CN112023063A - Double-iron-based mesoporous carbon nanomaterial integrating functions of nuclear magnetic imaging radiography and drug delivery and preparation method and application thereof - Google Patents

Double-iron-based mesoporous carbon nanomaterial integrating functions of nuclear magnetic imaging radiography and drug delivery and preparation method and application thereof Download PDF

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CN112023063A
CN112023063A CN202010857247.0A CN202010857247A CN112023063A CN 112023063 A CN112023063 A CN 112023063A CN 202010857247 A CN202010857247 A CN 202010857247A CN 112023063 A CN112023063 A CN 112023063A
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mesoporous carbon
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凌云
周亚明
张慧
陈珍霞
刘小锋
杨永泰
贾瑜
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Abstract

The invention relates to the technical field of functional nano materials, in particular to a Magnetic Resonance Imaging (MRI) integrated machineThe ferric phosphate and gamma iron oxide nanoparticles are uniformly dispersed in a mesoporous carbon framework, the particle size is 1-20 nm adjustable, the mass content of the ferric phosphate and the gamma iron oxide in the mesoporous carbon nanomaterial is 0.5-10%, and the molar ratio of the ferric phosphate to the gamma iron oxide is 1: 4. The nano material provided by the invention realizes T1/T2The nuclear magnetic resonance imaging contrast function and the drug delivery function are integrated, the characteristic of low cytotoxicity is achieved, meanwhile, the preparation method of the nano diagnosis and treatment material provided by the invention is simple, the raw materials are wide and easy to obtain, and the potential application prospect is achieved.

Description

Double-iron-based mesoporous carbon nanomaterial integrating functions of nuclear magnetic imaging radiography and drug delivery and preparation method and application thereof
Technical Field
The invention relates to the technical field of functional nano materials, in particular to a double-iron-based mesoporous carbon nano material integrating functions of nuclear magnetic imaging radiography and drug delivery, and a preparation method and application thereof.
Background
The diagnosis and treatment integrated nano material is a composite biomedical material integrating disease diagnosis and treatment functions, is a development direction of precise medical treatment, and is paid more and more attention by researchers in multiple fields. Nuclear magnetic resonance imaging contrast agents are divided into two categories: paramagnetic T1Weighted contrast agent and superparamagnetic T2The contrast agents are weighted. The combination of the nuclear magnetic imaging contrast agent and the porous material with the drug-loading function is a feasible method for developing the diagnosis and treatment integrated nano material.
Mesoporous carbon is a porous material with a mesoscopic ordered structure, and is one of the hot spots for the research of porous materials due to the characteristics of high specific surface area, adjustable pore channel structure and easy functionalization. On the other hand, because carbon has excellent biocompatibility, mesoporous carbon can be used as a carrier to be applied to the fields of biomedicine and the like, and has wide application value in the fields of biomedicine and pharmacy. The nuclear magnetic resonance imaging isA safe, rapid and accurate clinical diagnosis method without any harm to human body. In order to improve the sensitivity of nuclear magnetic resonance imaging, a contrast agent is required to be added during detection. As a contrast agent for magnetic resonance imaging, T is generally used1The materials of the contrast agent mainly include: chelate of gadolinium, GdPO4、Gd2O3、MnO2And the like. Albeit T1Contrast agents can brighten the image for clinical diagnosis, but gadolinium and manganese both have significant biological toxicity. T is2The weighted contrast agent materials consist essentially of: fe3O4、γ-Fe2O3And the like. Although iron-based materials have relatively good biocompatibility, T2The contrast agent darkens the image, and clinically, the contrast agent has low distinction degree with the artifact, so misdiagnosis is easy to cause. Therefore, the mesoporous nano material based on the iron-based nano particles is developed to realize T1And T2The set of weighted contrast imaging and drug delivery functions has wider prospect and application value.
Patent CN 106668878A discloses a set T1、T2The dual-mode integrated multifunctional mesoporous carbon spheres and the preparation method thereof, however, GdPO4 is mainly used as T in the above patent1A contrast agent. Research finds that the gadolinium contrast agent is easy to induce nephrogenic systemic fibrosis in the use process of a patient with nephropathy, and meanwhile, because gadolinium is a heavy metal and causes toxic and metal deposition and other side effects in the long-term use process, the gadolinium contrast agent can be used for replacing the gadolinium contrast agent and applied to T1Weighted imaging is imminent. While the iron element is an essential element of human body and has relatively good biocompatibility, a large number of reports show that the T can be improved by regulating the size of the iron-based nano particles1Weighting the imaging effect, but this also inevitably leads to T2Loss of signal. Based on this, it is of great significance to develop an iron-based dual-mode imaging contrast agent to circumvent Gd-based contrast agents.
Disclosure of Invention
The invention aims to solve the technical problems and provide a dual-iron-based mesoporous carbon nanomaterial integrating the functions of magnetic imaging radiography and drug delivery,the in vitro research of the functional mesoporous nano material shows that the functional mesoporous nano material has good biocompatibility and can enhance T1、T2The performance of magnetic resonance imaging, and the performance of delivering anticancer drug doxorubicin hydrochloride.
The invention also aims to provide a preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating the functions of magnetic imaging radiography and drug delivery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery is characterized in that contrast agent nanoparticles are uniformly wrapped in a carbon skeleton of mesoporous carbon, the mesoporous aperture of the dual-iron-based mesoporous carbon nanomaterial is 2-4 nm and has a two-dimensional hexagonal ordered mesostructure, the contrast agent nanoparticles are composed of paramagnetic iron metaphosphate and superparamagnetic gamma iron oxide nanoparticles, and the total mass content of the contrast agent nanoparticles is 0.5% -15% of that of the dual-iron-based mesoporous carbon nanomaterial.
Preferably, the particle size of the contrast agent nanoparticles is 1-20 nm, and the molar ratio of the paramagnetic iron metaphosphate to the superparamagnetic gamma iron oxide nanoparticles is 1: 4.
a preparation method of a double-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery comprises the following specific steps:
the method comprises the following steps: adding the solution dissolved with the iron cluster compound into a solution containing phenolic resin and a mesoporous pore-forming agent to prepare a uniformly mixed solution;
step two: preparing the mixed solution in the step one into a composite film by a volatilization induced self-assembly method;
step three: and roasting the composite film at high temperature in inert atmosphere, and performing surface hydrophilic treatment to obtain the double-iron-based mesoporous carbon nanomaterial integrating the functions of nuclear magnetic imaging radiography and drug delivery.
Preferably, the molecular formula of the iron cluster compound is: [ Fe ]9(μ3-O)4(O3PPh)3(O2CCMe3)13]The molecular weight is 2400-2500, most preferably 2413.5, and is crystallized in the monoclinic system, Cc space group.
Preferably, in the first step, the mass ratio of the iron cluster compound, the phenolic resin and the mesoporous pore-forming agent is 1 (20-100) to (3-16).
Preferably, in the first step, the mesoporous pore-forming agent is F127 or P123.
Preferably, in the step one, the solution in which the iron cluster compound is dissolved is one of THF, ethanol or acetone solution in which the iron cluster compound is dissolved, and the mass solubility of the iron cluster compound is 1.5-3 g/L; the solvent in the solution containing the phenolic resin and the mesoporous pore-forming agent is one of THF or ethanol.
Preferably, in the second step, the volatilization induces self-assembly, specifically, the solution obtained in the first step is spread in a culture dish, the thickness is kept to be not more than 3mm, then the solution is slowly volatilized, and then the culture dish is heated at 90-120 ℃ for 12-36 hours.
Preferably, in the third step, the inert atmosphere is at least one of nitrogen or VIII group gas, the high-temperature roasting carbonization temperature is 600-900 ℃, and the time is 2-5 hours; the surface hydrophilization treatment adopts 15 percent of H2O2And treating for 2 hours.
Double-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery in T1、T2Application in a dual-mode nuclear magnetic imaging radiography and drug-loading system.
Integrated T1The contrast agent is paramagnetic iron metaphosphate nanoparticles, integrated T2The contrast agent is superparamagnetic gamma iron oxide, iron metaphosphate and gamma iron oxide nanoparticles which are uniformly dispersed in the framework of mesoporous carbon.
In the present invention, we creatively select { Fe }9P3Successfully introduces two iron-based iron oxides of 5nm size and paramagnetic nano-particle iron metaphosphate as a metal precursorNanoparticles, successfully prepared a function in T1、T2Dual iron-based mesoporous carbon nanoparticles for dual mode MRI.
The invention provides a double-iron-based mesoporous carbon nano material T1/T2The nuclear magnetic resonance imaging performance is as follows: at 0.5T external field, T1The weighted imaging performance is 8-10 mM-1·s-1，T2The weighted imaging performance is 25-28 mM-1·s-1As the external field increases to 3.0T, T1The weighted imaging performance is reduced to 1-2 mM-1·s-1，T2The weighted imaging performance is increased to 85-95 mM-1·s-1。
The cytotoxicity and drug delivery performance of the double-iron-based mesoporous carbon nano material provided by the invention are as follows: after the obtained sample is incubated with HeLa cells for 4 hours, the CCK-8 method tests show that the cell survival rate is good, and the survival rate reaches 88 percent even in a high-concentration sample of 160 mu g/mL. Drug loading tests show that the material can load the antitumor drug adriamycin with the amount more than 100 mg/g. Drug delivery studies show that after the doxorubicin-loaded sample is incubated in HeLa cells for 0.5 hour, weak red fluorescence belonging to doxorubicin is observed in cytoplasm, and the red fluorescence is gradually enhanced with time, which indicates that the sample can deliver drugs into cells and has a certain slow release function.
Compared with the prior art, the double-iron-based mesoporous carbon nano material provided by the invention has the beneficial effects that:
(1) the invention provides a dual-iron-based mesoporous carbon nanomaterial for the first time, and T is realized1/T2Combination of magnetic imaging contrast with drug delivery functions.
(2) The invention provides a ferrous based mesoporous carbon nanomaterial, and contrast agent nanoparticles are paramagnetic iron metaphosphate and superparamagnetic gamma iron oxide which are uniformly wrapped in a carbon skeleton, so that the ferrous based mesoporous carbon nanomaterial has good biological safety.
(3) The invention provides a ferrous-based mesoporous carbon nanomaterial, which is prepared by one-step thermal decomposition of an iron cluster compound and phenolic resin, is disordered and fussy, prepares a mesoporous material, and introduces ferric metaphosphate and gamma iron oxide in steps, so that the ferrous-based mesoporous carbon nanomaterial is suitable for large-scale production.
(4) Compared with patent CN 106668878A, the invention adopts in-situ self-assembly technology to prepare the double-iron-based mesoporous carbon nano material by one-step thermal decomposition, skillfully avoids the trouble that solvent impregnation and adsorption may bring about agglomeration of nano particles, and has simple and effective preparation technology.
Drawings
FIG. 1 is a transmission electron microscope image of seven prepared dual-Fe-based mesoporous carbon nanomaterials.
Fig. 2 is a diagram of pore size distribution and specific surface area of seven prepared dual-iron-based mesoporous carbon nanomaterials.
FIG. 3 is an element distribution diagram of the prepared dual-Fe-based mesoporous carbon nanomaterial.
FIG. 4 is a high-resolution transmission electron microscope image of the prepared dual-Fe-based mesoporous carbon nanomaterial.
FIG. 5 is a nuclear magnetic resonance imaging data chart of the prepared dual-Fe-based mesoporous carbon nanomaterial.
Fig. 6 is a cytotoxicity data chart of the prepared dual-iron-based mesoporous carbon nanomaterial.
Fig. 7 is a data graph of drug loading of a prepared dual-iron-based mesoporous carbon nanomaterial.
Fig. 8 is a data diagram of cell drug delivery of a prepared dual-iron-based mesoporous carbon nanomaterial.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail.
Example 1
1) 0.1g F127 or equivalent P123 was dissolved in 5g tetrahydrofuran solution, then 0.6g (20 wt.%) of phenolic resole resin was added and stirred at room temperature for 0.5 h. Taking 24mg { Fe9P3The cluster was dissolved in 5g of tetrahydrofuran solution, and added to the above solution, and the mixed solution was stirred at room temperature for 2 hours to obtain a uniform reddish brown transparent solution.
2) Transferring the solution into a culture dish, volatilizing tetrahydrofuran at room temperature for 8h, and placing the culture dish in an oven at 100 ℃ for 24h to obtain the transparent dark red thin film material.
3) Scraping the material from a culture dish, grinding the material into powder, placing a sample in a tube furnace, roasting the sample for 3 hours at the temperature of 600 ℃ under the protection of high-purity nitrogen in an inert atmosphere, wherein the nitrogen flow is 90 ml/min–1The temperature rise rate is 1 ℃ min–1And obtaining the double-iron-based mesoporous carbon nano material.
The following specific examples 2-7 were prepared in the same manner as example 1, and the specific process parameters are shown in Table 1.
Table 1 examples 2-7 specific process parameters
Figure BDA0002646856430000051
The resulting product was tested and tested as follows:
FIG. 1 is a transmission electron microscope image of seven prepared dual-Fe-based mesoporous carbon nanomaterials in sequence, and it can be seen that the mesostructures of Fe/OMC-6-600 and Fe/OMC-12-600 samples are consistent with FDU-15, and very regular and parallel strip-shaped ordered mesoporous channels are presented, corresponding to the material [110 ]]The one-dimensional pore channels in the direction are arranged. The regularity of the mesostructure of the Fe/OMC-18-600 and Fe/OMC-24-600 samples is partially reduced, but the mesostructure is still presented as a strip-like ordered arrangement. In contrast, TEM images of Fe/OMC-30-600 samples showed significant distortion of the channel arrangement, indicating that the order of the mesostructure was destroyed. The grain size of the nano particles in the Fe/OMC-6-600 and Fe/OMC-12-600 samples is about 1-2 nm, and the nano particles are uniformly embedded in the carbon wall. The particle sizes of the nanoparticles in the Fe/OMC-18-600 and Fe/OMC-24-600 samples were 3nm and 5nm, respectively, and were uniformly dispersed in the carbon grid. Continue to increase { Fe9P3And (3) adding amount of the clusters, obviously increasing nano particles on the carbon material and having a particle size increasing trend, wherein TEM of a Fe/OMC-30-600 sample shows that the nano particles are obviously agglomerated, and the particle size reaches 20 nm. This result indicates that when { Fe }9P3When the adding amount of the cluster reaches 24mg, the synthesized Fe/OMC-24-600 sample can still maintain the ordered mesostructure and the dispersibility of the nano particles. In examining the differencesThe Fe/OMC-24-700 sample exhibited a [001 ] edge at the calcination temperature]Ordered structures with hexagonal arrangement in a wide range of directions. And TEM pictures of Fe/OMC-24-800 samples show that the strip-shaped pore channels are in fault and distortion. This result demonstrates that higher firing temperature can destroy the order of the composite material mesostructure and that TEM pictures show that the particle size of iron-based nanoparticles is gradually increased with the increase of firing temperature, and the particle size of nanoparticles in Fe/OMC-24-600, Fe/OMC-24-700 and Fe/OMC-24-800 samples is 5nm, 9nm and 15nm respectively.
The mesoporous structure of the sample is characterized by adopting a 77K nitrogen adsorption/desorption isotherm, and the test is carried out on an ASAP 2020 physical adsorption instrument. Before testing, the samples were degassed under vacuum at 200 ℃ for 10 hours beforehand. The specific surface area of the sample is calculated by a BET method, the pore size distribution is calculated by an isotherm desorption branch by a Barrett-Joyner-Halenda (BJH model), and figure 2 is a diagram of the pore size distribution and the specific surface area of seven double-iron-based mesoporous carbon nanomaterials, so that when { Fe is calculated, the pore size distribution and the specific surface area of the seven double-iron-based mesoporous carbon nanomaterials are shown in the figure9P3The adding amount of the clusters is increased from 0mg to 24mg, and the specific surface area of the mesoporous carbon composite material is increased from 730m2·g–1Becomes 662m2·g–1Pore volume from 0.37cm3·g–1Becomes 0.34cm3·g–1. When { Fe }9P3When the cluster is increased to 30mg, the specific surface area and the pore volume of the mesoporous carbon composite material are obviously reduced to 550m respectively2·g–1And 0.27cm3·g–1This is mainly related to the large density and reduced order of the mesopores of the iron-based material. It is known that as the firing temperature increases, the specific surface area and pore volume of the composite material increase significantly, mainly due to the increase in the micropore content of the mesoporous carbon skeleton.
Electron micrographs of the samples were taken with a field emission transmission electron microscope of the type Tecnai G2F 20S-Twin. The sample is prepared by ultrasonically dispersing the material in an ethanol solution for 10 minutes, and then dropping the material on a copper net or a nickel net to be dried for testing. From the results of the tests, it can be seen that the HAADF-STEM pictures of the Fe/OMC-24-600 sample show white circles, as shown in FIGS. 1, 3 and 4, as well as the high-resolution transmission electron micrograph, the high-angle annular dark field image-scanning transmission electron micrograph (HAADF-TEM), and the element distribution surface micrograph (EDS-mapping)The dots (i.e., nanoparticles) are uniformly dispersed in the carbon skeleton. EDS maps demonstrated uniform distribution of Fe, P, and O elements on the carbon material. HRTEM pictures showed that the nanoparticles were approximately 5nm, the characteristic lattice fringe spacing of the nanoparticles is indicated, 0.250nm and 0.278nm respectively correspond to gamma-Fe2O3And Fe (PO)3)3The lattice spacing of (a). From the HRTEM picture, gamma-Fe can be known2O3And Fe (PO)3)3Grown in situ in a mesoporous carbon skeleton.
Relaxation time T of the sample of example 11And T2The measurement was carried out on a 0.5T nuclear magnetic imager (MicroMRI, Nymei electronics, Inc. of Shanghai) at a test temperature of 32 ℃. In the determination of T1And T2In time, samples were prepared as aqueous solutions of different concentrations. T is1And T2The determination of (a) is carried out by an Inversion Recovery (IR) sequence and a CPMG sequence respectively; t is1And T2The weighted MRI images were acquired by Spin Echo (SE) sequence and Fast Spin Echo (FSE) sequence on the same instrument, respectively, at a test temperature of 32 deg.C, as shown in FIG. 5, it is known that r1Value of sum r2The value was 9.74mM-1·s-1And 26.59mM-1·s-1The results show that the material of the invention can be used as a contrast agent for T1、T2And (5) weighted nuclear magnetic imaging detection.
Cytotoxicity of the samples of example 1 was tested by the CCK-8 method as follows: HeLa cells were trypsinized and seeded in 96-well plates at 37 ℃ with 5% CO2Incubation was carried out for 24h under the conditions, and samples of example 1 were added at different concentrations, respectively, and incubation was continued for 4 h. Then, 10. mu.L of a dilution of CCK-8 medium was added to each well, the well plate was returned to an incubator at 37 ℃ for further incubation for about 2 hours, and viable cells were stained with CCK-8, and the OD at 450nm of each well was measured with a microplate reader (TECAN, Infinite M200, Germany), and the cell survival rate was calculated according to the following formula: cell survival (%) × (average absorbance in experimental group/average absorbance in control group) × 100%. As shown in FIG. 6, it can be seen that the cell viability can be maintained at 88% even when the concentration of the Fe/OMC-24-600 sample is as high as 160ug/mL, indicating that the Fe/OMC-24-600 sample has no obvious toxicity to the cells.
The sample of example 1 was vacuum activated at 200 ℃ for 10h before loading the drug doxorubicin hydrochloride (DOX) to remove the adsorbed material in the channels. 30mg of the obtained activated sample was dispersed in 2mL (1 mg. multidot.ml)–1) Then the mixture was stirred at room temperature for 12 hours in the dark. And finally, centrifugally separating, washing and collecting all upper-layer solutions of the material for UV-Vis analysis, measuring the absorbance value at the position of 481nm, and combining the concentration of the DOX solution before drug loading according to a DOX standard curve to obtain the drug loading rate of Fe/OMC-24-600. The above steps are repeated for the functionalized carbon pellets loaded with DOX until the adsorption saturation drug loading rate (%) of the material to doxorubicin hydrochloride is (drug content in drug-loaded nanoparticles/total amount of drug-loaded nanoparticles) × 100%, that is, as shown in fig. 7, it can be seen that the drug loading rate of Fe/OMC-24-600 is up to 112 mg/g.
Sample delivery of example 1 HeLa cells were used as effector cells and the uptake of drug loaded example 1 by HeLa cells was observed by fluorescence microscopy with the aid of blue fluorescence of DAPI. The method comprises the following steps: dispersing a certain amount of drug-loaded sample into DMEM culture solution with the concentration of 100 mu g/mL–1. The HeLa cells were then co-incubated with the material for 4h at 37 ℃, after which the medium was aspirated and the residual nanomaterial and solution washed out with PBS. After fixing the cells with 4% paraformaldehyde for 15min, washing with PBS for 3 times, adding DAPI, staining nuclei at 37 ℃ for 20min, washing with PBS for 2 times, and observing with a fluorescence microscope. As shown in FIG. 8, excitation wavelengths of doxorubicin and DAPI were 488nm and 405nm, respectively, and emission wavelengths were collected in the ranges of 580-680 and 550-650 nm.
The dual iron-based mesoporous carbon nanomaterials prepared in examples 2 to 7 were tested by the same method, and had similar effects to those of example 1.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are given by way of example only and are not limiting of the invention. The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A ferric base mesoporous carbon nano material integrating functions of magnetic imaging radiography and drug delivery is characterized in that the ferric base mesoporous carbon nano material is formed by uniformly wrapping contrast agent nano particles in a carbon skeleton of mesoporous carbon, the mesoporous aperture of the ferric base mesoporous carbon nano material is 2-4 nm, the ferric base mesoporous carbon nano material has a two-dimensional hexagonal ordered mesostructure, the contrast agent nano particles are composed of paramagnetic ferric phosphate and superparamagnetic gamma iron oxide nano particles, and the total mass content of the ferric base mesoporous carbon nano material is 0.5-15%.
2. The dual iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging contrast and drug delivery according to claim 1, wherein the particle size of contrast agent nanoparticles is 1-20 nm, and the molar ratio of paramagnetic iron metaphosphate to superparamagnetic gamma iron oxide nanoparticles is 1: 4.
3. the preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery according to claim 1, comprising the following specific steps of:
the method comprises the following steps: adding the solution dissolved with the iron cluster compound into a solution containing phenolic resin and a mesoporous pore-forming agent to prepare a uniformly mixed solution;
step two: preparing the mixed solution in the step one into a composite film by a volatilization induced self-assembly method;
step three: and roasting the composite film at high temperature in inert atmosphere, and performing surface hydrophilic treatment to obtain the double-iron-based mesoporous carbon nanomaterial integrating the functions of nuclear magnetic imaging radiography and drug delivery.
4. Set NMR imaging apparatus according to claim 3The preparation method of the double-iron-based mesoporous carbon nanomaterial with integrated shadow and drug delivery functions is characterized in that the molecular general formula of the iron cluster compound is as follows: [ Fe ]9(μ3-O)4(O3PPh)3(O2CCMe3)13]The molecular weight was 2400-.
5. The preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery according to claim 3, wherein in the first step, the mass ratio of the iron cluster compound, the phenolic resin and the mesoporous pore-forming agent is 1 (20-100) to (3-16).
6. The method for preparing a dual iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery according to claim 3, wherein in the first step, the mesoporous pore-forming agent is F127 or P123.
7. The preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging contrast and drug delivery according to claim 3, wherein in the first step, the solution in which the iron cluster compound is dissolved is one of THF (tetrahydrofuran), ethanol or acetone solution in which the iron cluster compound is dissolved, and the mass solubility of the iron cluster compound is 1.5-3 g/L; the solvent in the solution containing the phenolic resin and the mesoporous pore-forming agent is one of THF or ethanol.
8. The preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery according to claim 3, wherein in the second step, volatilization induces self-assembly, specifically, the solution obtained in the first step is spread in a culture dish, the thickness is kept to be not more than 3mm, the solution is slowly volatilized, and the culture dish is heated at 90-120 ℃ for 12-36 hours.
9. The preparation method of the dual-iron-based mesoporous carbon nanomaterial integrating functions of magnetic imaging radiography and drug delivery according to claim 3, wherein in the third step, the inert atmosphere is at least one of nitrogen or VIII group gas, the high-temperature roasting carbonization temperature is 600-900 ℃, and the time is 2-5 hours; the surface hydrophilic treatment is dipping for 2 hours by adopting hydrogen peroxide.
10. The dual-Fe-based mesoporous carbon nanomaterial integrating functions of magnetic imaging contrast and drug delivery as claimed in claim 1 or 2, wherein T is the number of atoms of the material1、T2Application in a dual-mode nuclear magnetic imaging radiography and drug-loading system.
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