CN111110844A - Preparation method and application of magnetic heat triggered free radical generated nano material - Google Patents
Preparation method and application of magnetic heat triggered free radical generated nano material Download PDFInfo
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- CN111110844A CN111110844A CN202010051665.0A CN202010051665A CN111110844A CN 111110844 A CN111110844 A CN 111110844A CN 202010051665 A CN202010051665 A CN 202010051665A CN 111110844 A CN111110844 A CN 111110844A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
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- -1 alkyl free radical Chemical class 0.000 description 4
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
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- A—HUMAN NECESSITIES
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- 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
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- A61K49/18—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes
- A61K49/1818—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles
- A61K49/1821—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
The invention discloses a preparation method and application of a magnetic heat triggered free radical generation nano material. Dispersing water-soluble mesoporous ferroferric oxide nano particles, azo initiator and phase change reagent into methanol, and stirring or ultrasonically treatingAnd after treatment, centrifuging and collecting precipitates to obtain the magneto-thermal triggering free radical generation nano material. Compared with the traditional photodynamic therapy which is limited by the penetration depth of oxygen and laser, the nano material prepared by the invention can generate alkyl free radicals under the action of magnetocaloric heat, has the advantages of non-oxygen dependence and no tissue penetration depth limitation, and also has T2The magnetic resonance contrast enhancement performance is weighted, so that the magnetic resonance contrast enhancement method is expected to be applied to the diagnosis and treatment of tumors.
Description
Technical Field
The invention belongs to the technical field of nano materials and nano medicine, and particularly relates to a preparation method and application of a magnetic heat triggered free radical generation nano material.
Background
Photodynamic therapy (PDT) has received much attention in the cancer treatment field because of its non-invasive, high efficiency and high accuracy. The photodynamic therapy method utilizes laser with specific wavelength to irradiate the photosensitizer so as to excite the photosensitizer, and the photosensitizer in an excited state transfers energy to oxygen around tumor tissues to generate free radicals with strong activity such as singlet oxygen and the like, and the singlet oxygen and adjacent biological macromolecules generate oxidation reaction to generate cytotoxicity effect, so that tumor cells are damaged and even die. However, there is still a need for improvement in conventional photodynamic therapy. The generation of active oxygen free radicals usually needs oxygen to be involved, but most advanced tumors have anoxic regions, so that the tumors are resistant to photodynamic and other treatment methods, and the treatment is incomplete and the tumors relapse. Meanwhile, due to the defect of poor laser tissue penetration, the photodynamic therapy is greatly limited in deep tumor treatment. Therefore, it is of great clinical value to develop new therapeutic strategies to overcome the disadvantages of poor photodynamic oxygen dependence and tissue penetration.
Aiming at the limitations of the photodynamic therapy on the great dependence on oxygen and low tissue penetration, the invention provides a magnetic-thermal triggering oxygen-independent alkyl free radical generation strategy for treating tumors. The present invention relates to the use of azo initiators, such as azobisisobutyrimidazoline hydrochloride (2, 2' -azobis [2- (2-imidazolin-2-yl) propane]dihydrazide, AIPH) and azobisisobutyramidine dihydrochloride (2, 2' -azobis (2-amidinopropane) dihydrazide, AAPH) are encapsulated in the mesoporous iron oxide nanoparticles through a phase change material. The azo initiators AIPH and AAPH are heat-sensitive substances, can be decomposed under the condition of hypoxia at a proper temperature to generate alkyl free radicals with strong activity, and can destroyMultiple cell components induce apoptosis, so as to achieve the purposes of effectively killing cancer cells and treating tumors. The mesoporous ferroferric oxide nano particles can be heated under the action of an alternating magnetic field to induce the azo compound AIPH or AAPH to pyrolyze and release alkyl free radicals, so that the controllable magnetic field triggering decomposition of the azo compound is realized. The magnetocalorically triggered alkyl radical generation strategy provided by the invention has the advantages of non-oxygen dependence and no tissue penetration depth limitation. Meanwhile, the ferroferric oxide nano particles have shortened T2The property of relaxation time, therefore, the magnetocalorically triggered free radical generating nanomaterial provided by the invention also has T2Weighting the magnetic resonance contrast enhancement performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a magneto-thermal triggering free radical generation nano material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a magnetic thermal triggering free radical generation nano material comprises the steps of dispersing water-soluble mesoporous ferroferric oxide nano particles, an azo initiator and a phase change reagent into methanol, stirring or ultrasonically treating a mixed solution for 1-10 hours, and centrifugally collecting obtained precipitates to obtain the magnetic thermal triggering free radical generation nano material.
The water-soluble mesoporous ferroferric oxide nano-particles are 0.001-1 part by weight, the azo initiator is 0.01-2 parts by weight, and the phase change reagent is 0.01-5 parts by weight. The aperture of the water-soluble mesoporous ferroferric oxide nano-particles is 6-20 nm. The azo initiator is azobisisobutyramidine hydrochloride (2, 2'-azobis [2- (2-imidazolin-2-yl) propane ] dihydrazide) or azobisisobutyramidine hydrochloride (2, 2' -azobis (2-amidinopropane) dihydrazide). The phase change reagent is lauric acid or tetradecanol.
The magneto-caloric triggered free radical generation nano material prepared by the invention can release free radicals under the condition that the magneto-caloric temperature is 38-50 ℃, so that the magneto-caloric triggered free radical generation nano material can be used for preparing tumor treatment medicines.
The invention has the following remarkable advantages:
(1) the magneto-caloric triggered free radical generation nano material provided by the invention can generate alkyl free radicals under the action of magneto-caloric, overcomes the defect of poor treatment effect caused by the limitation of tumor hypoxia microenvironment in the traditional photodynamic therapy, has the advantage of high tissue penetration depth, and can be used for treating tumors.
(2) The magnetocalorically triggered free radical generating nanomaterial provided by the invention has T2The weighted magnetic resonance contrast enhancement performance can also be used for diagnosing tumors.
(3) The preparation method disclosed by the invention is simple in process, low in cost, free of complex equipment and environment-friendly.
Drawings
FIG. 1 is a diagram showing a distribution of pore diameters of mesoporous ferroferric oxide used in the examples.
Fig. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (B) of the magnetocalorically thermally triggered radical generating nanomaterial prepared in example 1.
FIG. 3 is a UV spectrum of the magnetocalorically triggered radical generating nanomaterial prepared in example 1.
FIG. 4 shows T of prepared magnetocalorically triggered free radical generating nanomaterials with different Fe contents2Weighting the magnetic resonance imaging map.
FIG. 5 is a graph of UV spectra of the prepared magnetocalorically triggered radical generating nanomaterials and ABTS treated under an alternating magnetic field for different periods of time.
FIG. 6 is a confocal fluorescent photograph of the prepared magnetocalorically triggered free radical generating nanomaterial incubated with HepG-2 cells and double-stained with calcein and propidium iodide.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Adding 1.08g of ferric chloride hexahydrate into 80 mL of aqueous solution containing 0.72g of urea and 2.06g of sodium citrate, stirring for 30 min to uniformly disperse blocky ferric chloride, then slowly adding 0.5g of polyacrylamide, and continuously stirring for 30 min-1 h to completely dissolve the polyacrylamide; after stirring, transferring the mixture into a high-pressure reaction kettle, and reacting for 12 hours at 200 ℃; after the reaction is finished, centrifuging and collecting the precipitate to obtain the mesoporous ferroferric oxide nano-particles, wherein the pore size distribution is shown in figure 1.
Example 1
100mg of water-soluble mesoporous ferroferric oxide nano particles are dispersed in 5mL of methanol, 1g of AIPH and 0.5g of lauric acid are added, the mixture is stirred vigorously for 5 hours, and then the precipitate is collected by centrifugation and is dispersed in the water solution again.
Fig. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (B) of the magnetocalorically triggered radical-generating nanomaterial prepared according to this example.
FIG. 3 is a UV spectrum of the magnetocalorically triggered radical generating nanomaterial prepared in this example. The figure shows that AIPH has been successfully loaded on mesoporous ferroferric oxide nano-particles, and the loading rate of AIPH under the synthesis condition is 11.6%.
FIG. 4 is a T for magnetocalorically triggered free radical generating nanomaterials of varying Fe content prepared by the method of example 12Weighting the magnetic resonance imaging map. The figure shows better contrast enhancement performance.
The prepared mixed solution (0.4 mL) of the magnetocalorically thermally triggered free radical generating nanomaterial (1 mg/mL) and ABTS (1 mg/mL) was treated for different times (3 min, 7min, 10 min) under an alternating magnetic field (current 25A, power 3.3kW, coil diameter 10cm, number of turns 3), and the ultraviolet-visible light absorption spectrum was measured, with the results shown in FIG. 5. The figure shows that the absorption peak at 734nm gradually rises along with the increase of action time, and the synthesized nano material can generate free radicals in a magnetic field, so that ABTS is converted into ABTS+∙ free radicals.
The prepared magnetic heat triggered free radical generation nano material (0.5 mg/mL) and HepG2 cells (cell number 10)5~2×105) After incubation for 6 h, the cells were double-stained with calcein (2. mu.M) and propidium iodide (8. mu.M) for 30 min and observed using a fluorescence confocal microscope (excitation light wavelength 488 nm and 530 nm, respectively), and the results are shown in FIG. 6. The left picture is a picture obtained by direct double dyeing without the action of an alternating magnetic field, and the picture showsGreen fluorescence, indicating no cell death; the right picture is a picture of double staining after an alternating magnetic field (current 25A, power 3.3kW, coil diameter 10cm, number of turns 3) is applied for 10min, which shows a large amount of red fluorescence, indicating that free radicals generated by magnetocaloric triggering can cause a large amount of tumor cells to die.
Example 2
1mg of water-soluble mesoporous ferroferric oxide nano particles are dispersed in 0.5mL of methanol, 0.01g of AAPH and 0.01g of lauric acid are added, ultrasonic treatment is carried out for 1 hour at room temperature, then the precipitate is centrifugally collected and re-dispersed in the water solution.
Example 3
1g of water-soluble mesoporous ferroferric oxide nano particles are dispersed in 50mL of methanol, 2g of AIPH and 5g of tetradecanol are added and stirred for 10 hours, and then the mixture is centrifuged, collected and precipitated and is dispersed in the water solution again.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a magnetic thermal triggering free radical generation nano material is characterized by dispersing water-soluble mesoporous ferroferric oxide nano particles, an azo initiator and a phase change reagent into methanol, stirring or ultrasonically treating a mixed solution, and centrifugally collecting obtained precipitates to obtain the magnetic thermal triggering free radical generation nano material.
2. The method for preparing a magnetocalorically triggered radical generating nanomaterial according to claim 1, wherein the amount of the water-soluble mesoporous ferroferric oxide nanoparticles is 0.001 to 1 part by weight, the amount of the azo initiator is 0.01 to 2 parts by weight, and the amount of the phase change agent is 0.01 to 5 parts by weight.
3. The preparation method of the magnetocalorically triggered radical generating nanomaterial according to claim 1 or 2, wherein the pore size of the water-soluble mesoporous ferroferric oxide nanoparticles is 6-20 nm.
4. The method of claim 1 or 2, wherein the azo initiator is azobisisobutyrimidazoline hydrochloride or azobisisobutyramidine hydrochloride.
5. The method according to claim 1 or 2, wherein the phase-change agent is lauric acid or tetradecanol.
6. The method for preparing the magnetocalorically triggered radical generating nanomaterial according to claim 1, wherein the time for the stirring or the ultrasonic treatment is 1 to 10 hours.
7. A magnetocalorically triggered radical generating nanomaterial prepared according to any of the claims 1 to 6, characterized in that the nanomaterial releases radicals at a magnetocaloric temperature of 38 to 50 ℃.
8. Use of the magnetocalorically triggered radical generating nanomaterial according to claim 7 in the preparation of a medicament for the treatment of tumors.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115463250A (en) * | 2022-08-31 | 2022-12-13 | 武汉理工大学 | Gelatin-coated ferroferric oxide magnetic microsphere for promoting osteogenesis and preparation method and application thereof |
| WO2024025962A1 (en) * | 2022-07-27 | 2024-02-01 | William Marsh Rice University | Techniques for magnetic nanocluster-based combination therapy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108030932A (en) * | 2017-11-20 | 2018-05-15 | 苏州大学 | Mesoporous Fe3O4Composite material and preparation method thereof and the application in tumour MRI radiographies and photo-thermal/chemotherapy synergistic treatment |
| CN110279857A (en) * | 2019-07-26 | 2019-09-27 | 南京邮电大学 | Light power and photo-thermal joint nanometer therapeutic agent and its preparation method and application |
| CN110302379A (en) * | 2019-07-12 | 2019-10-08 | 南开大学 | A kind of monochromatic light activated nano particle and its preparation method and application |
-
2020
- 2020-01-17 CN CN202010051665.0A patent/CN111110844A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108030932A (en) * | 2017-11-20 | 2018-05-15 | 苏州大学 | Mesoporous Fe3O4Composite material and preparation method thereof and the application in tumour MRI radiographies and photo-thermal/chemotherapy synergistic treatment |
| CN110302379A (en) * | 2019-07-12 | 2019-10-08 | 南开大学 | A kind of monochromatic light activated nano particle and its preparation method and application |
| CN110279857A (en) * | 2019-07-26 | 2019-09-27 | 南京邮电大学 | Light power and photo-thermal joint nanometer therapeutic agent and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| ESTHER CAZARES-CORTES等: "Magnetic Nanoparticles Create Hot Spots in Polymer Matrix for Controlled Drug Release", 《NANOMATERIALS》 * |
| XIAOMIN LI等: "Single NIR Laser-Activated Multifunctional Nanoparticles for Cascaded Photothermal and Oxygen-Independent Photodynamic Therapy", 《NANO-MICRO LETT.》 * |
| 张慧娟: "物理调控型抗肿瘤药物精准递送系统研究", 《万方数据库》 * |
| 张琦: "用于医疗领域的新型复合相变材料制备及其热特性研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 申基生物: "诊疗一体化磁性Fe3O4-热引发剂复合纳米体系的肿瘤多模态成像及影像引导下的光热及热引发产生ROS的协同治疗应用研究", 《HTTPS://WWW.SOGOU.COM/LINK?URL=DSOYNZECC_P3QTNPGM1FYKMWRTNW7U2W_QPUZDPDIITVGGODX3Z1LG..》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024025962A1 (en) * | 2022-07-27 | 2024-02-01 | William Marsh Rice University | Techniques for magnetic nanocluster-based combination therapy |
| CN115463250A (en) * | 2022-08-31 | 2022-12-13 | 武汉理工大学 | Gelatin-coated ferroferric oxide magnetic microsphere for promoting osteogenesis and preparation method and application thereof |
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