CN113577294A - Preparation method of neodymium iron boron magnetic material/graphene composite drug-loaded carrier material - Google Patents
Preparation method of neodymium iron boron magnetic material/graphene composite drug-loaded carrier material Download PDFInfo
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 116
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- 239000003814 drug Substances 0.000 title claims abstract description 69
- 229940079593 drug Drugs 0.000 title claims abstract description 67
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000696 magnetic material Substances 0.000 title claims abstract description 42
- 239000012876 carrier material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
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- 239000002245 particle Substances 0.000 claims description 24
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- 238000002156 mixing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 claims description 6
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 claims description 6
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
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- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
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- 239000003937 drug carrier Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 201000011510 cancer Diseases 0.000 abstract description 5
- 229940044683 chemotherapy drug Drugs 0.000 abstract description 5
- 230000005389 magnetism Effects 0.000 abstract description 3
- 239000002246 antineoplastic agent Substances 0.000 abstract description 2
- 231100000135 cytotoxicity Toxicity 0.000 abstract description 2
- 230000003013 cytotoxicity Effects 0.000 abstract description 2
- 238000001727 in vivo Methods 0.000 abstract description 2
- 231100001231 less toxic Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 229930012538 Paclitaxel Natural products 0.000 description 18
- 229960001592 paclitaxel Drugs 0.000 description 18
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 6
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- 239000004917 carbon fiber Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- -1 graphene modified carbon fiber Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229940043263 traditional drug Drugs 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/337—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having four-membered rings, e.g. taxol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Chemical & Material Sciences (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a neodymium iron boron magnetic material/graphene composite drug-loaded carrier material, which couples the neodymium iron boron (NdFeB) magnetic material/graphene composite drug-loaded carrier material and loads medical chemotherapy drugs on the neodymium iron boron (NdFeB) magnetic material/graphene composite drug-loaded carrier material to form a novel means for treating malignant tumors. The method enhances the stability of the composite material, ensures that the loaded drug has more definite directional effect in the body, can realize the local concentration and release of the chemotherapeutic drug, and completes the targeted treatment on malignant tumors. The material has the advantages of stronger magnetism, higher magnetic saturation, low cytotoxicity and good stability, so that the material has more definite orientation in vivo, less toxic and side effects and the like. The material is expected to be widely applied to the novel field of medical drug carriers (such as chemotherapy drug carriers and immune drug carriers) and play a great role.
Description
Technical Field
The invention belongs to the field of material compounding and the field of drug-loaded carriers. In particular to a preparation method of two materials of neodymium iron boron material and graphene material, and the two materials are combined together to prepare a novel material which can be used as a drug-loaded carrier.
Background
The invention belongs to the field of novel magnetic drug carriers. Compared with the traditional drug-loaded material, the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material has the advantages of stronger magnetism, higher magnetic saturation, low cytotoxicity and good stability, so that the in-vivo orientation is more definite, the toxic and side effects are less, and the like. The graphene of the material is uniformly distributed on the surface of the carbon fiber, so that the surface area of the carbon fiber is increased, and the content of oxygen-containing active functional groups on the surface of the carbon fiber is increased. The composite material has high magnetic flux and good mechanical property, the graphene modified carbon fiber improves the mechanical property of the composite material, and the interface combination effect is better. The material is expected to be widely applied to the novel field of medical drug carriers (such as chemotherapy drug carriers and immune drug carriers) and play a great role.
The striding development of information technology requires that magnetic materials have the characteristics of high magnetic saturation strength, high magnetic permeability, light weight, easiness in processing and the like, and the conventional magnetic materials cannot meet the conditions. Most of the traditional magnetic materials such as ferrite, nickel-cobalt alloy and the like have the defects of brittleness, hardness, difficult processing and difficult molding of products with complex shapes and fine sizes.
Currently, NdFeB composite materials are mainly used in the fields of transportation, information industry, automation control, and the like. But has no related application in the field of drug carriers.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention researches and utilizes the NdFeB with high magnetism to prepare the composite material with good corrosion resistance, high magnetic saturation and good mechanical property, and the NdFeB particles are mixed into the carbon fiber reinforced epoxy composite material to obtain the composite material which has low density in comparison and is easier to process into a product with complex shape and high dimensional precision. Preparing a novel neodymium iron boron (NdFeB) magnetic material/graphene composite drug-loaded carrier material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a neodymium iron boron magnetic material/graphene composite drug-loaded carrier material comprises the following steps:
(1) preparing a neodymium iron boron magnetic material and carrying out surface treatment on neodymium iron boron particles: mixing the neodymium iron boron micro-fine powder with an organic additive to obtain a neodymium iron boron micro-fine powder mixture; sintering the obtained neodymium iron boron micro-fine powder mixture at 500-600 ℃ for 3-4 h to obtain a neodymium iron boron magnet; and pretreating the surface of the neodymium iron boron particles, and hermetically storing for later use.
(2) Preparing graphene and pretreating graphene
(3) Weighing the treated NdFeB powder with the required mass according to the proportion, mixing the treated NdFeB powder with graphene according to the mass ratio of 2.04:3.5, and stirring by using a magnetic stirrer to uniformly disperse the NdFeB powder; heating and preserving heat for 15-25 min at 75-85 ℃, heating to 95-105 ℃, and preserving heat for 1-3 h to obtain the drug-carrying carrier.
Further, in the step (1), the organic addition solvent is polybutene with a molecular weight of 400-1000; the organic addition solvent alkene accounts for 0.05-10% of the mass percent of the neodymium iron boron micro-fine powder mixture.
Further, in the step (1), the organic additive is a C5-C13 paraffin hydrocarbon solvent, wherein the organic additive solvent alkene accounts for 0.1-25% of the mass percent of the neodymium iron boron fine powder mixture.
Further, in the step (1), the organic additive is one or more than two of methyl caprylate, methyl nonanoate and methyl decanoate, wherein the organic additive solvent alkene accounts for 0.1-50% of the mass percent of the neodymium iron boron fine powder mixture.
Further, in the step (2), a modified Hummers method is usedPreparing graphite oxide: weighing the materials in a mass ratio of 12.3: 96.8 of graphite and potassium permanganate are uniformly mixed, added into a three-neck flask containing 98% mixed acid liquor of concentrated sulfuric acid and phosphoric acid (the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 4.7:1.2), continuously stirred and reacted for 10-14H, an obtained grey-green solution is subjected to ice-water bath for 1-3H, hydroxide is added to form a precipitate, the mass percentage of the hydroxide to the graphite is 10%, and then H with the volume ratio of 13% is slowly added2O2At this time, the solution rapidly changed from grayish green to bright yellow, and the solution was stirred continuously and dispersed uniformly by ultrasonic waves.
Further, in the step (2), a micromechanical peeling method is used for preparing graphene: and repeatedly separating graphene sheets from the highly oriented pyrolytic graphite through transparent photoresist, dissolving graphene remained on the photoresist in acetone, and adsorbing the graphene on the silicon sheets to separate the graphene by utilizing van der Waals force and capillary force between silicon wafers and the graphene sheets.
Further, in the step (2), the graphene is prepared by using a SiC pyrolytic epitaxial growth method: oxidizing the surface of graphite or H2 etching, heating to 1000 ℃ under electron bombardment to remove oxides, detecting the removal condition of the surface oxides by using Auger electron spectroscopy, and heating a sample to 1250-1450 ℃ after the oxides are completely removed to form a graphene layer.
The method has the beneficial effects that the neodymium iron boron (NdFeB) magnetic material/graphene composite drug-loaded carrier material is coupled, and medical chemical drugs are loaded on the neodymium iron boron (NdFeB) magnetic material/graphene composite drug-loaded carrier material, so that the method becomes a novel means for treating malignant tumors. The method enhances the stability of the composite material, ensures that the targeted effect of the loaded drug in the body is more definite, can realize the local concentration potential of the chemotherapeutic drug, and completes the targeted treatment on malignant tumors, thereby reducing the toxic and side effects of the drug to a greater extent, effectively reducing the systemic adverse reaction caused by chemotherapy by the material, and further widely benefiting a great number of malignant tumor patients.
Detailed Description
The present invention will be described in detail with reference to examples
Example 1
(1) Preparing an NdFeB magnetic material: mixing neodymium iron boron fine powder and organic additive ester substances (one or more of methyl caprylate, methyl nonanoate and methyl decanoate) in a mass percentage of 0.1-50 to obtain a neodymium iron boron fine powder mixture; sintering the obtained neodymium-iron-boron fine powder mixture and neodymium-iron-boron powder to obtain a neodymium-iron-boron magnet: surface treatment of NdFeB particles: carrying out surface treatment on NdFeB particles by KH550, preparing absolute ethyl alcohol and deionized water into an ethanol solution according to the volume ratio of 5:1, then adding KH550 with the mass being 2% of that of the NdFeB, and fully stirring for 10min by using a glass rod to uniformly disperse the KH550 in the ethanol solution; then, the NdFeB particles are slowly added into the solution while stirring, then the particles are rapidly stirred by a glass rod to be fully contacted with the diluent, the mixture is kept stand for 10min, then the mixture is placed in a blast drying oven and dried for 50h at the temperature of 45 ℃, and the mixture is taken out, ground, porphyrized and sealed for storage. (KH550 is an adhesion promoter-silane coupling agent, two types of functional groups in KH550 molecules have different properties, can change the polarity of the particle surface, and is often used for improving the interfacial bonding strength between two phases with different polarities, and KH550 molecules are long-chain molecules, can be wound with epoxy resin macromolecules to form a mutually-penetrated three-dimensional spatial network structure, can improve the wettability of inorganic particles in a resin matrix, and can remarkably improve the bonding of interfaces.)
(2) Preparing graphene by a SiC pyrolysis epitaxial growth method and pretreating the graphene. The surface of the graphite is etched by oxidation or H2, then under high vacuum (1.32X 10)-8Pa) electron bombardment is carried out, the temperature is heated to 1000 ℃ to remove oxides, Auger electron spectroscopy is used for detecting the removal condition of the oxides on the surface, and after the oxides are completely removed, the sample is heated to 1250-1450 ℃, so that a graphene layer can be formed; pretreatment of graphene: weighing a proper amount of graphene, adding the graphene into a three-necked bottle, then weighing 60ml of concentrated nitric acid by using a measuring cylinder, adding the concentrated nitric acid into the three-necked bottle, sealing, ultrasonically dispersing for 20min, placing the three-necked bottle into a water bath kettle at 80 ℃, heating, and connecting a condensation reflux device. Acid oxidation treatment was carried out for 4h under these conditions. Diluting the acid solution with deionized water after the reaction is finished, and repeatedly using deionized waterWashing and filtering, drying the recovered graphene at 95 ℃ for 36h, and putting the graphene into a dryer for later use.
(3) And weighing the treated NdFeB powder and graphene according to the required mass ratio, mixing the treated NdFeB powder and the graphene according to the mass ratio of 2.04:3.5, and stirring for 2 hours by using a magnetic stirrer to uniformly disperse the NdFeB powder. Fully stirring to uniformly mix the NdFeB powder and the graphene powder, heating and preserving heat for 20min at 80 ℃, heating to 100 ℃, and preserving heat for 2h to obtain the drug-loaded carrier.
(4) 2.5mg of NdFeB magnetic material/graphene composite drug carrier is immersed in 10ml of paclitaxel phosphate buffer solution (PBS, pH 7.4) of 75mg/ml and continuously shaken for 24 hours under the condition of keeping out of the light at room temperature, and then the mixture is kept stand for 15min and centrifuged. Obtaining the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel).
(5) The drug loading capacity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the carried drug is paclitaxel) is 94.3% through precise measurement, and after the drug is loaded, the saturation drug magnetization intensity of the NdFeB (NdFeB) magnetic material/graphene composite drug-loaded carrier (the carried drug is paclitaxel) is 93.4emu/g through measurement of a vibration sample magnetometer.
Example 2
(1) Preparing an NdFeB magnetic material: mixing neodymium iron boron fine powder with 0.05-10% of polybutene (molecular weight 400-1000) in percentage by mass of an organic additive to obtain a neodymium iron boron fine powder mixture; sintering the obtained neodymium-iron-boron fine powder mixture and neodymium-iron-boron powder to obtain a neodymium-iron-boron magnet; surface treatment of NdFeB particles: carrying out surface treatment on NdFeB particles by KH550, preparing absolute ethyl alcohol and deionized water into an ethanol solution according to the volume ratio of 5:1, then adding KH550 with the mass being 2% of that of the NdFeB, and fully stirring for 10min by using a glass rod to uniformly disperse the KH550 in the ethanol solution; then, the NdFeB particles are slowly added into the solution while stirring, then the particles are rapidly stirred by a glass rod to be fully contacted with the diluent, the mixture is kept stand for 5min, then the mixture is placed in a blast drying box and dried for 50h at the temperature of 55 ℃, and the mixture is taken out, ground, porphyrized and sealed for storage. (KH550 is an adhesion promoter-silane coupling agent, two types of functional groups in KH550 molecules have different properties, can change the polarity of the particle surface, and is often used for improving the interfacial bonding strength between two phases with different polarities, and KH550 molecules are long-chain molecules, can be wound with epoxy resin macromolecules to form a mutually-penetrated three-dimensional spatial network structure, can improve the wettability of inorganic particles in a resin matrix, and can remarkably improve the bonding of interfaces.)
(2) Graphite oxide was prepared and graphene was pretreated using a modified Hummers method: weighing a certain amount of graphite and potassium permanganate, uniformly mixing, adding the graphite and potassium permanganate into a three-neck flask filled with 98% mixed acid solution of concentrated sulfuric acid and phosphoric acid, continuously stirring for reaction for 12 hours to obtain a gray green solution, carrying out ice-water bath for 2 hours, adding hydroxide precipitate (the mass percentage of the graphite is 10%), and slowly adding 10mL of H2O2At the moment, the solution quickly changes from gray green to bright yellow, and ultrasonic dispersion is carried out for 1h after the solution is continuously stirred for 30 min; pretreatment of graphene: weighing a proper amount of graphene, adding the graphene into a three-necked bottle, then weighing 60ml of concentrated nitric acid by using a measuring cylinder, adding the concentrated nitric acid into the three-necked bottle, sealing, ultrasonically dispersing for 15min, placing the three-necked bottle into a water bath kettle at 95 ℃, heating, and connecting a condensation reflux device. Acid oxidation treatment was carried out for 5h under these conditions. And after the reaction is finished, diluting the acid liquor with deionized water, repeatedly washing and filtering with deionized water, drying the recovered graphene for 24 hours at 100 ℃, and putting the graphene into a dryer for later use.
(3) And weighing the treated NdFeB powder and graphene according to the required mass ratio, mixing the treated NdFeB powder and the graphene according to the mass ratio of 2.04:3.5, and stirring for 2 hours by using a magnetic stirrer to uniformly disperse the NdFeB powder. Fully stirring to uniformly mix the NdFeB powder and the graphene powder, heating and preserving heat for 20min at 80 ℃, heating to 100 ℃, and preserving heat for 2h to obtain the drug-loaded carrier.
(4) 2.5mg of NdFeB magnetic material/graphene composite drug-loaded carrier is immersed into 10ml of paclitaxel phosphate buffer solution (PBS, pH 7.4) under the condition of room temperature and light shielding for 24 hours with continuous shaking, and the mixture is kept stand for 15min and centrifuged. Obtaining the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel).
(5) The drug loading capacity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 90.1% through precise measurement, and after the drug is loaded, the saturation drug magnetization intensity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 97.5emu/g through measurement of a vibration sample magnetometer.
Example 3
Preparing an NdFeB magnetic material: (1) mixing neodymium iron boron fine powder with an organic additive hydrocarbon solvent (the hydrocarbon solvent is a paraffin solvent of C5-C13) by weight percentage of 0.1-25 to obtain a neodymium iron boron fine powder mixture; sintering the obtained neodymium-iron-boron fine powder mixture and neodymium-iron-boron powder to obtain a neodymium-iron-boron magnet; surface treatment of NdFeB particles: carrying out surface treatment on NdFeB particles by KH550, preparing absolute ethyl alcohol and deionized water into an ethanol solution according to the volume ratio of 5:1, then adding KH550 with the mass being 2% of that of the NdFeB, and fully stirring for 10min by using a glass rod to uniformly disperse the KH550 in the ethanol solution; then, the NdFeB particles are slowly added into the solution while stirring, then the particles are rapidly stirred by a glass rod to be fully contacted with the diluent, the mixture is kept stand for 10min, then the mixture is placed in a blast drying box and dried for 60h at the temperature of 50 ℃, and the mixture is taken out, ground, porphyrized and sealed for storage. (KH550 is an adhesion promoter-silane coupling agent, two types of functional groups in KH550 molecules have different properties, can change the polarity of the particle surface, and is often used for improving the interfacial bonding strength between two phases with different polarities, and KH550 molecules are long-chain molecules, can be wound with epoxy resin macromolecules to form a mutually-penetrated three-dimensional spatial network structure, can improve the wettability of inorganic particles in a resin matrix, and can remarkably improve the bonding of interfaces.)
(2) Preparing graphene by a micro-mechanical stripping method and pretreating the graphene: the method comprises the steps of repeatedly separating graphene sheets from large Highly Oriented Pyrolytic Graphite (HOPG) through transparent photoresist, dissolving graphene remained on the photoresist in acetone, and adsorbing the graphene on a silicon wafer to separate the graphene by utilizing van der Waals force and capillary force between the silicon wafer and the graphene sheets. Pretreatment of graphene: weighing a proper amount of graphene, adding the graphene into a three-necked bottle, then weighing 55ml of concentrated nitric acid by using a measuring cylinder, adding the concentrated nitric acid into the three-necked bottle, sealing, ultrasonically dispersing for 20min, placing the three-necked bottle into a water bath kettle at 90 ℃, heating, and connecting a condensation reflux device. Acid oxidation treatment was carried out for 6h under these conditions. And after the reaction is finished, diluting the acid liquor with deionized water, repeatedly washing and filtering with deionized water, drying the recovered graphene for 24 hours at 100 ℃, and putting the graphene into a dryer for later use.
(3) And weighing the treated NdFeB powder and graphene according to the required mass ratio, mixing the treated NdFeB powder and the graphene according to the mass ratio of 2.04:3.5, and stirring for 2 hours by using a magnetic stirrer to uniformly disperse the NdFeB powder. Fully stirring to uniformly mix the NdFeB powder and the graphene powder, heating and preserving heat for 20min at 80 ℃, heating to 100 ℃, and preserving heat for 2h to obtain the drug-loaded carrier.
(4) 2.5mg of NdFeB magnetic material/graphene composite drug carrier is immersed in 10ml of paclitaxel phosphate buffer solution (PBS, pH 7.4) of 75mg/ml and continuously shaken for 24 hours under the condition of keeping out of the light at room temperature, and then the mixture is kept stand for 15min and centrifuged. Obtaining the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel).
(5) The drug loading capacity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 95.2% through precise measurement, and after the drug is loaded, the saturation drug magnetization intensity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 87.1emu/g through measurement of a vibration sample magnetometer.
Comparative example 1
And preparation of Fe3O4Comparison with C nanocomposites
(1)Fe3O4The C nano composite material is prepared by an in-situ chemical synthesis method. First, 400mg of terephthalic acid and 300mg of FeCl were mixed3·6H2The O solution was slowly added to 40ml of DMF solution and urea was added dropwise to reach pH 11, and sonication was continued for 2 hours. The resulting solution was then transferred to a teflon-lined autoclave and heated at 160 ℃ for 2 hours. Placing the mixture into a centrifuge, respectively centrifuging the mixture for five times by using ethanol and deionized water, then placing the mixture into a drying box to dry the mixture for 10 hours at 80 ℃, and finally annealing the mixture for 2 hours at 450 ℃ in a tubular furnace under the atmosphere of argon.
(2) Composite materials andepirubicin loading, 2.5mg of the composite drug-loaded carrier was immersed in 10ml of 75mg/ml paclitaxel phosphate buffer solution (PBS, PH 7.4) under dark conditions at room temperature for 24 hours with continuous shaking, allowed to stand for 15min, and the mixture was centrifuged. To obtain Fe3O4And C nano composite material to compound carrier (the carried medicine is paclitaxel).
(3) The drug loading capacity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 85.8% through precise measurement, and after the drug is loaded, the saturation drug magnetization intensity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) is 69.1emu/g through measurement of a vibration sample magnetometer. The comparison shows that the drug loading capacity and magnetization intensity of the NdFeB magnetic material/graphene composite drug-loaded carrier (the loaded drug is paclitaxel) are obviously superior to those of Fe3O4And C nano composite material to compound carrier (the carried medicine is paclitaxel).
Claims (9)
1. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material is characterized by comprising the following steps:
(1) preparing a neodymium iron boron magnetic material and carrying out surface treatment on neodymium iron boron particles: mixing the neodymium iron boron micro-fine powder with an organic additive to obtain a neodymium iron boron micro-fine powder mixture; sintering the obtained neodymium iron boron micro-fine powder mixture for 3-4 h at 500-600 ℃ to obtain a neodymium iron boron magnet; pretreating the surface of the neodymium iron boron particles, and hermetically storing for later use;
(2) preparing graphene and pretreating the graphene;
(3) weighing the treated NdFeB powder with the required mass according to the proportion, mixing the treated NdFeB powder with graphene according to the mass ratio of 2.04:3.5, and stirring by using a magnetic stirrer to uniformly disperse the NdFeB powder; heating and preserving heat for 15-25 min at 75-85 ℃, heating to 95-105 ℃, and preserving heat for 1-3 h to obtain the drug-carrying carrier.
2. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (1), the organic addition solvent is polybutene with a molecular weight of 400-1000; the organic addition solvent alkene accounts for 0.05-10% of the mass percent of the neodymium iron boron micro-fine powder mixture.
3. The method for preparing neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (1), the organic additive is paraffin solvent of C5-C13, wherein the organic additive solvent alkene accounts for 0.1-25% of the neodymium iron boron fine powder mixture by mass percent.
4. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (1), the organic additive is one or more of methyl caprylate, methyl nonanoate and methyl decanoate, wherein the organic additive solvent alkene accounts for 0.1-50% of the neodymium iron boron fine powder mixture by mass.
5. The method for preparing the neodymium-iron-boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (2), the modified Hummers method is used for preparing graphite oxide: weighing the materials in a mass ratio of 12.3: uniformly mixing 96.8% of graphite, potassium permanganate and potassium permanganate, and adding the mixture into a three-neck flask filled with 98% of mixed acid liquor of concentrated sulfuric acid and phosphoric acid, wherein the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 4.7: 1.2; continuously stirring and reacting for 10-14H to obtain a gray-green solution, then carrying out ice-water bath for 1-3H, adding hydroxide to form a precipitate, wherein the mass percentage of the hydroxide to the graphite is 10%, and then slowly adding H with the volume ratio of 13%2O2At this time, the solution rapidly changed from grayish green to bright yellow, and the solution was stirred continuously and dispersed uniformly by ultrasonic waves.
6. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (2), a micromechanical peeling method is used for preparing graphene: and repeatedly separating graphene sheets from the highly oriented pyrolytic graphite through transparent photoresist, dissolving graphene remained on the photoresist in acetone, and adsorbing the graphene on the silicon sheets to separate the graphene by utilizing van der Waals force and capillary force between silicon wafers and the graphene sheets.
7. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (2), the graphene is prepared by using a SiC pyrolytic epitaxial growth method: oxidizing the surface of graphite or H2 etching, heating to 1000 ℃ under electron bombardment to remove oxides, detecting the removal condition of the surface oxides by using Auger electron spectroscopy, and heating a sample to 1250-1450 ℃ after the oxides are completely removed to form a graphene layer.
8. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (1), the neodymium iron boron particle surface is pretreated: carrying out surface treatment on NdFeB particles by KH550, preparing absolute ethyl alcohol and deionized water into an ethanol solution according to the volume ratio of 5:1, then adding KH550 with the mass being 2% of that of the NdFeB, and fully stirring for 10min by using a glass rod to uniformly disperse the KH550 in the ethanol solution; and slowly adding the NdFeB particles into the solution while stirring, quickly stirring by using a glass rod to enable the particles to be fully contacted with the diluent, standing for 5-10 min, then placing in a blast drying oven, drying for 50-65 h at the temperature of 45-55 ℃, taking out, grinding, and sealing for later use.
9. The preparation method of the neodymium iron boron magnetic material/graphene composite drug-loaded carrier material according to claim 1, wherein in the step (2), graphene is pretreated: adding graphene into a three-necked bottle, measuring 50-60 ml of concentrated nitric acid by using a measuring cylinder, adding the concentrated nitric acid into the three-necked bottle, sealing, ultrasonically dispersing for 15-20 min, heating the three-necked bottle in a water bath kettle at 80-95 ℃, and connecting a condensation reflux device; carrying out acid oxidation treatment for 4-6 h under the condition; and after the reaction is finished, diluting the acid liquor with deionized water, repeatedly washing and filtering with deionized water, drying the recovered graphene for 24-36 h at 95-100 ℃, and putting the graphene into a dryer for later use.
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