CN117946287B - Preparation method and application of antibacterial amino acid-based cellulose polymer - Google Patents
Preparation method and application of antibacterial amino acid-based cellulose polymer Download PDFInfo
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- CN117946287B CN117946287B CN202410355635.7A CN202410355635A CN117946287B CN 117946287 B CN117946287 B CN 117946287B CN 202410355635 A CN202410355635 A CN 202410355635A CN 117946287 B CN117946287 B CN 117946287B
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- tetraoxatetradecane
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- histidine
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 54
- 239000001913 cellulose Substances 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 229940024606 amino acid Drugs 0.000 claims description 29
- 229960002885 histidine Drugs 0.000 claims description 27
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 25
- -1 histidine quaternary ammonium salt Chemical class 0.000 claims description 23
- 229920001046 Nanocellulose Polymers 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 9
- 229940073608 benzyl chloride Drugs 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- LGEVPLDBBPWJIC-UHFFFAOYSA-N 3-[2-[2-[2-(2-carboxyethoxy)ethoxy]ethoxy]ethoxy]propanoic acid Chemical compound OC(=O)CCOCCOCCOCCOCCC(O)=O LGEVPLDBBPWJIC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- WCOJOHPAKJFUDF-UHFFFAOYSA-N 3-(1h-imidazol-5-yl)-2-(phenylmethoxycarbonylamino)propanoic acid Chemical compound C=1C=CC=CC=1COC(=O)NC(C(=O)O)CC1=CN=CN1 WCOJOHPAKJFUDF-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 210000000170 cell membrane Anatomy 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- 125000000487 histidyl group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C([H])=N1 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
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- WCOJOHPAKJFUDF-LBPRGKRZSA-N (2s)-3-(1h-imidazol-5-yl)-2-(phenylmethoxycarbonylamino)propanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC=1C=CC=CC=1)C1=CN=CN1 WCOJOHPAKJFUDF-LBPRGKRZSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 150000001483 arginine derivatives Chemical class 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002410 histidine derivatives Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the technical field of antibacterial materials, and discloses a preparation method and application of an antibacterial amino acid cellulose polymer. And simultaneously improves the hydrophilic property and the tensile strength of the cellulose-based film.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a preparation method and application of an antibacterial amino acid-based cellulose polymer.
Background
The antibacterial material is widely applied to the fields of clothing, food and medicine packaging, medical supplies and the like; common antibacterial agents mainly include natural compound antibacterial agents, amino acid antibacterial agents, quaternary ammonium salt antibacterial agents and the like. The amino acid antibacterial agent such as histidine derivative, arginine derivative and the like has the advantages of high biological activity, good biocompatibility, greenness, no toxicity and the like. The polymer has important application in high molecular materials.
Cellulose is the polysaccharide compound with the most abundant reserves in the world, is cheap and easy to obtain, has good film forming property, and has wide application prospect in packaging films, preservative films and the like. However, the cellulose material does not have antibacterial property, which is unfavorable for the practical application in the fields of food and drug packaging, medical supplies and the like. Chinese patent CN106905438B discloses a chitosan quaternary ammonium salt antibacterial cellulose and a preparation method thereof, wherein the cellulose is grafted with chitosan through amidation reaction, and then the chitosan is subjected to quaternization reaction to obtain the antibacterial cellulose with the surface grafted with chitosan quaternary ammonium salt, so that the antibacterial cellulose has excellent antibacterial performance. However, the hydrophilic property, mechanical strength and other properties of the cellulose material are not improved.
Disclosure of Invention
The invention solves the problem that the cellulose material does not have antibacterial property, and improves the tensile property of the cellulose material.
The technical scheme of the invention is as follows: a method for preparing an antibacterial amino acid-based cellulose polymer, which comprises the following steps: adding KH550 modified nanocrystalline cellulose, tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate into dimethyl sulfoxide solvent, dripping triethylamine as catalyst, uniformly mixing, reacting at 20-40 ℃ for 12-24h, filtering, washing filter cake with ethanol, and obtaining antibacterial amino acid cellulose polymer;
Further, the mass of the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and the tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate is respectively 10-35% and 18-60% of that of KH550 modified nanocrystalline cellulose.
Further, the preparation method of the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt comprises the following steps:
(1) Adding N-carbobenzoxy-L-histidine and tetraoxatetradecane-1, 14-diformyl chloride intermediate into tetrahydrofuran in ice bath, dripping triethylamine as catalyst, reacting at 20-30 deg.c for 5-8 hr, decompressing and distilling, and washing the product with N-hexane to obtain intermediate A. The preparation reaction formula is as follows:
；
(2) Adding an intermediate A and benzyl chloride into ethanol or acetonitrile solvent, condensing and refluxing for reaction for 60-72h at 75-85 ℃, distilling under reduced pressure, washing a product with acetone, then adding the product into methanol, adding a Pd/C catalyst, reacting for 6-12h in a hydrogen atmosphere of 0.2-0.3MPa, recovering the catalyst after suction filtration, distilling the filtrate under reduced pressure, and washing the product with acetone to obtain tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt. The preparation reaction formula is as follows:
。
further, the mass of N-benzyloxycarbonyl-L-histidine in (1) is 180-210% of the mass of tetraoxatetradecane-1, 14-dicarboxyl chloride intermediate.
Further, the mass of benzyl chloride in (2) is 32-40% of the mass of intermediate A.
Further, the preparation method of the tetraoxatetradecane-1, 14-dicarboxylic acid dichloride intermediate comprises the following steps: adding 45-60% of 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid into thionyl chloride, reacting for 4-7h at 60-70 ℃, and distilling under reduced pressure to obtain tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate. The preparation reaction formula is as follows:
。
further, the antibacterial amino acid-based cellulose polymer is applied to a hydrophilic antibacterial film material.
The invention has the technical effects that: according to the invention, KH550 modified nanocrystalline cellulose amino is used as a polymerization site, tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate are subjected to amidation crosslinking polymerization reaction, and a polymer containing a histidine structure and a quaternary ammonium salt structure is grafted in a nanocrystalline cellulose molecular chain, so that a novel antibacterial amino acid-based cellulose polymer is obtained. Wherein the histidine structure has good biological antibacterial activity; the quaternary ammonium salt structure has excellent antibacterial performance, has electropositive property, can interact with cell membranes with negative charges of bacteria, changes the permeability of the cell membranes of the bacteria, and enables biomass such as enzymes in the cell membranes of the bacteria to flow out, thereby inhibiting the growth and reproduction of the bacteria, and has excellent antibacterial performance on escherichia coli, staphylococcus aureus, candida albicans and the like.
The tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt prepared by the invention contains hydrophilic ether bond, quaternary ammonium salt group and carboxyl, and the tetraoxatetradecane-1, 14-dicarboxamide intermediate also contains hydrophilic ether bond, so that the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and the hydrophilic ether bond are crosslinked and polymerized into the nanocrystalline cellulose matrix, the hydrophilic performance of the cellulose-based film is obviously improved, and the water contact angle is obviously reduced. And after cellulose is crosslinked and modified, a stable chemical crosslinked network is formed in a cellulose matrix, and the tensile strength of the film material is obviously improved.
Detailed Description
The CAS number of the 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid is 32775-08-9.
N-benzyloxycarbonyl-L-histidine has a CAS number of 14997-58-1
Benzyl chloride with CAS number 100-44-7
KH550 has CAS number 919-30-2
The brand of nanocrystalline cellulose is S11212464, hubei Xinyu Hongshi biological medicine.
Mixing 90mL of ethanol and 10mL of distilled water, dropwise adding glacial acetic acid, and regulating the pH value to 4.5; then adding 0.48g KH550, adding 8g nanocrystalline cellulose after ultrasonic dispersion treatment, stirring and reacting for 4 hours at 75 ℃, adding the product into acetone to separate out precipitate, filtering and washing with acetone to obtain KH550 modified nanocrystalline cellulose.
Example 1
(1) 2.25G of 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid was added to 5g of thionyl chloride, reacted at 70℃for 6 hours, and distilled under reduced pressure to give a tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate. The structural formula is as follows:
。
(2) To 80mL of tetrahydrofuran was added 3g of tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate and 6.1g N-benzyloxycarbonyl-L-histidine in an ice bath, 4g of triethylamine as a catalyst was added dropwise, followed by reaction at 20℃for 5 hours, distillation under reduced pressure, and washing of the product with n-hexane to give intermediate A.
(3) 5G of intermediate A and 1.6g of benzyl chloride are added into 50mL of ethanol solvent, condensation reflux reaction is carried out for 72h at 75 ℃, reduced pressure distillation is carried out, acetone is used for washing products, then the products are added into 60mL of methanol, 0.4g of Pd/C catalyst is added, reaction is carried out for 8h in a hydrogen atmosphere of 0.3MPa, the catalyst is recovered after suction filtration, filtrate is distilled under reduced pressure, and acetone is used for washing products, thus obtaining tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt. The structural formula is as follows:
。
(4) 10g KH550 modified nanocrystalline cellulose, 1g tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and 1.8g tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate are added into 100mL dimethyl sulfoxide solvent, 0.8g triethylamine is dropwise added, the mixture is uniformly mixed and then reacted at 30 ℃ for 12 hours, and filter cakes are washed by ethanol after suction filtration, so that the amino acid-based cellulose polymer with antibacterial property is obtained.
Example 2
(1) 3G of 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid is added to 5g of thionyl chloride to react for 7h at 60 ℃, and reduced pressure distillation is carried out to obtain the tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate.
(2) To 50mL of tetrahydrofuran was added 3g of tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate and 5.4g N-benzyloxycarbonyl-L-histidine in an ice bath, 4g of triethylamine as a catalyst was added dropwise, followed by reaction at 25℃for 8 hours, distillation under reduced pressure, and washing of the product with n-hexane to give intermediate A.
(3) 5G of intermediate A and 2g of benzyl chloride are added into 70mL of acetonitrile solvent, condensation reflux reaction is carried out for 60 hours at 85 ℃, reduced pressure distillation is carried out, acetone is used for washing products, then the products are added into 80mL of methanol, 0.4g of Pd/C catalyst is added, reaction is carried out for 12 hours in a hydrogen atmosphere of 0.2MPa, the catalyst is recovered after suction filtration, filtrate is distilled under reduced pressure, and acetone is used for washing products, thus obtaining tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt.
(4) 10G KH550 modified nanocrystalline cellulose, 2.2g tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and 3.8g tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate are added into 140mL dimethyl sulfoxide solvent, 0.9g triethylamine is dropwise added, the mixture is uniformly mixed and then reacted at 20 ℃ for 24 hours, and filter cakes are washed by ethanol after suction filtration, so that the amino acid-based cellulose polymer with antibacterial property is obtained.
Example 3
(1) 3G of 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid is added to 5g of thionyl chloride, and the mixture is reacted for 4 hours at 70 ℃ and distilled under reduced pressure to obtain the tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate.
(2) 3G of tetraoxatetradecane-1, 14-diformyl chloride intermediate and 5.8g N-benzyloxycarbonyl-L-histidine were added to 60mL of tetrahydrofuran in an ice bath, 3.6g of triethylamine as a catalyst was added dropwise, and then reacted at 30℃for 5 hours, distilled under reduced pressure, and the product was washed with n-hexane to give intermediate A.
(3) 5G of intermediate A and 1.8g of benzyl chloride are added into 70mL of ethanol solvent, condensation reflux reaction is carried out for 72h at 75 ℃, reduced pressure distillation is carried out, acetone is used for washing products, then the products are added into 80mL of methanol, 0.45g of Pd/C catalyst is added, reaction is carried out for 6h in a hydrogen atmosphere of 0.3MPa, the catalyst is recovered after suction filtration, filtrate is distilled under reduced pressure, and acetone is used for washing products, thus obtaining tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt.
(4) 10G KH550 modified nanocrystalline cellulose, 3.5g tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and 6g tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate are added into 200mL dimethyl sulfoxide solvent, 1.1g of catalyst triethylamine is added dropwise, the mixture is reacted for 12 hours at 40 ℃ after uniform mixing, and filter cakes are washed by ethanol after suction filtration, so that the amino acid-based cellulose polymer with antibacterial property is obtained.
The difference between comparative example 1 and example 1 is that tetraoxatetradecane-1, 14-dicarboxamido histidine quaternary ammonium salt was not added in the preparation of antibacterial amino acid based cellulose polymer.
(1) 10G KH550 modified nanocrystalline cellulose and 1.8g tetraoxatetradecane-1, 14-diformyl chloride intermediate are added into 100mL dimethyl sulfoxide solvent, 0.8g triethylamine is added dropwise, the mixture is uniformly mixed and then reacted for 12 hours at 30 ℃, and filter cake is washed by ethanol after suction filtration, so that the amino acid-based cellulose polymer with antibacterial property is obtained.
Comparative example 2 and example 1 differ in that the conventional adipoyl chloride was used in place of tetraoxatetradecane-1, 14-dicarboxyl chloride intermediate in the preparation of the antimicrobial amino acid based cellulose polymer.
(1) 10G KH550 modified nanocrystalline cellulose, 1g tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and 1.8g adipoyl chloride are added into 100mL dimethyl sulfoxide solvent, 0.8g triethylamine is added dropwise, the mixture is uniformly mixed and then reacted for 12 hours at 30 ℃, and filter cakes are washed by ethanol after suction filtration, so that the amino acid cellulose polymer with antibacterial property is obtained.
Adding amino acid-based cellulose polymer or KH550 modified nanocrystalline cellulose into dimethyl sulfoxide, heating to 80 ℃, stirring for 1h, pouring into a mould, casting to form a film, and drying at 100 ℃ to obtain the cellulose-based film.
Taking bacterial suspension (with the concentration of 1X 10 6 CFU/mL) of staphylococcus aureus or escherichia coli as a test strain, transferring 0.5mL of bacterial suspension into a sterilization culture dish containing beef extract peptone culture medium, then attaching a cellulose-based film with the diameter of 2cm and the thickness of 1: 1mm on the surface of the culture medium, culturing 24: 24h in a constant-temperature incubator at 37 ℃, and measuring the diameter of a bacteriostasis ring after culturing. The larger the diameter of the inhibition zone, the better the antibacterial performance.
Comparative example 3 is a cellulose-based film made of KH550 modified nanocrystalline cellulose.
A water contact angle tester is adopted to test the water contact angle of the cellulose-based film; the cellulose-based film is placed on a sample stage of a water contact angle tester, a water drop is dripped on the surface of the cellulose-based film through a microinjector, the water contact angle is tested for 5 times, and the average value is obtained.
The tensile properties of the cellulose-based films were tested according to the method of ASTM D638. The stretching rate was 20mm/min. Test 3 times and take the average.
Through tests, the prepared cellulose-based film has larger antibacterial circle diameter to escherichia coli, staphylococcus aureus and candida albicans by taking the antibacterial amino acid-based cellulose polymer as a matrix in the examples 1-3, and has excellent antibacterial performance. This is because the amino group of KH550 modified nanocrystalline cellulose is used as a polymerization site, tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate are subjected to amidation crosslinking polymerization reaction, and a polymer containing a histidine structure and a quaternary ammonium salt structure is grafted in the molecular chain of nanocrystalline cellulose. Wherein the histidine structure has good biological antibacterial activity; the quaternary ammonium salt structure has excellent antibacterial performance, has positive electricity, can interact with a cell membrane with negative charges of bacteria, changes the permeability of the cell membrane of the bacteria, and enables biomass such as enzymes in the cell membrane of the bacteria to flow out, thereby inhibiting the growth and reproduction of the bacteria and showing excellent antibacterial performance.
Comparative example 1 when an antibacterial amino acid based cellulose polymer was prepared, a quaternary ammonium salt of tetraoxatetradecane-1, 14-dicarboxamide histidine was not added, and comparative example 3 prepared by modifying nanocrystalline cellulose with KH550, both of which contained no histidine active structure and no quaternary ammonium salt antibacterial structure, had no antibacterial performance.
The cellulose-based films prepared in examples 1 to 3 exhibited excellent hydrophilic properties with water contact angles of only 51.7 to 56.9 °. This is because tetraoxatetradecane-1, 14-dicarboxamido histidine quaternary ammonium salt contains hydrophilic ether bond, quaternary ammonium salt group and carboxyl, and tetraoxatetradecane-1, 14-dicarboxyl chloride intermediate also contains hydrophilic ether bond, so that both are crosslinked and polymerized into nanocrystalline cellulose matrix, the hydrophilic performance of cellulose-based film is obviously improved, and the water contact angle is obviously reduced. After cellulose is crosslinked and modified, a stable chemical crosslinking network is formed in a cellulose matrix, and the tensile strength of the film material is obviously improved; the hydrophilicity and tensile properties are much higher than those of comparative example 3.
The water contact angle of comparative example 1 is lower than comparative example 3 but higher than example 1. This is because the quaternary ammonium salt of tetraoxatetradecane-1, 14-dicarboxamido histidine was not added in the preparation of the amino acid based cellulose polymer of comparative example 1. The KH550 modified nanocrystalline cellulose is only crosslinked and modified by tetraoxatetradecane-1, 14-diformyl chloride intermediate, the film material does not contain hydrophilic quaternary ammonium salt and carboxyl, and the content of hydrophilic ether bond is lower than that of the example 1; therefore, the water contact angle was higher than that of example 1, and the hydrophilic property was poor.
Comparative example 2 an amino acid based cellulose polymer was prepared using conventional adipoyl chloride instead of tetraoxatetradecane-1, 14-dicarboxyl chloride intermediate. Resulting in a membrane material having a lower hydrophilic ether linkage content than that of example 1. Therefore, the water contact angle was higher than that of example 1, and the hydrophilic property was poor.
It should be noted that the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but the present invention is described in detail with reference to the foregoing embodiment, and it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. A method for preparing an antibacterial amino acid based cellulose polymer, characterized in that the method comprises the steps of: adding KH550 modified nanocrystalline cellulose, tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and tetraoxatetradecane-1, 14-dicarboxamide chloride intermediate into dimethyl sulfoxide solvent, dripping triethylamine as catalyst, uniformly mixing, reacting at 20-40 ℃ for 12-24h, filtering, washing filter cake with ethanol, and obtaining antibacterial amino acid cellulose polymer;
the structural formula of the tetraoxatetradecane-1, 14-diformyl chloride intermediate is as follows:
；
The preparation method of the tetraoxatetradecane-1, 14-diformyl chloride intermediate comprises the following steps: adding 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid into thionyl chloride, reacting for 4-7h at 60-70 ℃, and distilling under reduced pressure to obtain tetraoxatetradecane-1, 14-dicarboxylic acid chloride intermediate;
the structural formula of the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt is as follows:
；
The preparation method of the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt comprises the following steps:
(1) Adding N-carbobenzoxy-L-histidine and tetraoxatetradecane-1, 14-diformyl chloride intermediate into tetrahydrofuran in ice bath, dripping triethylamine as catalyst, reacting at 20-30 deg.c for 5-8 hr, decompressing and distilling, washing the product with N-hexane to obtain intermediate A;
(2) Adding the intermediate A and benzyl chloride into a solvent, condensing and refluxing for reaction for 60-72h at 75-85 ℃, distilling under reduced pressure, washing a product with acetone, then adding the product into methanol, adding a Pd/C catalyst, reacting for 6-12h in a hydrogen atmosphere, recovering the catalyst after suction filtration, distilling the filtrate under reduced pressure, and washing the product with acetone to obtain the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt.
2. The method for producing an antibacterial amino acid based cellulose polymer according to claim 1, wherein the mass of the tetraoxatetradecane-1, 14-dicarboxamide histidine quaternary ammonium salt and the tetraoxatetradecane-1, 14-dicarboxamide intermediate is 10 to 35% and 18 to 60% of the mass of the KH550 modified nanocrystalline cellulose, respectively.
3. The method for producing an antibacterial amino acid based cellulose polymer according to claim 1, wherein the mass of N-benzyloxycarbonyl-L-histidine in (1) is 180 to 210% of the mass of tetraoxatetradecane-1, 14-dicarboxyl chloride intermediate.
4. The method for producing an antibacterial amino acid-based cellulose polymer according to claim 1, wherein the mass of benzyl chloride in (2) is 32 to 40% of the mass of intermediate a.
5. The method for producing an antibacterial amino acid-based cellulose polymer according to claim 1, wherein the solvent in (2) is ethanol or acetonitrile.
6. The method for producing an antibacterial amino acid based cellulose polymer according to claim 1, wherein the pressure of the hydrogen atmosphere is controlled to be 0.2 to 0.3MPa in (2).
7. The method for producing an antibacterial amino acid based cellulose polymer according to claim 1, wherein the mass of 3,6,9, 12-tetraoxatetradecane-1, 14-dicarboxylic acid is 45 to 60% of the mass of thionyl chloride.
8. Use of an antibacterial amino acid-based cellulose polymer obtained by the production process according to any one of claims 1 to 7 in a hydrophilic antibacterial film material.
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| CN103724568A (en) * | 2013-12-31 | 2014-04-16 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose and preparation method thereof |
| CN105968215A (en) * | 2016-03-31 | 2016-09-28 | 北京理工大学 | Method for grafting nano-crystalline cellulose with amino acid |
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| CN113152090A (en) * | 2021-04-15 | 2021-07-23 | 东华大学 | Antibacterial and antiviral cellulose nanofiber filtering and protecting membrane and preparation method thereof |
| CN117385499A (en) * | 2023-12-11 | 2024-01-12 | 烟台云泷化学制品有限公司 | Preparation process of polyurethane-nylon composite fiber material |
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| CN103724568A (en) * | 2013-12-31 | 2014-04-16 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose and preparation method thereof |
| CN105968215A (en) * | 2016-03-31 | 2016-09-28 | 北京理工大学 | Method for grafting nano-crystalline cellulose with amino acid |
| CN107840895A (en) * | 2017-11-29 | 2018-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Cation-modified method of pure plant extraction nano-cellulose and products thereof and application |
| CN113152090A (en) * | 2021-04-15 | 2021-07-23 | 东华大学 | Antibacterial and antiviral cellulose nanofiber filtering and protecting membrane and preparation method thereof |
| CN117385499A (en) * | 2023-12-11 | 2024-01-12 | 烟台云泷化学制品有限公司 | Preparation process of polyurethane-nylon composite fiber material |
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