Fluorescent hyperbranched polysiloxane gas transmitter material and preparation method thereof

Abstract

The invention discloses a fluorescent hyperbranched polysiloxane gas transmitter material, amino acid and amino silane are subjected to a microwave reaction to generate an oligomer, and then the oligomer and dihydric alcohol are subjected to a condensation polymerization reaction to generate the fluorescent hyperbranched polysiloxane gas transmitter material, and the invention further discloses a preparation method of the fluorescent hyperbranched polysiloxane gas transmitter material. The method comprises the following steps: carrying out amidation reaction on amino acid and aminosilane to generate water, and then carrying out condensation polymerization reaction on the water and diol to generate the water. According to the present invention, the varieties of amino acids and amino silane are regulated and controlled, the microwave reaction is adopted to generate different varieties of oligomers, the oligomers and various dihydric alcohols are subjected to condensation polymerization to generate a variety of hyperbranched polysiloxane gas transmitter materials, and a series of hyperbranched polysiloxane gas transmitter materials containing a large amount of amino acids in the structure can be synthesized through the method, by virtue of good biocompatibility, chemical stability and unique fluorescence property, the nano-material can be used as a carrier of a gas transmitter material, so that efficient delivery and accurate release of gas transmitters can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of gaseous transmitter materials, and in particular relates to a fluorescent hyperbranched polysiloxane gaseous transmitter material and a preparation method thereof. Background Art

[0002] Gaseous transmitters have important applications in biomedicine and other fields. For example, gaseous transmitters such as nitric oxide, carbon monoxide, and hydrogen sulfide have shown great potential in regulating physiological functions and treating diseases. However, existing gaseous transmitter materials have problems such as poor release controllability and insufficient stability, which limit their application.

[0003] Fluorescent hyperbranched polysiloxane has good biocompatibility, chemical stability and unique fluorescence properties. As a carrier of gaseous transmitter materials, it can achieve efficient delivery and precise release of gaseous transmitters.

[0004] Therefore, there is a need for fluorescent hyperbranched polysiloxane gas transmitter materials and methods for preparing the same. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a fluorescent hyperbranched polysiloxane gas transmitter material in view of the deficiencies of the above-mentioned prior art. The fluorescent hyperbranched polysiloxane gas transmitter material is obtained by subjecting amino acids and aminosilane to microwaves and then polycondensing with diols, and has good biocompatibility, chemical stability and unique fluorescent properties. As a carrier of the gas transmitter material, the efficient delivery and precise release of the gas transmitter are achieved.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: fluorescent hyperbranched polysiloxane gas transmitter material, characterized in that the gas transmitter material is generated by reacting amino acid and aminosilane with microwaves to generate oligomers, and then reacting with diols through condensation reaction.

[0007] The present invention subjects amino acids and aminosilane to microwave treatment and then polycondensation with diols to obtain a fluorescent hyperbranched polysiloxane gas transmitter material. The fluorescent hyperbranched polysiloxane gas transmitter material containing a large amount of amino acids has good biocompatibility, chemical stability and unique fluorescent properties, and is used as a carrier of the gas transmitter material to achieve efficient delivery and precise release of the gas transmitter.

[0008] The fluorescent hyperbranched polysiloxane gas transmitter material is characterized in that the molar ratio of the amino acid to the aminosilane is 1:2 to 3. The present invention can synthesize hyperbranched polysiloxanes of different structures by regulating the type of aminosilane within the molar ratio of 1:2 to 3.

[0009] The fluorescent hyperbranched polysiloxane gas transmitter material is characterized in that the amino acid is arginine, cystine, cysteine, phenylalanine, tyrosine, histidine or tryptophan. The present invention enhances the gas adsorption capacity and fluorescence performance of the material by controlling the type of amino acid, and is suitable for different use requirements.

[0010] The fluorescent hyperbranched polysiloxane gas transmitter material is characterized in that the aminosilane is 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane. The present invention controls the type of aminosilane to facilitate the polycondensation reaction to form a stable hyperbranched structure.

[0011] The fluorescent hyperbranched polysiloxane gas transmitter material is characterized in that the diol is: dipropylene glycol, diethylene glycol, diethylene glycol, butanediol or propylene glycol. The present invention controls the type of diol, adjusts the crosslinking degree of the material, and optimizes the gas diffusion rate.

[0012] In addition, the present invention also provides a method for preparing a fluorescent hyperbranched polysiloxane gas transmitter material, characterized in that the method comprises the following steps:

[0013] Step 1: Mix the amino acid and aminosilane, and then put them into a microwave oven for microwave reaction to obtain an oligomer;

[0014] Step 2, weighing and counting the oligomers obtained in step 1, and then adding diol at a molar ratio of oligomer to diol of 1:2 to 4 to obtain a mixed solution;

[0015] Step 3, the mixed solution obtained in step 2 is first heated to 70°C to 90°C under nitrogen protection, and then continued to heat at a heating rate of 1°C / min. When a distillate is generated, the heating rate is continued at 2°C / min and the temperature of the distillate is maintained at 53°C to 57°C, until it is heated to 150°C and then kept warm. When the temperature of the distillate drops to 45°C and the mixed solution is yellow and viscous, the heating is stopped, and the mixture is cooled naturally to obtain a yellow viscous solution;

[0016] Step 4: dialyze the yellow viscous solution obtained in step 3 using a dialysis bag, and then perform rotary evaporation using a rotary evaporator to obtain a high-purity fluorescent hyperbranched polysiloxane gas transmitter material.

[0017] The present invention firstly conducts microwave reaction on amino acid and aminosilane, utilizes the fast heating and homogeneous characteristics of microwave reaction to promote synthesis, causes amidation reaction between carboxyl group of amino acid and amino group of aminosilane to generate oligomer and water, removes water to synthesize oligomer, then conducts polycondensation reaction on oligomer and diol, and simultaneously controls the temperature of distillate to remove byproduct ethanol, ensures that the reaction proceeds in the forward direction, and obtains fluorescent hyperbranched polysiloxane gas transmitter material.

[0018] The invention adopts nitrogen protection to prevent oxidation when the mixed solution is subjected to polycondensation reaction, firstly heats the mixture to 70-90°C to improve efficiency, continues heating at a heating rate of 1°C / min, and when a distillate is generated, continues heating at a heating rate of 2°C / min and keeps the temperature of the distillate at 53-57°C until the mixture is heated to 150°C and kept warm, so as to ensure that the polycondensation reaction is fully carried out, and as the reaction proceeds, the distillate decreases, the temperature of the distillate decreases, the heating is stopped, and the mixture is cooled naturally to obtain a yellow viscous solution.

[0019] The present invention uses dialysis to remove unreacted small molecular monomers and salt impurities to improve product purity; and obtains high-purity fluorescent hyperbranched polysiloxane gas transmitter material after removing low melting point impurities through rotary evaporation.

[0020] The above method is characterized in that the microwave reaction process in step 1 is: adjust the microwave oven to high heat for 4 to 6 minutes, then take it out and stir it with a glass rod, and then put it back into the microwave oven and adjust it to medium heat for 4 to 6 minutes. The present invention avoids local overheating and ensures reaction uniformity through intermittent microwave treatment.

[0021] The above method is characterized in that after the microwave reaction in step 1 is completed, a yellow supernatant is taken and then filtered with filter paper to obtain an oligomer. In the present invention, powder particles are removed by filtering with filter paper, thereby ensuring the purity of the product.

[0022] The above method is characterized in that the temperature of the rotary evaporation in step 4 is 40° C. to 60° C. The present invention fully removes impurities by controlling the temperature of the rotary evaporation.

[0023] The above method is characterized in that the high-purity fluorescent hyperbranched polysiloxane gas transmitter material in step 4 can release gas stably for a long time within five days. The high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared by the present invention can release gas stably for a long time within five days, laying a foundation for its biological application.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] 1. The present invention subjects amino acids and aminosilane to microwave treatment and then polycondensation with diols to obtain a fluorescent hyperbranched polysiloxane gas transmitter material. The fluorescent hyperbranched polysiloxane gas transmitter material containing a large amount of amino acids has good biocompatibility, chemical stability and unique fluorescent properties. It is used as a carrier of the gas transmitter material to achieve efficient delivery and precise release of the gas transmitter, thereby solving the problems of poor release controllability and insufficient stability of existing gas transmitter materials.

[0026] 2. The present invention conducts a microwave reaction between amino acids and aminosilane, and utilizes the rapid and homogeneous heating characteristics of microwave reaction to promote synthesis. The method is economical and convenient, does not require catalysts and solvents, and has a simple synthesis process. The carboxyl group of the amino acid and the amino group of the aminosilane undergo an amidation reaction to generate an oligomer, which is then subjected to a condensation reaction with a diol. At the same time, the by-product ethanol is removed by controlling the temperature of the distillate to ensure that the reaction proceeds in the forward direction, thereby obtaining a fluorescent hyperbranched polysiloxane gas transmitter material, which has the characteristics of long-term controllable sustained release of gas, good biocompatibility, and wide application, and is used in the fields of cell imaging and infection treatment.

[0027] 3. The present invention enhances the gas adsorption capacity and fluorescence performance of the material by controlling the type of amino acid, which is suitable for different usage requirements. By controlling the type of aminosilane, the polycondensation reaction is beneficial to form a stable hyperbranched structure. By controlling the type of diol, the crosslinking degree of the material is adjusted and the gas diffusion rate is optimized.

[0028] 4. The molecular weight of the fluorescent hyperbranched polysiloxane gas transmitter material prepared by the present invention is between 10,000 and 50,000, which conforms to the molecular weight distribution of typical polymer materials.

[0029] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a schematic diagram of the synthesis principle of the oligomer of Example 1 of the present invention.

[0031] Figure 2 This is a schematic diagram of the synthesis principle of the high-purity fluorescent hyperbranched polysiloxane gas transmitter material of Example 1 of the present invention.

[0032] Figure 3 This is the fluorescence spectrum of the high-purity fluorescent hyperbranched polysiloxane gas transmitter material obtained in Example 1 of the present invention.

[0033] Figure 4 This is the NO release curve of the high-purity fluorescent hyperbranched polysiloxane gas transmitter material obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Example 1

[0035] This embodiment includes the following steps:

[0036] Step 1: put arginine and 3-aminopropyltriethoxysilane in a glass bottle at a molar ratio of 1:2, then put the glass bottle into a microwave oven for high heat treatment for 5 minutes, take it out and stir it with a glass rod for 1 minute, then put it into the microwave oven for medium heat treatment for 5 minutes, take it out and let it stand, and finally take the yellow supernatant in the glass bottle and filter it to obtain an oligomer;

[0037] Step 2, weighing and counting the oligomer obtained in step 1, and then adding dipropylene glycol at a molar ratio of 1:2 to obtain a mixed solution;

[0038] Step 3, placing the mixed solution obtained in step 2 in a three-necked flask, and sequentially setting up reaction, stirring, condensation and collection systems, first heating to 80°C under a nitrogen protective atmosphere, and then continuing to heat at a heating rate of 1°C / min, and when a distillate is generated, continue heating at a heating rate of 2°C / min and keep the temperature of the distillate at 53°C to 57°C, until it is heated to 150°C and then kept warm, collecting the distillate, and stopping heating when the mixed solution becomes yellow and viscous and the temperature of the distillate drops to 45°C, and naturally cooling to obtain a yellow viscous solution;

[0039] Step 4: put the yellow viscous solution obtained in step 3 into a dialysis bag, use ethanol as the dialysate for 24 hours, and then use a rotary evaporator to perform rotary evaporation at 40°C to 60°C to obtain a high-purity fluorescent hyperbranched polysiloxane gas transmitter material.

[0040] After testing, the high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this embodiment has a purity of 99.99% and a molecular weight of 10,000 to 50,000. It has good biocompatibility, chemical stability and unique fluorescence properties. As a carrier of gas transmitter materials, it can achieve efficient delivery and precise release of gas transmitters.

[0041] In this embodiment, the amino acid can also be: cystine, cysteine, phenylalanine, tyrosine, histidine or tryptophan, the aminosilane can also be: 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane, and the diol can also be: diethylene glycol, diethylene glycol, butanediol or propylene glycol.

[0042] Figure 1 The synthesis principle diagram of the oligomer of this embodiment is as follows: Figure 1 It can be seen that in this example, arginine and 3-aminopropyltriethoxysilane are subjected to microwave treatment to cause the carboxyl group of arginine and the amino group of 3-aminopropyltriethoxysilane to undergo amidation reaction to obtain an oligomer.

[0043] Figure 2 The synthesis principle diagram of the high-purity fluorescent hyperbranched polysiloxane gas transmitter material of this embodiment is as follows: Figure 2 It can be seen that in this embodiment, the oligomer is subjected to a condensation reaction with dipropylene glycol to obtain a fluorescent hyperbranched polysiloxane gas transmitter material.

[0044] The high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this example was prepared into 20 mg / ml, 50 mg / ml and 100 mg / ml solutions, and then fluorescence tests were performed. The results are shown in FIG. Figure 3 , Figure 3 The curve on the left is fluorescence excitation, and the curve on the right is fluorescence emission. Figure 3 It can be seen that the high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this example has a fluorescent effect.

[0045] The high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this example was prepared into 20 mg / ml, 50 mg / ml and 100 mg / ml solutions, and then NO release test was performed using a NO test kit. The results are shown in FIG. Figure 4 , Figure 4 The vertical axis is the absorbance under 450nm excitation, which represents the amount of NO released. The slope of the curve reflects the release rate. Figure 4 It can be seen that the high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this example first releases NO violently at the concentration of 50 mg / ml and 100 mg / ml, and then the release reaches a plateau and becomes gentle.

[0046] Example 2

[0047] This embodiment includes the following steps:

[0048] Step 1, arginine and 3-aminopropyltriethoxysilane are placed in a glass bottle at a molar ratio of 1:3, and then the glass bottle is placed in a microwave oven for 6 minutes at high heat, taken out and stirred with a glass rod for 1 minute, and then placed in a microwave oven for another 4 minutes at medium heat, and then taken out and allowed to stand, and finally the yellow supernatant in the glass bottle is filtered to obtain an oligomer;

[0049] Step 2: weigh and count the oligomer obtained in step 1, and then add dipropylene glycol at a molar ratio of 1:3 to obtain a mixed solution;

[0050] Step 3, placing the mixed solution obtained in step 2 in a three-necked flask, and sequentially setting up reaction, stirring, condensation and collection systems, first heating to 90°C under a nitrogen protective atmosphere, and then continuing to heat at a heating rate of 1°C / min, and when a distillate is generated, continue heating at a heating rate of 2°C / min and keep the temperature of the distillate at 53°C to 57°C, and then heat to 150°C, collect the distillate, and stop heating when the mixed solution becomes yellow and viscous and the temperature of the distillate drops to 45°C, and cool naturally to obtain a yellow viscous solution;

[0051] Step 4: put the yellow viscous solution obtained in step 3 into a dialysis bag, use ethanol as the dialysate for 24 hours, and then use a rotary evaporator to perform rotary evaporation at 40°C to 60°C to obtain a high-purity fluorescent hyperbranched polysiloxane gas transmitter material.

[0052] After testing, the high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this embodiment has a purity of 99.99% and a molecular weight of 10,000 to 50,000. It has good biocompatibility, chemical stability and unique fluorescence properties. As a carrier of gas transmitter materials, it can achieve efficient delivery and precise release of gas transmitters.

[0053] In this embodiment, the amino acid can also be: cystine, cysteine, phenylalanine, tyrosine, histidine or tryptophan, the aminosilane can also be: 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane, and the diol can also be: diethylene glycol, diethylene glycol, butanediol or propylene glycol.

[0054] Example 3

[0055] This embodiment includes the following steps:

[0056] Step 1: put arginine and 3-aminopropyltriethoxysilane in a glass bottle at a molar ratio of 1:2.5, then put the glass bottle into a microwave oven for 4 minutes at high heat, take it out and stir it with a glass rod for 1 minute, then put it into the microwave oven for 6 minutes at medium heat, take it out and let it stand, and finally take the yellow supernatant in the glass bottle and filter it to obtain an oligomer;

[0057] Step 2: weigh and count the oligomer obtained in step 1, and then add dipropylene glycol at a molar ratio of 1:4 to obtain a mixed solution;

[0058] Step 3, placing the mixed solution obtained in step 2 in a three-necked flask, and sequentially setting up reaction, stirring, condensation and collection systems, first heating to 70°C under a nitrogen protective atmosphere, and then continuing to heat at a heating rate of 1°C / min, and when a distillate is generated, continue heating at a heating rate of 2°C / min and keep the temperature of the distillate at 53°C to 57°C, and then heat to 150°C, collect the distillate, and stop heating when the mixed solution becomes yellow and viscous and the temperature of the distillate drops to 45°C, and cool naturally to obtain a yellow viscous solution;

[0059] Step 4: put the yellow viscous solution obtained in step 3 into a dialysis bag, use ethanol as the dialysate for 24 hours, and then use a rotary evaporator to perform rotary evaporation at 40°C to 60°C to obtain a high-purity fluorescent hyperbranched polysiloxane gas transmitter material.

[0060] After testing, the high-purity fluorescent hyperbranched polysiloxane gas transmitter material prepared in this embodiment has a purity of 99.99% and a molecular weight of 10,000 to 50,000. It has good biocompatibility, chemical stability and unique fluorescence properties. As a carrier of gas transmitter materials, it can achieve efficient delivery and precise release of gas transmitters.

[0061] In this embodiment, the amino acid can also be: cystine, cysteine, phenylalanine, tyrosine, histidine or tryptophan, the aminosilane can also be: 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane, and the diol can also be: diethylene glycol, diethylene glycol, butanediol or propylene glycol.

[0062] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent change made to the above embodiment according to the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A fluorescent hyperbranched polysiloxane gas transmitter material, characterized in that: The gas transmitter material is prepared by reacting amino acid and aminosilane by microwave to generate oligomer, and then reacting the oligomer with diol by condensation polymerization.

2. The fluorescent hyperbranched polysiloxane gas transmitter material according to claim 1, characterized in that: The molar ratio of the amino acid to the aminosilane is 1:2-3.

3. The fluorescent hyperbranched polysiloxane gas transmitter material according to claim 1, characterized in that: The amino acid is: arginine, cystine, cysteine, phenylalanine, tyrosine, histidine or tryptophan.

4. The fluorescent hyperbranched polysiloxane gas transmitter material according to claim 1, characterized in that: The aminosilane is: 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane.

5. The fluorescent hyperbranched polysiloxane gas transmitter material according to claim 1, characterized in that: The diol is: dipropylene glycol, diethylene glycol, diethylene glycol, butanediol or propylene glycol.

6. A method for preparing the fluorescent hyperbranched polysiloxane gas transmitter material according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: Step 1: Mix the amino acid and aminosilane, and then put them into a microwave oven for microwave reaction to obtain an oligomer; Step 2, weighing and counting the oligomers obtained in step 1, and then adding diol at a molar ratio of oligomer to diol of 1:2 to 4 to obtain a mixed solution; Step 3, the mixed solution obtained in step 2 is first heated to 70°C to 90°C under nitrogen protection, and then continued to heat at a heating rate of 1°C / min. When a distillate is generated, the heating rate is continued at 2°C / min and the temperature of the distillate is maintained at 53°C to 57°C, until it is heated to 150°C and then kept warm. When the temperature of the distillate drops to 45°C and the mixed solution is yellow and viscous, the heating is stopped, and the mixture is cooled naturally to obtain a yellow viscous solution; Step 4: dialyze the yellow viscous solution obtained in step 3 using a dialysis bag, and then perform rotary evaporation using a rotary evaporator to obtain a high-purity fluorescent hyperbranched polysiloxane gas transmitter material.

7. The method according to claim 6, characterized in that The process of the microwave reaction in step 1 is: adjust the microwave oven to high heat for 4min to 6min, then take it out and stir it with a glass rod, and then put it back into the microwave oven and adjust it to medium heat for 4min to 6min.

8. The method according to claim 6, characterized in that After the microwave reaction in step 1 is completed, the yellow supernatant is taken and then filtered with filter paper to obtain an oligomer.

9. The method according to claim 6, characterized in that The temperature of the rotary evaporation in step 4 is 40°C to 60°C.

10. The method according to claim 6, characterized in that The high-purity fluorescent hyperbranched polysiloxane gas transmitter material described in step 4 can release gas stably for a long time within five days.

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