WO2025213489A1 - 一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用 - Google Patents

一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用

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WO2025213489A1
WO2025213489A1 PCT/CN2024/087922 CN2024087922W WO2025213489A1 WO 2025213489 A1 WO2025213489 A1 WO 2025213489A1 CN 2024087922 W CN2024087922 W CN 2024087922W WO 2025213489 A1 WO2025213489 A1 WO 2025213489A1
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long
ultra
afterglow
small
infrared
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王静
朱芸菲
邹睿
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Sun Yat Sen University
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Sun Yat Sen University
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/67—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/681—Chalcogenides
    • C09K11/682—Chalcogenides with zinc or cadmium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/001—Preparation for luminescence or biological staining
    • A61K49/0013—Luminescence
    • A61K49/0017—Fluorescence in vivo
    • A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/001—Preparation for luminescence or biological staining
    • A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
    • A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/006—Compounds containing chromium, with or without oxygen or hydrogen, and containing two or more other elements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/6456—Spatial resolved fluorescence measurements; Imaging
    • G01N21/6458—Fluorescence microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

Definitions

  • the present invention belongs to the technical field of near-infrared long-afterglow nanomaterials, and more specifically, relates to ultra-small, high-performance near-infrared long-afterglow nanoparticles, and a preparation method and application thereof.
  • Long-lasting luminescent materials are materials that continue to emit light for an extended period after excitation ceases. Due to their unique, ultra-long-lifetime luminescence, near-infrared long-lasting luminescent materials can be excited in vitro and then imaged in vivo. Compared to traditional quantum dots and upconversion luminescent materials, near-infrared long-lasting luminescent materials can be excited in vitro, avoiding the interference of background fluorescence from biological tissues caused by continuous excitation. Furthermore, near-infrared light emission falls within the biological optical window and possesses strong penetrating power. Therefore, near-infrared long-lasting luminescent materials offer the advantage of an ultra-high signal-to-noise ratio in in vivo optical imaging applications, demonstrating great potential for application.
  • Existing strategies for preparing near-infrared long-lasting luminescent materials primarily include high-temperature solid-phase methods, sol-gel methods, hydrothermal methods, and silica template methods.
  • the near-infrared long-lasting luminescent materials produced by the high-temperature solid-phase method have large particle sizes, making them unsuitable for in vivo imaging.
  • the sol-gel and hydrothermal methods can produce near-infrared long-lasting luminescent nanomaterials with particle sizes less than 100 nanometers, the resulting nanoparticles are often highly agglomerated and tend to accumulate in organs such as the liver, spleen, and lungs.
  • the particle size of near-infrared long-lasting luminescent materials produced by the silica template method depends on the size of the silica template, and currently, this method cannot be applied to silica templates smaller than 50 nanometers.
  • near-infrared, long-lasting luminescent nanomaterials with a particle size less than 5 nm can be excreted through the kidneys and have higher metabolic efficiency. Therefore, near-infrared, long-lasting luminescent nanomaterials with a particle size less than 5 nm should theoretically have less background interference and higher biosafety.
  • the particle size of nanomaterials decreases their luminescence performance generally decreases. Therefore, the development of near-infrared, long-lasting luminescent nanomaterials with smaller particle sizes and longer-lasting luminescence duration has become an important issue that needs to be addressed.
  • Patent publication number CN105754595A discloses a long afterglow nanomaterial.
  • Zinc nitrate solution, gallium nitrate solution, sodium germanate solution and chromium nitrate solution are mixed and stirred together, and ammonia water is quickly added to adjust the pH of the mixed solution to 10.
  • the mixed solution is then transferred to a high-temperature hydrothermal reactor and reacted at 120°C for 24 hours.
  • the resulting long-afterglow material has uniform size, increasing from 7nm to 80nm, and produces high brightness and long duration under visible light excitation.
  • the prepared long-afterglow nanomaterial composition is ZnGa2O4 : 0.75 %Cr
  • the particle size is 7nm
  • the afterglow decay image shows an afterglow time of only 3 hours, which is still difficult to meet practical application requirements.
  • the primary purpose of the present invention is to provide a method for preparing ultra-small, high-performance near-infrared long-afterglow nanoparticles.
  • the average diameter of the prepared near-infrared long-afterglow nanoparticles is less than 5 nanometers, and they can produce near-infrared long-afterglow emission with a wavelength between 600 nanometers and 800 nanometers.
  • the long-afterglow luminescence can last for up to more than 5 hours.
  • the second object of the present invention is to provide a method for preparing ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles to obtain ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles.
  • the third object of the present invention is to provide an application of ultra-small, high-performance near-infrared long-afterglow nanoparticles in optical imaging of living organisms, molecular labeling, or in the preparation of medical diagnostic reagents.
  • the present invention claims protection for a method for preparing ultra-small, high-performance, near-infrared, long-afterglow nanoparticles, comprising the following steps:
  • Gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and a long-chain alkyl glycol are added to a mixed solution containing oleic acid, oleylamine and octadecene, stirred, evacuated, heated to 50 to 110 ° C, and kept warm; the long-chain alkyl glycol contains 10 to 18 carbon atoms;
  • the present invention adopts a mixed solvent of oleic acid, oleylamine and octadecene as a reaction system, which limits the growth of the near-infrared long-afterglow nanoparticles while also utilizing the organic groups attached to the surface of the particles to improve the dispersibility of the nanoparticles.
  • the prepared nanoparticles not only have a smaller particle size, but also reduce the agglomeration of the nanoparticles.
  • the introduction of long-chain alkyl glycol can promote the decomposition of the acetylacetonate raw material, improve the crystallinity of the near-infrared long-afterglow nanoparticles, and thus enhance the near-infrared long-afterglow luminescence performance.
  • step S3 If a low-boiling-point short-chain alkyl glycol is introduced into the reaction system, the heating temperature in step S3 will not be able to be raised to the optimal reaction temperature, and the ultra-small, high-performance near-infrared long-afterglow nanoparticles of the present invention cannot be prepared.
  • the present invention adopts three-stage heating to prepare the ultra-small high-performance near-infrared long afterglow nanoparticles.
  • the purpose of the first heating stage is to completely dissolve the acetylacetonate in the mixed solvent of oleic acid, oleylamine, and octadecene;
  • the purpose of the second heating stage is to promote the decomposition of the acetylacetonate to form small crystals;
  • the purpose of the third heating stage is to promote the growth of the crystals, ultimately producing the high-performance infrared long-lasting nanoparticles.
  • the long-lasting nanoparticles produced by the present invention not only have a smaller average diameter but also have a longer-lasting luminescence duration.
  • the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and long-chain diol is 2: (0.6-1.4): (1 ⁇ 10-4-2 ⁇ 10-3 ): (1-40). Further preferably, the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and long-chain diol is 2: (1.0-1.1): (1 ⁇ 10-3-1.5 ⁇ 10-3 ): (5-15).
  • the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and long-chain diol is 2: 1: 1.42 ⁇ 10-3 : 10.
  • the luminescence intensity of the prepared ultra-small, high-performance near-infrared long-lasting glow nanoparticles is higher.
  • the volume ratio of oleic acid, oleylamine, and octadecene is 1:(0.5-1.5):(1-4). Further preferably, the volume ratio of oleic acid, oleylamine, and octadecene is 1:(0.8-1.2):(1.5-2.5).
  • the long-chain alkyl glycol described in the present invention may contain 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, etc., or an interval range formed by any of the above values, such as 10 to 14 carbon atoms, 12 to 18 carbon atoms, etc., but the present invention is not limited thereto.
  • the long-chain alkyl diol contains 12 to 16 carbon atoms. Further preferably, the long-chain alkyl diol is selected from one or more of 1,2-dodecanediol, 1,2-tetradecanediol, or 1,2-hexadecanediol. Further preferably, the long-chain alkyl diol is 1,2-tetradecanediol.
  • the holding time is 0.5 to 3 hours. Further preferably, the holding time is 0.8 to 1.5 hours.
  • step S2 the temperature is raised to 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, etc., or an interval formed by any of the above values, such as 160°C to 190°C, 170°C to 210°C, etc., under nitrogen protection.
  • the present invention is not limited thereto.
  • step S2 the temperature is raised to 180-220°C.
  • the holding time is 0.5 to 5 hours, and further preferably, the holding time is 1 to 3 hours.
  • step S3 the temperature is further increased to 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, or any range formed by the above values, such as 260°C to 290°C, 270°C to 310°C, etc., but the present invention is not limited thereto. Further preferably, in step S3, the temperature is further increased to 290 to 320°C.
  • the holding time is 0.4 to 2 hours. More preferably, the holding time is 0.6 to 1 hour.
  • step S1 the temperature is raised to 70-90°C.
  • the post-processing includes centrifugation, resuspension and washing.
  • the present invention seeks to protect the ultra-small, high-performance, near-infrared, long-afterglow nanoparticles prepared by the above-mentioned method for preparing the ultra-small, high-performance, near-infrared, long-afterglow nanoparticles.
  • the average diameter of the ultra-small, high-performance near-infrared long-lasting-glow nanoparticles is less than 5 nm. Further preferably, the average diameter of the ultra-small, high-performance near-infrared long-lasting-glow nanoparticles is 3.5 to 4.5 nm.
  • the chemical formula of the ultra-small, high-performance near-infrared, long-lasting nanoparticles is ZnyGa2CrxO4 , where 1 ⁇ 10-4 ⁇ x ⁇ 2 ⁇ 10-3 , and 0.6 ⁇ y ⁇ 1.4.
  • ZnyGa2O4 serves as the matrix
  • Cr3 + serves as the activating ion.
  • the present invention seeks to protect the use of ultra-small, high-performance near-infrared long-afterglow nanoparticles in optical imaging of living organisms, molecular labeling, or in the preparation of medical diagnostic reagents.
  • the ultra-small, high-performance near-infrared long-afterglow nanoparticles provided by the present invention have an average diameter of less than 5 nanometers and a long-afterglow luminescence performance with a luminescence duration of more than 4 hours.
  • the nanoparticles can also be used in fields such as subcellular organelle imaging, molecular labeling and in vivo fine optical imaging. Therefore, applications in the above fields should also be within the scope of protection of the present invention.
  • the present invention has the following beneficial effects:
  • the present invention provides a method for preparing ultra-small, high-performance, near-infrared long-afterglow nanoparticles.
  • the method uses a mixed solution of oleic acid, oleylamine, and octadecene as a reaction medium, a long-chain diol as a reaction regulating reagent, and utilizes specifically regulated amounts of zinc acetylacetonate and chromium acetylacetonate, as well as reaction temperature and time, to prepare ultra-small, high-performance, near-infrared long-afterglow nanoparticles with an average diameter of less than 5 nanometers and good dispersibility.
  • the nanoparticles can effectively avoid high aggregation in organs such as the liver, spleen, and lungs.
  • the nanoparticles also have excellent long-afterglow luminescence performance and can be effectively excited by 265-nanometer ultraviolet light to generate near-infrared long-afterglow emission with a wavelength between 600 nanometers and 800 nanometers.
  • the maximum long-afterglow luminescence duration exceeds 5 hours, can achieve better in vivo imaging effects, and has broad application prospects in the fields of optical imaging and biomedical diagnostic reagent development.
  • FIG1 is a TEM image of ultra-small, high-performance, near-infrared, long-afterglow nanoparticles provided in Example 1.
  • FIG2 is a particle size distribution diagram of the ultra-small, high-performance near-infrared long-afterglow nanoparticles provided in Example 1.
  • FIG3 is an XRD diagram of the ultra-small, high-performance near-infrared long-afterglow nanoparticles provided in Example 1.
  • FIG4 is an excitation-emission spectrum of the ultra-small, high-performance near-infrared long-afterglow nanoparticles provided in Example 1, wherein the dotted line is the excitation spectrum and the solid line is the emission spectrum.
  • FIG5 is an emission spectrum of ultra-small, high-performance near-infrared long-afterglow nanoparticles with different Zn 2+ contents provided in Examples 1 to 5.
  • FIG6 is an emission spectrum diagram of ultra-small, high-performance, near-infrared, long-afterglow nanoparticles with different Cr 3+ contents provided in Example 1 and Examples 6 to 10.
  • FIG7 is an emission spectrum of ultra-small, high-performance near-infrared long-afterglow nanoparticles prepared by adding different amounts of 1,2-tetradecanediol as provided in Comparative Example 1, Example 1, and Examples 11 to 14.
  • FIG8 is an emission spectrum of ultra-small, high-performance near-infrared long-afterglow nanoparticles prepared at different reaction temperatures provided in Example 1 and Examples 15 to 19.
  • FIG9 is a long afterglow luminescence attenuation curve and a long afterglow emission spectrum of the ultra-small high-performance near-infrared long afterglow nanoparticles provided in Example 1.
  • FIG10 is a TEM image and afterglow decay imaging image of ultra-small high-performance near-infrared long afterglow nanoparticles prepared with different contents of 1,2-tetradecanediol provided in Example 1 and Examples 11 to 14.
  • the present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
  • Example 1 Preparation method of ultra-small high-performance near-infrared long-lasting glow nanoparticles
  • Gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol (molar ratio of 2:1:0.00142:10) were added to a three-necked flask containing a mixed solution of 10 mL of oleic acid, 10 mL of oleylamine and 20 mL of octadecene. The mixture was heated to 80°C under vacuum while stirring and kept warm for 0.5 h.
  • step (2) The reaction product of step (1) was heated to 200°C under nitrogen protection and kept at this temperature for 1 hour.
  • step (3) The reaction product of step (3) is cooled, centrifuged, resuspended, and washed multiple times to obtain ultra-small, high-performance near-infrared long-afterglow nanoparticles.
  • Example 2 The difference between Example 2 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:0.8:0.00142:10.
  • Example 3 The difference between Example 3 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:0.9:0.00142:10.
  • Example 4 The difference between Example 4 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1.1:0.00142:10.
  • Example 5 The difference between Example 5 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1.2:0.00142:10.
  • Example 6 The difference between Example 6 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00058:10.
  • Example 7 The difference between Example 7 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00086:10.
  • Example 8 The difference between Example 8 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00114:10.
  • Example 9 The difference between Example 9 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00172:10.
  • Example 10 The difference between Example 10 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.002:10.
  • Examples 11-14 A method for preparing ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles
  • Example 11 The difference between Example 11 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00142:2.
  • Example 12 The difference between Example 12 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00142:5.
  • Example 13 The difference between Example 13 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00142:15.
  • Example 14 The difference between Example 14 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00142:20.
  • Example 15 The difference between Example 15 and Example 1 is that in step (3), the temperature is continued to be raised to 290°C.
  • Example 16 The difference between Example 16 and Example 1 is that in step (3), the temperature is continued to be raised to 300°C.
  • Example 17 The difference between Example 17 and Example 1 is that in step (3), the temperature is continued to be raised to 320°C.
  • Example 18 The difference between Example 18 and Example 1 is that in step (3), the temperature is continued to be raised to 330°C.
  • Example 19 The difference between Example 19 and Example 1 is that in step (3), the temperature is continued to be raised to 340°C.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate and 1,2-tetradecanediol is 2:1:0.00142:0, that is, no 1,2-tetradecanediol is added in Comparative Example 1.
  • Example 1 The ultra-small, high-performance, near-infrared, long-lasting nanoparticles prepared in Example 1 were dissolved in a cyclohexane solution and dropped onto a copper mesh. Transmission electron microscopy was used to observe the morphology and size of the nanoparticles.
  • Figure 1 is a TEM image of the ultra-small, high-performance, near-infrared, long-lasting nanoparticles provided in Example 1. As shown in Figure 1, Example 1 successfully produced ultra-small, high-performance, near-infrared, long-lasting nanoparticles with an average diameter of less than 5 nanometers and excellent dispersibility.
  • Figure 2 is a size distribution diagram of the ultra-small, high-performance near-infrared long-lasting nanoparticles provided in Example 1 (200 nanoparticles were randomly selected for statistics). As shown in Figure 2, the average size of the ultra-small, high-performance near-infrared long-lasting nanoparticles prepared in Example 1 is 3.76 nanometers.
  • the ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles prepared in Example 1 were measured using an X-ray powder diffractometer .
  • FIG3 shows an XRD pattern of the ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles provided in Example 1.
  • FIG3 shows that the XRD pattern of the ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles prepared is consistent with the standard card of ZnGa2O4 (JCPDS: 381240), indicating a pure phase.
  • the ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles prepared in Example 1 were measured using a fluorescence spectrometer.
  • Figure 4 shows the excitation-emission spectrum of the ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles provided in Example 1.
  • the emission wavelength of the nanoparticles lies between 600 and 800 nanometers, with the main emission peak at 695 nanometers.
  • the ultra-small, high-performance, near-infrared, long-afterglow nanoparticles prepared in each embodiment and comparative example were measured using a fluorescence spectrometer.
  • Figure 5 shows the emission spectra of ultra-small, high-performance, near-infrared, long-lasting-glow nanoparticles with varying Zn2 + contents, as provided in Examples 1 to 5.
  • the luminescence intensity of the nanoparticles increases first and then decreases with increasing Zn2+ content.
  • the nanoparticles exhibit optimal optical properties when the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate, and 1,2-tetradecanediol is 2:1:0.00142:10.
  • Figure 6 shows the emission spectra of ultra-small, high-performance, near-infrared, long-afterglow nanoparticles with varying Cr 3+ contents, as provided in Examples 1 and 6-10.
  • the luminescence intensity of the nanoparticles increases first and then decreases with increasing Cr 3+ content.
  • the nanoparticles achieve optimal optical performance when the molar ratio of gallium acetylacetonate, zinc acetylacetonate, chromium acetylacetonate, and 1,2-tetradecanediol is 2:1:0.00142:10.
  • Figure 7 shows the emission spectra of ultra-small, high-performance near-infrared, long-lasting-glow nanoparticles prepared by adding different amounts of 1,2-tetradecanediol, as provided in Comparative Example 1, Example 1, and Examples 11-14.
  • the luminescence intensity of the nanoparticles increases and then decreases with increasing amounts of 1,2-tetradecanediol.
  • the optical properties of the nanoparticles are optimal when the amount of 1,2-tetradecanediol added is 10 mmol, thus selecting 10 mmol as the optimal amount of 1,2-tetradecanediol.
  • Figure 8 shows the emission spectra of ultra-small, high-performance near-infrared, long-lasting-glow nanoparticles prepared at different reaction temperatures, as provided in Examples 1 and 15-19. As shown in Figure 8, the luminescence intensity of the nanoparticles increases first and then decreases with increasing reaction temperature. The optical properties of the nanoparticles are optimal at a reaction temperature of 310°C, making 310°C the optimal reaction temperature.
  • the ultra-small, high-performance near-infrared long-afterglow nanoparticles prepared in Example 1 were used to perform a long-afterglow luminescence test.
  • the specific operations are as follows: after irradiating the nanoparticles with 265-nanometer ultraviolet light for 1 minute, the afterglow intensity of the nanoparticles was measured by a small animal optical imaging system to obtain a long-afterglow luminescence attenuation curve; after irradiating the nanoparticles with 265-nanometer ultraviolet light for 1 minute, the long-afterglow emission spectrum was immediately obtained by measuring with a fluorescence spectrometer.
  • Figure 9 shows the long-afterglow luminescence decay curve and long-afterglow emission spectrum of the ultra-small, high-performance near-infrared long-afterglow nanoparticles provided in Example 1.
  • the long-afterglow emission spectrum of the nanoparticles is essentially identical to the spectral shape of the emission spectrum in Figure 1.
  • the afterglow emission band lies between 600 and 800 nanometers, with the main emission peak slightly shifted to 705 nanometers.
  • the long-afterglow luminescence lasts for more than five hours.
  • Figure 10 is a TEM image and afterglow decay imaging image of ultra-small high-performance near-infrared long afterglow nanoparticles prepared with different contents of 1,2-tetradecanediol provided in Example 1 and Examples 11 to 14.
  • the average diameter and long afterglow luminescence duration of the ultra-small high-performance near-infrared long afterglow nanoparticles prepared in Examples 11 to 14 are shown in Table 1 below.
  • the ultra-small, high-performance near-infrared long-lasting luminescence nanoparticles provided by the present invention have an average diameter of less than 5 nanometers and a long-lasting luminescence duration exceeding 4 hours.
  • the ultra-small, high-performance near-infrared long-lasting luminescence nanoparticles prepared in Example 1 have a long-lasting luminescence duration exceeding 5 hours.

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Abstract

本发明公开了一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用。所述制备方法包括以下步骤：S1.将乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链烷基二醇加入到含有油酸、油胺和十八烯的混合溶液中，搅拌，抽真空，加热至50～110℃，所述长链烷基二醇含有10～18个碳原子；S2.氮气保护下升温至160～240℃，保温；S3.继续升温至260～340℃，保温，后处理，获得所述超小高性能近红外长余辉纳米颗粒。本发明制备获得的超小高性能近红外长余辉纳米颗粒的平均直径在5纳米以下，同时具有优异的长余辉发光持续时间，在光学成像和生物医学诊疗试剂开发领域具有广阔应用前景。

Description

一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用 技术领域
本发明属于近红外长余辉纳米材料的技术领域，更具体地，涉及一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用。
背景技术
长余辉发光材料是一种在激发停止后仍然可以持续发光很长一段时间的发光材料。凭借着其独特的超长寿命发光，近红外长余辉发光材料可以在体外进行激发，然后进入活体进行成像。相比于传统的量子点和上转换发光材料，近红外长余辉发光材料可在体外激发，避免了持续激发造成的生物组织自身的背景荧光干扰。与此同时，近红外光的发射处于生物光学窗口中，穿透力强。因此近红外长余辉发光材料在生物活体光学成像应用中具有超高信噪比的优势，展现出极大的应用前景。
现有近红外长余辉发光材料的制备策略主要有高温固相法、溶胶凝胶法、水热法和二氧化硅模板法。其中，高温固相法制得的近红外长余辉发光材料的粒径较大，不适用于生物活体成像；而溶胶凝胶法、水热法能够得到粒径小于100纳米的近红外长余辉发光纳米材料，但是制得的纳米颗粒往往非常团聚，容易在肝脏、脾脏和肺等器官高度聚集，不但导致高的背景信号，还将对这些器官造成潜在的毒性，限制了其在活体成像和细胞示踪等领域的应用。二氧化硅模板法制得的近红外长余辉发光材料的粒径则依赖于二氧化硅模板的尺寸，目前仍无法在尺寸小于50纳米的二氧化硅模板中实现该方法的应用。
多项研究表明，粒径小于5nm的近红外长余辉发光纳米材料可通过肾脏排泄，具有更高的代谢效率，因此，粒径小于5nm的近红外长余辉发光材料在理论上将具有更小的背景干扰和更高的生物安全性。然而随着纳米材料的粒径逐渐变小，其发光性能一般而言也逐渐减弱。因此，如何探索一种粒径更小，但是长余辉持续发光时间更好的近红外长余辉发光纳米材料成为亟需解决的重要问题。
专利公开号CN105754595A公开了一种长余辉纳米材料，将硝酸锌溶液、硝酸镓溶液、锗酸钠溶液以及硝酸铬溶液一起混合搅拌迅速加入氨水，调节混合溶液pH至10；然后将混合溶液转移至高温水热釜中，于120℃反应24h。制备获 得的长余辉材料尺寸均一，尺寸可从7nm增加到80nm，在可见光激发下产生亮度高、持续时间长。然而当制备的长余辉纳米材料成分组成为ZnGa2O4:0.75％Cr时，颗粒尺寸为7nm，在余辉衰减图像中，其余辉时间仅为3h，仍然难以满足实际的应用需求。
发明内容
针对上述现有的技术问题，本发明的首要目的在于提供一种超小高性能近红外长余辉纳米颗粒的制备方法，制备获得的近红外长余辉纳米颗粒的平均直径小于5纳米，能够产生波长位于600纳米至800纳米之间的近红外长余辉发射，长余辉发光持续时间最长可超过5小时。
本发明的第二个目的在于提供一种超小高性能近红外长余辉纳米颗粒的制备方法制备获得的超小高性能近红外长余辉纳米颗粒。
本发明的第三个目的在于提供一种超小高性能近红外长余辉纳米颗粒在生物活体光学成像、分子标记或在制备医学诊疗试剂中的应用。
为了实现上述目的，本发明是通过以下技术方案予以实现的：
本发明请求保护一种超小高性能近红外长余辉纳米颗粒的制备方法，包括以下步骤：
S1.将乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链烷基二醇加入到含有油酸、油胺和十八烯的混合溶液中，搅拌，抽真空，加热至50～110℃，保温；所述长链烷基二醇含有10～18个碳原子；
S2.氮气保护下升温至160～240℃，保温；
S3.继续升温至260～340℃，保温，后处理，获得所述超小高性能近红外长余辉纳米颗粒。
本发明采用油酸、油胺和十八烯的混合溶剂作为反应体系，限制近红外长余辉纳米颗粒晶粒长大的同时也利用颗粒表面附着的有机基团提高纳米颗粒的分散性。制备获得的纳米颗粒不仅具有更小的粒径，同时也降低了纳米颗粒团聚。而长链烷基二醇的引入则可促进乙酰丙酮盐原料的分解，提高近红外长余辉纳米颗粒的结晶性，从而提升近红外长余辉发光性能。而如果在反应体系中引入低沸点的短链烷基二元醇，将导致步骤S3中的加热温度无法提升至最佳反应温度，不能够制备获得本发明超小高性能近红外长余辉纳米颗粒。
进一步地，本发明采用三段式加热制备获得所述超小高性能近红外长余辉纳 米颗粒，其中第一段加热目的是将乙酰丙酮盐完全溶解于油酸、油胺和十八烯的混合溶剂中；第二段加热目的是促使乙酰丙酮盐分解，形成小晶粒；而第三段加热目的是帮助晶粒生长，最终制备获得所述高性能红外长余辉纳米颗粒。本发明制备的长余辉纳米颗粒不仅具有更小的平均直径，而且具有更为优异的长余辉发光持续时间。
优选地，所述步骤S1中，所述乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链二元醇的摩尔比为2：(0.6～1.4)：(1×10-4～2×10-3)：(1～40)。进一步优选地，所述乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链二元醇的摩尔比为2：(1.0～1.1)：(1×10-3～1.5×10-3)：(5～15)。进一步优选地，所述乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链二元醇的摩尔比为2：1：1.42×10-3：10。在上述优选范围下，制备获得的超小高性能近红外长余辉纳米颗粒的发光强度更高。
优选地，所述步骤S1中，所述油酸、油胺和十八烯的体积比为1：(0.5～1.5)：(1～4)。进一步优选地，所述油酸、油胺和十八烯的体积比为1：(0.8～1.2)：(1.5～2.5)。
具体地，本发明中所述长链烷基二醇可以含有10个碳原子、11个碳原子、12个碳原子、13个碳原子、14个碳原子、15个碳原子、16个碳原子、17个碳原子、18个碳原子等，或上述任意数值形成的区间范围，如10～14个碳原子、12～18个碳原子等，本发明不限于此。
优选地，所述长链烷基二醇含有12～16个碳原子。进一步优选地，所述长链烷基二醇选自1,2-十二烷二醇、1,2-十四烷二醇或1,2-十六烷二醇中的一种或多种。进一步优选地，所述长链烷基二醇为1,2-十四烷二醇。
优选地，所述步骤S2中，所述保温的时间为0.5～3h。进一步优选地，所述保温的时间为0.8～1.5h。
具体地，所述步骤S2中，氮气保护下升温至160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃等，或上述任意数值形成的区间范围，如160℃～190℃、170℃～210℃等，本发明不限于此。进一步优选地，所述步骤S2中，升温至180～220℃。
优选地，所述步骤S3中，所述保温的时间为0.5～5h。进一步优选地，所述保温的时间为1～3h。
具体地，所述步骤S3中，继续升温至260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃等，或上述任意数值形成的区间范围，如260℃～290℃、270℃～310℃等，本发明不限于此。进一步优选地，所述步骤S3中，继续升温至290～320℃。
优选地，所述步骤S1中，所述保温的时间为0.4～2h。进一步优选地，所述保温的时间为0.6～1h。
进一步优选地，所述步骤S1中，升温至70～90℃。
优选地，所述后处理包括离心、重悬、洗涤。
进一步地，本发明请求保护上述超小高性能近红外长余辉纳米颗粒的制备方法制备获得的超小高性能近红外长余辉纳米颗粒。
优选地，所述超小高性能近红外长余辉纳米颗粒的平均直径小于5nm。进一步优选地，所述超小高性能近红外长余辉纳米颗粒的平均直径为3.5～4.5nm。
优选地，所述超小高性能近红外长余辉纳米颗粒的化学式为ZnyGa2CrxO4，其中，1×10-4≤x≤2×10-3，0.6≤y≤1.4。其中，ZnyGa2O4为基质，Cr3+为激活离子。优选地，0.0005≤x≤0.002，0.8≤y≤1.2。进一步优选地，0.001≤x≤0.0015，1.0≤y≤1.1。
进一步地，本发明请求保护一种超小高性能近红外长余辉纳米颗粒在生物活体光学成像、分子标记或在制备医学诊疗试剂中的应用。
本发明提供的超小高性能近红外长余辉纳米颗粒的平均直径小于5纳米和具有发光持续时间超过4小时的长余辉发光性能，纳米颗粒经过适当的功能化修饰，也可以用于亚细胞器成像、分子标记和活体精细光学成像等领域中，因此上述领域中的应用也应当在本发明的保护范围内。
与现有技术相比，本发明具有以下有益效果：
本发明提供了一种超小高性能近红外长余辉纳米颗粒的制备方法，所述方法以油酸、油胺、十八烯的混合溶液作为反应介质，长链二元醇作为反应调控试剂，利用特定调控的乙酰丙酮锌、乙酰丙酮铬用量以及反应的温度和时间，制备得到了一种平均直径在5纳米以下、具有良好分散性的超小高性能近红外长余辉纳米颗粒，能够有效避免在肝脏、脾脏和肺等器官的高度聚集；同时所述纳米颗粒还具有优异的长余辉发光性能，能够被265纳米紫外光有效激发，产生波长位于600纳米至800纳米之间的近红外长余辉发射，最大长余辉发光持续时间超过5 小时，能够实现更好的活体成像效果，在光学成像和生物医学诊疗试剂开发领域具有广阔应用前景。
附图说明
图1为实施例1提供的超小高性能近红外长余辉纳米颗粒的TEM图。
图2为实施例1提供的超小高性能近红外长余辉纳米颗粒的粒径分布图。
图3为实施例1提供的超小高性能近红外长余辉纳米颗粒的XRD图。
图4为实施例1提供的超小高性能近红外长余辉纳米颗粒的激发发射光谱图，其中虚线为激发光谱，实线为发射光谱。
图5为实施例1～5提供的不同Zn2+含量的超小高性能近红外长余辉纳米颗粒的发射光谱图。
图6为实施例1和实施例6～10提供的不同Cr3+含量超小高性能近红外长余辉纳米颗粒的发射光谱图。
图7为对比例1、实施例1和实施例11～14提供的添加不同含量1,2-十四烷二醇制备得到的超小高性能近红外长余辉纳米颗粒的发射光谱图。
图8为实施例1和实施例15～19提供的不同反应温度制备得到的超小高性能近红外长余辉纳米颗粒的发射光谱图。
图9为实施例1提供的超小高性能近红外长余辉纳米颗粒的长余辉发光衰减曲线图和长余辉发射光谱图。
图10为实施例1以及实施例11～14提供的不同含量1,2-十四烷二醇制备得到的超小高性能近红外长余辉纳米颗粒的TEM图和余辉衰减成像图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1一种超小高性能近红外长余辉纳米颗粒的制备方法
(1)将乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇(摩尔比为2：1：0.00142：10)加入到含有10mL油酸、10mL油胺和20mL十八烯混合溶液的三口烧瓶中，一边搅拌一边抽真空下，加热至80℃并保温0.5小时。
(2)步骤(1)反应产物在氮气保护下升温至200℃，并保温1小时。
(3)继续升温至310℃，并保温2小时。
(4)步骤(3)反应产物进行冷却，多次离心、重悬、洗涤后，得到超小高性能近红外长余辉纳米颗粒。
实施例2～5一种超小高性能近红外长余辉纳米颗粒的制备方法
实施例2和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：0.8：0.00142：10。
实施例3和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：0.9：0.00142：10。
实施例4和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1.1：0.00142：10。
实施例5和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1.2：0.00142：10。
实施例6～10一种超小高性能近红外长余辉纳米颗粒的制备方法
实施例6和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00058：10。
实施例7和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00086：10。
实施例8和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00114：10。
实施例9和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00172：10。
实施例10和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.002：10。
实施例11～14一种超小高性能近红外长余辉纳米颗粒的制备方法
实施例11和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：2。
实施例12和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：5。
实施例13和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：15。
实施例14和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：20。
实施例15～19一种超小高性能近红外长余辉纳米颗粒的制备方法
实施例15和实施例1的区别在于：步骤(3)中，继续升温至290℃。
实施例16和实施例1的区别在于：步骤(3)中，继续升温至300℃。
实施例17和实施例1的区别在于：步骤(3)中，继续升温至320℃。
实施例18和实施例1的区别在于：步骤(3)中，继续升温至330℃。
实施例19和实施例1的区别在于：步骤(3)中，继续升温至340℃。
对比例1
对比例1和实施例1的区别在于：乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：0，即对比例1中未加入1,2-十四烷二醇。
测试例1超小高性能近红外长余辉纳米颗粒的表征和性能测试
将实施例1制备的超小高性能近红外长余辉纳米颗粒溶于环己烷溶液中，滴于铜网上，采用透射电镜观察纳米颗粒的形貌与大小。图1为实施例1提供的超小高性能近红外长余辉纳米颗粒的TEM图。从图1可知，实施例1成功制备得到平均直径小于5纳米的超小高性能近红外长余辉纳米颗粒，且具有优异的分散性。
图2为实施例1提供的超小高性能近红外长余辉纳米颗粒的尺寸分布图(随机选取200个纳米颗粒进行统计)。从图2可知，实施例1制备得到的超小高性能近红外长余辉纳米颗粒的平均尺寸为3.76纳米。
采用X射线粉末衍射仪测定实施例1制备的超小高性能近红外长余辉纳米颗粒。图3为实施例1提供的超小高性能近红外长余辉纳米颗粒的XRD图，从图3可知，制备得到的超小高性能近红外长余辉纳米颗粒的XRD图谱与ZnGa2O4的标准卡片(JCPDS:381240)一致，为纯相。
采用荧光光谱仪测定实施例1制备的超小高性能近红外长余辉纳米颗粒。图4为实施例1提供的超小高性能近红外长余辉纳米颗粒的激发发射光谱图，从图4可知，纳米颗粒的发射波段位于600纳米与800纳米之间，主发射峰位于695纳米。
采用荧光光谱仪测定各实施例和对比例制备的超小高性能近红外长余辉纳米颗粒。
图5为实施例1～5提供的不同Zn2+含量的超小高性能近红外长余辉纳米颗粒的发射光谱图。从图5可知，随着Zn2+含量的提高，纳米颗粒的发光强度呈现先升后降的趋势，当乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：10时，纳米颗粒的光学性能最佳。
图6为实施例1和实施例6～10提供的不同Cr3+含量超小高性能近红外长余辉纳米颗粒的发射光谱图。从图6可知，随着Cr3+含量的提高，纳米颗粒的发光强度呈现先升后降的趋势，当乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和1,2-十四烷二醇的摩尔比为2：1：0.00142：10时，纳米颗粒的光学性能最佳。
图7为对比例1、实施例1和实施例11～14提供的添加不同含量1,2-十四烷二醇制备得到的超小高性能近红外长余辉纳米颗粒的发射光谱图。从图7可知，随着1,2-十四烷二醇添加量的提高，纳米颗粒的发光强度呈现先升后降的趋势，1,2-十四烷二醇添加量为10mmol时，纳米颗粒的光学性能最佳，因此最佳1,2-十四烷二醇添加量选择为10mmol。
图8为实施例1和实施例15～19提供的不同反应温度制备得到的超小高性能近红外长余辉纳米颗粒的发射光谱图。从图8可知，随着反应温度的提高，纳米颗粒的发光强度呈现先升后降的趋势，反应温度为310℃时，纳米颗粒的光学性能最佳，因此最佳反应温度选择为310℃。
采用实施例1制备的超小高性能近红外长余辉纳米颗粒进行长余辉发光测试，具体操作如下所示为：采用265纳米紫外光照射纳米颗粒1分钟后，通过小动物光学成像系统测定纳米颗粒的余辉强度，获得长余辉发光衰减曲线；采用265纳米紫外光照射纳米颗粒1分钟后，立即由荧光光谱仪测定，获得长余辉发射光谱。
图9为实施例1提供的超小高性能近红外长余辉纳米颗粒的长余辉发光衰减曲线图和长余辉发射光谱图。从图9可知，纳米颗粒的长余辉发射光谱与图1中发射光谱的光谱形状基本一致，余辉发射波段位于600纳米与800纳米之间，主发射峰稍有偏移，位于705纳米，且长余辉发光持续时间超过5个小时。
图10为实施例1以及实施例11～14提供的不同含量1,2-十四烷二醇制备得到的超小高性能近红外长余辉纳米颗粒的TEM图和余辉衰减成像图。实施例1 以及实施例11～14制备超小高性能近红外长余辉纳米颗粒的平均直径和长余辉发光持续时间如下表1所示。
表1
由图10和表1可知，本发明提供的超小高性能近红外长余辉纳米颗粒的平均直径小于5纳米，且长余辉发光持续时间均超过4h。其中，实施例1制备的超小高性能近红外长余辉纳米颗粒的长余辉发光持续时间超过5小时。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例为申请人真实试验结果加以论证。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种超小高性能近红外长余辉纳米颗粒的制备方法，其特征在于，包括以下步骤：
    S1.将乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链烷基二醇加入到含有油酸、油胺和十八烯的混合溶液中，搅拌，抽真空，加热至50～110℃，保温；所述长链烷基二醇含有10～18个碳原子；
    S2.氮气保护下升温至160～240℃，保温；
    S3.继续升温至260～340℃，保温，后处理，获得所述超小高性能近红外长余辉纳米颗粒。
  2. 根据权利要求1所述制备方法，其特征在于，所述步骤S1中，所述乙酰丙酮镓、乙酰丙酮锌、乙酰丙酮铬和长链烷基二醇的摩尔比为2：(0.6～1.4)：(1×10-4～2×10-3)：(1～40)。
  3. 根据权利要求1所述制备方法，其特征在于，所述步骤S1中，所述油酸、油胺和十八烯的体积比为1：(0.5～1.5)：(1～4)。
  4. 根据权利要求1所述制备方法，其特征在于，所述长链烷基二醇含有12～16个碳原子。
  5. 根据权利要求1所述制备方法，其特征在于，所述步骤S2中，所述保温的时间为0.5～3h。
  6. 根据权利要求1所述制备方法，其特征在于，所述步骤S3中，所述保温的时间为0.5～5h。
  7. 权利要求1～6任一项所述制备方法制备获得的超小高性能近红外长余辉纳米颗粒。
  8. 根据权利要求7所述超小高性能近红外长余辉纳米颗粒，其特征在于，所述超小高性能近红外长余辉纳米颗粒的平均直径为3.5～4.5nm。
  9. 根据权利要求7或8所述超小高性能近红外长余辉纳米颗粒，其特征在于，所述超小高性能近红外长余辉纳米颗粒的化学式为ZnyGa2CrxO4；其中，1×10-4≤x≤2×10-3，0.6≤y≤1.4。
  10. 权利要求7～9任一项所述超小高性能近红外长余辉纳米颗粒在生物活体光学成像、分子标记或在制备医学诊疗试剂中的应用。
PCT/CN2024/087922 2024-04-12 2024-04-16 一种超小高性能近红外长余辉纳米颗粒及其制备方法和应用 Pending WO2025213489A1 (zh)

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CN114437718A (zh) * 2020-11-05 2022-05-06 中国科学院化学研究所 一种醇类辅助制备长余辉纳米晶体的方法
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CN117025212A (zh) * 2023-07-07 2023-11-10 江南大学 一种超小双发射长余辉基比率探针的构建及肿瘤成像应用

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