CN114573808A - Double-bond-terminated ion-responsive hyperbranched polymer and preparation method and application thereof - Google Patents
Double-bond-terminated ion-responsive hyperbranched polymer and preparation method and application thereof Download PDFInfo
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- CN114573808A CN114573808A CN202210264623.4A CN202210264623A CN114573808A CN 114573808 A CN114573808 A CN 114573808A CN 202210264623 A CN202210264623 A CN 202210264623A CN 114573808 A CN114573808 A CN 114573808A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/36—Amides or imides
- C08F122/38—Amides
- C08F122/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
Abstract
The invention discloses a preparation method of a terminal double-bond ion-responsive hyperbranched polymer, which comprises the following steps: (1) adding double-end double-bond monomer and histamine dihydrochloride into an organic solvent to dissolve to form a mixed solution; (2) adding organic base into the mixed solution to adjust the pH, and then placing the mixed solution in an oil bath to be heated and react away from light to obtain the terminal double-bond ion-responsive hyperbranched polymer. The invention also discloses the double-bond-terminated ion-responsive hyperbranched polymer prepared by the preparation method and application of the double-bond-terminated ion-responsive hyperbranched polymer as an ion-responsive material. The terminal double-bond ion-responsive hyperbranched polymer prepared by the invention has excellent ion responsiveness, water solubility and biocompatibility.
Description
Technical Field
The invention belongs to the technical field of hyperbranched polymers, and particularly relates to a terminal double-bond ion-responsive hyperbranched polymer and a preparation method and application thereof.
Background
Hyperbranched polymers attract a great deal of attention due to their special topological structure, and compared with linear polymers, hyperbranched polymers have good solubility, low crystallinity and high density of terminal functional groups. Through reasonable design, the prepared hyperbranched polymer has multiple branch points, molecular chains are not easy to tangle, and terminal functional groups can be designed according to requirements, so that the hyperbranched polymer is easy to modify and is beneficial to synthesizing various functional materials. Because the biocompatibility of the material is obviously better than that of small molecules, the material also plays an important role in the preparation of biomedical materials. For example, chinese patent publication No. CN114106348A discloses phenylboronic acid modified intracellular degradable hyperbranched poly (β -amino ester), a preparation method thereof, and a protein delivery application thereof, and belongs to the field of biomedical materials. The adopted scheme is as follows: preparing hyperbranched poly (beta-amino ester) by acrylate monomers (triacrylate monomers, tetraacrylate monomers and the like) and small molecular amine by a Michael addition strategy; and then the hyperbranched poly (beta-amino ester) is terminated by using a terminating agent containing a phenylboronic acid group to prepare the phenylboronic acid modified functional hyperbranched poly (beta-amino ester), and the result of the product is determined by nuclear magnetism. The preparation method is simple and efficient, the used raw materials are cheap and easy to obtain, the synthesis path is simple, and the production cost is reduced. For example, chinese patent publication No. CN111718494A discloses a reduction-responsive hyperbranched poly β -amino ester having high gene delivery ability, and a preparation method and application thereof, wherein the polymer is polymerized by a michael addition method of "a 2+ B3+ C2" to have a hyperbranched structure.
Imidazole structures contained in histamine molecules can chelate various metal ions to realize in-situ fixation of the metal ions in materials, but the toxicity of small molecules limits the direct application in biomedical materials. Therefore, how to provide a hyperbranched polymer which can integrate ionic responsiveness and addition polymerization simultaneously is a research focus in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a terminal double-bond ion-responsive hyperbranched polymer, and the prepared terminal double-bond ion-responsive hyperbranched polymer has excellent ion responsiveness, water solubility and biocompatibility.
The invention provides the following technical scheme:
a preparation method of a double-bond-terminated ion-responsive hyperbranched polymer comprises the following steps:
(1) adding double-end double-bond monomer and histamine dihydrochloride into an organic solvent to dissolve to form a mixed solution;
(2) adding organic base into the mixed solution to adjust the pH, and then placing the mixed solution into an oil bath to be heated and react away from light to obtain the terminal double-bond ion-responsive hyperbranched polymer (hyperbranched poly beta amino ester HPAE).
The hyperbranched polymer prepared by reacting histamine molecules with double-bond monomers can realize the integration of ion responsiveness and addition polymerization, thereby providing more possibilities for the preparation of biomedical materials.
Further, in step (1), the double bond monomers used include, but are not limited to, Methylene Bisacrylamide (MBA) and polyethylene glycol diacrylate (PEGDA).
Further, in the step (1), the organic solvent used is one or a combination of several of dimethyl sulfoxide, absolute ethyl alcohol, methanol, acetonitrile, acetone and N, N-dimethylformamide.
Furthermore, in the step (1), the molar ratio of the double bond to the amino active hydrogen is 3:1-1.05: 1.
Further, in step (2), the organic base used includes but is not limited to triethylamine, and the pH is adjusted to 8-11.
Further, in the step (2), the reaction is carried out for 1 to 10 hours under the condition of oil bath at the temperature of between 50 and 100 ℃ and protection from light.
Further, the preparation method further comprises the following steps: placing the mixed solution in an oil bath, heating for reaction in a dark place to obtain a reaction mixed solution, cooling to room temperature, filtering, washing with a precipitator, and then carrying out vacuum drying to obtain the purified terminal double-bond ion-responsive hyperbranched polymer: hyperbranched poly beta amino ester HPAE.
Further, the precipitating agents used include, but are not limited to, methyl tert-butyl ether and diethyl ether.
Preferably, the purified HPAE is stored at a temperature below 4 ℃.
The invention also provides the terminal double-bond ion-responsive hyperbranched polymer prepared by the preparation method.
The invention also provides application of the terminal double-bond ion-responsive hyperbranched polymer as an ion-responsive material.
The invention also provides a response test of the terminal double-bond ion-responsive hyperbranched polymer to different types of metal ions.
Any proportion of aqueous solution of the terminal double-bond hyperbranched polymer is used in the ion response.
The ion soundThe metal ion salt is selected from CaCl2、CuSO4、CuCl2、AgNO3Or ZnSO4Or a combination of at least two thereof.
The invention also provides a method for testing the biocompatibility of the terminal double-bond ion-responsive hyperbranched polymer.
The biocompatibility test result is represented by the survival rate of L929 cells which are respectively incubated for 24h and 48h in the end double-bond hyperbranched polymer HPAE aqueous solution and are calculated by an MTT method.
The invention takes histamine dihydrochloride (HIS) and double-bond monomer as raw materials, the double bond of double-end double-bond micromolecule monomer and amino active hydrogen of histamine dihydrochloride (HIS) are utilized to carry out Michael addition reaction under the alkalescent condition, and the hyperbranched poly beta amino ester HPAE with double bond end capping, excellent ion responsiveness, water solubility and biocompatibility is prepared by purification.
The invention utilizes a reaction system of a one-pot method, has simple preparation method and mild reaction conditions, the prepared hyperbranched polymer has good water solubility and ion responsiveness, and the terminal group is double bond, so that the subsequent modification reaction can be conveniently carried out.
Drawings
FIG. 1 is a schematic diagram of the synthesis of hyperbranched poly-beta-amino ester HPAE1 in example 1.
FIG. 2 is a drawing of the hyperbranched poly-beta-amino ester HPAE1 of example 11H-NMR spectrum.
Fig. 3 shows photographs taken after dropping each of the aqueous solutions of the various metal ions into the 20% concentration aqueous solution of HPAE 1.
FIG. 4 is a schematic diagram of the synthesis of hyperbranched poly-beta-amino ester HPAE2 in example 2.
FIG. 5 shows AgNO3Photograph taken after dropping the aqueous solution into the 10% strength aqueous solution of HPAE 2.
Figure 6 is a graph of L929 cell viability after 24h and 48h incubation in aqueous HPAE1 and HPAE2, respectively.
Detailed Description
The following is a detailed description of the present invention, but the present invention is not limited to the following examples.
Example 1
Preparation of hyperbranched poly β -amino ester HPAE 1:
methylene bisacrylamide (MBA,6.940g,45mmol) and histamine dihydrochloride (HIS,1.900g,10mmol) were added to 30mL of dimethyl sulfoxide and allowed to dissolve well in a round bottom flask with a molar ratio of double bonds to amino active hydrogens of 3: 1. And adding triethylamine into the mixed solution to adjust the pH value to 8, and then placing the mixed solution in an oil bath at 60 ℃ to be heated and react for 6 hours in a dark place. And naturally cooling to room temperature after the reaction is finished. The specific synthetic principle is shown in fig. 1, Methylene Bisacrylamide (MBA) and histamine dihydrochloride (HIS) are used as raw materials, and the hyperbranched poly beta amino ester' HPAE1 is generated through reaction under certain conditions. Wherein dimethyl sulfoxide (DMSO) is used as solvent, and Triethylamine (TEA) is used as catalyst.
Purification of hyperbranched poly β amino ester HPAE 1:
filtering the reaction mixed solution to remove salt precipitate generated in the reaction process; then, the reaction mixture was sufficiently washed with 5 times the amount of methyl t-butyl ether as the product to remove the solvent and unreacted monomers, and the polymer was vacuum-dried to remove the excess purifying agent. The purified HPAE1 was stored in a refrigerator at-20 ℃.
The purified HPAE1 is subjected to1Characterization of H-NMR spectrum, it is apparent from FIG. 2 that new peaks H (4.30ppm) and i (2.93ppm) are produced, indicating that the double bond reacts with the amino active hydrogen and the Michael addition proceeds successfully. No peak of amino active hydrogen was found and the related double bond peaks d (6.38ppm), e (5.91ppm) and f (5.81ppm) remained, demonstrating that the product was successfully capped with double bonds and further modification reactions could be carried out. This demonstrates the successful synthesis of a double-bond-terminated hyperbranched poly β -amino ester, HPAE 1.
Verification of ion responsiveness of hyperbranched poly β amino ester HPAE 1:
adding 0.2mol/L of CaCl2、CuSO4、CuCl2、AgNO3And ZnSO4The aqueous solution was respectively added dropwise to 20% HPAE1 aqueous solution, and the appearance was recorded by photographing and there was a flocculent precipitate formed instantaneouslyThe HPAE1 product was shown to be responsive to a variety of ions.
Biocompatibility verification of hyperbranched poly-beta-amino ester HPAE 1:
the viability of the cells was tested using the MTT method. First, L929 cells were incubated at 37 ℃ with 5% CO2In a 96-well plate in a humid environment for 24 h. The old medium in the well plate was then removed and 200 μ L of a 10% aqueous solution of HPAE1 was added to each well. After 24h and 48h incubation, the matrix in the wells was replaced with 180. mu.L of fresh medium and 20. mu.L of MTT, wrapped with tinfoil, mixed thoroughly, and placed into a 37 ℃ incubator to react for 4h in the dark. All matrices were then removed, 150 μ l of LDMSO was added to each well and the well plates were shaken well. The absorbance of the solution at 570nm in each well was measured using a TECAN Infinite model 200 microplate reader, each set comprising 6 samples, the results measured on untreated cells being used as a control. Cell viability was calculated according to the following formula:
wherein, AbsHPAEAnd AbscontrolRepresents the absorbance of cells cultured in HPAE1 aqueous solution and cell culture medium, respectively. The calculated survival rates of the L929 cells all exceed 90%, indicating that HPAE1 has good biocompatibility.
Example 2
Preparation of hyperbranched poly β -amino ester HPAE 2:
polyethylene glycol diacrylate 700(PEGDA700,11.025g,15.75mmol) and histamine dihydrochloride (HIS,1.900g,10mmol) were added to 30mL of N, N-dimethylformamide and allowed to dissolve well in a round bottom flask with a molar ratio of double bonds to amino active hydrogens of 1.05: 1. And adding triethylamine into the mixed solution to adjust the pH value to 8, and then placing the mixed solution in an oil bath at 60 ℃ to be heated and react for 6 hours in a dark place. And naturally cooling to room temperature after the reaction is finished. The specific synthetic principle is shown in fig. 4, and the hyperbranched poly-beta-amino ester HPAE2 is generated by taking polyethylene glycol diacrylate 700(PEGDA700) and histamine dihydrochloride (HIS) as raw materials and reacting under certain conditions. Wherein N, N-Dimethylformamide (DMF) is used as a solvent, and Triethylamine (TEA) is used as a catalyst.
Purification of hyperbranched poly β amino ester HPAE 2:
filtering the reaction mixed solution to remove salt precipitate generated in the reaction process; then, the reaction mixture was sufficiently washed with 5 times the amount of diethyl ether as the product to remove the solvent and unreacted monomers, and the polymer was vacuum-dried to remove the excess purifying agent. The purified HPAE2 was stored in a refrigerator at-20 ℃.
Verification of ion responsiveness of hyperbranched poly β amino ester HPAE 2:
0.2mol/L of AgNO3The aqueous solution was added dropwise to a 10% strength aqueous solution of HPAE2, and a phenomenon of photographical recording was noted, in which a flocculent precipitate formed instantaneously, indicating that the HPAE2 product was on Ag+The responsiveness of (c).
Biocompatibility verification of hyperbranched poly-beta-amino ester HPAE 2:
the viability of the cells was tested using the MTT method. First, L929 cells were incubated at 37 ℃ with 5% CO2In a 96-well plate in a humid environment for 24 h. The old medium in the well plate was then removed and 200 μ L of a 10% aqueous solution of HPAE2 was added to each well. After 24h and 48h incubation, the matrix in the wells was replaced with 180. mu.L of fresh medium and 20. mu.L of MTT, wrapped with tinfoil, mixed thoroughly, and placed into a 37 ℃ incubator to react for 4h in the dark. All matrices were then removed, 150 μ l of LDMSO was added to each well and the well plates were shaken well. The absorbance of the solution at 570nm in each well was measured using a TECAN Infinite 200 microplate reader, each group containing 6 specimens, and the results obtained with untreated cells served as a control group. Cell viability was calculated according to the following formula:
wherein, AbsHPAEAnd AbscontrolRepresents the absorbance of cells cultured in HPAE2 aqueous solution and cell culture medium, respectively. The calculated survival rates of the L929 cells all exceed 90%, indicating that HPAE2 has good biocompatibility.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a double-bond-terminated ion-responsive hyperbranched polymer is characterized by comprising the following steps:
(1) adding double-end double-bond monomer and histamine dihydrochloride into an organic solvent to dissolve to form a mixed solution;
(2) adding organic base into the mixed solution to adjust the pH, and then placing the mixed solution in an oil bath to be heated and react away from light to obtain the terminal double-bond ion-responsive hyperbranched polymer.
2. The method for preparing the double-end ion-responsive hyperbranched polymer as claimed in claim 1, wherein in the step (1), the double-end double-bond monomer is selected from methylene bisacrylamide or polyethylene glycol diacrylate.
3. The method for preparing the double-bond-terminated ion-responsive hyperbranched polymer according to claim 1, wherein in the step (1), the organic solvent is one or a combination of at least two selected from dimethyl sulfoxide, absolute ethanol, methanol, acetonitrile, acetone or N, N-dimethylformamide.
4. The method for preparing the double-ended ion-responsive hyperbranched polymer as claimed in claim 1, wherein in the step (1), the molar ratio of the double bonds in the double-ended monomer to the amino-active hydrogen in histamine dihydrochloride is 3:1-1.05: 1.
5. The method for preparing the double-bond-terminated ion-responsive hyperbranched polymer as claimed in claim 1, wherein in the step (2), an organic base is added to adjust the pH to 8-11, and then the mixture is subjected to light-shielding reaction for 1-10h under 50-100 ℃ oil bath.
6. The method for preparing the double-bond-terminated ion-responsive hyperbranched polymer according to claim 1, wherein the method comprises: and placing the mixed solution in an oil bath, heating for reaction in a dark place to obtain a reaction mixed solution, cooling to room temperature, filtering, washing with a precipitator, and then carrying out vacuum drying to obtain the purified terminal double-bond ion-responsive hyperbranched polymer.
7. The method for preparing the double-bond-terminated ion-responsive hyperbranched polymer according to claim 6, wherein the precipitating agent is selected from methyl tert-butyl ether or diethyl ether, and the double-bond-terminated ion-responsive hyperbranched polymer is stored at a temperature of less than 4 ℃.
8. A terminal double-bond ion-responsive hyperbranched polymer prepared by the preparation method of any one of claims 1 to 7.
9. Use of the double-bond-terminated ion-responsive hyperbranched polymer of claim 8 as an ion-responsive material.
10. The use of the double-ended ion-responsive hyperbranched polymer as claimed in claim 9, wherein the metal ion salt suitable for use in the ion response is selected from CaCl2、CuSO4、CuCl2、AgNO3Or ZnSO4Or a combination of at least two thereof.
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| CN202210264623.4A CN114573808B (en) | 2022-03-17 | 2022-03-17 | Terminal double bond ion response hyperbranched polymer and preparation method and application thereof |
| NL2032456A NL2032456B1 (en) | 2022-03-17 | 2022-07-12 | Terminal double-bond ion-responsive hyperbranched polymer and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006109945A1 (en) * | 2005-04-13 | 2006-10-19 | Sungkyunkwan University Foundation For Corporate Collaboration | Temperature and ph sensitive block copolymer and polymeric hydrogles using the same |
| JP2010024388A (en) * | 2008-07-22 | 2010-02-04 | Hakuto Co Ltd | Polymerizable multi-branched compound and method for producing the same |
| CN101850121A (en) * | 2010-01-26 | 2010-10-06 | 北京科技大学 | Hyperbranched polyurethane hydrogel for controlled release of medicament and preparation method thereof |
| WO2020240034A1 (en) * | 2019-05-31 | 2020-12-03 | University College Dublin | Hyaluronic acid-based hybrid hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107626002B (en) * | 2017-10-02 | 2021-11-16 | 杭州亚慧生物科技有限公司 | Response type medical gel and preparation method and application thereof |
| CN111718494A (en) | 2020-06-09 | 2020-09-29 | 苏州大学 | Reduction responsive hyperbranched poly-beta-amino ester with high-efficiency gene delivery capacity and preparation method and application thereof |
| CN114106348B (en) | 2021-11-12 | 2023-07-07 | 西安交通大学 | Phenylboronic acid modified intracellular degradable hyperbranched poly (beta-amino ester), preparation method and protein delivery application thereof |
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- 2022-07-12 NL NL2032456A patent/NL2032456B1/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006109945A1 (en) * | 2005-04-13 | 2006-10-19 | Sungkyunkwan University Foundation For Corporate Collaboration | Temperature and ph sensitive block copolymer and polymeric hydrogles using the same |
| JP2010024388A (en) * | 2008-07-22 | 2010-02-04 | Hakuto Co Ltd | Polymerizable multi-branched compound and method for producing the same |
| CN101850121A (en) * | 2010-01-26 | 2010-10-06 | 北京科技大学 | Hyperbranched polyurethane hydrogel for controlled release of medicament and preparation method thereof |
| WO2020240034A1 (en) * | 2019-05-31 | 2020-12-03 | University College Dublin | Hyaluronic acid-based hybrid hydrogel |
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