WO2022246725A1 - Rare-earth core-shell nanomaterial and preparation method therefor - Google Patents

Rare-earth core-shell nanomaterial and preparation method therefor Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
rare earth
solution
earth core
nanomaterial
shell
Prior art date
Application number
PCT/CN2021/096293
Other languages
French (fr)
Chinese (zh)
Inventor
郑海荣
盛宗海
胡德红
Original Assignee
深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Priority to PCT/CN2021/096293 priority Critical patent/WO2022246725A1/en
Publication of WO2022246725A1 publication Critical patent/WO2022246725A1/en

Links

Images

Classifications

    • 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

Definitions

  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

A preparation method for a rare-earth core-shell nanomaterial, comprising: performing first mixing treatment on a terbium salt, a lutetium salt, an alkali, and a solvent to form a first solution; performing second mixing treatment on the first solution and ammonium fluoride to obtain a second solution; placing the second solution in a hydrothermal kettle for reaction to obtain a rare-earth core nanomaterial, the rare-earth core nanomaterial comprising nanoparticles having a molecular formula of NaLuf4:Tb; performing third mixing treatment on a yttrium salt, the rare-earth core nanomaterial, the alkali, and the solvent to form a third solution; performing fourth mixing treatment on the third solution and ammonium fluoride to obtain a fourth solution; and placing the fourth solution in the hydrothermal kettle for reaction to obtain a rare-earth core-shell nanomaterial, the rare-earth core-shell nanomaterial comprising a shell layer having a molecular formula of NaYF4. By means of the method, a rare-earth luminescent nanomaterial is prepared using a water-phase system, the process is simple, and the obtained rare-earth core-shell nanomaterial has regular morphology and can yield a strong luminescence effect under the excitation of X-rays, thereby facilitating application of the rare-earth core-shell nanomaterial in biological imaging.

Description

稀土核壳纳米材料及其制备方法Rare earth core-shell nanomaterial and preparation method thereof 技术领域technical field
本申请涉及纳米材料领域，具体涉及一种稀土核壳纳米材料及其制备方法。The present application relates to the field of nanomaterials, in particular to a rare earth core-shell nanomaterial and a preparation method thereof.
背景技术Background technique
稀土发光纳米材料是一类能够将激发能量储存于材料中，并在激发光停止照射后将储存的能量以辐射发光的形式释放出来的一类光致发光材料。稀土发光纳米材料具有发射窄、寿命长、抗光漂白等诸多优点，在生物标记和生物成像方面有着重要的应用价值。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.
目前用于生物成像的稀土发光纳米材料的激发光为红外波段，但红外光具有组织穿透性差、立体性差等缺陷，进而导致稀土发光纳米材料的发光效率低、成像效果差。X射线对人体有很好的穿透性，有利于应用在生物成像中，然而目前以X射线作为激发光实现生物成像的稀土发光纳米材料种类较少，并且制备方法复杂，生产成本高，合成时间长，所得的稀土发光纳米材料稳定性差，不利于推广使用。At present, 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. However, there are few kinds of rare earth luminescent nanomaterials that use X-rays as excitation light to realize biological imaging, and 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.
发明内容Contents of the invention
有鉴于此，本申请提供了一种稀土核壳纳米材料及其制备方法，该方法采用水相体系制备稀土发光纳米材料，提高了稀土发光纳米材料的稳定性，并且制备工艺简单，成本低，有利于大规模生产，所得的稀土核壳纳米材料不仅形貌规则、粒度均一，并且在X射线激发下可产生较强的发光效应，有利于将其应用在生物成像中。本申请还提供了一种稀土核壳纳米材料，该材料具有良好的稳定性和较高的发光效率，可应用在生物标记和生物成像等领域。In view of this, 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.
本申请第一方面提供了一种稀土核壳纳米材料的制备方法，包括以下步骤：The first aspect of the present application provides a method for preparing rare earth core-shell nanomaterials, comprising the following steps:
将铽盐、镥盐、碱和溶剂进行第一混合处理形成第一溶液；所述溶剂包括体积比为1:(0.1-10):(0.1-10)的水、正丁醇和油酸；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);
将所述第一溶液与氟化铵进行第二混合处理得到第二溶液；将所述第二溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核纳米材料；所述稀土核纳米材料包括β-NaLuF 4:Tb； 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 ; The rare earth core nanomaterial includes β-NaLuF 4 : Tb;
将钇盐、所述稀土核纳米材料、所述碱和所述溶剂进行第三混合处理形成第三溶液；performing a third mixing treatment on the yttrium salt, the rare earth core nanomaterial, the alkali, and the solvent to form a third solution;
将所述第三溶液与氟化铵进行第四混合处理得到第四溶液；将所述第四溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核壳纳米材料，所述稀土核壳纳米材料的壳层包括NaYF 4。 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 .
本申请采用水相合成法制备得到分子式为β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料，其中，β-NaLuF 4:Tb为稀土核壳纳米材料的核体，NaYF 4为稀土核壳纳米材料的壳体。本申请的水相合成法中，溶剂中的正丁醇、油酸能够和水形成微乳液，从而吸附溶液中的金属离子，使反应在微乳液的微泡中进行，提高稀土纳米材料的结构均一性，使稀土核壳纳米材料具有较窄的粒度分布和分散性能；并且所得稀土核壳纳米材料晶相纯度高、发光性能稳定，有利于应用在生物成像中。 This application adopts the aqueous phase synthesis method to prepare rare earth core-shell nanomaterials with molecular formula β-NaLuF 4 :Tb@NaYF 4 , wherein β-NaLuF 4 :Tb is the core body of rare earth core-shell nanomaterials, and NaYF 4 is rare earth core-shell Housings of nanomaterials. In the aqueous phase synthesis method of the present application, 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.
可选地，所述铽盐包括氯化铽、醋酸铽和硝酸铽中的一种或多种。Optionally, the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate.
可选地，所述镥盐包括氯化镥、硝酸镥和醋酸镥中的一种或多种。Optionally, the lutetium salt includes one or more of lutetium chloride, lutetium nitrate and lutetium acetate.
可选地，所述第一溶液中，所述铽盐和所述镥盐的摩尔比为1:(4-99)。Optionally, in the first solution, the molar ratio of the terbium salt to the lutetium salt is 1:(4-99).
可选地，所述第一溶液中，所述铽盐和所述镥盐的摩尔浓度之和c 1为0.1mol·L -1-2mol·L -1。 Optionally, in the first solution, 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 .
可选地，所述第二溶液中，所述铽盐和所述镥盐的摩尔浓度之和c 1与所述氟化铵的摩尔浓度c F1之比为1:(1-50)。 Optionally, in the second solution, 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).
可选地，所述碱包括氢氧化钠和氢氧化钾中的一种或多种。Optionally, the alkali includes one or more of sodium hydroxide and potassium hydroxide.
可选地，所述正丁醇和油酸的体积比为1:(0.1-10)。Optionally, the volume ratio of n-butanol and oleic acid is 1:(0.1-10).
可选地，所述第三溶液中，所述钇盐的摩尔浓度为0.1mol·L -1-2mol·L -1。 Optionally, in the third solution, the molar concentration of the yttrium salt is 0.1 mol·L -1 -2 mol·L -1 .
可选地，所述第三溶液中，所述钇盐与所述稀土核纳米材料的摩尔比为1:(10-100)。Optionally, in the third solution, the molar ratio of the yttrium salt to the rare earth core nanomaterial is 1:(10-100).
可选地，所述第四溶液中，所述钇盐与所述氟化铵的摩尔浓度之比为1:(1-50)。Optionally, in the fourth solution, the molar concentration ratio of the yttrium salt to the ammonium fluoride is 1:(1-50).
可选地，所述第一溶液和所述第三溶液的pH为10-12。Optionally, the pH of the first solution and the third solution is 10-12.
可选地，所述第一混合处理、所述第二混合处理、所述第三混合处理和所述第四混合处理采用探头超声进行混合，所述探头超声的功率为50W-500W。Optionally, 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.
可选地，所述第一混合处理、所述第二混合处理、所述第三混合处理和所述第四混合处理的温度为0℃-10℃。Optionally, 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.
本申请通过水相合成法合成了高度均匀、单分散的β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料，该制备方法步骤简单，反应条件易于控制，生产成本低，制得的稀土核壳纳米材料余辉明亮，余辉时间长，并且化学性质稳定，无放射性，对人体具有较高的安全性。 The present application synthesized highly uniform and monodisperse β-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.
本申请第二方面提供了一种稀土核壳纳米材料，所述稀土核壳纳米材料包括稀土核纳米材料和包覆在所述稀土核纳米材料表面的壳层；所述稀土核纳米材料包括β-NaLuF 4:Tb；所述稀土核壳纳米材料的壳层包括NaYF 4。 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 β - NaLuF 4 :Tb; the shell layer of the rare earth core-shell nanomaterial includes NaYF 4 .
附图说明Description of drawings
图1为本申请一实施方式提供的稀土核壳纳米材料的制备方法；Fig. 1 is the preparation method of the rare earth core-shell nanomaterial provided by an embodiment of the present application;
图2为本申请实施例1提供的稀土核壳纳米材料的透射电镜图；Figure 2 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
图3为本申请实施例2提供的稀土核壳纳米材料的透射电镜图；3 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 2 of the present application;
图4为本申请实施例3提供的稀土核壳纳米材料的透射电镜图；Figure 4 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 3 of the present application;
图5为本申请实施例4提供的稀土核壳纳米材料的透射电镜图；Figure 5 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 4 of the present application;
图6为本申请实施例5提供的稀土核壳纳米材料的透射电镜图；Figure 6 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 5 of the present application;
图7为本申请实施例6提供的稀土核壳纳米材料的透射电镜图；Figure 7 is a transmission electron microscope image of the rare earth core-shell nanomaterial provided in Example 6 of the present application;
图8为本申请实施例1提供的稀土核壳纳米材料的粒径分布图；Figure 8 is a particle size distribution diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
图9为本申请实施例1提供的稀土核壳纳米材料的发光性能图；Figure 9 is a diagram of the luminescence properties of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
图10为本申请实施例1提供的稀土核壳纳米材料的发光光谱图；Figure 10 is the luminescent spectrum diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
图11为本申请实施例1提供的稀土核壳纳米材料的活体成像图；Figure 11 is an in vivo imaging diagram of the rare earth core-shell nanomaterial provided in Example 1 of the present application;
图12为本申请实施例1提供的稀土核壳纳米材料的生物毒性测试图。Fig. 12 is a biotoxicity test chart of the rare earth core-shell nanomaterial provided in Example 1 of the present application.
具体实施方式Detailed ways
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of this application.
目前用于生物成像的稀土发光纳米材料的激发光为红外波段，然而红外光具有组织穿透性差、立体性差等缺陷，导致成像效果差。X射线对人体有很好的穿透性，可以不直接接触人体而穿透皮肤和肌肉直接看到体内的骨骼情况。因此，研究和发展基于X射线激发的新型稀土发光纳米材料对于生物医学成像、诊断和治疗具有重要的意义。为促进稀土发光纳米材料在生物成像中应用，本申请提供了一种以X射线作为激发光实现生物成像的稀土核壳纳米材料β-NaLuF 4:Tb@NaYF 4，其中，稀土核壳纳米材料的核体包括β-NaLuF 4:Tb，稀土核壳纳米材料的壳体包括NaYF 4。 At present, the excitation light of rare earth luminescent nanomaterials used for biological imaging is in the infrared band. However, 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. In order to promote the application of rare earth luminescent nanomaterials in biological imaging, this application provides a rare earth core-shell nanomaterial β-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 β-NaLuF 4 :Tb, and the shell of the rare earth core-shell nanomaterial includes NaYF 4 .
本申请中，稀土核壳纳米材料的核体β-NaLuF 4:Tb可由X射线激发并产生 较强的荧光。NaLuF 4:Tb的晶相为体心立方结构(β-)，体心立方结构的NaLuF 4:Tb具有更高的晶化程度和较少的表面缺陷，因此发光亮度高，且发光性能稳定。稀土核壳纳米材料的壳体NaYF 4可以完善稀土核壳纳米材料的表面晶格，降低表面散射，并且抑制荧光猝灭的现象，从而提高表面离子之间的能量传递效率，使稀土核壳纳米材料具有较高的发光效率。 In this application, the core body β-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 (β-), 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.
本申请中，β-NaLuF 4:Tb表示铽掺杂的氟化镥钠，其中，Tb和Lu的摩尔比为1:(4-99)。本申请一些实施方式中，Tb和Lu的摩尔比为1:(4-10)。在氟化镥钠中掺杂铽可以调节稀土核壳纳米材料的发光性能，使稀土核壳纳米材料具有合适的余辉发射时长。 In this application, β-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.
本申请实施方式中，稀土核壳纳米材料的余辉发射时长为5天至30天，稀土核壳纳米材料的余辉发射时长具体可以但不限于为5天、10天、15天、20天、25天或30天。若稀土核壳纳米材料的余辉发射时长过短，则生物成像过程的时间较短，成像的效果差；若余辉发射时长过长，则会不利于后续的成像检测以及体外诊断试纸条的重复使用，因此应控制稀土核壳纳米材料的余辉发射时长，以保证具有较好成像效果并且不影响体内多次注射以及体外诊断试纸条的重复使用。In the embodiment of the present application, 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.
本申请实施方式中，稀土核壳纳米材料的核体的粒径为1-300nm。稀土核壳纳米材料的核体的粒径具体可以但不限于为1nm、10nm、50nm、100nm、200nm或300nm。本申请实施方式中，稀土核壳纳米材料的壳体的厚度为1-40nm。稀土核壳纳米材料的壳体的厚度具体可以但不限于为1nm、10nm、30nm、40nm或50nm。本申请实施方式中，稀土核壳纳米材料中，核体的粒径与壳体的厚度之比为1:(1-10)。核体的粒径与壳体的厚度之比具体可以但不限于为1:1、1:3、1:5或1:10。控制核体的粒径与壳体的厚度能够保证稀土核壳纳米材料具有稳定的发光性能和较高的发光效率。In the embodiment of the present application, 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. In the embodiment of the present application, 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. In the embodiment of the present application, in the rare earth core-shell nanomaterial, 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.
本申请实施方式中，稀土核壳纳米材料为球状颗粒，球状颗粒具有较小的比表面积，颗粒表面对发光离子的淬灭作用小，颗粒的发光效率高。本申请实施方式中，稀土核壳纳米材料的平均粒径为50nm-200nm。稀土核壳纳米材料β-NaLuF 4:Tb@NaYF 4的平均粒径具体可以但不限于为50nm、70nm、90nm、95nm、100nm、105nm、110nm、130nm、150nm或200nm。 In the embodiment of the present application, 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. In the embodiment of the present application, 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 β-NaLuF 4 :Tb@NaYF 4 can be, but not limited to, 50nm, 70nm, 90nm, 95nm, 100nm, 105nm, 110nm, 130nm, 150nm or 200nm.
本申请提供的稀土核壳纳米材料β-NaLuF 4:Tb@NaYF 4可以在X射线激发下实现荧光发射，具有较高的发光效率和稳定的发光性能，有利于应用在生物成像中。 The rare earth core-shell nanomaterial β-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.
本申请还提供了上述稀土核壳纳米材料β-NaLuF 4:Tb@NaYF 4的制备方法，请参阅图1，图1为本申请一实施方式提供的稀土核壳纳米材料的制备方法，包括： The present application also provides a preparation method of the above-mentioned rare earth core-shell nanomaterial β-NaLuF 4 :Tb@NaYF 4 , please refer to FIG. 1 . FIG. 1 is a preparation method of the rare earth core-shell nanomaterial provided in an embodiment of the present application, including:
步骤100：将铽盐、镥盐、碱和溶剂进行第一混合处理形成第一溶液；Step 100: performing a first mixing treatment on terbium salt, lutetium salt, alkali and solvent to form a first solution;
步骤200：将第一溶液与氟化铵进行第二混合处理得到第二溶液；将第二溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核纳米材料；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;
步骤300：将钇盐、稀土核纳米材料、碱和溶剂进行第三混合处理形成第三溶液；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;
步骤400：将第三溶液与氟化铵进行第四混合处理得到第四溶液；将第四溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核壳纳米材料。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 .
本申请步骤100中，溶剂包括水、正丁醇和油酸。正丁醇可以作为助表面活性剂促进油酸与水形成微乳液体系，微乳液体系具有较大的反应界面，可以提高反应速率并有利于形成结构均匀、单分散的纳米粒子。本申请实施方式中，水、正丁醇和油酸的体积比为1:(0.1-10):(0.1-10)。本申请一些实施方式中，水、正丁醇和油酸的体积比为1:(0.1-1):(0.1-1)，水的体积比较高时有利于提高产物稀土核纳米材料在水中的分散性能。在上述体积比范围下，可以形成各向同性 的热力学稳定的微乳液体系，从而保证形成高度均匀、单分散的稀土核纳米材料。In step 100 of the present application, 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. In the embodiment of the present application, the volume ratio of water, n-butanol and oleic acid is 1:(0.1-10):(0.1-10). In some embodiments of the present application, 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.
本申请中，加入碱可调节反应体系的pH值，进而改变反应体系中铽盐和镥盐的溶解度，从而控制反应速率，除此之外，pH值还会影响各晶面的相对生长速度，从而形成不同结构的晶体。本申请实施方式中，第一溶液的pH为10-12。在上述pH条件下，有利于反应快速并稳定地进行，并且可以促进β-NaLuF 4:Tb稀土核壳纳米材料的生成。本申请一些实施方式中，碱包括氢氧化钠和氢氧化钾中的一种或多种。 In this application, 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. In addition, the pH value will also affect the relative growth rate of each crystal plane. Thus forming crystals with different structures. In the embodiment of the present application, 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 β-NaLuF 4 :Tb rare earth core-shell nanomaterials. In some embodiments of the present application, the alkali includes one or more of sodium hydroxide and potassium hydroxide.
本申请实施方式中，铽盐包括氯化铽、醋酸铽和硝酸铽中的一种或多种。本申请实施方式中，镥盐包括氯化镥、硝酸镥和醋酸镥中的一种或多种。本申请实施方式中，铽盐和镥盐的摩尔比为1:(4-99)。本申请一些实施方式中，铽盐和镥盐的摩尔比为1:(4-10)。铽盐和镥盐的摩尔比具体可以但不限于为1:4、1:6、1:10、1:15、1:20、1:40、1:60或1:99。本申请实施方式中，铽盐和镥盐的摩尔浓度之和c 1为0.1mol·L -1-2mol·L -1。 In the embodiment of the present application, the terbium salt includes one or more of terbium chloride, terbium acetate and terbium nitrate. In the embodiment of the present application, the lutetium salt includes one or more of lutetium chloride, lutetium nitrate and lutetium acetate. In the embodiment of the present application, 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. In the embodiment of the present application, 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 .
本申请实施方式中，第一混合处理是采用探头超声进行混合，探头超声的功率为50W-500W，探头超声的时间为10min-30min。本申请一些实施方式中，探头超声的功率为50W-200W，探头超声的时间为15min-25min。在第一混合处理过程中进行超声可以促进反应物均匀分散在微乳液体系中，保证反应稳定进行。In the embodiment of the present application, 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.
本申请一些实施方式中，步骤100具体包括：将0.1g-4g的氢氧化钠与0.1mL-100mL的去离子水混合形成碱液；向碱液中加入0.1mL-100mL的体积比为1:(0.1-10)的油酸和正丁醇混合液形成微乳液体系；按照1:(4-99)的摩尔比称取铽盐和镥盐，并配成总摩尔浓度为0.1mol·L -1-2mol·L -1的稀土溶液，将稀土溶液加入微乳液体系中，在0℃-10℃进行超声处理10min-30min得到第一溶 液。 In some embodiments of the present application, 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.
本申请步骤200中，第二溶液中，铽盐和镥盐的摩尔浓度之和c 1与氟化铵的摩尔浓度c F1之比为1:(1-50)。本申请实施方式中，第二混合处理是采用探头超声进行混合，探头超声的功率为50W-500W，探头超声的时间为30min-100min。其中第二混合处理时探头超声的功率具体可以但不限于为50W、100W、200W、300W、400W或500W。在第二混合处理过程中，超声处理一方面可以使微乳液体系产生急剧的运动，包括气核的出现、微泡的长大和微泡的爆裂，从而扩大微乳液的反应界面，促进稀土核纳米材料的生成和发育，并且缩短反应时间。另一方面，超声处理可以利用超声能量进行分散，通过剪切破碎机理控制颗粒尺寸，从而形成结构均一且单分散的稀土核纳米材料。 In step 200 of the present application, in the second 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). In the embodiment of the present application, 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. In the second mixing process, on the one hand, 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. On the other hand, 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.
本申请中，将第二溶液置于水热釜中进行水热反应，水热反应的温度为100℃-300℃。本申请一些实施方式中，水热反应的反应温度为170℃-250℃，采用较高的反应温度有利于形成良好结晶度的稀土核纳米材料。本申请实施方式中，水热反应的反应时间为1h-72h。本申请一些实施方式中，水热反应的反应时间为2h-55h。本申请实施方式中，水热反应结束后将反应釜冷却至室温，以(1000-100000)r·min -1的转速将反应液离心1min-30min，去除上清液后得到白色沉淀，白色沉淀即为β-NaLuF 4:Tb。本申请实施方式中，β-NaLuF 4:Tb的收率为40％-60％，β-NaLuF 4:Tb的收率具体可以但不限于为40％、50％、55％或60％。本申请一些实施方式中，将白色沉淀用乙醇洗涤后分散在1mL-50mL水中，并在0℃-10℃下储存。 In the present application, the second 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, and a higher reaction temperature is conducive to the formation of rare earth core nanomaterials with good crystallinity. 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. In the embodiment of the present application, after the hydrothermal reaction is completed, 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 β-NaLuF 4 :Tb. In the embodiment of the present application, the yield of β-NaLuF 4 :Tb is 40%-60%, and the yield of β-NaLuF 4 :Tb can be, but not limited to, 40%, 50%, 55% or 60%. In some embodiments of the present application, the white precipitate is washed with ethanol, dispersed in 1 mL-50 mL of water, and stored at 0°C-10°C.
本申请步骤300中，溶剂包括水、正丁醇和油酸，水、正丁醇和油酸的体积比为1:(0.1-10):(0.1-10)。在微乳液体系下，有利于在稀土核纳米材料表面形成稳定的壳层，从而有效抑制稀土纳米材料的表面猝灭、钝化稀土核纳米材料表面的晶格缺陷、隔离外界不利因素的干扰，进而大幅提高材料的荧光效率。 本申请实施方式中，钇盐包括氯化钇、硝酸钇和醋酸钇中的一种或多种，碱包括氢氧化钠和氢氧化钾中的一种或多种。本申请实施方式中，第三溶液的pH为10-12。In step 300 of the present application, 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). Under the microemulsion system, it is beneficial to form a stable shell on the surface of rare earth core nanomaterials, thereby effectively inhibiting the surface quenching of rare earth nanomaterials, passivating lattice defects on the surface of rare earth core nanomaterials, and isolating the interference of external unfavorable factors. In turn, the fluorescence efficiency of the material is greatly improved. In the embodiment of the present application, 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. In the embodiment of the present application, the pH of the third solution is 10-12.
本申请实施方式中，第三溶液中钇盐与稀土核纳米材料的摩尔比为1:(10-100)。钇盐与稀土核纳米材料的摩尔比具体可以但不限于为1:10、1:30、1:50、1:70或1:100。在上述摩尔比范围下，所得的稀土核壳纳米材料能够具有较高的发光效率和良好的稳定性。本申请实施方式中，钇盐的摩尔浓度为0.1mol·L -1-2mol·L -1。钇盐的摩尔浓度具体可以但不限于为0.1mol·L -1、0.5mol·L -1、1mol·L -1或2mol·L -1。 In the embodiment of the present application, 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. In the embodiments of the present application, 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 .
本申请实施方式中，第三混合处理是采用探头超声进行混合，探头超声的功率为50W-500W，探头超声的时间为10min-30min。在第三混合处理过程中进行超声可以促进反应物均匀分散在微乳液体系中，保证反应稳定进行。In the embodiment of the present application, 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.
本申请一些实施方式中，步骤300具体包括：将0.1g-4g的氢氧化钠与0.1mL-100mL的去离子水混合形成碱液；向碱液中加入0.1mL-100mL的体积比为1:(0.1-10)的油酸和正丁醇混合液形成微乳液体系；将0.1mmol-2mmol的钇盐溶解在1mL-10mL水中并将钇盐溶液加入微乳液体系，按照钇盐与稀土核纳米材料的摩尔比为1:(10-100)的比例，将稀土核纳米材料β-NaLuF 4:Tb加入微乳液体系中，在0℃-10℃进行超声处理1min-30min得到第三溶液。 In some embodiments of the present application, 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 β-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.
本申请步骤400中，第四溶液中，钇盐与氟化铵的摩尔浓度之比为1:(1-50)。钇盐与氟化铵的摩尔浓度之比具体可以但不限于为1:1、1:5、1:10、1:20或1:50。本申请实施方式中，第四混合处理是采用探头超声进行混合，探头超声的功率为50W-500W，探头超声的时间为1min-100min。本申请一些实施方式中，探头超声的功率为100W-200W，探头超声的时间为50min-70min。在第四混合处理过程中，超声处理从而扩大微乳液的反应界面，促进NaYF 4均匀包覆在稀 土核纳米材料表面，从而形成结构均一且单分散的稀土核壳纳米材料。 In step 400 of the present application, in the fourth 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. In the embodiment of the present application, 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. In the fourth mixing process, 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.
本申请中，将第四溶液置于水热釜中进行水热反应，水热反应的温度为100℃-300℃。本申请一些实施方式中，水热反应的反应温度为170℃-250℃。本申请实施方式中，水热反应的反应时间为1h-72h。本申请一些实施方式中，水热反应的反应时间为2h-55h。本申请实施方式中，水热反应结束后将反应釜冷却至室温，以(1000-100000)r·min -1的转速将反应液离心1min-30min，去除上清液后得到白色沉淀，白色沉淀即为NaLuF 4:Tb@NaYF 4，将白色沉淀用乙醇洗涤后烘干储存。本申请实施方式中，在步骤400中，NaLuF 4:Tb@NaYF 4的收率为40％-60％，NaLuF 4:Tb@NaYF 4的收率具体可以但不限于为40％、50％、55％或60％。 In the present application, 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. In the embodiment of the present application, after the hydrothermal reaction is completed, 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. In the embodiment of the present application, in step 400, 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%.
本申请通过超声微乳液法合成了高度均匀、单分散的NaLuF 4:Tb@NaYF 4稀土核壳纳米材料。该方法采用水相合成稀土核壳纳米材料，制备工艺简单、生产成本低，所得的稀土核壳纳米材料不仅性质稳定、无放射性、不会对人和环境造成危害，并且在X射线激发下可产生较强的发光效应，可用于生物成像，从而为生物成像材料提供更多的选择。 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.
下面分多个实施例对本申请的技术方案进行进一步的说明。The technical solution of the present application will be further described in the following by a plurality of embodiments.
实施例1Example 1
一种稀土核壳纳米材料的制备方法，包括以下步骤：A preparation method of rare earth core-shell nanomaterials, comprising the following steps:
(1)合成稀土核纳米材料：(1) Synthesis of rare earth core nanomaterials:
a.将0.5gNaOH加入到装有10mL去离子水的50mL锥形瓶中；再将15mL正丁醇和5mL油酸加入锥形瓶，将细胞破碎仪的超声探头浸没于溶液内，在冰浴下(0℃)探头超声处理2min，形成黄色透明的微乳液；将0.4mmol的LuCl 3·6H 2O和0.1mmol的Tb(NO 3) 3配成浓度为0.5mol·L -1的水溶液后将水溶液加入微乳液中，冰浴下探头超声处理3min，得到第一溶液，第一溶液的pH 为12；将10mmol的NH 4F加入第一溶液并在冰浴下探头超声处理1h，得到第二溶液，第二溶液为白色乳浊液。 a. Add 0.5g NaOH to a 50mL Erlenmeyer flask filled with 10mL deionized water; then add 15mL n-butanol and 5mL oleic acid into the Erlenmeyer flask, immerse the ultrasonic probe of the cell disruptor in the solution, and place in an ice bath (0°C) the probe was sonicated for 2 min to form a yellow transparent microemulsion; 0.4 mmol of LuCl 3 ·6H 2 O and 0.1 mmol of Tb(NO 3 ) 3 were prepared into an aqueous solution with a concentration of 0.5 mol·L -1 The aqueous solution was added to the microemulsion, and the probe was sonicated for 3 minutes under an ice bath to obtain the first solution. The pH of the first solution was 12; solution, the second solution is a white emulsion.
b.将第二溶液装入50mL聚四氟乙烯反应釜中，在200℃下加热6h，反应结束后冷却至室温，将反应液以15000r·min -1的速率离心5min，除去中上层清液得到白色沉淀；将白色沉淀用乙醇依次洗涤3次后，得到β-NaLuF 4:Tb稀土核纳米材料，反应的产率为45％。将β-NaLuF 4:Tb分散于4mL水中得到β-NaLuF 4:Tb分散液，在4℃下储存。 b. Put the second solution into a 50mL polytetrafluoroethylene reactor, heat at 200°C for 6h, cool to room temperature after the reaction, centrifuge the reaction solution at a rate of 15000r·min -1 for 5min, and remove the supernatant A white precipitate was obtained; after washing the white precipitate with ethanol three times in sequence, the β-NaLuF 4 :Tb rare earth core nanomaterial was obtained, and the reaction yield was 45%. β-NaLuF 4 :Tb was dispersed in 4 mL of water to obtain a β-NaLuF 4 :Tb dispersion, which was stored at 4°C.
(2)合成稀土核壳纳米材料：(2) Synthesis of rare earth core-shell nanomaterials:
c.将0.5gNaOH加入到装有10mL去离子水的50mL锥形瓶中；再将15mL正丁醇和5mL油酸加入锥形瓶，将细胞破碎仪的超声探头浸没于溶液内，在冰浴下(0℃)探头超声处理2min，形成黄色透明的微乳液；将0.5mmol的YCl 3·6H 2O溶解在4mL水中得到水溶液，并将水溶液加入微乳液中，再将步骤(1)中的β-NaLuF 4:Tb分散液加入微乳液，冰浴下探头超声处理3min，得到第三溶液，其中，第三溶液的pH为12；将10mmol的NH 4F加入第三溶液并在冰浴下探头超声处理1min，得到第四溶液，第四溶液为白色乳浊液。 c. Add 0.5g NaOH to a 50mL Erlenmeyer flask filled with 10mL deionized water; then add 15mL n-butanol and 5mL oleic acid to the Erlenmeyer flask, immerse the ultrasonic probe of the cell disruptor in the solution, and place in an ice bath (0°C) ultrasonically treat the probe for 2 min to form a yellow transparent microemulsion; dissolve 0.5 mmol of YCl 3 6H 2 O in 4 mL of water to obtain an aqueous solution, and add the aqueous solution to the microemulsion, and then add the β in step (1) -NaLuF 4 : Tb dispersion was added to the microemulsion, and the probe was sonicated for 3 minutes under an ice bath to obtain a third solution, wherein the pH of the third solution was 12; 10 mmol of NH 4 F was added to the third solution and probed under an ice bath After ultrasonic treatment for 1 min, the fourth solution was obtained, and the fourth solution was a white emulsion.
d.将第四溶液装入50mL聚四氟乙烯反应釜中，在200℃下加热6h，反应结束后冷却至室温，将反应液以15000r·min -1的速率离心5min，除去中上层清液得到沉淀；将沉淀用乙醇依次洗涤3次后，烘干得到β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料，反应的产率为50％。 d. Put the fourth solution into a 50mL polytetrafluoroethylene reactor, heat at 200°C for 6h, cool to room temperature after the reaction, centrifuge the reaction solution at a rate of 15000r·min -1 for 5min, and remove the supernatant A precipitate was obtained; the precipitate was washed with ethanol three times in sequence, and then dried to obtain a β-NaLuF 4 :Tb@NaYF 4 rare earth core-shell nanomaterial with a reaction yield of 50%.
实施例2Example 2
一种稀土核壳纳米材料的制备方法，包括以下步骤：A preparation method of rare earth core-shell nanomaterials, comprising the following steps:
(1)合成稀土核纳米材料：(1) Synthesis of rare earth core nanomaterials:
a.将0.5gNaOH加入到装有10mL去离子水的50mL锥形瓶中；再将15mL正丁醇和5mL油酸加入锥形瓶，搅拌20min后得到黄色透明的微乳液；将 0.4mmol的LuCl 3·6H 2O和0.1mmol的Tb(NO 3) 3配成浓度为0.5mol·L -1的水溶液后将水溶液加入微乳液中，搅拌30min得到第一溶液；将10mmol的NH 4F加入第一溶液后搅拌1h得到第二溶液，第二溶液为白色乳浊液。 a. Add 0.5g NaOH to a 50mL Erlenmeyer flask containing 10mL deionized water; then add 15mL n-butanol and 5mL oleic acid into the Erlenmeyer flask, stir for 20min to obtain a yellow transparent microemulsion; add 0.4mmol of LuCl 3 ·6H 2 O and 0.1mmol of Tb(NO 3 ) 3 were formulated into an aqueous solution with a concentration of 0.5mol·L -1 , then the aqueous solution was added to the microemulsion, and stirred for 30 minutes to obtain the first solution; 10mmol of NH 4 F was added to the first The solution was then stirred for 1 h to obtain a second solution, which was a white emulsion.
b.将第二溶液装入50mL聚四氟乙烯反应釜中，在200℃下加热48h，反应结束后冷却至室温，将反应液以15000r·min -1的速率离心5min，除去中上层清液得到白色沉淀；将白色沉淀用乙醇依次洗涤3次后，得到β-NaLuF 4:Tb稀土核纳米材料，反应的产率为50％。将β-NaLuF 4:Tb分散于4mL水中得到β-NaLuF 4:Tb分散液，在4℃下储存。 b. Put the second solution into a 50mL polytetrafluoroethylene reactor, heat at 200°C for 48h, cool to room temperature after the reaction, centrifuge the reaction solution at a rate of 15000r·min -1 for 5min, and remove the supernatant A white precipitate was obtained; after washing the white precipitate with ethanol three times in sequence, the β-NaLuF 4 :Tb rare earth core nanomaterial was obtained, and the yield of the reaction was 50%. β-NaLuF 4 :Tb was dispersed in 4 mL of water to obtain a β-NaLuF 4 :Tb dispersion, which was stored at 4°C.
(2)合成稀土核壳纳米材料：(2) Synthesis of rare earth core-shell nanomaterials:
c.将0.5gNaOH加入到装有10mL去离子水的50mL锥形瓶中；再将15mL正丁醇和5mL油酸加入锥形瓶搅拌20min后得到黄色透明的微乳液；将0.5mmol的YCl 3·6H 2O溶解在4mL水中得到水溶液，并将水溶液加入微乳液中，再将步骤(1)中的β-NaLuF 4:Tb分散液加入微乳液；将10mmol的NH 4F加入第三溶液并搅拌1h，得到第四溶液，第四溶液为白色乳浊液。 c. 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 . 6H 2 O was dissolved in 4 mL of water to obtain an aqueous solution, and the aqueous solution was added to the microemulsion, and then the β-NaLuF 4 :Tb dispersion in step (1) was added to the microemulsion; 10 mmol of NH 4 F was added to the third solution and stirred After 1 h, the fourth solution was obtained, which was a white emulsion.
d.将第四溶液装入50mL聚四氟乙烯反应釜中，在200℃下加热48h，反应结束后冷却至室温，将反应液以15000r·min -1的速率离心5min，除去中上层清液得到沉淀；将沉淀用乙醇依次洗涤3次后，烘干得到β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料，反应的产率为60％。 d. Put the fourth solution into a 50mL polytetrafluoroethylene reactor, heat at 200°C for 48h, cool to room temperature after the reaction, centrifuge the reaction solution at a rate of 15000r·min -1 for 5min, and remove the supernatant A precipitate was obtained; the precipitate was washed with ethanol three times in sequence, and then dried to obtain a β-NaLuF 4 :Tb@NaYF 4 rare earth core-shell nanomaterial with a reaction yield of 60%.
实施例3Example 3
实施例3与实施例1的区别在于步骤a和步骤b中，水、油酸与正丁醇的体积比均为1:1:1。The difference between embodiment 3 and embodiment 1 is that in step a and step b, the volume ratio of water, oleic acid and n-butanol is 1:1:1.
实施例4Example 4
实施例4与实施例1的区别在于步骤a和步骤b中，水、油酸与正丁醇的体积比均为1:1:2。The difference between embodiment 4 and embodiment 1 is that in step a and step b, the volume ratio of water, oleic acid and n-butanol is 1:1:2.
实施例5Example 5
实施例5与实施例1的区别在于，实施例5中探头超声处理是在室温条件(25℃)进行。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.).
实施例6Example 6
实施例6与实施例1的区别在于，实施例6中第一溶液与第三溶液的pH为10。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.
效果实施例Effect Example
为验证本申请制得的稀土核壳纳米材料的结构和性能，本申请还提供了效果实施例。In order to verify the structure and performance of the rare earth core-shell nanomaterials prepared in this application, this application also provides effect examples.
1)采用透射电镜对实施例1-6的稀土核壳纳米材料的形貌进行表征。1) The morphology of the rare earth core-shell nanomaterials in Examples 1-6 was characterized by transmission electron microscopy.
请参阅图2-图7，其中，图2为本申请实施例1提供的稀土核壳纳米材料的透射电镜图；图3为本申请实施例2提供的稀土核壳纳米材料的透射电镜图；图4为本申请实施例3提供的稀土核壳纳米材料的透射电镜图；图5为本申请实施例4提供的稀土核壳纳米材料的透射电镜图；图6为本申请实施例5提供的稀土核壳纳米材料的透射电镜图；图7为本申请实施例6提供的稀土核壳纳米材料的透射电镜图。由图2-图7可以看出，实施例1-6成功合成了结构均一、单分散的稀土核壳纳米材料。请参阅图8，图8为本申请实施例1提供的稀土核壳纳米材料的粒径分布图，由图8可以看出，实施例1的稀土核壳纳米材料粒径分布集中在80nm-150nm，稀土核壳纳米材料的平均粒径为110nm。采用相同的方法对实施例2-6的稀土核壳纳米材料进行表征，得到实施例2-6的稀土核壳纳米材料的结构参数，表征结果请参阅表1，表1为实施例1-6的稀土核壳纳米材料的结构参数表。Please refer to Fig. 2-Fig. 7, wherein 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. It can be seen from Figures 2 to 7 that in Examples 1-6, rare earth core-shell nanomaterials with uniform structure and monodisperse were successfully synthesized. Please refer to Figure 8, Figure 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. Use the same method to characterize the rare earth core-shell nanomaterials of Examples 2-6, and obtain the structural parameters of the rare earth core-shell nanomaterials of Examples 2-6. Please refer to Table 1 for the characterization results, and Table 1 is Examples 1-6. Structural parameter table of rare earth core-shell nanomaterials.
表1实施例1-6的稀土核壳纳米材料的结构参数表Table 1 The structure parameter table of the rare earth core-shell nanomaterial of embodiment 1-6
实验组test group 平均粒径(nm)Average particle size (nm) 壳层厚度(nm)Shell thickness (nm)
实施例1Example 1 110110 2020
实施例2Example 2 200200 3030
实施例3Example 3 150150 2525
实施例4Example 4 200200 3030
实施例5Example 5 120120 2020
实施例6Example 6 150150 2727
2)对实施例1的稀土核壳纳米材料的发光性能进行测试，测试过程具体为：将实施例1的β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料分散在水中，分散液的质量浓度为10mg/mL，取100μL分散液置于辐射剂量为10Gy的X射线下辐照，辐照后记录发光情况。请参阅图9，图9为本申请实施例1提供的稀土核壳纳米材料的发光性能图，由图9可以看出关闭X射线源后，β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料在0-14天内，具有明显的余辉发光，随余辉变弱，在28天时余辉基本不可见，适当的余辉发射时间有利于后续的成像检测以及体外诊断试纸条的重复使用。 2) Test the luminescent performance of the rare earth core-shell nanomaterial of Example 1. The test process is specifically: dispersing the β-NaLuF 4 : Tb@NaYF 4 rare earth core-shell nanomaterial of Example 1 in water, the quality of the dispersion is With a concentration of 10 mg/mL, 100 μL of the dispersion was taken and irradiated under X-rays with a radiation dose of 10 Gy, and the luminescence was recorded after irradiation. Please refer to Fig. 9, 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. 9 that after the X-ray source is turned off, β-NaLuF 4 :Tb@NaYF 4 The material has obvious afterglow luminescence within 0-14 days. As the afterglow becomes weaker, the afterglow is basically invisible at 28 days. Appropriate afterglow emission time is conducive to subsequent imaging detection and repeated use of in vitro diagnostic test strips.
采用荧光光谱仪测试稀土核壳纳米材料的发光性能，测试过程具体为：将实施例1的β-NaLuF 4:Tb@NaYF 4稀土核壳纳米材料分散在水中，分散液的质量浓度为10mg/mL，取100μL分散液置于辐射剂量为10Gy的X射线下辐照，辐照半小时后采用荧光光谱仪测量稀土核壳纳米材料的发光光谱。请参阅图10，图10为本申请实施例1提供的稀土核壳纳米材料的发光光谱图，由图10可以看出，稀土核壳纳米材料的发射峰波长为490nm、540nm、580nm、620nm。 Using a fluorescence spectrometer to test the luminescent properties of rare earth core-shell nanomaterials, the test process is as follows: disperse the β-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 μL 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. 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.
取100μL稀土核壳纳米材料的分散液在辐射剂量为10Gy的X射线下辐照后，将分散液皮下注射到小鼠体内，通过小动物活体成像进行发光检测(无激发光条件下检测发射光)，请参阅图11，图11为本申请实施例1提供的稀 土核壳纳米材料的活体成像图。由图11可以看出，稀土核壳纳米材料具有较强的发光性能，可以清晰地观测出机体的状态，从而实现有效的治疗。Take 100 μL of the dispersion of rare earth core-shell nanomaterials and irradiate it with X-rays at a radiation dose of 10 Gy, then inject the dispersion subcutaneously into mice, and perform luminescence detection by live imaging of small animals (detection of emission light without excitation light ), please refer to FIG. 11, which 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.
3)对实施例1的稀土核壳纳米材料的生物毒性进行测试，测试过程具体为：将实施例1稀土核壳纳米材料配制成分散液，按照10mg/kg的量通过尾静脉注射将分散液注入小鼠体内作为实验组，对照组为注射磷酸盐缓冲液(PBS)，一周后取小鼠的各器官进行HE染色，请参阅图12，图12为本申请实施例1提供的稀土核壳纳米材料的生物毒性测试图，由图12可以看出注射分散液后小鼠的各器官组织均正常，即稀土核壳纳米材料对生物体并无毒性。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. Injected into the mice as the experimental group, the control group was injected with phosphate buffered saline (PBS), and after a week, the organs of the mice were taken for HE staining, please refer to Figure 12, Figure 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.
以上所述是本申请的优选实施方式，但并不能因此而理解为对本申请范围的限制。应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。The above descriptions are preferred implementations of the present application, but should not be construed as limiting the scope of the present application. It should be pointed out that those skilled in the art can make some improvements and modifications without departing from the principle of the present application, and these improvements and modifications are also regarded as the protection scope of the present application.

Claims (10)

  1. 一种稀土核壳纳米材料的制备方法，其特征在于，包括以下步骤：A method for preparing rare earth core-shell nanomaterials, comprising the following steps:
    将铽盐、镥盐、碱和溶剂进行第一混合处理形成第一溶液；所述溶剂包括体积比为1:(0.1-10):(0.1-10)的水、正丁醇和油酸；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);
    将所述第一溶液与氟化铵进行第二混合处理得到第二溶液；将所述第二溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核纳米材料；所述稀土核纳米材料包括β-NaLuF 4:Tb； 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 ; The rare earth core nanomaterial includes β-NaLuF 4 : Tb;
    将钇盐、所述稀土核纳米材料、所述碱和所述溶剂进行第三混合处理形成第三溶液；performing a third mixing treatment on the yttrium salt, the rare earth core nanomaterial, the alkali, and the solvent to form a third solution;
    将所述第三溶液与氟化铵进行第四混合处理得到第四溶液；将所述第四溶液置于水热釜中，在100℃-300℃下反应1h-72h，得到稀土核壳纳米材料，所述稀土核壳纳米材料的壳层包括NaYF 4。 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 .
  2. 如权利要求1所述的制备方法，其特征在于，所述第一混合处理、所述第二混合处理、所述第三混合处理和所述第四混合处理采用探头超声进行混合，所述探头超声的功率为50W-500W。The preparation method according to claim 1, characterized in that, the first mixing treatment, the second mixing treatment, the third mixing treatment and the fourth mixing treatment use probe ultrasound for mixing, and the probe The power of ultrasound is 50W-500W.
  3. 如权利要求1或2所述的制备方法，其特征在于，所述第一混合处理、所述第二混合处理、所述第三混合处理和所述第四混合处理的温度为0℃-10℃。The preparation method according to claim 1 or 2, characterized in that, the temperature of the first mixing treatment, the second mixing treatment, the third mixing treatment and the fourth mixing treatment is 0°C-10 ℃.
  4. 如权利要求1-3任一项所述的制备方法，其特征在于，所述第一溶液和所述第三溶液的pH为10-12。The preparation method according to any one of claims 1-3, characterized in that the pH of the first solution and the third solution is 10-12.
  5. 如权利要求1-4任一项所述的制备方法，其特征在于，所述正丁醇和油酸的体积比为1:(0.1-10)。The preparation method according to any one of claims 1-4, wherein the volume ratio of said n-butanol and oleic acid is 1:(0.1-10).
  6. 如权利要求1-5任一项所述的制备方法，其特征在于，所述第一溶液中，所述铽盐和所述镥盐的摩尔比为1:(4-99)。The preparation method according to any one of claims 1-5, characterized in that, in the first solution, the molar ratio of the terbium salt to the lutetium salt is 1:(4-99).
  7. 如权利要求1-6任一项所述的制备方法，其特征在于，所述第一溶液 中，所述铽盐和所述镥盐的摩尔浓度之和c 1为0.1mol·L -1-2mol·L -1；所述第二溶液中，所述铽盐和所述镥盐的摩尔浓度之和c 1与所述氟化铵的摩尔浓度c F1之比为1:(1-50)。 The preparation method according to any one of claims 1-6, characterized in that, in the first solution, the sum c 1 of the molar concentrations of the terbium salt and the lutetium salt is 0.1mol·L -1 - 2mol L −1 ; in the second solution, the ratio of the sum c of the molar concentrations of the terbium salt and the lutetium salt to the molar concentration c F of the ammonium fluoride is 1:(1-50) .
  8. 如权利要求1-7任一项所述的制备方法，其特征在于，所述第三溶液中，所述钇盐的摩尔浓度为0.1mol·L -1-2mol·L -1；所述钇盐与所述稀土核纳米材料的摩尔比为1:(10-100)。 The preparation method according to any one of claims 1-7, characterized in that, in the third solution, the molar concentration of the yttrium salt is 0.1mol·L -1 -2mol·L -1 ; the yttrium The molar ratio of the salt to the rare earth core nanomaterial is 1:(10-100).
  9. 如权利要求1-8任一项所述的制备方法，所述第四溶液中，所述钇盐与所述氟化铵的摩尔浓度之比为1:(1-50)。The preparation method according to any one of claims 1-8, in the fourth solution, the ratio of the molar concentration of the yttrium salt to the ammonium fluoride is 1:(1-50).
  10. 一种稀土核壳纳米材料，其特征在于，采用如权利要求1-9任一项所述制备方法制备得到，所述稀土核壳纳米材料包括稀土核纳米材料和包覆在所述稀土核纳米材料表面的壳层；所述稀土核纳米材料包括β-NaLuF 4:Tb；所述稀土核壳纳米材料的壳层包括NaYF 4。 A rare earth core-shell nanomaterial, characterized in that it is prepared by the preparation method according to any one of claims 1-9, and the rare earth core-shell nanomaterial comprises a rare earth core nanomaterial and a rare earth core nanomaterial coated on the rare earth core nanomaterial. The shell layer on the surface of the material; the rare earth core nanomaterial includes β-NaLuF 4 :Tb; the shell layer of the rare earth core shell nanomaterial includes NaYF 4 .
PCT/CN2021/096293 2021-05-27 2021-05-27 Rare-earth core-shell nanomaterial and preparation method therefor WO2022246725A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/096293 WO2022246725A1 (en) 2021-05-27 2021-05-27 Rare-earth core-shell nanomaterial and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/096293 WO2022246725A1 (en) 2021-05-27 2021-05-27 Rare-earth core-shell nanomaterial and preparation method therefor

Publications (1)

Publication Number Publication Date
WO2022246725A1 true WO2022246725A1 (en) 2022-12-01

Family

ID=84229434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/096293 WO2022246725A1 (en) 2021-05-27 2021-05-27 Rare-earth core-shell nanomaterial and preparation method therefor

Country Status (1)

Country Link
WO (1) WO2022246725A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173222A (en) * 2013-03-15 2013-06-26 吉林大学 Water soluble NaYF4@NaGdF4 nanocrystalline with upconversion core-shell structure and preparation method thereof
CN103911143A (en) * 2014-04-10 2014-07-09 合肥工业大学 Preparation method of NaReF4 nanomaterial with core-shell structure
WO2017054037A1 (en) * 2015-09-28 2017-04-06 Macquarie University Controlled growth of three-dimensional heterogeneous nanocrystals
CN108785672A (en) * 2018-06-29 2018-11-13 中国人民解放军第四军医大学 A kind of nanoparticle-photosensitizer coupled system of novel excitation of X-rays photodynamic therapy deep tumor and its application
CN111876154A (en) * 2020-05-15 2020-11-03 福州大学 Rare earth doped fluoride long afterglow particle and preparation method and application thereof
CN112794358A (en) * 2021-01-14 2021-05-14 南方科技大学 Rare earth doped sodium yttrium fluoride core-shell structure nano material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173222A (en) * 2013-03-15 2013-06-26 吉林大学 Water soluble NaYF4@NaGdF4 nanocrystalline with upconversion core-shell structure and preparation method thereof
CN103911143A (en) * 2014-04-10 2014-07-09 合肥工业大学 Preparation method of NaReF4 nanomaterial with core-shell structure
WO2017054037A1 (en) * 2015-09-28 2017-04-06 Macquarie University Controlled growth of three-dimensional heterogeneous nanocrystals
CN108785672A (en) * 2018-06-29 2018-11-13 中国人民解放军第四军医大学 A kind of nanoparticle-photosensitizer coupled system of novel excitation of X-rays photodynamic therapy deep tumor and its application
CN111876154A (en) * 2020-05-15 2020-11-03 福州大学 Rare earth doped fluoride long afterglow particle and preparation method and application thereof
CN112794358A (en) * 2021-01-14 2021-05-14 南方科技大学 Rare earth doped sodium yttrium fluoride core-shell structure nano material and preparation method thereof

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 *

Similar Documents

Publication Publication Date Title
Zhao et al. Multifunctional core–shell upconverting nanoparticles for imaging and photodynamic therapy of liver cancer cells
CN103589432B (en) Rear-earth-doped lithium lutetium fluoride nano material and its preparation and application
CN108130069B (en) Rare earth up-conversion nano diagnosis and treatment agent and preparation method thereof
Wang et al. Morphology control of lanthanide doped NaGdF4 nanocrystals via one-step thermolysis
CN112080278B (en) Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof
CN108904800B (en) Up-conversion nano hybrid system based on nano palladium heterogeneous growth, preparation method and application
CN112480925B (en) Near-infrared two-region luminous long-afterglow nanoprobe based on X-ray excitation, preparation method and application thereof in living body imaging analysis
CN112940726B (en) Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof
CN114836216B (en) Rare earth nanocomposite capable of improving singlet oxygen generation, preparation method and application thereof
WO2023041005A1 (en) Virus-like hollow oxide loaded near-infrared two-b region excited rare earth nanocrystal, preparation method therefor and application thereof
CN109233831B (en) Rare earth cerium ion doped rare earth disilicate small-size nanocrystal and preparation method and application thereof
CN113004900A (en) LiErF4Up-conversion nano luminescent material with base core-shell structure and preparation method thereof
CN111269720A (en) Rare earth doped double long afterglow nano material and its preparation method and use
CN112680223A (en) Zinc-germanium oxide long-afterglow luminescent material and preparation method thereof
CN105641695B (en) It is a kind of that tumor vascular targeted anticancer medicine being destroyed under alternating magnetic field or radio-frequency driven using magnetic micro-nano material
CN105602566B (en) A kind of rear-earth-doped NaGdF4Upper conversion nano crystalline substance and preparation method thereof
CN106753373A (en) A kind of ytterbium thulium codope gadolinium oxide upper conversion fluorescent nano particle and preparation method thereof
CN113292988A (en) Rare earth core-shell nano material and preparation method thereof
CN108175859B (en) Multimode magnetic photo-thermal diagnosis and treatment integrated nanoprobe and preparation method and application thereof
WO2022246725A1 (en) Rare-earth core-shell nanomaterial and preparation method therefor
CN113088288A (en) Rare earth fluorescent material with high quantum yield and preparation method thereof
CN110724517B (en) Rare earth/chlorophyll composite probe and preparation method and application thereof
CN111110844A (en) Preparation method and application of magnetic heat triggered free radical generated nano material
Min et al. Rare-earth doped hexagonal NaYbF 4 nanoprobes with size-controlled and NIR-II emission for multifunctional applications
CN114425092B (en) MRI/NIR II dual-mode imaging spray contrast agent and preparation method and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21942305

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21942305

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 21942305

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 28/05/2024)