CN111748108A - Preparation method of recyclable N-halamine hydrogel capable of selectively sterilizing - Google Patents

Preparation method of recyclable N-halamine hydrogel capable of selectively sterilizing Download PDF

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CN111748108A
CN111748108A CN202010637903.6A CN202010637903A CN111748108A CN 111748108 A CN111748108 A CN 111748108A CN 202010637903 A CN202010637903 A CN 202010637903A CN 111748108 A CN111748108 A CN 111748108A
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董阿力德尔图
高悦
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Inner Mongolia University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides

Abstract

The invention relates to the field of biomedical polymer materials, in particular to a preparation method of recyclable and selectively bactericidal N-halamine hydrogel. Which comprises the following steps: preparation of MAG (2-methacrylamide glucopyranose), preparation of homopolymer pMAG, preparation of pMAG-Cl, preparation of antibacterial hydrogel and the like. The hydrogel prepared by the invention has good biocompatibility, no toxicity, no harm and strong mechanical property, and can realize selective sterilization and cyclic utilization. The sterilizing rate to colibacillus can reach 100 percent, and the sterilizing rate to staphylococcus aureus and pseudomonas aeruginosa is weak and can reach 20 to 30 percent at most. When the hydrogels with different PVA contents are respectively contacted with GLC-82 cells for 24h, the cell survival rates are all higher than the blank value, thereby showing that the hydrogels with different PVA contents have no cytotoxicity and are helpful for cell proliferation.

Description

Preparation method of recyclable N-halamine hydrogel capable of selectively sterilizing
Technical Field
The invention relates to the field of biomedical polymer materials, in particular to a preparation method of recyclable and selectively bactericidal N-halamine hydrogel.
Background
With the rapid development of economy, people pay more and more attention to health-related problems. And the related medical problems caused by bacterial infection are becoming the hot spots of clinical research. The antibacterial material endows the biomedical material with certain antibacterial property by a physical or chemical method, thereby reducing the spread of bacteria and finally reducing the occurrence of related diseases.
The hydrogel is a hydrophilic three-dimensional network structure polymer material, can swell in water, absorb and retain a large amount of water, is insoluble in water, and can keep the shape after reaching the swelling balance. First, hydrogels have properties similar to extracellular matrix, approaching living tissue than any other synthetic biomaterial; in addition, substances such as protein and the like are not easily adhered to the surface of the hydrogel, so that the hydrogel has good biocompatibility when contacting with blood, body fluid and human tissues; thirdly, the hydrogel has excellent permeability due to the three-dimensional network structure, thereby facilitating the transportation of nutrients and metabolites and being capable of sustaining the survival and propagation of cells around the hydrogel. Because of the excellent biocompatibility of the hydrogel, the hydrogel has wide application in the field of biomedical materials, such as tissue engineering, drug release, wound dressings, molecular printing, corneal contact lenses, shape memory materials, artificial skin, biosensors and the like, and in recent years, the antibacterial hydrogel becomes a novel dressing which effectively prevents bacterial invasion and further wound injury.
At present, most of common antibacterial hydrogels are compounded by inorganic antibacterial agents and bulk materials, such as nano-silver-containing hydrogels and antibiotics-containing hydrogels, and the release-type hydrogels have the defects of environmental pollution, short-term effectiveness and the like. In addition, the method for preparing the antibacterial hydrogel is that antibacterial molecules are grafted on the surface of the material or micromolecule antibacterial monomers are introduced, and then the antibacterial hydrogel is formed by utilizing polymerization and chemical or physical methods for crosslinking. However, the hydrogel prepared by the method cannot realize selective sterilization, and few antibacterial hydrogels can not be recycled.
Disclosure of Invention
The technical problems to be solved by the invention are as follows:
the invention aims to provide a recyclable N-halamine antibacterial hydrogel capable of selectively sterilizing and a preparation method thereof. The antibacterial high polymer material is prepared by introducing Sodium Alginate (SA), polyvinyl alcohol (PVA) and N-halamine. The hydrogel prepared by the invention has good biocompatibility, no toxicity, no harm and strong mechanical property, and can realize selective sterilization and cyclic utilization.
The technical scheme adopted by the invention is as follows:
a preparation method of N-halamine antibacterial hydrogel capable of being recycled and selectively sterilized comprises the following steps:
1) preparation of MAG (2-methacrylamide glucopyranose): 5 parts by mass of D (+) -glucosamine hydrochloride and 5 parts by mass of anhydrous K2CO3And mixing, adding into 119 parts by mass of anhydrous methanol, reacting in an ice bath for 4 hours, purifying by using a silica gel chromatographic column, and vacuum-drying the purified sample for 24 hours to obtain MAG. The chemical reaction equation is as follows:
Figure BDA0002570162100000021
2) preparation of homopolymer pMAG: 0.8 part by mass of the synthesized MAG and 0.04 part by mass of an initiator AIBN (azobisisobutyronitrile) are mixed, 9.5 parts by mass of DMF (N-N-dimethylformamide) is added as a reaction solvent, the mixture reacts for 10 hours at 70 ℃, a reaction product is dialyzed for 3 days by a dialysis bag, and a homopolymer pMAG is obtained after freeze drying. The chemical reaction equation is as follows:
3) preparation of pMAG-Cl: diluting 1.1 part by mass of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25 part by mass of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing for 3 days with a dialysis bag, and freeze-drying to obtain pMAG-Cl, wherein the chemical reaction equation of the pMAG-Cl is as follows:
Figure BDA0002570162100000032
wherein n is 2220-3555.
4) Dissolving 0.4-1.2 parts by mass of polyvinyl alcohol (PVA) in distilled water at 95 ℃, adding 0.3 part by mass of SA (sodium alginate), stirring to dissolve, adding 0.03-0.12 part by mass of pMAG-Cl, pouring the mixed solution into a mold, and storing for 22h at-22 ℃ in a refrigerator;
5) unfreezing the frozen hydrogel, and then adding 0.1mol/L CaCl into the hydrogel2Soaking the solution for 0.5-2h to obtain the final product, namely the antibacterial hydrogel.
The beneficial effects obtained by the invention are as follows:
selective sterilization: the N-halamine antibacterial hydrogel capable of being recycled and selectively sterilized, which is prepared by the invention, can be used for selective sterilization, the sterilization rate of Escherichia coli can reach 100%, and the sterilization rates of Staphylococcus aureus and Pseudomonas aeruginosa are weak, and can reach 20% -30% at most.
Can be recycled: the N-halamine antibacterial hydrogel capable of being recycled and selectively sterilized is subjected to 5 times of recycling, the sterilization rate can reach 100%, and the N-halamine antibacterial hydrogel can be recycled for many times on the premise that the hydrogel is not damaged.
Drawings
FIG. 1 is a schematic of the antibacterial hydrogel synthesis route;
FIG. 2 is a graph of the H-nuclear magnetic hydrogen spectrum of MAG (2-methacrylamide glucopyranose);
FIG. 3 is an infrared spectrum of MAG and pMAG;
FIG. 4 is a UV spectrum of pMAG and pMAG-Cl;
FIG. 5 XPS plots of pMAG and pMAG-Cl;
FIG. 6 is a scanning electron micrograph of a hydrogel;
FIG. 7 is a water loss profile of a hydrogel;
FIG. 8 is a swelling diagram of a hydrogel;
FIG. 9 stress-strain curves for hydrogels of different PVA content;
FIG. 10 is a graph of tensile modulus for hydrogels of different PVA content;
FIG. 11 stress-strain curves for hydrogels with different soaking times;
FIG. 12 is a graph of tensile modulus of hydrogels with different soaking times;
FIG. 13 stress-strain curves for hydrogels of different pMAG-Cl contents.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Wherein the schemes for the synthesis of the antibacterial hydrogels of examples 1-8 are shown in FIG. 1.
Example 1
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.4g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.06g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 2
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3Mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, and passing through siliconAnd (5) purifying the gel chromatography column, and drying the purified sample in vacuum for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.8g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.06g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 3
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 1.2g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.06g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 4
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.4g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.03g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 5
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.4g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.12g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and soaking the hydrogel in 0.1mol/L CaCl2 solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 6
Mixing 5g D (+) -aminograpeSugar hydrochloride with 5g of anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 1.2g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.12g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 1h to obtain the final product, namely the antibacterial hydrogel.
Example 7
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.8g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.06g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 0.5h to obtain the final product, namely the antibacterial hydrogel.
Example 8
Mixing 5g D (+) -glucosamine hydrochloride with 5g anhydrous K2CO3And mixing, adding into 119mL of anhydrous methanol, reacting in ice bath for 4h, purifying by a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG. 0.8g of the MAG synthesized above was mixed with 0.04g of Azobisisobutyronitrile (AIBN), which is an initiator, 9.5mL of N-N-Dimethylformamide (DMF) was added as a reaction solvent, and reacted at 70 ℃ for 10 hours, and then the reaction product was dialyzed with a dialysis bag for 3 days, and freeze-dried to obtain a homopolymer pMAG thereof. Diluting 1.1mL of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25g of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing with a dialysis bag for 3 days, and freeze-drying to obtain pMAG-Cl; 0.8g of polyvinyl alcohol was dissolved in distilled water at about 95 ℃ and 0.3g of sodium alginate was added thereto, followed by stirring and dissolving, and then 0.06g of pMAG-Cl was added thereto. Pouring the mixed solution into a mold, and storing the mixed solution for 22 hours at the temperature of-22 ℃ in a refrigerator; unfreezing the frozen hydrogel, and adding 0.1mol/L CaCl into the hydrogel2And soaking the solution for 2 hours to obtain the final product, namely the antibacterial hydrogel.
Example 9
The N-halamine antibacterial hydrogel capable of being recycled and selectively sterilized (mass ratio SA: PVA is 0.3: 0.4, 0.3: 0.8, 0.3: 1.2) prepared by the invention is respectively mixed with 106The cfu/mL of escherichia coli, staphylococcus aureus and pseudomonas aeruginosa have the effects of 100 percent of sterilization rate on the escherichia coli, and the sterilization rate on the staphylococcus aureus and the pseudomonas aeruginosa is very weak and can reach 20 to 30 percent at most, so that the escherichia coli is selectively sterilized. When hydrogels with different PVA contents (0.4g, 0.8g and 1.2g) were contacted with GLC-82 cells for 24h, the cell viability was higher than the blank value, which indicates that the PVA hydrogels with different contents have no cytotoxicity and are helpful for cell proliferation.
Example 10
The N-halamine antibacterial hydrogel capable of being recycled and selectively sterilized (the mass ratio of SA to PVA is 0.3: 0.4, 0.3: 0.8 and 0.3: 1.2) prepared by the method is sterilized at one time (namely, active chlorine (Cl) in the hydrogel is sterilized at one time)+、N-Cl、ClO-) All released), the other piece is added with active chlorine (Cl)+、N-Cl、ClO-) The hydrogel is covered with active chlorine (Cl) on another hydrogel in a short time+、N-Cl、ClO-) Can be released into the hydrogel, and the hydrogel has a sterilization function, so that the hydrogel can be recycled. The invention has 5 times of circulation, the sterilization rate can reach 100 percent, and the invention can realize repeated recycling on the premise of no damage to the hydrogel.
The MAG (2-methacrylamide glucopyranose) prepared in examples 1-8 was tested accordingly:
as shown in FIG. 2, H-nuclear magnetic hydrogen spectrum data (D) of MAG (2-methacrylamide glucopyranose)2O) ═ 5.61ppm and ═ 5.38ppm are the chemical shift values for the two hydrogens on C ═ C, respectively ═ 5.13ppm and ═ 4.69ppm are the chemical shift values for α -CH and β -CH on the 1-position carbon of the glucopyranose ring, respectively, ═ 3.36 to 3.81ppm are the chemical shift values for the hydrogens on the 5 carbons of the glucose ring other than the 1-position carbon, and ═ 1.84ppm is CH3Chemical shift values of upper hydrogen. The peak area ratio of the above characteristic peaks was about 1:1:0.52:0.43:6: 3. The successful synthesis of MAG (2-methacrylamide glucopyranose) was demonstrated.
As shown in FIG. 3, the infrared absorption spectrum data (KBr) of MAG (2-methacrylamide glucopyranose) and pMAG: as can be seen by comparison, in MAG, 3090cm-1A 1654cm stretching vibration absorption peak of C-H bond at the left and right-1The stretching vibration absorption peak of C ═ C bond was observed on the left and right, and the characteristic absorption peak was not observed in pMAG. Successful pMAG synthesis was demonstrated by the disappearance of the C-H bond and C-C bond stretching shock absorption peaks.
The pMAG-Cl prepared in examples 1 to 8 were tested correspondingly:
iodometric assay of pMAG-Cl: the iodometry can measure the available chlorine content in the N-halamine, and on the other hand, because of obvious color change in the titration process, the qualitative judgment can be carried out on the content. An aqueous solution of pMAG-Cl was transparent and colorless. To which H was added2SO4And KI, changed to light yellowDemonstration of the active Cl in N-Halamine I-Oxidation to form I2，I2With excess of I-Form I by bonding3 -And I is3 -Light yellow at low concentrations. The solution turned bluish-black after addition of starch, which also demonstrates that I2And I3 -Is present. With Na2S2O3The titration is carried out on the standard solution, and the blue-black color can be observed to gradually become lighter until the colorless is recovered, and the titration end point is obtained. The presence of available chlorine in pMAG-Cl was demonstrated by iodometry, indicating successful synthesis of pMAG-Cl.
As shown in FIG. 4, UV spectral data of pMAG-Cl: after 1% KI solution and 2mol/L H are added2SO4In the solution and the solution of pMAG-Cl, obvious absorption peaks exist at 288nm and 350nm, which proves that the synthesis of pMAG-Cl is successful.
As shown in FIG. 5, XPS data for pMAG-Cl: 102eV, 152eV, 200eV, 285eV, 400eV, and 532eV are electron binding energies of Si 2p, Si 2s, Cl 2p, C1 s, N1 s, and O1 s, respectively. It is to be noted that Si is not an element contained in the sample, and the electron binding energy of Si 2p and Si 2s is generated by the substrate on which the sample is fixed. The electron binding energy of N1 s was only slightly changed before and after chlorination of the sample. From the figure, it can be observed that pMAG-Cl has a distinct Cl 2p peak at 200eV, indicating the presence of available chlorine. This indicated that pMAG-Cl was successfully synthesized.
The antimicrobial hydrogels prepared in examples 1-8 were tested accordingly:
as shown in fig. 6, scanning electron microscopy of hydrogels: and (3) putting the prepared hydrogel sample into freeze drying for 24h, and taking a small block for measuring a scanning electron microscope. It can be seen that the hydrogel exhibits a distinct pore structure, indicating that the synthesized hydrogel has a double network structure.
As shown in fig. 7-8, water loss and swelling tests: to measure the water content of the hydrogel, a hydrogel sample having a diameter of about 2cm and a thickness of about 2mm was taken. And weighing the mass of the hydrogel at fixed time intervals. As can be seen from the figure, the water loss rate of the hydrogel shows a tendency of first-speed and last-slow, and after 24 hours, the quality of the hydrogel basically does not change any more, and the water content is calculated according to a formula, and the water content of the hydrogel is about 92.36 percent.
Qd＝(Ws-Wd)/Ws×100％
Wherein, WsIs the initial mass of the hydrogel sample, WdIs the mass of the hydrogel sample after drying.
To measure the swelling ratio of the hydrogel, a hydrogel sample having a diameter of about 2cm and a thickness of about 2mm was taken, and was freeze-dried for 24 hours and then taken out. The dried sample was immersed in a phosphate buffer solution (pH 7.3), the hydrogel was taken out at regular intervals, and the solution on the surface of the hydrogel was wiped off as dry as possible with filter paper, and the mass was measured. After a period of time, the quality of the hydrogel basically does not change any more, and the swelling ratio of the hydrogel is calculated according to a formula.
Qw＝(M1-M0)/M0×100％
Wherein M is0Is the mass of the dried hydrogel, M1Is the mass of the hydrogel after being soaked in the buffer solution. As shown, after soaking for about 3 hours, the hydrogel mass was substantially unchanged and the swelling ratio was about 650% to 750%.
As shown in fig. 9-13, mechanical strength of the hydrogels was tested: the mechanical strength was measured by the tensile method to conclude that: firstly, controlling other components to be unchanged, and gradually increasing the strength and tensile modulus of the hydrogel when the content of polyvinyl alcohol (PVA) is increased; secondly, the longer the soaking time in the calcium chloride solution is, the strength of the hydrogel is gradually increased, and the tensile modulus is also gradually increased; and thirdly, controlling other components to be unchanged, and gradually reducing the strength of the hydrogel and the corresponding tensile modulus when the content of pMAG-Cl is gradually increased, because the addition of the macromolecular N-halamine hinders the formation of a network structure.

Claims (1)

1. A preparation method of N-halamine hydrogel capable of being recycled and selectively sterilized is characterized by comprising the following steps:
1) preparation of MAG (2-methacrylamide glucopyranose): 5 parts by mass of D (+) -glucosamine hydrochloride and 5 parts by mass of anhydrous K2CO3Mixing, adding into 119 parts by mass of anhydrous methanol, reacting in ice bath for 4h, purifying by using a silica gel chromatographic column, and vacuum-drying the purified sample for 24h to obtain MAG;
2) preparation of homopolymer pMAG: mixing 0.8 mass part of the synthesized MAG with 0.04 mass part of initiator AIBN (azobisisobutyronitrile), adding 9.5 mass parts of DMF (N-N-dimethylformamide) as a reaction solvent, reacting for 10 hours at 70 ℃, dialyzing the reaction product for 3 days by using a dialysis bag, and freeze-drying to obtain homopolymer pMAG;
3) preparation of pMAG-Cl: diluting 1.1 part by mass of 10% NaClO solution to 3% -5%, adjusting the pH to 7 +/-0.02 with hydrochloric acid, adding 0.25 part by mass of pMAG into the NaClO solution, magnetically stirring for 12h, dialyzing for 3 days with a dialysis bag, and freeze-drying to obtain pMAG-Cl;
4) dissolving 0.4-1.2 parts by mass of PVA (polyvinyl alcohol) in distilled water at 95 ℃, adding 0.3 part by mass of SA (sodium alginate), stirring to dissolve, adding 0.03-0.12 part by mass of pMAG-Cl, pouring the mixed solution into a mold, and storing for 22 hours at-22 ℃ in a refrigerator;
5) unfreezing the frozen hydrogel, and then adding 0.1mol/L CaCl into the hydrogel2Soaking the solution for 0.5-2h to obtain the antibacterial hydrogel.
CN202010637903.6A 2020-07-06 2020-07-06 Preparation method of recyclable N-halamine hydrogel capable of selectively sterilizing Pending CN111748108A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087926A (en) * 2021-04-01 2021-07-09 内蒙古大学 Preparation method and application of light-controlled injectable hydrogel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070275030A1 (en) * 2006-05-25 2007-11-29 The General Hospital Corporation Dba Massachusetts General Hospital Anti-cross-linking agents and methods for inhibiting cross-linking of injectable hydrogel formulations
CN107397961A (en) * 2017-09-05 2017-11-28 陕西师范大学 A kind of method for improving the anti-Escherichia coli performance of polyethyleneimine
CN107496975A (en) * 2017-08-14 2017-12-22 浙江大学 A kind of polyvinyl alcohol with optical Response antibacterial/sodium alginate carries liquid medicine gel dressing and preparation method thereof
CN107517961A (en) * 2017-08-21 2017-12-29 深圳市号芯环保科技有限公司 A kind of Inorganic whisker type tridimensional network anti-biotic material and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070275030A1 (en) * 2006-05-25 2007-11-29 The General Hospital Corporation Dba Massachusetts General Hospital Anti-cross-linking agents and methods for inhibiting cross-linking of injectable hydrogel formulations
CN107496975A (en) * 2017-08-14 2017-12-22 浙江大学 A kind of polyvinyl alcohol with optical Response antibacterial/sodium alginate carries liquid medicine gel dressing and preparation method thereof
CN107517961A (en) * 2017-08-21 2017-12-29 深圳市号芯环保科技有限公司 A kind of Inorganic whisker type tridimensional network anti-biotic material and preparation method
CN107397961A (en) * 2017-09-05 2017-11-28 陕西师范大学 A kind of method for improving the anti-Escherichia coli performance of polyethyleneimine

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ELBADAWY A. KAMOUN ET AL.: "《Poly (vinyl alcohol)-alginate physically crosslinked hydrogel membranes for wound dressing applications: Characterization and bio-evaluation》", 《ARABIAN JOURNAL OF CHEMISTRY》 *
WANJUN CHEN ET AL.: "《Engineering a multifunctional N-halamine-based antibacterial hydrogel》", 《CHEMICAL ENGINEERING JOURNAL》 *
左华江等: "高分子抗菌剂的研究现状", 《化工进展》 *
张毅等: "聚乙烯醇水凝胶功能化改性研究进展", 《材料导报》 *
袁玉奇: "《基于含糖聚合物的多功能抗菌表面的构建》", 《中国优秀博硕士学位论文全文数据库 工程材料I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087926A (en) * 2021-04-01 2021-07-09 内蒙古大学 Preparation method and application of light-controlled injectable hydrogel
CN113087926B (en) * 2021-04-01 2023-07-28 内蒙古大学 Preparation method and application of light-regulating injectable hydrogel

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