CN111375061B - Prussian blue and aminated UIO-66 hybrid material and preparation method and application thereof - Google Patents
Prussian blue and aminated UIO-66 hybrid material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Prussian blue and aminated UIO-66 hybrid material, a preparation method and application thereof, wherein the hybrid material is Prussian blue nanoparticle modified UIO-66-NH2Porous material composed of nanoparticles. The preparation method of the hybrid material comprises the following steps: adding prussian blue nano-particles, 2-amino terephthalic acid and zirconium chloride into dimethylformamide, stirring uniformly to obtain turbid liquid, carrying out hydrothermal reaction on the turbid liquid at the temperature of 80-120 ℃ for 20-24h, centrifuging, washing and drying after the reaction is finished, thus obtaining the hybrid material of prussian blue and aminated UIO-66. The hybrid material can catalyze H2O2Production of O2The hybrid material can reduce the drug resistance of the anti-tumor drug, realize the synergistic treatment of photothermal treatment and chemotherapy on hypoxic tumor cells, and improve the anti-cancer efficiency, so the hybrid material can be used for preparing the anti-tumor drug. The preparation method of the hybrid material is simple, convenient to operate and low in preparation cost.
Description
Technical Field
The invention relates to the technical field of antitumor drugs, and particularly relates to a prussian blue and aminated UIO-66 hybrid material, and a preparation method and application thereof.
Background
Cancer is still one of the main threats to human health at present, and how to improve the treatment efficiency of cancer is always the research direction of researchers.
Among the reported MOFs for drug delivery, UIO-66 has a good application due to its high biocompatibility and biosafety. Based on that the pH value of cancer cells is lower than that of normal cells, ligand terephthalic acid is changed into other functional groups 2-amino terephthalic acid to coordinate with Zr, a Zr metal organic framework material with corresponding pH can be prepared, and after drug loading, the anticancer drug is subjected to pH controllable release, is released in the cancer cells, and reduces the toxicity to the normal cells.
However, since the oxygen content of tumor cells is low, the long-term use of anticancer drugs can generate drug resistance, resulting in the decrease of the tumor treatment efficiency of the drugs. Therefore, there is a need to improve drug resistance and to assist other therapies to improve the efficacy of treatment of drug resistant tumors.
Compared with normal cells, a large amount of H is accumulated in tumor cells2O2However, one of the common problems in chemotherapy treatment of tumors is drug resistance, which causes many factors of drug resistance, and hypoxia is one of them, and under the condition of insufficient oxygen, the expression of drug-resistant proteins such as P-glycoprotein and multidrug resistance-related proteins is often caused. Thus, catalytically decomposing H in tumor cells2O2Production of O2And the method helps to avoid the related problems caused by tumor hypoxia.
On the other hand, Photothermal therapy (PTT) is a novel treatment method that is non-invasive and does not produce toxic and side effects accompanying radiotherapy and chemotherapy, and theoretically can treat all solid tumors, and Photothermal therapy is to selectively accumulate photosensitizers to tumor sites and then apply near-infrared illumination to local tumor sites. In the process of illumination, the photosensitizer absorbs near infrared light and efficiently converts the near infrared light into heat energy, so that local high temperature (over 42 ℃) is generated in the tumor, and the temperature exceeds the survival temperature of cells, and the cells are killed, thereby achieving the purpose of treatment. Because the photosensitizer distribution of normal tissues around the tumor is very little, and excessive temperature can not be generated, normal cells are not damaged, and the safety and the effectiveness of the photosensitizer in treatment are ensured. Factors influencing the photo-thermal performance of the material are considered, so that the photo-thermal treatment is better applied to the field of cancer treatment, and further has important significance for benefiting mankind.
Prussian blue, also known as iron blue, is an ancient blue dye, and is widely applied to various fields due to excellent properties of photo-physics, magnetism, electrochemistry, structure and the like. The Prussian blue is a classical complex, a ligand of the Prussian blue is six cyano groups, a central ion is a ferrous ion, the cyano groups and the ferrous ion form a hexacyanoferrate (II) acid radical (showing negative 4 valence on the whole) serving as an inner coordination layer (inner boundary) of the Prussian blue together through coordination bonds, and an outer trivalent iron ion and a potassium ion serving as an outer coordination layer (outer boundary) of the Prussian blue are connected with the hexacyanoferrate (II) acid radical in an ionic bond mode through ionic bonds, so that the Prussian blue can catalyze hydrogen peroxide to generate oxygen, the oxygen content in cancer cells is increased, and the drug resistance of anticancer drugs is reduced. The prussian blue has stronger near infrared absorption capacity, is a good photosensitizer, can convert light energy into heat energy under the irradiation of near infrared light, is approved by the U.S. FDA for treating radioactivity, has high molar extinction coefficient and effective 808nm NIR photothermal conversion capacity, and becomes the next-generation PTT treatment medicine.
Therefore, the development of prussian blue-based antitumor drugs has important significance for tumor treatment.
Disclosure of Invention
Based on the prior art, the invention provides a hybrid material of Prussian blue and aminated UIO-66, a preparation method and application thereof, the hybrid material can reduce the drug resistance of anti-tumor drugs, and can realize the synergistic treatment of photothermal treatment and chemotherapy on hypoxic tumor cells to improve the anti-cancer efficiency, so that the hybrid material can be used for preparing the anti-tumor drugs.
The preparation method of the hybrid material is simple, convenient to operate and low in preparation cost.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a hybrid material of Prussian blue and aminated UIO-66 is a Prussian blue nanoparticle modified UIO-66-NH2Porous material composed of nanoparticles.
A preparation method of a hybrid material of Prussian blue and aminated UIO-66 comprises the following steps:
adding prussian blue nano-particles, 2-amino terephthalic acid and zirconium chloride into dimethylformamide, stirring uniformly to obtain turbid liquid, carrying out hydrothermal reaction on the turbid liquid at the temperature of 80-120 ℃ for 20-24h, centrifuging, washing and drying after the reaction is finished, thus obtaining the hybrid material of prussian blue and aminated UIO-66.
Further, the mass ratio of the prussian blue nanoparticles to the 2-aminoterephthalic acid to the zirconium chloride is 5-40: 20-30:20-40.
Further, the drying method is drying at 30-60 ℃.
An application of a hybrid material of Prussian blue and aminated UIO-66 in preparing an anti-tumor medicament.
Furthermore, the anti-tumor drug is an adriamycin drug.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the hybrid material of the invention has low biological toxicity and strong stability, and can not be decomposed in vivo.
2. The hybrid material can be used as a carrier of antitumor drug adriamycin, has unique pH responsiveness, enables the drug adriamycin to be released in a specific weak acid environment, hardly releases the drug adriamycin under a neutral alkaline condition, and reduces the toxic and side effects of the drug adriamycin on normal cells.
3. The hybrid material has excellent photo-thermal performance, can convert light energy into heat energy under the irradiation of near infrared light, exceeds the limit temperature of cancer cell survival so as to kill cancer cells, and can be used as a release carrier of anticancer drug adriamycin.
4. The hybrid material can catalyze hydrogen peroxide to generate oxygen, improve the oxygen concentration in hypoxic tumor cells, reduce the drug resistance of an anticancer drug adriamycin and enhance the anticancer efficiency.
5. The hybrid material provided by the invention has the advantages of simple preparation method, synthesis through simple hydrothermal reaction, simple and easily controlled reaction conditions, low preparation cost and suitability for industrial production.
Drawings
FIG. 1 is a graph showing the effect of the hybrid material of Prussian blue and aminated UIO-66 prepared in example 1 on doxorubicin loading.
FIG. 2 is a graph showing the effect of hybrid materials of Prussian blue and aminated UIO-66 prepared in example 1 on the controlled release of doxorubicin under different pH conditions under light conditions.
Fig. 3 is a graph showing the effect of photothermal properties of prussian blue prepared in comparative example 1 under near-infrared light irradiation.
FIG. 4 is a graph showing the photothermal effect of the hybrid material of Prussian blue and aminated UIO-66 prepared in example 1 under the irradiation of near-infrared light.
FIG. 5 is a graph of the photo-thermal stability effect of the hybrid material of Prussian blue and aminated UIO-66 prepared in example 1.
FIG. 6 shows the catalytic H of hybrid material of Prussian blue and aminated UIO-66 prepared in example 12O2And (5) decomposing effect graphs.
FIG. 7 is a cytotoxicity diagram of hybrid materials of Prussian blue and aminated UIO-66 prepared in example 1.
FIG. 8 is an SEM image of a hybrid material of Prussian blue and aminated UIO-66 prepared in example 1.
FIG. 9 is a TEM image of a hybrid material of Prussian blue prepared in example 1 with aminated UIO-66.
FIG. 10 is a diagram of the hybrid material EDS of Prussian blue prepared in example 1 with aminated UIO-66.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
1. Dissolving 131.7mg of potassium ferricyanide and 3g of PVP (polyvinylpyrrolidone) in 200mL of deionized water, dripping 40 mL0.01M hydrochloric acid while stirring, stirring for 30 minutes, transferring the obtained mixed solution to a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 20 hours at 80 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with ethanol for three times, then washing with water for three times, and drying the obtained solid at 60 ℃ to obtain Prussian blue nanoparticles;
2. adding 18.5mg of Prussian blue nano-particles into 10mL of DMF, carrying out ultrasonic dispersion by using an ultrasonic disruptor, adding 37.3mg of zirconium chloride and 22mg of 2-amino terephthalic acid, carrying out ultrasonic dispersion by using the ultrasonic disruptor, transferring the obtained turbid liquid into a polytetrafluoroethylene reaction kettle, carrying out reaction for 24 hours at 120 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with water for three times, then washing the solid with ethanol for three times, drying the obtained solid at 60 ℃, obtaining a hybrid material of Prussian blue and amination UIO-66, and marking the hybrid material as UIO-66-NH2/PB。
The Prussian blue and aminated UIO-66 hybrid material prepared in the example was scanned by a scanning electron microscope, the SEM image obtained is shown in FIG. 8, and the morphology measured in FIG. 8 is shown together with PB and UIO-66-NH2By comparing the morphologies of the above materials alone, it can be seen that the obtained material was UIO-66-NH2And hybrid materials of PB.
The Prussian blue and aminated UIO-66 hybrid material prepared in the example is scanned by a transmission electron microscope, the obtained TEM image is shown in FIG. 9, and as can be seen from FIG. 9, Prussian blue nanoparticles are loaded on UIO-66-NH2The above.
The Prussian blue prepared in the example and the hybrid material of aminated UIO-66 are subjected to energy spectrum analysis, the obtained EDS diagram is shown in FIG. 10, and the PB and the UIO-66-NH can be proved by the diagram in FIG. 102Rather than simple mixing, there is a force.
Comparative example 1
Dissolving 131.7mg of potassium ferricyanide and 3g of PVP (polyvinylpyrrolidone) in 200mL of deionized water, dripping 40 mL0.01M hydrochloric acid while stirring, stirring for 30 minutes, transferring the obtained mixed solution to a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 20 hours at 80 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with ethanol for three times, then washing with water for three times, and drying the obtained solid at 60 ℃ to obtain the Prussian blue nanoparticles.
Example 2
1. Dissolving 131.7mg of potassium ferricyanide and 3g of PVP (polyvinylpyrrolidone) in 200mL of deionized water, dripping 40 mL0.01M hydrochloric acid while stirring, stirring for 30 minutes, transferring the obtained mixed solution to a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 20 hours at 80 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with ethanol for three times, then washing with water for three times, and drying the obtained solid at 60 ℃ to obtain Prussian blue nanoparticles;
2. adding 9.3mg of Prussian blue nano-particles into 10mL of DMF, carrying out ultrasonic dispersion by using an ultrasonic disruptor, adding 37.3mg of zirconium chloride and 22mg of 2-amino terephthalic acid, carrying out ultrasonic dispersion by using the ultrasonic disruptor, transferring the obtained turbid liquid into a polytetrafluoroethylene reaction kettle, carrying out reaction for 24 hours at 120 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with water for three times, then washing the solid with ethanol for three times, and drying the obtained solid at 60 ℃ to obtain the hybrid material of Prussian blue and amination UIO-66.
Example 3
1. Dissolving 131.7mg of potassium ferricyanide and 3g of PVP (polyvinylpyrrolidone) in 200mL of deionized water, dripping 40 mL0.01M hydrochloric acid while stirring, stirring for 30 minutes, transferring the obtained mixed solution to a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 20 hours at 80 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with ethanol for three times, then washing with water for three times, and drying the obtained solid at 60 ℃ to obtain Prussian blue nanoparticles;
2. adding 37mg of Prussian blue nano particles into 10mL of DMF, carrying out ultrasonic dispersion by using an ultrasonic disruptor, adding 37.3mg of zirconium chloride and 22mg of 2-amino terephthalic acid, carrying out ultrasonic dispersion by using the ultrasonic disruptor, transferring the obtained turbid liquid into a polytetrafluoroethylene reaction kettle, carrying out reaction for 24 hours at 120 ℃, carrying out centrifugal separation after the reaction is finished, washing the obtained solid with water for three times, then washing the solid with ethanol for three times, then centrifuging, and drying the obtained solid at 60 ℃ to obtain the hybrid material of Prussian blue and aminated UIO-66.
Test I, the prussian blue and aminated UIO-66 hybrid material is used as a drug loading effect test
The test method comprises the following steps:
preparing 20ml of 0.1g/L adriamycin solution, adding 0.1g of the hybrid material of prussian blue and aminated UIO-66 prepared in the example 1 into the adriamycin solution, standing for 3 days, taking supernatant liquor every 24 hours, measuring the absorbance of the supernatant liquor, and obtaining the concentration of adriamycin in the supernatant liquor according to the absorbance of the supernatant liquor, thereby calculating the drug loading rate of the prussian blue nano particles and the aminated UIO-66 hybrid material to the adriamycin at 24 hours, 48 hours and 72 hours.
And (3) test results:
the results are shown in fig. 1, and it can be seen from fig. 1 that the drug loading rate of the hybrid material of prussian blue and aminated UIO-66 prepared in example 1 on doxorubicin is about 1.1mg at 24h, the drug loading rate is about 49%, the drug loading rate of the hybrid material of prussian blue and aminated UIO-66 prepared in example 1 on doxorubicin is about 1.38mg at 48h, the drug loading rate is about 61%, and the drug loading rate of the hybrid material of prussian blue and aminated UIO-66 prepared in example 1 on doxorubicin is about 1.53mg at 72h, and the drug loading rate is about 67.7%.
Second, the drug controlled release effect test of the hybrid material of Prussian blue and aminated UIO-66 of the present invention
The test method comprises the following steps:
1. preparing 20ml of 0.1g/L adriamycin solution, adding 0.1g of Prussian blue nano-particles and aminated UIO-66 hybrid material prepared in the embodiment 1, standing for 3 days, centrifuging, and drying the centrifuged solid at 60 ℃ for 6 hours to obtain the hybrid material of the Prussian blue nano-particles and aminated UIO-66 carrying the adriamycin, which is called a drug-carrying sample for short;
2. two dialysis bags (USA import dialysis bag, Cat No: MD10, MWCO: 14000D, Nominal Flat Width:10mm) with a length of 3-4cm are taken and put into deionized water to be boiled for standby;
3. preparing a buffer solution with the pH value of 7.4 and a buffer solution with the pH value of 5.8 by using citric acid and disodium hydrogen phosphate respectively;
4. weighing three parts of 0.0150g of drug-loaded sample, respectively placing three parts of 0.0150g of drug-loaded sample in three dialysis bags, respectively adding 1mL of buffer solution with pH value of 5.8 into two dialysis bags, respectively adding 1mL of buffer solution with pH value of 7.4 into the other dialysis bag, respectively placing the dialysis bags filled with the buffer solution with pH value of 7.4 into a culture bottle A filled with 25mL of buffer solution with pH value of 7.4, respectively placing the two dialysis bags filled with the buffer solution with pH value of 5.8 into two culture bottles B filled with 25mL of buffer solution with pH value of 5.8, respectively placing the culture bottles A and one culture bottle B into a THZ-series constant-temperature shaking table, setting the constant-temperature shaking table to be in a constant-temperature condition of 37 ℃, simulating the temperature of a human body, and simultaneously irradiating the other culture bottle B by near infrared light with 808 nm;
5. taking the liquid in the two culture bottles every half an hour in the first 4 hours, taking deionized water as a reference, measuring the washing and absorbing luminosity of the taken liquid at 460nm, then taking the liquid in the two culture bottles every 1 hour, taking the deionized water as a reference, measuring the washing and absorbing luminosity of the taken liquid at 460nm, and stopping measuring until the absorbance values of the liquid in the two culture bottles tend to be stable;
and (3) test results:
as shown in fig. 2, it can be seen from fig. 2 that the hybrid material of prussian blue and aminated UIO-66 prepared in example 1 has higher release efficiency for doxorubicin under acidic conditions (at pH 5.8), i.e., more easily releases the loaded drug doxorubicin under acidic conditions, and based on the pH difference between cancer cells and normal cells, the hybrid material of prussian blue and aminated UIO-66 prepared in example 1 can specifically release the drug in acidic environment, thereby providing a basis for reducing damage to normal cells in actual treatment and providing an effective practical reference basis for an anticancer tumor drug loading system.
The 808nm near infrared light can rapidly raise the temperature of the hybrid material of prussian blue nanoparticles and aminated UIO-66 to 50 ℃, as can be seen from fig. 2, under the photo-thermal condition (50 ℃), the hybrid material of prussian blue and aminated UIO-66 can release doxorubicin as quickly as possible under the acidic condition (when the pH is 5.8), the release is more thorough, and under the photo-thermal condition (50 ℃), the temperature exceeds the survival temperature of cancer cells, and the cancer cells can be killed.
Test III, photo-thermal performance test of the hybrid material of Prussian blue and aminated UIO-66
The experimental method comprises the following steps:
1. preparing three parts of 1.5mL prussian blue turbid solutions with concentrations of 0.02mg/mL, 0.05mg/mL and 0.2mg/mL (0.002 g PB is weighed and dispersed in 10mL deionized water to obtain 0.2mg/mL PB turbid solution, and then the PB turbid solution is diluted into turbid solutions with different concentrations), using deionized water as a control solution, irradiating the three parts of prussian blue turbid solution and deionized water by near infrared light with a wavelength of 808nm for 10min, measuring the temperature change of the three parts of prussian blue solution and the deionized water before and after the irradiation of the three parts of prussian blue solution and the deionized water by the near infrared light in real time in the near infrared light irradiation process, and drawing a temperature change curve;
2. three turbid solutions (marked as UIO-66-NH) of the Prussian blue nanoparticles prepared in the example 1 and the aminated UIO-66 hybrid material with the concentrations of 0.02mg/mL, 0.05mg/mL and 0.2mg/mL are prepared2/PB turbid solution), using deionized water as control solution, irradiating three portions of UIO-66-NH with near infrared light of 808nm2the/PB turbid liquid and deionized water are used for 10min, and three UIO-66-NH parts are measured in real time in the near infrared light irradiation process2The temperature change of the turbid solution of the PB turbid solution and the deionized water before and after the irradiation of the near infrared light is carried out, and a temperature change curve is drawn;
the experimental results are as follows:
1. the result of the photo-thermal performance test of the prussian blue is shown in fig. 3, and as can be seen from fig. 3, after the deionized water is irradiated by near infrared light for 10min, the temperature of the deionized water is increased by about 5 ℃, and the change is small; after the prussian blue turbid liquid of 0.02mg/mL is irradiated by near infrared light for 10min, the temperature is increased by about 34 ℃, after the prussian blue turbid liquid of 0.05mg/mL is irradiated by the near infrared light for 10min, the temperature is increased by about 37 ℃, and after the PB turbid liquid of 0.2mg/mL is irradiated by the laser for 10min, the temperature is rapidly increased and is increased by about 49 ℃, and the temperature rising speed is higher, so that the prussian blue has better photothermal property; meanwhile, the higher the concentration of the Prussian blue turbid liquid is, the stronger the photo-thermal property is under the condition of the same laser irradiation time; irradiating 0.2mg/mL prussian blue turbid solution for 4.5min, and increasing the temperature from 25 deg.C to 71 deg.C to a temperature exceeding the critical value (42 deg.C) for killing tumor cells by photothermal radiation;
2. example 1 light of Prussian blue nanoparticles prepared with aminated UIO-66 hybrid MaterialThe thermal performance test results are shown in FIG. 4, and it can be seen from FIG. 4 that 0.05mg/mL of UIO-66-NH2After the/PB turbid solution is irradiated by near infrared light for 10min, the temperature is close to 44 ℃, the temperature exceeds the limit temperature of cell survival, and 0.20mg/mL of UIO-66-NH2After the irradiation of the near infrared light for 10min, the temperature of the/PB turbid liquid is close to 54 ℃, and the survival temperature of cancer cells is already exceeded, so that the Prussian blue nanoparticles and the aminated UIO-66 hybrid material prepared in example 1 can be used for performing photothermal therapy on tumor cells.
Fourth, test of photo-thermal stability of the hybrid material of Prussian blue and aminated UIO-66 of the present invention
The test method comprises the following steps: UIO-66-NH with the concentration of 0.20mg/mL is prepared2Irradiating the/PB aqueous solution for 5min by near infrared, raising the temperature of the solution to 45 ℃, and naturally cooling for 5min, wherein the process is circulated for 5 times.
And (3) test results:
the results are shown in FIG. 5, and it can be seen from FIG. 5 that the Prussian blue nanoparticles prepared in example 1 and the aminated UIO-66 hybrid material undergo 5 photo-thermal cycles, and during each cycle, UIO-66-NH2The survival limit temperature of cancer cells can still be exceeded by the/PB, and therefore, the Prussian blue nano-particles and the aminated UIO-66 hybrid material prepared in the embodiment 1 have good photo-thermal stability and have good application prospects in photo-thermal treatment of tumor cells.
Experiment five, the hybrid material of Prussian blue and aminated UIO-66 of the invention catalyzes H2O2Effect test of decomposition
The test method comprises the following steps:
1. preparing a hydrogen peroxide solution with 0.5mol/mL of acidic condition (pH is 5.8) and a hydrogen peroxide solution with 0.5mol/mL of neutral condition (pH is 7.4) by using buffer solutions respectively;
2. measuring the dissolved oxygen amount in a hydrogen peroxide solution with pH value of 5.8 and a hydrogen peroxide solution with pH value of 7.4 respectively;
3. weighing 10mg UIO-66-NH in two parts respectively2/PB, two portions of UIO-66-NH2The solution was added to a hydrogen peroxide solution at pH 5.8 and pH 7.4, respectively, and the pH was measured at 1min intervals at 5.8And the dissolved oxygen in hydrogen peroxide solution at pH 7.4;
4. weighing 10mg UIO-66-NH in two parts respectively2Two portions of UIO-66-NH are added2Adding into hydrogen peroxide solution with pH value of 5.8 and pH value of 7.4, respectively, and measuring the dissolved oxygen amount in the hydrogen peroxide solution with pH value of 5.8 and pH value of 7.4 every 1 min;
and (3) test results:
the results are shown in FIG. 6, from which it can be seen that UIO-66-NH prepared in example 12the/PB is capable of catalyzing the decomposition of hydrogen peroxide to oxygen under acidic conditions, and UIO-66-NH2Under both acidic and neutral conditions, hydrogen peroxide can hardly be catalyzed to generate oxygen, so that the prussian blue nanoparticles prepared in example 1 and the aminated UIO-66 hybrid material can improve oxygen concentration of hypoxic tumor cells and reduce drug resistance of anticancer drugs.
Test VI, the Prussian blue and aminated UIO-66 hybrid material biosafety test of the invention
The test method comprises the following steps: HeLa cell line (human cervical carcinoma) was grown in DMEM medium containing 10% FBS and 1% penicillin/streptomycin, and the medium was transferred to 5% CO2And culturing at 37 ℃ in an incubator for 24 hours. HeLa cells were inoculated to UIO-66-NH added at concentrations of 5, 15, 20, 25. mu.M, respectively2The final volume of each well was 200. mu.L in 96-well plate wells of the/PB turbid solution (dispersed with PBS) and DMEM medium (control), 20000 cells were added to each well, incubated for 24 hours, and the absorbance at 490nm of each well was measured by the MTT method, and the cell viability was determined from the measured absorbance.
And (3) test results:
the results are shown in fig. 7, and it can be seen from fig. 7 that the survival rate of the cells after the prussian blue nanoparticles prepared in example 1 and the aminated UIO-66 hybrid material are incubated together for 24 hours is higher than 80%, which indicates that the prussian blue nanoparticles and the aminated UIO-66 hybrid material have low cytotoxicity and good biosafety.
Claims (6)
1. Prussian blue and aminated UIO-66 hybrid materialCharacterized in that: the hybrid material is Prussian blue nanoparticle modified UIO-66-NH2Porous material composed of nanoparticles.
2. A method for preparing a prussian blue-aminated UIO-66 hybrid material according to claim 1, comprising the steps of:
adding prussian blue nano-particles, 2-amino terephthalic acid and zirconium chloride into dimethylformamide, uniformly stirring to obtain turbid liquid, carrying out hydrothermal reaction on the turbid liquid at the temperature of 80-120 ℃ for 20-24h, centrifuging, washing and drying after the reaction is finished, thus obtaining the hybrid material of prussian blue and aminated UIO-66.
3. The method for preparing a hybrid material of prussian blue and aminated UIO-66 according to claim 2, characterized in that: the mass ratio of the Prussian blue nano-particles to the 2-amino terephthalic acid to the zirconium chloride is 1-8: 4-6:4-8.
4. The method for preparing a hybrid material of prussian blue and aminated UIO-66 according to claim 2, characterized in that: the drying method is drying at 30-60 ℃.
5. Use of a hybrid material of prussian blue and aminated UIO-66 according to claim 1 in the preparation of an antitumor drug.
6. Use of a hybrid material of prussian blue with aminated UIO-66 according to claim 5, characterized in that: the anti-tumor drug is an adriamycin drug.
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| "Prussian blue modified metal–organic framework MIL-101(Fe) with intrinsic peroxidase-like catalytic activity as a colorimetric biosensing platform";Fengjuan Cui等;《RSC Advances》;20151109;第5卷;第98215-98221页 * |
| "普鲁士蓝对罗丹明B的光催化降解研究";程实等;《苏州科技学院学报（自然科学版）》;20091231;第26卷(第4期);第39-42页 * |
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