CN111012908A - Satellite-shaped UCGM nano composite material and preparation method thereof - Google Patents

Satellite-shaped UCGM nano composite material and preparation method thereof Download PDF

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CN111012908A
CN111012908A CN201911231316.0A CN201911231316A CN111012908A CN 111012908 A CN111012908 A CN 111012908A CN 201911231316 A CN201911231316 A CN 201911231316A CN 111012908 A CN111012908 A CN 111012908A
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ucgm
ucnps
satellite
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胡勇
蒋炜
朱剑锋
张泰兴
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Nanjing University Shenzhen Research Institute
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Abstract

A satellite-like UCGM nano-composite material is prepared from UCNPs and g-C3N4Nanoparticles and then CeOxReaction systemTogether and modified with Met. Under the protection of high-temperature argon, under the mixed solvent of oleic acid, oleylamine and octadecene, trifluoroacetate of gadolinium, ytterbium, thulium and neodymium is respectively added to synthesize up-conversion nanoparticles (UCNPs), and then acidolysis and high-temperature high-pressure reaction are carried out to obtain graphene carbonitride (g-C)3N4) Mixing the nanoparticles with UCNPs in ethanol solution, adding cerium nitrate (Ce (NO)3)3·6H2O), stirring at normal temperature, finally adding a sodium hydroxide solution, reacting, performing centrifugal separation, modifying in an aqueous solution by using PEG, and adding metformin to finally obtain a final product UCGM. The invention uses g-C with better biological affinity3N4Nanoparticles as photodynamic therapy materials and stimulating g-C3N4Photodynamic therapy is carried out.

Description

Satellite-shaped UCGM nano composite material and preparation method thereof
Technical Field
The invention relates to a satellite-shaped UCGM nano composite material, a preparation method and application thereof, belonging to the field of biological material research.
Background
According to the world cancer report issued by the world health organization at the beginning of 2014, 2200 ten thousand new cancer cases will be released every year in the next 20 years, and the number of cancer deaths at the same period will rise to 1300 ten thousand cases. And is influenced by population growth and aging, 20 percent of new cancer patients worldwide are in China, and at present, 1 of 5 people in China die of cancer. The traditional cancer treatment means comprises three main means of surgery, radiotherapy and drug therapy. According to different stages of tumor development, corresponding treatment measures can be adopted to achieve the optimal treatment effect. However, each treatment means has major disadvantages, in recent years, with the deepening of research, the application of various nano materials with better biocompatibility to the treatment of tumors is continuously concerned by extensive researchers, compared with the traditional tumor treatment means, various novel treatment means such as photothermal treatment, photodynamic treatment and the like which rely on nano materials are greatly improved, although the treatment effect is greatly improved, the problems of easy recurrence, easy metastasis and the like cannot be solved, the root is that the tumor treatment is not thorough, which is related to the special environment of the tumor, the tumor is in a dead oxygen state for a long time due to the rapid proliferation of the tumor, particularly, the deep tumor is in an extreme severe environment, oxygen is lack, various antioxidants are over-expressed, and no matter the traditional treatment means or the emerging treatment means can not play a good role in the deep part of the tumor, in addition, in the case of such a harsh deep tumor environment, the nano material cannot penetrate into the deep part of the tumor, so that the tumor is difficult to cure.
Rare earth doped upconversion fluorescent nanoparticles (UCNPs, including silica-coated UCNPs) and g-C3N4The nanometer material has attracted much attention as a biological nanometer material with better biological compatibility. The Yang Li and the like (Acs Nano2016,10,2766-2773) use transition metal compounds such as gadolinium and the like to synthesize UCNPs with the particle size of about 50nm, the Nano particles can absorb light with the wavelength of 808nm and convert the light into light with the wavelength of about 500nm, and activate rhodamine B photosensitizer adsorbed on the surface to carry out photodynamic therapy, thereby effectively overcoming the condition of insufficient light penetration of low-wavelength light. Ming-Hsien Chan et al (Inorg. chem.2016,55,10267-10277) synthesized UCNPs capable of being converted into ultraviolet band light, and g-C was modified on the surface3N4Quantum dots for photodynamic therapy. Kai Dong et al (adv. Mater.2013,25, 4452-4458) from Cu2And O, starting from the preparation of the CuS hollow nanospheres with holes on the surface, loading an anticancer drug camptothecin in the holes for combined therapy of chemotherapy and thermotherapy, wherein the method adopts a combined therapy mode, and compared with a single therapy mode, the method effectively improves the treatment effect. The above experiments all have a certain improvement in the therapeutic effect, but have no effective treatment for deep tumor deficiencies.
Disclosure of Invention
The invention aims to provide a satellite-shaped UCGM nano composite material and a preparation method thereof. The satellite-like UCGM nano composite material refers to cerium oxide (CeO)x) Rare earth doped up-conversion fluorescent nanoparticles UCNPs and graphene nitrogen carbide (g-C) are compounded3N4) And modified with Met, this surrounding structure is called a satellite-like UCGM nanocomposite.
The technical scheme adopted by the invention for solving the problems is as follows: a satellite-like UCGM nano-composite material is prepared from UCNPs and g-C3N4Nanoparticles and then CeOxReaction is repeatedTaken together and modified with Met.
The satellite-shaped UCGM nano composite material comprises UCNPs and g-C when UCGM nano particles are synthesized3N4Nano particles, wherein the mass ratio of the nano particles is 2: 1 to 1: 1.
the preparation method of the nano composite material, UCNPs, comprises the steps of firstly, respectively adding trifluoroacetate of gadolinium, ytterbium, thulium or neodymium into mixed solvent of oleic acid, oleylamine and octadecene under the protection of high-temperature argon to synthesize rare earth doped up-conversion nanoparticles (UCNPs), and then carrying out acidolysis and high-temperature and high-pressure reaction to obtain graphene nitrogen carbide (g-C)3N4) Mixing the nanoparticles with UCNPs in ethanol solution, adding cerium nitrate (Ce (NO)3)36H2O), stirring at normal temperature, finally adding 10-100uL of 0.1M sodium hydroxide solution, centrifugally separating after reaction, finally adding 5-10mg metformin (Met) for reaction (the reaction time is more than 10H and is overnight) after modification by 100-500mg PEG-CHO in aqueous solution, centrifugally separating, and freeze-drying to obtain the final product UCGM.
When the satellite-shaped UCGM nano composite material is used for synthesizing UCNPs, the volume ratio of the solvent is 1:1:2 to 1:1:3, and the ratio of oleic acid to oleylamine to octadecene is 1:1: 2.
The satellite-shaped UCGM nano composite material is added with trifluoroacetate of gadolinium, ytterbium, thulium and neodymium according to a molar ratio of 15: 2: 1:2 to 15: 2: 2: 2.
The satellite-shaped UCGM nano composite material is used for synthesizing g-C3N4The heating temperature of the urea used by the nano particles is 500-.
When the satellite-shaped UCGM nano composite material is prepared, g-C is synthesized3N4The nano-particles are under the conditions of high temperature and high pressure of 140 ℃ and 200 ℃ and the reaction time is between 12 and 48 hours.
Under the protection of high-temperature argon, under the mixed solvent of oleic acid, oleylamine and octadecene, respectively adding trifluoroacetate of gadolinium, ytterbium, thulium and neodymium to synthesize up-conversion nanoparticles (UCNPs), and then synthesizing the up-conversion nanoparticlesAcidolysis, high-temperature and high-pressure reaction to obtain graphene nitrogen carbide (g-C)3N4) Mixing the nanoparticles with UCNPs in ethanol solution, adding cerium nitrate (Ce (NO)3)3·6H2O), stirring at normal temperature, finally adding a sodium hydroxide solution, carrying out centrifugal separation after reaction, finally modifying with PEG in an aqueous solution, adding metformin (Met) for reacting overnight, carrying out centrifugal separation, and carrying out freeze drying to obtain a final product UCGM.
Has the advantages that: the invention uses g-C with better biological affinity3N4The nano particles as the photodynamic therapy material are compounded with UCNPs under the alkaline condition and finally modified with Met and CeOxAnd Met can well solve the problem of tumor hypoxia, and near infrared is converted into ultraviolet light to stimulate g-C through the light energy conversion effect of UCNPs3N4The photodynamic therapy is carried out, and the solution of hypoxia effectively increases the photodynamic therapy effect and the g-C3N4The penetration depth in the tumor increases the tumor treatment effect.
The satellite-shaped UCGM nano composite material and the preparation method provided by the invention have the following advantages: 1) the nano composite material disclosed by the invention is economic and environment-friendly in raw materials, small in toxic and side effects and large in biological application prospect.
2) The UCGM nano composite material prepared by the invention uses g-C with better biological affinity3N4The photosensitizer has wide absorption wavelength, can absorb up-conversion fluorescence and has certain absorption to external exciting light.
3) CeO for use in the inventionxThe coating layer has good biocompatibility, and can intelligently respond to a tumor microenvironment, reduce tumor hypoxia and increase g-C3N4Permeability within the tumor.
4) The UCGM nano composite material synthesized by the invention has unique structure, g-C3N4Can be separated from the main structure in the tumor microenvironment, and can penetrate into deeper tumor cells for deep treatment of tumors.
Drawings
FIG. 1 is a flow chart of a method for preparing the satellite-shaped UCGM nanocomposite material of the present invention.
Figure 2 is a TEM image of a satellite-like UCGM nanocomposite.
Figure 3 is a high definition TEM magnification of a satellite-like UCGM nanocomposite.
FIG. 4 is a response H of a satellite-like UCGM nanocomposite2O2A TEM image of (a).
Detailed Description
The preparation method of the satellite-shaped UCGM nano composite material comprises the following steps:
(1) synthesis of UCNPs: taking 1-2mmol of gadolinium trifluoroacetate, 0.1-0.2mmol of ytterbium trifluoroacetate and 0.05-0.1mmol of thulium trifluoroacetate, adding the mixture into a mixed solvent of 3-4mL of oleic acid, 3-4mL of oleylamine and 7-10mL of octadecene, heating for 30-60min at the temperature of 290 ℃ and 330 ℃ under the protection of argon, then adding 1-2mmol of gadolinium trifluoroacetate, 0.1-0.2mmol of ytterbium trifluoroacetate and 0.1-0.2mmol of neodymium trifluoroacetate, heating for 30-60min at the temperature of 290 ℃ and 330 ℃, and then centrifuging ethanol for multiple times of washing to obtain UCNPs.
(2) Heating urea at the temperature rising speed of 5-10 ℃/min to the temperature of 500-plus-one-year-old-year-3N4Nanoparticles.
(3) Taking 5-10mg of UCNPs and 5-10mg of g-C3N4Dispersing in ethanol solution, adding Ce (NO)3)3·6H2And O is stirred for 10-30min, then 0.1M sodium hydroxide is added for reaction for 2-4 hours, and the UCGM nano composite material is obtained by centrifugation, washing and drying.
The invention is described in further detail below with reference to the figures and examples.
Example (b):
the preparation method of the satellite-shaped UCGM nano composite material (the specific process is shown in figure 1):
(1) synthesis of UCNPs: adding 1mmol of gadolinium trifluoroacetate, 0.1mmol of ytterbium trifluoroacetate and 0.05mmol of thulium trifluoroacetate into a mixed solvent of 3.5mL of oleic acid, 3.5mL of oleylamine and 7.5mL of octadecene, heating at 330 ℃ for 30min under the protection of argon, then adding 1mmol of gadolinium trifluoroacetate, 0.1mmol of ytterbium trifluoroacetate and 0.1mmol of neodymium trifluoroacetate, heating at 310 ℃ for 60min, and then centrifuging ethanol for multiple times of washing to obtain UCNPs.
(2) Heating urea at a heating rate of 5 ℃/min to 550 ℃, preserving heat for 4 hours, fixedly dispersing the obtained yellow into 1000mL of deionized water, respectively adding 10mL of concentrated sulfuric acid and concentrated nitric acid, stirring for 24 hours at normal temperature, dispersing the obtained white solid into water, transferring the white solid into a reaction kettle, heating at 180 ℃ for 24 hours to obtain g-C3N4Nanoparticles.
(3) Taking 10mg of UCNPs and 5mg of g-C3N4Dispersing in ethanol solution, adding Ce (NO)3)3·6H2And O is stirred for 30min, and then 0.1M sodium hydroxide is added for reaction for 2 hours, and the UCGM nano composite material is obtained by centrifugation, washing and drying.
Response H of the satellite-like UCGM nanocomposite prepared in the above example2O2The transmission electron microscope image is shown in FIG. 4, and the nano material can well follow H2O2Function, structural destruction, external g-C3N4The main material is separated, which shows that the material obtained by the invention can well influence the tumor microenvironment.

Claims (7)

1. A satellite-shaped UCGM nano composite material is characterized in that UCNPs and g-C are mixed3N4Nanoparticles and then CeOxThe reactions are complexed together and modified with Met.
2. The satellite-like UCGM nanocomposite of claim 1, wherein said satellite-like UCGM nanocomposite is selected from UCNPs and g-C when used to synthesize UCGM nanoparticles3N4Nano particles, wherein the mass ratio of the nano particles is 2: 1 to 1: 1.
3. the method of claim 1 or 2, wherein the UCNPs are prepared by exposing UCNPs to oleic acid and oleylamine under the protection of high temperature argon gasRespectively adding trifluoroacetate of gadolinium, ytterbium, thulium and neodymium into a mixed solvent of octadecene to synthesize rare earth doped up-conversion nanoparticles (UCNPs), and then carrying out acidolysis on graphene carbonitrides (g-C) obtained by using a reaction kettle for reaction3N4) Mixing the nanoparticles with UCNPs in ethanol solution, adding cerium nitrate (Ce (NO)3)36H2O), stirring at normal temperature, adding 10-100uL of 0.1M sodium hydroxide solution, performing centrifugal separation after reaction, finally modifying with 100 mg PEG-CHO in aqueous solution, adding 5-10mg metformin (Met) for reaction (the reaction time is more than 10H, overnight), performing centrifugal separation, and performing freeze drying to obtain the final product UCGM.
4. The preparation method of claim 3, wherein the solvent used in the synthesis of UCNPs is selected from the group consisting of oleic acid, oleylamine, and octadecene at a volume ratio of 1:1:2 to 1:1: 3.
5. The method as claimed in claim 3, wherein said satellite-like UCGM nanocomposite is prepared by adding trifluoroacetate of gadolinium, ytterbium, thulium and neodymium in a molar ratio of 15: 2: 1:2 to 15: 2: 2: 2.
6. The method as set forth in claim 3, wherein the satellite-like UCGM nanocomposite is used in the synthesis of g-C3N4The heating temperature of the urea used by the nano particles is 500-.
7. The method as set forth in claim 3, wherein the satellite-like UCGM is prepared by synthesizing g-C3N4The heating condition of the nano particles is 140 ℃ to 200 ℃, and the reaction time is 12 to 48 hours.
CN201911231316.0A 2019-12-05 2019-12-05 Satellite-shaped UCGM nano composite material and preparation method thereof Withdrawn CN111012908A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113736464A (en) * 2021-08-23 2021-12-03 湖北大学 Rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material, battery and preparation method
WO2022089672A1 (en) * 2020-10-27 2022-05-05 上海交通大学医学院附属第九人民医院 Tumor cell detection kit using nitrogen-doped carbon fluorescent quantum dots and method of use therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEI JIANG 等: ""H2O2-Sensitive Upconversion Nanocluster Bomb for Tri-Mode Imaging-Guided Photodynamic Therapy in Deep Tumor Tissue"", 《ADV. HEALTHCARE MATER》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022089672A1 (en) * 2020-10-27 2022-05-05 上海交通大学医学院附属第九人民医院 Tumor cell detection kit using nitrogen-doped carbon fluorescent quantum dots and method of use therefor
CN113736464A (en) * 2021-08-23 2021-12-03 湖北大学 Rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material, battery and preparation method

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