CN111747652B

CN111747652B - Mesoporous bioactive glass composite material with up-conversion luminescence property and preparation method thereof

Info

Publication number: CN111747652B
Application number: CN202010560980.6A
Authority: CN
Inventors: 叶松; 廖华珍; 王德平
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2020-03-27
Filing date: 2020-06-18
Publication date: 2021-05-11
Anticipated expiration: 2040-06-18
Also published as: CN111747652A

Abstract

The invention relates to a mesoporous bioactive glass composite material with up-conversion luminescence property, a preparation method and application thereof₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals or NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals wherein RE₁Is Tm, Er or Ho, RE₂Is Y or Gd, 0<x≤35mol％，0<y≤5mol％，0<m≤20mol％，0<n is less than or equal to 30mol percent. The preparation method comprises rare earth doped up-conversion nanometerPreparation of crystal and composition of mesoporous borosilicate bioactive glass and rare earth doped up-conversion nanocrystalline. Compared with the prior art, the method can enable the bioactive glass to obtain 980nm or 808nm excited up-conversion visible light emission, realize dynamic monitoring of the degradation and mineralization process of the bioactive glass, effectively reduce the damage to cell tissues, reduce the spontaneous light effect of the biological tissues and improve the signal-to-noise ratio.

Description

Mesoporous bioactive glass composite material with up-conversion luminescence property and preparation method thereof

Technical Field

The invention relates to the field of material preparation, in particular to a mesoporous bioactive glass composite material with up-conversion luminescence property, and preparation and application thereof.

Background

The bioactive glass is a material which can repair, replace and regenerate body tissues and can enable the tissues and the material to form bonding effect. Research shows that the degradation rate of the bioactive glass is controllable, and the product has the effects of promoting cell proliferation and enhancing osteoblast gene expression. In addition, hydroxyapatite generated by the mineralization of bioactive glass is an important inorganic mineral phase of bone tissues, shows excellent bioactivity and can promote the repair of the bone tissues. However, the degradation and mineralization mechanism of bioactive glass involves complex physical and chemical processes such as exchange among various ions and generation of new phases, and the reaction process of each stage cannot be precisely quantified at present. Meanwhile, the difference of biological individuals can cause the difference of the reaction degree of the implant and the tissue, so the invention of the bioactive glass which can monitor the degradation and mineralization process in real time has very important significance for theoretical research and clinical application.

The up-conversion luminescence is an inverse photon which absorbs a plurality of low-energy photons and then emits a high-energy photonIn the Thogs process, the rare earth ion doped up-conversion nano fluorescent material has the advantages of narrow emission band, good light stability, long fluorescence life and the like. The selection of the doped matrix is very important for obtaining high-efficiency up-conversion luminescence, namely NaLnF₄(Ln＝Y,Gd,Lu)、LaF₃、CaF₂Fluoride, which is typified by others, is currently an important host material for up-conversion luminescence due to its lower phonon energy. In addition, the 808nm and 980nm infrared light is used as the excitation light for up-conversion luminescence, so that the damage to cell tissues and the self-luminescence effect of biological tissues can be effectively reduced. Therefore, in recent years, rare earth ion doped up-conversion fluoride nano luminescent materials are widely researched in the fields of biological marking, biological imaging, drug-loaded drug-released substance tracing and the like.

Hydroxyapatite is formed in the process of mineralizing the bioactive glass, meanwhile, a plurality of high phonon energy groups are introduced, and the change of the local environment has obvious influence on the overall intensity of converted luminescence on the rare earth and the relative intensity of luminescence with different wavelengths. Therefore, by compounding the rare earth doped up-conversion luminescent material in the bioactive glass matrix and monitoring the degradation and mineralization process by virtue of optical signals, the dynamic detection of the implant in a physiological environment can be obtained, and scientific basis and accurate individualized treatment are provided for the clinical application of the bioactive glass in bone tissue repair.

Disclosure of Invention

The invention aims to solve the problems and provide a mesoporous bioactive glass composite material with up-conversion luminescence property, and preparation and application thereof.

The purpose of the invention is realized by the following technical scheme:

the mesoporous bioactive glass composite material with the up-conversion luminescence property comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals or NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals wherein RE₁Is Tm, Er or Ho, RE₂Is Y or Gd, 0<x≤35mol％，0<y≤5mol％，0<m≤20mol％，0<n is less than or equal to 30mol percent. Wherein, NaYF₄:xYb³⁺,yRE₁ ³⁺As a nucleus, NaRE₂F₄As a shell, NaRE₂F₄:mYb³⁺,nNd³⁺Is a shell, mesoporous borosilicate bioactive glass is wrapped on rare earth doped up-conversion nanocrystalline, NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄The grain diameter of the core-shell structure nanocrystal is 10-50nm, and the particle diameter is NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄The grain diameter of the core-shell structure nanocrystal is 20-60 nm.

Preferably, the NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄The core-shell structure nanocrystal is alpha-NaYF₄:xYb³⁺,yRE₁ ³ ⁺@NaRE₂F₄Core-shell structure nanocrystals or beta-NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals, the NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄The core-shell structure nanocrystal is alpha-NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structure nanocrystals or beta-NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals.

Preferably, the rare earth doped up-conversion nanocrystals are surface modified.

Preferably, the mesoporous borosilicate bioactive glass is prepared from a mesoporous borosilicate bioactive glass precursor, and the molar ratio of the mesoporous borosilicate bioactive glass precursor to the up-conversion nanocrystal is (20-100): 1.

A preparation method of the mesoporous bioactive glass composite material with the up-conversion luminescence property comprises the preparation of rare earth doped up-conversion nanocrystals and the compounding of mesoporous borosilicate bioactive glass and the rare earth doped up-conversion nanocrystals.

Preferably, when the rare earth doped up-conversion nanocrystal is NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄When the core-shell structure nanocrystal is prepared, the preparation of the rare earth doped up-conversion nanocrystal specifically comprises the following steps:

(S1a) taking YCl₃·6H₂O、YbCl₃·6H₂O and RE₁Cl₃·6H₂Adding O into the mixed solution of oleic acid and l-octadecene, stirring and heating, and then cooling;

(S1b) adding a methanol solution containing sodium hydroxide or sodium oleate and a methanol solution of ammonium fluoride into the solution obtained in the step (S1a), stirring and heating for the first time, discharging methanol, continuing stirring and heating for the second time, and cooling;

(S1c) centrifugally separating the solution obtained in the step (S1b), and washing the solution by adopting a mixed solution of cyclohexane and ethanol to obtain NaYF₄:Yb³⁺,RE₁ ³⁺The nuclear nanocrystalline is dispersed in cyclohexane solution;

(S1d) taking RE₂Cl₃·6H₂O, adding the NaYF into the mixed solution of oleic acid and l-octadecene, stirring and heating, cooling for the first time, and adding the NaYF obtained in the step (S1c)₄:Yb³⁺,RE₁ ³⁺Discharging cyclohexane from the cyclohexane solution of the nuclear nanocrystal, and then cooling for the second time;

(S1e) adding a methanol solution of sodium hydroxide or sodium oleate and a methanol solution of ammonium fluoride into the solution obtained in the step (S1d), stirring and heating for the first time, discharging methanol, continuing stirring and heating for the second time, and cooling;

(S1f) centrifugally separating the solution obtained in the step (S1e), and washing the solution by adopting a mixed solution of cyclohexane and ethanol to obtain NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals.

Preferably, when the rare earth doped up-conversion nanocrystal is NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄When the core-shell structure nanocrystal is prepared, the preparation of the rare earth doped up-conversion nanocrystal specifically comprises the following steps:

(S1d) taking RE₂Cl₃·6H₂O、YbCl₃·6H₂O and NdCl₃·6H₂O, adding the NaYF into the mixed solution of oleic acid and l-octadecene, stirring and heating, cooling for the first time, and adding the NaYF obtained in the step (S1c)₄:Yb³⁺,RE₁ ³⁺Discharging cyclohexane from the cyclohexane solution of the nuclear nanocrystal, and then cooling for the second time;

(S1f) centrifugally separating the solution obtained in the step (S1e), and washing the solution by adopting a mixed solution of cyclohexane and ethanol to obtain NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺Core-shell structure nanocrystalline, then dispersed in cyclohexane solution;

(S1g) taking RE₂Cl₃·6H₂Adding O into the mixed solution of oleic acid and l-octadecene, stirring and heating, cooling for the first time, and adding the NaYF obtained in the step (S1f)₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺Discharging cyclohexane from the cyclohexane solution of the core-shell structure nanocrystal, and then cooling for the second time;

(S1h) adding a methanol solution of sodium hydroxide or sodium oleate and a methanol solution of ammonium fluoride into the solution obtained in the step (S1g), stirring and heating for the first time, discharging methanol, continuing stirring and heating for the second time, and cooling;

(S1i) centrifugally separating the solution obtained in the step (S1h), and washing the solution by adopting a mixed solution of cyclohexane and ethanol to obtain NaYF₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals.

Wherein, in the step (S1a), the stirring speed for stirring and heating is 300-400r/min, the stirring time is 30-60min, the heating temperature is 150-200 ℃, the heating time is 30-60min, and the cooling temperature is room temperature, which are all performed in the inert atmosphere. YCl₃·6H₂O、YbCl₃·6H₂O and RE₁Cl₃·6H₂The molar ratio of O is (0.64-0.89): (0.1-0.35): 0.01-0.03), and the volume ratio of oleic acid and l-octadecene is 6: 15.

In the step (S1b), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 300-400r/min, the stirring time is 60-100min, the heating temperature is 270-300 ℃, the heating time is 60-100min, and the cooling temperature is room temperature, which are all performed in the inert atmosphere. The addition ratio of sodium hydroxide/sodium oleate and methanol was 2.5mmol:10mL, the addition ratio of ammonium fluoride and methanol was 4mmol:10mL, and the molar ratio of sodium hydroxide/sodium oleate and ammonium fluoride was 2.5: 4.

In the step (S1c), the rotation speed of the centrifugation is 8000-10000r/min, and the time of the centrifugation is 5-10 min. The volume ratio of cyclohexane to ethanol is 1: 10.

In the step (S1d), the stirring speed of stirring and heating is 300-. (RE)₂Cl₃·6H₂Amount of O added or RE₂Cl₃·6H₂O、YbCl₃·6H₂O and NdCl₃·6H₂Total addition amount of O) and (YCl)₃·6H₂O、YbCl₃·6H₂O and RE₁Cl₃·6H₂Total addition of O) was 1:1, and the volume ratio of oleic acid to l-octadecene was 6: 15.

In the step (S1e), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 400r/min, the stirring time is 150min, the heating temperature is 300 ℃ and 300 ℃, the heating time is 150min and the cooling temperature is room temperature, which are all performed in the inert atmosphere. The addition ratio of sodium hydroxide/sodium oleate and methanol was 2.5mmol:10mL, the addition ratio of ammonium fluoride and methanol was 4mmol:10mL, and the molar ratio of sodium hydroxide/sodium oleate and ammonium fluoride was 2.5: 4.

In the step (S1f), the rotation speed of the centrifugation is 8000-10000r/min, and the time of the centrifugation is 5-10 min. The volume ratio of cyclohexane to ethanol is 1: 10. The prepared rare earth doped up-conversion nanocrystals are dispersed in a cyclohexane solution.

In the step (S1g), the stirring speed of stirring and heating is 300-. (RE)₂Cl₃·6H₂Amount of O added) and (YCl)₃·6H₂O、YbCl₃·6H₂O and RE₁Cl₃·6H₂Total addition of O) was 1:1, and the volume ratio of oleic acid to l-octadecene was 6: 15.

In the step (S1h), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 400r/min, the stirring time is 150min, the heating temperature is 300 ℃ and 300 ℃, the heating time is 150min and the cooling temperature is room temperature, which are all performed in the inert atmosphere.

In the step (S1i), the rotation speed of the centrifugation is 8000-10000r/min, and the time of the centrifugation is 5-10 min. The prepared rare earth doped up-conversion nanocrystal can be dispersed in a cyclohexane solution.

Preferably, the compounding of the mesoporous borosilicate bioactive glass and the rare earth-doped upconversion nanocrystal specifically comprises the following steps:

(S2a) taking a hexadecyl trimethyl ammonium bromide aqueous solution, adding a cyclohexane solution of rare earth doped up-conversion nanocrystalline, stirring and heating for the first time, stirring and heating for the second time, discharging cyclohexane, cooling, and adding an ethanol solution;

(S2b) sequentially adding tetraethyl orthosilicate, ammonia water, tributyl borate, triethyl phosphate and calcium nitrate tetrahydrate into the solution obtained in the step (S2a), stirring and heating, then centrifugally separating, washing and drying, and then carrying out heat treatment to remove the template agent and residual organic matters, thus obtaining the mesoporous bioactive glass composite material with up-conversion luminescence property.

(S3a) taking a hexadecyl trimethyl ammonium bromide solution, adding a cyclohexane solution of rare earth doped up-conversion nanocrystalline, stirring and heating for the first time, and stirring and heating for the second time after ultrasonic treatment to drain out cyclohexane;

(S3b) adding the solution obtained in the step (S3a) into an ethanol water solution, sequentially adding a sodium hydroxide solution and tetraethyl orthosilicate for reaction, centrifuging and washing, and dispersing the reaction product into the ethanol solution to obtain a surface-modified rare earth-doped up-conversion nanocrystalline solution;

(S3c) taking a hexadecyl trimethyl ammonium bromide solution, adding the surface-modified rare earth-doped up-conversion nanocrystalline solution obtained in the step (S3b), and stirring and heating;

(S2b) sequentially adding tetraethyl orthosilicate, ammonia water, tributyl borate, triethyl phosphate and calcium nitrate tetrahydrate into the solution obtained in the step (S3c), stirring and heating, then centrifugally separating, washing and drying, and then carrying out heat treatment to remove the template agent and residual organic matters, thus obtaining the mesoporous bioactive glass composite material with up-conversion luminescence property.

Wherein, in the step (S2a), the stirring speed of the first stirring and heating is 300-400r/min, the stirring time is 30-60min, the heating temperature is 40 ℃, the heating time is 30-60min, the stirring speed of the second stirring and heating is 300-400r/min, the stirring time is 15-30min, the heating temperature is 70-80 ℃, the heating time is 15-30min, and the cooling temperature is 40 ℃. The cetyl trimethyl ammonium bromide solution contains cetyl trimethyl ammonium bromide (marked as CTAB) and a solvent, the solvent is water or a mixed solution of water and ethanol, when the solvent is water, the addition ratio of the cetyl trimethyl ammonium bromide to the water is 0.15g:80mL, and when the solvent is a mixed solution of water and ethanol, the addition ratio of the cetyl trimethyl ammonium bromide to the water and the ethanol is 0.15g:80mL:30 mL.

In the step (S2b), the stirring speed for stirring and heating is 400-. The addition ratio of tetraethyl orthosilicate, ammonia water, tributyl borate, triethyl phosphate and calcium nitrate tetrahydrate was 1.63mL:1mL:1.950mL:0.250mL:1.546g, and the concentration of ammonia water was 25 wt%.

In the step (S3a), the stirring speed for the first stirring and heating is 400r/min, the stirring time is 10min, the heating temperature is 40 ℃, the heating time is 10min, the ultrasonic power is 1000-1500W, the ultrasonic time is 30min, the stirring speed for the second stirring and heating is 400r/min, the stirring time is 15-30min, the heating temperature is 70-80 ℃, and the heating time is 15-30 min.

In the step (S3b), the rotation speed of the centrifugation is 8000-10000r/min, and the time of the centrifugation is 5-10 min. The ethanol water solution comprises ethanol and water, the volume ratio of the solution obtained in the step (S3a), the ethanol and the water is 10:3:20, the mass ratio of the sodium hydroxide solution to the tetraethyl orthosilicate is (150-) (300-) (600-) (1000), and the concentration of the sodium hydroxide solution is 2 mol/L.

In the step (S3c), the stirring speed for stirring and heating is 300-400r/min, the stirring time is 30min, the heating temperature is 40 ℃, and the heating time is 30 min. The addition ratio of the cetyltrimethylammonium bromide to water in the cetyltrimethylammonium bromide aqueous solution was 0.1g:20mL, and the volume ratio of the cetyltrimethylammonium bromide aqueous solution to the rare earth-doped cyclohexane solution of the upconverting nanocrystal was 10: 1.

The mesoporous bioactive glass composite material with the up-conversion luminescence property is applied to dynamic monitoring of the degradation and mineralization process of bioactive glass.

Compared with the prior art, the invention provides a method for preparing a mesoporous bioactive glass composite material with up-conversion luminescence property, which comprises the steps of firstly preparing rare earth doped up-conversion nanocrystalline (with a core-shell structure or a core-shell structure) with up-conversion luminescence property, then adding the rare earth doped up-conversion nanocrystalline into the preparation process of the mesoporous bioactive glass, and finally annealing to remove a template agent and residual organic matters to obtain the mesoporous bioactive glass capable of emitting visible light under excitation of 980nm or 808 nm. In addition, the rare earth doped up-conversion nanocrystalline can be subjected to surface modification and then compounded with the mesoporous bioactive glass, so that the degradation and mineralization process of the bioactive glass can be dynamically monitored. In addition, the 980nm or 808nm excitation wavelength can effectively reduce the damage to cell tissues, reduce the spontaneous light effect of biological tissues and improve the signal to noise ratio.

Compared with the prior art, the invention has the following advantages:

(1) by compounding the rare earth doped up-conversion nanocrystalline with the bioactive glass, the bioactive glass composite material with up-conversion luminescence performance can be obtained, and dynamic monitoring of degradation and mineralization processes of the bioactive glass is realized.

(2) The rare earth doped up-conversion nanocrystalline is subjected to surface modification, so that the rare earth doped up-conversion nanocrystalline can be more uniformly dispersed in a bioactive glass precursor solution, and can be better compounded with bioactive glass.

(3) The invention obtains NaYF₄:xYb³⁺,yRE³⁺@NaYF₄/NaGdF₄Core-shell structured nanocrystals and NaYF₄:xYb³ ⁺,yRE³⁺@NaYF₄/NaGdF₄:mYb³⁺,nNd³⁺@NaYF₄/NaGdF₄A core-shell structured nanocrystal, wherein the core-shell structured nanocrystal can be excited by a 980nm laser and emit visible light, and the core-shell structured nanocrystal can be excited by a 808nm laser and emit visible light.

(4) In the invention, oleic acid is used as a surfactant and a high-boiling point solvent, 1-octadecene is used as a high-boiling point solvent, sodium oleate is used for accelerating the nucleation rate of a beta phase and can efficiently promote alpha-NaYF₄To beta-NaYF₄Transformation of beta-NaYF₄Relative to alpha-NaYF₄More favorable for up-conversion luminescence.

(5) The preparation method is simple and convenient to operate and high in repeatability.

Drawings

FIG. 1 is a graph of upconversion luminescence spectrum of a mesoporous bioactive glass composite material with upconversion luminescence property obtained in example 1 of the present invention under excitation at 980 nm;

FIG. 2 is a TEM image of the upconversion luminescent nanocrystals obtained in example 1 of the present invention;

FIG. 3 is a TEM image of a mesoporous bioactive glass composite material with up-conversion luminescence property obtained in example 2 of the present invention;

FIG. 4 is an XRD pattern of a sample of the mesoporous bioactive glass composite material with up-conversion luminescence property obtained in example 3 of the invention after being soaked in an SBF solution for 14 days;

FIG. 5 is a TEM image of a mesoporous bioactive glass composite material with up-conversion luminescence property obtained in example 4 of the invention;

FIG. 6 is a graph of an upconversion luminescence spectrum of a mesoporous bioactive glass composite material with an upconversion luminescence property obtained in example 5 of the present invention under the excitation of 808 nm;

fig. 7 is an upconversion luminescence spectrum of the mesoporous bioactive glass composite material with upconversion luminescence property obtained in example 6 of the present invention under the excitation of 808 nm.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments.

Example 1

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:18Yb³⁺,2Er³⁺@NaYF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

preparation of 980nm excited NaYF₄:18Yb³⁺,2Er³⁺@NaYF₄Core-shell structured nanocrystals

(1) Weighing 0.80mmol YCl₃·6H₂O，0.18mmol YbCl₃·6H₂O，0.02mmol ErCl₃·6H₂Adding O into a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ under an argon environment, preserving heat for 40min, cooling to room temperature after the rare earth is dissolved, and stirring at the speed of 300-400 r/min;

(2) weighing 2.5mmol of sodium hydroxide and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium hydroxide and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dripping the two solutions into the solution obtained in the step (1), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until the methanol is exhausted, wherein the stirring speed is 300-400 r/min;

(3) stirring the solution obtained in the step (2) under the protection of argon, heating to 300 ℃, preserving heat for 60min, and then naturally cooling to room temperature, wherein the stirring speed is 300-400 r/min;

(4) centrifuging the solution obtained in step (3) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Er³⁺Carrying out nuclear nanocrystalline, and dispersing the obtained nuclear nanocrystalline in 4mL of cyclohexane solution;

(5) weighing 1mmol YCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ under an argon environment, preserving heat for 40min, cooling to 80 ℃ after the rare earth is dissolved, preserving heat, and stirring at the speed of 300-400 r/min;

(6) incubating the solution obtained in (5) at 80 ℃ and adding 1mL of NaYF obtained in (4)₄:Yb³⁺,Er³⁺Nucleating a nanocrystalline cyclohexane solution, and naturally cooling to room temperature after the cyclohexane in the solution is discharged;

(7) weighing 2.5mmol of sodium hydroxide and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium hydroxide and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dropwise adding the two solutions into the solution obtained in the step (6), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(8) stirring the solution obtained in the step (7) under the protection of argon, heating to 300 ℃, preserving heat for 120min, and then naturally cooling to room temperature, wherein the stirring speed is 300-400 r/min;

(9) centrifuging the solution obtained in step (8) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain 980nm excited NaYF₄:Yb³⁺,Er³⁺@NaYF₄Core-shell structured nanocrystals, and the resulting upconverted core-shell structured nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing the composite material with the mol ratio of the up-conversion nanocrystalline to the bioactive glass precursor of about 1:20

(1) Weighing 0.15g of CTAB, dissolving in 80mL of deionized water, stirring for 15min at the temperature of 40 ℃ and the rotating speed of 300-400r/min, then adding an up-conversion nanocrystalline cyclohexane solution containing about 0.8mmol of up-conversion luminescent nanocrystals prepared in 4mL (one) into the CTAB aqueous solution, stirring for 30min at the temperature of 40 ℃ and the rotating speed of 300-400r/min, then stirring for 15-30min at the rotating speed of 300-400r/min at the temperature of 75 ℃, cooling the cyclohexane to 40 ℃ again after the cyclohexane is completely discharged, and then adding 40mL of ethanol solution and stirring for 30min at the rotating speed of 300-400 r/min;

(2) a total of 18.2mmol of bioactive glass precursor reactants were prepared, namely: adding 1.63mL of tetraethyl orthosilicate dropwise into the solution obtained in the step (1), stirring at the rotating speed of 300-400r/min for 10min at 40 ℃, adding 1mL of 25 wt% ammonia water into the solution, stirring for 10min, adding 1.950mL of tributyl borate and 0.250mL of triethyl phosphate, stirring for 30min, then weighing 1.546g of calcium nitrate tetrahydrate, adding into the solution, and stirring at 40 ℃ for 3-4 h;

(3) centrifuging the solution obtained in the step (2) for 5-10min at the rotating speed of 4000r/min by using a centrifuge, respectively washing the obtained white centrifugal product for 2-3 times by using 30mL of ethanol and 30mL of deionized water, separating for 5-10min at the rotating speed of 4000-8000r/min by using the centrifuge again, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h;

(4) and (4) putting the product obtained in the step (3) into a muffle furnace, carrying out heat treatment for 5h at 450 ℃, removing a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with the up-conversion luminescence property. The up-conversion luminescence spectrum of the bioactive glass composite material under the excitation of 980nm is shown in figure 1, and the emission peaks can be seen to be positioned at 530nm (green light), 550nm (green light) and 660nm (red light). The TEM image of the up-conversion core-shell structure nanocrystal is shown in FIG. 2, and it can be seen that the nanocrystal particles are spherical, uniform, and have good dispersibility and an average particle size of about 13 nm.

Example 2

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:10Yb³⁺,1Ho³⁺@NaGdF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

preparation of 980nm excited NaYF₄:10Yb³⁺,1Ho³⁺@NaGdF₄Core-shell structured nanocrystals

(1) Weighing 0.89mmol YCl₃·6H₂O，0.10mmol YbCl₃·6H₂O，0.01mmol HoCl₃·6H₂O is stirred and heated to 160 ℃ in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid under the argon environment, the temperature is kept for 40min, the rare earth is cooled to room temperature after being dissolved, and the stirring speed is 400 r/min;

(3) stirring the solution obtained in the step (2) under the protection of argon, heating to 300 ℃, preserving heat for 90min, and then naturally cooling to room temperature, wherein the stirring speed is 300-400 r/min;

(4) centrifuging the solution obtained in the step (3) by a centrifuge at the rotating speed of 8000r/min for 5-1Separating for 0min, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Ho³⁺Carrying out nuclear nanocrystalline, and dispersing the obtained nuclear nanocrystalline in 4mL of cyclohexane solution;

(5) weighing 1mmol GdCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ under an argon environment, preserving heat for 40min, cooling to 80 ℃ after the rare earth is dissolved, preserving heat, and stirring at the speed of 300-400 r/min;

(6) incubating the solution obtained in (5) at 80 ℃ and adding 1ml of NaYF obtained in (4)₄:Yb³⁺,Ho³⁺Nucleating a nanocrystalline cyclohexane solution, and naturally cooling to room temperature after the cyclohexane in the solution is discharged;

(9) centrifuging the solution obtained in step (8) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain 980nm excited NaYF₄:10Yb³⁺,1Ho³⁺@NaGdF₄Core-shell structure nanocrystals, and the resulting upconverted core-shell structure nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing the composite material with the mol ratio of the up-conversion nanocrystalline to the bioactive glass precursor of about 1:100

(1) Weighing 0.1g of CTAB, dissolving in 20mL of deionized water, stirring for 10min at the temperature of 40 ℃ and the rotating speed of 300-400r/min, adding the up-conversion luminescence nanocrystalline cyclohexane solution containing about 0.4mmol of up-conversion luminescence nanocrystalline prepared in 2mL (one) into the CTAB aqueous solution, carrying out ultrasonic treatment for 30min at the power of 1000-1500W, stirring for 15-30min at the temperature of 70-80 ℃ to drain out the cyclohexane, and stirring at the speed of 300-400r/min to obtain the CTAB-stable up-conversion nanocrystalline aqueous solution;

(2) adding 10mL of the CTAB stable upconversion nanocrystalline aqueous solution (about 0.2mmol of upconversion nanocrystalline) obtained in the step (1) into a mixed solution of 20mL of deionized water and 3mL of ethanol, simultaneously dropwise adding 150 mu L of sodium hydroxide solution with the concentration of 2mol/L, slowly dropwise adding 600 mu L of tetraethyl orthosilicate while stirring at the temperature of 70 ℃, reacting for 15min at the temperature of 70 ℃, wherein the stirring speed is 300-400 r/min;

(3) centrifuging the reaction product obtained in the step (2) by a centrifuge at the rotating speed of 8000r/min for 5-10min, washing the reaction product by 25mL of ethanol and 25mL of water for 2 times respectively, and finally dispersing the product in 15mL of ethanol solution to obtain surface-modified up-conversion nanocrystalline solution;

(4) weighing 0.15g CTAB, dissolving in a mixed solution of 30mL ethanol and 80mL deionized water, adding 15mL (3) of the surface-modified up-conversion nanocrystalline ethanol solution into the CTAB solution, and stirring at the temperature of 40 ℃ for 30min at the stirring speed of 300-400 r/min;

(5) a total of 18.2mmol of bioactive glass precursor reactants were prepared, namely: adding 1.63mL of tetraethyl orthosilicate dropwise into the solution obtained in the step (4), stirring at the rotating speed of 300-400r/min for 10min at 40 ℃, adding 1mL of 25 wt% ammonia water into the solution, stirring for 10min, adding 1.950mL of tributyl borate and 0.250mL of triethyl phosphate, stirring for 30min, then weighing 1.546g of calcium nitrate tetrahydrate, adding into the solution, and stirring at 40 ℃ for 3-4 h;

(6) centrifuging the solution obtained in the step (5) for 5-10min at the rotating speed of 4000r/min by using a centrifuge, washing the obtained white centrifugal product with 30mL of ethanol and 30mL of deionized water for 2-3 times respectively, separating for 5-10min at the rotating speed of 4000 by using the centrifuge again, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h;

(7) and (3) putting the product obtained in the step (6) into a muffle furnace, carrying out heat treatment for 5h at 500 ℃, removing a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with the up-conversion luminescence property. The TEM image of the bioactive glass composite is shown in fig. 3, and it can be seen that the bioactive glass is coated on the upconversion nanocrystal, and the bioactive glass composite is spherical.

Example 3

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:30Yb³⁺,5Tm³⁺@NaGdF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

preparation of 980nm excited NaYF₄:30Yb³⁺,5Tm³⁺@NaGdF₄Core-shell structured nanocrystals

(1) Weighing 0.65mmol YCl₃·6H₂O，0.30mmol YbCl₃·6H₂O，0.05mmol TmCl₃·6H₂O is stirred and heated to 160 ℃ in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid under the argon environment, the temperature is kept for 40min, the rare earth is cooled to room temperature after being dissolved, and the stirring speed is 400 r/min;

(3) stirring the solution obtained in the step (2) under the protection of argon, heating to 300 ℃, preserving heat for 70min, and then naturally cooling to room temperature, wherein the stirring speed is 300-400 r/min;

(4) centrifuging the solution obtained in step (3) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Tm³⁺Carrying out nuclear nanocrystalline, and dispersing the obtained nuclear nanocrystalline in 4mL of cyclohexane solution;

(6) the solution obtained in (5) was incubated at 80 ℃ and 1ml of NaYF obtained in (4) was added₄:Yb³⁺,Tm³⁺Nucleus nanocrystalline cyclohexane solution, and naturally cooling to room temperature after the cyclohexane solution in the solution is drained;

(8) stirring the solution obtained in the step (7) under the protection of argon, heating to 300 ℃, preserving heat for 130min, and then naturally cooling to room temperature, wherein the stirring speed is 300-400 r/min;

(9) centrifuging the solution obtained in the step (8) for 300-400min at the rotating speed of 8000r/min by using a centrifugal machine, separating the product, adding cyclohexane and ethanol solution into the product according to a certain ratio (the volume ratio is 1:10) and repeatedly cleaning for 3-4 times to obtain 980nm excited NaYF₄:30Yb³⁺,5Tm³⁺@NaGdF₄Core-shell structured nanocrystals, and the resulting upconverted core-shell structured nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing composite material with 980nm excited up-conversion nanocrystalline and bioactive glass precursor molar ratio of about 1:50

(1) Weighing 0.1g CTAB, dissolving in 20mL deionized water, stirring at the temperature of 40 ℃ and the rotating speed of 300-400r/min for 10min, adding the up-conversion luminescence nanocrystalline cyclohexane solution containing about 0.4mmol up-conversion luminescence nanocrystalline prepared in 2mL (one) into the CTAB aqueous solution, carrying out ultrasonic treatment at the power of 1000-1500W for 30min, and then stirring at the temperature of 70-80 ℃ for 15-30min to drain the cyclohexane to obtain the CTAB stable up-conversion nanocrystalline aqueous solution;

(2) adding 20mL of the CTAB stable up-conversion nanocrystalline aqueous solution obtained in the step (1) into a mixed solution of 40mL of deionized water and 6mL of ethanol, simultaneously dropwise adding 300 mu L of a sodium hydroxide solution with the concentration of 2mol/L, slowly dropwise adding 1000 mu L of tetraethyl orthosilicate while stirring at the temperature of 70 ℃, reacting for 20min at the temperature of 70 ℃, wherein the stirring speed is 300-400 r/min;

(3) centrifuging the reaction product obtained in the step (2) by a centrifuge at the rotating speed of 8000r/min for 5-10min, washing the reaction product by 25mL of ethanol and 25mL of deionized water for 2 times respectively, and finally dispersing the product in 15mL of ethanol solution to obtain surface-modified up-conversion nanocrystalline solution;

(4) dissolving 0.1g CTAB in 30mL of ethanol and 80mL of deionized water, then adding 15mL (3) of the surface-modified up-conversion nanocrystalline ethanol solution into the CTAB solution, and stirring at the temperature of 40 ℃ for 30min at the stirring speed of 300-400 r/min;

(5) a total of 18.2mmol of bioactive glass precursor reactants were prepared, namely: adding 1.63mL of tetraethyl orthosilicate dropwise into the solution obtained in the step (4), stirring at the rotating speed of 300-400r/min for 10min at 40 ℃, then adding 1mL of 25 wt% ammonia water into the solution, stirring for 10min, then adding 1.950mL of tributyl borate and 0.250mL of triethyl phosphate and stirring for 30min, and then weighing 1.546g of calcium nitrate tetrahydrate and adding the mixture into the solution and stirring for 3-4h at 40 ℃;

(6) centrifuging the solution obtained in the step (5) for 5-10min at the rotating speed of 4000r/min by using a centrifuge, washing the obtained white centrifugal product with 30mL of ethanol and 30mL of deionized water for 2-3 times respectively, separating for 5min at the rotating speed of 4000r/min by using the centrifuge again, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h; (7) and (4) putting the product obtained in the step (6) into a muffle furnace, carrying out heat treatment for 5h at 600 ℃, removing a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with the up-conversion luminescence property. The XRD pattern of the bioactive glass composite material after being soaked in the SBF solution for 14 days is shown in figure 4, and the diffraction peak of hydroxyapatite indicated by an arrow appears after being soaked for 14 days, which indicates that the bioactive glass composite material has good in-vitro mineralization performance and bioactivity.

Example 4

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:20Yb³⁺,2Er³⁺@NaYF₄:10Yb³⁺,30Nd³⁺@NaYF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

firstly, preparing NaYF excited at 808nm₄:20Yb³⁺,2Er³⁺@NaYF₄:10Yb³⁺,30Nd³⁺@NaYF₄Core-shell structured upconversion nanocrystals

(1) Weighing 0.78mmol YCl₃·6H₂O，0.20mmol YbCl₃·6H₂O，0.02mmol ErCl₃·6H₂O is stirred and heated to 160 ℃ at the speed of 400r/min in the mixed solution of 15mL of 1-octadecene and 6mL of oleic acid under the argon environment, the temperature is kept for 40min, and the mixed solution is cooled to the room temperature after the rare earth is dissolved;

(2) weighing 2.5mmol sodium oleate and 4mmol ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol ammonium fluoride in 10mL methanol solution, gradually dripping the two solutions into the solution (1), stirring and heating to 60 ℃ at the speed of 300-400r/min under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(3) stirring the solution obtained in the step (2) at the speed of 300-;

(4) centrifuging the solution obtained in step (3) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Er³⁺Core nanocrystals, and dispersing the obtained core nanocrystals in 4mIn a cyclohexane solution;

(5) weighing 0.6mmol YCl₃·6H₂O，0.10mmol YbCl₃·6H₂O and 0.3mmol NdCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ at the speed of 400r/min under the condition of introducing argon, preserving heat for 40min, and cooling to 80 ℃ after the rare earth is dissolved and preserving heat;

(6) keeping the temperature of the solution obtained in the step (5) at 80 ℃, and adding 2ml of NaYF obtained in the step (4)₄:Yb³⁺,Er³⁺Nucleus nanocrystalline cyclohexane solution, and naturally cooling to room temperature after the cyclohexane solution in the solution is drained;

(7) weighing 2.5mmol of sodium oleate and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 300-400W to dissolve the sodium oleate and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dropwise adding the two solutions into the solution obtained in the step (6), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(8) stirring the solution obtained in the step (7) at the speed of 300-;

(9) centrifuging the solution obtained in step (8) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:20Yb³⁺,2Er³⁺@NaYF₄:10Yb³⁺,30Nd³⁺Core-shell structure nanocrystals, and dispersing the obtained up-conversion core-shell structure nanocrystals in 4mL of cyclohexane solution;

(10) weighing 1mmol YCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ at the speed of 400r/min under the condition of introducing argon, preserving heat for 40min, and cooling to 80 ℃ after the rare earth is dissolved and preserving heat;

(11) incubating the solution obtained in (10) at 80 ℃ and adding 1ml of NaYF obtained in (9)₄:20Yb³⁺,2Er³ ⁺@NaYF₄:10Yb³⁺,30Nd³⁺Cyclohexane solution of core-shell structure nanocrystalCooling naturally to room temperature after cyclohexane in the solution is drained;

(12) weighing 2.5mmol sodium oleate and 4mmol ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol ammonium fluoride in 10mL methanol solution, gradually dripping the two solutions into the solution obtained in the step (11), stirring and heating to 60 ℃ at the speed of 300-400r/min under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(13) stirring the solution obtained in the step (12) at the speed of 300-;

(14) centrifuging the solution obtained in step (13) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:20Yb³⁺,2Er³⁺@NaYF₄:10Yb³⁺,30Nd³⁺@NaYF₄Core-shell structured nanocrystals, and the resulting upconverted core-shell structured nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing the composite material with the molar ratio of 808nm excited up-conversion nanocrystalline to bioactive glass precursor being about 1:20

(1) Weighing 0.15g CTAB in 80mL deionized water, stirring for 15min at the rotating speed of 300-400r/min under the heat preservation of 40 ℃, adding the up-conversion nanocrystalline cyclohexane solution containing about 0.8mmol of up-conversion nanocrystalline prepared in 4mL (one) into the CTAB aqueous solution, stirring for 30min at the rotating speed of 300-400r/min under the heat preservation of 40 ℃, then stirring for 15-30min at the rotating speed of 300-400r/min under the heat preservation of 70-80 ℃, cooling to 40 ℃ after the cyclohexane is discharged, and then adding 40mL ethanol solution and stirring for 30min at the rotating speed of 300-400 r/min;

(2) a total of 18.2mmol of bioactive glass precursor reactants were prepared, namely: adding 1.63mL of tetraethyl orthosilicate dropwise into the solution obtained in the step (1), stirring at the rotating speed of 300-400r/min for 10min at 40 ℃, then adding 1mL of 25 wt% ammonia water into the solution, stirring for 10min, then adding 1.950mL of tributyl borate and 0.250mL of triethyl phosphate and stirring for 30min, and then weighing 1.546g of calcium nitrate tetrahydrate and adding the mixture into the solution and stirring for 3-4h at 40 ℃;

(3) centrifuging the solution obtained in the step (2) for 5-10min at the rotation speed of 4000r/min of a centrifuge, washing the obtained white centrifugal product with 30mL of ethanol and 30mL of deionized water for 2-3 times respectively, separating for 5-10min at the rotation speed of 4000r/min again by using the centrifuge, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h; (4) and (4) putting the product obtained in the step (3) into a muffle furnace, performing heat treatment for 4 hours at 600 ℃, removing a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with the 808nm excitation up-conversion luminescence property. The TEM image of the bioactive glass composite is shown in fig. 5, and it can be seen that the bioactive glass encapsulates the upconversion nanocrystals, and the composite is in the form of spherical particles with a size of about 150 nm.

Example 5

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:15Yb³⁺,2Ho³⁺@NaGdF₄:20Yb³⁺,20Nd³⁺@NaGdF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

firstly, preparing NaYF excited at 808nm₄:15Yb³⁺,2Ho³⁺@NaGdF₄:20Yb³⁺,20Nd³⁺@NaGdF₄Core-shell structured upconversion nanocrystals

(1) Weighing 0.83mmol YCl₃·6H₂O，0.15mmol YbCl₃·6H₂O，0.02mmol HoCl₃·6H₂O is put into a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirred and heated to 160 ℃ at the rotating speed of 400r/min under the argon environment, the temperature is kept for 40min, and the mixed solution is cooled to the room temperature after the rare earth is dissolved;

(2) weighing 2.5mmol sodium oleate and 4mmol ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol ammonium fluoride in 10mL methanol solution, gradually dripping the two solutions into the solution obtained in the step (1), stirring and heating to 60 ℃ at the rotating speed of 300-400r/min under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(3) stirring the solution obtained in the step (2) at the rotating speed of 300-;

(4) centrifuging the solution obtained in step (3) for 5010min at 8000r/min with a centrifuge, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Ho³⁺Carrying out nuclear nanocrystalline, and dispersing the obtained nuclear nanocrystalline in 4mL of cyclohexane solution;

(5) 0.6mmol GdCl was weighed₃·6H₂O，0.20mmol YbCl₃·6H₂O and 0.20mmol of NdCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ at the rotating speed of 400r/min under the condition of introducing argon, preserving heat for 40min, and cooling to 80 ℃ after the rare earth is dissolved and preserving heat;

(6) incubating the solution obtained in (5) at 80 ℃ and adding 2ml of NaYF obtained in (4)₄:Yb³⁺,Ho³⁺A nuclear nanocrystalline cyclohexane solution is naturally cooled to room temperature after cyclohexane in the solution is drained;

(7) weighing 2.5mmol of sodium oleate and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dropwise adding the two solutions into the solution (6), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(8) stirring the solution obtained in the step (7) at the rotating speed of 300-;

(9) centrifuging the solution obtained in step (8) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:15Yb³⁺,2Ho³⁺@NaGdF₄:20Yb³⁺,20Nd³⁺Core-shell structure nanocrystals, and dispersing the obtained up-conversion core-shell structure nanocrystals in 4mL of cyclohexane solution;

(10) weighing 1mmol GdCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ at the rotating speed of 400r/min under the condition of introducing argon, preserving heat for 40min, and cooling to 80 ℃ after the rare earth is dissolved and preserving heat;

(11) incubating the solution obtained in (10) at 80 ℃ and adding 1ml of NaYF obtained in (9)₄:15Yb³⁺,2Ho³ ⁺@NaGdF₄:20Yb³⁺,20Nd³⁺Cyclohexane solution of the core-shell structure nanocrystal, and naturally cooling to room temperature after cyclohexane in the solution is drained;

(12) weighing 2.5mmol sodium oleate and 4mmol ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol ammonium fluoride in 10mL methanol solution, gradually dripping the two solutions into the solution obtained in the step (11), stirring and heating to 60 ℃ at the speed of 300-400/min under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(13) stirring the solution obtained in the step (12) at the speed of 300-;

(14) centrifuging the solution obtained in step (13) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:15Yb³⁺,2Ho³⁺@NaGdF₄:20Yb³⁺,20Nd³⁺@NaGdF₄Core-shell structured nanocrystals, and the resulting upconverted core-shell structured nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing the composite material with the molar ratio of the 808nm excited up-conversion nanocrystalline to the bioactive glass precursor being about 1:50

(1) Weighing 0.1g CTAB, dissolving in 20mL deionized water, stirring for 10min at the rotation speed of 300-400r/min under the heat preservation at 40 ℃, adding the up-conversion luminescence nanocrystalline cyclohexane solution containing about 0.4mmol up-conversion luminescence nanocrystalline prepared in 2mL (one) into the CTAB aqueous solution, carrying out ultrasonic treatment for 30min at the power of 1000-1500r/min, then carrying out heat preservation at 70-80 ℃, stirring for 15-30min at the rotation speed of 300-400r/min, and exhausting cyclohexane to obtain the CTAB stable up-conversion nanocrystalline aqueous solution;

(2) adding 20mL of the CTAB stable up-conversion nanocrystalline aqueous solution obtained in the step (1) into a mixed solution of 40mL of deionized water and 6mL of ethanol, simultaneously dropwise adding 300 mu L of a sodium hydroxide solution with the concentration of 2mol/L, slowly dropwise adding 800 mu L of tetraethyl orthosilicate while stirring at the rotation speed of 300-400r/min under the heat preservation of 70 ℃, and reacting for 20min under the heat preservation of 70 ℃;

(4) dissolving 0.1g CTAB in 30mL of ethanol and 80mL of deionized water, then adding 15mL of the surface modified up-conversion nanocrystalline ethanol solution obtained in the step (3) into the CTAB solution, and stirring for 30min at the rotation speed of 400r/min at the temperature of 40 ℃;

(6) centrifuging the solution obtained in the step (5) for 5-10min at the rotating speed of 4000r/min by using a centrifuge, washing the obtained white centrifugal product with 30mL of ethanol and 30mL of deionized water for 2-3 times respectively, separating for 5-10min at the rotating speed of 4000r/min by using the centrifuge, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h;

(7) and (3) putting the product obtained in the step (6) into a muffle furnace, carrying out heat treatment for 5h at 450 ℃, removing a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with the 808nm excitation up-conversion luminescence property. An up-conversion luminescence spectrogram of the bioactive glass composite material under the excitation of 808nm is shown in fig. 6, and it can be seen that emission peaks are respectively located at 490nm, 550nm and 652nm, and corresponding luminescence colors are respectively blue light, green light and red light.

Example 6

A mesoporous bioactive glass composite material with up-conversion luminescence performance comprises rare earth-doped up-conversion nanocrystals and mesoporous borosilicate bioactive glass wrapped on the surfaces of the rare earth-doped up-conversion nanocrystals, wherein the rare earth-doped up-conversion nanocrystals are NaYF₄:35Yb³⁺,1Tm³⁺@NaGdF₄:5Yb³⁺,10Nd³⁺@NaYF₄The core-shell structure nanocrystal is prepared by a preparation method comprising the following steps:

firstly, preparing NaYF excited at 808nm₄:35Yb³⁺,1Tm³⁺@NaGdF₄:5Yb³⁺,10Nd³⁺@NaYF₄Core-shell structured upconversion nanocrystals

(1) Weighing 0.64mmol YCl₃·6H₂O，0.35mmol YbCl₃·6H₂O，0.01mmol TmCl₃·6H₂O is stirred and heated to 160 ℃ at the speed of 400r/min in the mixed solution of 15mL of 1-octadecene and 6mL of oleic acid under the argon environment, the temperature is kept for 40min, and the mixed solution is cooled to the room temperature after the rare earth is dissolved;

(2) weighing 2.5mmol sodium oleate and 4mmol ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol ammonium fluoride in 10mL methanol solution, gradually dripping the two solutions into the solution (1), stirring and heating to 60 ℃ at the speed of 300-400r/min under the protection of argon, and keeping the temperature for 45min until the methanol solution is drained;

(3) stirring the solution obtained in the step (2) at the speed of 300-;

(4) centrifuging the solution obtained in step (3) with a centrifuge at 8000r/min for 5-10min, and separating the productAdding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:Yb³⁺,Tm³⁺Carrying out nuclear nanocrystalline, and dispersing the obtained nuclear nanocrystalline in 4mL of cyclohexane solution;

(5) 0.85mmol GdCl was weighed₃·6H₂O，0.05mmol YbCl₃·6H₂O and 0.1mmol of NdCl₃·6H₂Dissolving O in a mixed solution of 15mL of 1-octadecene and 6mL of oleic acid, stirring and heating to 160 ℃ at the speed of 400r/min under the condition of introducing argon, preserving heat for 40min, and cooling to 80 ℃ after the rare earth is dissolved and preserving heat;

(6) keeping the temperature of the solution obtained in the step (5) at 80 ℃, and adding 2ml of NaYF obtained in the step (4)₄:Yb³⁺,Tm³⁺A nuclear nanocrystalline cyclohexane solution is naturally cooled to room temperature after cyclohexane in the solution is drained;

(7) weighing 2.5mmol of sodium oleate and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dropwise adding the two solutions into the solution obtained in the step (6), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until the methanol solution is exhausted;

(8) stirring the solution obtained in the step (7) at the speed of 300-;

(9) centrifuging the solution obtained in step (8) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:35Yb³⁺,1Tm³⁺@NaGdF₄:5Yb³⁺,10Nd³⁺Core-shell structure nanocrystals, and dispersing the obtained up-conversion core-shell structure nanocrystals in 4mL of cyclohexane solution;

(11) will (10)) The solution obtained in (1) is incubated at 80 ℃ and NaYF obtained in (1 m 9) is added₄:35Yb³⁺,1Tm³⁺@NaGdF₄:5Yb³⁺,10Nd³⁺The method comprises the following steps of (1) preparing a core-shell structure nanocrystalline cyclohexane solution, and naturally cooling to room temperature after the cyclohexane solution in the solution is drained;

(12) weighing 2.5mmol of sodium oleate and 4mmol of ammonium fluoride, respectively carrying out ultrasonic treatment for 15-20min at the power of 1000-1500W to dissolve the sodium oleate and the 4mmol of ammonium fluoride in 10mL of methanol solution, gradually dripping the two solutions into the solution obtained in the step (11), stirring and heating to 60 ℃ under the protection of argon, and keeping the temperature for 45min until methanol is exhausted;

(13) stirring the solution obtained in the step (12) at the speed of 300-;

(14) centrifuging the solution obtained in step (13) with a centrifuge at 8000r/min for 5-10min, separating the product, adding cyclohexane and ethanol solution at a certain ratio (volume ratio of 1:10) into the product, and repeatedly cleaning for 3-4 times to obtain NaYF₄:35Yb³⁺,1Tm³⁺@NaGdF₄:5Yb³⁺,10Nd³⁺@NaYF₄Core-shell structured nanocrystals, and the resulting upconverting core-shell structured nanocrystals were dispersed in 4mL of cyclohexane solution.

(II) preparing the composite material with the molar ratio of 808nm excited up-conversion nanocrystalline to bioactive glass precursor being about 1:100

(1) Weighing 0.15g of CTAB in 80mL of deionized water, stirring for 15min at the rotation speed of 300-400r/min under the heat preservation at 40 ℃, then adding the up-conversion nanocrystalline cyclohexane solution containing about 0.2mmol of up-conversion nanocrystalline prepared in 1mL of deionized water into the CTAB aqueous solution, stirring for 30min at the rotation speed of 300-400r/min under the heat preservation at 40 ℃, then stirring for 15-30min at the rotation speed of 300-400r/min under the heat preservation at 70-80 ℃, cooling to 40 ℃ after the cyclohexane is discharged, and then adding 40mL of ethanol solution and stirring for 30 min;

(3) centrifuging the solution obtained in the step (2) for 5-10min at the rotating speed of 4000r/min by using a centrifuge, washing the obtained white centrifugal product with 30mL of ethanol and 30mL of deionized water for 2-3 times respectively, separating for 5-10min at the rotating speed of 4000r/min by using the centrifuge again, and drying the obtained white product in an oven at the temperature of 50-60 ℃ for 24 h;

(4) and (4) putting the product obtained in the step (3) into a muffle furnace, carrying out heat treatment for 5h at 450 ℃ to remove a CTAB template agent, residual organic matters and the like, and controlling the heating rate at 1 ℃/min to finally obtain the mesoporous borosilicate bioactive glass composite material with 808nm excitation up-conversion luminescence performance. The up-conversion luminescence spectrum of the bioactive glass composite material under the excitation of 808nm is shown in FIG. 7, and the emission peaks of the emission spectrum can be seen to be located at 456nm (blue light), 475nm (blue light) and 650nm (red light).

In conclusion, the mesoporous borosilicate bioactive glass composite material which can be excited by lasers of 980nm and 808nm and emits visible light and has up-conversion luminescence performance can be prepared, and the mesoporous borosilicate bioactive glass composite material can be used for dynamically monitoring the degradation and mineralization process of bioactive glass.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The mesoporous bioactive glass composite material with the up-conversion luminescence property is characterized by comprising rare earth-doped up-conversion nanocrystals and a coatingMesoporous borosilicate bioactive glass on the surface of rare earth-doped up-conversion nanocrystalline, wherein the rare earth-doped up-conversion nanocrystalline is NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals or NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE_2(1-m-n)F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals wherein RE₁Is Tm, Er or Ho, RE₂Is Y or Gd, 0<x≤35mol％，0<y≤5mol％，0<m≤20mol％，0<n≤30mol％。

2. The mesoporous bioactive glass composite material with upconversion luminescence properties according to claim 1, wherein the rare earth doped upconversion nanocrystal is surface modified.

3. A method for preparing the mesoporous bioactive glass composite material with upconversion luminescence properties according to claim 1, wherein the preparation method comprises preparation of rare earth doped upconversion nanocrystals and composition of mesoporous borosilicate bioactive glass and rare earth doped upconversion nanocrystals.

4. The method for preparing a mesoporous bioactive glass composite material with up-conversion luminescence property according to claim 3, wherein the rare earth doped up-conversion nanocrystal is NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄When the core-shell structure nanocrystal is prepared, the preparation of the rare earth doped up-conversion nanocrystal specifically comprises the following steps:

(S1f) centrifuging the solution obtained in the step (S1e), and washing the solution with a mixed solution of cyclohexane and ethanol to obtain NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE₂F₄Core-shell structured nanocrystals.

5. The method for preparing a mesoporous bioactive glass composite material with up-conversion luminescence property according to claim 3, wherein the rare earth doped up-conversion nanocrystal is NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE_2(1-m-n)F₄:mYb³ ⁺,nNd³⁺@NaRE₂F₄When the core-shell structure nanocrystal is prepared, the preparation of the rare earth doped up-conversion nanocrystal specifically comprises the following steps:

(S1a) taking YCl₃·6H₂O、YbCl₃·6H₂O and RE₁Cl₃·6H₂O, to oleic acidStirring and heating the mixed solution of l-octadecene, and then cooling;

(S1f) centrifuging the solution obtained in the step (S1e), and washing the solution with a mixed solution of cyclohexane and ethanol to obtain NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE_2(1-m-n)F₄:mYb³⁺,nNd³⁺Core-shell structure nanocrystalline, then dispersed in cyclohexane solution;

(S1g) taking RE₂Cl₃·6H₂Adding O into the mixed solution of oleic acid and l-octadecene, stirring and heating, cooling for the first time, and adding NaY obtained in the step (S1f)_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE_2(1-m-n)F₄:mYb³⁺,nNd³⁺Cyclohexane solution of core-shell structure nanocrystal is cooled for the second time after cyclohexane is exhaustedBut;

(S1i) centrifuging the solution obtained in the step (S1h), and washing the solution with a mixed solution of cyclohexane and ethanol to obtain NaY_(1-x-y)F₄:xYb³⁺,yRE₁ ³⁺@NaRE_2(1-m-n)F₄:mYb³⁺,nNd³⁺@NaRE₂F₄Core-shell structured nanocrystals.

6. The method for preparing a mesoporous bioactive glass composite material with up-conversion luminescence property according to claim 4 or 5,

in the step (S1a), the stirring speed of stirring and heating is 300-;

in the step (S1b), the stirring speed of the first stirring and heating is 300-400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 300-400r/min, the stirring time is 60-100min, the heating temperature is 270-300 ℃, the heating time is 60-100min, and the cooling temperature is room temperature, which are all performed in the inert atmosphere;

in the step (S1c), the rotation speed of centrifugation is 8000-10000r/min, and the time of centrifugation is 5-10 min;

in the step (S1d), the stirring speed of stirring and heating is 300-;

in the step (S1e), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 400r/min, the stirring time is 150min, the heating temperature is 300 ℃ and 150min, and the cooling temperature is room temperature, which are all carried out in the inert atmosphere;

in the step (S1f), the rotation speed of centrifugation is 8000-10000r/min, and the time of centrifugation is 5-10 min;

in the step (S1g), the stirring speed of stirring and heating is 300-;

in the step (S1h), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 40-60min, the heating temperature is 60-65 ℃, the heating time is 40-60min, the stirring speed of the second stirring and heating is 400r/min, the stirring time is 150min, the heating temperature is 300 ℃ and 150min, and the cooling temperature is room temperature, which are all carried out in the inert atmosphere;

in the step (S1i), the rotation speed of the centrifugation is 8000-10000r/min, and the time of the centrifugation is 5-10 min.

7. The method for preparing the mesoporous bioactive glass composite material with the upconversion luminescence property according to claim 3, wherein the compounding of the mesoporous borosilicate bioactive glass and the rare earth doped upconversion nanocrystal specifically comprises the following steps:

(S2b) sequentially adding tetraethyl orthosilicate, ammonia water, tributyl borate, triethyl phosphate and calcium nitrate tetrahydrate into the solution obtained in the step (S2a), stirring and heating, then centrifugally separating, washing and drying, and then carrying out heat treatment to obtain the mesoporous bioactive glass composite material with the up-conversion luminescence property.

8. The method for preparing the mesoporous bioactive glass composite material with the upconversion luminescence property according to claim 3, wherein the compounding of the mesoporous borosilicate bioactive glass and the rare earth doped upconversion nanocrystal specifically comprises the following steps:

(S2b) sequentially adding tetraethyl orthosilicate, ammonia water, tributyl borate, triethyl phosphate and calcium nitrate tetrahydrate into the solution obtained in the step (S3c), stirring and heating, then centrifugally separating, washing and drying, and then carrying out heat treatment to obtain the mesoporous bioactive glass composite material with the up-conversion luminescence property.

9. The method for preparing a mesoporous bioactive glass composite material with up-conversion luminescence property according to claim 7 or 8,

in the step (S2a), the stirring speed of the first stirring and heating is 300-400r/min, the stirring time is 30-60min, the heating temperature is 40 ℃, the heating time is 30-60min, the stirring speed of the second stirring and heating is 300-400r/min, the stirring time is 15-30min, the heating temperature is 70-80 ℃, the heating time is 15-30min, and the cooling temperature is 40 ℃;

in the step (S2b), the stirring speed of stirring and heating is 400-;

in the step (S3a), the stirring speed of the first stirring and heating is 400r/min, the stirring time is 10min, the heating temperature is 40 ℃, the heating time is 10min, the ultrasonic power is 800-1200W, the ultrasonic time is 30min, the stirring speed of the second stirring and heating is 400r/min, the stirring time is 15-30min, the heating temperature is 70-80 ℃, and the heating time is 15-30 min;

in the step (S3b), the rotation speed of centrifugation is 8000-10000r/min, and the time of centrifugation is 5-10 min;

in the step (S3c), the stirring speed for stirring and heating is 300-400r/min, the stirring time is 30min, the heating temperature is 40 ℃, and the heating time is 30 min.

10. Use of the mesoporous bioactive glass composite material having upconversion luminescence properties according to claim 1 or 2 for dynamically monitoring the degradation mineralization process of bioactive glass.