CN110857335B - Two-dimensional metal-organic framework structure nanosheet and preparation method and application thereof - Google Patents
Two-dimensional metal-organic framework structure nanosheet and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional metal-organic framework structure nanosheet and a preparation method and application thereof. The preparation method comprises the following steps: providing a mixed solution containing tetraphenylporphyrin, gadolinium metal ions, an organic solvent and water, adjusting the proportion of the organic solvent to the water in the mixed solution, and carrying out solvothermal reaction to obtain a two-dimensional metal-organic framework structure nanosheet with uniform size distribution; and carrying out hydrogen protonation treatment on the nanosheets to obtain protonated two-dimensional metal-organic framework nanosheets. The two-dimensional metal-organic framework structure nanosheet can be used in magnetic resonance imaging analysis or photodynamic therapy of tumors. The nano-sheet with uniform size distribution is obtained by adjusting the proportion of the mixed solution and carrying out solvent heat treatment, and the ultraviolet-visible absorption intensity and range of the nano-sheet are improved by hydrogen protonation treatment, so that the nano-sheet has sensitive magnetic resonance imaging and photodynamic treatment effects on tumors.
Description
Technical Field
The invention relates to a preparation method of a metal-organic framework nano material with uniform size, in particular to a method for preparing a two-dimensional metal-organic framework structure nanosheet by using the characteristic of coordination of gadolinium metal ions and porphyrin through a solvothermal technology, and application of the nanosheet in magnetic resonance imaging analysis and photodynamic therapy of tumors, and belongs to the technical field of metal-organic framework nano materials.
Background
The metal-organic framework has the characteristics of good crystallinity, structure adjustability, high specific surface area, ordered pore structure and the like, so that the metal-organic framework is endowed with the applications in various aspects such as gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like. Although metal-organic framework structural materials are largely prepared and researched, the direct construction of metal-organic frameworks into two-dimensional nanosheets still remains challenging, and therefore, the development of a simple and effective method for synthesizing two-dimensional metal-organic framework nanomaterials is of great significance.
Disclosure of Invention
The invention mainly aims to provide a two-dimensional metal-organic framework structure nanosheet and a preparation method thereof, so as to overcome the defects in the prior art.
The invention also aims to provide application of the two-dimensional metal-organic framework structure nanosheets in magnetic resonance imaging analysis and photodynamic therapy of tumors.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a two-dimensional metal-organic framework structure nanosheet, which comprises the following steps:
providing a mixed solution containing tetraphenylporphyrin, gadolinium metal ions, an organic solvent and water;
carrying out solvothermal reaction on the mixed solution to obtain a two-dimensional metal-organic framework structure nanosheet with uniform size distribution; and the number of the first and second groups,
and carrying out hydrogen protonation treatment on the nanosheets to obtain protonated two-dimensional metal-organic framework nanosheets.
The embodiment of the invention also provides a two-dimensional metal-organic framework structure nanosheet prepared by the method, the size of the nanosheet is 120-180 nm, the thickness of the nanosheet is 15-25 nm, a Soret ultraviolet-visible absorption peak exists at 420nm, and a Q band ultraviolet-visible absorption peak exists at 665 nm.
The embodiment of the invention also provides application of the two-dimensional metal-organic framework structure nanosheet in magnetic resonance imaging analysis or photodynamic therapy of tumors.
Further, the application includes: and (3) carrying out magnetic resonance imaging analysis on the tumor by using the two-dimensional metal-organic framework structure nanosheet at the temperature of 20-35 ℃ and the field intensity of 0.5-3.0T.
Further, the application includes: in the photodynamic therapy with the two-dimensional metal-organic framework structure nanosheet, the wavelength of a laser is 500-900 nm, and the light intensity is 10-200 mW/cm2The irradiation time is 5-30 min.
Accordingly, embodiments of the present invention also provide a photodynamic therapeutic agent, which includes the aforementioned two-dimensional metal-organic framework structured nanosheet.
Compared with the prior art, the invention utilizes the specific photodynamic therapy performance of porphyrin molecules and the magnetic resonance imaging characteristics of gadolinium metal ions, the nanosheets with uniform size distribution are obtained by adjusting the proportion of the precursor mixed solution and carrying out solvothermal treatment, and compared with other irregular nanomaterials, the nano-sheet has more uniform particle size distribution, can controllably adjust the size of the nano-sheet on the basis of uniform particle size, the ultraviolet visible absorption intensity and range of the nanosheets are improved through hydrogen protonation, so that the relaxation performance of gadolinium which is a component in the protonated nanosheets with the two-dimensional metal-organic framework structure and the singlet oxygen yield of porphyrin are increased doubly, the contrast performance of gadolinium and the photodynamic treatment effect of porphyrin are enhanced finally, and the performances of two components of porphyrin and gadolinium are improved doubly, so that the nanosheets have sensitive magnetic resonance imaging and photodynamic treatment effects on tumors.
Drawings
Fig. 1 is a schematic diagram of two-dimensional metal-organic framework nanosheets formed from gadolinium and porphyrin as used in magnetic resonance imaging and photodynamic therapy of living animals in an exemplary embodiment of the present invention.
Fig. 2 is a scanning electron microscope photograph of the two-dimensional metal-organic framework nanosheet obtained in example 11 of the present invention.
Fig. 3 is a schematic structural diagram of a two-dimensional metal-organic framework nanosheet obtained in example 11 of the present invention.
Fig. 4 is a graph showing the ultraviolet-visible absorption curve before and after protonation of the two-dimensional metal-organic framework structure nanosheet obtained in example 11 of the present invention.
Fig. 5 is a schematic structural diagram of the two-dimensional metal-organic framework nanosheet obtained in example 11 of the present invention before and after protonation.
Fig. 6 is a magnetic resonance imaging diagram of a tumor-bearing nude mouse using the two-dimensional metal-organic framework nanosheet synthesized in example 11 of the present invention.
Fig. 7 a-7 f are confocal images of tumor cells with two-dimensional metal-organic framework nanosheets synthesized in example 11 of the present invention.
Fig. 8 is a histogram of photodynamic therapy effect on tumor cells before and after protonation of the two-dimensional metal-organic framework nanosheet synthesized in example 11 of the present invention.
Fig. 9a to 9f are scanning electron microscope photographs of two-dimensional metal-organic framework nanosheets of different particle size structures obtained by controlling in an exemplary embodiment of the present invention.
Detailed Description
Aiming at the defects of the prior art, the inventor of the invention provides the technical scheme of the invention through long-term research and massive practice. In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Porphyrin as a commonly used organic ligand for synthesizing a metal-organic framework has excellent performances of good light, thermochemical stability, high light capture coefficient and the like, can convert ground-state molecular oxygen into singlet oxygen under the condition of illumination, and the singlet oxygen can effectively destroy the function of cancer cells and can be used for photodynamic therapy. Meanwhile, the gadolinium-based compound with paramagnetism can effectively reduce longitudinal relaxation time under a magnetic field and improve the magnetic resonance imaging effect of the tumor. Therefore, the gadolinium compound with the magnetic resonance imaging performance is combined with porphyrin with the photodynamic therapy performance to directly synthesize the nano material with the two-dimensional metal-organic framework structure, so that the nano material can be used for early imaging diagnosis and treatment of tumors, and has great academic significance and social benefit.
In view of the above, the invention utilizes the characteristic that tetraphenylporphyrin molecules and gadolinium metal ions can form coordinate bonds under certain conditions, and combines gadolinium and porphyrin to prepare a two-dimensional metal-organic framework nanosheet with uniform particle size distribution by adjusting the proportion of a mixed solution and performing a solvent heat treatment method, and simultaneously performs hydrogen protonation treatment on the prepared two-dimensional metal-organic framework nanosheet to enhance the ultraviolet absorption intensity and range, so that the sensitivity of the nanosheet in the aspect of magnetic resonance imaging is improved, and the two-dimensional nanosheet can be effectively used for photodynamic therapy of tumors, thereby effectively enhancing the magnetic resonance imaging and photodynamic therapy effects of tumors.
As one aspect of the technical scheme of the invention, the invention relates to a preparation method of a two-dimensional metal-organic framework structure nanosheet, which comprises the following steps:
providing a mixed solution containing tetraphenylporphyrin, gadolinium metal ions, an organic solvent and water;
carrying out solvothermal reaction on the mixed solution to obtain a two-dimensional metal-organic framework structure nanosheet with uniform size distribution; and the number of the first and second groups,
and carrying out hydrogen protonation treatment on the nanosheets to obtain protonated two-dimensional metal-organic framework nanosheets.
The size of the two-dimensional metal-organic framework structure nanosheet is 120-180 nm, and the thickness of the nanosheet is 15-25 nm.
In some embodiments, the method of making comprises: the tetraphenylporphyrin solution, the gadolinium metal ion aqueous solution and the organic solvent are uniformly mixed to form the mixed solution (also called as precursor solution).
Further, the tetraphenylporphyrin solution includes tetraphenylporphyrin and a first solvent.
Furthermore, the concentration of tetraphenylporphyrin in the tetraphenylporphyrin solution is 0.1-10.0 mmol/L.
Specifically, the preparation of the tetraphenylporphyrin solution comprises the following steps: 0.1-10.0 mg of meso-tetra (4-carboxyphenyl) porphine is weighed and added into 1-50 mL of N, N-dimethylformamide organic solvent to enable the concentration of the meso-tetra (4-carboxyphenyl) porphine to be 0.1-10.0 mmol/L.
Still further, the tetraphenylporphyrin may be meso-tetra (4-carboxyphenyl) porphin, but is not limited thereto.
Further, the first solvent includes, but is not limited to, N-dimethylformamide, dimethylsulfoxide, chloroform, or any one or a combination of two or more of N, N-dimethylformamide containing 1 to 25wt% of ethanol, dimethylsulfoxide containing 1 to 25wt% of ethanol, chloroform containing 1 to 25wt% of ethanol, and the like.
In some embodiments, the concentration of gadolinium metal ions in the gadolinium metal ion aqueous solution is 0.1 to 10.0 mmol/L.
Further, the gadolinium metal ion is derived from any one or a combination of two or more of chloride, nitrate, sulfate, acetate, phosphate, and the like of gadolinium metal ion, but is not limited thereto.
In some more specific embodiments, the preparation method specifically comprises: firstly, mixing a tetraphenylporphyrin solution and a gadolinium metal ion aqueous solution, and then adding an organic solvent to adjust the volume ratio of the organic solvent to water in the mixed solution to 1: 10-10: 1.
further, the organic solvent for adjustment in the solution includes any one or a combination of two or more of N, N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, chloroform, and the like, but is not limited thereto.
In some more specific embodiments, the preparation method of the two-dimensional metal-organic framework nanosheet may include the following steps:
(1) tetraphenylporphyrin and gadolinium metal ions are uniformly mixed to form a mixed solution (also called as a precursor solution);
(2) adjusting the proportion of an organic solvent and water in the precursor solution and carrying out solvothermal reaction to obtain a two-dimensional metal-organic framework structure nanosheet with uniform size distribution;
(3) carrying out hydrogen protonation treatment on the prepared nanosheet to enhance the ultraviolet-visible absorption intensity and range;
(4) the protonated nanosheets are used for magnetic resonance imaging analysis and photodynamic therapy of tumors.
In some embodiments, the temperature of the solvothermal reaction is 50-160 ℃ and the time is 1-6 h.
In some embodiments, the method of making comprises: and contacting the two-dimensional metal-organic framework structure nanosheet with an acid solution, and performing the hydrogen protonation treatment to obtain a protonated two-dimensional metal-organic framework structure nanosheet.
Further, the type of the acid solution used for the hydrogen protonation treatment may be any one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, oxalic acid, formic acid, and the like, but is not limited thereto.
Further, the concentration of the acid solution used for hydrogen protonation treatment is 0.1-1000 mmol/L, and the pH value is 0.2-7.0.
The two-dimensional metal-organic framework structure nanosheet prepared by the method is 120-180 nm in size and particle size, 15-25 nm in thickness, strong Soret band absorption at 420nm in ultraviolet visible absorption and weak absorption at four Q bands at 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
Another aspect of the embodiments of the present invention also provides an application of the two-dimensional metal-organic framework nanosheets in magnetic resonance imaging analysis or photodynamic therapy of tumors.
Further, the application includes: and (3) carrying out magnetic resonance imaging analysis on the tumor by using the two-dimensional metal-organic framework structure nanosheet at the temperature of 20-35 ℃ and the field intensity of 0.5-3.0T.
Further, the application includes: in the photodynamic therapy with the two-dimensional metal-organic framework structure nanosheet, the wavelength of a laser is 500-900 nm, and the light intensity is 10-200 mW/cm2The irradiation time is 5-30 min.
Accordingly, another aspect of an embodiment of the present invention also provides a photodynamic therapeutic agent comprising the aforementioned two-dimensional metal-organic framework structured nanosheets.
By the technical scheme, the nano-sheets with uniform size distribution are obtained by adjusting the proportion of the mixed solution and carrying out solvothermal treatment, and the ultraviolet visible absorption intensity and range of the nano-sheets are improved by hydrogen protonation treatment, so that the nano-sheets have sensitive magnetic resonance imaging and photodynamic treatment effects on tumors.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Meso-tetra (4-carboxyphenyl) porphine used in this example was purchased from Aladdin reagents; gadolinium chloride was purchased from Sigma-Aldrich reagent; n, N-dimethylformamide was purchased from the national pharmaceutical group. Preparing 5.0mmol/L meso-tetra (4-carboxyphenyl) porphin solution by using N, N-dimethylformamide as a solvent, and preparing 5.0mmol/L gadolinium chloride solution by using water as a solvent. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of gadolinium chloride solution are added into a round-bottom flask, 20mL of N, N-dimethylformamide is added, and the mixture is stirred uniformly to form a precursor solution. And heating the precursor solution which is uniformly mixed under stirring for reaction at the temperature of 50 ℃ for 4 hours, cooling and washing the product for multiple times by using N, N-dimethylformamide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of hydrochloric acid solution with the concentration of 0.1mol/L and the pH value of 1.0, stirring at room temperature for 30min to obtain the protonated two-dimensional metal-organic framework nanosheet, wherein the size of the nanosheet is 120nm, the thickness of the nanosheet is 15nm, the ultraviolet visible absorption shows strong Soret band absorption at 420nm, and four Q bands at 500-700 nm are weak absorption. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Time-varying magnetic resonance imaging results are obtained. Putting lotus in the airTwo-dimensional nanosheets prepared by respectively carrying out tail vein injection and intratumoral injection on tumor nude mice, and then vertically and uniformly irradiating the tumors for 30min by adopting 660nm light with the light intensity of 100mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 2
In this embodiment, N-dimethylformamide is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphin, and then water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium sulfate. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of gadolinium sulfate solution are added into a round-bottom flask, 15mL of N, N-dimethylformamide is added, 5mL of ethanol is added, and the mixture is stirred uniformly to form a precursor solution. And heating the precursor solution which is uniformly mixed under stirring for reaction at the temperature of 100 ℃ for 5 hours, cooling and washing the product for multiple times by using N, N-dimethylformamide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of sulfuric acid solution with the concentration of 0.005mol/L and the pH value of about 2.0, and stirring at room temperature for 20min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 150nm, the thickness of the material is 20nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning imaging, wherein the temperature is kept at 25 ℃. Obtaining time-varying magnetic resonanceAnd (5) imaging results. Two-dimensional nanosheets prepared by respectively carrying out caudal vein injection and intratumoral injection on tumor-bearing nude mice are vertically and uniformly irradiated on tumors by adopting 660nm light for 5 min. The light intensity is 200mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 3
In this embodiment, N-dimethylformamide is used as a solvent to prepare a 10mmol/L solution of meso-tetra (4-carboxyphenyl) porphin, and then water is used as a solvent to prepare a 10mmol/L solution of gadolinium nitrate. 1mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of gadolinium nitrate solution are added into a round-bottom flask, 10mL of N, N-dimethylformamide is added, 5mL of ethanol is added, 5mL of deionized water is added, and the mixture is stirred uniformly to form a precursor solution. And heating the precursor solution which is uniformly mixed under stirring for reaction at the temperature of 50 ℃ for 6 hours, cooling and washing the product for multiple times by using N, N-dimethylformamide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of an acetic acid solution with the concentration of 0.05mol/L and the pH value of about 6.0, and stirring at room temperature for 30min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the ultraviolet-visible light absorption material is 180nm, the thickness of the ultraviolet-visible light absorption material is 25nm, strong Soret band absorption occurs at 420nm, and four Q band weak absorption occurs at 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, transferring the nude mouse to a 3.0T magnetic resonance imaging instrument for scanning imaging, and keeping the temperature atAt 25 ℃. Time-varying magnetic resonance imaging results are obtained. Two-dimensional nanosheets prepared by respectively carrying out caudal vein injection and intratumoral injection on tumor-bearing nude mice are vertically and uniformly irradiated on tumors by adopting 660nm light for 10 min. The light intensity is 150mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 4
In this example, 0.1mmol/L of meso-tetra (4-carboxyphenyl) porphine solution is prepared by using dimethyl sulfoxide as a solvent, and 0.1mmol/L of gadolinium chloride solution is prepared by using water as a solvent. 20mL of meso-tetra (4-carboxyphenyl) porphin solution and 10mL of gadolinium chloride solution are added into a round-bottom flask and stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at 160 ℃ for 1 hour, cooling and washing the product for multiple times by using dimethyl sulfoxide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of nitric acid solution with the concentration of 0.1mmol/L and the pH value of about 5.0, and stirring at room temperature for 30min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 130nm, the thickness of the material is 18nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 3.0T magnetic resonance imaging instrument for scanning imaging, wherein the temperature is kept at 25 ℃. Time-varying magnetic resonance imaging results are obtained.Injecting two-dimensional nanosheets prepared by caudal vein and intratumoral injection of tumor-bearing nude mice respectively, and vertically and uniformly irradiating tumors for 5min by adopting 660nm light with the light intensity of 200mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 5
In this example, dimethylsulfoxide is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium nitrate. 2mL of meso-tetra (4-carboxyphenyl) porphine solution and 2mL of gadolinium nitrate solution are added into a round-bottom flask, 15mL of dimethyl sulfoxide is added, 5mL of ethanol is added, 5mL of deionized water is added, and the mixture is stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at the temperature of 120 ℃ for 3 hours, cooling and washing the product for multiple times by using dimethyl sulfoxide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of nitric acid solution with the concentration of 0.01mol/L and the pH value of about 2.0, and stirring at room temperature for 10min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the ultraviolet-visible light absorption material is 160nm, the thickness of the ultraviolet-visible light absorption material is 22nm, strong Soret band absorption occurs at 420nm, and four Q band weak absorption occurs at 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Obtaining time-varying magnetic resonanceLike the result. And (3) respectively injecting the tumor-bearing nude mice into the tail vein and the tumor to prepare two-dimensional nanosheets, and then vertically and uniformly irradiating the tumor for 30min by adopting light with the wavelength of 600 nm. The light intensity is 90mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 6
In this example, dimethylsulfoxide is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium sulfate. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 2mL of gadolinium sulfate solution are added into a round-bottom flask, 15mL of dimethyl sulfoxide is added, 5mL of ethanol is added, 5mL of deionized water is added, and the mixture is stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at the temperature of 120 ℃ for 3 hours, cooling and washing the product for multiple times by using dimethyl sulfoxide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of nitric acid solution with the concentration of 0.001mol/L and the pH value of about 3.0, and stirring at room temperature for 10min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 140nm, the thickness of the material is 19nm, the ultraviolet visible absorption is strong Soret band absorption at 420nm, and four Q band weak absorption at 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. To obtain a time-dependent changeAnd (5) magnetic resonance imaging results. And (3) respectively injecting the tumor-bearing nude mice into the tail vein and the tumor to prepare two-dimensional nanosheets, and then vertically and uniformly irradiating the tumor for 30min by adopting light with the wavelength of 600 nm. The light intensity is 90mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 7
In this example, chloroform is used as a solvent to prepare a 10mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and water is used as a solvent to prepare a 10mmol/L solution of gadolinium chloride. 1mL of meso-tetrakis (4-carboxyphenyl) porphine solution and 1mL of gadolinium chloride solution were added to a round-bottom flask, 5mL of ethanol and 15mL of chloroform were added, and the mixture was stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at the temperature of 80 ℃ for 2 hours, cooling and washing the product with ethanol for multiple times after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework nanosheet. Centrifuging 2mL of the nanosheet dispersion, adding 2mL of nitric acid solution with the concentration of 0.63mol/L and the pH value of about 0.2, and stirring at room temperature for 5min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 170nm, the thickness of the material is 23nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 0.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Time-varying magnetic resonance imaging results are obtained. Respectively culturing nude mice with tumorTwo-dimensional nanosheets prepared by tail vein and intratumoral injection are vertically and uniformly irradiated on the tumor for 30min by adopting 660nm light with the light intensity of 10mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 8
In this example, chloroform is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium nitrate. 2mL of meso-tetrakis (4-carboxyphenyl) porphine solution and 2mL of gadolinium nitrate solution were added to a round bottom flask, 10mL of chloroform was added, 5mL of ethanol was added, 5mL of deionized water was added, and the mixture was stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at the temperature of 80 ℃ for 6 hours, cooling and washing the product with ethanol for multiple times after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of hydrochloric acid solution with the concentration of 0.0001mol/L and the pH value of about 7.0, and stirring at room temperature for 30min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the ultraviolet-visible light absorption material is 160nm, the thickness of the ultraviolet-visible light absorption material is 22nm, strong Soret band absorption occurs at 420nm, and four Q band weak absorption occurs at 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Time-varying magnetic resonance imaging results are obtained. Respectively carrying out tail vein on tumor-bearing nude miceAnd two-dimensional nanosheets prepared by intratumoral injection, and then the tumor is vertically and uniformly irradiated by 900nm light for 5 min. The light intensity is 200mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 9
In this example, chloroform is used as a solvent to prepare a 10mmol/L solution of meso-tetra (4-carboxyphenyl) porphine, and water is used as a solvent to prepare a 10mmol/L solution of gadolinium sulfate. 1mL of meso-tetra (4-carboxyphenyl) porphin solution and 1mL of gadolinium sulfate solution are added into a round-bottom flask, 5mL of chloroform is added, 10mL of ethanol is added, 5mL of deionized water is added, and the mixture is stirred uniformly to form a precursor solution. And (3) heating and reacting the uniformly mixed precursor solution under stirring at the temperature of 80 ℃ for 6 hours, cooling and washing the product with ethanol for multiple times after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of nitric acid solution with the concentration of 1mol/L and the pH value of about 1.0, and stirring at room temperature for 10min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 150nm, the thickness of the material is 20nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Time-varying magnetic resonance imaging results are obtained. The preparation method comprises injecting tumor-bearing nude mice into tail vein and tumorAnd then 660nm light is adopted to vertically and uniformly irradiate the tumor for 30 min. The light intensity is 90mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 10
In this embodiment, N-dimethylformamide is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphin, and then water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium chloride. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 2mL of gadolinium chloride solution are added into a round-bottom flask, 18mL of deionized water is added, 2mL of ethanol is added, and the mixture is stirred uniformly to form a precursor solution. And heating the precursor solution which is uniformly mixed under stirring for reaction at the temperature of 100 ℃ for 6 hours, cooling and washing the product for multiple times by using N, N-dimethylformamide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the nanosheet dispersion, adding 2mL of hydrochloric acid solution with the concentration of 0.01mol/L and the pH value of about 2.0, and stirring at room temperature for 15min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 170nm, the thickness of the material is 24nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning imaging, wherein the temperature is kept at 20 ℃. Time-varying magnetic resonance imaging results are obtained. Respectively carrying out tail vein injection and intratumoral injection on tumor-bearing nude miceAnd irradiating the prepared two-dimensional nanosheet, and then vertically and uniformly irradiating the tumor for 30min by adopting 500nm light. The light intensity is 90mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Example 11
In this embodiment, N-dimethylformamide is used as a solvent to prepare a 5.0mmol/L solution of meso-tetra (4-carboxyphenyl) porphin, and then water is used as a solvent to prepare a 5.0mmol/L solution of gadolinium chloride. 2mL of meso-tetra (4-carboxyphenyl) porphin solution and 2mL of gadolinium chloride solution are added into a round-bottom flask, 18mL of N, N-dimethylformamide is added, 2mL of ethanol is added, and the mixture is stirred uniformly to form a precursor solution. And heating the precursor solution which is uniformly mixed under stirring for reaction at the temperature of 120 ℃ for 5 hours, cooling and washing the product for multiple times by using N, N-dimethylformamide and ethanol after the reaction is finished to obtain the gadolinium-porphyrin combined two-dimensional metal-organic framework structure nanosheet. Centrifuging 2mL of the dispersion liquid of the nanosheet, adding 2mL of hydrochloric acid solution with the concentration of 0.1mol/L and the pH value of about 1.0, and stirring at room temperature for 10min to obtain the protonated two-dimensional metal-organic framework nanosheet. The particle size of the material is 150nm, the thickness of the material is 20nm, strong Soret band absorption occurs at 420nm in ultraviolet visible absorption, and weak absorption occurs at four Q bands of 500-700 nm. After protonation, the particle size and the thickness range are unchanged, the Soret band of ultraviolet visible absorption is not changed obviously, the weak absorption of four Q bands at 500-700 nm disappears, and the strong Q band absorption appears at 665 nm.
The nanosheets prepared in the example were used for magnetic resonance imaging of living nude mice and photodynamic therapy of tumors. Athymic nude mice were bred and tumor implantation was performed until the tumor diameter reached about 5 mm. Injecting carbamate solution into the abdominal cavity of a tumor-growing nude mouse to anaesthetize the nude mouse, fixing the nude mouse on a fixer, injecting 200 mu L physiological saline solution containing two-dimensional nano-sheets into tail vein, and then transferring the nude mouse to a 1.5T magnetic resonance imaging instrument for scanning and imaging, wherein the temperature is kept at 35 ℃. Time-varying magnetic resonance imaging results are obtained. The tumor-bearing nude mice are respectively tailedThe two-dimensional nano-sheets prepared by intravenous injection and intratumoral injection are vertically and uniformly irradiated on the tumor for 30min by adopting 660nm light. The light intensity is 90mW/cm2. After the light irradiation, the nude mice were kept under SPF conditions. After 7 days, repeating the experimental steps once, wherein the period is 24 days in total, and obtaining the photodynamic treatment result of the two-dimensional nanosheets on the tumor.
Fig. 1 is a schematic diagram of two-dimensional metal-organic framework nanosheets formed from gadolinium and a porphyrin for use in magnetic resonance imaging and photodynamic therapy of living animals. As can be seen from fig. 2 to 7, the prepared two-dimensional metal-organic framework nanosheets have uniform particle size distribution, the particle size is about 150nm, and phagocytosis of cells is facilitated, and fig. 4, 5 and 8 illustrate that the ultraviolet-visible absorption intensity and range of the two-dimensional metal-organic framework nanosheets at 665nm are simultaneously improved, and the absorption wavelength can effectively penetrate through tissues, so that the practical application of photodynamic therapy is facilitated. Figure 6 demonstrates the magnetic resonance contrast performance of the nanosheets, and when the nanosheets are imaged by a 1.5T small animal magnetic resonance imager, the response signals of the nanosheets are obviously enhanced with time, are strongest after 4h and can last for a longer time.
Fig. 9a to 9f show scanning electron microscope photographs of two-dimensional metal-organic framework nanosheets of different particle size structures obtained by modulation in an exemplary embodiment of the present invention.
Where the unexplained elements are referred to as being prior art or being implemented using prior art.
In summary, according to the technical solutions of embodiments 1 to 11, the nanosheets with uniform size distribution are obtained by adjusting the ratio of the mixed solution and performing solvothermal treatment, and the ultraviolet-visible absorption intensity and range of the nanosheets are improved by hydrogen protonation treatment, so that the nanosheets have sensitive magnetic resonance imaging and photodynamic therapy effects on tumors.
In addition, the inventor also refers to the mode of examples 1-11, tests are carried out by using other raw materials and conditions listed in the specification, and the two-dimensional metal-organic framework structure nanosheets which have sensitive magnetic resonance imaging and photodynamic therapy effects on tumors are also successfully prepared.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (16)
1. A preparation method of a two-dimensional metal-organic framework structure nanosheet is characterized by comprising the following steps:
providing a mixed solution containing tetraphenylporphyrin, gadolinium metal ions, an organic solvent and water, wherein the tetraphenylporphyrin is meso-tetra (4-carboxyphenyl) porphin;
carrying out solvothermal reaction on the mixed solution to obtain a two-dimensional metal-organic framework structure nanosheet with uniform size distribution; and the number of the first and second groups,
and carrying out hydrogen protonation treatment on the nanosheet to obtain a protonated two-dimensional metal-organic framework structure nanosheet, wherein the two-dimensional metal-organic framework structure nanosheet has a Soret ultraviolet-visible absorption peak at a position of 420nm and a Q band ultraviolet-visible absorption peak at a position of 665 nm.
2. The method of claim 1, wherein: the size of the two-dimensional metal-organic framework structure nanosheet is 120-180 nm, and the thickness of the nanosheet is 15-25 nm.
3. The production method according to claim 1, characterized by comprising: and uniformly mixing the tetraphenylporphyrin solution, the gadolinium metal ion aqueous solution and the organic solvent to form the mixed solution.
4. The production method according to claim 3, characterized in that: the tetraphenylporphyrin solution includes tetraphenylporphyrin and a first solvent.
5. The method of claim 4, wherein: the concentration of tetraphenylporphyrin in the tetraphenylporphyrin solution is 0.1-10.0 mmol/L.
6. The method of claim 4, wherein: the first solvent is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide, chloroform, N-dimethylformamide containing 1-25 wt% of ethanol, dimethyl sulfoxide containing 1-25 wt% of ethanol and chloroform containing 1-25 wt% of ethanol.
7. The method of claim 1, wherein: the gadolinium metal ions are derived from any one or a combination of more than two of chloride, nitrate, sulfate, acetate and phosphate of gadolinium metal ions.
8. The production method according to claim 3, characterized in that: the concentration of gadolinium metal ions in the gadolinium metal ion aqueous solution is 0.1-10.0 mmol/L.
9. The production method according to claim 3, characterized by comprising: firstly, mixing a tetraphenylporphyrin solution and a gadolinium metal ion aqueous solution, and then adding an organic solvent to adjust the volume ratio of the organic solvent to water in the mixed solution to 1: 10-10: 1.
10. the method of claim 9, wherein: the organic solvent is selected from one or the combination of more than two of N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol and chloroform.
11. The method of claim 1, wherein: the temperature of the solvothermal reaction is 50-160 ℃, and the time is 1-6 h.
12. The production method according to claim 1, characterized by comprising: and contacting the two-dimensional metal-organic framework structure nanosheet with an acid solution, and performing the hydrogen protonation treatment to obtain a protonated two-dimensional metal-organic framework structure nanosheet.
13. The method of manufacturing according to claim 12, wherein: the acid solution is selected from one or the combination of more than two of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, oxalic acid and formic acid.
14. The method of manufacturing according to claim 12, wherein: the concentration of the acid solution is 0.1-1000 mmol/L, and the pH value is 0.2-7.0.
15. Two-dimensional metal-organic framework structured nanosheets produced by the method of any one of claims 1-14, having a size ranging from 120 to 180nm, a thickness ranging from 15 to 25nm, a Soret band uv-vis absorption peak at 420nm, and a Q band uv-vis absorption peak at 665 nm.
16. A photodynamic therapeutic agent, characterized by comprising the two-dimensional metal-organic framework structured nanosheet of claim 15.
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