CN111298141A - Iron and dopamine coordination-based nanoparticle photothermal conversion material and preparation method and application thereof - Google Patents
Iron and dopamine coordination-based nanoparticle photothermal conversion material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photothermal conversion materials, and discloses a nanoparticle photothermal conversion material based on coordination of iron and dopamine, and a preparation method and application thereof. The preparation method comprises the following operation steps: firstly, preparing a nano-level iron-based metal organic framework by using a hydrothermal synthesis method; and then combining the dopamine in the nanoscale iron-based metal organic framework through the coordination of phenolic hydroxyl on the dopamine and iron on the iron-based metal organic framework under the action of a coordination bond to obtain the iron and dopamine coordination-based nanoparticle photothermal conversion material. The material can be well applied to photothermal therapy medicine preparation, photoacoustic imaging, nuclear magnetic imaging, medicine loading or functional modification.
Description
Technical Field
The invention belongs to the technical field of photothermal conversion materials, and particularly relates to a nanoparticle photothermal conversion material based on coordination of iron and dopamine, and a preparation method and application thereof.
Background
As one of the important methods for constructing nano materials, chemical self-assembly is widely focused and applied in molecular catalysis, energy materials and surface engineering, particularly in the fields of life science and nano medicine. During the self-assembly process, the basic building blocks are organized or aggregated into a stable structure through noncovalent interactions. Transition metal-ligand coordination has received much attention because of its ease of design and control, as compared to hydrogen bonding, pi-pi interactions, electrostatic interactions, and dipolar interactions. Chemical self-assembly combines the rich reactivity of transition metal ions with highly structured ligands for selective directed coordination transformations. On the one hand, the transition metal ions themselves have excellent properties, and the unsaturated coordination sites of the metal ions provide more possibilities for further functionalization. On the other hand, the functional groups of the ligand are capable of hydrogen bonding, electrostatic, hydrophobic and steric interactions with the substrate. The combination of these elements can in turn impart unique physical and chemical properties to the nanomaterial through the synthesized structure.
The metal center accepting the external electron pair and the organic ligand with rich functional groups play a very critical role in the coordinately driven self-assembly, i.e. the spontaneous formation of a metal-ligand bond between the lewis acid acceptor (metal) and the lewis basic donor (organic ligand). The self-assembly process is usually carried out spontaneously in a solvent environment under certain conditions, which also results in the inability of fine manual control of the synthesis process. During the preparation process, due to steric hindrance and the like, metal ions can be coordinated with large organic ligands and can be combined with small solvent molecules to meet the requirement of coordination numbers of the large organic ligands, such as water, ethanol, methanol, DMF and the like. In addition, these small molecules sometimes also bind to organic ligands in the form of weak interactions (mostly hydrogen bonds).
Nanomaterials utilize a large number of metal ions, ligands and substrates to achieve a large amount of reactivity, wherein the reactivity of the coordination compounds is based primarily on modulation of their redox properties, substrate accessibility and/or lewis acidity of their metal centers. This is achieved by modulating the donor/acceptor characteristics of the ligands and by controlling their geometry and arrangement around the metal center. In recent years, the treatment of tumors by combining nano-materials with photothermal therapy (i.e., thermotherapy) has received great attention.
Photothermal Therapy (PTT) is a method of locally heating a tumor part to change the environment of tumor cells and enable the tumor cells to undergo programmed apoptosis or necrosis, thereby achieving the purpose of treatment. When the temperature at the tissue site rises above 42 ℃, the cells initiate a programmed apoptosis mechanism and when the temperature rises further above 45 ℃ the cells will necrose. The degree of cell damage caused by thermal energy depends on the temperature and the time of exposure to thermal energy, which is particularly evident for tumor cells. The key point of photothermal therapy is the nanomaterial with good photothermal conversion efficiency. In the construction process of the coordination compound, coordination nanoparticles with high light-heat conversion efficiency can be constructed through reasonable design.
However, the current research focuses more on the use of the properties of the precursor materials to construct nanoparticles, and the functions of the synthesized nanoparticles depend on the properties of the precursor compounds, so that it is difficult to develop and apply new functions, or load photosensitizers or thermosensitive agents and chemotherapeutic drugs inside the nanoparticles. These methods usually require complicated synthesis steps, are high in synthesis energy consumption, and the photothermal conversion performance and the treatment capacity of the material are more dependent on the loading capacity of the nano material and the amount of the loaded drug. Meanwhile, more biotoxic components can be introduced by an excessively complex construction scheme, so that the further application of the compound in the field of biological medicine is limited. In addition, methods for forming nanoparticles based on coordination of iron and polyphenols have been reported in part (Naturecommunications,2015,6, 8003; Advanced health materials, 2016,5, 772; nanoscales, 2017,9, 12609; International Journal of Nanomedicine, 2017, 12, 7207; Small, 2018,14,1702700), however, this class of materials does not have a stable coordination structure, requires the addition of a large amount of stabilizer during synthesis to form nanoparticles, and is difficult to control in morphology and particle size. Therefore, a novel nano material which is simple and convenient to synthesize, low in price, good in biocompatibility and more important, and has good photo-thermal conversion capability is urgently needed to be searched.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary object of the present invention is to provide a method for preparing nanoparticle photothermal conversion material based on coordination of iron and dopamine.
The invention further aims to provide the nanoparticle photothermal conversion material based on coordination of iron and dopamine, which is prepared by the preparation method.
Still another object of the present invention is to provide the application of the nanoparticle photothermal conversion material based on coordination of iron and dopamine.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nanoparticle photothermal conversion material based on iron and dopamine coordination comprises the following operation steps: firstly, preparing a nano-level iron-based metal organic framework (Fe-MOFs) by a hydrothermal synthesis method; and then combining dopamine in the nanoscale iron-based metal organic framework through the coordination of phenolic hydroxyl on the dopamine and iron on the nanoscale iron-based metal organic framework under the action of a coordination bond to obtain the iron and dopamine coordination-based nanoparticle photothermal conversion material (DA-Fe-MOFs).
The preparation method of the nanoparticle photothermal conversion material based on iron and dopamine coordination specifically comprises the following operation steps:
(1) 9.72g of ferric chloride hexahydrate (FeCl) was weighed3·6H2O) and 3.24g of trimesic acid (trimesic acid) are fully dissolved in 120mL of pure water, and are stirred and mixed uniformly to obtain a mixed solution;
(2) transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 36-48 h at 130 ℃, obtaining brown yellow suspension after the reaction is finished, naturally cooling to room temperature, removing supernatant through centrifugation, repeatedly washing and centrifuging the precipitate by using methanol and water, wherein the centrifugation speed is 8000-10000r/min, and the centrifugation time is 10-20min each time until the supernatant is basically colorless; drying the solid obtained by centrifugation in an oven at 60-70 ℃ to obtain brown yellow powder, namely the nano-scale iron-based metal organic framework; drying the nanoscale iron-based metal organic frame at the temperature of 130-140 ℃ overnight to remove the bound water in the material and fully activate the material;
(3) weighing 0.4g of the nanoscale iron-based metal organic framework obtained in the step (2) and 0.2g of dopamine hydrochloride (DA & HCl), dispersing the nanoscale iron-based metal organic framework and the dopamine hydrochloride in a mixed solvent of 50mL of anhydrous methanol and anhydrous Tetrahydrofuran (THF), then adding 0.1g of sodium hydride (NaH), stirring at the stirring speed of 1000-2000r/min at room temperature in a dark place under the protection of nitrogen for 24 hours, and obtaining a dark purple suspension after the reaction is finished;
(4) carrying out rotary evaporation on the dark purple suspension obtained in the step (3), wherein the rotating speed is 100r/min, the temperature is 45 ℃, and removing the solvent to obtain dark purple powder; repeatedly washing and centrifuging for 3-6 times by using methanol and water, wherein the centrifugation rotation speed is 8000-10000r/min, the centrifugation time is 10-20min each time, wrapping the obtained precipitate by using common filter paper, putting the wrapped precipitate into a Soxhlet extractor, refluxing for 24h by using methanol for purification, drying the obtained dark purple solid powder to obtain the nanoparticle photothermal conversion material based on coordination of iron and dopamine, and storing the material at the temperature of 4 ℃ in a dark place.
The mass ratio of ferric trichloride hexahydrate to benzenetricarboxylic acid in the step (1) in the reaction is 3:1, and the ferric trichloride hexahydrate and the benzenetricarboxylic acid can be increased or decreased in proportion in a proper amount under the condition of ensuring complete water solubility.
The times of repeated washing and centrifugation in the step (2) are 3-6 times; the number of times of repeated washing and centrifugation in the step (4) is 3-6 times.
The mass ratio of the nanoscale iron-based metal organic framework in the step (3) to the dopamine hydrochloride and the sodium hydride in the reaction is 4:2:1, and the nanoscale iron-based metal organic framework can be increased or decreased proportionally and properly under the same conditions.
In the mixed solvent of the anhydrous methanol and the anhydrous tetrahydrofuran in the step (3), the volume ratio of the anhydrous methanol to the anhydrous tetrahydrofuran is 1: 1.
all operations and conditions in the step (3) are carried out under the conditions of no water and no oxygen and under the protection of nitrogen, all reagents are anhydrous reagents which are prepared on site, and nitrogen is introduced for 30-60 min to remove dissolved oxygen before use.
The nanoparticle photothermal conversion material based on coordination of iron and dopamine, which is prepared by the preparation method, has the particle size of below 200 nm.
The iron and dopamine coordination based nanoparticle photothermal conversion material is applied to photothermal therapy drug preparation, photoacoustic imaging, nuclear magnetic imaging, drug loading or functional modification.
Before the iron and dopamine coordination based nanoparticle photothermal conversion material is applied, phospholipid polyethylene glycol (DSPE-mPEG) is modified on the material to enhance the biocompatibility of the material, and the method comprises the following specific steps: mixing the iron and dopamine coordination based nanoparticle photothermal conversion material with phospholipid polyethylene glycol according to the mass ratio of 1:1, and stirring at room temperature in a dark place for 24 hours at the rotating speed of 1000r/min to obtain DA-Fe-MOF-PEG.
The principle of the invention is as follows:
around the difficulties and challenges of the existing photothermal conversion nano material in the application research of biomedical diagnosis and treatment, the invention aims to endow the material with new functions according to the reasonable design of coordination bonds from the perspective of coordination chemistry, construct the photothermal conversion nano material with high biocompatibility, high biological utilization efficiency and high diagnosis and treatment efficiency, and develop the research of living tumor treatment. The invention synthesizes materials with high photothermal conversion efficiency according to key points (formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds) and excellent structural performance of molecular structure formation in coordination chemistry, thereby realizing photothermal therapy and photoacoustic imaging. The particle size of the synthesized nano particles is below 200nm, the nano particles have good stability and low biotoxicity in a body fluid environment, and the nano particles can be used as a good reagent for tumor photothermal therapy without other medicines or heat-sensitive agents.
Compared with the prior art, the invention has the following advantages and effects:
(1) at present, the application of the photothermal conversion material in the biomedical field mainly focuses on encapsulating and releasing drug models such as photosensitizer or thermosensitive agent in nano particles, and the schemes mainly depend on the excellent performance of the loaded chemical reagent; the invention makes the material have excellent photo-thermal conversion efficiency by designing the molecular structure, can directly carry out photo-thermal treatment on the tumor without loading other drug molecules, and simplifies the existing report.
(2) The DA-Fe-MOF nano photothermal conversion material prepared by the invention has good photothermal conversion performance, can effectively raise the temperature under the laser irradiation of a near infrared band (808nm), and the photothermal conversion efficiency can reach more than 40% through calculation, so that cancer cells are effectively killed;
(3) the DA-Fe-MOF nano photothermal conversion material prepared by the invention has excellent photothermal stability and biocompatibility, has extremely low biotoxicity to normal cells, and has good biological stability in a body fluid environment.
(4) The preparation method is simple and quick, and expensive instruments and equipment are not needed; the material is green and environment-friendly, the preparation raw materials have no biotoxicity, and reagents which affect the environment such as organic surfactants and the like do not need to be added in the preparation process; the preparation cost is low, and the raw materials are low in cost and easy to obtain.
(5) The DA-Fe-MOF nano photothermal conversion material prepared by the invention has good morphology and nano-scale size, the particle size distribution is uniform, and the addition of common stabilizers such as polyvinylpyrrolidone (PVP) and the like is not needed in the synthesis process.
(6) The DA-Fe-MOF nano photothermal conversion material prepared by the invention has the characteristics of large aperture and large specific surface area, a large number of potential sites for drug loading and modification are arranged on the surface and inside the aperture, and the iron element in the material has good magnetic resonance characteristics and potential nuclear magnetic resonance imaging capability. The material has very wide application prospect in the field of the biomedicine integrating photothermal therapy and tumor diagnosis and treatment.
(7) The DA-Fe-MOF nano photothermal conversion material prepared by the invention has good photoacoustic imaging capability. Can realize good photoacoustic radiography under low concentration, and has great potential in the fields of photoacoustic imaging in vivo, photoacoustic guided tumor treatment and the like.
The material has very wide application prospect in the field of the biomedicine integrating photothermal therapy and tumor diagnosis and treatment due to the advantages.
Drawings
FIG. 1 is the hydrated particle size test results for Fe-MOF prepared in the inventive examples;
FIG. 2 is the result of a hydrated particle size test of DA-Fe-MOF prepared in the inventive example;
FIG. 3 is a transmission electron micrograph of Fe-MOF prepared in the inventive example;
FIG. 4 is a transmission electron micrograph of DA-Fe-MOF prepared in the inventive example;
FIG. 5 shows the results of photothermal testing of DA-Fe-MOF prepared in the examples of the invention;
FIG. 6 shows the results of the photothermal cycling stability test of DA-Fe-MOF prepared in the examples of the present invention;
FIG. 7 shows the results of cell viability tests of Fe-MOF, DA-Fe-MOF, DA-Fe-MOF-PEG prepared in the examples of the present invention;
FIG. 8 shows photothermal therapy test results for DA-Fe-MOF-PEG prepared in the examples of the present invention;
FIG. 9 shows the result of photoacoustic imaging test of DA-Fe-MOF-PEG prepared in the example of the present invention.
Detailed description of the invention
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1:
a preparation method of a nanoparticle photothermal conversion material based on iron and dopamine coordination specifically comprises the following operation steps:
(1) 9.72g of ferric chloride hexahydrate (FeCl) was weighed3·6H2O) and 3.24g of trimesic acid (trimesic acid) are fully dissolved in 120mL of pure water, and are stirred and mixed uniformly to obtain a mixed solution;
(2) transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 36-48 h at 130 ℃, obtaining brown yellow suspension after the reaction is finished, naturally cooling to room temperature, removing supernatant through centrifugation, repeatedly washing and centrifuging the precipitate for 3-6 times by using methanol and water, wherein the centrifugation speed is 8000 plus 10000r/min, and the centrifugation time is 10-20min each time until the supernatant is basically colorless; drying the solid obtained by centrifugation in an oven at 60-70 ℃ to obtain brown yellow powder, namely the nano-scale iron-based metal organic framework (Fe-MOF); drying the nanoscale iron-based metal-organic frame at 130 ℃ overnight to remove the bound water in the material and fully activate the material; as shown in FIG. 1, the synthesized nano-scale iron-based metal organic framework (Fe-MOF) has a hydrated particle size of about 160 nm; as shown in fig. 3, the synthesized nanoparticles have good water dispersibility and regular morphology;
(3) weighing 0.4g of the nanoscale iron-based metal organic framework obtained in the step (2) and 0.2g of dopamine hydrochloride (DA & HCl), dispersing the nanoscale iron-based metal organic framework and 0.2g of dopamine hydrochloride in a mixed solvent of 50mL of anhydrous methanol and anhydrous tetrahydrofuran (the volume ratio of the anhydrous methanol to the anhydrous tetrahydrofuran is 1: 1), adding 0.1g of sodium hydride (NaH), stirring and reacting at room temperature in a dark place for 24 hours under the protection of nitrogen, wherein the stirring speed is 2000r/min in a stirring manner, and obtaining a dark purple suspension after the reaction is finished; all operations and conditions in the step are carried out under the protection of anhydrous oxygen-free nitrogen, all reagents are anhydrous reagents, the reagents are prepared at present, and nitrogen is introduced for 30-60 min to remove dissolved oxygen before use
(4) Carrying out rotary evaporation on the dark purple suspension obtained in the step (3), wherein the rotating speed is 100r/min, the temperature is 45 ℃, and removing the solvent to obtain dark purple powder; repeatedly cleaning and centrifuging for 3-6 times by using methanol and water, wherein the centrifugation rotation speed is 8000-10000r/min, the centrifugation time is 10-20min each time, wrapping the obtained precipitate by using common filter paper, putting the wrapped precipitate into a Soxhlet extractor, refluxing for 24h by using methanol for purification, drying the obtained dark purple solid powder, and obtaining the nanoparticle photothermal conversion material DA-Fe-MOF based on coordination of iron and dopamine, and storing the obtained product at the temperature of 4 ℃ in a dark place. As shown in figure 2, the hydrated particle size of the synthesized nano-grade iron-based metal organic framework (DA-Fe-MOF) is about 160nm, and as shown in figure 4, the synthesized nano-particles have good water dispersibility, regular morphology and uniform size.
Example 2
The photothermal therapeutic effect of the DA-Fe-MOF-PEG loaded nanomaterial prepared in example 1 was further examined below.
1. Test of photothermal conversion ability
The method comprises the following steps: preparing the prepared DA-Fe-MOF-PEG nano material into PBS solution with a certain gradient concentration by using PBS buffer salt, wherein the material concentrations are respectively 0, 100,200,300, 500 and 800 mu g/mL, respectively placing 2mL of the solution into a quartz cuvette, and using near-infrared laser with the wavelength of 808nm to irradiate the solution at the wavelength of 2W/cm2Irradiating for 10min under the laser power of (1), and detecting the temperature rising capability of the material. Meanwhile, a material solution with the concentration of 400 mu g/mL is taken to repeat 5 times of heating tests, and the photo-thermal stability of the material solution is verified.
As a result: as shown in FIG. 5, the material of the present invention has good photothermal conversion ability under the irradiation of near-infrared laser. When the concentration is more than 500 mug/mL, the final concentration of temperature rise can reach more than 40 ℃. Meanwhile, the nanoparticles synthesized by the method have good photo-thermal stability, as shown in fig. 6, the nanoparticles still have good photo-thermal conversion effect after 5 repeated photo-thermal conversion tests, and the photo-thermal stability of the material is good. The photothermal conversion efficiency was calculated to be about 40.78%.
2. Material cytotoxicity test
The method comprises the following steps: the normal human kidney epithelial cell line 293T cell line is selected, and the cell culture method is not particularly limited as long as it is a method well known to those skilled in the art. In the present invention, cells were allowed to contain 5% (v/v) CO at 37 ℃2The culture medium is DMEM medium containing 10% inactivated fetal calf serum. Use of 293T cells for cytotoxicityAnd (6) testing. First, the cells were cultured at 1X 104The density of (2) was inoculated in a 96-well plate, and 200. mu.L of a culture medium (DMEM containing 10% inactivated fetal bovine serum) was added to each well. Place 96-well plates at 37 ℃ with 5% (v/v) CO2The culture box is used for culturing for 24 hours. Cells were replaced with fresh medium at 200. mu.L per well. 293T cells are cultured in a 96-well plate until the cells adhere to the wall, a DMEM culture medium is used for preparing DA-Fe-MOF-PEG culture medium mixed liquid containing materials with certain concentrations, the material concentrations are respectively 0,5, 10, 50, 100,200,300,400,500, 800 and 1000 mu g/mL, DA-Fe-MOF-PEG and 293T cells are incubated for 24 hours, and nanoparticles are made to fully enter the cells through endocytosis. Cell viability was determined using the thiazole blue colorimetric method well known to those skilled in the art. The culture medium was discarded, washed 2 times with PBS buffer, and then fresh culture medium was added. mu.L of 5mg/mL 3- (4, 5-dimethylthiazole-2) -2, 5-diphenyltetrazolium bromide (MTT) solution was added to each well, the solution in the wells was discarded after 4h incubation in an incubator, and 150. mu.L dimethyl sulfoxide (DMSO) was added to each well. The absorbance of each well at 490nm was measured using a microplate reader with shaking for 5min before measurement. Cell viability was calculated according to the following formula:
cell viability (%) - (sample A/blank) X100%
As a result: as shown in FIG. 7, the materials at different concentrations did not exhibit significant cytotoxicity after 24h of incubation with 293T cells, and the cells treated with the materials still had considerably higher cell activity than the cells in the normal culture environment.
3. Photothermal therapy effect detection
The method comprises the following steps: the 4T1 cell line is selected, and the cell culture method is not particularly limited as long as it is a method well known to those skilled in the art. In the present invention, it is preferred that the cells contain 5% (v/v) CO at 37 ℃2The culture medium is DMEM medium containing 10% inactivated fetal calf serum. 4T1 cells were used for cytotoxicity assays. First, the cells were cultured at 1X 103The density of (2) was inoculated in a 96-well plate, and 200. mu.L of a culture medium (DMEM containing 10% inactivated fetal bovine serum) was added to each well. The 96-well plate was placed in an incubator containing 5% (v/v) CO2 at 37 ℃ for cultureAnd (5) cultivating for 24 hours. Cells were replaced with fresh medium at 200. mu.L per well. After 4T1 cells are cultured in a 96-well plate until the cells adhere to the wall, a DMEM culture medium is used for preparing DA-Fe-MOF-PEG culture medium mixed liquid containing materials with certain concentrations, the material concentrations are respectively 0, 10, 25, 50, 100,200,300,400 and 500 mu g/mL, DA-Fe-MOF-PEG and 4T1 cells are incubated for 24 hours, and the nanoparticles are made to fully enter the cells through endocytosis. 4T1 cells were divided into 4 groups and treated as follows: adding DPBS (blank control group) into the culture medium, performing only 808nm laser irradiation without adding any reagent (laser group), adding DA-Fe-MOF-PEG of the invention without performing 808nm laser irradiation (material group), adding DA-Fe-MOF-PEG and performing 808 near infrared irradiation (treatment group). In the laser group and the treatment group, cells (808nm, 2W/cm) were irradiated with an infrared semiconductor laser2) And 5 min. Cell viability following cell treatment was determined using thiazole blue colorimetry, which is well known to those skilled in the art. The culture medium was discarded, washed 2 times with PBS buffer, and then fresh culture medium was added. mu.L of 5mg/mL MTT solution was added to each well, incubated in an incubator for 4h and the well liquid was discarded, and 150. mu.L DMSO was added to each well. The absorbance of each well at 490nm was measured using a microplate reader with shaking for 5min before measurement. Cell viability was calculated according to the following formula:
cell viability (%) - (sample A/blank) X100%
As a result: as shown in FIG. 8, the control group, the laser group and the material group did not cause significant cell death, and the survival rate of 4T1 cells was significantly reduced after laser irradiation, and gradually decreased with increasing concentration after 808nm near-infrared irradiation, and decreased to less than 10% when the concentration was greater than 400. mu.g/mL. The result shows that DA-Fe-MOF-PEG has more excellent biocompatibility and higher photothermal conversion efficiency, and after 4T1 cells are treated by the DA-Fe-MOF-PEG nano material, the tumor cells can be effectively killed by increasing the environmental temperature of the tumor cells under the irradiation of near infrared light.
4. Photoacoustic imaging test
The method comprises the following steps: the test method is not particularly limited, and may be any method known to those skilled in the art. And (3) testing conditions are as follows: the wavelength range is set to be 600-950 nm, preferably 800nm, and the background absorption is set to be 950 nm. And preparing the prepared DA-Fe-MOF-PEG nano material into a solution with a certain gradient concentration by using pure water, wherein the material concentration is respectively 100,200,300,400 and 500 mu g/mL, respectively placing the solution into a photoacoustic test die body, and detecting by using a photoacoustic imager.
As a result: as shown in fig. 9, the nanoparticles prepared by the present invention have good photoacoustic imaging capability, and as the concentration increases, the photoacoustic signal gradually increases, showing concentration dependence.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a nanoparticle photothermal conversion material based on iron and dopamine coordination is characterized by comprising the following operation steps: firstly, preparing a nano-level iron-based metal organic framework by using a hydrothermal synthesis method; and then combining dopamine in the nanoscale iron-based metal organic framework through the coordination of phenolic hydroxyl on the dopamine and iron on the nanoscale iron-based metal organic framework under the action of a coordination bond to obtain the iron and dopamine coordination-based nanoparticle photothermal conversion material.
2. The preparation method according to claim 1, characterized by comprising the following steps:
(1) weighing 9.72g of ferric trichloride hexahydrate and 3.24g of benzenetricarboxylic acid, fully dissolving in 120mL of pure water, and uniformly stirring and mixing to obtain a mixed solution;
(2) transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 36-48 h at 130 ℃, obtaining brown yellow suspension after the reaction is finished, naturally cooling to room temperature, removing supernatant through centrifugation, repeatedly washing and centrifuging the precipitate by using methanol and water, wherein the centrifugation speed is 8000-10000r/min, and the centrifugation time is 10-20min each time until the supernatant is basically colorless; drying the solid obtained by centrifugation in an oven at 60-70 ℃ to obtain brown yellow powder, namely the nano-scale iron-based metal organic framework; drying the nanoscale iron-based metal organic frame at the temperature of 130-140 ℃ overnight to remove the bound water in the material and fully activate the material;
(3) weighing 0.4g of the nanoscale iron-based metal organic framework obtained in the step (2) and 0.2g of dopamine hydrochloride, dispersing the nanoscale iron-based metal organic framework and the dopamine hydrochloride into 50mL of a mixed solvent of anhydrous methanol and anhydrous tetrahydrofuran, then adding 0.1g of sodium hydride, stirring at the stirring speed of 1000-2000r/min at room temperature in a dark place under the protection of nitrogen, and reacting for 24 hours to obtain a dark purple suspension after the reaction is finished;
(4) carrying out rotary evaporation on the dark purple suspension obtained in the step (3), wherein the rotating speed is 100r/min, the temperature is 45 ℃, and removing the solvent to obtain dark purple powder; repeatedly washing and centrifuging for 3-6 times by using methanol and water, wherein the centrifugation rotation speed is 8000-10000r/min, the centrifugation time is 10-20min each time, wrapping the obtained precipitate by using common filter paper, putting the wrapped precipitate into a Soxhlet extractor, refluxing for 24h by using methanol for purification, drying the obtained dark purple solid powder to obtain the nanoparticle photothermal conversion material based on coordination of iron and dopamine, and storing the material at the temperature of 4 ℃ in a dark place.
3. The method of claim 2, wherein: the times of repeated washing and centrifugation in the step (2) are 3-6 times; the number of times of repeated washing and centrifugation in the step (4) is 3-6 times.
4. The method of claim 2, wherein: in the mixed solvent of the anhydrous methanol and the anhydrous tetrahydrofuran in the step (3), the volume ratio of the anhydrous methanol to the anhydrous tetrahydrofuran is 1: 1.
5. the method of claim 2, wherein: all operations and conditions in the step (3) are carried out under the conditions of no water and no oxygen and under the protection of nitrogen, all reagents are anhydrous reagents which are prepared on site, and nitrogen is introduced for 30-60 min to remove dissolved oxygen before use.
6. An iron and dopamine coordination-based nanoparticle photothermal conversion material prepared by the preparation method according to any one of claims 1 to 5, characterized in that: the particle size of the material is below 200 nm.
7. Use of the nanoparticle photothermal conversion material based on iron and dopamine complexation according to claim 6 in photothermal therapy drug preparation, photoacoustic imaging, nuclear magnetic imaging, drug loading or functional modification.
8. Use according to claim 7, characterized in that: before the nano-particle photothermal conversion material based on iron and dopamine coordination is applied, phospholipid polyethylene glycol is modified on the material to enhance the biocompatibility of the material, and the method specifically comprises the following steps: mixing the iron and dopamine coordination based nanoparticle photothermal conversion material with phospholipid polyethylene glycol according to the mass ratio of 1:1, and stirring at room temperature in a dark place for 24 hours at the rotating speed of 1000r/min to obtain DA-Fe-MOF-PEG.
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