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Superbright monochromatic upconversion nanoprobe for excitation/emission in biological window as well as preparation method and application of superbright monochromatic upconversion nanoprobe

A nano-probe and window technology, applied in the field of ultra-bright monochromatic up-conversion nano-probe and its preparation, can solve the problems of limited application, damage and destruction of biological tissue, achieve high sensitive signal-to-noise ratio, and overcome penetration depth Limited, high signal-to-noise ratio effects

Active Publication Date: 2021-12-21
NANJING FORESTRY UNIV
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Problems solved by technology

However, UCNPs still face three focal issues that need to be resolved in bioimaging applications: (1) The thermal effect caused by excitation light: due to Yb 3+ Absorption around 975nm (Yb 3+ : 2 f 7 / 2 → 2 f 5 / 2 ), with yb 3+ UCNPs as sensitizers using 980nm near-infrared light as excitation light
980nm laser irradiation will produce overheating effect, which in turn will lead to damage and destruction of biological tissues, and reduce the penetration ability of excitation light
Therefore, looking for near-infrared light with weak absorption by water molecules as excitation light in the biological window is expected to solve the problems of overheating effect and shallow penetration depth caused by excitation light irradiation.
(2) The problem of multi-peak emission of rare earth ions: with Er 3+ 、Ho 3+ or Tm 3+ UCNPs as activators, in addition to being able to emit red light (~660nm, Er 3+ : 4 f 9 / 2 → 4 I 15 / 2 、Ho 3+ : 5 f 5 → 5 I 8 ) and near-infrared light (~800nm, Tm 3+ : 3 h 4 → 3 h 6 ), there are also short-wavelength luminescence located outside the biological window
The UCNPs reported in the current research cannot achieve the low thermal effect of the excitation light, ensure single-band emission, and take into account high luminous intensity, which limits its application in deep tissue bioimaging.

Method used

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  • Superbright monochromatic upconversion nanoprobe for excitation/emission in biological window as well as preparation method and application of superbright monochromatic upconversion nanoprobe
  • Superbright monochromatic upconversion nanoprobe for excitation/emission in biological window as well as preparation method and application of superbright monochromatic upconversion nanoprobe
  • Superbright monochromatic upconversion nanoprobe for excitation/emission in biological window as well as preparation method and application of superbright monochromatic upconversion nanoprobe

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Embodiment 1

[0031]A highly efficient near-infrared region-excited red light-emitting fluorescent probe material with a molecular formula of α-NaYF 4 :30%Yb / 2%Er / 35%Mn@CaF 2 :20%Yb@NaNdF 4 : 10% Yb, the preparation method is as follows:

[0032] (1) α-NaYF 4 : Preparation of 30%Yb / 2%Er / 35%Mn nanocrystals. Weigh 0.264 mmol of yttrium chloride, 0.24 mmol of ytterbium chloride, 0.016 mmol of erbium chloride and 0.28 mmol of manganese chloride into a three-necked flask, then add 8 ml of oleic acid and 12 ml of 1- Octadecene was heated under the action of magnetic stirring while passing nitrogen gas. The mixed solution was heated to 150° C. and kept for 30 minutes to obtain a yellow transparent solution, and then cooled down to room temperature naturally. Then, slowly dropwise add a methanol solution dissolved with 2 mmoles of sodium hydroxide and 3 mmoles of ammonium fluoride, stir evenly, then raise the temperature to 50° C. and keep the temperature for 1 hour. Then the mixed solution w...

Embodiment 2

[0037] A highly efficient near-infrared region-excited yellow light-emitting fluorescent probe material with a molecular formula of α-NaYF 4 :30%Yb / 2%Er / 10%Mn@CaF 2 :20%Yb@NaNdF 4 : 10% Yb, the preparation method is as follows:

[0038] (1) α-NaYF 4 : Preparation of 30%Yb / 2%Er / 10%Mn nanocrystals. Weigh 0.464 mmol of yttrium chloride, 0.24 mmol of ytterbium chloride, 0.016 mmol of erbium chloride, 0.08 mmol of manganese chloride, 8 ml of oleic acid and 12 ml of 1-octadecene into a three-necked flask , heated while blowing nitrogen gas under the action of magnetic stirring. The mixed solution was heated to 150° C. and kept for 30 minutes to obtain a yellow transparent solution, and then cooled down to room temperature naturally. Then, slowly dropwise add a methanol solution dissolved with 2 mmoles of sodium hydroxide and 3 mmoles of ammonium fluoride, stir evenly, then raise the temperature to 50° C. and keep the temperature for 1 hour. Then the mixed solution was heated u...

Embodiment 3

[0042] A highly efficient near-infrared region-excited green light-emitting fluorescent probe material with a molecular formula of NaYF 4 :30%Yb / 2%Er@CaF 2 :20%Yb@NaNdF 4 : 10% Yb, the preparation method is as follows:

[0043] (1)NaYF 4 : Preparation of 30%Yb / 2%Er nanocrystals. Weigh 0.544 mmol of yttrium chloride, 0.24 mmol of ytterbium chloride, 0.016 mmol of erbium chloride, 8 milliliters of oleic acid and 12 milliliters of 1-octadecene and add them to a three-necked flask. Heating was carried out under nitrogen gas. The mixed solution was heated to 150° C. and kept for 30 minutes to obtain a yellow transparent solution, and then cooled down to room temperature naturally. Then, slowly dropwise add a methanol solution dissolved with 2 mmoles of sodium hydroxide and 3 mmoles of ammonium fluoride, stir evenly, then raise the temperature to 50° C. and keep the temperature for 1 hour. Then the mixed solution was heated up to 110° C. for 30 minutes to remove water and meth...

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Abstract

The invention discloses a superbright monochromatic upconversion nanoprobe for excitation / emission in a biological window as well as a preparation method and application of the superbright monochromatic upconversion nanoprobe, and belongs to the technical field of preparation of rare earth luminescent nanomaterials and biological living body imaging. The nanoprobe provided by the invention is a nano-particle which is formed by co-doping Nd<3+>, Yb<3+>, Er<3+> and Mn<2+> and has a multi-layer core-shell structure, and the chemical composition of the nanoprobe is alpha-NaYF4:Yb / Er / Mn coated CaF2:Yb coated NaNdF4:Yb. Through component optimization and structural design, the prepared up-conversion probe material obtains high-quantum-efficiency single-band red light emission under the excitation of 808nm near-infrared light. The up-conversion fluorescent probe material is unique in structure and stable in performance, has the advantages of high tissue penetration depth, high sensitivity, high resolution, high signal-to-noise ratio and the like when being applied to mouse living body imaging analysis, and has a good application prospect in the aspect of biological imaging.

Description

technical field [0001] The invention belongs to the technical field of preparation of rare earth luminescent nanomaterials and biological imaging, and more specifically relates to an ultra-bright monochromatic up-conversion nanoprobe excited / emitted in a biological window, its preparation method and application. Background technique [0002] As a new imaging method, optical imaging technology has the advantages of high sensitivity, high spatial resolution, low cost, simplicity and speed, and has great application value in biomedical research and clinical treatment. Biological tissues have phenomena such as absorption and scattering of light, which limits the application of optical imaging technology in the biological field. Generally speaking, biological tissues have strong absorption and scattering of visible light (400-700nm) and infrared light (>1000nm), but weak absorption and scattering of light in the range of 650-1000nm (biological window), and have high tissue pen...

Claims

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Application Information

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IPC IPC(8): C09K11/85
CPCC09K11/7705
Inventor 丁明烨崔松松刘璇史寅彪陆依杨小飞
Owner NANJING FORESTRY UNIV
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