CN111004623B - Porphyrin fluorescent material and preparation method thereof - Google Patents
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Abstract
The invention relates to a porphyrin fluorescent material and a preparation method thereof, wherein a complex formed by tetracarboxyl phenyl porphyrin (TCPP) and gadolinium is combined with Polyethyleneimine (PEI) to synthesize the fluorescent material with good water solubility, and fluorescent materials with different colors can be obtained according to different proportions of the complex and the polyethyleneimine, so that the full color change is realized, and white fluorescent materials can be prepared from fluorescent materials with three colors of red, green and blue, so that the fluorescent material has wide application prospect in the aspect of illumination.
Description
Technical Field
The invention relates to a fluorescent material and a preparation method thereof, in particular to a fluorescent material of porphyrin coordination compound and a preparation method thereof.
Background
With the development of the photoelectric field in recent years, more and more scientists are focusing on white light fluorescent materials and application thereof. Generally, white light fluorescent materials are prepared from three primary colors (red, green and blue, with wavelengths of 380-750 nm) according to a coordinated proportion. Such as molecular design with chromogenic functional groups; quantum dots, rare earth nanomaterials or supramolecules, and the like. However, most materials have poor water solubility, low quantum efficiency and high toxicity, so that the materials are limited in specific application.
In recent years, people try to apply carbon dots, rare earth hybrid materials and the like to make novel white light fluorescent materials, increase the biocompatibility of the white light fluorescent materials, expand the further application of the materials and make a great breakthrough. If the change of the amino position in benzene ring is utilized, the full-color carbon dot fluorescent material is synthesized, and the flexible film is prepared. Materials with different fluorescent colors are separated from the same raw materials by utilizing the characteristics of quantum dots, and are applied to cell and living body imaging. These new materials have different applications, but they must have good water solubility at the end. Porphyrin organic matters widely exist in organisms, but have limited water solubility, and how to improve the water solubility of the porphyrin organic matters on the premise of ensuring coordination with rare earth elements becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the problems of low quantum efficiency, high toxicity, poor water solubility and the like of the existing white light fluorescent material, the invention provides a porphyrin coordination compound fluorescent material and a preparation method thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a porphyrin fluorescent material is prepared from gadolinium complex of tetra-carboxyl phenyl porphyrin and polyethylenimine.
According to the invention, gadolinium complex of tetra-carboxyl phenyl porphyrin and polyethyleneimine are adopted to react, and the material with good water solubility and fluorescence characteristic is obtained through the interaction of amino in polyethyleneimine and carboxyl of tetra-carboxyl phenyl porphyrin.
According to the fluorescent material, materials with different colors can be obtained according to different proportions of gadolinium complex of tetracarboxyl phenyl porphyrin and polyethyleneimine: when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:1.8-2.2, the fluorescent material is red; when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:3.8-4.2, the fluorescent material is green; when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:9.8-10.2, the fluorescent material is blue.
Further, the preparation method of the porphyrin fluorescent material comprises the following steps: gadolinium complex of tetracarboxylphenyl porphyrin and polyethyleneimine are reacted for 3-5 hours at 160-180 ℃, slowly cooled to room temperature, and placed in a dialysis bag with molecular weight of 500 for 18 hours, thus obtaining the fluorescent material.
The preparation method of the fluorescent material is simple, and the fluorescent material is prepared by carrying out hydrothermal reaction on gadolinium complexes of tetracarboxyl phenyl porphyrin and polyethyleneimine.
The preparation method of the gadolinium complex of the tetracarboxyl phenyl porphyrin comprises the following steps: the tetracarboxyl phenyl porphyrin, the soluble gadolinium salt and the solvent are sequentially put into a hydrothermal reaction kettle to react for 23-25 hours at 120-140 ℃ to obtain the catalyst.
Further, the soluble gadolinium salt is GdCl 3 ·6H 2 O。
Further, the molar ratio of the tetracarboxyphenylporphyrin to the soluble gadolinium salt is 1:1.8-2.2.
Alternatively, the solvent is N, N-Dimethylformamide (DMF), acetic acid, and ethanol.
Further, the volume ratio of N, N-dimethylformamide, acetic acid and ethanol is 7:0.11-0.12:2.9-3.
The tetracarboxyl phenyl porphyrin (TCPP) has four carboxyl groups, and can coordinate with rare earth elements well. In the hydrothermal reaction kettle, the coordination rate of rare earth ions can be improved through high-temperature hydrothermal reaction.
The preparation method of the tetracarboxy phenyl porphyrin is realized by the following steps:
step a: taking pyrrole and methyl p-formylbenzoate, adding an organic solvent, carrying out reflux reaction for 1.8-2.2 hours under the protection of inert gas, and standing the product in an environment of-18 ℃ for 12 hours to obtain 5,10,15, 20-tetra (4-methoxyphenyl) porphyrin (TCPPOMe);
step b: adding 5,10,15, 20-tetra (4-methoxyphenyl) porphyrin (TCPPOMe) into an organic solvent, adding a strong alkali solution, reacting for 2.5-3.5 hours at 50-70 ℃, cooling to room temperature, removing the solvent, and acidifying to obtain the tetracarboxyphenylporphyrin.
Preferably, the organic solvent in the step a is propionic acid, and the molar ratio of pyrrole to methyl paraformylbenzoate is 1:1-1.2.
Preferably, the organic solvent in the step b is tetrahydrofuran and methanol with a volume ratio of 1:1-1.2.
Preferably, the strong base solution in the step b is a KOH or NaOH aqueous solution with the concentration of 4-5 mol/L, and the addition amount is 1/5-1/4.
A white fluorescent material is prepared by mixing a red fluorescent material, a green fluorescent material and a blue fluorescent material, wherein the molar ratio of the red fluorescent material to the green fluorescent material to the blue fluorescent material is 3:2.9-3.0:4.9-5.0 based on the molar ratio of gadolinium ions in the fluorescent material.
The invention breaks through the way of the traditional white light material color-division region regulation synthesis, adopts homologous raw materials, and prepares the white light material.
In the preparation of the fluorescent material, porphyrin ligand Tetra Carboxyl Phenyl Porphyrin (TCPP) is selected, and four carboxyl groups of the porphyrin ligand Tetra Carboxyl Phenyl Porphyrin (TCPP) can be well coordinated with rare earth elements. In order to improve the water solubility, a novel fluorescent material having both water solubility and porphyrin properties is synthesized by combining porphyrin with Polyethyleneimine (PEI) having good water solubility by utilizing the reaction of carboxyl groups and amino groups. The material combines TCPP, gd and PEI by adopting a hydrothermal method to obtain the novel luminescent material Gd-TCPP@PEI. On the one hand, gd-TCPP@PEI can greatly enhance water solubility and retain red fluorescence of porphyrin. On the other hand, the full color change of Gd-TCPP@PEI can be realized by adjusting the conditions of the dosage, the temperature, the reaction time and the like of PEI, and a white fluorescent material is prepared. The white fluorescent material can be used in the field of illumination.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a nuclear magnetic spectrum of 5,10,15, 20-tetrakis (4-methoxyphenyl) porphyrin prepared in example 1;
FIG. 2 is a nuclear magnetic spectrum of tetracarboxyphenylporphin prepared in example 4;
FIG. 3 is a graph of Gd-TCPP prepared in example 7 as characterized by an x-ray diffractometer at room temperature;
FIG. 4 is a fluorescence spectrum of the red fluorescent material prepared in example 11;
FIG. 5 is a fluorescence spectrum of the green fluorescent material prepared in example 15;
FIG. 6 is a fluorescence spectrum of the blue fluorescent material prepared in example 19;
FIG. 7 is a fluorescence spectrum of the white fluorescent material prepared in example 23;
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
33mL of propionic acid was placed in a 100mL three-necked flask, and fresh pyrrole 0.014mol and methyl p-formylbenzoate 0.014mol were added to the flask in N 2 Under the protection ofThe reaction was refluxed for 2 hours. At the end of the reaction, the product was left to stand for 12 hours at-18℃and filtered and washed with cold methanol to give the violet precipitate TCPPOMe, which was dried in a vacuum oven. The nuclear magnetic spectrum diagram is shown in figure 1.
Example 2
33mL of propionic acid was placed in a 100mL three-necked flask, and fresh pyrrole 0.014mol and methyl p-formylbenzoate 0.017mol were added to the flask in N 2 The reaction was refluxed for 2.2 hours under protection. At the end of the reaction, the product was left to stand for 12 hours at-18℃and filtered and washed with cold methanol to give the violet precipitate TCPPOMe, which was dried in a vacuum oven.
Example 3
33mL of propionic acid was placed in a 100mL three-necked flask, and fresh pyrrole 0.014mol and methyl p-formylbenzoate 0.016mol were added to the flask, at N 2 The reaction was refluxed under protection for 1.8 hours. At the end of the reaction, the product was left to stand for 12 hours at-18℃and filtered and washed with cold methanol to give the violet precipitate TCPPOMe, which was dried in a vacuum oven.
Example 4
0.2g of TCPPOMe is dissolved in 10mL of a mixed solvent of tetrahydrofuran and methanol (v: v=1:1), 2mL of an aqueous solution containing KOH 8.92mmol is added, the reaction is carried out for 2 hours at 60 ℃, the solvent is removed after cooling to room temperature, distilled water is added until the solid is completely dissolved, 1M HCl solution is added to the solution until no precipitate is precipitated, and the solution is filtered and washed with distilled water and then placed in a vacuum drying oven for later use. The nuclear magnetic spectrum is shown in figure 2.
Example 5
0.2g of TCPPOMe is dissolved in 10mL of a mixed solvent of tetrahydrofuran and methanol (v: v=1:1.2), then 2.5mL of an aqueous solution containing 8mmol of NaOH is added for reaction for 2.5 hours at 70 ℃, the solvent is removed after cooling to room temperature, distilled water is added until the solid is completely dissolved, then 1M HCl solution is added into the solution until no precipitate is precipitated, and the solution is filtered and washed with distilled water and then placed into a vacuum drying box for use.
Example 6
0.2g of TCPPOMe is dissolved in 10mL of a mixed solvent of tetrahydrofuran and methanol (v: v=1:1), 2mL of an aqueous solution containing KOH 10mmol is added, the reaction is carried out for 3.5 hours at 50 ℃, the solvent is removed after cooling to room temperature, distilled water is added until the solid is completely dissolved, 1M HCl solution is added to the solution until no precipitate is precipitated, and the solution is filtered and washed with distilled water and then placed in a vacuum drying oven for later use.
Example 7
Tetracarboxyphenyl porphyrin 0.015mmol and GdCl 3 ·6H 2 O0.03 mmol, DMF (N, N-dimethylformamide) 3.5mL,60 mu L acetic acid and ethanol 1.5mL are sequentially put into a 30mL polytetrafluoroethylene reaction kettle liner, after sealing, the mixture is slowly heated to 130 ℃ for 24 hours, after the reaction is completed, the mixture is slowly cooled to room temperature, gd-TCPP purple solid is obtained, the mixture is washed by distilled water and then dried for later use, and an x-ray diffraction diagram of the mixture is shown in figure 3.
Example 8
Tetracarboxyphenyl porphyrin 0.015mmol and GdCl 3 ·6H 2 O0.027 mmol, DMF (N, N-dimethylformamide) 3.5mL,55 mu L acetic acid and ethanol 1.5mL are sequentially put into a 30mL polytetrafluoroethylene reaction kettle liner, after sealing, the mixture is slowly heated to 120 ℃ for reaction for 25 hours, after the reaction is completed, the mixture is slowly cooled to room temperature, gd-TCPP purple solid is obtained, and the mixture is washed by distilled water and dried for standby.
Example 9
Tetracarboxyphenyl porphyrin 0.015mmol and GdCl 3 ·6H 2 O0.033 mmol, DMF (N, N-dimethylformamide) 3.5mL,60 mu L acetic acid and ethanol 1.45mL are sequentially put into a 30mL polytetrafluoroethylene reaction kettle liner, after sealing, the mixture is slowly heated to 140 ℃ for 23 hours, after the reaction is completed, the mixture is slowly cooled to room temperature, gd-TCPP purple solid is obtained, and the mixture is washed by distilled water and dried for standby.
Example 10
Tetracarboxyphenyl porphyrin 0.015mmol and GdCl 3 ·6H 2 O0.03 mmol, DMF (N, N-dimethylformamide) 3.5mL,60 mu L acetic acid and ethanol 1.5mL are sequentially put into a 30mL polytetrafluoroethylene reaction kettle liner, after sealing, the mixture is slowly heated to 140 ℃ for reaction for 25 hours, and after the reaction is completed, the mixture is slowly cooled to room temperature to obtain Gd-TCPP purple solid is dried for standby after washing with distilled water.
Example 11
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 1mL of polyethyleneimine aqueous solution (PEI) (10 mg/mL) and 4mL of water, and reacted at 170 ℃ for 4 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having red fluorescence, the fluorescence spectrum of which is shown in fig. 4.
Example 12
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 1mL of polyethylenimine aqueous solution (PEI) (9 mg/mL) and 4mL of water, and reacted at 160 ℃ for 5 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having red fluorescence.
Example 13
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP), 10mL of water was added, followed by 1mL of polyethyleneimine aqueous solution (PEI) (11 mg/mL) and 4mL of water, and the mixture was reacted at 180℃for 3 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having red fluorescence.
Example 14
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 1mL of polyethylenimine aqueous solution (PEI) (9 mg/mL) and 4mL of water, and reacted at 170 ℃ for 3 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having red fluorescence.
Example 15
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 2mL of Polyethyleneimine (PEI) aqueous solution (10 mg/mL) and 3mL of water, and reacted at 170 ℃ for 4 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having green fluorescence, the fluorescence spectrum of which is shown in fig. 5.
Example 16
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 2mL of Polyethyleneimine (PEI) aqueous solution (9.5 mg/mL) and 3mL of water, and reacted at 180 ℃ for 3 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having green fluorescence.
Example 17
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 2mL of Polyethyleneimine (PEI) aqueous solution (10.5 mg/mL) and 3mL of water, and reacted at 160 ℃ for 5 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having green fluorescence.
Example 18
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 2mL of Polyethyleneimine (PEI) aqueous solution (10.5 mg/mL) and 3mL of water, and reacted at 180 ℃ for 4 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having green fluorescence.
Example 19
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 5mL of Polyethyleneimine (PEI) aqueous solution (10 mg/mL), reacted at 170 ℃ for 4 hours, slowly cooled to room temperature, and placed in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having blue fluorescence, the fluorescence spectrum of which is shown in fig. 6.
Example 20
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 5mL of Polyethyleneimine (PEI) aqueous solution (9.8 mg/mL), reacted at 160 ℃ for 5 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having blue fluorescence.
Example 21
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 5mL of Polyethyleneimine (PEI) aqueous solution (10.2 mg/mL), reacted at 180 ℃ for 3 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having blue fluorescence.
Example 22
To 5mg of gadolinium-coordinated tetracarboxylic phenyl porphyrin (Gd-TCPP) was added 10mL of water, followed by 5mL of Polyethyleneimine (PEI) aqueous solution (10 mg/mL), reacted at 170 ℃ for 5 hours, slowly cooled to room temperature, and left in a dialysis bag having a molecular weight of 500 for 18 hours, to obtain an aqueous solution having blue fluorescence.
Example 23
The red fluorescent aqueous solution of example 11, the green fluorescent aqueous solution of example 15 and the blue fluorescent aqueous solution of example 19 in a molar ratio of 3:3:5 are mixed to obtain a white light fluorescent material, wherein the molar ratio of the red fluorescent aqueous solution to the green fluorescent aqueous solution to the blue fluorescent aqueous solution is calculated by the molar ratio of gadolinium ions in the fluorescent material, and a spectrum diagram of the white light fluorescent material is shown in fig. 7.
Example 24
The red fluorescent aqueous solution of the example 12, the green fluorescent aqueous solution of the example 16 and the blue fluorescent aqueous solution of the example 20 with a molar ratio of 3:2.9:5 are mixed to prepare the white light fluorescent material, wherein the molar ratio of the red fluorescent aqueous solution, the green fluorescent aqueous solution and the blue fluorescent aqueous solution is calculated by the molar ratio of gadolinium ions in the fluorescent material.
Example 25
The red fluorescent aqueous solution of example 13, the green fluorescent aqueous solution of example 17 and the blue fluorescent aqueous solution of example 21 are mixed in a molar ratio of 3:3:4.9 to obtain a white light fluorescent material, wherein the molar ratio of the red fluorescent aqueous solution, the green fluorescent aqueous solution and the blue fluorescent aqueous solution is calculated as the molar ratio of gadolinium ions in the fluorescent material.
Example 26
The red fluorescent aqueous solution of example 14, the green fluorescent aqueous solution of example 18 and the blue fluorescent aqueous solution of example 22 in a molar ratio of 3:2.9:4.9 are mixed to obtain a white light fluorescent material, wherein the molar ratio of the red fluorescent aqueous solution, the green fluorescent aqueous solution and the blue fluorescent aqueous solution is calculated as the molar ratio of gadolinium ions in the fluorescent material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A porphyrin fluorescent material is characterized by being prepared from gadolinium complexes of tetracarboxyl phenyl porphyrin and polyethyleneimine;
when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:1.8-2.2, the fluorescent material is red;
when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:3.8-4.2, the fluorescent material is green;
when the mass ratio of gadolinium complex of tetracarboxyl phenyl porphyrin to polyethyleneimine is 1:9.8-10.2, the fluorescent material is blue;
the preparation method of the porphyrin fluorescent material is completed through the following steps: and (3) reacting the gadolinium complex of the tetracarboxyl phenyl porphyrin with polyethyleneimine for 3-5 hours at 160-180 ℃, and removing impurities with molecular weight below 500 by using a dialysis means after the reaction is finished to obtain the fluorescent material.
2. The method for preparing a porphyrin fluorescent material according to claim 1, wherein gadolinium complex of tetra-carboxyphenyl porphyrin and polyethyleneimine are reacted for 3-5 hours at 160-180 ℃, and impurities with molecular weight below 500 are removed by dialysis means after the reaction is completed, so as to obtain the fluorescent material.
3. The method for preparing the porphyrin fluorescent material according to claim 2, wherein the method for preparing the gadolinium complex of the tetra-carboxyphenyl porphyrin comprises the following steps: the tetracarboxyl phenyl porphyrin, the soluble gadolinium salt and the solvent are sequentially put into a hydrothermal reaction kettle to react for 23-25 hours at 120-140 ℃ to obtain the catalyst.
4. The method for preparing a porphyrin-like fluorescent material according to claim 3, wherein the soluble gadolinium salt is GdCl 3 ·6H 2 O。
5. The method for preparing a porphyrin-like fluorescent material according to claim 3, wherein the molar ratio of the tetracarboxyl phenyl porphyrin to the soluble gadolinium salt is 1:1.8-2.2.
6. The method for preparing a porphyrin-like fluorescent material according to claim 3, wherein the solvent is N, N-dimethylformamide, acetic acid and ethanol in a volume ratio of 7:0.11-0.12:2.9-3.
7. The method for preparing a porphyrin-like fluorescent material according to claim 3, wherein the tetra-carboxyphenyl porphyrin is prepared by the following method:
step a: taking pyrrole and methyl p-formylbenzoate, adding an organic solvent, and carrying out reflux reaction for 1.8-2.2 hours under the protection of inert gas to obtain 5,10,15, 20-tetra (4-methoxyphenyl) porphyrin;
step b: adding 5,10,15, 20-tetra (4-methoxyphenyl) porphyrin into an organic solvent, adding a strong alkali solution, reacting for 2.5-3.5 hours at 50-70 ℃, cooling to room temperature, removing the solvent, and acidifying to obtain the tetracarboxyl phenyl porphyrin.
8. The method for preparing a porphyrin-like fluorescent material according to claim 7, wherein the organic solvent in the step a is propionic acid, and the molar ratio of pyrrole to methyl p-formylbenzoate is 1:1-1.2; the organic solvent in the step b is tetrahydrofuran and methanol with the volume ratio of 1:1-1.2; the strong alkali solution is KOH or NaOH aqueous solution with the concentration of 4-5 mol/L, and the addition amount is 1/5-1/4.
9. A white fluorescent material, which is prepared by mixing the red fluorescent material, the green fluorescent material and the blue fluorescent material according to claim 1, wherein the molar ratio of the red fluorescent material, the green fluorescent material and the blue fluorescent material is 3:2.9-3.0:4.9-5.0 based on the molar ratio of gadolinium ions in the fluorescent material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284647A (en) * | 1988-03-18 | 1994-02-08 | Schering Aktiengesellschaft | Mesotetraphenylporphyrin complex compounds, process for their production and pharmaceutical agents containing them |
| WO1998024775A1 (en) * | 1996-12-04 | 1998-06-11 | Schering Aktiengesellschaft | Method for producing metal complex carboxylic acid amides |
| CN101805362A (en) * | 2010-03-30 | 2010-08-18 | 中国医学科学院生物医学工程研究所 | Porphyrin modified by diethylenetriamine pentaacetic acid gadolinium and preparation method and application thereof |
| CN103223171A (en) * | 2013-04-03 | 2013-07-31 | 华南理工大学 | Porphyrin and uptransition rare earth nanocomposite, preparation method and application thereof |
| CN105153420A (en) * | 2015-08-18 | 2015-12-16 | 江南大学 | Water-soluble porphyrin based polymer capable of detecting heavy metal ions |
| CN107011511A (en) * | 2017-06-01 | 2017-08-04 | 西南大学 | A kind of protoporphyrin fluorescent carbon point and preparation method and application |
| CN108414489A (en) * | 2018-03-19 | 2018-08-17 | 西北师范大学 | A kind of pair of transmitting silica fluorescent probe is in detection Cu2+In application |
-
2019
- 2019-12-20 CN CN201911327424.8A patent/CN111004623B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284647A (en) * | 1988-03-18 | 1994-02-08 | Schering Aktiengesellschaft | Mesotetraphenylporphyrin complex compounds, process for their production and pharmaceutical agents containing them |
| WO1998024775A1 (en) * | 1996-12-04 | 1998-06-11 | Schering Aktiengesellschaft | Method for producing metal complex carboxylic acid amides |
| CN101805362A (en) * | 2010-03-30 | 2010-08-18 | 中国医学科学院生物医学工程研究所 | Porphyrin modified by diethylenetriamine pentaacetic acid gadolinium and preparation method and application thereof |
| CN103223171A (en) * | 2013-04-03 | 2013-07-31 | 华南理工大学 | Porphyrin and uptransition rare earth nanocomposite, preparation method and application thereof |
| CN105153420A (en) * | 2015-08-18 | 2015-12-16 | 江南大学 | Water-soluble porphyrin based polymer capable of detecting heavy metal ions |
| CN107011511A (en) * | 2017-06-01 | 2017-08-04 | 西南大学 | A kind of protoporphyrin fluorescent carbon point and preparation method and application |
| CN108414489A (en) * | 2018-03-19 | 2018-08-17 | 西北师范大学 | A kind of pair of transmitting silica fluorescent probe is in detection Cu2+In application |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Metal-Organic Framework Nanosheets with High Relaxation Rate and Singlet Oxygen Yield;Yuewu Zhao et al.;《 Chem. Mater.》;20181023;7511-7520 * |
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