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WO2012126281A1 - Nanomatériau fluorescent à base de graphène, sa préparation et son utilisation - Google Patents

Nanomatériau fluorescent à base de graphène, sa préparation et son utilisation Download PDF

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Publication number
WO2012126281A1
WO2012126281A1 PCT/CN2012/000357 CN2012000357W WO2012126281A1 WO 2012126281 A1 WO2012126281 A1 WO 2012126281A1 CN 2012000357 W CN2012000357 W CN 2012000357W WO 2012126281 A1 WO2012126281 A1 WO 2012126281A1
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WO
WIPO (PCT)
Prior art keywords
graphene
graphene fluorescent
fluorescent
nanomaterial
nanographene
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Ceased
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PCT/CN2012/000357
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English (en)
Chinese (zh)
Inventor
韩梅
范楼珍
张沫
商维虎
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    • 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
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • 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
    • A61K49/0069—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the agent being in a particular physical galenical form
    • A61K49/0089—Particulate, powder, adsorbate, bead, sphere
    • A61K49/0091—Microparticle, microcapsule, microbubble, microsphere, microbead, i.e. having a size or diameter higher or equal to 1 micrometer
    • A61K49/0093—Nanoparticle, nanocapsule, nanobubble, nanosphere, nanobead, i.e. having a size or diameter smaller than 1 micrometer, e.g. polymeric 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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment

Definitions

  • the present invention relates to a fluorescent nanomaterial and its preparation and use, and in particular to a graphene fluorescent nanomaterial, a preparation method thereof, and application in the field of biology and medicine. Background technique
  • Carbon materials are a common and special material on the earth. With the development of nanotechnology, carbon nanomaterials have become the frontier of technological innovation in the past 20 years. Due to the special properties exhibited by the nano-size of the material, it provides a new way for the study of the behavior and interaction mechanism of cells, sub-cells and single-molecule atoms. However, due to its low water solubility and low activity, carbon nanomaterials have limited its application in many research fields such as analytical chemistry, materials science and biotechnology. As one of the carbon materials, graphene is generally described as a flat sheet of a single atom thickness of sp 2 bond carbon atoms densely packed in a honeycomb lattice. 142nm ⁇ The carbon-carbon bond length in the graphene is about 0.
  • Graphene is the basic building block of some carbon allotropes, including graphite, carbon nanotubes, and fullerenes.
  • the low water solubility and poor biocompatibility of common graphene limits its biological and pharmaceutical applications.
  • a graphene fluorescent nanomaterial is prepared by reacting nanographene obtained by electrochemical method with hydrazine hydrate to bond a certain amount of hydrazide groups on the edge carbon atoms of graphene.
  • the material has stable fluorescence, high water solubility, good biocompatibility, and the ability to successfully label cells, especially stem cells.
  • it can be used not only as a biomarker, imaging and tracer in the biological field, but also as a drug carrier in the medical field and for the detection, diagnosis and treatment of diseases. Summary of the invention
  • the invention provides a novel graphene fluorescent nanomaterial.
  • the graphene fluorescent nano material of the invention is connected with a hydrazide group on the edge carbon atom of the nano graphene, so that it can emit a special yellow fluorescence, which reduces the agglomeration of the nanoparticles, enhances the luminescence stability, and improves the Biocompatible and water soluble.
  • the graphene fluorescent nanomaterial of the present invention preferably has a size of less than 20 nm, more preferably 2 to 18 ⁇ .
  • the exemplary general formula of the graphene fluorescent nanomaterial of the present invention is as follows, wherein the hydrazide group is attached to the edge carbon atom of the graphene, the number and position of which are not limited by the following formula.
  • the present invention also provides a method of preparing the graphene fluorescent nanomaterial.
  • the method for preparing the graphene fluorescent nano material of the present invention comprises the steps of: electrolyzing graphite in an electrolyte solution to obtain nano graphene, and then adding hydrazine hydrate, preferably at room temperature or below, stirring to obtain the graphene fluorescent nanometer. material.
  • the preparation process of the graphene fluorescent nanomaterial of the present invention comprises the following steps:
  • reaction product (2) adding hydrazine hydrate, preferably at room temperature or below, stirring to obtain a reaction product;
  • the graphene fluorescent nano material of the invention since it has good biocompatibility and water solubility and excellent fluorescence stability, it can be used not only as a biomarker, imaging and tracer in the biological field, but also It can be used as a pharmaceutical carrier in the field of medicine as well as for the detection, diagnosis and treatment of diseases.
  • FIG. 1 is a transmission electron micrograph of a graphite iridium fluorescent nanomaterial according to an embodiment of the present invention
  • FIG. 3 is a schematic view showing the structure of a graphene fluorescent nanomaterial according to an embodiment of the present invention.
  • FIG. 4 is a fluorescence spectrum diagram of an aqueous solution of a graphene fluorescent nanomaterial according to an embodiment of the present invention.
  • Figure 5 is a graph showing the analysis of cytotoxicity of graphene fluorescent nanomaterials according to an embodiment of the present invention.
  • FIG. 6 is a live cell development of graphene fluorescent nanomaterials in accordance with one embodiment of the present invention. detailed description
  • High-purity graphite rod (China Steel Group Shanghai New Graphite Material Co., Ltd., 6 X 300 mm) as the working electrode, platinum plate as the counter electrode, 7ml 0.1 mol/L NaOH aqueous solution as the electrolyte, control current intensity is 120mA, room temperature The lower constant current was electrolyzed for 3 hours to obtain a black solution. To the solution, 1 ml of an 80% by weight hydrazine hydrate solution was added, and the magnetization magnetic force was added thereto, and the mixture was stirred at room temperature for 6 hours.
  • the product was then centrifuged, and the supernatant was taken out and poured into a dialysis bag (Beijing Huamei Transmission Technology Co., Ltd., MD-25 MW3500).
  • the dialysis bag was immersed in 500 ml of distilled water, and distilled water was replaced 5 times in 36 hours.
  • An aqueous solution of the reaction product of pure graphene and hydrazine hydrate is obtained. 4 (TC dry to obtain a black solid powder, and 100 ml of the aqueous solution obtained by dialysis can obtain about 1 mg of a black solid powder.
  • the transmission electron micrograph of the material shown in FIG. 1 shows that the graphene fluorescence of the present invention
  • the nanomaterial is less than 20 nm.
  • the graphene fluorescent nanomaterial of the present invention has a certain amount of a hydrazide group attached to the edge of the graphene.
  • the fluorescence spectrum of the aqueous solution of the material shown in FIG. 4 shows that: the aqueous solution of the graphene fluorescent nanomaterial of the present invention has a maximum emission wavelength of about 550 nm and a wide range of excitation emission wavelengths when excited by an excitation wavelength of 340-410 nm. Fluorescent luminosity and stable luminescence, different from ordinary carbon nanomaterials.
  • the graphene fluorescent nanomaterial of the present invention was prepared in accordance with the procedure of Example 1, in which the reaction of hydrazine hydrate with graphene was carried out at 0 °C.
  • An aqueous solution obtained by dialysis of 100 ml can obtain about 1 mg of a black solid powder.
  • the characterization results of the obtained product were the same as those of the product prepared in Example 1, and reference may be made to Figs.
  • the graphene fluorescent nanomaterial of the present invention was prepared in accordance with the procedure of Example 1, in which the reaction of hydrazine hydrate with graphene was carried out at 60 °C. 100 ml of the aqueous solution obtained by the dialysis gave about 0.4 mg of a black solid powder.
  • the characterization results of the obtained product were the same as those of the product prepared in Example 1, and can be referred to Fig. 1 - 4.
  • Example 4 Application of Graphene Fluorescent Nanomaterials of the Invention in Biological and Medical Applications
  • the graphene fluorescent nanomaterial of the present invention is at a higher concentration (50 ug/mL) against tumor cells such as breast cancer (MCF-7) and glioma cells (SY5Y).
  • the growth has a certain inhibitory effect, and is particularly suitable as a carrier material for antitumor drugs.
  • Normal cells such as stem cells such as neural stem cells (N), pancreatic stem cells (P), and cardiac stem cells (C) do not exhibit cytotoxicity at concentrations up to 100 ug/mL. This solves the problem of cytotoxic side effects in the current application of commonly used biological imaging agents.
  • the cells to be tested were inoculated to a six-well plate in which slides were placed at a density of 1 - 5 X 10 5 /well, and cultured for 24 hours, to be attached.
  • the graphene fluorescent nanomaterial of the present invention can enter cells (especially stem cells) and develop in the cytoplasm, thus, the graphene fluorescence of the present invention
  • a major feature of nanomaterials is the traceable markers that can be used for stem cells.
  • the graphene fluorescent nano material of the present invention has strong fluorescence and stable luminescence, and the excitation emission wavelength range of the material is wide, it can be used together with other cell imaging agents to jointly explore the difference in cytoplasm and nucleus. performance. Thereby, the shortcomings of the current cell imaging agent single, unstable and cytotoxic are overcome.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Biomedical Technology (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

La présente invention concerne un nanomatériau fluorescent à base de graphène obtenu suite à la production de nanographène par un procédé électrochimique, puis à la réaction du nanographène avec un hydrate d'hydrazine. Ledit nanomatériau fluorescent à base de graphène présente une bonne biocompatibilité et peut être utilisé pour le marquage de cellules, notamment de cellules souches. Ce nanomatériau fluorescent à base de graphène peut non seulement être utilisé en tant que biomarqueur, substance révélatrice et traceur dans le domaine biologique, mais également en tant que vecteur de médicament et en vue de la détection, du diagnostic et du traitement de maladies dans le domaine médical.
PCT/CN2012/000357 2011-03-22 2012-03-22 Nanomatériau fluorescent à base de graphène, sa préparation et son utilisation Ceased WO2012126281A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110068978.8A CN102690648B (zh) 2011-03-22 2011-03-22 石墨烯荧光纳米材料、其制备及应用
CN201110068978.8 2011-03-22

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Cited By (1)

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CN111285356A (zh) * 2018-12-10 2020-06-16 天津工业大学 一种小尺寸石墨烯量子点的制备方法

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CN104181258B (zh) * 2013-05-24 2016-01-20 北京蛋白质组研究中心 基于石墨烯的糖蛋白n-糖链一步法富集-衍生化处理及maldi-tof-ms分析方法
CN105088261B (zh) * 2014-05-14 2017-10-20 国能纳米科技有限公司 石墨烯的制备方法
CN108276988A (zh) * 2018-02-06 2018-07-13 叶剑 一种新型荧光纳米材料的制备方法
CN108467028B (zh) * 2018-04-26 2021-10-12 上海大学 智能石墨烯量子点团簇的制备方法及应用
EP3597594A1 (fr) * 2018-07-17 2020-01-22 Graphenano Medical Care, S.L. Produit à base de graphène et ses utilisations thérapeutiques

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CN101634032A (zh) * 2009-08-14 2010-01-27 南京大学 石墨烯的绿色快速电化学制备方法
US20100028681A1 (en) * 2008-07-25 2010-02-04 The Board Of Trustees Of The Leland Stanford Junior University Pristine and Functionalized Graphene Materials
CN101818059A (zh) * 2010-03-29 2010-09-01 中国科学院合肥物质科学研究院 一种高荧光量子产率氧化石墨烯的制备方法

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US20100028681A1 (en) * 2008-07-25 2010-02-04 The Board Of Trustees Of The Leland Stanford Junior University Pristine and Functionalized Graphene Materials
CN101634032A (zh) * 2009-08-14 2010-01-27 南京大学 石墨烯的绿色快速电化学制备方法
CN101818059A (zh) * 2010-03-29 2010-09-01 中国科学院合肥物质科学研究院 一种高荧光量子产率氧化石墨烯的制备方法

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CN111285356A (zh) * 2018-12-10 2020-06-16 天津工业大学 一种小尺寸石墨烯量子点的制备方法

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CN102690648B (zh) 2016-05-18

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