WO2022246725A1 - Nanomatériau noyau-enveloppe de terre rare et procédé de préparation associé - Google Patents

Nanomatériau noyau-enveloppe de terre rare et procédé de préparation associé Download PDF

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WO2022246725A1
WO2022246725A1 PCT/CN2021/096293 CN2021096293W WO2022246725A1 WO 2022246725 A1 WO2022246725 A1 WO 2022246725A1 CN 2021096293 W CN2021096293 W CN 2021096293W WO 2022246725 A1 WO2022246725 A1 WO 2022246725A1
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rare earth
solution
earth core
nanomaterial
shell
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Chinese (zh)
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郑海荣
盛宗海
胡德红
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深圳先进技术研究院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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

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  • the present application relates to the field of nanomaterials, in particular to a rare earth core-shell nanomaterial and a preparation method thereof.
  • Rare earth luminescent nanomaterials are a type of photoluminescent material that can store excitation energy in the material and release the stored energy in the form of radioluminescence after the excitation light stops irradiating. Rare earth luminescent nanomaterials have many advantages such as narrow emission, long lifetime, and resistance to photobleaching, and have important application values in biomarkers and bioimaging.
  • the excitation light of rare earth luminescent nanomaterials used for biological imaging is in the infrared band, but infrared light has defects such as poor tissue penetration and poor three-dimensionality, which in turn leads to low luminous efficiency and poor imaging effect of rare earth luminescent nanomaterials.
  • X-rays have good penetrability to the human body, which is conducive to the application in biological imaging.
  • the preparation methods are complicated, and the production cost is high. If the time is long, the resulting rare earth luminescent nanomaterial has poor stability, which is unfavorable for popularization and use.
  • the application provides a rare earth core-shell nanomaterial and a preparation method thereof.
  • the method uses an aqueous phase system to prepare a rare earth luminescent nanomaterial, which improves the stability of the rare earth luminescent nanomaterial, and has a simple preparation process and low cost. It is conducive to large-scale production, and the obtained rare earth core-shell nanomaterials not only have regular shape and uniform particle size, but also can produce strong luminescent effect under X-ray excitation, which is conducive to its application in biological imaging.
  • the present application also provides a rare earth core-shell nano material, which has good stability and high luminous efficiency, and can be applied in the fields of biomarkers, bioimaging and the like.
  • the first aspect of the present application provides a method for preparing rare earth core-shell nanomaterials, comprising the following steps:
  • the terbium salt, the lutetium salt, the alkali and the solvent are subjected to a first mixed treatment to form a first solution;
  • the solvent includes water, n-butanol and oleic acid with a volume ratio of 1:(0.1-10):(0.1-10);
  • the rare earth core nanomaterial includes ⁇ -NaLuF 4 : Tb;
  • the third solution is mixed with ammonium fluoride to obtain the fourth solution; the fourth solution is placed in a hydrothermal kettle and reacted at 100°C-300°C for 1h-72h to obtain the rare earth core-shell nano material, the shell layer of the rare earth core-shell nanomaterial includes NaYF 4 .
  • This application adopts the aqueous phase synthesis method to prepare rare earth core-shell nanomaterials with molecular formula ⁇ -NaLuF 4 :Tb@NaYF 4 , wherein ⁇ -NaLuF 4 :Tb is the core body of rare earth core-shell nanomaterials, and NaYF 4 is rare earth core-shell Housings of nanomaterials.
  • n-butanol and oleic acid in the solvent can form a microemulsion with water, thereby adsorbing metal ions in the solution, so that the reaction is carried out in the microbubbles of the microemulsion, and the structure of the rare earth nanomaterial is improved.
  • Uniformity so that the rare earth core-shell nanomaterial has a narrow particle size distribution and dispersion performance; and the obtained rare earth core-shell nanomaterial has high crystal phase purity and stable luminescence performance, which is beneficial for application in biological imaging.
  • the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate.
  • the lutetium salt includes one or more of lutetium chloride, lutetium nitrate and lutetium acetate.
  • the molar ratio of the terbium salt to the lutetium salt is 1:(4-99).
  • the sum c 1 of the molar concentrations of the terbium salt and the lutetium salt is 0.1 mol ⁇ L -1 -2 mol ⁇ L -1 .
  • the ratio of the sum c 1 of the molar concentrations of the terbium salt and the lutetium salt to the molar concentration c F1 of the ammonium fluoride is 1:(1-50).
  • the alkali includes one or more of sodium hydroxide and potassium hydroxide.
  • the volume ratio of n-butanol and oleic acid is 1:(0.1-10).
  • the molar concentration of the yttrium salt is 0.1 mol ⁇ L -1 -2 mol ⁇ L -1 .
  • the molar ratio of the yttrium salt to the rare earth core nanomaterial is 1:(10-100).
  • the molar concentration ratio of the yttrium salt to the ammonium fluoride is 1:(1-50).
  • the pH of the first solution and the third solution is 10-12.
  • the first mixing process, the second mixing process, the third mixing process and the fourth mixing process are mixed using probe ultrasound, and the power of the probe ultrasound is 50W-500W.
  • the temperatures of the first mixing treatment, the second mixing treatment, the third mixing treatment and the fourth mixing treatment are 0°C-10°C.
  • the present application synthesized highly uniform and monodisperse ⁇ -NaLuF 4 : Tb@NaYF 4 rare earth core-shell nanomaterials through the aqueous phase synthesis method.
  • the preparation method is simple, the reaction conditions are easy to control, and the production cost is low.
  • the prepared rare earth core Shell nanomaterials have bright afterglow, long afterglow time, stable chemical properties, no radioactivity, and high safety to the human body.
  • the second aspect of the present application provides a rare earth core-shell nanomaterial
  • the rare earth core-shell nanomaterial includes a rare earth core nanomaterial and a shell layer coated on the surface of the rare earth core nanomaterial;
  • the rare earth core nanomaterial includes ⁇ - NaLuF 4 :Tb;
  • the shell layer of the rare earth core-shell nanomaterial includes NaYF 4 .
  • Fig. 1 is the preparation method of the rare earth core-shell nanomaterial provided by an embodiment of the present application
  • Figure 2 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
  • Example 3 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 2 of the present application.
  • Figure 4 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 3 of the present application.
  • Figure 5 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 4 of the present application.
  • Figure 6 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 5 of the present application.
  • Figure 7 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 6 of the present application.
  • Figure 8 is a particle size distribution diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
  • Figure 9 is a diagram of the luminescence properties of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
  • Figure 10 is the luminescent spectrum diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
  • Figure 11 is an in vivo imaging diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
  • Fig. 12 is a biotoxicity test chart of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
  • the excitation light of rare earth luminescent nanomaterials used for biological imaging is in the infrared band.
  • infrared light has defects such as poor tissue penetration and poor three-dimensionality, resulting in poor imaging effects.
  • X-rays have good penetrability to the human body, and can penetrate the skin and muscles to directly see the bones in the body without directly contacting the human body. Therefore, the research and development of new rare earth luminescent nanomaterials based on X-ray excitation is of great significance for biomedical imaging, diagnosis and treatment.
  • this application provides a rare earth core-shell nanomaterial ⁇ -NaLuF 4 :Tb@NaYF 4 that uses X-rays as excitation light to achieve bioimaging, wherein the rare earth core-shell nanomaterial
  • the core body includes ⁇ -NaLuF 4 :Tb
  • the shell of the rare earth core-shell nanomaterial includes NaYF 4 .
  • the core body ⁇ -NaLuF 4 :Tb of the rare earth core-shell nanomaterial can be excited by X-rays and generate strong fluorescence.
  • the crystal phase of NaLuF 4 : Tb is a body-centered cubic structure ( ⁇ -), and NaLuF 4 : Tb with a body-centered cubic structure has a higher degree of crystallization and fewer surface defects, so it has high luminous brightness and stable luminescent performance.
  • the shell NaYF 4 of rare earth core-shell nanomaterials can improve the surface lattice of rare earth core-shell nanomaterials, reduce surface scattering, and suppress the phenomenon of fluorescence quenching, thereby improving the energy transfer efficiency between surface ions and making rare earth core-shell nanomaterials
  • the material has high luminous efficiency.
  • ⁇ -NaLuF 4 :Tb means terbium-doped sodium lutetium fluoride, wherein the molar ratio of Tb to Lu is 1:(4-99). In some embodiments of the present application, the molar ratio of Tb and Lu is 1:(4-10). Doping terbium in lutetium sodium fluoride can adjust the luminescent properties of rare earth core-shell nanomaterials, so that the rare earth core-shell nanomaterials have a suitable afterglow emission time.
  • the afterglow emission duration of the rare earth core-shell nanomaterial is 5 days to 30 days, and the afterglow emission duration of the rare earth core-shell nanomaterial can be, but not limited to, 5 days, 10 days, 15 days, 20 days, 25 days. days or 30 days. If the afterglow emission time of rare earth core-shell nanomaterials is too short, the biological imaging process will be shorter and the imaging effect will be poor; if the afterglow emission time is too long, it will be unfavorable for subsequent imaging detection and repetition of in vitro diagnostic test strips Therefore, the afterglow emission time of rare earth core-shell nanomaterials should be controlled to ensure better imaging effect and not affect the repeated use of multiple injections in vivo and in vitro diagnostic test strips.
  • the particle size of the core body of the rare earth core-shell nanomaterial is 1-300 nm.
  • the particle size of the core body of the rare earth core-shell nanomaterial can be, but not limited to, 1 nm, 10 nm, 50 nm, 100 nm, 200 nm or 300 nm.
  • the thickness of the shell of the rare earth core-shell nanomaterial is 1-40 nm. Specifically, the thickness of the shell of the rare earth core-shell nanomaterial can be, but not limited to, 1 nm, 10 nm, 30 nm, 40 nm or 50 nm.
  • the ratio of the particle size of the core to the thickness of the shell is 1:(1-10).
  • the ratio of the particle size of the core to the thickness of the shell may be, but not limited to, 1:1, 1:3, 1:5 or 1:10. Controlling the particle size of the core body and the thickness of the shell can ensure that the rare earth core-shell nanomaterial has stable luminescence performance and high luminescence efficiency.
  • the rare earth core-shell nanomaterial is a spherical particle, and the spherical particle has a small specific surface area, the quenching effect of the particle surface on the luminescent ion is small, and the luminous efficiency of the particle is high.
  • the average particle size of the rare earth core-shell nanomaterial is 50nm-200nm.
  • the average particle size of the rare earth core-shell nanomaterial ⁇ -NaLuF 4 :Tb@NaYF 4 can be, but not limited to, 50nm, 70nm, 90nm, 95nm, 100nm, 105nm, 110nm, 130nm, 150nm or 200nm.
  • the rare earth core-shell nanomaterial ⁇ -NaLuF 4 :Tb@NaYF 4 provided by this application can realize fluorescence emission under X-ray excitation, has high luminous efficiency and stable luminescent performance, and is beneficial for application in biological imaging.
  • FIG. 1 is a preparation method of the rare earth core-shell nanomaterial provided in an embodiment of the present application, including:
  • Step 100 performing a first mixing treatment on terbium salt, lutetium salt, alkali and solvent to form a first solution;
  • Step 200 performing a second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle and reacting at 100°C-300°C for 1h-72h to obtain a rare earth core nanomaterial;
  • Step 300 performing a third mixing treatment on the yttrium salt, the rare earth core nanomaterial, the alkali and the solvent to form a third solution;
  • Step 400 Perform fourth mixing treatment on the third solution and ammonium fluoride to obtain the fourth solution; place the fourth solution in a hydrothermal kettle and react at 100°C-300°C for 1h-72h to obtain rare earth core-shell nanomaterials .
  • the solvent includes water, n-butanol and oleic acid.
  • N-butanol can be used as a co-surfactant to promote the formation of microemulsion system between oleic acid and water.
  • the microemulsion system has a large reaction interface, which can increase the reaction rate and facilitate the formation of uniform and monodisperse nanoparticles.
  • the volume ratio of water, n-butanol and oleic acid is 1:(0.1-10):(0.1-10).
  • the volume ratio of water, n-butanol and oleic acid is 1:(0.1-1):(0.1-1), and when the volume of water is relatively high, it is beneficial to improve the dispersion of the product rare earth core nanomaterial in water performance. Under the above volume ratio range, an isotropic thermodynamically stable microemulsion system can be formed, thereby ensuring the formation of highly uniform, monodisperse rare earth core nanomaterials.
  • the pH value of the reaction system can be adjusted by adding alkali, thereby changing the solubility of terbium salt and lutetium salt in the reaction system, thereby controlling the reaction rate.
  • the pH value will also affect the relative growth rate of each crystal plane. Thus forming crystals with different structures.
  • the pH of the first solution is 10-12. Under the above pH conditions, it is beneficial for the reaction to proceed rapidly and stably, and can promote the formation of ⁇ -NaLuF 4 :Tb rare earth core-shell nanomaterials.
  • the alkali includes one or more of sodium hydroxide and potassium hydroxide.
  • the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate.
  • the lutetium salt includes one or more of lutetium chloride, lutetium nitrate and lutetium acetate.
  • the molar ratio of the terbium salt and the lutetium salt is 1:(4-99). In some embodiments of the present application, the molar ratio of the terbium salt and the lutetium salt is 1:(4-10).
  • the molar ratio of the terbium salt to the lutetium salt may be, but not limited to, 1:4, 1:6, 1:10, 1:15, 1:20, 1:40, 1:60 or 1:99.
  • the sum c 1 of the molar concentrations of the terbium salt and the lutetium salt is 0.1 mol ⁇ L -1 -2 mol ⁇ L -1 .
  • the first mixing process is to use probe ultrasound for mixing, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 10min-30min. In some embodiments of the present application, the power of the probe ultrasound is 50W-200W, and the time of the probe ultrasound is 15min-25min. Ultrasonication during the first mixing process can promote the uniform dispersion of the reactants in the microemulsion system and ensure the stable progress of the reaction.
  • step 100 specifically includes: mixing 0.1g-4g of sodium hydroxide with 0.1mL-100mL of deionized water to form a lye; adding 0.1mL-100mL to the lye with a volume ratio of 1: (0.1-10) oleic acid and n-butanol mixed solution to form a microemulsion system; weigh terbium salt and lutetium salt according to the molar ratio of 1:(4-99), and prepare the total molar concentration of 0.1mol L -1 -2mol ⁇ L -1 rare earth solution, adding the rare earth solution into the microemulsion system, and performing ultrasonic treatment at 0°C-10°C for 10min-30min to obtain the first solution.
  • the ratio of the sum c 1 of the molar concentration of terbium salt and lutetium salt to the molar concentration c F1 of ammonium fluoride is 1:(1-50).
  • the second mixing process is to use probe ultrasound for mixing, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 30min-100min.
  • the ultrasonic power of the probe during the second mixing process may specifically be, but not limited to, 50W, 100W, 200W, 300W, 400W or 500W.
  • ultrasonic treatment can cause the microemulsion system to produce sharp movements, including the appearance of gas nuclei, the growth of microbubbles, and the bursting of microbubbles, thereby expanding the reaction interface of the microemulsion and promoting the nano-particles of rare earth nuclei. The generation and development of materials, and shorten the reaction time.
  • ultrasonic treatment can use ultrasonic energy to disperse and control the particle size through the shear crushing mechanism, thereby forming rare earth core nanomaterials with uniform structure and monodisperse.
  • the second solution is placed in a hydrothermal kettle for hydrothermal reaction, and the temperature of the hydrothermal reaction is 100°C-300°C.
  • the reaction temperature of the hydrothermal reaction is 170°C-250°C, and a higher reaction temperature is conducive to the formation of rare earth core nanomaterials with good crystallinity.
  • the reaction time of the hydrothermal reaction is 1h-72h. In some embodiments of the present application, the reaction time of the hydrothermal reaction is 2h-55h.
  • the reaction kettle is cooled to room temperature, and the reaction solution is centrifuged at a speed of (1000-100000) r min- 1 for 1min-30min, and the supernatant is removed to obtain a white precipitate, the white precipitate That is ⁇ -NaLuF 4 :Tb.
  • the yield of ⁇ -NaLuF 4 :Tb is 40%-60%, and the yield of ⁇ -NaLuF 4 :Tb can be, but not limited to, 40%, 50%, 55% or 60%.
  • the white precipitate is washed with ethanol, dispersed in 1 mL-50 mL of water, and stored at 0°C-10°C.
  • the solvent includes water, n-butanol and oleic acid, and the volume ratio of water, n-butanol and oleic acid is 1:(0.1-10):(0.1-10).
  • the volume ratio of water, n-butanol and oleic acid is 1:(0.1-10):(0.1-10).
  • the yttrium salt includes one or more of yttrium chloride, yttrium nitrate and yttrium acetate, and the base includes one or more of sodium hydroxide and potassium hydroxide.
  • the pH of the third solution is 10-12.
  • the molar ratio of the yttrium salt to the rare earth core nanomaterial in the third solution is 1:(10-100).
  • the molar ratio of the yttrium salt to the rare earth core nanomaterial may be, but not limited to, 1:10, 1:30, 1:50, 1:70 or 1:100. In the above molar ratio range, the obtained rare earth core-shell nanomaterial can have high luminous efficiency and good stability.
  • the molar concentration of the yttrium salt is 0.1 mol ⁇ L -1 -2 mol ⁇ L -1 .
  • the molar concentration of the yttrium salt may be, but not limited to, 0.1 mol ⁇ L -1 , 0.5 mol ⁇ L -1 , 1 mol ⁇ L -1 or 2 mol ⁇ L -1 .
  • the third mixing process is to use probe ultrasound for mixing, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 10min-30min. Ultrasound in the third mixing process can promote the uniform dispersion of the reactants in the microemulsion system and ensure the stable progress of the reaction.
  • step 300 specifically includes: mixing 0.1g-4g of sodium hydroxide with 0.1mL-100mL of deionized water to form a lye; adding 0.1mL-100mL to the lye with a volume ratio of 1: (0.1-10) oleic acid and n-butanol mixture form a microemulsion system; dissolve 0.1mmol-2mmol yttrium salt in 1mL-10mL water and add the yttrium salt solution to the microemulsion system, according to the yttrium salt and rare earth core nanomaterials
  • the molar ratio is 1:(10-100), the rare earth core nanomaterial ⁇ -NaLuF 4 :Tb is added into the microemulsion system, and ultrasonic treatment is performed at 0°C-10°C for 1min-30min to obtain the third solution.
  • the molar concentration ratio of yttrium salt to ammonium fluoride is 1:(1-50).
  • the molar concentration ratio of the yttrium salt to the ammonium fluoride may be, but not limited to, 1:1, 1:5, 1:10, 1:20 or 1:50.
  • the fourth mixing process is to use probe ultrasound for mixing, the power of the probe ultrasound is 50W-500W, and the time of the probe ultrasound is 1min-100min. In some embodiments of the present application, the power of the probe ultrasound is 100W-200W, and the time of the probe ultrasound is 50min-70min.
  • the ultrasonic treatment expands the reaction interface of the microemulsion, and promotes NaYF 4 to evenly coat the surface of the rare earth core nanomaterial, thereby forming a uniform and monodisperse rare earth core-shell nanomaterial.
  • the fourth solution is placed in a hydrothermal kettle for hydrothermal reaction, and the temperature of the hydrothermal reaction is 100°C-300°C. In some embodiments of the present application, the reaction temperature of the hydrothermal reaction is 170°C-250°C. In the embodiment of the present application, the reaction time of the hydrothermal reaction is 1h-72h. In some embodiments of the present application, the reaction time of the hydrothermal reaction is 2h-55h.
  • the reaction kettle is cooled to room temperature, and the reaction solution is centrifuged at a speed of (1000-100000) r min- 1 for 1min-30min, and the supernatant is removed to obtain a white precipitate, the white precipitate That is NaLuF 4 :Tb@NaYF 4 , the white precipitate was washed with ethanol and then dried and stored.
  • the yield of NaLuF 4 :Tb@NaYF 4 is 40%-60%, and the yield of NaLuF 4 :Tb@NaYF 4 can be, but not limited to, 40%, 50%, 55% or 60%.
  • This application synthesized highly uniform and monodisperse NaLuF 4 :Tb@NaYF 4 rare earth core-shell nanomaterials by ultrasonic microemulsion method.
  • the method adopts aqueous phase synthesis of rare earth core-shell nanomaterials, the preparation process is simple, and the production cost is low.
  • the obtained rare earth core-shell nanomaterials are not only stable in properties, non-radioactive, and will not cause harm to humans and the environment, but also can be activated under X-ray excitation. It produces a strong luminescent effect and can be used for biological imaging, thus providing more choices for biological imaging materials.
  • a preparation method of rare earth core-shell nanomaterials comprising the following steps:
  • a preparation method of rare earth core-shell nanomaterials comprising the following steps:
  • 0.5gNaOH is joined in the 50mL Erlenmeyer flask that 10mL deionized water is housed; Then 15mL n-butanol and 5mL oleic acid are added into the Erlenmeyer flask and stirred for 20min to obtain a yellow transparent microemulsion; 0.5mmol of YCl 3 .
  • step a and step b the volume ratio of water, oleic acid and n-butanol is 1:1:1.
  • step a and step b the volume ratio of water, oleic acid and n-butanol is 1:1:2.
  • Example 5 The difference between Example 5 and Example 1 is that the sonication of the probe in Example 5 is carried out at room temperature (25° C.).
  • Example 6 The difference between Example 6 and Example 1 is that the pH of the first solution and the third solution in Example 6 is 10.
  • this application also provides effect examples.
  • FIG. 2 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 1 of the present application
  • Fig. 3 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 2 of the present application
  • Figure 4 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 3 of the present application
  • Figure 5 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 4 of the present application
  • Figure 6 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 5 of the present application Transmission electron micrograph of the rare earth core-shell nanomaterial
  • FIG. 7 is a transmission electron micrograph of the rare earth core-shell nanomaterial provided in Example 6 of the present application.
  • FIG. 8 is the particle size distribution diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application, as can be seen from Figure 8, the particle size distribution of the rare earth core-shell nanomaterial in Example 1 is concentrated at 80nm-150nm , the average particle size of rare earth core-shell nanomaterials is 110nm.
  • Table 1 for the characterization results, and Table 1 is Examples 1-6. Structural parameter table of rare earth core-shell nanomaterials.
  • Table 1 The structure parameter table of the rare earth core-shell nanomaterial of embodiment 1-6
  • Example 1 110 20
  • Example 2 200 30
  • Example 3 150 25 Example 4 200 30
  • Fig. 9 is the luminescent performance diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application. It can be seen from Fig.
  • the test process is as follows: disperse the ⁇ -NaLuF 4 : Tb@NaYF 4 rare earth core-shell nanomaterials of Example 1 in water, and the mass concentration of the dispersion is 10mg/mL , Take 100 ⁇ L of the dispersion and place it under X-ray irradiation with a radiation dose of 10Gy. After half an hour of irradiation, use a fluorescence spectrometer to measure the luminescence spectrum of the rare earth core-shell nanomaterial. Please refer to Fig. 10, Fig.
  • FIG. 10 is the luminescence spectrum diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application. It can be seen from Fig. 10 that the emission peak wavelengths of the rare earth core-shell nanomaterial are 490nm, 540nm, 580nm, and 620nm.
  • FIG. 11 is an in vivo imaging diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application. It can be seen from Figure 11 that rare earth core-shell nanomaterials have strong luminescence properties, and can clearly observe the state of the body, thereby achieving effective treatment.
  • Example 3 The biotoxicity of the rare earth core-shell nanomaterial in Example 1 was tested.
  • the test process was as follows: the rare earth core-shell nanomaterial in Example 1 was formulated into a dispersion, and the dispersion was injected through the tail vein according to the amount of 10 mg/kg.
  • FIG. 12 is the rare earth core-shell provided in Example 1 of the present application
  • the biotoxicity test chart of the nanomaterials from Figure 12, it can be seen that the organs and tissues of the mice are normal after injection of the dispersion solution, that is, the rare earth core-shell nanomaterials are not toxic to organisms.

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  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé de préparation d'un nanomatériau noyau-enveloppe de terre rare, comprenant : la réalisation d'un premier traitement de mélange sur un sel de terbium, un sel de lutécium, un alcali et un solvant pour former une première solution ; la réalisation d'un second traitement de mélange sur la première solution et le fluorure d'ammonium pour obtenir une seconde solution ; le dépôt de la seconde solution dans une chaudière hydrothermique pour une réaction pour obtenir un nanomatériau à noyau de terre rare, le nanomatériau à noyau de terre rare comprenant des nanoparticules ayant une formule moléculaire de NaLuf4:Tb ; la réalisation d'un troisième traitement de mélange sur un sel d'yttrium, le nanomatériau de noyau de terre rare, l'alcali et le solvant pour former une troisième solution ; la réalisation d'un quatrième traitement de mélange sur la troisième solution et le fluorure d'ammonium pour obtenir une quatrième solution ; et le dépôt de la quatrième solution dans la chaudière hydrothermique pour une réaction pour obtenir un nanomatériau noyau-enveloppe de terre rare, le nanomatériau noyau-enveloppe de terre rare comprenant une couche d'enveloppe ayant une formule moléculaire de NaYF4. Au moyen du procédé, un nanomatériau luminescent de terres rares est préparé à l'aide d'un système en phase aqueuse, le procédé est simple, et le nanomatériau noyau-enveloppe de terre rare obtenu présente une morphologie régulière et peut produire un fort effet de luminescence sous l'excitation de rayons X, ce qui facilite l'application du nanomatériau noyau-enveloppe de terre rare en imagerie biologique.
PCT/CN2021/096293 2021-05-27 2021-05-27 Nanomatériau noyau-enveloppe de terre rare et procédé de préparation associé WO2022246725A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173222A (zh) * 2013-03-15 2013-06-26 吉林大学 水溶性NaYF4@NaGdF4上转换核壳结构纳米晶及其制备方法
CN103911143A (zh) * 2014-04-10 2014-07-09 合肥工业大学 一种NaReF4核壳结构纳米材料的制备方法
WO2017054037A1 (fr) * 2015-09-28 2017-04-06 Macquarie University Croissance contrôlée de nanocristaux hétérogènes tridimensionnels
CN108785672A (zh) * 2018-06-29 2018-11-13 中国人民解放军第四军医大学 一种新型x射线激发光动力学治疗深部肿瘤的纳米粒-光敏剂耦合系统及其应用
CN111876154A (zh) * 2020-05-15 2020-11-03 福州大学 一种稀土掺杂的氟化物长余辉粒子及其制备方法以及应用
CN112794358A (zh) * 2021-01-14 2021-05-14 南方科技大学 稀土掺杂氟化钇钠核壳结构纳米材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173222A (zh) * 2013-03-15 2013-06-26 吉林大学 水溶性NaYF4@NaGdF4上转换核壳结构纳米晶及其制备方法
CN103911143A (zh) * 2014-04-10 2014-07-09 合肥工业大学 一种NaReF4核壳结构纳米材料的制备方法
WO2017054037A1 (fr) * 2015-09-28 2017-04-06 Macquarie University Croissance contrôlée de nanocristaux hétérogènes tridimensionnels
CN108785672A (zh) * 2018-06-29 2018-11-13 中国人民解放军第四军医大学 一种新型x射线激发光动力学治疗深部肿瘤的纳米粒-光敏剂耦合系统及其应用
CN111876154A (zh) * 2020-05-15 2020-11-03 福州大学 一种稀土掺杂的氟化物长余辉粒子及其制备方法以及应用
CN112794358A (zh) * 2021-01-14 2021-05-14 南方科技大学 稀土掺杂氟化钇钠核壳结构纳米材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OU XIANGYU; QIN XIAN; HUANG BOLONG; ZAN JIE; WU QINXIA; HONG ZHONGZHU; XIE LILI; BIAN HONGYU; YI ZHIGAO; CHEN XIAOFENG; WU YIMING;: "High-resolution X-ray luminescence extension imaging", NATURE, NATURE PUBLISHING GROUP UK, LONDON, vol. 590, no. 7846, 1 January 1900 (1900-01-01), London, pages 410 - 415, XP037372149, ISSN: 0028-0836, DOI: 10.1038/s41586-021-03251-6 *

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