Preparation method of mussel-inspired multifunctional polyaspartamide derivative polymer

Abstract

The application relates to a preparation method of a mussel-biomimetic multifunctional polyaspartamide derivative polymer, belonging to the field of water-soluble polymers. In the polyaspartamide derivative polymer PolyAspAm (DOPA / API / EA), mussel-biomimetic functional groups and 1-(3-aminopropyl) imidazole functional groups are introduced, so that the problem of single functionalization of traditional polyaspartamide derivative polymers can be solved. The polyaspartamide derivative polymer PolyAspAm (DOPA / API / EA) can be applied to different fields such as biosensors and medical dressing antibacterial agents as self-healing, antibacterial, CO2 adsorption and other polymer materials.

Description

Technical Field

[0001] This invention relates to the field of water-soluble polymers, specifically to a mussel-inspired multifunctional polyasparagine-derived polymer and its preparation method. Background Technology

[0002] Polyasparagine is a class of synthetic protein polymers possessing amide groups and various side groups. Due to the reactivity of the succinimide ring on polysuccinimide, polyasparagine can readily yield different functional groups (such as hydrophilic, hydrophobic, acidic, basic, stimuli-responsive, chelating, or bioactive groups) through ammonolysis. Polyasparagine with different functional groups can be used to develop polymers or gels that are heat-responsive, pH-responsive, redox-responsive, and CO2-responsive, thus gaining wide applications. This new generation of green chemical polymers has many advantages, including readily available raw materials, non-toxicity, good biocompatibility, biodegradability, environmental reliability, relatively simple synthesis, and ease of chemical modification.

[0003] Marine mussels, in their rocky coastal habitats, are firmly anchored to surfaces using tough, self-healing protein fibers known as shell threads. These threads, composed of 25-30 different types of underwater mussel adhesion proteins (UMAPs), can withstand the impact of high-energy waves. The 3,4-dihydroxyphenylalanine (DOPA), a catechol function, contained in these adhesion proteins plays a crucial role in mussel adhesion, forming bonds with various organic and inorganic surfaces. The catechol groups can form strong coordination complexes with different metal ions, creating strong, reversible interactions and enabling rapid self-repair.

[0004] Imidazole rings are ubiquitous in nature, and imidazole functional groups play crucial roles in many structures within the human body, particularly histamine and histidine. Imidazoles offer numerous biophysical interactions, including their ability to form hydrogen bonds with drugs and proteins. Imidazole-based polymers readily associate with biomolecules via hydrogen bonding and provide electrostatic interactions, aggregation, and self-assembly. Imidazole polymers exhibit excellent electrical conductivity, conductivity, and electrochemical stability, making them suitable for fabricating various sensors, such as pH sensors, gas sensors, and biosensors. By modifying their structure, imidazole polymers can be used to prepare materials with different morphologies and functions, such as nanoparticles and porous materials, which can be applied to material modification and catalytic reactions. Polymers containing imidazole groups can also serve as antibacterial, antiviral, and anticancer agents, and can be used to prepare biodegradable drug delivery systems. The design of novel imidazole macromolecules remains a promising and emerging field of research. Summary of the Invention

[0005] The purpose of this invention is to address the problem and shortcomings of polyasparagine-derived polymers having limited functionalization, and to provide a method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer, thereby solving the problems existing in the background art.

[0006] The mussel-inspired multifunctional polyasparagine-derived polymer of the present invention is characterized by the following structural formula:

[0007]

[0008] Where x is an integer from 10 to 30, y is an integer from 10 to 30, and z is an integer from 40 to 70;

[0009] The preparation method of the mussel-inspired multifunctional polyasparagine-derived polymer of the present invention comprises the following steps:

[0010] (1) Weigh a certain amount of polysuccinimide and put it into a 250ml round bottom flask. Dissolve it in N,N-dimethylformamide, add dopamine hydrochloride, triethylamine and sodium hydrosulfide, and react at a nitrogen protection temperature of 70-90℃ for 20-30 hours. Then add 1-(3-aminopropyl)imidazole, heat to 40-70℃, stir for 30-60 hours, add ethanolamine after the reaction is completed, and cool to room temperature and stir for 20-40 hours.

[0011] In step (1), the ratio of N,N-dimethylformamide solvent to the molar number of succinimide units in polysuccinimide is 1.5–4.5 L: 1 mol.

[0012] In step (1), the dopamine is dopamine hydrochloride, and its molar number is 0.5 to 2 times the molar number of succinimide units;

[0013] In step (1), triethylamine is used to neutralize the hydrochloric acid in dopamine hydrochloride, and the number of moles is 0.2 to 0.8 times the number of moles of dopamine hydrochloride;

[0014] In step (1), sodium hydrosulfide is used as an antioxidant, and its molar number is 0.2 to 1 times that of dopamine hydrochloride.

[0015] In step (1), the number of 1-(3-aminopropyl)imidazolium moles is 0.2 to 2 times the number of succinimide units;

[0016] In step (1), the number of moles of ethanolamine is 0.5 to 1 times the number of moles of dopamine hydrochloride;

[0017] (2) The obtained reactants are placed in a dialysis bag, dialyzed with deionized water for 1-3 days, and then freeze-dried under vacuum to obtain the final product PolyAspAm (DOPA / API / EA).

[0018] In step (2), the vacuum freeze-drying temperature is -50 to 0°C and the time is 12 to 72 hours.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] By introducing mussel-like dopamine and imidazole functional groups into the polyasparagine-derived polymer PolyAspAm (DOPA / API / EA), it acquires multifunctional properties and can be applied to materials with self-healing, antibacterial, and CO2 adsorption capabilities. Attached Figure Description

[0021] Figure 1 NMR spectroscopy of the mussel-inspired multifunctional polyasparagine-derived polymer prepared in Example 1 of this invention. 1 HNMR spectrum; Detailed Implementation

[0022] To better understand the present invention, the following description is based on embodiments, but the implementation of the present invention is not limited thereto.

[0023] Example 1

[0024] 0.05 mol of polysuccinimide was weighed and placed in a 250 mL round-bottom flask, dissolved in 50 mL of N,N-dimethylformamide, and 25 mmol of dopamine hydrochloride, 10 mmol of triethylamine, and 10 mmol of sodium hydrosulfide were added. The reaction was carried out at 70 °C under nitrogen protection for 25 hours. Then, 10 mmol of 1-(3-aminopropyl)imidazole was added, and the mixture was heated to 50 °C and stirred for 40 hours. After the reaction was completed, 25 mmol of ethanolamine was added, and the temperature was lowered to room temperature and stirred for 20 hours. The resulting reactants were placed in a dialysis bag, dialyzed against deionized water for 2 days, and then freeze-dried under vacuum to obtain the final product PolyAspAm (DOPA / API / EA).

[0025] Figure 1 NMR spectroscopy of PolyAspAm (DOPA / API / EA) showed the biomimetic multifunctional polyasparagine-derived polymer from mussels. 1 ¹H NMR spectrum. After a series of ammonolysis reactions, peaks a, b, and c in the PolyAspAm (DOPA / API / EA) spectrum represent aromatic protons of the dopamine phenyl group, and peaks i, j, and k represent the three methylene protons in the API component. Peaks d, e, and f represent the three heteroaromatic proton monomers of the imidazole ring. m and l represent the methylene protons of the EA side chain.

[0026] Table 1 shows that the results indicate that 63 mol% of the dopamine group was conjugated into the polymer backbone, while the 1-(3-aminopropyl)imidazole and ethanolamine groups accounted for 25 mol% and 43 mol%, respectively.

[0027] Table 1. Number of each group in polyasparagine derivative copolymer PolyAspAm (DOPA / API / EA)

[0028] dopamine 32 1-(3-aminopropyl)imidazolium 25 ethanolamine 43

Claims

1. A mussel-inspired multifunctional polyasparagine-derived polymer, characterized in that: Its structural formula is shown below. Where x is an integer from 10 to 30, y is an integer from 10 to 30, and z is an integer from 40 to 70.

2. The method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer according to claim 1, characterized in that: The steps are as follows: (1) Weigh a certain amount of polysuccinimide and place it in a 250ml round-bottom flask. Dissolve it in N,N-dimethylformamide, add dopamine hydrochloride, triethylamine and sodium hydrosulfide, and react at a nitrogen protection temperature of 70~90℃ for 20~30 hours. Then add 1-(3-aminopropyl)imidazolium, heat to 40~70℃ and stir for 30~60 hours. After the reaction is completed, add ethanolamine, cool to room temperature and stir for 20~40 hours. (2) The obtained reactants are placed in a dialysis bag, dialyzed with deionized water for 1-3 days, and then freeze-dried under vacuum to obtain the mussel biomimetic multifunctional polyasparagine derivative polymer as described in claim 1.

3. The method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer as described in claim 2, characterized in that: In step (1), the ratio of the volume of N,N-dimethylformamide solvent to the number of moles of succinimide units in polysuccinimide is 1.5~4.5 L:1 mol.

4. The method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer as described in claim 2, characterized in that: In step (1), the number of moles of dopamine hydrochloride is 0.5 to 2 times the number of moles of succinimide units in polysuccinimide; triethylamine is used to neutralize the hydrochloric acid in dopamine hydrochloride, and its moles are 0.2 to 0.8 times the number of moles of dopamine hydrochloride; sodium hydrosulfide is used as an antioxidant, and its moles are 0.2 to 1 times the number of moles of dopamine hydrochloride.

5. The method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer as described in claim 2, characterized in that: In step (1), the number of 1-(3-aminopropyl)imidazolium moles is 0.2 to 2 times the number of succinimide units in polysuccinimide; the number of ethanolamine moles is 0.5 to 1 times the number of dopamine hydrochloride moles.

6. The method for preparing a mussel-inspired multifunctional polyasparagine-derived polymer as described in claim 2, characterized in that: In step (2), the temperature for vacuum freeze drying is -50~0℃ and the time is 12~72h.

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