CN112704736A - CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof - Google Patents
CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112704736A CN112704736A CN202110024243.9A CN202110024243A CN112704736A CN 112704736 A CN112704736 A CN 112704736A CN 202110024243 A CN202110024243 A CN 202110024243A CN 112704736 A CN112704736 A CN 112704736A
- Authority
- CN
- China
- Prior art keywords
- dimensional
- ceo
- mxene
- nano
- composite
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 82
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 74
- 238000002428 photodynamic therapy Methods 0.000 claims abstract description 18
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 14
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 210000004881 tumor cell Anatomy 0.000 abstract description 5
- 230000036284 oxygen consumption Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- 239000000523 sample Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000015624 blood vessel development Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001146 hypoxic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- 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
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Geology (AREA)
- Epidemiology (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
The invention provides CeO2the/MXene composite two-dimensional material comprises two-dimensional CeO doped with each other2Nanometer material and two-dimensional MXene nanometer material, the two-dimensional MXene nanometer material and two-dimensional CeO2The mass ratio of the nano-materials is 0.5 to 2. By means of two-dimensional CeO2The mutual matching of the nano material and the two-dimensional MXene nano material can effectively solve the problems that the oxygen content in the tumor cells is low during the tumor photodynamic therapy, the accurate matching of oxygen and photosensitizer cannot be realized simultaneously in space and time, the oxygen consumption is high, the space transmission is slow and great, and the likeThe technical problem of PDT efficiency is solved. The invention also provides CeO2A preparation method and application of a/MXene composite two-dimensional material are provided.
Description
Technical Field
The invention relates to the technical field of biomedical nano materials, in particular to CeO2The invention also relates to CeO2The invention also relates to a preparation method of the/MXene composite two-dimensional material, and the invention also relates to CeO2Preparation of/MXene composite two-dimensional materialThe application of the photosensitizer for photodynamic therapy of tumor.
Background
Photodynamic therapy (PDT), as a non-invasive medical technique, has the advantages of low toxicity, small side effect, broad-spectrum anticancer, high targeting, and the like, compared with conventional treatment means such as surgery, chemotherapy, radiotherapy, and the like. However, the rapid proliferation of tumor cells, incomplete and unevenly distributed blood vessel development, and thus insufficient supply of oxygen and the like in the tumor cells are likely to occur, resulting in an anaerobic state. Since PDT therapy relies on oxygen to produce singlet oxygen, the tumor local hypoxic microenvironment greatly limits the production of Reactive Oxygen Species (ROS) during PDT, reducing PDT efficiency. The current oxygen generation mode can not realize accurate matching of oxygen and photosensitizer in space and time, and the PDT efficiency is greatly influenced by the problems of fast oxygen consumption and slow space transfer.
Disclosure of Invention
In view of the above, the present invention provides a CeO2The invention also relates to CeO2The invention also relates to a preparation method of the/MXene composite two-dimensional material, and the invention also relates to CeO2The application of the/MXene composite two-dimensional material in preparing the photosensitizer for tumor photodynamic therapy aims to solve the problems of fast oxygen consumption, slow space transfer and the like in the treatment process of the conventional PDT photosensitizer.
In a first aspect, the present invention provides a CeO2the/MXene composite two-dimensional material comprises two-dimensional CeO doped with each other2Nanometer material and two-dimensional MXene nanometer material, the two-dimensional MXene nanometer material and two-dimensional CeO2The mass ratio of the nano-materials is 0.5 to 2.
Preferably, the two-dimensional MXene nano material and the two-dimensional CeO2The mass ratio of the nano material is 4: 3.
Preferably, the two-dimensional MXene nano material is two-dimensional Ti3C2And (3) nano materials.
CeO according to the invention2the/MXene composite two-dimensional material simultaneously contains two-dimensional CeO2Nanomaterials and two-dimensional MXene nanomaterials. As shown in the reaction formula, 2CeO2+H2O2+6H+＝2Ce3++4H2O+O2Two-dimensional CeO2The nano material can promote the generation of oxygen and improve the content of oxygen in a tumor microenvironment. The two-dimensional MXene nano material has excellent light absorption efficiency, and can excite oxygen to generate singlet oxygen under red light (660 nm) and near infrared light (808-,
thereby improving the photodynamic treatment efficiency of the tumor. By means of two-dimensional CeO2The mutual matching of the nano material and the two-dimensional MXene nano material can effectively solve the technical problems that the oxygen content in tumor cells is low, the accurate matching of oxygen and photosensitizer cannot be realized in space and time, the oxygen consumption is high, the space transmission is slow and great, and the like, which influence the PDT efficiency, during the tumor photodynamic therapy.
In a second aspect, the present invention also provides the CeO according to any one of the first aspect2The preparation method of the/MXene composite two-dimensional material comprises the following steps:
providing two-dimensional CeO2Nano material and two-dimensional MXene nano material prepared by mixing two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in water to obtain two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, centrifuging, collecting the precipitate to obtain CeO2the/MXene composite two-dimensional material.
Preferably, the two-dimensional CeO2The preparation process of the nano material is as follows: providing cerium nitrate, dissolving the cerium nitrate in ethylene glycol, stirring and uniformly mixing to obtain an ethylene glycol solution of the cerium nitrate, transferring the ethylene glycol solution of the cerium nitrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 18-30 h at 170-190 ℃;
after cooling, the reaction mixed system is placed at 4000-8000 r/min for centrifugation for 10-30 min, and precipitates are collected to obtain two-dimensional CeO2And (3) nano materials.
Preferably, in the glycol solution of cerium nitrate, the concentration of cerium nitrate is 20-60 mg/ml, and the stirring time is 20-60 min.
Preferably, the reaction temperature in the high-pressure reaction kettle is 180 ℃, and the reaction time is 20 hours;
centrifugally collecting the precipitate, washing the precipitate for 1-3 times by using deionized water and ethanol to obtain two-dimensional CeO2And (3) nano materials.
Preferably, in the two-dimensional CeO2In a nano-material dispersion, two-dimensional CeO2The concentration of the nano material is 1-5 mg/ml, and the concentration of the two-dimensional MXene nano material in the two-dimensional MXene nano material dispersion liquid is 1-5 mg/ml.
Preferably, the mixing is carried out in a stirring manner for 8-48 h, then the mixture is centrifuged at 4000-12000 rpm for 20-40 min, precipitates are collected and washed by deionized water and ethanol for 1-3 times respectively, and CeO is prepared2the/MXene composite two-dimensional material.
CeO according to the second aspect of the present invention2The preparation method of the/MXene composite two-dimensional material has the advantages of simple steps, low cost, suitability for large-scale industrial production and the like, and the prepared CeO2the/MXene composite two-dimensional material has excellent singlet oxygen generating effect, can greatly improve PDT efficiency, and has great application prospect in tumor treatment.
In a third aspect, the present invention also provides CeO as defined in the first aspect of the present invention2The application of the/MXene composite two-dimensional material in preparing a photosensitizer for tumor photodynamic therapy.
CeO according to the invention2the/MXene composite two-dimensional material is applied to preparing a photosensitizer for tumor photodynamic therapy by virtue of two-dimensional CeO2The nano material improves the oxygen content of a tumor microenvironment, and then generates a large amount of singlet oxygen by means of the photodynamic effect of the two-dimensional MXene nano material, thereby playing a role in killing tumor cells.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a picture of a two-dimensional material provided in example 1 of the present invention;
FIG. 2 shows the detection of CeO in example 1 of the present invention2An ultraviolet-visible scanning spectrogram of a probe DPBF selected for the photodynamic performance of the/MXene composite two-dimensional material;
FIG. 3 shows the singlet oxygen detection probe DPBF for CeO in example 1 of the present invention2The ultraviolet-visible spectrum detection diagram of singlet oxygen generated by the MXene composite two-dimensional material under the tumor simulation microenvironment under total illumination for 15 minutes;
FIG. 4 shows CeO in FIG. 32And (3) calculating a fitting graph of the yield of singlet oxygen of the/MXene composite two-dimensional material.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
In a first aspect, the present invention provides a CeO2the/MXene composite two-dimensional material comprises two-dimensional CeO doped with each other2Nanometer material and two-dimensional MXene nanometer material, the two-dimensional MXene nanometer material and two-dimensional CeO2The mass ratio of the nano-materials is 0.5 to 2.
Preferably, the two-dimensional MXene nano material and the two-dimensional CeO2The mass ratio of the nano material is 4: 3.
Preferably, the two-dimensional MXene nano material is two-dimensional Ti3C2And (3) nano materials.
In a second aspect, the present invention also provides the CeO according to any one of the first aspect2The preparation method of the/MXene composite two-dimensional material comprises the following steps:
providing two-dimensional CeO2Nano material and two-dimensional MXene nano material prepared by mixing two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in water to obtainTo two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, centrifuging, collecting the precipitate to obtain CeO2the/MXene composite two-dimensional material.
Preferably, the two-dimensional CeO2The preparation process of the nano material is as follows: providing cerium nitrate, dissolving the cerium nitrate in ethylene glycol, stirring and uniformly mixing to obtain an ethylene glycol solution of the cerium nitrate, transferring the ethylene glycol solution of the cerium nitrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 18-30 h at 170-190 ℃;
after cooling, the reaction mixed system is placed at 4000-8000 r/min for centrifugation for 10-30 min, and precipitates are collected to obtain two-dimensional CeO2And (3) nano materials.
Preferably, in the glycol solution of cerium nitrate, the concentration of cerium nitrate is 20-60 mg/ml, and the stirring time is 20-60 min.
Preferably, the reaction temperature in the high-pressure reaction kettle is 180 ℃, and the reaction time is 20 hours;
centrifugally collecting the precipitate, washing the precipitate for 1-3 times by using deionized water and ethanol to obtain two-dimensional CeO2And (3) nano materials.
Preferably, in the two-dimensional CeO2In a nano-material dispersion, two-dimensional CeO2The concentration of the nano material is 1-5 mg/ml, and the concentration of the two-dimensional MXene nano material in the two-dimensional MXene nano material dispersion liquid is 1-5 mg/ml.
Preferably, the mixing is carried out in a stirring manner for 8-48 h, then the mixture is centrifuged at 4000-12000 rpm for 20-40 min, the precipitate is collected and washed with deionized water and ethanol for 1-3 times to prepare CeO2the/MXene composite two-dimensional material.
In a third aspect, the present invention also provides CeO as defined in the first aspect of the present invention2The application of the/MXene composite two-dimensional material in preparing a photosensitizer for tumor photodynamic therapy.
CeO is illustrated in detail by the following specific examples2Preparation process of/MXene composite two-dimensional material and prepared CeO2/MXene compounding the two-dimensional material.
Example 1
Providing 3mg of two-dimensional CeO2Nano material and 3mg of two-dimensional MXene nano material, wherein the two-dimensional MXene nano material is Ti3C2. Two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in 10ml of water to obtain two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, stirring for 12h, transferring to the condition of 4000rpm, centrifuging for 40min, collecting the precipitate, washing with deionized water and ethanol alternately, and centrifuging for 3 times to obtain CeO2the/MXene composite two-dimensional material. Prepared CeO2the/MXene composite two-dimensional material is shown in FIG. 1 a.
In a specific embodiment, two-dimensional CeO2The nano material is prepared by the following method:
(1) 0.59g of cerous nitrate hexahydrate was provided and dissolved in 15mL of ethylene glycol, stirred at room temperature for 30min and then transferred to a 50mL polytetrafluoroethylene-lined autoclave and reacted at 180 ℃ for 24 h.
(2) Cooling the mixed solution after the reaction in the step (1), centrifuging for 30min at 4000r/min, pouring out supernatant, repeatedly washing for 3 times by using deionized water and ethanol respectively, and drying for 12 hours at 60 ℃ to obtain solid powder, namely two-dimensional CeO2And (3) nano materials. Prepared two-dimensional CeO2The nanomaterial is shown in figure 1 b.
Example 2
Providing 1mg of two-dimensional CeO2Nano material and 1mg two-dimensional MXene nano material, wherein the two-dimensional MXene nano material is Ti3C2. Two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in 10ml of water to obtain two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, stirring for 8h, transferring to 12000rpm, centrifuging for 20min, collecting precipitate, washing with deionized water and ethanol alternately, and centrifuging for 2 times to obtain CeO2the/MXene composite two-dimensional material.
In a specific embodiment, two-dimensional CeO2The nano material is prepared by the following method:
(1) 0.9g of cerous nitrate hexahydrate was provided and dissolved in 15mL of ethylene glycol, stirred at room temperature for 60min and then transferred to a 50mL polytetrafluoroethylene-lined autoclave and reacted at 190 ℃ for 48 h.
(2) Cooling the mixed solution after the reaction in the step (1), centrifuging for 20min at 6000r/min, pouring out supernatant, repeatedly washing for 3 times by using deionized water and ethanol respectively, and drying for 12 hours at 60 ℃ to obtain solid powder, namely the two-dimensional CeO2And (3) nano materials.
Example 3
Providing 5mg of two-dimensional CeO2Nano material and 2.5mg two-dimensional MXene nano material, wherein the two-dimensional MXene nano material is Ti3C2. Two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in 10ml of water to obtain two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, stirring for 10h, transferring to 8000rpm, centrifuging for 30min, collecting precipitate, washing with deionized water and ethanol alternately, and centrifuging for 3 times to obtain CeO2the/MXene composite two-dimensional material.
In a specific embodiment, two-dimensional CeO2The nano material is prepared by the following method:
(1) 0.3g of cerous nitrate hexahydrate was provided and dissolved in 15mL of ethylene glycol, stirred at room temperature for 20min and then transferred to a 50mL polytetrafluoroethylene-lined autoclave and reacted at 170 ℃ for 18 h.
(2) Cooling the mixed solution after the reaction in the step (1), centrifuging for 10min at 8000r/min, pouring out supernatant, repeatedly washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 12 hours to obtain solid powder, namely two-dimensional CeO2And (3) nano materials.
Effect embodiment: CeO prepared in example 12The detection steps of the active oxygen generating capacity of the/MXene composite two-dimensional material are as follows.
The CeO prepared in example 1 was taken2Preparing 10mL of solution with the concentration of 200ppm by using deionized water for the/MXene composite two-dimensional material, and preparing the prepared CeO2Placing the/MXene, the DPBF probe and the hydrogen peroxide solution in a sample cell to ensure that the concentrations of the/MXene, the DPBF probe and the hydrogen peroxide solution in the sample cell are respectively 20ppm, 15ppm and 0.1 mM; deoxidizing through a nitrogen bubbling solution until the content of dissolved oxygen in the solution reaches below a detection limit, irradiating the solution by using 808nm laser, performing spectral scanning on a sample cell every 1 minute, recording a characteristic peak of DPBF in the sample cell at a wavelength of 410nm, and finally making a fitting curve for quantitative calculation of singlet oxygen according to the change of the characteristic absorption peak of the DPBF along with the extension of irradiation time.
As shown in FIG. 2, in order to ensure the accuracy and stringency of the experimental results, the characteristic absorption peak of the singlet oxygen detection probe DPBF should be controlled to be between 0.1 and 1. Therefore, the DPBF with different concentrations is respectively subjected to spectrum scanning (the three curves from top to bottom are 20ppm, 15ppm and 10ppm in sequence), and the optimal use concentration of the DPBF is determined to be controlled to be 15 ppm.
As shown in FIG. 3, DPBF as a singlet oxygen detection probe can be irreversibly oxidized by singlet oxygen, resulting in a decrease of the characteristic peak of DPBF at 410nm, and as the illumination time is prolonged in FIG. 3, the regular decrease of the characteristic peak (the corresponding curves from top to bottom are 0min, 1min, 2min and 3min … … 15min) can be seen from the Bopu scan, which fully proves the generation of singlet oxygen in the reaction system.
As shown in FIG. 4, DPBF is a common probe for quantitative detection of singlet oxygen, and one of the terms in the formula for quantitative calculation is the slope of the curve (i.e., FIG. 4) of the absorbance of DPBF at 410nm as a function of irradiation time, wherein R square is 0.98, and R square is 0.96 after adjustment.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. CeO (CeO)2the/MXene composite two-dimensional material is characterized by comprising two-dimensional CeO doped with each other2Nanometer material and two-dimensional MXene nanometer material, the two-dimensional MXene nanometer material and two-dimensional CeO2The mass ratio of the nano-materials is 0.5 to 2.
2. The CeO of claim 12the/MXene composite two-dimensional material is characterized in that the two-dimensional MXene nano material and two-dimensional CeO2The mass ratio of the nano material is 4: 3.
3. The CeO of claim 12the/MXene composite two-dimensional material is characterized in that the two-dimensional MXene nano material is two-dimensional Ti3C2And (3) nano materials.
4. The CeO according to any one of claims 1 to 32The preparation method of the/MXene composite two-dimensional material is characterized by comprising the following steps:
providing two-dimensional CeO2Nano material and two-dimensional MXene nano material prepared by mixing two-dimensional CeO2The nanometer material and the two-dimensional MXene nanometer material are respectively dispersed in water to obtain two-dimensional CeO2Preparing the two-dimensional CeO from the nano material dispersion liquid and the two-dimensional MXene nano material dispersion liquid2Mixing the nanometer material dispersion liquid and the two-dimensional MXene nanometer material dispersion liquid, centrifuging, collecting the precipitate to obtain CeO2the/MXene composite two-dimensional material.
5. The CeO of claim 42The preparation method of the/MXene composite two-dimensional material is characterized in that the two-dimensional CeO2The preparation process of the nano material is as follows: providing cerium nitrate, dissolving the cerium nitrate in ethylene glycol, stirring and uniformly mixing to obtain an ethylene glycol solution of the cerium nitrate, transferring the ethylene glycol solution of the cerium nitrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 18-30 h at 170-190 ℃;
after cooling, the reaction mixture isCentrifuging the mixed system at 4000-8000 r/min for 10-30 min, collecting precipitate to obtain two-dimensional CeO2And (3) nano materials.
6. The CeO of claim 52The preparation method of the/MXene composite two-dimensional material is characterized in that in the glycol solution of cerium nitrate, the concentration of the cerium nitrate is 20-60 mg/ml, and the stirring time is 20-60 min.
7. The CeO of claim 52The preparation method of the/MXene composite two-dimensional material is characterized in that the reaction temperature in the high-pressure reaction kettle is 180 ℃, and the reaction time is 20 hours;
centrifugally collecting the precipitate, washing the precipitate for 1-3 times by using deionized water and ethanol to obtain two-dimensional CeO2And (3) nano materials.
8. The CeO of claim 42The preparation method of the/MXene composite two-dimensional material is characterized in that the two-dimensional CeO2In a nano-material dispersion, two-dimensional CeO2The concentration of the nano material is 1-5 mg/ml, and the concentration of the two-dimensional MXene nano material in the two-dimensional MXene nano material dispersion liquid is 1-5 mg/ml.
9. The CeO of claim 42The preparation method of the/MXene composite two-dimensional material is characterized in that the mixing is carried out in a stirring mode for 8-48 hours, then the mixture is centrifuged at 4000-12000 rpm for 20-40 min, precipitates are collected and washed by deionized water and ethanol for 1-3 times respectively to prepare CeO2the/MXene composite two-dimensional material.
10. The CeO of any one of claims 1 to 32The application of the/MXene composite two-dimensional material in preparing a photosensitizer for tumor photodynamic therapy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110024243.9A CN112704736A (en) | 2021-01-08 | 2021-01-08 | CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110024243.9A CN112704736A (en) | 2021-01-08 | 2021-01-08 | CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112704736A true CN112704736A (en) | 2021-04-27 |
Family
ID=75548609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110024243.9A Pending CN112704736A (en) | 2021-01-08 | 2021-01-08 | CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112704736A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694197A (en) * | 2021-10-29 | 2021-11-26 | 深圳市第二人民医院(深圳市转化医学研究院) | Photothermal/photodynamic synergistic tumor phototherapy reagent and preparation method and application thereof |
| CN115779940A (en) * | 2022-12-08 | 2023-03-14 | 安徽师范大学 | CeO2-x/MXene composite material with double simulated enzyme properties and preparation method and application thereof |
| CN118425246A (en) * | 2024-04-26 | 2024-08-02 | 吉林工程技术师范学院 | CeO (CeO)2/Ti3C2TxComposite material, preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310455A (en) * | 2014-10-10 | 2015-01-28 | 九江学院 | Preparation method of cerium oxide nanosheet |
| CN105536834A (en) * | 2015-12-09 | 2016-05-04 | 陕西科技大学 | Method for preparing cerium dioxide/two-dimensional layered titanium carbide composite material through precipitation process |
| CN105536833A (en) * | 2015-12-09 | 2016-05-04 | 陕西科技大学 | Method for preparing cerium dioxide/two-dimensional layered titanium carbide composite material through hydrothermal process |
| CN108355632A (en) * | 2018-03-16 | 2018-08-03 | 中国科学院山西煤炭化学研究所 | A kind of oxide nano-slice and preparation method thereof and composite catalyst |
| CN108440696A (en) * | 2018-02-09 | 2018-08-24 | 中南大学 | A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink |
| CN108704637A (en) * | 2018-06-07 | 2018-10-26 | 南京理工大学 | MXene/CeO2The preparation method of composite material |
| CN109439188A (en) * | 2018-11-15 | 2019-03-08 | 北京林业大学 | A kind of super-hydrophobic photo-thermal coating and preparation method thereof |
-
2021
- 2021-01-08 CN CN202110024243.9A patent/CN112704736A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310455A (en) * | 2014-10-10 | 2015-01-28 | 九江学院 | Preparation method of cerium oxide nanosheet |
| CN105536834A (en) * | 2015-12-09 | 2016-05-04 | 陕西科技大学 | Method for preparing cerium dioxide/two-dimensional layered titanium carbide composite material through precipitation process |
| CN105536833A (en) * | 2015-12-09 | 2016-05-04 | 陕西科技大学 | Method for preparing cerium dioxide/two-dimensional layered titanium carbide composite material through hydrothermal process |
| CN108440696A (en) * | 2018-02-09 | 2018-08-24 | 中南大学 | A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink |
| CN108355632A (en) * | 2018-03-16 | 2018-08-03 | 中国科学院山西煤炭化学研究所 | A kind of oxide nano-slice and preparation method thereof and composite catalyst |
| CN108704637A (en) * | 2018-06-07 | 2018-10-26 | 南京理工大学 | MXene/CeO2The preparation method of composite material |
| CN109439188A (en) * | 2018-11-15 | 2019-03-08 | 北京林业大学 | A kind of super-hydrophobic photo-thermal coating and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JIYOU SHEN等: "Built-in electric field induced CeO2/Ti3C2-MXene Schottky-junction for coupled photocatalytic tetracycline degradation and CO2 reduction", 《CERAMICS INTERNATIONAL》 * |
| 吕仁江等: "溶剂热合成片状介孔CeO2及光致发光性能", 《化学研究与应用》 * |
| 周文静: "氧化铈/二维碳化钛复合材料的制备及其性能研究", 《硕士电子期刊》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694197A (en) * | 2021-10-29 | 2021-11-26 | 深圳市第二人民医院(深圳市转化医学研究院) | Photothermal/photodynamic synergistic tumor phototherapy reagent and preparation method and application thereof |
| CN115779940A (en) * | 2022-12-08 | 2023-03-14 | 安徽师范大学 | CeO2-x/MXene composite material with double simulated enzyme properties and preparation method and application thereof |
| CN118425246A (en) * | 2024-04-26 | 2024-08-02 | 吉林工程技术师范学院 | CeO (CeO)2/Ti3C2TxComposite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tian et al. | A Metal‐Free Mesoporous Carbon Dots/Silica Hybrid Type I Photosensitizer with Enzyme‐Activity for Synergistic Treatment of Hypoxic Tumor | |
| CN112704736A (en) | CeO (CeO)2/MXene composite two-dimensional material and preparation method and application thereof | |
| CN104030360B (en) | A kind of MoS2the controlledly synthesis of nanometer sheet and synchronous surface method of modifying | |
| CN113908277B (en) | Preparation method of photoresponse single-atom catalytic function nano-drug material | |
| CN108939072A (en) | A kind of nano-carrier and preparation method thereof for photodynamic therapy | |
| Han et al. | Metal-organic frameworks-derived bimetallic nanozyme platform enhances cytotoxic effect of photodynamic therapy in hypoxic cancer cells | |
| CN105412927A (en) | Prussian blue nano particle with high photo-thermal performance and of manganese-doped hollow structure and preparation method of prussian blue nano particle | |
| Liu et al. | Dual-path modulation of hydrogen peroxide to ameliorate hypoxia for enhancing photodynamic/starvation synergistic therapy | |
| Yao et al. | π–π conjugation promoted nanocatalysis for cancer therapy based on a covalent organic framework | |
| Wu et al. | Enhanced chemodynamic and photoluminescence efficiencies of Fe–O 4 coordinated carbon dots via the core–shell synergistic effect | |
| CN104027806B (en) | Nanometer material of mesoporous silica coated trimanganese tetroxide for modifying CuS nano particles, as well as preparation method and application thereof | |
| Peng et al. | Oxygen vacancy-enhanced photothermal performance and reactive oxygen species generation for synergistic tumour therapy | |
| Wang et al. | Progress on the luminescence mechanism and application of carbon quantum dots based on biomass synthesis | |
| CN113648414B (en) | Metal ion coordinated carbon dot/titanium dioxide heterojunction and preparation method and application thereof | |
| CN116531505A (en) | Ferriporphyrin-based covalent organic framework nano-enzyme and synthesis method and application thereof | |
| CN114477108B (en) | Preparation method of near-infrared light-responsive manganese ion-doped vanadium diselenide nanosheet | |
| CN109395078B (en) | MoO (MoO)2-ICG multifunctional nano-particles and preparation method and application thereof | |
| CN116785446A (en) | CeO (CeO) 2 /Fe 3 O 4 Hybrid porous carbon nanoparticles and preparation thereof | |
| CN114736209B (en) | Zinc-europium-porphyrin phosphorus cluster material and preparation method and application thereof | |
| CN114177289B (en) | Composite nano material for photodynamic and photothermal combined treatment and preparation method and application thereof | |
| CN110694063A (en) | Two-dimensional ultrathin SnSe2-PEG (polyethylene glycol) nanosheet material as well as preparation method and application thereof | |
| CN115448366A (en) | Preparation method and application of near-infrared light response manganese-doped tungsten oxide composite material | |
| CN112156186B (en) | Infrared dye-sensitized carbon nitride ternary heterojunction nano material and preparation method and application thereof | |
| CN117919413B (en) | Preparation method and application of nano platform capable of triggering generation of hydroxyl free radical and alkyl free radical simultaneously | |
| CN112451685B (en) | Composite nano-particle with photoacoustic development and photothermal treatment functions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220919 Address after: 518042 24F, block C, Neo Green Plaza, No. 6009, Shennan Avenue, Tian'an community, Shatou street, Futian District, Shenzhen, Guangdong Applicant after: Shenzhen everything Sensor Technology Co.,Ltd. Address before: 518052-1606, East and west block, Yihai Plaza, 18 Chuangye Road, Nanguang community, Nanshan street, Nanshan District, Shenzhen City, Guangdong Province Applicant before: Shenzhen all things Innovation Group Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210427 |
|
| RJ01 | Rejection of invention patent application after publication |