aqueous solution of calcium nitrate and ion presoma is provided；
Rare earth precursor aqueous solution is provided；
Sodium phosphate aqueous solution is provided；
Sodium fluoride aqueous solution is provided；
By the mixed aqueous solution of calcium nitrate and ion presoma, rare earth precursor aqueous solution, sodium phosphate aqueous solution, sodium fluoride
Aqueous solution and mixed solution mixing, carry out hydro-thermal reaction, obtain hydrothermal product；
The hydrothermal product is started at 19~25 DEG C, after being heated to 700 DEG C with the rate of 1 DEG C/min, then constant temperature 2h,
Then natural cooling obtains the fluorescent material.
The present invention also provides the preparation methods of the fluorescent material described in above-mentioned technical proposal, which is characterized in that when described
When rare earth apatite fluorescent material is rear-earth-doped hydroxyapatite nanoparticle, comprising the following steps:
Forerunner's nitric acid solution is provided；
Calcium phosphate aqueous solution is provided；
Ammonium dibasic phosphate solution is provided；
Concentrated ammonia liquor is provided；
Forerunner's nitric acid solution, calcium phosphate aqueous solution, ammonium dibasic phosphate solution and concentrated ammonia liquor are mixed, hydro-thermal reaction is carried out,
Obtain the fluorescent material.
The present invention also provides a kind of fluorescent materials of glucan package, including fluorescent material described in above-mentioned technical proposal
And glucan, the glucan are wrapped in the surface of fluorescent material described in above-mentioned technical proposal.
Preferably, the mass ratio of the glucan and fluorescent material is 1~3:1.
The present invention also provides the preparation methods of the fluorescent material of the glucan package described in above-mentioned technical proposal, including with
Lower step:
The fluorescent material is mixed with hexamethylene, obtains mixed liquor；
It after glucan is mixed with water, then mixes with the mixed liquor, and tetrahydrofuran is added, obtain suspension；
It is centrifuged after carrying out ultrasonication to the suspension, obtains the fluorescent material of the glucan package.
The present invention also provides the fluorescent materials described in above-mentioned technical proposal, the package of glucan described in above-mentioned technical proposal
Application of the fluorescent material in fluorescence imaging field.
The present invention provides a kind of fluorescent material, the fluorescent material is that ion doping enhancing can bio-imaging rare earth phosphorus ash
Stone fluorescent material, the ion include Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+, the rare earth apatite fluorescent material includes dilute
Soil doping fluor-apatite nano material or rear-earth-doped hydroxyapatite nanoparticle.The present invention passes through different radii ion Ba2+、
Sr2+、Na+、Mg2+、Zn2+Or Cd2+The mode of ion doping, ion doping are mainly displacement doping, substitute original rare earth apatite
Ca in fluorescent material2+Position, to change the local crystalline field symmetry of former fluorescent nano material, so that electron transition probability
It changes, and then improves fluorescence intensity.
Further, the fluorescent material of glucan package provided by the invention, wraps fluorescent material using glucan
The hydrophily for realizing the material is wrapped up in, can be used for biological cell fluorescence imaging.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is embodiment 1FA:Yb3+Ho3+The photo of fluor-apatite nano material；
Fig. 2 is 3%Ba made from embodiment 12+The TEM spectrogram of the fluorescent material of ion doping；
Fig. 3 is Ba made from embodiment 12+The fluorogram of the fluorescent material of ion doping；
Fig. 4 is 3%Sr made from embodiment 22+The TEM spectrogram of the fluorescent material of ion doping；
Fig. 5 is Sr made from embodiment 22+The fluorogram of the fluorescent material of ion doping；
Fig. 6 is 3%Na made from embodiment 3+The TEM spectrogram of the fluorescent material of ion doping；
Fig. 7 is Na made from embodiment 3+The fluorogram of the fluorescent material of ion doping；
Fig. 8 is 3%Mg made from embodiment 42+The TEM spectrogram of the fluorescent material of ion doping；
Fig. 9 is Mg made from embodiment 4+The fluorogram of the fluorescent material of ion doping；
Figure 10 is FA:Yb3+Ho3+Doping concentration is the Ba of 0%, 1%, 3%, 5% concentration respectively2+、Sr2+、Na+、Mg2+From
Fluorescence spectra after son；
Figure 11 is that sodium ion adulterates FA:Yb3+Ho3+, glucan and glucan package fluorescent material FT-IR map.
Specific embodiment
The present invention provides a kind of fluorescent material, the fluorescent material is that ion doping enhancing can bio-imaging rare earth phosphorus ash
Stone fluorescent material, the ion include Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+, the rare earth apatite fluorescent material includes dilute
Soil doping fluor-apatite nano material or rear-earth-doped hydroxyapatite nanoparticle.
In the present invention, the fluorescent material includes upconverting fluorescent material and downconversion fluorescent material, when the fluorescence
When material is upconverting fluorescent material, the rare earth apatite fluorescent material is rare earth apatite upconverting fluorescent material, works as institute
State fluorescent material be downconversion fluorescent material when, the rare earth apatite fluorescent material be rare earth apatite down-conversion fluorescent material
Material.
In the present invention, the mole of the fluorescent material intermediate ion preferably accounts for ion and Ca2+Mole summation 0~
35%, more preferably 1~9%, further preferably 3~7%, most preferably 5%.
In the present invention, when the rare earth apatite fluorescent material is preferably rare earth apatite upconverting fluorescent material,
Rare earth element in the rare earth apatite upconverting fluorescent material preferably includes mischmetal, the ytterbium of ytterbium (Yb) Yu holmium (Ho)
(Yb) with the mischmetal of erbium (Er), ytterbium (Yb) and thulium (Tm) mischmetal, when the rare earth apatite fluorescent material is preferred
When for rare earth apatite downconversion fluorescent material, the rare earth element in the rare earth apatite downconversion fluorescent material is preferably terbium
(Tb) or europium (Eu).In the present invention, the Yb is the sensitizer of upper conversion doping, and Ho, Er and Tm are swashing for upper conversion doping
Agent living.In the present invention, terbium (Tb) is used alone or europium (Eu) can be realized the enhancing of lower conversion.
In the present invention, when the rare earth apatite fluorescent material preferably includes ytterbium, the ytterbium is in the rare earth phosphorus ash
A mole doping percentage composition in stone fluorescent material is preferably 0~60%, when the rare earth apatite fluorescent material preferably includes
When holmium, erbium or thulium, mole doping percentage composition of the holmium, erbium or thulium in the rare earth apatite fluorescent material is independently excellent
It is selected as 0~5%.
In the present invention, the molecular formula of the fluor-apatite (FA) is Ca10(PO4)6F2, the molecule of hydroxyapatite (HA)
Formula is Ca10(PO4)6(OH)2。
In a specific embodiment of the present invention, the rear-earth-doped fluor-apatite nano material is preferably FA:Yb3+,Ho3+/
Yb3+,Er3+/Yb3+,Tm3+/Eu3+/Tb3+；The rear-earth-doped hydroxyapatite nanoparticle is preferably HA:Yb3+,Ho3+/Yb3 +,Er3+/Yb3+,Tm3+/Eu3+/Tb3+。
The present invention also provides the preparation methods of the fluorescent material described in above-mentioned technical proposal, when the rare earth apatite is glimmering
When luminescent material is rear-earth-doped fluor-apatite nano material, comprising the following steps:
Octadecylamine, oleic acid and ethyl alcohol are mixed, mixed solution is obtained；
The mixed aqueous solution of calcium nitrate and ion presoma is provided；
Rare earth precursor aqueous solution is provided；
Sodium phosphate aqueous solution is provided；
Sodium fluoride aqueous solution is provided；
By the mixed aqueous solution of calcium nitrate and ion presoma, rare earth precursor aqueous solution, sodium phosphate aqueous solution, sodium fluoride
Aqueous solution and mixed solution mixing, carry out hydro-thermal reaction, obtain hydrothermal product；
The hydrothermal product is started at 19~25 DEG C, after being heated to 700 DEG C with the rate of 1 DEG C/min, then constant temperature 2h,
Then natural cooling obtains the fluorescent material.
The present invention mixes octadecylamine, oleic acid and ethyl alcohol, obtains mixed solution.In the present invention, the matter of the octadecylamine
Amount and the volume ratio of oleic acid and ethyl alcohol are preferably 0~1g:0~8mL:0~32mL, more preferably 0.5g:4mL:16mL.
In the present invention, the ion presoma preferably include barium nitrate, strontium nitrate, magnesium nitrate, sodium nitrate, zinc nitrate or
Cadmium nitrate.
Mixed aqueous solution, rare earth precursor aqueous solution, sodium phosphate water of the present invention to the calcium nitrate and ion presoma
The concentration of solution and sodium fluoride aqueous solution does not have special restriction, and the mole that can obtain the ion accounts for ion and Ca2+'s
0~35% fluorescent material of mole summation.
In the present invention, the temperature of the hydro-thermal reaction is preferably 130~230 DEG C, and more preferably 160 DEG C, the time is preferred
For 12~for 24 hours, more preferably 16h.
After hydro-thermal reaction, the present invention preferably by the system cooled to room temperature after the hydro-thermal reaction, obtains water
Hot.
In the present invention, after the rate with 1 DEG C/min is heated to 700 DEG C, then after constant temperature 2h, rare earth ion is lived
Change, products therefrom can shine under laser excitation after activation.
The present invention also provides the preparation methods of the fluorescent material described in above-mentioned technical proposal, which is characterized in that when described
When rare earth apatite fluorescent material is rear-earth-doped hydroxyapatite nanoparticle, comprising the following steps:
Forerunner's nitric acid solution is provided；
Calcium phosphate aqueous solution is provided；
Ammonium dibasic phosphate solution is provided；
Concentrated ammonia liquor is provided；
Forerunner's nitric acid solution, calcium phosphate aqueous solution, ammonium dibasic phosphate solution and concentrated ammonia liquor are mixed, hydro-thermal reaction is carried out,
Obtain the fluorescent material.
In the present invention, forerunner's nitric acid solution preferably include barium nitrate solution, strontium nitrate solution, magnesium nitrate solution,
Sodium nitrate solution, zinc nitrate solution or nitric acid cadmium solution.The present invention does not have special limit to the concentration of forerunner's nitric acid solution
It is fixed.
In the present invention, forerunner's nitric acid solution is preferably pressed with the concentration of calcium phosphate aqueous solution and ammonium dibasic phosphate solution
According to by (Ca2+Cation in+forerunner nitric acid solution) molar ratio of/P is equal to and 0.5~2 mixes, and more preferably 1.67.?
In the present invention, the dosage of the concentrated ammonia liquor concentration is preferably that the pH value of adjusting reaction system is 6.5~10, more preferably 9.
In the present invention, the temperature of the hydro-thermal reaction is preferably 130~230 DEG C, and more preferably 170 DEG C, the time is preferred
For 2~12h, more preferably 3h.
After hydro-thermal reaction, the present invention preferably by the system cooled to room temperature after gained hydro-thermal reaction, obtains water
Hot.The hydrothermal product is preferably repeatedly centrifuged and is washed to obtain white gels object with deionized water by the present invention, will
The white gels object naturally dry is simultaneously ground with agate mortar, and the fluorescent material is obtained.
The present invention also provides a kind of fluorescent materials of glucan package, including fluorescent material described in above-mentioned technical proposal
And glucan, the glucan are wrapped in the surface of fluorescent material described in above-mentioned technical proposal.
In the present invention, the mass ratio of the glucan and fluorescent material is preferably 1~3:1, preferably 2:1.
The present invention also provides the preparation methods of the fluorescent material of the glucan package described in above-mentioned technical proposal, including with
Lower step:
The fluorescent material is mixed with hexamethylene, obtains mixed liquor；
It after glucan is mixed with water, then mixes with the mixed liquor, and tetrahydrofuran is added, obtain suspension；
It is centrifuged after carrying out ultrasonication to the suspension, obtains the fluorescent material of the glucan package.
In the present invention, the amount ratio of the fluorescent material and hexamethylene is preferably 10mg:1mL.
In the present invention, the amount ratio of the glucan and water is preferably 10mg:1mL.
The present invention does not have special restriction to the dosage of the tetrahydrofuran, can obtain suspension.
In the present invention, the ultrasonication can make the rare earth apatite fluorescent material in fluorescent material evenly dispersed
In the solution.The present invention does not have special restriction to the power of the ultrasonication and time, can be realized it is evenly dispersed i.e.
Can, in an embodiment of the present invention, the ultrasonication preferably carries out 2h at room temperature.
In the present invention, the revolving speed of the centrifugation is preferably 6000rpm, and the time is preferably 3min.
After the completion of centrifugation, the present invention preferably successively respectively washs gained centrifugation product three times with pure water and ethyl alcohol.The present invention
There is no special restriction to the mode of washing of the pure water and ethyl alcohol, is using technical solution well known to those skilled in the art
It can.
The present invention also provides the fluorescent materials described in above-mentioned technical proposal, the package of glucan described in above-mentioned technical proposal
Application of the fluorescent material in fluorescence imaging field.
In the present invention, the fluorescent material of the glucan package is preferably applied in cell imaging device.
Below with reference to embodiment to fluorescent material provided by the invention, glucan package fluorescent material and preparation method and
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Prepare FA:Yb3+Ho3+The step of it is as follows:
(1) 0.5g octadecylamine is dissolved in the oleic acid of 4mL and the ethyl alcohol of 16mL, and in the high pressure of polytetrafluoroethyllining lining
Magnetic agitation is carried out in kettle.
(2) 7mL, the calcium nitrate of 0.28mol are added in deionized water；Ln(NO3)3, (Ln=0.20molYb3++
0.02molHo3+, 2mL)；0.20mol, 7mL sodium phosphate；The sodium fluoride of 2mL, 0.24mol, obtain mixture.
(3) it is added in autoclave after mixture being stirred 10min, in 160 DEG C of hydro-thermal process 16h.
(4) natural cooling at room temperature collects white precipitate with 4000rpm centrifugation 10min, later in 0 DEG C of air
700 DEG C of activation 2h are again heated to 1 DEG C of rate per minute, obtain white powder, i.e. FA:Yb3+Ho3+。
Fig. 1 is FA:Yb3+Ho3+The photo of fluor-apatite nano material, wherein Yb3+Doping is 18%, Ho3+Doping
For 2% (molar ratio).
Ba2+It is prepared by the fluorescent material of ion doping
(1) 0.5g octadecylamine is dissolved in the oleic acid of 4mL and the ethyl alcohol of 16mL, in the autoclave of polytetrafluoroethyllining lining
In carry out magnetic agitation 10min.
(2) prepare the total 7mL of aqueous solution of calcium nitrate and barium nitrate, wherein adjust barium nitrate doping concentration X, respectively 0,
1%, 3%, 5%, 7% and 9%, respectively correspond doping mol be x=0.00mol, 0.02mol, 0.06mol, 0.10mol,
0.14mol, 0.18mol, corresponding calcium nitrate are (0.28-x) mol, carry out magnetic agitation 10min.
(3) the total 2mL (Ln=0.20molYb of aqueous solution of ytterbium nitrate and holmium nitrate is prepared3++0.02molHo3+, 2mL), into
Row magnetic agitation 10min.
(4) the aqueous solution 7mL of 0.20mol sodium phosphate is prepared, magnetic agitation 10min is carried out.
(5) the aqueous solution 2mL of 0.24mol sodium fluoride is prepared, magnetic agitation 10min is carried out.
(6) after above four kinds of solution being distinguished uniform stirring, uniform stirring after the above solution is added in autoclave
After 10min, in 160 DEG C of hydro-thermal process 16h.
(7) cooled to room temperature at room temperature collects white precipitate with 4000rpm centrifugation 10min, make at 0 DEG C
With mini type high temperature sintering furnace, 2h is activated after being heated to 700 DEG C with the rate of 1 DEG C/min, obtains white powder, i.e. Ba2+Ion
The fluorescent material of doping.
To 3%Ba2+The fluorescent material of doping carries out TEM test, as a result as shown in Fig. 2, as shown in Figure 2, length is about
180nm is in rodlike.
Fig. 3 is 0%, 1%, 3% and 5%Ba made from embodiment 12+The fluorogram of the fluorescent material of ion doping, by Fig. 3
It is found that barium ions doping realizes the enhancing of up-conversion fluorescence intensity.
Embodiment 2
Sr2+It is prepared by the fluorescent material of ion doping
Ba is prepared with embodiment 12+The method of the fluorescent material of ion doping is identical, and difference, which is only that, replaces barium nitrate
For strontium nitrate, while strontium nitrate doping concentration X is adjusted, respectively 0,1%, 3% and 5%, respectively corresponding doping mol is x=
0.00mol, 0.02mol, 0.06mol, 0.10mol obtain Sr2+The fluorescent material of ion doping.
To 3%Sr2+The fluorescent material of doping carries out TEM test, as a result as shown in figure 4, as shown in Figure 4, realizing Sr2+
Doping.
Fig. 5 is Sr made from embodiment 22+The fluorogram of the fluorescent material of doping, as shown in Figure 5, Sr2+Doping realizes
The enhancing of up-conversion fluorescence intensity.
Embodiment 3
Na+It is prepared by the fluorescent material of ion doping
Ba is prepared with embodiment 12+The method of the fluorescent material of ion doping is identical, and difference, which is only that, replaces barium nitrate
For sodium nitrate, while sodium nitrate doping concentration X is adjusted, respectively 0,1%, 3% and 5%, respectively corresponding doping mol is x=
0.00mol, 0.02mol, 0.06mol, 0.10mol obtain Na+The fluorescent material of ion doping.
To 3%Na+The fluorescent material of doping carries out TEM test, as a result as shown in fig. 6, it will be appreciated from fig. 6 that realizing Na+'s
Doping.
Fig. 7 is Na made from embodiment 3+The fluorogram of the fluorescent material of doping, as shown in Figure 7, Na+Doping realizes
The enhancing of conversion fluorescence intensity.
Embodiment 4
Mg2+It is prepared by the fluorescent material of ion doping
Ba is prepared with embodiment 12+The method of the fluorescent material of ion doping is identical, and difference, which is only that, replaces barium nitrate
For magnesium nitrate, while magnesium nitrate doping concentration X is adjusted, respectively 0,1%, 3% and 5%, respectively corresponding doping mol is x=
0.00mol, 0.02mol, 0.06mol, 0.10mol obtain Mg2+The fluorescent material of ion doping.
To 3%Mg2+The fluorescent material of doping carries out TEM test, as a result as shown in figure 8, as shown in Figure 8, realizing Mg2+
Doping.
Fig. 9 is Mg made from embodiment 42+The fluorogram of the fluorescent material of doping, as shown in Figure 9, Mg2+Doping realizes
The enhancing of up-conversion fluorescence intensity.
Embodiment 5
Zn2+It is prepared by the fluorescent material of ion doping
Ba is prepared with embodiment 12+The method of the fluorescent material of ion doping is identical, and difference, which is only that, replaces barium nitrate
For zinc nitrate, while zinc nitrate doping concentration X is adjusted, respectively 0,1%, 3% and 5%, respectively corresponding doping mol is x=
0.00mol, 0.02mol, 0.06mol, 0.10mol obtain Zn2+The fluorescent material of ion doping.
To 3%Zn2+The fluorescent material of doping carries out TEM test, as a result proves to realize Zn2+Doping.
To Zn made from embodiment 52+The fluorescent material of doping carries out fluorescence spectrometry, as a result proves Zn2+Doping is realized
The enhancing of up-conversion fluorescence intensity.
Embodiment 6
Cd2+It is prepared by the fluorescent material of ion doping
Ba is prepared with embodiment 12+The method of the fluorescent material of ion doping is identical, and difference, which is only that, replaces barium nitrate
For cadmium nitrate, while cadmium nitrate doping concentration X is adjusted, respectively 0,1%, 3% and 5%, respectively corresponding doping mol is x=
0.00mol, 0.02mol, 0.06mol, 0.10mol obtain Cd2+The fluorescent material of ion doping.
To 3%Cd2+The fluorescent material of doping carries out TEM test, as a result proves to realize Cd2+Doping.
To Cd made from embodiment 62+The fluorescent material of doping carries out fluorescence spectrometry, as a result proves Cd2+Doping is realized
The enhancing of up-conversion fluorescence intensity.
Figure 10 is FA:Yb3+Ho3+Doping concentration is the Ba of 0%, 1%, 3%, 5% concentration respectively2+、Sr2+、Na+、Mg2+From
Shown in fluorescence spectra after son, undoped FA:Yb is compared3+Ho3+Nano material is compared, and can be played and be mentioned after Doped ions
The effect of high fluorescent.When doping concentration is Ba2+When 5%, Sr2+When 1%, Na+When 3%, Mg2+There is luminous intensity when 5%
Larger promotion.
Embodiment 7
Glucan coats ion doping FA:Yb3+,Ho3+Preparation method:
(1) FA:Yb of the doping of sodium ion made from Example 33+Ho3+5mL hexamethylene is added in nano particle 50mg
(cyclohexane) it in, is uniformly mixed.
(2) glucan (Dextran) 100mg is dissolved in 10mL pure water, and aforesaid liquid is added in 50mL flask, and
Be added 10mL tetrahydro bark mutter (tetrahyfrofuran) formed suspension.
(3) ultrasonication mixed solution is used, keeps nano particle evenly dispersed in the solution, is placed in and stirs 2h at room temperature,
Obtain the ion doping FA:Yb coated through glucan3+Ho3+Nano material.
(4) the ion doping FA:Yb of glucan cladding is collected in finally centrifugation (6000rpm, 3min)3+Ho3+, and use pure water
It is respectively washed three times with ethyl alcohol.
Figure 11 is that sodium ion adulterates FA:Yb3+Ho3+, glucan and glucan package fluorescent material FT-IR map, wherein
A is that sodium ion adulterates FA:Yb3+Ho3+, b is glucan, and c is that glucan wraps up fluorescent material, and as shown in Figure 11, glucan is
It is successfully wrapped in nano-material surface, therefore the composite material after package has hydrophily, the FA:Yb after glucan-modified3+
Ho3+Na+In 2930cm-1Place occurs shrinking concussion peak, and for the absorption peak of appearance from the group of glucan, test result confirms FA:
Yb3+Ho3+Na+Nano material oneself successfully modified with glucan.
Embodiment 8
Ba2+The preparation method of rare earth doped hydroxyapatite nanoparticle:
Forerunner's nitric acid solution barium nitrate is provided；
Calcium phosphate aqueous solution is provided；
Ammonium dibasic phosphate solution is provided；Concentrated ammonia liquor is to adjust pH value as 9.
At 37 DEG C, by forerunner's nitric acid solution, calcium phosphate aqueous solution, ammonium dibasic phosphate solution, ammonium hydroxide mixed solution, forerunner's nitre
The concentration of acid solution and calcium phosphate aqueous solution and ammonium dibasic phosphate solution is from according to by (Ca2++Ba2+)/P molar ratio is equal to 1.67,
Hydro-thermal reaction is carried out, is heated to 170 DEG C, constant temperature 3h, cooled to room temperature obtains hydrothermal product, and gained emulsion is carried out
White gels object is obtained after being repeatedly centrifuged and washing with deionized water, by its naturally dry and grinds to obtain with agate mortar
Ba2+Fluorescent material.
To Ba2+The fluorescent material of doping carries out TEM test, as a result proves to realize Ba2+Doping.
To Ba obtained2+The fluorescent material of doping carries out fluorescence spectrometry, as a result proves Ba2+Doping, which realizes, to be turned
Change the enhancing of fluorescence intensity.
Embodiment 9
Glucan coats the preparation method of fluorescent material made from embodiment 8:
(1) Ba made from Example 82+The fluorescent material 50mg of doping is added in 5mL hexamethylene (cyclohexane),
It is uniformly mixed.
(2) glucan (Dextran) 100mg is dissolved in 10mL pure water, and aforesaid liquid is added in 50mL flask, and
Be added 10mL tetrahydro bark mutter (tetrahyfrofuran) formed suspension.
(3) ultrasonication mixed solution is used, keeps nano particle evenly dispersed in the solution, is placed in and stirs 2h at room temperature,
Obtain the Ba coated through glucan2+The fluorescent material of doping.
(4) Ba of glucan cladding is collected in finally centrifugation (6000rpm, 3min)2+The fluorescent material of doping, and with pure water and
Ethyl alcohol respectively washs three times.
Ba is wrapped up to glucan made from embodiment 92+The fluorescent material of doping carries out FT-IR test, as a result with embodiment 7
It is similar, it is known that, glucan is successfully wrapped in nano-material surface.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of fluorescent material, which is characterized in that the fluorescent material is that ion doping enhancing can bio-imaging rare earth apatite
Fluorescent material, the ion include Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+, the rare earth apatite fluorescent material includes rare earth
Adulterate fluor-apatite nano material or rear-earth-doped hydroxyapatite nanoparticle.
2. fluorescent material according to claim 1, which is characterized in that the mole of the fluorescent material intermediate ion accounts for ion
With Ca2+Mole summation 0~35%.
3. fluorescent material according to claim 1, which is characterized in that when the rare earth apatite fluorescent material is rare earth phosphorus
When lime stone upconverting fluorescent material, the rare earth element in the rare earth apatite upconverting fluorescent material includes the mixing of ytterbium and holmium
The mischmetal of rare earth, the mischmetal of ytterbium and erbium or ytterbium and thulium, when the rare earth apatite fluorescent material is rare earth apatite
When downconversion fluorescent material, the rare earth element in the rare earth apatite downconversion fluorescent material is terbium or europium.
4. fluorescent material according to claim 3, which is characterized in that when the rare earth apatite fluorescent material includes ytterbium
When, a mole doping percentage composition of the ytterbium in the rare earth apatite fluorescent material is 0~60%, when the rare earth phosphorus ash
When stone fluorescent material includes holmium, erbium or thulium, mole doping hundred of the holmium, erbium or thulium in the rare earth apatite fluorescent material
Point content independently is 0~5%.
5. the preparation method of the described in any item fluorescent materials of Claims 1 to 4, which is characterized in that when the rare earth apatite
When fluorescent material is rear-earth-doped fluor-apatite nano material, comprising the following steps:
Octadecylamine, oleic acid and ethyl alcohol are mixed, mixed solution is obtained；
The mixed aqueous solution of calcium nitrate and ion presoma is provided；
Rare earth precursor aqueous solution is provided；
Sodium phosphate aqueous solution is provided；
Sodium fluoride aqueous solution is provided；
The mixed aqueous solution of calcium nitrate and ion presoma, rare earth precursor aqueous solution, sodium phosphate aqueous solution, sodium fluoride is water-soluble
Liquid and mixed solution mixing, carry out hydro-thermal reaction, obtain hydrothermal product；
The hydrothermal product is started at 19~25 DEG C, after being heated to 700 DEG C with the rate of 1 DEG C/min, then constant temperature 2h, then
Natural cooling obtains the fluorescent material.
6. the preparation method of the described in any item fluorescent materials of Claims 1 to 4, which is characterized in that when the rare earth apatite
When fluorescent material is rear-earth-doped hydroxyapatite nanoparticle, comprising the following steps:
Forerunner's nitric acid solution is provided；
Calcium phosphate aqueous solution is provided；
Ammonium dibasic phosphate solution is provided；
Concentrated ammonia liquor is provided；
Forerunner's nitric acid solution, calcium phosphate aqueous solution, ammonium dibasic phosphate solution and concentrated ammonia liquor are mixed, hydro-thermal reaction is carried out, obtains
The fluorescent material.
7. a kind of fluorescent material of glucan package, which is characterized in that including the described in any item phosphors of Claims 1 to 4
Material and glucan, the glucan are wrapped in the surface of the fluorescent material.
8. the fluorescent material of glucan package according to claim 7, which is characterized in that the glucan and fluorescent material
Mass ratio be 1~3:1.
9. the preparation method of the fluorescent material of the package of glucan described in claim 7 or 8, which is characterized in that including following step
It is rapid:
The fluorescent material is mixed with hexamethylene, obtains mixed liquor；
It after glucan is mixed with water, then mixes with the mixed liquor, and tetrahydrofuran is added, obtain suspension；
It is centrifuged after carrying out ultrasonication to the suspension, obtains the fluorescent material of the glucan package.
10. the phosphor of the package of glucan described in the described in any item fluorescent materials of Claims 1 to 4, claim 7 or 8
Expect the application in fluorescence imaging field.
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