CN111004623B - A kind of porphyrin fluorescent material and preparation method thereof - Google Patents

Abstract

The invention relates to a porphyrin-based fluorescent material and a preparation method thereof. A complex formed by tetracarboxyphenylporphyrin (TCPP) and gadolinium is combined with polyethyleneimine (PEI) to synthesize a fluorescent material with good water solubility. Fluorescent materials of different colors can be obtained according to the different ratios of the complex and polyethyleneimine, and then full color change can be achieved, and white fluorescent materials can be prepared from fluorescent materials of red, green and blue colors, which have broad lighting applications. application prospects.

Description

A kind of porphyrin fluorescent material and preparation method thereof

technical field

The invention relates to a fluorescent material and a preparation method thereof, in particular to a fluorescent material of a porphyrin coordination compound and a preparation method thereof.

Background technique

In recent years, with the development of the optoelectronic field, more and more scientists have begun to pay attention to white light fluorescent materials and their applications. Generally speaking, white light fluorescent materials are prepared by coordinating ratios of three primary colors (red, green, blue, wavelength 380-750nm). Such as molecular design with chromogenic functional groups; assembly adjustment of quantum dots, rare earth nanomaterials or supramolecules, etc. However, due to the poor water solubility, low quantum efficiency and high toxicity of most materials, their specific applications are very limited.

In recent years, people have tried to use carbon dots, rare earth hybrid materials, etc. to make new white light fluorescent materials, increase their biocompatibility, expand the further application of materials, and have made major breakthroughs. For example, the change of the amino position in the benzene ring is used to synthesize a full-color carbon dot fluorescent material and make a flexible film. Using the characteristics of quantum dots, materials with different fluorescent colors are separated from the same raw material, and applied to cell and in vivo imaging. Although these new materials have different applications, they must have good water solubility in the final analysis. Porphyrins exist widely in living organisms, but their water solubility is very limited. On the premise of ensuring coordination with rare earth elements, how to improve their water solubility has become an urgent problem to be solved.

Contents of the invention

Aiming at the problems of low quantum efficiency, high toxicity and poor water solubility of existing white light fluorescent materials, the invention provides a fluorescent material of a porphyrin coordination compound and a preparation method thereof.

In order to achieve the above-mentioned purpose of the invention, the present invention has adopted following technical scheme:

A porphyrin fluorescent material is prepared from gadolinium complex of tetracarboxyphenyl porphyrin and polyethyleneimine.

The present invention adopts the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine to react, through the interaction between the amino group in polyethyleneimine and the carboxyl group of tetracarboxyphenylporphyrin, to obtain the compound with good water solubility and fluorescence characteristics. Material.

The fluorescent material of the present invention can obtain materials of different colors according to the different ratios of the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine: when the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine When the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine is 1:3.8-4.2, the fluorescent material is green; when When the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin to polyethyleneimine is 1:9.8-10.2, the fluorescent material is blue.

Further, a method for preparing a porphyrin-based fluorescent material, comprising the following steps: reacting the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine at 160-180°C for 3-5 hours, slowly reducing to At room temperature, place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain a fluorescent material.

The preparation method of the fluorescent material of the invention is simple, and the gadolinium complex of tetracarboxyphenyl porphyrin and polyethyleneimine are hydrothermally reacted to obtain the finished product.

The preparation method of the gadolinium complex of tetracarboxyphenylporphyrin is as follows: put tetracarboxyphenylporphyrin, soluble gadolinium salt and solvent in sequence in a hydrothermal reaction kettle, and react at 120°C-140°C for 23-25 hours to obtain .

Further, the soluble gadolinium salt is GdCl ₃ ·6H ₂ O.

Further, the molar ratio of tetracarboxyphenylporphyrin to soluble gadolinium salt is 1:1.8-2.2.

Optionally, 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.

Tetracarboxyphenylporphyrin (TCPP) has four carboxyl groups that can coordinate well with rare earth elements. In the hydrothermal reactor, the coordination rate of rare earth ions can be increased through high temperature hydrothermal reaction.

The preparation method of tetracarboxyphenyl porphyrin is realized in the following steps:

Step a: Take pyrrole and methyl p-formylbenzoate, add an organic solvent, reflux under the protection of an inert gas for 1.8-2.2 hours, and place the product at -18°C for 12 hours to obtain 5,10, 15,20-Tetrakis(4-methoxyphenyl)porphyrin (TCPPOMe);

Step b: Add 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (TCPPOMe) into an organic solvent, add a strong base solution, react at 50°C-70°C for 2.5-3.5 hours, and cool After reaching room temperature, the solvent was removed, and then acidified to obtain tetracarboxyphenylporphyrin.

Preferably, the organic solvent described in step a is propionic acid, and the molar ratio of pyrrole and methyl p-formylbenzoate is 1:1-1.2.

Preferably, the organic solvent in step b is tetrahydrofuran and methanol in a volume ratio of 1:1-1.2.

Preferably, the strong alkali solution in step b is 4-5 mol/L KOH or NaOH aqueous solution, and the addition amount is 1/5-1/4.

A white fluorescent material, made by mixing red fluorescent material, green fluorescent material and blue fluorescent material, wherein the molar ratio of red fluorescent material, green fluorescent material, and blue fluorescent material is 3 based on the molar ratio of gadolinium ions in the fluorescent material :2.9-3.0:4.9-5.0.

The invention breaks through the conventional way of regulating and synthesizing white light materials by color regions, and uses homologous raw materials to prepare white light materials.

In the preparation of the above-mentioned fluorescent material, the porphyrin ligand tetracarboxyphenylporphyrin (TCPP) is selected, and its four carboxyl groups can well coordinate with rare earth elements. In order to improve its water solubility, the reaction between carboxyl and amino groups is used to combine polyethyleneimine (PEI) with good water solubility with porphyrin to synthesize a new type of fluorescent material with both water solubility and porphyrin properties. This material uses a hydrothermal method to combine TCPP, Gd and PEI to obtain a new type of luminescent material Gd-TCPP@PEI. On the one hand, Gd–TCPP@PEI can greatly enhance the water solubility and retain the red fluorescence of porphyrin. On the other hand, by adjusting the amount of PEI, temperature, reaction time and other conditions, the full color change of Gd–TCPP@PEI can be realized, and white fluorescent materials can be prepared. The white fluorescent material can be used in the lighting field.

Description of drawings

The present invention will be further described below in conjunction with accompanying drawing and embodiment, in the accompanying drawing:

Fig. 1 is the nuclear magnetic spectrum of the 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin prepared in embodiment 1;

Fig. 2 is the nuclear magnetic spectrogram of the tetracarboxyphenylporphine prepared in embodiment 4;

Fig. 3 is the collection of illustrations characterized by an x-ray diffractometer at room temperature of Gd-TCPP prepared in Example 7;

Fig. 4 is the fluorescent spectrum of the red fluorescent material prepared in embodiment 11;

Fig. 5 is the fluorescent spectrum of the green fluorescent material prepared in embodiment 15;

Fig. 6 is the fluorescent spectrum of the blue fluorescent material prepared by embodiment 19;

Fig. 7 is the fluorescent spectrum of the white fluorescent material prepared in embodiment 23;

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Example 1

Put 33mL of propionic acid into a 100mL three-necked flask, add 0.014mol of fresh pyrrole and 0.014mol of methyl p-formylbenzoate, and reflux for 2 hours under the protection of _N2 . After the reaction, the product was placed in a -18°C environment for 12 hours, filtered and washed with cold methanol to obtain a purple precipitate TCPPOMe, which was placed in a vacuum oven for drying. Its NMR spectrum is shown in Figure 1.

Example 2

Put 33mL of propionic acid into a 100mL three-neck flask, add 0.014mol of fresh pyrrole and 0.017mol of methyl p-formylbenzoate, and reflux for 2.2 hours under the protection of _N2 . After the reaction, the product was placed in a -18°C environment for 12 hours, filtered and washed with cold methanol to obtain a purple precipitate TCPPOMe, which was placed in a vacuum oven for drying.

Example 3

Put 33mL of propionic acid into a 100mL three-neck flask, add 0.014mol of fresh pyrrole and 0.016mol of methyl p-formylbenzoate, and reflux for 1.8 hours under the protection of _N2 . After the reaction, the product was placed in a -18°C environment for 12 hours, filtered and washed with cold methanol to obtain a purple precipitate TCPPOMe, which was placed in a vacuum oven for drying.

Example 4

Dissolve 0.2g TCPPOMe in a mixed solvent of 10mL tetrahydrofuran and methanol (v:v=1:1), then add 2mL aqueous solution containing KOH 8.92mmol, react at 60°C for 2 hours, remove the solvent after cooling to room temperature, and then Distilled water was added until the solid was completely dissolved, then 1M HCl solution was added to the solution until no more precipitates were precipitated, filtered and washed with distilled water, and then placed in a vacuum drying oven for use. Its NMR spectrum is shown in Figure 2.

Example 5

Dissolve 0.2g TCPPOMe in a mixed solvent of 10mL tetrahydrofuran and methanol (v:v=1:1.2), then add 2.5mL of an aqueous solution containing 8mmol of NaOH, react at 70°C for 2.5 hours, remove the solvent after cooling to room temperature, and then Distilled water was added until the solid was completely dissolved, then 1M HCl solution was added to the solution until no more precipitates were precipitated, filtered and washed with distilled water, and then placed in a vacuum drying oven for use.

Example 6

Dissolve 0.2g TCPPOMe in a mixed solvent of 10mL tetrahydrofuran and methanol (v:v=1:1), then add 2mL aqueous solution containing KOH 10mmol, react at 50°C for 3.5 hours, remove the solvent after cooling to room temperature, and then add Distilled water until the solid was completely dissolved, then added 1M HCl solution to the solution until no more precipitates were precipitated, filtered and washed with distilled water, and then placed in a vacuum oven for use.

Example 7

Put 0.015mmol of tetracarboxyphenylporphyrin, 0.03mmol of GdCl ₃ 6H ₂ O, 3.5mL of DMF (N,N-dimethylformamide), 60μL of acetic acid and 1.5mL of ethanol into a 30mL polytetrafluoroethylene reactor In the inner lining, after sealing, heat slowly to 130°C and react for 24 hours. After the reaction is completed, cool slowly to room temperature to obtain Gd-TCPP purple solid, which is washed with distilled water and dried for later use. Its x-ray diffraction pattern is shown in Figure 3.

Example 8

Put 0.015mmol of tetracarboxyphenylporphyrin, 0.027mmol of GdCl ₃ 6H ₂ O, 3.5mL of DMF (N,N-dimethylformamide), 55μL of acetic acid and 1.5mL of ethanol into a 30mL polytetrafluoroethylene reactor In the lining, after sealing, heat slowly to 120°C and react for 25 hours. After the reaction is completed, cool slowly to room temperature to obtain Gd-TCPP purple solid, which is washed with distilled water and dried for later use.

Example 9

Put 0.015mmol of tetracarboxyphenylporphyrin, 0.033mmol of GdCl ₃ 6H ₂ O, 3.5mL of DMF (N,N-dimethylformamide), 60μL of acetic acid and 1.45mL of ethanol into a 30mL polytetrafluoroethylene reactor in sequence In the lining, after sealing, heat slowly to 140°C and react for 23 hours. After the reaction is completed, cool slowly to room temperature to obtain Gd-TCPP purple solid, which is washed with distilled water and dried for later use.

Example 10

Put 0.015mmol of tetracarboxyphenylporphyrin, 0.03mmol of GdCl ₃ 6H ₂ O, 3.5mL of DMF (N,N-dimethylformamide), 60μL of acetic acid and 1.5mL of ethanol into a 30mL polytetrafluoroethylene reactor In the lining, after sealing, heat slowly to 140°C and react for 25 hours. After the reaction is completed, cool slowly to room temperature to obtain Gd-TCPP purple solid, which is washed with distilled water and dried for later use.

Example 11

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 1 mL of polyethyleneimine aqueous solution (PEI) (10 mg/mL) and 4 mL of water, and react at 170 ° C for 4 hours, Slowly lower to room temperature, and place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with red fluorescence, the fluorescence spectrum of which is shown in Figure 4.

Example 12

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 1 mL of polyethyleneimine aqueous solution (PEI) (9 mg/mL) and 4 mL of water, and react at 160 ° C for 5 hours, Slowly lower to room temperature and place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with red fluorescence.

Example 13

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 1 mL of polyethyleneimine aqueous solution (PEI) (11 mg/mL) and 4 mL of water, and react at 180 ° C for 3 hours, Slowly lower to room temperature and place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with red fluorescence.

Example 14

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 1 mL of polyethyleneimine aqueous solution (PEI) (9 mg/mL) and 4 mL of water, and react at 170 ° C for 3 hours, Slowly lower to room temperature and place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with red fluorescence.

Example 15

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 2 mL of polyethyleneimine (PEI) aqueous solution (10 mg/mL) and 3 mL of water, and react at 170 ° C for 4 hours, Slowly lower to room temperature, and place in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with green fluorescence, the fluorescence spectrum of which is shown in Figure 5.

Example 16

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 2 mL of polyethyleneimine (PEI) aqueous solution (9.5 mg/mL) and 3 mL of water, and react at 180 °C for 3 hours , slowly lowered to room temperature, and placed in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with green fluorescence.

Example 17

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 2 mL of polyethyleneimine (PEI) aqueous solution (10.5 mg/mL) and 3 mL of water, and react at 160 °C for 5 hours , slowly lowered to room temperature, and placed in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with green fluorescence.

Example 18

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 2 mL of polyethyleneimine (PEI) aqueous solution (10.5 mg/mL) and 3 mL of water, and react at 180 °C for 4 hours , slowly lowered to room temperature, and placed in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with green fluorescence.

Example 19

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 5 mL of polyethyleneimine (PEI) aqueous solution (10 mg/mL), react at 170 ° C for 4 hours, slowly drop to At room temperature, place it in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with blue fluorescence, the fluorescence spectrum of which is shown in Figure 6.

Example 20

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 5 mL of polyethyleneimine (PEI) aqueous solution (9.8 mg/mL), react at 160 ° C for 5 hours, slowly drop to to room temperature and placed in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with blue fluorescence.

Example 21

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 5 mL of polyethyleneimine (PEI) aqueous solution (10.2 mg/mL), react at 180 ° C for 3 hours, slowly drop to to room temperature and placed in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with blue fluorescence.

Example 22

Add 10 mL of water to 5 mg of gadolinium-coordinated tetracarboxyphenylporphyrin (Gd-TCPP), then add 5 mL of polyethyleneimine (PEI) aqueous solution (10 mg/mL), react at 170 ° C for 5 hours, and slowly drop to At room temperature, place it in a dialysis bag with a molecular weight of 500 for 18 hours to obtain an aqueous solution with blue fluorescence.

Example 23

Take 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 with a molar ratio of 3:3:5, and mix the three fluorescent aqueous solutions to prepare a white fluorescent material, wherein red, green 1. The molar ratio of the blue fluorescent aqueous solution is based on the molar ratio of gadolinium ions in the fluorescent material, and the spectrum of the white fluorescent material prepared by it is shown in FIG. 7 .

Example 24

Take the red fluorescent aqueous solution of Example 12, the green fluorescent aqueous solution of Example 16, and the blue fluorescent aqueous solution of Example 20 with a molar ratio of 3:2.9:5, and mix the three fluorescent aqueous solutions to prepare a white fluorescent material, wherein red, green , The molar ratio of the blue fluorescent aqueous solution is calculated by the molar ratio of gadolinium ions in the fluorescent material.

Example 25

Take 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 with a molar ratio of 3:3:4.9, and mix the three fluorescent aqueous solutions to prepare a white fluorescent material, wherein red, green , The molar ratio of the blue fluorescent aqueous solution is calculated by the molar ratio of gadolinium ions in the fluorescent material.

Example 26

Take 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 with a molar ratio of 3:2.9:4.9, and mix the three fluorescent aqueous solutions to prepare a white fluorescent material, wherein red, green , The molar ratio of the blue fluorescent aqueous solution is calculated by the molar ratio of gadolinium ions in the fluorescent material.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (9)

1. A porphyrin fluorescent material, characterized in that it is prepared from gadolinium complexes of tetracarboxyphenylporphyrin and polyethyleneimine; When the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin to polyethyleneimine is 1:1.8-2.2, the fluorescent material is red; When the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin to polyethyleneimine is 1:3.8-4.2, the fluorescent material is green; When the mass ratio of the gadolinium complex of tetracarboxyphenylporphyrin to polyethyleneimine is 1:9.8-10.2, the fluorescent material is blue; The preparation method of the porphyrin-based fluorescent material is completed through the following steps: reacting the gadolinium complex of tetracarboxyphenylporphyrin and polyethyleneimine at 160°C-180°C for 3-5 hours, and using Dialysis means to remove impurities with a molecular weight below 500 to obtain fluorescent materials. 2. the preparation method of a kind of porphyrin fluorescent material described in claim 1 is characterized in that, the gadolinium complex of described tetracarboxyphenylporphyrin and polyethyleneimine are reacted at 160 ℃-180 ℃ for 3 -5 hours, after the reaction is completed, use dialysis means to remove impurities with a molecular weight below 500 to obtain a fluorescent material. 3. the preparation method of a kind of porphyrin fluorescent material as claimed in claim 2, is characterized in that, the preparation method of the gadolinium complex of described tetracarboxyphenylporphyrin is: tetracarboxyphenylporphyrin, soluble The gadolinium salt and the solvent are sequentially placed in a hydrothermal reaction kettle, and reacted at 120°C-140°C for 23-25 hours to obtain the product. 4 . The preparation method of a porphyrin-based fluorescent material according to claim 3 , wherein the soluble gadolinium salt is GdCl ₃ ·6H ₂ O. 5. The preparation method of a kind of porphyrin fluorescent material as claimed in claim 3, is characterized in that, the molar ratio of described tetracarboxyphenylporphyrin and soluble gadolinium salt is 1:1.8-2.2. 6. the preparation method of a kind of porphyrin fluorescent material as claimed in claim 3 is characterized in that, described solvent is the N,N-dimethylformamide that volume ratio is 7:0.11-0.12:2.9-3 , acetic acid and ethanol. 7. the preparation method of a kind of porphyrin fluorescent material as claimed in claim 3, is characterized in that, described tetracarboxyphenyl porphyrin adopts following method to prepare: Step a: Take pyrrole and methyl p-formylbenzoate, add an organic solvent, and reflux under the protection of an inert gas for 1.8-2.2 hours to obtain 5,10,15,20-tetrakis(4-methoxyphenyl) porphyrin; Step b: Add 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin into an organic solvent, add a strong base solution, react at 50°C-70°C for 2.5-3.5 hours, and cool to room temperature Removal of solvent and acidification to obtain tetracarboxyphenyl porphyrin. 8. the preparation method of a kind of porphyrin fluorescent material as claimed in claim 7 is characterized in that, organic solvent described in the described step a is propionic acid, and the mol ratio of pyrrole and methyl p-formylbenzoate is 1:1-1.2; the organic solvent described in the step b is tetrahydrofuran and methanol with a volume ratio of 1:1-1.2; the strong alkali solution is 4-5mol/L KOH or NaOH aqueous solution, and the addition amount is 1 /5～1/4. 9. A white fluorescent material, characterized in that it is prepared by mixing the red fluorescent material, green fluorescent material and blue fluorescent material according to claim 1, wherein the moles of red fluorescent material, green fluorescent material, and blue fluorescent material The ratio is 3:2.9-3.0:4.9-5.0 based on the molar ratio of gadolinium ions in the fluorescent material.