CN109206620B - Bionic water response shape memory polyamino acid material and preparation method thereof - Google Patents
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Abstract
The invention provides a bionic water-responsive shape memory polyamino acid material, which comprises an A block with a beta-folding structure and a hydrophilic B block, wherein the A block is connected with the B block, the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of polyamino acid with an alpha-spiral structure and/or at least one of hydrophilic pyridine derivatives, and the polyamino acid is selected from polyglutamate, poly-leucine, poly-valine and poly-tyrosine.
Description
Technical Field
The invention belongs to the field of bionic water response shape memory polymer materials, and particularly relates to a bionic water response shape memory polyamino acid material and a preparation method thereof.
Background
The natural spider silk has the advantages of high specific strength, excellent elasticity, good toughness and the like, and is inspired by the natural spider silk, and the research on the bionic material of the spider silk is always a hotspot in the field of bionics. Spider silks can be rapidly and substantially reduced in size under water/high humidity conditions, referred to as the super-shrinkage of spider silks. The super-contracted spider silk can be recovered under the stimulation of water/high humidity after being stretched and deformed, and the restoring force is very large, because the hydrogen bonds of the amorphous alpha-helical region of the spider silk can be damaged by water molecules in a wet state, the elasticity of the chain is increased, and the beta-folding crystalline region is not influenced. Spider silk is therefore considered a natural water-responsive Shape Memory Polymer (SMP) material. Water-responsive SMP materials are also gaining increasing interest in both academia and industry because water is the most common source of irritation, is simple and convenient, and is the safest and most immediate source of irritation for living organisms. However, the research of the water response SMP material imitating the spider silk structure is not reported yet.
Disclosure of Invention
The invention aims to provide a bionic water-responsive shape memory polyamino acid material and a preparation method thereof, and aims to solve the problem that the prior art does not relate to a water-responsive SMP material with an imitated spider silk structure.
The invention is realized by the bionic water-response shape memory polyamino acid material, which comprises an A block with a beta-folding structure and a hydrophilic B block, wherein the A block is connected with the B block, the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of polyamino acid with an alpha-spiral structure and/or at least one of hydrophilic pyridine derivatives, and the polyamino acid is selected from polyglutamate, poly-leucine, poly-valine and poly-tyrosine.
And a preparation method of the bionic water response shape memory polyamino acid material, which comprises the following steps:
providing an A block with a beta-sheet structure and a hydrophilic B block, wherein the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of poly-amino acids with an alpha-spiral structure and/or at least one of hydrophilic pyridine derivatives, and the poly-amino acids are selected from polyglutamate, poly-leucine, poly-valine and poly-tyrosine;
dissolving the A block and the B block in an organic solvent containing lithium salt, adding diisocyanate and a catalyst, and reacting to obtain the bionic water response shape memory polyamino acid material, wherein the reaction temperature is 10-150 ℃, and the reaction time is 0.5-10 h.
The bionic water-responsive shape-memory polyamino acid material provided by the invention has the advantages that the polyamino acid with an alpha-helical structure or an amorphous hydrophilic pyridine derivative provides a reversible hydrogen bond switch, and at least one of poly-L-alanine containing a beta-folding structure, a poly-L-glycine block, L-alanine and an L-glycine copolymer forms a network node to play a role in shape fixation, so that the connected high polymer material has the water-responsive shape memory characteristic, the shape memory fixation rate of the high polymer material is over 95 percent, and the recovery rate of the high polymer material is over 90 percent. The bionic water-responsive shape memory polymer material provided by the invention has good water responsiveness, biocompatibility and biodegradability, and is expected to be widely applied to the application fields of textiles, biology, medicine, sensing, biomedical appliances and the like.
The preparation method of the bionic water response shape memory polyamino acid material provided by the invention is characterized in that under the action of a catalyst and in an organic solvent containing lithium salt, diisocyanate is used as a connecting agent to connect the A block and the B block to obtain the bionic water response shape memory polyamino acid material. The method is simple and easy to operate and easy to control, and the bionic water response shape memory polyamino acid material with good water response, biocompatibility and biodegradability can be obtained.
Drawings
FIG. 1 is a schematic diagram of a bionic water-responsive shape-memory polyamino acid material provided by an embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following 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.
The embodiment of the invention provides a bionic water-response shape memory polyamino acid material, which comprises an A block with a beta-folding structure and a hydrophilic B block, wherein the A block is connected with the B block, the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of polyamino acid with an alpha-spiral structure and/or at least one of hydrophilic pyridine derivatives, and the polyamino acid is selected from polyglutamate, polylysine, polyvaline and poly tyrosine.
In the embodiment of the invention, the A block forms a network node, and the B block provides a reversible hydrogen bond switch, so that the polyamino acid material has excellent recovery rate in water. Wherein the poly-L-alanine, poly-L-glycine, copolymer of L-alanine and L-glycine has a degree of polymerization of 4 to 14 so as to form a beta-sheet crystalline region.
In the embodiment of the invention, preferably, the mass percentage of the A block is 5-50% based on 100% of the total mass of the bionic water response shape memory polyamino acid material. If the content of the A block is too high, the mass fraction of the network nodes is too high, so that the material is too brittle; if the content of the A block is too low, the shape memory property is not good.
Preferably, the a block and the B block are linked by a diisocyanate, particularly preferably hexamethylene diisocyanate. The diisocyanate, particularly hexamethylene diisocyanate, is adopted to connect the A block and the B block, so that the operation is simple, the reaction activity is good, and the shape memory and recovery rate of the connected material are good. Here, it should be understood that the diisocyanate is only one preferred way to achieve the attachment of the a blocks to the B blocks, and not the only way to attach the a blocks to the B blocks.
According to the bionic water-responsive shape-memory polyamino acid material provided by the embodiment of the invention, a polyamino acid with an alpha-helical structure or an amorphous hydrophilic pyridine derivative provides a reversible hydrogen bond switch, and at least one of poly-L-alanine, poly-L-glycine block, L-alanine and L-glycine copolymer containing a beta-folding structure forms a network node to play a role in shape fixation, so that the connected macromolecular material has a water-responsive shape memory characteristic, and the schematic diagram of the principle is shown in figure 1. The shape memory fixation rate of the bionic water response shape memory polyamino acid material reaches more than 95%, and the recovery rate reaches more than 90%. The bionic water-responsive shape memory polymer material provided by the invention has good water responsiveness, biocompatibility and biodegradability, and is expected to be widely applied to the application fields of textiles, biology, medicine, sensing, biomedical appliances and the like.
The embodiment of the invention also provides a preparation method of the bionic water response shape memory polyamino acid material, which comprises the following steps:
s01, providing an A block with a beta-sheet structure and a hydrophilic B block, wherein the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of poly-amino acids with an alpha-spiral structure and/or at least one of hydrophilic pyridine derivatives, and the poly-amino acids are selected from polyglutamate, poly-leucine, poly-valine and poly-tyrosine;
s02, dissolving the A block and the B block in an organic solvent containing lithium salt, adding diisocyanate and a catalyst, and reacting to obtain the bionic water response shape memory polyamino acid material, wherein the reaction temperature is 10-150 ℃, and the reaction time is 0.5-10 h.
Specifically, in the step S01, the selection and content of the a block having the β -sheet structure and the hydrophilic B block are as described above, and are not repeated herein for brevity.
As a specific example, the preparation method of the a block is: providing L-alanine-N-internal carboxylic anhydride and/or L-glycine-N-internal carboxylic anhydride, and carrying out polymerization reaction on the L-alanine-N-internal carboxylic anhydride and/or the L-glycine-N-internal carboxylic anhydride under the action of a primary amine initiator to obtain the A block. Wherein the primary amine is selected from at least one of ethylenediamine, butanediamine, hexanediamine and polyether diamine.
As a specific example, the preparation method of the polyamino acid with the alpha-helical structure comprises the following steps: providing amino acid-N-internal carboxylic anhydride, and carrying out polymerization reaction on the amino acid-N-internal carboxylic anhydride under the action of a primary amine initiator to obtain the polyamino acid with an alpha-helical structure, wherein the amino acid-N-internal carboxylic anhydride comprises glutamate-N-internal carboxylic anhydride, leucine-N-internal carboxylic anhydride, valine-N-internal carboxylic anhydride and tyrosine-N-internal carboxylic anhydride. Wherein the primary amine is selected from at least one of ethylenediamine, butanediamine, hexanediamine and polyether diamine.
As a specific example, the preparation method of the hydrophilic pyridine derivative comprises: polypropylene glycol, 2-hydroxyl pyridine derivatives and diisocyanate are placed in a reaction system and subjected to polymerization reaction to obtain the hydrophilic pyridine derivatives, wherein the 2-hydroxyl pyridine derivatives comprise 2, 6-hydroxymethylpyridine, 2, 6-hydroxyethylpyridine and N, N-bis (2-hydroxyethyl) isonicotinamide, and the preferred 2-hydroxyl pyridine derivatives have better reactivity with the diisocyanate. It is further preferred that the molar ratio of the polypropylene glycol, the pyridine derivative having 2 hydroxyl groups and the diisocyanate is 2:1:2, in order to ensure that the pyridine derivative is linked to the polypropylene glycol.
In the above step S02, since the a block is insoluble in a conventional organic solvent, the embodiment of the present invention dissolves the a block in an organic solvent containing a lithium salt, and the solubility of the a block can be effectively increased by adding a lithium salt to the organic solvent. Preferably, the concentration of the lithium salt in the organic solvent is 0.1 to 10 mol/L. Specifically, the lithium salt is at least one of LiCl and LiBr. In the embodiment of the invention, the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Adding diisocyanate and catalyst into the reaction system. Wherein the catalyst is at least one of stannous octoate and dibutyltin dilaurate; the diisocyanate is preferably hexamethylene diisocyanate. The diisocyanate, particularly hexamethylene diisocyanate, is adopted to connect the A block and the B block, so that the operation is simple, the reaction activity is good, and the shape memory and recovery rate of the connected material are good. Preferred catalysts are more favorable for the linking of the specific A and B blocks of the examples of this invention.
In the embodiment of the invention, the bionic water response shape memory polyamino acid material can be obtained by reacting for 0.5-10h at the temperature of 10-150 ℃. Preferably, the reaction temperature is 60-120 ℃, and the reaction time is 3-6h, so as to ensure the sufficient connection of the A block and the B block.
The preparation method of the bionic water response shape memory polyamino acid material provided by the embodiment of the invention is obtained by connecting the A block and the B block by adopting diisocyanate as a connecting agent in an organic solvent containing lithium salt under the action of a catalyst. The method is simple and easy to operate and easy to control, and the bionic water response shape memory polyamino acid material with good water response, biocompatibility and biodegradability can be obtained.
The following description will be given with reference to specific examples.
Example 1
A method for preparing poly (L-alanine) having a β -sheet structure, comprising the steps of:
1.15g (0.01mol) of L-alanine-N-carboxyanhydride was dissolved in 5mL of anhydrous dimethyl sulfoxide, 0.5mL of polypropylene glycol diamine having a molecular weight of 1000g/mol was added with stirring, the reaction was stirred at 25 ℃ for 72 hours, the reaction mixture was precipitated with 30mL of diethyl ether, filtered, washed with diethyl ether 3 times, and vacuum-dried at 25 ℃ for 24 hours to give poly (L-alanine) having a terminal group of primary amine with a yield of 75%.
Example 2
A method for preparing poly (L-glycine) having a β -sheet structure, comprising the steps of:
1.01g (0.01mol) of L-glycine-N-carboxyanhydride was dissolved in 5mL of anhydrous dimethyl sulfoxide, 0.11mL of polypropylene glycol diamine having a molecular weight of 500g/mol was added with stirring, the reaction was stirred at 25 ℃ for 72 hours, the reaction mixture was precipitated with 35mL of diethyl ether, filtered, washed with diethyl ether 3 times, and vacuum-dried at 30 ℃ for 24 hours to give poly (L-glycine) having a primary amine as a terminal group at a yield of 80%.
Example 3
A method for preparing poly (L-glutamic acid- γ -benzyl ester) having an α -helical structure, comprising the steps of:
dissolving 1.0g (0.0038mol) of L-glutamic acid-gamma-benzyl ester-N-inner carboxylic anhydride in 5mL of anhydrous dimethyl sulfoxide, adding 0.08mL of polypropylene glycol diamine with the molecular weight of 400g/mol under stirring, stirring and reacting for 72h at 25 ℃, settling the reaction mixture by 50mL of diethyl ether, filtering, washing 3 times by the diethyl ether, and drying for 24h under vacuum at 25 ℃ to obtain the poly (L-glutamic acid-gamma-benzyl ester) with the end group of primary amine, wherein the yield is 80%.
Example 4
A method for preparing pyridine derivatives having hydrophilicity, comprising the steps of:
3.15g (0.015mol) of N, N-bis (2-hydroxyethyl) isonicotinamide was dissolved in 50mL of anhydrous N, N-dimethylformamide, 5.04g (0.03mol) of hexamethylene diisocyanate and 12g of polypropylene glycol (molecular weight 400g/mol) were added under stirring, and the mixture was stirred at 80 ℃ for 10 hours to react, and the solvent was extracted to obtain a pyridine-containing polypropylene glycol having a hydroxyl group as a terminal group.
Example 5
A preparation method of a bionic water response shape memory polyamino acid material comprises the following steps:
0.5g of poly (L-alanine) prepared in example 1 and 1.5g of poly (L-glutamic acid-benzyl ester) prepared in example 3 were dissolved in 15mL of dimethyl sulfoxide containing LiBr, 0.09g of hexamethylene diisocyanate and 0.01mL of stannous octoate were added under stirring, reacted at 85 ℃ for 5 hours under stirring, cooled to room temperature, cast into a film, and oven-dried at 80 ℃. The obtained polyamino acid polymer material has the water response shape memory characteristic, the shape memory fixation rate of the polyamino acid polymer material reaches 97 percent, and the recovery rate of the polyamino acid polymer material reaches 92 percent.
Example 6
A preparation method of a bionic water response shape memory polyamino acid material comprises the following steps:
1g of poly (L-glycine) prepared in example 2 and 2g of the hydroxyl-terminated polypropylene glycol containing pyridine prepared in example 4 were dissolved in 15mL of dimethyl sulfoxide containing LiBr, and 0.4g of hexamethylene diisocyanate and 0.01mL of dibutyltin dilaurate were added under stirring, reacted at 85 ℃ for 6 hours under stirring, cooled to room temperature, cast into a film, and oven-dried at 80 ℃. The obtained polymer material has the water response shape memory characteristic, and the shape memory fixing rate of the polymer material reaches 96 percent and the recovery rate of the polymer material reaches 91 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A bionic water-responsive shape memory polyamino acid material is characterized by comprising an A block with a beta-folded structure and a hydrophilic B block, wherein the A block is connected with the B block, the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, and the B block is a hydrophilic pyridine derivative; the preparation method of the hydrophilic pyridine derivative comprises the following steps: polypropylene glycol, 2-hydroxyl pyridine derivatives and diisocyanate are placed in a reaction system and subjected to polymerization reaction to obtain the hydrophilic pyridine derivatives, wherein the 2-hydroxyl pyridine derivatives comprise 2, 6-hydroxymethylpyridine, 2, 6-hydroxyethylpyridine and N, N-bis (2-hydroxyethyl) isonicotinamide, and the molar ratio of the polypropylene glycol to the 2-hydroxyl pyridine derivatives to the diisocyanate is 2:1: 2.
2. The biomimetic water-responsive shape memory polyamino acid material according to claim 1, wherein the mass percentage of the A block is 5-50% based on 100% of the total mass of the biomimetic water-responsive shape memory polyamino acid material.
3. The biomimetic water-responsive shape memory polyamino acid material of claim 1, wherein the a block and the B block are linked by a diisocyanate.
4. A method for preparing a biomimetic water-responsive shape memory polyamino acid material according to any one of claims 1-3, comprising the following steps:
providing an A block with a beta-sheet structure and a hydrophilic B block, wherein the A block is at least one of poly-L-alanine, poly-L-glycine, L-alanine and L-glycine copolymer, the B block is at least one of hydrophilic pyridine derivatives, and the preparation method of the hydrophilic pyridine derivatives comprises the following steps: placing polypropylene glycol, a pyridine derivative containing 2 hydroxyl groups and diisocyanate into a reaction system, and carrying out polymerization reaction to obtain the hydrophilic pyridine derivative, wherein the pyridine derivative containing 2 hydroxyl groups comprises 2, 6-hydroxymethylpyridine, 2, 6-hydroxyethylpyridine and N, N-bis (2-hydroxyethyl) isonicotinamide, and the molar ratio of the polypropylene glycol to the pyridine derivative containing 2 hydroxyl groups to the diisocyanate is 2:1: 2;
dissolving the A block and the B block in an organic solvent containing lithium salt, adding diisocyanate and a catalyst, and reacting to obtain the bionic water response shape memory polyamino acid material, wherein the reaction temperature is 10-150 ℃, and the reaction time is 0.5-10 h.
5. The method for preparing a biomimetic water-responsive shape memory polyamino acid material according to claim 4, wherein the reaction temperature is 60-120 ℃, and the reaction time is 3-6 h.
6. The method for preparing a biomimetic water-responsive shape memory polyamino acid material according to claim 4, wherein the preparation method of the A block comprises the following steps:
providing L-alanine-N-internal carboxylic anhydride and/or L-glycine-N-internal carboxylic anhydride, and carrying out polymerization reaction on the L-alanine-N-internal carboxylic anhydride and/or the L-glycine-N-internal carboxylic anhydride under the action of a primary amine initiator to obtain the A block.
7. The method of claim 6, wherein the primary amine is at least one selected from the group consisting of ethylenediamine, butanediamine, hexanediamine, and polyetherdiamine.
8. The method for preparing a biomimetic water-responsive shape memory polyamino acid material according to any one of claims 4-7, wherein the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; and/or
The catalyst is at least one of stannous octoate and dibutyltin dilaurate; and/or
The diisocyanate is hexamethylene diisocyanate; and/or
The lithium salt is at least one of LiCl and LiBr.
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