CN106587645B - Biological glass fiber material with up-conversion luminescence effect and preparation method thereof - Google Patents

Biological glass fiber material with up-conversion luminescence effect and preparation method thereof Download PDF

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CN106587645B
CN106587645B CN201611077719.0A CN201611077719A CN106587645B CN 106587645 B CN106587645 B CN 106587645B CN 201611077719 A CN201611077719 A CN 201611077719A CN 106587645 B CN106587645 B CN 106587645B
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calcium fluoride
composite material
spinning
biological glass
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CN106587645A (en
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陶选宁
方思懿
方明
李翔
朱伟强
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Zhejiang Kangfeishi Medical Technology Co Ltd
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Zhejiang Kangfeishi Medical Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/30—Methods of making the composites

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

According to the invention, the upconversion luminescent calcium fluoride nanoparticles with the particle size of 5-10 nm are prepared by a hydrothermal method, and the bioglass fiber composite material doped with the upconversion luminescent nanoparticles is prepared by combining sol-gel with an electrostatic spinning method, so that the method is simple and convenient, and the operability is strong. The obtained fiber has controllable size, uniform distribution and good continuity. The fiber composite material prepared by the invention has the advantages of good biocompatibility, strong bioactivity, degradability and the like, and has wide application prospect in biomedicine, such as important application in the fields of tissue engineering scaffolds, biological probes, tissue or cell imaging, drug tracing and the like.

Description

biological glass fiber material with up-conversion luminescence effect and preparation method thereof
Technical Field
The invention belongs to the technical field of applied inorganic advanced nano materials, and particularly relates to a biological glass fiber material with an up-conversion luminescence effect and a preparation method thereof, which can be applied to the fields of tissue scaffold materials, biological tissue imaging, medicine tracing and the like.
Background
The bioglass is an important inorganic medical material invented by Larry Hench in the sixties of the last century, and the bioglass mainly comprises silicon-based oxide such as SiO2、CaO、P2O5And the like. Because of its good biocompatibility, strong biological activity and biodegradability, it is especially suitable for biological engineeringThe glass can form hydroxyapatite bone structure in body fluid, can form strong combination with natural bone, and has important application in tissue engineering, so that the glass has been continuously and widely researched. However, because bioglass is a complex change process in body fluid, the degree of reaction progress generated in different stages cannot be well quantified at present, which limits the clinical application of bioglass, and therefore, the invention of bioglass capable of monitoring the change process in real time has great significance. In recent years, in view of the rare earth up-conversion luminescent material having excellent properties such as low excitation light source energy, small tissue damage, excellent optical property, good chemical stability, small biological tissue absorption, large penetrating power and the like, the rare earth up-conversion luminescent material is introduced into a biological glass matrix, so that optical signal monitoring in a change process can be well realized, and the change process of the biological glass is scientifically grasped.
However, the existing rare earth up-conversion luminescent material-bioglass composite material has many defects, such as biotoxicity, poor luminescent intensity, even due to material compounding, the Si-O-Si network integrity of bioglass is greatly reduced, the bioglass degradation is accelerated, and the release of non-bioferrindly rare earth materials is caused, so that the problems of inflammation and the like are caused.
disclosure of Invention
In view of the above technical description, the present invention provides a bioglass fiber material with good biocompatibility, high luminous efficiency and luminous intensity, and up-conversion luminous effect, and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
The composite material consists of biological glass fibers and calcium fluoride nanoparticles loaded inside the biological glass fibers, the size of the biological glass fibers is controllable between 50 and 500 nanometers, and the size of the calcium fluoride nanoparticles is 5 to 10 nanometers. (the high crystallinity and small size of the particles gives the cap composite fiber strong photoluminescence properties)
a preparation method of a calcium fluoride nanoparticle and biological glass fiber composite material is characterized by comprising the following steps:
(1) According to the chemical formula Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+Weighing calcium nitrate tetrahydrate, erbium nitrate pentahydrate and ytterbium nitrate pentahydrate according to the molar ratio of the elements, wherein the total amount is 4 mmol; then, the solution A is added to 80mL of deionized water together with 8mmol of trisodium citrate to obtain a solution A. Then 8mmol of sodium fluoborate is added into 40 ml of deionized water to obtain a solution B. Solution B was added to solution a by a peristaltic pump and the pH of the solution was adjusted to 7 with ammonia.
(2) And transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 5-7 h. And centrifuging until the reaction kettle is cooled to room temperature (20-25 ℃), centrifuging and cleaning reactants in the reaction kettle to obtain a white precipitate, and drying in an oven at 80 ℃ to obtain the rare earth doped calcium fluoride up-conversion luminescent nanoparticles.
(3) Preparing a bioglass precursor solution: 1.67g of tetraethyl orthosilicate, calcium nitrate tetrahydrate in a molar ratio of 70: 30 adding 10mL of ethanol solution containing 200 microliter of acetic acid and 600 microliter of water, adding polyvinylpyrrolidone with a certain amount of molecular weight of 1300000, controlling the concentration of the polyvinylpyrrolidone to be 0.06-0.12 g/mL, stirring uniformly, and then adding 2.5mL of ethanol solution of rare earth doped calcium fluoride up-conversion luminescent nano-particles with the concentration of 2 mg/mL. And stirring for 1.5h to obtain a spinning precursor.
(4) The spinning precursor is transferred into an injector, the spinning precursor is spun into fiber shape at a certain speed by an electrostatic spinning device, a grounded flat plate with aluminum foil is used as a receiving device, and then the receiving device is placed into an oven for drying for 12 hours. And finally, sintering the mixture for 5 hours at 550 ℃ in a muffle furnace to obtain the up-conversion luminescent calcium fluoride nano-particle and biological glass fiber composite material.
further, in the step 4, the spinning flow rate is controlled to be 0.6-0.8mL/h, and the spinning voltage value range is 7-8 kV.
the invention has the beneficial effects that:
(1) The synthesized luminescent calcium fluoride nanoparticles have small particle size and high luminous intensity, and can be well used as an optical signal tracking material. On the other hand, the Si-O bond of the bioglass is not broken, and the stability of the material is improved from the whole structure.
(2) The composite fiber material prepared by the preparation method has stable performance and strong controllability, and the used solvent is ethanol, so that the composite fiber material is green and pollution-free.
(3) The biological glass fiber material with the up-conversion luminescence effect has important application prospects in the fields of tissue engineering, biological tissue imaging and drug tracing.
Drawings
Fig. 1 is an upconversion luminescence curve of the composite fiber prepared in example 1.
FIG. 2 is a scanning electron microscope image of the rare earth doped calcium fluoride up-conversion luminescent nanoparticles prepared by the present invention.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the drawings and specific embodiments, but the present invention is not limited to the embodiments, and those skilled in the art can make modifications according to the actual situations.
Example 1
This example follows Li X, Li Y, Chen X, et al, optical Monitoring and minimization on Photocolloidal emission Bioactive Nanofibers [ J]preparation of CaTiO, described in Langmuir,2016,32(13):3226-32333:Yb3+,Er3+@ BG nanofibrers. The method comprises the following specific steps:
(1) Preparing CaTiO3 Yb and Er nano-particles by adopting a coprecipitation method, and then ultrasonically dispersing the CaTiO3 Yb and Er nano-particles in an ethanol solution to enable the concentration of the nano-particles to be 2mg/ml to obtain a solution B;
(2) Dissolving 1.67g of tetraethyl orthosilicate, 0.675g of calcium nitrate and 0.21g of triethyl phosphate in a mixed solvent of 10mL of ethanol and 400 mul of deionized water, adding 0.2mL of acetic acid with the mass fraction of more than or equal to 99% as a catalyst, stirring for 1.5 hours, adding 3mL of dimethylformamide solution, then adding 0.9 g of PVP powder with the molecular weight of 1300000, and continuing stirring to obtain a solution A;
(3) Dropwise adding 10ml of the solution B into the stirred solution A, and uniformly mixing to obtain a solution C;
(4) Taking a grounded flat plate with an aluminum foil as a receiving device, spinning by using the solution C, controlling the flow rate to be 0.8ml/h, controlling the receiving distance to be 15cm and the voltage value range to be 7-10kV, and then drying the spun composite fiber in a forced air drying oven at 80 ℃ for 12 h; in the spinning process, a halogen tungsten lamp and a high-speed camera are matched to observe the spinning process in real time, and the size of the fiber is controlled by observing the angle of the Taylor cone.
(5) And (3) putting the dried composite fiber into a crucible for heat treatment in a sintering furnace, raising the temperature to 600 ℃ at the rate of 5 ℃/min in the air, and preserving the heat for 3h to obtain the biological glass fiber with near infrared light response and capable of monitoring the mineralization activity.
Example 2
In the light of example 1, CaF is first prepared by coprecipitation2:Yb3+,Er3+Nanoparticle, further preparation of CaF by electrospinning2:Yb3+,Er3+@ BG nanofibrers. In the spinning process, a tungsten halogen lamp and a high-speed camera are matched to observe the spinning process in real time, and the size of the fiber is controlled by observing the angle of the Taylor cone, so that the size of the fiber is consistent with that of the fiber in the embodiment 1.
Example 3
(1) According to the chemical formula Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+Weighing calcium nitrate tetrahydrate, erbium nitrate pentahydrate and ytterbium nitrate pentahydrate according to the molar ratio of the elements, wherein the total amount is 4 mmol; then, the solution A is added to 80mL of deionized water together with 8mmol of trisodium citrate to obtain a solution A. Then 8mmol of sodium fluoborate is added into 40 ml of deionized water to obtain a solution B. Solution B was added to solution a by a peristaltic pump and the pH of the solution was adjusted to 7 with ammonia.
(2) and transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 5 hours. And centrifuging until the reaction kettle is cooled to room temperature (20-25 ℃), centrifuging and cleaning reactants in the reaction kettle to obtain a white precipitate, and drying in an oven at 80 ℃ to obtain the rare earth doped calcium fluoride up-conversion luminescent nanoparticles.
(3) Preparing a bioglass precursor solution: 1.67g of tetraethyl orthosilicate, calcium nitrate tetrahydrate in a molar ratio of 70: 30 adding 10mL of ethanol solution containing 200 microliter of acetic acid and 600 microliter of water, adding polyvinylpyrrolidone with a certain amount of molecular weight of 1300000, controlling the concentration of the polyvinylpyrrolidone to be 0.06g/mL, stirring uniformly, and then adding 2.5mL of ethanol solution of rare earth doped calcium fluoride up-conversion luminescent nano-particles with the concentration of 2 mg/mL. And stirring for 1.5h to obtain a spinning precursor.
(4) The spinning precursor is transferred into an injector, the spinning precursor is spun into fiber shape at a certain speed by an electrostatic spinning device, a grounded flat plate with aluminum foil is used as a receiving device, and then the receiving device is placed into an oven for drying for 12 hours. And finally, sintering the mixture for 5 hours at 550 ℃ in a muffle furnace to obtain the up-conversion luminescent calcium fluoride nano-particle and biological glass fiber composite material.
The composite materials prepared in the embodiments 1-3 are observed by a TEM (transmission electron microscope), and the three composite materials are respectively composed of biological glass fibers and nano particles loaded in the biological glass fibers, wherein the size of the biological glass fibers is about 150-170 nanometers; the size of calcium carbonate in the composite material prepared in example 1 is 100-150 nm. The size of the calcium fluoride nanoparticles in the composite material prepared in example 2 is 50-80 nm, and the size of the calcium fluoride nanoparticles in the composite material prepared in example 3 is 5-10 nm.
Degrading the three materials prepared in examples 1-3 in simulated body fluid, wherein after 2 months, the degradation degree of bioglass in the up-conversion luminescent calcium fluoride nanoparticle and bioglass fiber composite material prepared in example 3 is 14%, the degradation degree of up-conversion luminescent calcium carbonate nanoparticle and bioglass fiber composite material prepared in example 1 is 38%, and the degradation degree of up-conversion luminescent calcium fluoride nanoparticle and bioglass fiber composite material prepared in example 2 is 29%; undoped bioglass was additionally subjected to a degradation test, and after 2 months, the degree of degradation was 13%.
It is presumed that the size of the nanoparticle supported inside the bioglass fiber has an important influence on bioglass degradation under the same production conditions. Generally, one skilled in the art would slow the degradation by varying the ratio of bioglass precursor to internally loaded particles in the spin precursor. In fact, the degradation rate is not changed at all, and the degradation time is prolonged only by increasing the content of the bioglass, and meanwhile, the fluorescence effect is weakened due to the fact that the content of the bioglass is too high. The invention creatively provides a composite material of calcium fluoride nano-particles and biological glass fibers by researching a degradation mechanism, wherein the size of the calcium fluoride nano-particles loaded in the biological glass fibers is 5-10 nanometers. Due to the small size of the particles, the integrity of a biological glass Si-O-Si network is not damaged, the degradation of the biological glass Si-O-Si network is not accelerated, and meanwhile, due to the high crystallinity and the small size of the particles, the composite fiber has stronger photoluminescence performance, and can realize 980nm infrared light excitation and emit green light with a wave band of 550-560nm and red light with a wave band of 660-670nm as shown in figure 1 a. Compared with the up-conversion luminescent calcium fluoride nano-particles, the crystallinity of the nano-particles is improved due to sintering after compounding, so that the luminescent property is improved. Fig. 1b is a high resolution scanning chart of the upconversion luminescent calcium fluoride nanoparticle and bioglass fiber composite material, and it can be seen from the figure that the nanoparticle (d (111) ═ 0.316nm) outer layer has an amorphous bioglass phase.
Example 4
In this example, rare earth-doped calcium fluoride up-conversion luminescent nanoparticles were prepared by changing the hydrothermal reaction conditions in example 3, and the growth mechanism of the rare earth-doped calcium fluoride up-conversion luminescent nanoparticles in the present invention was studied.
(1) According to the chemical formula Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+Weighing calcium nitrate tetrahydrate, erbium nitrate pentahydrate and ytterbium nitrate pentahydrate according to the molar ratio of the elements, wherein the total amount is 4 mmol; then, the solution A is added to 80mL of deionized water together with 8mmol of trisodium citrate to obtain a solution A. Then 8mmol of sodium fluoborate is added into 40 ml of deionized water to obtain a solution B. Solution B was added to solution a by a peristaltic pump and the pH of the solution was adjusted to 7 with ammonia.
(2) The solution was transferred to a polytetrafluoroethylene reaction vessel for hydrothermal reaction, and the time and temperature of the hydrothermal reaction are shown in table 1. And centrifuging until the reaction kettle is cooled to room temperature (20-25 ℃), centrifuging and cleaning reactants in the reaction kettle to obtain a white precipitate, and drying in an oven at 80 ℃ to obtain the rare earth doped calcium fluoride up-conversion luminescent nanoparticles. The sizes of the nanoparticles are shown in Table 1
according to the results, the rare earth doped calcium fluoride up-conversion luminescent nano particles are sensitive to temperature and reaction time, and the preparation method provided by the invention is a technical scheme obtained through a large number of experimental analyses and strict logical reasoning.

Claims (3)

1. A composite material of calcium fluoride nano-particles and biological glass fibers is characterized in that,
The chemical general formula of the calcium fluoride nano-particles is Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+；
The composite material is composed of biological glass fibers and calcium fluoride nanoparticles loaded inside the biological glass fibers, the size of the biological glass fibers is controllable between 50 and 500 nanometers, the size of the calcium fluoride nanoparticles is 5 to 10 nanometers, and the composite fibers have strong photoluminescence performance due to high crystallinity and small scale of the particles.
2. A method for preparing the calcium fluoride nanoparticle and bioglass fiber composite material as claimed in claim 1, which comprises the following steps:
(1) According to the chemical formula Ca1-0.18-0.02F2:0.18Yb3+,0.02Er3+The molar ratio of each element in the mixture is weighed to obtain calcium nitrate tetrahydrateErbium nitrate pentahydrate and ytterbium nitrate pentahydrate, the total amount being 4 mmol; then adding 8mmol of trisodium citrate into 80mL of deionized water to obtain a solution A; then adding 8mmol of sodium fluoborate into 40 ml of deionized water to obtain a solution B; adding the solution B into the solution A through a peristaltic pump, and adjusting the pH of the solution with ammonia water to 7;
(2) transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 5-7 h; centrifuging, after the reaction kettle is cooled to room temperature (20-25 ℃), centrifugally cleaning reactants in the reaction kettle to obtain a white precipitate, and drying the white precipitate in an oven at 80 ℃ to obtain rare earth doped calcium fluoride up-conversion luminescent nanoparticles;
(3) preparing a bioglass precursor solution: 1.67g of tetraethyl orthosilicate, calcium nitrate tetrahydrate in a molar ratio of 70: 30 adding 10mL of ethanol solution containing 200 microliters of acetic acid and 600 microliters of water, adding polyvinylpyrrolidone with a certain amount of molecular weight of 1300000, controlling the concentration of the polyvinylpyrrolidone to be 0.06-0.12 g/mL, stirring uniformly, and then adding 2.5mL of ethanol solution of rare earth doped calcium fluoride up-conversion luminescent nanoparticles with the concentration of 2 mg/mL; continuously stirring for 1.5h to obtain a spinning precursor;
(4) Transferring the spinning precursor into an injector, spinning the spinning precursor into a fibrous shape at a certain speed by using an electrostatic spinning device, taking a grounded flat plate with an aluminum foil as a receiving device, and then putting the receiving device into an oven for drying for 12 hours; and finally, sintering the mixture for 5 hours at 550 ℃ in a muffle furnace to obtain the up-conversion luminescent calcium fluoride nano-particle and biological glass fiber composite material.
3. The method for preparing a calcium fluoride nanoparticle and bioglass fiber composite material as claimed in claim 2, wherein in the step 4, the spinning flow rate is controlled to be 0.6-0.8mL/h, and the spinning voltage value is controlled to be 7-8 kV.
CN201611077719.0A 2016-11-29 2016-11-29 Biological glass fiber material with up-conversion luminescence effect and preparation method thereof Active CN106587645B (en)

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