CN114796588A - Magnetic micron embolism thermotherapy medium and preparation and application thereof - Google Patents

Magnetic micron embolism thermotherapy medium and preparation and application thereof Download PDF

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CN114796588A
CN114796588A CN202210407445.6A CN202210407445A CN114796588A CN 114796588 A CN114796588 A CN 114796588A CN 202210407445 A CN202210407445 A CN 202210407445A CN 114796588 A CN114796588 A CN 114796588A
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embolism
micron
thermotherapy
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刘晓丽
王思尧
唐倩倩
樊海明
吕毅
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First Affiliated Hospital of Medical College of Xian Jiaotong University
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Abstract

The invention relates to a magnetic micron embolism thermotherapy medium and preparation and application thereof. Adopting a 'hydrothermal and reduction' method, and in a closed reaction kettle, Fe 3+ As a reaction precursor, adding inorganic salt, controlling different reaction times, and preparing 'olive-shaped' alpha-Fe at a certain reaction temperature 2 O 3 Micro grains of rice, further tubular furnace solid-gasThe magnetic micro-rice grains with the shape of rugby are obtained by the reduction reaction. The method has simple process and low preparation cost, and can realize large-scale preparation; the prepared magnetic micron medium has uniform particle size and shape, good crystallinity, controllable size range, high saturation magnetization, excellent heating effect under the action of a medium-frequency electromagnetic field and higher heat conversion efficiency, and the magnetic micron particles are endowed with the potential of further loading drugs by surface porosity, so that the magnetic micron medium is expected to realize in-situ liver cancer embolism thermotherapy or thermo-chemotherapy under the guidance of imaging, and has potential application in the field of interventional therapy of in-situ tumors.

Description

Magnetic micron embolism thermotherapy medium and preparation and application thereof
Technical Field
The invention belongs to the technical field of biomedicine, relates to a micron material, and particularly relates to a magnetic micron embolism heat treatment medium and preparation and application thereof.
Background
The tumor thermotherapy adopts a physical method to increase the temperature of the whole body or local tumor, and makes the tumor tissue and normal tissue have different tolerance to heat to ensure that tumor cells die at 46-50 ℃ without damage of the normal cells at the temperature. Local thermotherapy generally uses ultrasound, microwaves, alternating magnetic fields, radio frequency and the like, and the method has small traumatism, is easy to operate and control temperature, so that the method is frequently used. However, these therapies all have some limitations, the first: the tumor tissue and the normal tissue can not be effectively distinguished, and the damage to the edge of the tumor tissue is limited; secondly, the method comprises the following steps: the vascular structure and microcirculation in tumor tissues are not sound compared with normal tissues, so that the absorption of heat by the tumor tissues cannot reach the maximum efficiency; third, the heat dose in the tissue is not uniformly distributed and has limited effect on large deep tumors. Therefore, it is important to develop efficient, conformable hyperthermia for tumors.
Magnetic induction hyperthermia has attracted much attention since the proposal of Gichrist in 1957, and the research on magnetic induction hyperthermia medium is endlessly developed. The artery embolism heat treatment is a treatment mode combining artery embolism treatment with magnetic induction heat treatment, and is characterized in that a magnetic embolism medium is introduced into a blood supply artery of a tumor by an intervention method, and then the blood supply artery is placed in an external alternating magnetic field for induction heating, namely, heat treatment auxiliary treatment is carried out on the basis of embolizing tumor blood vessels, and the purpose of efficiently treating the tumor is achieved under the double effects. Compared with the arterial embolism chemotherapy, the medicine has smaller side effect and can realize repeated and multiple noninvasive treatments to a certain extent. Meanwhile, tumor cells after embolism are in an anoxic state, are more sensitive to thermal reaction, are more beneficial to apoptosis of the tumor cells, and have the advantages of low treatment cost, wide application range and short treatment time. At present, magnetic induction thermotherapy for arterial embolism mainly focuses on research on an embolism medium and a magnetic field generation device, in the embolism medium, compared with the situation that nano-scale magnetic particles easily enter a circulatory system through a capillary network, a large potential safety hazard exists, and micron-scale arterial embolism medium can block a capillary bed of a tumor and cannot enter venous circulation through a capillary vessel in an arterial embolism process, so that the magnetic induction thermotherapy for arterial embolism has development potential and utilization rate.
At present, in the preparation of micron-sized magnetic induction arterial embolization particles, a surfactant, an oily medium and an aqueous medium are mainly added into precursor nano particles by an emulsification method and mixed to form colostrum. Then the compound emulsion is prepared by an emulsifying device in a low-temperature environment, and the magnetic induction thermotherapy embolism particles are obtained after stirring and curing. In the process, the emulsification process is complicated, the additives are more, some toxic reagents are inevitably used, and the toxic reagents are difficult to remove in the later period, so that the biocompatibility of the emulsion is reduced. In addition, the controllability of the number of the coated nanoparticles in the process of forming the colostrum is poor, and the size of the particles formed by final solidification is not uniform, so that the magnetocaloric performance is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a magnetic micron embolism heat treatment medium and preparation and application thereof, wherein the reaction temperature and the reaction time are adjusted, the reduction temperature and time of a tubular furnace are screened, the heat conversion efficiency and the performance of magnetic particles are improved, and the obtained micron-sized magnetic induction heat treatment embolism medium with high magnetic heat conversion efficiency overcomes the problem of low magnetic heat conversion efficiency of the existing magnetic induction heat treatment in interventional embolism application, so as to promote the further development of the magnetic induction artery embolism heat treatment.
In order to achieve the purpose, the invention adopts the technical scheme that:
a magnetic micrometer embolism thermotherapy medium has an ellipsoidal shape,the grain diameter is 0.5-50 μm, and the component is gamma-Fe 2 O 3 、Fe 3 O 4 And Fe or gamma-Fe 2 O 3 With Fe 3 O 4 Of (2) or Fe 3 O 4 And Fe.
In one embodiment, the magnetic micrometer embolism thermotherapy medium has saturation magnetization of 70-180emu/g, and can increase the temperature to 10-70 ℃ under the action of medium-frequency electromagnetic field.
In one embodiment, the magnetic micro-embolism thermotherapy medium has a surface pore size of 1-50 nm.
In one embodiment, the major axis length of the ellipsoid is much greater than the minor axis length.
The invention also provides a preparation method of the magnetic micron embolism heat treatment medium, which comprises the following steps:
step 1, in FeCl 3 Adding inorganic salt into the aqueous solution, fully stirring and reacting at high temperature;
step 2, after the reaction is finished, washing and centrifuging and collecting brick red precipitate to obtain alpha-Fe 2 O 3 Microparticles;
step 3, mixing alpha-Fe 2 O 3 Drying the particles in vacuum, introducing H 2 And (3) reducing the/Ar mixed gas at high temperature to obtain magnetic black solid powder, namely the magnetic micron embolism thermotherapy medium.
In one embodiment, said step 1, FeCl 3 The concentration of (A) is 0.01-5M, and the volume is 0.1mL-10 mL; the inorganic salt is one or more of ammonium dihydrogen phosphate, sodium chloride or sodium sulfate, wherein the concentration of ammonium dihydrogen phosphate is 0.001-0.1M, the volume is 0.1-2 mL, the concentration of sodium chloride and sodium sulfate is 0.01-2 mL, and the volume is 0.001-0.2M.
In one embodiment, in the step 1, the high-temperature reaction is carried out in a polytetrafluoroethylene inner container of the hydrothermal kettle, the reaction temperature is 180 ℃ and 240 ℃, and the reaction time is 0.5-80 h; in the step 2, washing and centrifuging with absolute ethyl alcohol and deionized water, wherein the centrifugal rotation speed is 1000-10000rpm/min, and the centrifugal washing is carried out for 1-10 times.
In one embodiment, said step 3, the vacuum drying temperature is 40-80 deg.c,introducing a quartz tube furnace in a horizontal type, wherein the quartz tube furnace comprises the following components in percentage by volume (1-10): (90-99) H 2 The flow rate of the/Ar mixed gas is 100-400sccm, the reduction temperature is 300-600 ℃, and the reaction time is 0.5-5 h.
The magnetic micron embolism heat treatment medium can be used for preparing heat treatment agents and loading chemotherapy medicaments.
In one embodiment, the chemotherapeutic drug is at least one of an anthracycline, a platinum antineoplastic, paclitaxel, and gemcitabine.
Compared with the existing preparation of magnetic micron embolism thermotherapy medium, the invention has simple process and low preparation cost, and can realize large-scale preparation; the prepared magnetic micron medium has uniform particle size and shape, good crystallinity, controllable size range, high saturation magnetization, excellent heating effect under the action of a medium-frequency electromagnetic field and higher heat conversion efficiency, and the magnetic micron particles are endowed with the potential of further loading drugs by surface porosity, so that the magnetic micron medium is expected to realize in-situ liver cancer embolism thermotherapy or thermo-chemotherapy under the guidance of imaging, and has potential application in the field of interventional therapy of in-situ tumors.
Drawings
FIG. 1 is a schematic diagram of the magnetic micron embolism heat therapy medium of the present invention.
FIG. 2 is Fe of example 1 of the present invention 3 O 4 Scanning Electron Microscope (SEM) images of micron embolization hyperthermia media.
FIG. 3 is Fe in example 1 of the present invention 3 O 4 X-ray diffraction (XRD) pattern of the micron embolization hyperthermia medium.
FIG. 4 is Fe in example 1 of the present invention 3 O 4 Magnetic hysteresis of micron embolism thermotherapy medium.
FIG. 5 is an SEM image of Fe-containing micron embolization hyperthermia media of example 2 of the present invention.
Figure 6 is an XRD pattern of Fe-containing micron embolization hyperthermia media of example 2 of the present invention.
FIG. 7 is a hysteresis loop plot of Fe-containing micro-embolic hyperthermia medium of example 2 of the present invention.
Fig. 8 shows (a) temperature rise curve and (b) Specific Absorption Rate (SAR) of Fe-containing micro embolization hyperthermia medium of example 2 of the present invention at different field strengths.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
The invention relates to a magnetic micrometer embolism thermotherapy medium, the shape of which is an ellipsoid shape or can be called as a football shape, illustratively, the length of a long axis is far longer than that of a short axis, and two ends can be standard ellipses or sharp angles. The magnetic micrometer embolism thermotherapy medium has particle diameter of 0.5-50 μm, and has magnetism, and its component can be pure substance or mixture, and when pure substance, it can be selected from gamma-Fe 2 O 3 、Fe 3 O 4 Or Fe; when the mixture is used, gamma-Fe can be selected 2 O 3 With Fe 3 O 4 Or Fe 3 O 4 Mixing with Fe.
The saturation magnetization range of the magnetic micron embolism thermotherapy medium is preferably 70-180emu/g, the temperature of the magnetic micron embolism thermotherapy medium can be raised to 10-70 ℃ under the action of a medium-frequency electromagnetic field, and the temperature rise temperature is related to the intensity of the electromagnetic field.
The surface of the magnetic micron embolism heat treatment medium has a micropore structure with the aperture size of 1-50 nm.
Referring to FIG. 1, the invention adopts a 'hydrothermal + reduction' method, in a closed reaction kettle, Fe 3+ Adding inorganic salt as a reaction precursor, controlling different reaction times, and preparing olive-shaped alpha-Fe at a certain reaction temperature 2 O 3 Carrying out tubular furnace solidification-gas reduction reaction on the micro-rice grains to obtain the rugby-ball-shaped magnetic micro-rice grains. The preparation method optimizes the hydrothermal method for preparing alpha-Fe 2 O 3 Method of making fine particles, realizing alpha-Fe 2 O 3 The size of the particles can be controlled, and magnetic Fe with high magnetocaloric conversion efficiency is synthesized by screening the reduction temperature 3 O 4 And (3) microparticles. The preparation method specifically comprises the following steps:
step 1, in FeCl 3 Adding inorganic salt into the aqueous solution, fully stirring, and then transferring into a polytetrafluoroethylene inner container of a hydrothermal kettle for high-temperature reaction at 180 ℃ and 240 ℃.
Wherein FeCl 3 The concentration of (A) can be 0.01-5M, and the volume can be 0.1mL-10 mL; the inorganic salt is one or more of ammonium dihydrogen phosphate, sodium chloride or sodium sulfate, wherein the concentration of ammonium dihydrogen phosphate can be 0.001-0.1M, the volume can be 0.1-2 mL, the concentrations of sodium chloride and sodium sulfate can be 0.01-2 mL, the volume can be 0.001-0.2M, and the high-temperature reaction time is 0.5-80 h.
Step 2, after the reaction is finished, washing and centrifuging by using absolute ethyl alcohol and deionized water, and collecting brick red precipitate to obtain alpha-Fe 2 O 3 And (3) microparticles.
Wherein, the rotation speed of centrifugation can be 1000-10000rpm/min, and the times of centrifugation and washing are 1-10 times.
Step 3, mixing alpha-Fe 2 O 3 Vacuum drying the particles, transferring into horizontal quartz tube furnace, and introducing H 2 And heating the/Ar mixed gas by a program and reducing the gas at high temperature to obtain magnetic black solid powder, namely the magnetic micron embolism heat treatment medium.
Wherein the vacuum drying temperature can be 40-80 deg.C, and H 2 The volume percentage of the/Ar mixed gas is (1-10): (90-99), the flow rate is 100 and 400 sccm. The reduction temperature is 300 ℃ and 600 ℃, and the reaction time is 0.5-5 h.
The magnetic micron embolism heat treatment medium can be used for preparing a heat treatment agent, can be used for in-situ liver cancer embolism heat treatment or thermo-chemotherapy under the guidance of imaging, and has potential application in the field of in-situ tumor interventional therapy.
The magnetic micron embolism thermotherapy medium can also be used for loading chemotherapeutic drugs. Wherein the chemotherapy drug is at least one of anthracycline antibiotic, platinum antineoplastic drug, paclitaxel and gemcitabine.
The following are two specific embodiments of the invention
Example 1: "Rugby" magnetic Fe 3 O 4 Micron embolism thermotherapy medium:
synthesis of 'Rugby shape' alpha-Fe by hydrothermal method 2 O 3 And (3) microparticles: accurately measuring 3.0mL FeCl 3 (0.5mol/L) and 1.5mL NH 4 H 2 PO 4 (0.02mol/L) solution is stirred evenly in a beaker, and water is added until the total volume is40mL, fully stirring and mixing, transferring to a 50mL polytetrafluoroethylene hydrothermal reaction kettle, and keeping the temperature at 220 ℃ for reacting for 8 hours respectively. After the reaction is finished, washing and centrifuging (8000r/min) by using absolute ethyl alcohol and deionized water, and collecting brick red precipitate to obtain alpha-Fe 2 O 3 And (3) microparticles.
"Rugby" magnetic Fe 3 O 4 Preparing a micron embolism thermotherapy medium: alpha-Fe is mixed 2 O 3 The particles were dried under vacuum at 60 ℃ and 100mg of alpha-Fe was weighed 2 O 3 The particles were placed in a horizontal quartz tube furnace and 5%/95% (H) was fed at a flow rate of 200sccm 2 Ar) mixed gas, the temperature is raised to 450 ℃ through 30min program and the mixture is reduced for 2h, and black solid powder is obtained.
FIG. 2 shows "Rugby-shaped" magnetic Fe 3 O 4 SEM image of micrometer embolism thermotherapy medium shows that Fe is prepared 3 O 4 The particle size is uniform; FIG. 3 is an XRD pattern of the prepared material, showing that the material is Fe 3 O 4 A crystalline phase; FIG. 4 is an XRD pattern of the prepared material, showing that the material is Fe 3 O 4 A crystalline phase; FIG. 5 shows the magnetic Fe prepared 3 O 4 Magnetic hysteresis curves of the particles, magnetic Fe detected by a Vibrating Sample Magnetometer (VSM) 3 O 4 Magnetic properties of the particles. Anhydrous ethanol repeatedly washes magnetic Fe 3 O 4 And (3) after the particles are placed in an oven to be dried, grinding the particles into powder, weighing 8-10mg of sample on an analytical balance, carrying out parameter calibration on the VSM by using a standard sample, setting the magnetic field range to be 0-20000Oe, placing the sample on a saddle area of a VSM rod to be characterized, and obtaining the saturation magnetization of the sample to be 70emu/g from the figure.
Example 2: "Rugby" magnetic Fe-containing micron embolism thermotherapy medium:
reference example 1 method for preparing "rugby-shape" alpha-Fe 2 O 3 And (3) microparticles. alpha-Fe is mixed 2 O 3 The particles were dried under vacuum at 60 ℃ and 100mg of alpha-Fe was weighed 2 O 3 The particles were placed in a horizontal quartz tube furnace and 5%/95% (H) was fed at a flow rate of 300sccm 2 Ar) mixed gas, and the mixture is heated to 500 ℃ by a program of 30min and reduced for 4h to obtain black solid powder.
FIG. 5 is an SEM image of "football-shaped" magnetic Fe micron embolism heat treatment medium, and it can be seen that the prepared particles are uniform in size; FIG. 6 is an XRD pattern of the as-prepared material, showing that the material contains a crystalline phase of Fe; FIG. 7 is a hysteresis chart of the prepared magnetic particles, the magnetic properties of the magnetic particles are detected by VSM, the saturation magnetization of the magnetic particles is 93emu/g, and the magnetic microparticles with higher magnetization are prepared by regulating and controlling the reduction temperature. In the experiment for measuring the magnetocaloric temperature rise curve, 1mL of the magnetic particle dispersion system is respectively added into a centrifuge tube, the centrifuge tube is placed in a medium-frequency alternating magnetic field (365kHz), the magnetic field intensity is respectively 20Oe, 30Oe, 40Oe and 50Oe, the temperature change of the solution is tested by a magnetocaloric instrument SupMag M5 (Seisan supermagnetic nano-biotechnology), 1s is arranged in the instrument to record the temperature change curve along with the time, and the temperature change curve is recorded. Fig. 8 shows (a) temperature rise curves and (b) Specific Absorption Rate (SAR) of magnetic particles at different field strengths, from which it can be seen that at a field strength of 50Oe, SAR reaches 2391 Watt/g.

Claims (10)

1. A magnetic micrometer embolism thermotherapy medium is characterized by that its external form is an ellipsoid shape, grain size is 0.5-50 micrometers, and its component is gamma-Fe 2 O 3 、Fe 3 O 4 And Fe or gamma-Fe 2 O 3 With Fe 3 O 4 Of (2) or Fe 3 O 4 And Fe.
2. The magnetic micron embolism heat treatment medium of claim 1, wherein the saturation magnetization of the magnetic micron embolism heat treatment medium is 70-180emu/g, and the temperature can be raised to 10-70 ℃ under the action of a medium-frequency electromagnetic field.
3. The magnetic micron embolic thermal therapy medium of claim 1, wherein the pore size of the surface of the magnetic micron embolic thermal therapy medium is 1-50 nm.
4. A magnetic micrometer plug hyperthermia medium according to claim 1, wherein the major axis of the ellipsoid is substantially longer than the minor axis.
5. A preparation method of magnetic micron embolism thermotherapy medium comprises the following steps:
step 1, in FeCl 3 Adding inorganic salt into the aqueous solution, fully stirring and reacting at high temperature;
step 2, after the reaction is finished, washing and centrifuging and collecting brick red precipitate to obtain alpha-Fe 2 O 3 Microparticles;
step 3, mixing alpha-Fe 2 O 3 Drying the particles in vacuum, introducing H 2 And (3) reducing the/Ar mixed gas at high temperature to obtain magnetic black solid powder, namely the magnetic micron embolism thermotherapy medium.
6. The method for preparing magnetic micrometer embolism heat treatment medium according to claim 5, wherein in step 1, FeCl is adopted 3 The concentration of (A) is 0.01-5M, and the volume is 0.1mL-10 mL; the inorganic salt is one or more of ammonium dihydrogen phosphate, sodium chloride or sodium sulfate, wherein the concentration of ammonium dihydrogen phosphate is 0.001-0.1M, the volume is 0.1-2 mL, the concentration of sodium chloride and sodium sulfate is 0.01-2 mL, and the volume is 0.001-0.2M.
7. The method for preparing a magnetic micron embolism heat treatment medium as defined in claim 5 or 6, wherein in the step 1, the high temperature reaction is carried out in a polytetrafluoroethylene inner container of a hydrothermal kettle at 180-240 ℃ for 0.5-80 h; in the step 2, washing and centrifuging with absolute ethyl alcohol and deionized water, wherein the centrifugal rotation speed is 1000-10000rpm/min, and the centrifugal washing is carried out for 1-10 times.
8. A method for preparing magnetic micrometer embolism heat therapy medium according to claim 5, wherein in the step 3, the vacuum drying temperature is 40-80 ℃, and the volume percentage of the vacuum drying temperature is (1-10): (90-99) H 2 The flow rate of the/Ar mixed gas is 100-400sccm, the reduction temperature is 300-600 ℃, and the reaction time is 0.5-5 h.
9. Use of the magnetic micro-embolization hyperthermia medium of claim 1 for the preparation of a hyperthermia agent and for loading a chemotherapeutic drug.
10. The use of claim 9, wherein the chemotherapeutic agent is at least one of an anthracycline, a platinum antineoplastic agent, paclitaxel, and gemcitabine.
CN202210407445.6A 2022-04-19 2022-04-19 Magnetic micron embolism thermotherapy medium and preparation and application thereof Pending CN114796588A (en)

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