CN117257940A - Nickel-cobalt-iron series high-entropy magnetic nano powder for magnetic hyperthermia and preparation method thereof - Google Patents
Nickel-cobalt-iron series high-entropy magnetic nano powder for magnetic hyperthermia and preparation method thereof Download PDFInfo
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- 239000011858 nanopowder Substances 0.000 title claims abstract description 78
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical class [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 206010020843 Hyperthermia Diseases 0.000 title claims description 15
- 230000036031 hyperthermia Effects 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 15
- 206010028980 Neoplasm Diseases 0.000 claims abstract description 8
- 238000002560 therapeutic procedure Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 69
- 239000002245 particle Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 7
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 7
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
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- 239000000843 powder Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011553 magnetic fluid Substances 0.000 abstract description 2
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- 229940124597 therapeutic agent Drugs 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
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- 238000004458 analytical method Methods 0.000 description 4
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- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
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- 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
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- 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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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention belongs to the technical field of nano material production, and particularly relates to nickel-cobalt-iron series high-entropy magnetic nano powder for magnetic thermal therapy and a preparation method thereof. The beneficial effects of the invention are as follows: the method is simple to operate, simple in synthesis method, fine and uniform in powder and excellent in magnetic and thermal properties. The magnetic nano powder can be used as a magnetic thermal therapeutic agent of tumor cells, when an alternating magnetic field with the intensity of 46Oe and the frequency of 266KHz is applied, the specific loss power of the high-entropy magnetic nano powder under the magnetic fluid concentration of 5mg/ml is up to 527W/g, and the magnetic nano powder is a cheap high-performance magnetic thermal therapeutic material and can be applied to the biomedical fields such as tumor magnetic thermal therapy and the like.
Description
Technical Field
The invention belongs to the field of biological application of nano materials, and particularly relates to nickel-cobalt-iron series high-entropy magnetic nano powder for magnetic hyperthermia and a preparation method thereof.
Background
Currently, malignant tumors are seriously threatening the health and life of human beings, and are one of the most leading causes of death in human beings. Magnetic hyperthermia based on Magnetic Nano Particles (MNP) is a novel tumor targeting treatment means which has been developed faster in recent years, and has the advantages of remarkable curative effect, high safety, small side effect and the like, thus becoming a research hot spot for current tumor treatment.
Under the external magnetic field, the magnetic material can convert the magnetic loss energy into heat and is applied to the field of disease treatment. Since the sensitivity of tumor cells to temperature is higher than that of normal cells, the superparamagnetic nanoparticle suspension is injected into tumor tissues, so that the tumor tissues in living bodies can be heated under the action of an alternating magnetic field, and the cancer cells can be killed. At present, the therapeutic effect of magnetic particle hyperthermia has been proved in vitro experiments and clinical experiments, but the magnetic hyperthermia agent has the biggest challenges of low magnetocaloric conversion efficiency, the magnetic nanoparticles used at present show superparamagnetism at nanometer scale, and heat is generated only by relaxation behavior in alternating magnetic field, and the specific loss power is low, such as Fe applied widely in medical treatment 3 O 4 Powder, which is difficult to break through 100W/g than the loss power (specific loss power, SLP). Therefore, the development of the magnetic nano material with high magnetocaloric efficiency has important scientific significance and practical application value.
Disclosure of Invention
Aiming at the practical problem that the heat generating performance of the magnetic hyperthermia agent in the prior art can not be well improved, the invention aims to provide the medical magnetic hyperthermia high-entropy nanometer powder which has the characteristics of simple preparation process, rapid heat generation in an alternating magnetic field and good biocompatibility preservation, and the preparation method thereof.
The aim of the invention is achieved by the following technical scheme: the expression of the high-entropy magnetic nano powder is as follows: ni (Ni) x Co 1-x Fe 2 O 4 Wherein 0 < x < 1.
Further, the high-entropy magnetic nano powder has a fcc+fcc+hcp three-phase structure, and the average particle size is 5-10nm.
Further, when x=0.1, the expression of the high-entropy magnetic nano powder is: ni (Ni) 0.1 Co 0.9 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 527W/g, and the average particle size is 7nm.
Further, when x=0.2, the expression of the high-entropy magnetic nano powder is: ni (Ni) 0.2 Co 0.8 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 230W/g, and the average particle size is 7.5nm.
Further, when x=0.3, the expression of the high-entropy magnetic nano powder is: ni (Ni) 0.3 Co 0.7 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 319W/g, and the average particle size is 7.5nm.
Further, when x=0.4, the expression of the high-entropy magnetic nano powder is: ni (Ni) 0.4 Co 0.6 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 146W/g, and the average particle size is 9.5nm.
Another object of the present invention is to provide a method for preparing the above high entropy magnetic nano powder, which specifically comprises the following steps:
s1) taking ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol as raw materials, and weighing the raw materials according to the design components;
s2) mixing the raw materials weighed in the step S1), placing the mixture in a container, magnetically stirring the mixture at a certain rotating speed, and simultaneously adopting two heating and heat preservation processes to react to obtain a mixture;
and S3) cooling the mixture to room temperature, washing with a solvent, centrifugally drying, and grinding to obtain the nickel-cobalt-iron series high-entropy magnetic nano powder.
Further, the magnetic stirring time in the step S2) is 25-35min, and the rotating speed of the magnetic stirrer is 300-400rpm;
the specific process for the two-time temperature rise and heat preservation comprises the following steps: the first heating temperature is 210-230 ℃, the heat preservation time is 1.5-2.5h, the second heating temperature is 280-300 ℃, and the condensing reflux time is 1.8-2.2h.
Further, the centrifugal speed in the step S3) is 5000-9000rpm, the centrifugal time is 3-5min, the drying temperature is 60-65 ℃, and the drying time is 11-12h.
The high-entropy magnetic nano powder prepared by the method is applied to the biomedical field of tumor magnetocaloric treatment.
The beneficial effects of the invention are as follows: due to the adoption of the technical scheme, the invention breaks through the design concept of the high-entropy alloy multi-principal element based alloy, uses the low-principal element magnetic nano alloy material used in the traditional sense as the magnetic hyperthermia agent, and develops the Ni with high specific loss power by using the cheap and easily obtained raw materials such as acetylacetone metal x Co 1-x Fe 2 O 4 High entropy magnetic nano powder.
The pyrolysis method adopted by the invention is a general simple chemical method, and the preparation process uses dibenzyl ether, oleic acid, oleylamine and 1, 2-hexadecanediol as reaction solvents, oxidizing agents and reducing agents, wherein the oleic acid also serves as a stabilizer to control Ni x Co 1-x Fe 2 O 4 Growth of high entropy magnetic nano-powder and prevention of powder agglomeration. Therefore, the preparation process of the invention can be carried out in basic medium, and Ni in each part can be well controlled x Co 1-x Fe 2 O 4 The heat generating capacity of the high-entropy magnetic nano powder is obviously enhanced compared with that of the traditional magnetic nano material. The prepared nano powder with the average particle size of 5-10nm is dispersed in an aqueous solvent, and the temperature rise can be enabled to exceed 42 ℃ only in 5 min. The high entropy magnetic nano powder with the magnetic fluid concentration of 5mg/ml has a large SLP value 527W/g under the condition of lower magnetic field intensity (46 Oe). Therefore, the high-entropy magnetic nano powder prepared by the invention is an ideal high-performance magnetic hyperthermia agent material and has great market application potential.
Drawings
FIG. 1 is Ni 0.1 Co 0.9 Fe 2 O 4 、Ni 0.2 Co 0.8 Fe 2 O 4、 Ni 0.3 Co 0.7 Fe 2 O 4、 Ni 0.4 Co 0.6 Fe 2 O 4 X-ray diffraction pattern of high entropy magnetic nanopowder.
FIG. 2 is a transmission electron microscope image of the surface morphology of the high entropy magnetic nanopowder, wherein FIG. 2 (a) is Ni 0.1 Co 0.9 Fe 2 O 4 Sample, FIG. 2 (b) is Ni 0.2 Co 0.8 Fe 2 O 4 The sample, FIG. 2 (c) is Ni 0.3 Co 0.7 Fe 2 O 4 The sample, FIG. 2 (d) is Ni 0.4 Co 0.6 Fe 2 O 4 And (3) a sample.
FIG. 3 is Ni 0.1 Co 0.9 Fe 2 O 4 An elemental distribution image of the sample.
FIG. 4 is Ni concentration of 5mg/ml 0.1 Co 0.9 Fe 2 O 4 、Ni 0.2 Co 0.8 Fe 2 O 4、 Ni 0.3 Co 0.7 Fe 2 O 4、 Ni 0.4 Co 0.6 Fe 2 O 4 High entropy magnetic nanopowder is imaged at a heat generation rate under an alternating magnetic field of intensity 46Oe and frequency 266 KHz.
FIG. 5 is Ni concentration of 5mg/ml 0.1 Co 0.9 Fe 2 O 4 、Ni 0.2 Co 0.8 Fe 2 O 4、 Ni 0.3 Co 0.7 Fe 2 O 4、 Ni 0.4 Co 0.6 Fe 2 O 4 SLP value of high entropy magnetic nano powder under 46Oe and alternating magnetic field with frequency of 266 KHz.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and the examples.
The invention relates to Ni which can be used for magnetic thermal therapy x Co 1-x Fe 2 O 4 The preparation process of high entropy magnetic nanometer powder includes the steps of heating ferric acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol for certain period, heating and refluxing for the second time while magnetically stirring to obtain mixture, washing with alcohol and cyclohexane, centrifuging and drying to obtain Ni x Co 1-x Fe 2 O 4 Is high-entropy magnetic nano powder.
The preparation method specifically comprises the following steps:
s1) starting iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether, 1, 2-hexadecanediol from the nominal composition Ni of the alloy powder x Co 1-x Fe 2 O 4 Respectively weighing after converting the components into mass according to atomic percent,
s2) transferring the solution obtained by mixing the raw materials to a four-necked flask, magnetically stirring,
s3) heating the obtained mixed solution, simultaneously magnetically stirring, heating to a certain temperature, preserving heat to increase the concentration of the crystal nucleated monomer and reach a certain saturation, carrying out burst nucleation on the system, further increasing the reaction temperature, carrying out condensation reflux for a certain time, redissolving small particles to form large particles, finally forming high-entropy magnetic nano powder, cooling to obtain a mixture,
s4) washing the mixture obtained in the step S3) with alcohol and cyclohexane, centrifuging to obtain black precipitate, drying in a vacuum drying oven, and grinding to obtain Ni x Co 1-x Fe 2 O 4 Is high-entropy magnetic nano powder.
The magnetic stirring time in the step S2) is 30min, and the rotating speed of the magnetic stirrer is 300-400rpm.
In the step S3), the first heating temperature is 220 ℃, the heat preservation time is 2h, the second heating temperature is 290 ℃, and the condensing reflux time is 2h.
The centrifugal speed in the step S4) is 5000-9000rpm, the centrifugal time is 3-5min, the drying temperature is 60-65 ℃, and the drying time is 11-12h.
The Ni is obtained x Co 1-x Fe 2 O 4 Nominal component Ni of high entropy magnetic nano powder x Co 1-x Fe 2 O 4 Wherein x is more than 0 and less than 1, and the marked components are atomic percent.
The Ni is obtained x Co 1-x Fe 2 O 4 The magnetic nano powder has a three-phase structure of fcc+fcc+hcp and an average particle size of 5-10nm.
The Ni is obtained x Co 1-x Fe 2 O 4 An aqueous dispersion of high entropy magnetic nanopowder with a specific loss power SLP value up to 527W/g.
Example 1 use of Ni 0.1 Co 0.9 Fe 2 O 4 The nominal component of the high entropy magnetic nano powder is prepared by mixing raw materials required by alloy, namely ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol raw materials, and mixing the raw materials by using the nominal component Ni of the alloy powder 0.1 Co 0.9 Fe 2 O 4 The materials were weighed after being converted into mass according to atomic percentages, and the mixed solution was transferred to a four-necked flask and magnetically stirred. Heating the obtained mixed solution, simultaneously magnetically stirring, carrying out heat preservation when the mixed solution is heated to a certain temperature, improving the monomer concentration of crystal nucleation and reaching a certain saturation, carrying out system burst nucleation, further improving the reaction temperature, condensing and refluxing for a certain time, redissolving small particles to form large particles, finally forming high-entropy magnetic nano powder, and cooling to obtain the mixture. Washing the obtained mixture with ethanol and cyclohexane, centrifuging to obtain black precipitate, drying in vacuum drying oven, and grinding to obtain Ni 0.1 Co 0.9 Fe 2 O 4 High entropy magnetic nano powder.
For the Ni prepared 0.1 Co 0.9 Fe 2 O 4 The high-entropy magnetic nano powder is subjected to X-ray diffraction pattern test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, ni can be seen 0.1 Co 0.9 Fe 2 O 4 The high-entropy magnetic nano powder has fcc+fcc+hcp structure. FIG. 2 (a) is Ni 0.1 Co 0.9 Fe 2 O 4 The powder of the sample was seen to be spherical in shape and had an average particle diameter of 7nm as seen from a transmission electron micrograph of the sample. Next, ni is prepared 0.1 Co 0.9 Fe 2 O 4 The high-entropy magnetic nano powder is set with a sample concentration of 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field strength is 46Oe, and the magnetic field frequency is 266 kHz) for in-vitro heating test. FIG. 3 is Ni 0.1 Co 0.9 Fe 2 O 4 The element distribution image of the sample shows that Fe, co and Ni elements are uniformly distributed in the powder sample, and the sample has a core-shell structure. FIG. 4 shows a sample temperature rise rate curve with a concentration of 5mg/mL, and Ni can be found 0.1 Co 0.9 Fe 2 O 4 The faster temperature rise rate of the samples of (a) and the temperature rise in a short period of 5min all exceeded 42 ℃. FIG. 5 shows the specific loss power of a sample having a concentration of 5mg/mL, from which it can be seen that Ni has a concentration of 5mg/mL 0.1 Co 0.9 Fe 2 O 4 The specific loss power value of the sample is 527W/g, which shows that the sample has excellent magnetic heat property and is expected to be applied to research and development of high-performance magnetic hyperthermia agents.
Example 2 use of Ni 0.2 Co 0.8 Fe 2 O 4 The nominal component of the high entropy magnetic nano powder is prepared by mixing raw materials required by alloy, namely ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol raw materials, and mixing the raw materials by using the nominal component Ni of the alloy powder 0.2 Co 0.8 Fe 2 O 4 The materials were weighed after being converted into mass according to atomic percentages, and the mixed solution was transferred to a four-necked flask and magnetically stirred. Heating the obtained mixed solution, and simultaneously magnetically stirringStirring, heating to a certain temperature, preserving heat to increase the concentration of the crystal nucleation monomer and reach a certain saturation, carrying out burst nucleation on the system, further increasing the reaction temperature, condensing and refluxing for a certain time, redissolving small particles to form large particles, finally forming high-entropy magnetic nano powder, and cooling to obtain a mixture. Washing the obtained mixture with ethanol and cyclohexane, centrifuging to obtain black precipitate, drying in vacuum drying oven, and grinding to obtain Ni 0.2 Co 0.8 Fe 2 O 4 High entropy magnetic nano powder.
For the Ni prepared 0.2 Co 0.8 Fe 2 O 4 The high-entropy magnetic nano powder is subjected to X-ray diffraction pattern test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, ni can be seen 0.2 Co 0.8 Fe 2 O 4 The high-entropy magnetic nano powder has fcc+fcc+hcp structure. FIG. 2 (b) is Ni 0.2 Co 0.8 Fe 2 O 4 The powder of the sample was seen to be spherical in shape and had an average particle diameter of 7.5nm as seen from a transmission electron micrograph of the sample. Next, ni is prepared 0.2 Co 0.8 Fe 2 O 4 The high-entropy magnetic nano powder is set with a sample concentration of 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field strength is 46Oe, and the magnetic field frequency is 266 kHz) for in-vitro heating test. FIG. 4 shows a sample temperature rise rate curve with a concentration of 5mg/mL, and Ni can be found 0.2 Co 0.8 Fe 2 O 4 The faster temperature rise rate of the samples of (a) and the temperature rise in a short period of 5min all exceeded 42 ℃. FIG. 5 shows the specific loss power of a sample having a concentration of 5mg/mL, from which it can be seen that Ni has a concentration of 5mg/mL 0.2 Co 0.8 Fe 2 O 4 The specific loss power value of the sample is 230W/g, which shows that the sample has excellent magnetic heat property and is expected to be applied to research and development of high-performance magnetic hyperthermia agents.
Example 3 use of Ni 0.3 Co 0.7 Fe 2 O 4 The nominal components of the high entropy magnetic nano powder are the raw materials required by alloy, such as ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediolThe material consists of the nominal component Ni of alloy powder 0.3 Co 0.7 Fe 2 O 4 The materials were weighed after being converted into mass according to atomic percentages, and the mixed solution was transferred to a four-necked flask and magnetically stirred. Heating the obtained mixed solution, simultaneously magnetically stirring, carrying out heat preservation when the mixed solution is heated to a certain temperature, improving the monomer concentration of crystal nucleation and reaching a certain saturation, carrying out system burst nucleation, further improving the reaction temperature, condensing and refluxing for a certain time, redissolving small particles to form large particles, finally forming high-entropy magnetic nano powder, and cooling to obtain the mixture. Washing the obtained mixture with ethanol and cyclohexane, centrifuging to obtain black precipitate, drying in vacuum drying oven, and grinding to obtain Ni 0.3 Co 0.7 Fe 2 O 4 High entropy magnetic nano powder.
For the Ni prepared 0.3 Co 0.7 Fe 2 O 4 The high-entropy magnetic nano powder is subjected to X-ray diffraction pattern test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, ni can be seen 0.3 Co 0.6 Fe 2 O 4 The high-entropy magnetic nano powder has fcc+fcc+hcp structure. FIG. 2 (c) is Ni 0.3 Co 0.7 Fe 2 O 4 The powder of the sample was seen to be spherical in shape and had an average particle diameter of 7.5nm as seen from a transmission electron micrograph of the sample. Next, ni is prepared 0.3 Co 0.7 Fe 2 O 4 The high-entropy magnetic nano powder is set with a sample concentration of 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field strength is 46Oe, and the magnetic field frequency is 266 kHz) for in-vitro heating test. FIG. 4 shows a sample temperature rise rate curve with a concentration of 5mg/mL, and Ni can be found 0.3 Co 0.7 Fe 2 O 4 The faster temperature rise rate of the samples of (a) and the temperature rise in a short period of 5min all exceeded 42 ℃. FIG. 5 shows the specific loss power of a sample having a concentration of 5mg/mL, from which it can be seen that Ni has a concentration of 5mg/mL 0.3 Co 0.7 Fe 2 O 4 The specific loss power value of the sample is 319W/g, which shows that the sample has excellent magnetic heat property and is expected to be applied to research and development of high-performance magnetic hyperthermia agents.
Example 4 use of Ni 0.4 Co 0.6 Fe 2 O 4 The nominal component of the high entropy magnetic nano powder is prepared by mixing raw materials required by alloy, namely ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol raw materials, and mixing the raw materials by using the nominal component Ni of the alloy powder 0.4 Co 0.6 Fe 2 O 4 The materials were weighed after being converted into mass according to atomic percentages, and the mixed solution was transferred to a four-necked flask and magnetically stirred. Heating the obtained mixed solution, simultaneously magnetically stirring, carrying out heat preservation when the mixed solution is heated to a certain temperature, improving the monomer concentration of crystal nucleation and reaching a certain saturation, carrying out system burst nucleation, further improving the reaction temperature, condensing and refluxing for a certain time, redissolving small particles to form large particles, finally forming high-entropy magnetic nano powder, and cooling to obtain the mixture. Washing the obtained mixture with ethanol and cyclohexane, centrifuging to obtain black precipitate, drying in vacuum drying oven, and grinding to obtain Ni 0.4 Co 0.6 Fe 2 O 4 High entropy magnetic nano powder.
For the Ni prepared 0.4 Co 0.6 Fe 2 O 4 The high-entropy magnetic nano powder is subjected to X-ray diffraction pattern test and analysis, and the result is shown in figure 1. By comparison with the standard peak position, ni can be seen 0.4 Co 0.6 Fe 2 O 4 The high-entropy magnetic nano powder has fcc+fcc+hcp structure. FIG. 2 (d) is Ni 0.4 Co 0.6 Fe 2 O 4 The powder of the sample was seen to be spherical in shape and had an average particle diameter of 9.5nm as seen from a transmission electron micrograph of the sample. Next, ni is prepared 0.4 Co 0.6 Fe 2 O 4 The high-entropy magnetic nano powder is set with a sample concentration of 5mg/mL, and is placed in an alternating magnetic field (the applied magnetic field strength is 46Oe, and the magnetic field frequency is 266 kHz) for in-vitro heating test. FIG. 4 shows a sample temperature rise rate curve with a concentration of 5mg/mL, and Ni can be found 0.4 Co 0.6 Fe 2 O 4 The faster temperature rise rate of the samples of (a) and the temperature rise in a short period of 5min all exceeded 42 ℃. FIG. 5 calculatesSpecific loss power of 5mg/mL sample, from which it can be seen that Ni concentration is 5mg/mL 0.4 Co 0.6 Fe 2 O 4 The specific loss power value of the sample is 146W/g, and the magneto-thermal property of the sample is superior to that of Fe commonly used in the current medical field 3 O 4 The powder is expected to be applied to the research and development of high-performance magnetic hyperthermia agents.
The Ni used for the magnetic thermal therapy provided by the embodiment of the application x Co 1-x Fe 2 O 4 The high-entropy magnetic nano powder and the preparation method thereof are described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (10)
1. The nickel-cobalt-iron high-entropy magnetic nano powder for magnetic hyperthermia is characterized by comprising the following expression: ni (Ni) x Co 1-x Fe 2 O 4 Wherein 0 < x < 1.
2. The high-entropy magnetic nano-powder according to claim 1, wherein the high-entropy magnetic nano-powder has a fcc+fcc+hcp three-phase structure, and an average particle size of 5-10nm.
3. The high-entropy magnetic nano-powder according to claim 1, wherein when x=0.1, the expression of the high-entropy magnetic nano-powder is: ni (Ni) 0.1 Co 0.9 Fe 2 O 4 Specific loss power SL of high-entropy magnetic nano powderThe P value was 527W/g and the average particle diameter was 7nm.
4. The high-entropy magnetic nano-powder according to claim 1, wherein when x=0.2, the expression of the high-entropy magnetic nano-powder is: ni (Ni) 0.2 Co 0.8 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 230W/g, and the average particle size is 7.5nm.
5. The high-entropy magnetic nano-powder according to claim 1, wherein when x=0.3, the expression of the high-entropy magnetic nano-powder is: ni (Ni) 0.3 Co 0.7 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 319W/g, and the average particle size is 7.5nm.
6. The high-entropy magnetic nano-powder according to claim 1, wherein when x=0.4, the expression of the high-entropy magnetic nano-powder is: ni (Ni) 0.4 Co 0.6 Fe 2 O 4 The specific loss power SLP value of the high-entropy magnetic nano powder is 146W/g, and the average particle size is 9.5nm.
7. A method for preparing a high entropy magnetic nano-powder according to any of claims 1-6, characterized in that the method comprises in particular the steps of:
s1) taking ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, oleic acid, oleylamine, dibenzyl ether and 1, 2-hexadecanediol as raw materials, and weighing the raw materials according to the design components;
s2) mixing the raw materials weighed in the step S1), placing the mixture in a container, magnetically stirring the mixture at a certain rotating speed, and simultaneously adopting two heating and heat preservation processes to react to obtain a mixture;
and S3) cooling the mixture to room temperature, washing with a solvent, centrifugally drying, and grinding to obtain the nickel-cobalt-iron series high-entropy magnetic nano powder.
8. The method according to claim 7, wherein the magnetic stirring time in S2) is 25 to 35min, and the rotation speed of the magnetic stirrer is 300 to 400rpm;
the specific process for the two-time temperature rise and heat preservation comprises the following steps: the first heating temperature is 210-230 ℃, the heat preservation time is 1.5-2.5h, the second heating temperature is 280-300 ℃, and the condensing reflux time is 1.8-2.2h.
9. The method according to claim 7, wherein the centrifugation speed in S3) is 5000-9000rpm, the centrifugation time is 3-5min, the drying temperature is 60-65 ℃, and the drying time is 11-12h.
10. Use of the high entropy magnetic nano-powder prepared by the method according to any one of claims 1-9 in the biomedical field of tumor magnetocaloric therapy.
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