CN110205126B - Fluorescent material, glucan-coated fluorescent material, and preparation method and application thereof - Google Patents

Fluorescent material, glucan-coated fluorescent material, and preparation method and application thereof Download PDF

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CN110205126B
CN110205126B CN201910649257.2A CN201910649257A CN110205126B CN 110205126 B CN110205126 B CN 110205126B CN 201910649257 A CN201910649257 A CN 201910649257A CN 110205126 B CN110205126 B CN 110205126B
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fluorescent material
rare earth
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CN110205126A (en
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邹鹏
李金华
佟嘉欣
彭凯
柴克炜
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Changchun University of Science and Technology
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    • 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
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    • 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 invention provides a fluorescent material, a glucan-coated fluorescent material, a preparation method and application thereof, and belongs to the field of fluorescent materials. The invention passes through ions Ba with different radiuses2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The doping mode is that ion doping is mainly substitutional doping to replace Ca in the original rare-earth apatite fluorescent material2+The symmetry of the local crystal field of the original nano material is changed, so that the electron transition probability is changed, and the fluorescence intensity is further improved.

Description

Fluorescent material, glucan-coated fluorescent material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a fluorescent material, a glucan-coated fluorescent material, a preparation method and application thereof.
Background
With the rapid development of nano science and nano technology, rare earth nano luminescent materials have become popular for the wide research of scientists, and especially, the novel luminescent nano materials applied to biomedicine have attracted wide attention. For the traditional fluorescent material, the rare earth up-conversion material uses near-infrared laser as an excitation source, and the tissue penetration capability is strong. However, the low fluorescence intensity of the rare earth doped fluorescent nano material is still one of the key technical problems facing biological imaging at present. The apatite up-conversion nano material has good photochemical stability, long fluorescence life, wide emission spectrum band and biocompatibility. Some existing research teams change the content of rare earth ions to improve the fluorescence intensity of the apatite nano material, but the fluorescence intensity of the apatite nano material serving as a fluorescence probe is still low, and the apatite nano material is not beneficial to biological imaging.
Disclosure of Invention
In view of the above, the present invention aims to provide a fluorescent material, a dextran-wrapped fluorescent material, and a preparation method and an application thereof. The fluorescent material provided by the invention has high fluorescence intensity and is beneficial to enhancing biological imaging.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fluorescent material, which is an ion-doped enhanced biological imaging rare-earth apatite fluorescent material, wherein ions comprise Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The rare earth apatite fluorescent material comprises a rare earth doped fluorapatite nano material or a rare earth doped hydroxyapatite nano material.
Preferably, the molar amount of the ions in the fluorescent material is the ratio of the ions to Ca 2+0 of the sum of the molar amounts of～35％。
Preferably, when the rare earth apatite phosphor material is a rare earth apatite up-conversion phosphor material, the rare earth element in the rare earth apatite up-conversion phosphor material includes the mischmetal of ytterbium and holmium, the mischmetal of ytterbium and erbium, or the mischmetal of ytterbium and thulium, and when the rare earth apatite phosphor material is a rare earth apatite down-conversion phosphor material, the rare earth element in the rare earth apatite down-conversion phosphor material is terbium or europium.
Preferably, when the rare-earth apatite fluorescent material comprises ytterbium, the molar doping percentage content of the ytterbium in the rare-earth apatite fluorescent material is 0-60%, and the molar doping percentage content of the holmium, erbium or thulium in the rare-earth apatite fluorescent material is independently 0-5%.
The invention also provides a preparation method of the fluorescent material in the technical scheme, and when the rare-earth apatite fluorescent material is a rare-earth doped fluorapatite nano material, the preparation method comprises the following steps:
mixing octadecylamine, oleic acid and ethanol to obtain a mixed solution;
providing a mixed aqueous solution of calcium nitrate and an ionic precursor;
providing a rare earth precursor aqueous solution;
providing an aqueous sodium phosphate solution;
providing an aqueous sodium fluoride solution;
mixing a mixed aqueous solution of calcium nitrate and an ion precursor, a rare earth precursor aqueous solution, a sodium phosphate aqueous solution, a sodium fluoride aqueous solution and a mixed solution, and carrying out hydrothermal reaction to obtain a hydrothermal product;
and heating the hydrothermal product to 700 ℃ at the speed of 1 ℃/min at the temperature of 19-25 ℃, keeping the temperature for 2h, and naturally cooling to obtain the fluorescent material.
The invention also provides a preparation method of the fluorescent material in the technical scheme, which is characterized by comprising the following steps of:
providing a precursor nitric acid solution;
providing an aqueous calcium phosphate solution;
providing a diammonium phosphate solution;
providing concentrated ammonia water;
and mixing the precursor nitric acid solution, the calcium phosphate aqueous solution, the diammonium phosphate solution and the concentrated ammonia water, and carrying out hydrothermal reaction to obtain the fluorescent material.
The invention also provides a fluorescent material wrapped by glucan, which comprises the fluorescent material and the glucan, and the glucan is wrapped on the surface of the fluorescent material.
Preferably, the mass ratio of the glucan to the fluorescent material is 1-3: 1.
the invention also provides a preparation method of the glucan-coated fluorescent material in the technical scheme, which comprises the following steps:
mixing the fluorescent material with cyclohexane to obtain a mixed solution;
mixing glucan and water, mixing the mixture with the mixed solution, and adding tetrahydrofuran to obtain a suspension;
and carrying out ultrasonic treatment on the suspension, and then centrifuging to obtain the glucan-coated fluorescent material.
The invention also provides the fluorescent material in the technical scheme and application of the fluorescent material wrapped by glucan in the technical scheme in the field of fluorescence imaging.
The invention provides a fluorescent material, which is an ion-doped enhanced biological imaging rare-earth apatite fluorescent material, wherein ions comprise Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The rare earth apatite fluorescent material comprises a rare earth doped fluorapatite nano material or a rare earth doped hydroxyapatite nano material. The invention passes through ions Ba with different radiuses2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The ion doping mode is mainly substitutional doping and replaces Ca in the original rare-earth apatite fluorescent material2+The local crystal field symmetry of the original fluorescent nano material is changed, so that the electron transition probability is changed, and the fluorescence intensity is further improved.
Furthermore, the glucan-coated fluorescent material provided by the invention realizes the hydrophilicity of the material by coating the fluorescent material with the glucan, and can be used for biological cell fluorescence imaging.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows example 1FA Yb3+Ho3+A photograph of the fluorapatite nanomaterial;
FIG. 2 shows 3% Ba obtained in example 12+A TEM spectrum of the ion-doped fluorescent material;
FIG. 3 shows Ba obtained in example 12+A fluorescence map of the ion-doped fluorescent material;
FIG. 4 shows 3% Sr produced in example 22+A TEM spectrum of the ion-doped fluorescent material;
FIG. 5 shows Sr obtained in example 22+A fluorescence map of the ion-doped fluorescent material;
FIG. 6 shows 3% Na obtained in example 3+A TEM spectrum of the ion-doped fluorescent material;
FIG. 7 shows Na obtained in example 3+A fluorescence map of the ion-doped fluorescent material;
FIG. 8 is 3% Mg obtained in example 42+A TEM spectrum of the ion-doped fluorescent material;
FIG. 9 shows Mg prepared in example 4+A fluorescence map of the ion-doped fluorescent material;
FIG. 10 shows FA: Yb3+Ho3+Respectively doping Ba with the concentration of 0%, 1%, 3% and 5%2+、Sr2+、Na+、Mg2+Fluorescence spectrogram after ionization;
FIG. 11 shows Na ion-doped FA: Yb3+Ho3+And glucan encapsulate the FT-IR spectrum of the fluorescent material.
Detailed Description
The invention provides a fluorescent material, which is an ion-doped enhanced biological imaging rare-earth apatite fluorescent material, wherein ions comprise Ba2+、Sr2+、Na+、Mg2+、Zn2+Or Cd2+The rare earth apatite fluorescent material comprises a rare earth doped fluorapatite nano material or a rare earth doped hydroxyapatite nano material.
In the present invention, the fluorescent material includes an up-conversion fluorescent material and a down-conversion fluorescent material, and when the fluorescent material is the up-conversion fluorescent material, the rare earth apatite fluorescent material is a rare earth apatite up-conversion fluorescent material, and when the fluorescent material is the down-conversion fluorescent material, the rare earth apatite fluorescent material is a rare earth apatite down-conversion fluorescent material.
In the present invention, the molar amount of the ions in the fluorescent material is preferably in the range of the ions and Ca2+The total molar amount of (c) is 0 to 35%, more preferably 1 to 9%, still more preferably 3 to 7%, and most preferably 5%.
In the present invention, when the rare earth apatite phosphor is preferably a rare earth apatite up-conversion phosphor, the rare earth element in the rare earth apatite up-conversion phosphor preferably comprises a mixed rare earth of ytterbium (Yb) and holmium (Ho), a mixed rare earth of ytterbium (Yb) and erbium (Er), and a mixed rare earth of ytterbium (Yb) and thulium (Tm), and when the rare earth apatite phosphor is preferably a rare earth apatite down-conversion phosphor, the rare earth element in the rare earth apatite down-conversion phosphor is preferably terbium (Tb) or europium (Eu). In the present invention, Yb is a sensitizer for up-conversion doping, and Ho, Er, and Tm are activators for up-conversion doping. In the present invention, the enhancement of down-conversion can be achieved using terbium (Tb) or europium (Eu) alone.
In the invention, when the rare-earth apatite fluorescent material preferably comprises ytterbium, the molar doping percentage content of the ytterbium in the rare-earth apatite fluorescent material is preferably 0-60%, and when the rare-earth apatite fluorescent material preferably comprises holmium, erbium or thulium, the molar doping percentage content of the holmium, erbium or thulium in the rare-earth apatite fluorescent material is independently preferably 0-5%.
In the present invention, the molecular formula of the Fluorapatite (FA) is Ca10(PO4)6F2The molecular formula of Hydroxyapatite (HA) is Ca10(PO4)6(OH)2。
In a specific embodiment of the invention, the rare earth doped fluorapatite nano-material is preferably FA: Yb3+,Ho3+/Yb3+,Er3+/Yb3+,Tm3+/Eu3+/Tb3+(ii) a The preferable rare earth doped hydroxyapatite nano material is HA to Yb3+,Ho3+/Yb3 +,Er3+/Yb3+,Tm3+/Eu3+/Tb3+。
The invention also provides a preparation method of the fluorescent material in the technical scheme, and when the rare-earth apatite fluorescent material is a rare-earth doped fluorapatite nano material, the preparation method comprises the following steps:
mixing octadecylamine, oleic acid and ethanol to obtain a mixed solution;
providing a mixed aqueous solution of calcium nitrate and an ionic precursor;
providing a rare earth precursor aqueous solution;
providing an aqueous sodium phosphate solution;
providing an aqueous sodium fluoride solution;
mixing a mixed aqueous solution of calcium nitrate and an ion precursor, a rare earth precursor aqueous solution, a sodium phosphate aqueous solution, a sodium fluoride aqueous solution and a mixed solution, and carrying out hydrothermal reaction to obtain a hydrothermal product;
and heating the hydrothermal product to 700 ℃ at the speed of 1 ℃/min at the temperature of 19-25 ℃, keeping the temperature for 2h, and naturally cooling to obtain the fluorescent material.
The invention mixes octadecylamine, oleic acid and ethanol to obtain a mixed solution. In the invention, the volume ratio of the mass of the octadecylamine to the volume of the oleic acid and the ethanol is preferably 0-1 g: 0-8 mL: 0 to 32mL, more preferably 0.5 g: 4mL of: 16 mL.
In the present invention, the ionic precursor preferably includes barium nitrate, strontium nitrate, magnesium nitrate, sodium nitrate, zinc nitrate, or cadmium nitrate.
The concentrations of the mixed aqueous solution of the calcium nitrate and the ion precursor, the aqueous solution of the rare earth precursor, the aqueous solution of the sodium phosphate and the aqueous solution of the sodium fluoride are not particularly limited, and the molar weight of the ions in the ions and the Ca can be obtained2+0 to 35% of the total molar amount of the fluorescent material.
In the invention, the temperature of the hydrothermal reaction is preferably 130-230 ℃, more preferably 160 ℃, and the time is preferably 12-24 hours, more preferably 16 hours.
After the hydrothermal reaction is finished, the system after the hydrothermal reaction is preferably naturally cooled to room temperature to obtain a hydrothermal product.
In the invention, after the rare earth ions are heated to 700 ℃ at the speed of 1 ℃/min and then are kept at the constant temperature for 2h, the rare earth ions are activated, and the activated product can emit light under the excitation of a laser.
The invention also provides a preparation method of the fluorescent material in the technical scheme, which is characterized by comprising the following steps of:
providing a precursor nitric acid solution;
providing an aqueous calcium phosphate solution;
providing a diammonium phosphate solution;
providing concentrated ammonia water;
and mixing the precursor nitric acid solution, the calcium phosphate aqueous solution, the diammonium phosphate solution and the concentrated ammonia water, and carrying out hydrothermal reaction to obtain the fluorescent material.
In the present invention, the precursor nitric acid solution preferably includes a barium nitrate solution, a strontium nitrate solution, a magnesium nitrate solution, a sodium nitrate solution, a zinc nitrate solution, or a cadmium nitrate solution. The concentration of the precursor nitric acid solution is not particularly limited in the present invention.
In the present invention, the concentrations of the precursor nitric acid solution, the calcium phosphate aqueous solution and the diammonium phosphate solution are preferably determined according to (Ca)2++ cation in precursor nitric acid solution)/mole of PThe ratio is 0.5 to 2, and more preferably 1.67. In the invention, the dosage of the concentrated ammonia water concentration is preferably 6.5-10, and more preferably 9.
In the invention, the temperature of the hydrothermal reaction is preferably 130-230 ℃, more preferably 170 ℃, and the time is preferably 2-12 h, more preferably 3 h.
After the hydrothermal reaction is finished, the system obtained after the hydrothermal reaction is naturally cooled to room temperature to obtain a hydrothermal product. According to the invention, the hydrothermal product is preferably centrifuged for multiple times and washed by deionized water to obtain a white gel, and the white gel is naturally dried and ground by an agate mortar to obtain the fluorescent material.
The invention also provides a fluorescent material wrapped by glucan, which comprises the fluorescent material and the glucan, and the glucan is wrapped on the surface of the fluorescent material.
In the invention, the mass ratio of the glucan to the fluorescent material is preferably 1-3: 1, preferably 2: 1.
The invention also provides a preparation method of the glucan-coated fluorescent material in the technical scheme, which comprises the following steps:
mixing the fluorescent material with cyclohexane to obtain a mixed solution;
mixing glucan and water, mixing the mixture with the mixed solution, and adding tetrahydrofuran to obtain a suspension;
and carrying out ultrasonic treatment on the suspension, and then centrifuging to obtain the glucan-coated fluorescent material.
In the present invention, the ratio of the amount of the fluorescent material to cyclohexane is preferably 10mg to 1 mL.
In the present invention, the ratio of the amount of glucan to water is preferably 10mg to 1 mL.
The amount of the tetrahydrofuran used in the invention is not particularly limited, and the suspension can be obtained.
In the present invention, the ultrasonic treatment enables the rare earth apatite fluorescent material in the fluorescent material to be uniformly dispersed in the solution. In the present invention, the power and time of the ultrasonic treatment are not particularly limited, and the ultrasonic treatment may be performed at room temperature for 2 hours.
In the present invention, the rotation speed of the centrifugation is preferably 6000rpm, and the time is preferably 3 min.
After completion of the centrifugation, the present invention preferably washes the obtained centrifuged product three times with pure water and ethanol in this order. The washing method of the pure water and ethanol is not particularly limited, and the technical scheme known to those skilled in the art can be adopted.
The invention also provides the fluorescent material in the technical scheme and application of the fluorescent material wrapped by glucan in the technical scheme in the field of fluorescence imaging.
In the present invention, the dextran-coated fluorescent material is preferably applied to a cell imaging device.
The following examples are provided to illustrate the fluorescent material, the dextran-coated fluorescent material, the preparation method and the application of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of FA: Yb3+Ho3+The steps are as follows:
(1) 0.5g of octadecylamine was dissolved in 4mL of oleic acid and 16mL of ethanol and magnetically stirred in a Teflon lined autoclave.
(2) Adding 7mL of 0.28mol of calcium nitrate into deionized water; ln (NO)3)3，(Ln＝0.20molYb3++0.02molHo3+2 mL); 0.20mol, 7mL sodium phosphate; 2mL, 0.24mol of sodium fluoride, to give a mixture.
(3) The mixture was stirred for 10min and then placed in an autoclave and hydrothermally treated at 160 ℃ for 16 h.
(4) Naturally cooling at room temperature, centrifuging at 4000rpm for 10min to collect white precipitate, heating to 700 deg.C in air at 0 deg.C at a rate of 1 deg.C per minute, and activating for 2 hr to obtain white powder, namely FA: Yb3+Ho3+。
FIG. 1 shows FA: Yb3+Ho3+Photograph of fluorapatite nano-material, in which Yb3+The doping amount is 18 percent, Ho3+The doping amount is 2% (molar ratio).
Ba2+Preparation of ion-doped fluorescent material
(1) 0.5g of octadecylamine was dissolved in 4mL of oleic acid and 16mL of ethanol and magnetically stirred in a Teflon-lined autoclave for 10 min.
(2) A total of 7mL of aqueous solutions of calcium nitrate and barium nitrate were prepared, wherein doping concentrations X of barium nitrate were adjusted to 0, 1%, 3%, 5%, 7% and 9%, respectively, and corresponding doping mol were X ═ 0.00mol, 0.02mol, 0.06mol, 0.10mol, 0.14mol and 0.18mol, respectively, and corresponding calcium nitrate was (0.28-X) mol, and magnetic stirring was performed for 10 min.
(3) A total of 2mL of aqueous solutions of ytterbium nitrate and holmium nitrate were prepared (Ln ═ 0.20mol Yb3++0.02molHo3+2mL) was magnetically stirred for 10 min.
(4) 7mL of an aqueous solution of 0.20mol of sodium phosphate was prepared, and magnetic stirring was performed for 10 min.
(5) 2mL of an aqueous solution of 0.24mol of sodium fluoride was prepared, and magnetic stirring was performed for 10 min.
(6) And respectively and uniformly stirring the four solutions, adding the solutions into a high-pressure reaction kettle, uniformly stirring for 10min, and carrying out hydrothermal treatment at 160 ℃ for 16 h.
(7) Naturally cooling to room temperature at room temperature, centrifuging at 4000rpm for 10min to collect white precipitate, heating to 700 deg.C at 1 deg.C/min in a small high temperature sintering furnace at 0 deg.C for 2 hr to obtain white powder, i.e. Ba2+An ion-doped fluorescent material.
For 3% of Ba2+The doped fluorescent material was subjected to TEM test, and the result is shown in FIG. 2, and it is understood from FIG. 2 that the length thereof is about 180nm in a rod shape.
FIG. 3 is 0%, 1%, 3% and 5% Ba obtained in example 12+Fig. 3 shows the fluorescence image of the ion-doped fluorescent material, and barium ion doping enhances the upconversion fluorescence intensity.
Example 2
Sr2+Preparation of ion-doped fluorescent material
With preparation of Ba in example 12+The ion-doped fluorescent material has the same method except that barium nitrate is replaced by strontium nitrate, the doping concentration X of the strontium nitrate is adjusted to be 0, 1 percent, 3 percent and 5 percent respectively, and the doping mol is respectively 0.00mol, 0.02mol, 0.06mol and 0.10mol, so as to obtain Sr2+An ion-doped fluorescent material.
To 3% of Sr2+TEM test of the doped fluorescent material showed that Sr was realized as shown in FIG. 4, as can be seen from FIG. 42+Doping of (3).
FIG. 5 shows Sr obtained in example 22+FIG. 5 shows the fluorescence of the doped phosphor material, Sr2+The doping achieves an enhancement of the up-conversion fluorescence intensity.
Example 3
Na+Preparation of ion-doped fluorescent material
With preparation of Ba in example 12+The method of the ion-doped fluorescent material is the same, except that barium nitrate is replaced by sodium nitrate, and the doping concentration X of the sodium nitrate is adjusted to be 0, 1%, 3% and 5%, respectively, and the doping mol X is 0.00mol, 0.02mol, 0.06mol and 0.10mol, respectively, to obtain Na+An ion-doped fluorescent material.
For 3% Na+The TEM test of the doped fluorescent material showed that Na was realized as shown in FIG. 6, as can be seen from FIG. 6+Doping of (3).
FIG. 7 shows Na obtained in example 3+FIG. 7 shows the fluorescence of the doped fluorescent material, Na+The doping achieves an enhancement of the up-conversion fluorescence intensity.
Example 4
Mg2+Preparation of ion-doped fluorescent material
With preparation of Ba in example 12+The method of the ion-doped fluorescent material is the same, except that barium nitrate is replaced by magnesium nitrate, and the doping concentration X of the magnesium nitrate is adjusted to be 0, 1%, 3% and 5%, respectively, and the doping mol is 0.00mol and 002mol, 0.06mol, 0.10mol, to obtain Mg2+An ion-doped fluorescent material.
For 3% Mg2+The TEM test of the doped fluorescent material showed that Mg was realized as shown in FIG. 8, as can be seen from FIG. 82+Doping of (3).
FIG. 9 shows Mg prepared in example 42+FIG. 9 shows the fluorescence of the doped phosphor, Mg2+The doping achieves an enhancement of the up-conversion fluorescence intensity.
Example 5
Zn2+Preparation of ion-doped fluorescent material
With preparation of Ba in example 12+The method of the ion-doped fluorescent material is the same, except that barium nitrate is replaced by zinc nitrate, the doping concentration X of the zinc nitrate is adjusted to be 0%, 1%, 3% and 5%, and the doping mol is 0.00mol, 0.02mol, 0.06mol and 0.10mol, so as to obtain Zn2+An ion-doped fluorescent material.
For 3% Zn2+TEM test of the doped fluorescent material proves that Zn is realized2+Doping of (3).
Zn prepared in example 52+The doped fluorescent material is subjected to fluorescence spectrum measurement, and the result proves that Zn is2+The doping achieves an enhancement of the up-conversion fluorescence intensity.
Example 6
Cd2+Preparation of ion-doped fluorescent material
With preparation of Ba in example 12+The method of the ion-doped fluorescent material is the same, and the difference is only that the barium nitrate is replaced by cadmium nitrate, the doping concentration X of the cadmium nitrate is adjusted to be 0 percent, 1 percent, 3 percent and 5 percent respectively, and the doping mol is respectively 0.00mol, 0.02mol, 0.06mol and 0.10mol, so that Cd is obtained2+An ion-doped fluorescent material.
For 3% Cd2+TEM test of the doped fluorescent material proves that Cd is realized2+Doping of (3).
For Cd prepared in example 62+The result of the fluorescence spectrum measurement of the doped fluorescent material proves that Cd2+The doping achieves an enhancement of the up-conversion fluorescence intensity.
FIG. 10 shows FA: Yb3+Ho3+Respectively doping Ba with the concentration of 0%, 1%, 3% and 5%2+、Sr2+、Na+、Mg2+The fluorescence spectrum after ion shows that Yb is compared with undoped FA3+Ho3+Compared with the nanometer material, the nanometer material can play a role in improving the fluorescence intensity after being doped with ions. When the doping concentration is Ba2+At 5%, Sr 2+1% of Na+At 3%, Mg2+The luminous intensity is greatly improved when the luminous intensity is 5 percent.
Example 7
Dextran-coated ion-doped FA: Yb3+,Ho3+The preparation method comprises the following steps:
(1) taking the sodium ion doped FA: Yb prepared in example 33+Ho3+50mg of nanoparticles were added to 5mL of cyclohexane (cyclohexane) and mixed well.
(2) Dextran (Dextran)100mg was dissolved in 10mL of pure water, and the above liquid was added to a 50mL flask, and 10mL of tetrahydrofuran (Tetrahydrofurofuran) was added to form a suspension.
(3) Treating the mixed solution with ultrasonic wave to uniformly disperse the nanoparticles in the solution, stirring at room temperature for 2h to obtain ion-doped FA: Yb coated by dextran3+Ho3+And (3) nano materials.
(4) Finally, the ion-doped FA and Yb coated by glucan is collected by centrifugation (6000rpm, 3min)3+Ho3+And washed three times with each of pure water and ethanol.
FIG. 11 shows Na ion-doped FA: Yb3+Ho3+And glucan and the FT-IR spectrum of the glucan-coated fluorescent material, wherein a is FA and Yb doped with sodium ions3+Ho3+B is glucan, c is glucan-coated fluorescent material, as can be seen from fig. 11, glucan has been successfully coated on the surface of the nano material, so that the coated composite material has hydrophilicity, and FA modified by glucan is Yb3+Ho3+Na+At 2930cm-1The contraction shock peak appears, the absorption peak appears from the group of glucan, and the test result shows thatConfirmation of FA: Yb3+Ho3+Na+Nanomaterials have been successfully modified with dextran.
Example 8
Ba2+The preparation method of the rare earth-doped hydroxyapatite nano material comprises the following steps:
providing a precursor nitric acid solution barium nitrate;
providing an aqueous calcium phosphate solution;
providing a diammonium phosphate solution; concentrated ammonia water to adjust the pH value to 9.
Mixing the precursor nitric acid solution, the calcium phosphate aqueous solution, the diammonium hydrogen phosphate solution and the ammonia water solution at 37 ℃, wherein the concentration of the precursor nitric acid solution, the calcium phosphate aqueous solution and the diammonium hydrogen phosphate solution is determined according to the concentration ratio (Ca)2++Ba2+) The mol ratio of/P is equal to 1.67, hydrothermal reaction is carried out, the mixture is heated to 170 ℃, the temperature is kept for 3 hours, the mixture is naturally cooled to room temperature to obtain a hydrothermal product, the obtained emulsion is centrifuged for a plurality of times and washed by deionized water to obtain a white gel, the white gel is naturally dried and ground by an agate mortar to obtain Ba2+A fluorescent material.
For Ba2+TEM test of the doped fluorescent material proves the realization of Ba2+Doping of (3).
For the prepared Ba2+The doped fluorescent material is subjected to fluorescence spectrum measurement, and the result proves that Ba is2+The doping achieves an enhancement of the up-conversion fluorescence intensity.
Example 9
The preparation method of the fluorescent material prepared in example 8 comprises the following steps:
(1) ba obtained in example 8 was taken2+50mg of doped fluorescent material was added to 5mL of cyclohexane (cyclohexane) and mixed well.
(2) Dextran (Dextran)100mg was dissolved in 10mL of pure water, and the above liquid was added to a 50mL flask, and 10mL of tetrahydrofuran (Tetrahydrofurofuran) was added to form a suspension.
(3) Treating the mixed solution with ultrasonic wave to uniformly disperse the nanoparticles in the solution, and stirring at room temperature for 2h to obtain dextran-coated Ba2+A doped fluorescent material.
(4) Finally, the dextran-coated Ba was collected by centrifugation (6000rpm, 3min)2+Doped fluorescent material and washed three times with pure water and ethanol each.
Ba was encapsulated in the glucan obtained in example 92+The FT-IR test of the doped fluorescent material is similar to that of example 7, and the dextran is successfully coated on the surface of the nano material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. The fluorescent material is characterized in that the fluorescent material is an ion-doped enhanced biological imaging rare-earth apatite fluorescent material, and the ions are Cd2+The rare earth apatite fluorescent material is a rare earth doped fluorapatite nano material, the rare earth elements in the rare earth doped fluorapatite nano material comprise mixed rare earth of ytterbium and holmium, the mol doping percentage content of ytterbium in the rare earth doped fluorapatite nano material is 18%, and the mol doping percentage content of holmium in the rare earth doped fluorapatite nano material is 2%; cd in the fluorescent material2+In molar amount of ions and Ca2+1, 3 or 5% of the sum of the molar amounts.
2. The method for producing a fluorescent material according to claim 1, comprising the steps of:
mixing octadecylamine, oleic acid and ethanol to obtain a mixed solution;
providing a mixed aqueous solution of calcium nitrate and an ionic precursor;
providing a rare earth precursor aqueous solution;
providing an aqueous sodium phosphate solution;
providing an aqueous sodium fluoride solution;
mixing a mixed aqueous solution of calcium nitrate and an ion precursor, a rare earth precursor aqueous solution, a sodium phosphate aqueous solution, a sodium fluoride aqueous solution and a mixed solution, and carrying out hydrothermal reaction to obtain a hydrothermal product;
and heating the hydrothermal product to 700 ℃ at the speed of 1 ℃/min at the temperature of 19-25 ℃, keeping the temperature for 2h, and naturally cooling to obtain the fluorescent material.
3. A glucan-coated fluorescent material, which comprises the fluorescent material of claim 1 and glucan, wherein the glucan is coated on the surface of the fluorescent material.
4. The glucan coated fluorescent material according to claim 3, wherein the mass ratio of the glucan to the fluorescent material is 1-3: 1.
5. the method of preparing a glucan coated fluorescent material of claim 3 or 4, comprising the steps of:
mixing the fluorescent material with cyclohexane to obtain a mixed solution;
mixing glucan and water, mixing the mixture with the mixed solution, and adding tetrahydrofuran to obtain a suspension;
and carrying out ultrasonic treatment on the suspension, and then centrifuging to obtain the glucan-coated fluorescent material.
6. Use of the fluorescent material of claim 1, the dextran encapsulated fluorescent material of claim 3 or 4 in the field of fluorescence imaging.
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