CN116162181B - Chitosan-tricarboxylic acid derivative and preparation method and application thereof - Google Patents
Chitosan-tricarboxylic acid derivative and preparation method and application thereof Download PDFInfo
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- CN116162181B CN116162181B CN202111410342.7A CN202111410342A CN116162181B CN 116162181 B CN116162181 B CN 116162181B CN 202111410342 A CN202111410342 A CN 202111410342A CN 116162181 B CN116162181 B CN 116162181B
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- chitosan
- tricarboxylic acid
- derivative
- acid derivative
- tricarboxylic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001661 Chitosan Polymers 0.000 claims abstract description 94
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 239000002537 cosmetic Substances 0.000 claims abstract description 9
- 235000013305 food Nutrition 0.000 claims abstract description 9
- -1 carboxybutyl Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000006196 deacetylation Effects 0.000 claims description 8
- 238000003381 deacetylation reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 229940054190 hydroxypropyl chitosan Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 34
- 210000004027 cell Anatomy 0.000 abstract description 14
- 244000005700 microbiome Species 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 210000002390 cell membrane structure Anatomy 0.000 abstract description 4
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- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 28
- 150000003628 tricarboxylic acids Chemical class 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 150000007524 organic acids Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 235000015278 beef Nutrition 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 235000005985 organic acids Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMJBYMUCKBYSCP-UHFFFAOYSA-N Hydroxycitric acid Chemical compound OC(=O)C(O)C(O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 210000000170 cell membrane Anatomy 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000005711 Benzoic acid Substances 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- JOMKFSZNMGIRPJ-UHFFFAOYSA-N OC(=O)C(O)C(O)(C(O)=O)C(O)C(O)=O Chemical compound OC(=O)C(O)C(O)(C(O)=O)C(O)C(O)=O JOMKFSZNMGIRPJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- ODBLHEXUDAPZAU-UHFFFAOYSA-N isocitric acid Chemical compound OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
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- 239000004334 sorbic acid Substances 0.000 description 3
- 229940075582 sorbic acid Drugs 0.000 description 3
- LILJHFUMPIGWSQ-UHFFFAOYSA-N 1,3-dihydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(O)C(C(O)=O)C(O)C(O)=O LILJHFUMPIGWSQ-UHFFFAOYSA-N 0.000 description 2
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 2
- QRYRORQUOLYVBU-VBKZILBWSA-N Carnosic acid Natural products CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 description 2
- 108010087806 Carnosine Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- CQOVPNPJLQNMDC-UHFFFAOYSA-N N-beta-alanyl-L-histidine Natural products NCCC(=O)NC(C(O)=O)CC1=CN=CN1 CQOVPNPJLQNMDC-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CQOVPNPJLQNMDC-ZETCQYMHSA-N carnosine Chemical compound [NH3+]CCC(=O)N[C@H](C([O-])=O)CC1=CNC=N1 CQOVPNPJLQNMDC-ZETCQYMHSA-N 0.000 description 2
- 229940044199 carnosine Drugs 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007273 lactonization reaction Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000006241 metabolic reaction Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 235000010241 potassium sorbate Nutrition 0.000 description 2
- 239000004302 potassium sorbate Substances 0.000 description 2
- 229940069338 potassium sorbate Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000193755 Bacillus cereus Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 240000006024 Lactobacillus plantarum Species 0.000 description 1
- 235000013965 Lactobacillus plantarum Nutrition 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 229920002385 Sodium hyaluronate Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
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- 125000003636 chemical group Chemical group 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
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- 229940072205 lactobacillus plantarum Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
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- 210000003463 organelle Anatomy 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CHHHXKFHOYLYRE-STWYSWDKSA-M potassium sorbate Chemical group [K+].C\C=C\C=C\C([O-])=O CHHHXKFHOYLYRE-STWYSWDKSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/716—Glucans
- A61K31/722—Chitin, chitosan
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
Abstract
The invention belongs to the technical field of antibacterial substances, and discloses a chitosan-tricarboxylic acid derivative, a preparation method and application thereof. The chitosan-tricarboxylic acid derivative has a structure comprising a chitosan or chitosan derivative structure and a tricarboxylic acid substance or tricarboxylic acid derivative structure, wherein an ionic bond is formed between an amino group of the chitosan or chitosan derivative structure and a carboxyl group of the tricarboxylic acid substance or tricarboxylic acid derivative structure. Under the common acid-base condition of food or cosmetics, the chitosan-tricarboxylic acid derivative provided by the invention destroys the cell membrane structure of harmful microorganisms through chitosan, so that the tricarboxylic acid part can enter microorganism cells, disorder the metabolic activity of the cells and inhibit the activity of the microorganisms, thereby the chitosan-tricarboxylic acid derivative provided by the invention has excellent antibacterial property, and the chitosan-tricarboxylic acid derivative provided by the invention has good stability to temperature.
Description
Technical Field
The invention belongs to the technical field of antibacterial substances, and particularly relates to a chitosan-tricarboxylic acid derivative, a preparation method and application thereof.
Background
The antibacterial substances generally act on cell walls and cell membranes of microorganisms and enzyme and other links in key steps in biochemical metabolic reactions, enter the cells while weakening the cell walls and the cell membranes, react with organelles participating in the metabolic reactions, inhibit the normal biochemical reactions of the microorganisms, and play roles in inhibiting and even killing the microorganisms. Therefore, when the antibacterial substance has the above functions at the same time, the antibacterial effect thereof is remarkably improved.
It is known that chitosan has a good antibacterial effect, mainly derived from its weakening of the structure of microbial cell membranes. Most commercially available chitosan is obtained by first extracting chitin from fishery by-products (e.g., shrimp or crab shells) and then deacylating with alkali or acid. Chitin is a naturally occurring polymer formed from β -1,4 glycosidic linkages linking N-acetyl-D-glucosamine and D-glucosamine. Chitin can be processed to achieve partial or complete removal of acetyl groups and to obtain chitosan.
Weak organic acids are another class of compounds with good antimicrobial efficacy, such as acetic acid, lactic acid, sorbic acid and benzoic acid. These organic acids are also widely used in the food and cosmetic industries as preservatives in additives. Organic acids can enter cells, disrupt cellular metabolic activity, and thereby inhibit microbial activity. However, these weak organic acids need to exert their antimicrobial action at a system pH close to their pKa value (acidity coefficient, also known as acid dissociation constant), since under such conditions these weak organic acids exist predominantly in undissociated molecular form and can enter cells; when the pH value of the system deviates from the pKa of the system to be larger, the more weak organic acid exists in the form of dissociated ions, and cannot enter cells, so that the antibacterial effect of the weak organic acid is lost.
Compared with common antibacterial organic acids, the tricarboxylic acid compound has no advantage in terms of antibacterial efficacy, because compared with common organic acid antibacterial substances, the tricarboxylic acid compound has relatively stronger acidity, is easily dissociated in common food and cosmetic systems, namely under the condition that the pH is 3.8-7, and mainly exists in an ionic state, thereby greatly reducing the possibility that the tricarboxylic acid compound enters cells, and further greatly reducing the antibacterial property of the tricarboxylic acid compound.
Accordingly, there is a need to provide a novel antibacterial substance having good antibacterial properties.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the chitosan-tricarboxylic acid derivative, the preparation method and the application thereof, wherein the chitosan-tricarboxylic acid derivative has obviously improved antibacterial performance compared with chitosan or acetic acid, lactic acid, sorbic acid, benzoic acid and the like, and the chitosan-tricarboxylic acid derivative has good stability to temperature.
The invention is characterized in that: the invention solves two technical problems. One is that chitosan is used as the use scene restriction of antibiotic substance, because chitosan can act on the cell barrier, destroys cell membrane structure, but can not get into the cell, uses chitosan alone, needs higher concentration just has better antibiotic effect, and use cost increases, can't extensively popularize. The other is the use of tricarboxylic acids as antibacterial substances. Because tricarboxylic acid is a strong organic acid, and exists in the form of dissociated ions in systems such as foods and cosmetics with pH of 3.8-7, the tricarboxylic acid cannot enter the cell barrier, and has the same capability of disturbed cell metabolism as weak organic acids such as lactic acid, acetic acid, benzoic acid, sorbic acid and the like, but cannot play a role. The invention provides a chitosan-tricarboxylic acid derivative (compound), which is prepared by combining and compounding chitosan and tricarboxylic acid, wherein the chitosan and the tricarboxylic acid are combined through ionic bonds, and the chitosan-tricarboxylic acid derivative has the functions of destroying cell membranes of the chitosan and disturbing intracellular metabolism of the tricarboxylic acid simultaneously because of the synergistic effect of the chitosan and the tricarboxylic acid. Therefore, under the common acid-base condition of food or cosmetics, the chitosan-tricarboxylic acid derivative provided by the invention destroys the cell membrane structure through chitosan, so that the tricarboxylic acid part can enter into microorganism cells, disorder the metabolic activity of the cells and inhibit the activity of the microorganisms, thereby the chitosan-tricarboxylic acid derivative provided by the invention has excellent antibacterial property, and the chitosan-tricarboxylic acid derivative provided by the invention has good stability to temperature.
In a first aspect the present invention provides a chitosan-tricarboxylic acid derivative.
Specifically, the chitosan-tricarboxylic acid derivative comprises a chitosan or chitosan derivative structure and a tricarboxylic acid substance or tricarboxylic acid derivative structure, wherein an ionic bond is formed between an amino group of the chitosan or chitosan derivative structure and a carboxyl group of the tricarboxylic acid substance or tricarboxylic acid derivative structure.
Preferably, the chitosan derivative is at least one selected from carboxymethyl chitosan, carboxybutyl chitosan, hydroxyethyl chitosan and hydroxypropyl chitosan.
Preferably, the molecular weight of the chitosan or chitosan derivative is between 1 and 1000kDa; further preferably, the molecular weight of the chitosan or chitosan derivative is between 10 and 900kDa. The chitosan or chitosan derivative with the molecular weight range has better antibacterial property.
Preferably, the chitosan or chitosan derivative has a degree of deacetylation of 60% -99%. The higher the degree of deacetylation, the more glucosamine units can be guaranteed and the more amino groups can be provided to react with the tricarboxylic acid species or tricarboxylic acid derivative to form a salt.
Preferably, the tricarboxylic acid derivative is selected from tricarboxylic lactone species.
Preferably, the tricarboxylic acid material is selected from propane-1, 2, 3-tricarboxylic acid or a derivative of propane-1, 2, 3-tricarboxylic acid; further preferably, the derivative of propane-1, 2, 3-tricarboxylic acid is selected from at least one of 1-hydroxypropane-1, 2, 3-tricarboxylic acid, 2-hydroxypropane-1, 2, 3-tricarboxylic acid, 1, 2-dihydroxypropane-1, 2, 3-tricarboxylic acid, 1, 3-dihydroxypropane-1, 2, 3-tricarboxylic acid, 1,2, 3-trihydroxypropane-1, 2, 3-tricarboxylic acid.
Preferably, the tricarboxylic acid derivative is selected from at least one of 5-oxolane 2, 3-dicarboxylic acid, 2-hydroxy-5-oxolane 2, 3-dicarboxylic acid, 3-hydroxy-5-oxolane 2, 3-dicarboxylic acid, and any 2s,2s-, 2s,3r-, 2r,3 s-or 3r,3 r-stereoisomers of the tricarboxylic acid derivative. These are tricarboxylic acid lactone substances which are obtainable by hydroxylation of tricarboxylic acids, in particular by molecular lactonization of carboxyl groups and hydroxyl groups on the same hydroxylated tricarboxylic acid molecule, which form a molecular lactone ring structure, which can be carried out naturally or by catalysis of enzymes produced by plants, microorganisms. The reaction of the tricarboxylic acid lactone with the chitosan or chitosan derivative has the same reaction mechanism as the formation of the chitosan-tricarboxylic acid salt, because the lactonization of the tricarboxylic acid does not affect the amino group with the chitosan or chitosan derivative, nor the process of forming the ionic bond.
Preferably, a chitosan-tricarboxylic acid derivative has a structural formula shown in formula I or formula II:
wherein R is 1 represents-H, a carboxyl-containing alkyl group, or a hydroxyl-containing alkyl group;
R 2 、R 3 、R 4 and respectively and independently represents-H or-OH, wherein the value of x is 1-10000.
Preferably, the alkyl carbon number in the carboxyl-containing alkyl is 1-6; further preferably, the number of alkyl carbons in the carboxyl group-containing alkyl group is 1 to 5; more preferably, the number of alkyl carbons in the carboxyl group-containing alkyl group is 1 to 4.
The chitosan-tricarboxylic acid derivative contains a chitosan structure and a tricarboxylic acid or tricarboxylic acid lactone structure, and ionic bonds are formed between carboxyl groups of the tricarboxylic acid or tricarboxylic acid lactone and amino groups of the chitosan, so that the chitosan-tricarboxylic acid salt is formed.
In a second aspect, the present invention provides a process for the preparation of a chitosan-tricarboxylic acid derivative.
Specifically, the preparation method of the chitosan-tricarboxylic acid derivative comprises the following steps:
and mixing chitosan or chitosan derivative, tricarboxylic acid substance or tricarboxylic acid derivative for reaction to obtain the chitosan-tricarboxylic acid derivative.
Preferably, the chitosan derivative is at least one selected from carboxymethyl chitosan, carboxybutyl chitosan, hydroxyethyl chitosan and hydroxypropyl chitosan.
Preferably, the molecular weight of the chitosan or chitosan derivative is between 1 and 1000kDa; further preferably, the molecular weight of the chitosan or chitosan derivative is between 10 and 900kDa. The chitosan with the molecular weight range has better antibacterial property.
Preferably, the chitosan or chitosan derivative has a degree of deacetylation of 60% -99%. The higher the degree of deacetylation, the more glucosamine units can be guaranteed and the more amino groups can be provided to react with the tricarboxylic acid species or tricarboxylic acid derivative to form a salt.
Preferably, the tricarboxylic acid derivative is selected from tricarboxylic lactone species.
Preferably, the tricarboxylic acid material is selected from propane-1, 2, 3-tricarboxylic acid or a derivative of propane-1, 2, 3-tricarboxylic acid; further preferably, the derivative of propane-1, 2, 3-tricarboxylic acid is selected from at least one of 1-hydroxypropane-1, 2, 3-tricarboxylic acid, 2-hydroxypropane-1, 2, 3-tricarboxylic acid, 1, 2-dihydroxypropane-1, 2, 3-tricarboxylic acid, 1, 3-dihydroxypropane-1, 2, 3-tricarboxylic acid, 1,2, 3-trihydroxypropane-1, 2, 3-tricarboxylic acid.
Preferably, the tricarboxylic acid derivative is selected from at least one of 5-oxolane 2, 3-dicarboxylic acid, 2-hydroxy-5-oxolane 2, 3-dicarboxylic acid, 3-hydroxy-5-oxolane 2, 3-dicarboxylic acid, and any 2s,2s-, 2s,3r-, 2r,3 s-or 3r,3 r-stereoisomers of the tricarboxylic acid derivative. 5-oxolane 2, 3-dicarboxylic acid, 2-hydroxy-5-oxolane 2, 3-dicarboxylic acid, 3-hydroxy-5-oxolane 2, 3-dicarboxylic acid, and any 2S,2S-, 2S,3R-, 2R,3S-, or 3R, 3R-stereoisomers of said tricarboxylic acid derivatives.
Preferably, the mass ratio of the chitosan or chitosan derivative, the tricarboxylic acid substance or tricarboxylic acid derivative is 1: (0.5-1.7); further preferably, the mass ratio is 1: (0.8-1.2).
Preferably, the chitosan or chitosan derivative, the tricarboxylic acid material or tricarboxylic acid derivative is mixed in a solvent.
Preferably, the pH of the mixture formed by mixing the chitosan or chitosan derivative, the tricarboxylic acid substance or tricarboxylic acid derivative is 2.8-3.7; further preferably, the pH is 3.0-3.5. The purpose of controlling the pH within a suitable range is to ensure that most of the tricarboxylic acid species are present in the system predominantly in undissociated molecular form, preventing multiple chitosan molecules from reacting with the same organic acid.
Preferably, the temperature of the reaction is 45-90 ℃; further preferably, the temperature of the reaction is 65-75 ℃.
Preferably, the reaction time is 0.5 to 1.2 hours; further preferably, the reaction time is 0.8 to 1.0 hours.
Preferably, after the reaction is finished, the method further comprises the processes of freeze drying, cleaning and grinding. Aims at separating and purifying.
The reaction progress, expressed as the salt formation substitution rate, is 10% -99%.
Salt formation substitution rate= (number of glucosamine groups reacted with tricarboxylic acid substance or tricarboxylic acid derivative to form salt/total number of glucosamine groups) ×100%.
Further preferably, the salt-forming substitution rate is 90% -99%. The high salt formation substitution rate means that more tricarboxylic acid molecules are connected to chitosan molecules, so that more efficient antibacterial effect can be stimulated.
In a third aspect the invention provides the use of a chitosan-tricarboxylic acid derivative.
The chitosan-tricarboxylic acid derivative is applied to the preparation of cosmetics, foods or medicines.
Compared with the prior art, the invention has the following beneficial effects:
the chitosan-tricarboxylic acid derivative provided by the invention has the effects of damaging cell membranes of chitosan and disturbing intracellular metabolism of tricarboxylic acid. Therefore, under the common acid-base condition of food or cosmetics, the chitosan provided by the invention destroys the cell membrane structure of harmful microorganisms through chitosan, so that tricarboxylic acid or tricarboxylic acid derivative part can enter microorganism cells, disorder the metabolic activity of the cells and inhibit the activity of microorganisms, thereby the chitosan-tricarboxylic acid derivative provided by the invention has excellent antibacterial property, and the chitosan-tricarboxylic acid derivative provided by the invention has good stability to temperature.
Drawings
FIG. 1 is a diagram of natural chitosan 1 H-NMR (nuclear magnetic resonance hydrogen spectrum) spectrum;
FIG. 2 is a schematic illustration of 5-oxolane 2, 3-dicarboxylic acid 1 H-NMR spectrum;
FIG. 3 is a schematic diagram of a chitosan-5-oxolane 2, 3-dicarboxylic acid derivative obtained in example 2 of the present invention 1 H-NMR chart.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: preparation of chitosan-tricarboxylic acid derivatives
A chitosan-tricarboxylic acid derivative has a structural formula shown in formula I:
wherein R is 1 、R 2 、R 3 、R 4 And each independently represents-H (chitosan has a molecular weight of 280000Da, so that the value of x is also determined).
The preparation method of the chitosan-tricarboxylic acid derivative comprises the following steps:
10g of propane-1, 2, 3-tricarboxylic acid was dissolved in 1L of water, 10g of natural chitosan (natural chitosan having a molecular weight of 280000Da and a degree of deacetylation of 85%) was further added to form a mixture, then the pH of the mixture was adjusted to 3.2 with HCl, and reacted under magnetic stirring at 150 rpm for 1 hour under heating at 70℃followed by freeze-drying, and the product was ground into powder, washed with ethanol 5 times (the purpose of ethanol washing was to remove excess unreacted propane-1, 2, 3-tricarboxylic acid because propane-1, 2, 3-tricarboxylic acid was soluble in ethanol, and the chitosan-propane-1, 2, 3-tricarboxylic acid derivative was insoluble in ethanol), and then freeze-dried, and ground again into powder, to obtain a chitosan-propane-1, 2, 3-tricarboxylic acid derivative, i.e., a chitosan-tricarboxylic acid derivative.
Example 2
A chitosan-tricarboxylic acid derivative has a structural formula shown in formula II:
wherein R is 1 、R 2 、R 3 、R 4 And each independently represents-H (chitosan has a molecular weight of 280000Da, so that the value of x is also determined).
The preparation method of the chitosan-tricarboxylic acid derivative comprises the following steps:
10g of 5-oxolane 2, 3-dicarboxylic acid was dissolved in 1L of water, 10g of natural chitosan (natural chitosan molecular weight: 280000Da, degree of deacetylation: 85%) was added to form a mixture, the pH of the mixture was then adjusted to 3.2 with HCl, and reacted under magnetic stirring at 150 rpm and heating at 70℃for 1 hour, followed by freeze-drying, and the product was ground into a powder, washed with ethanol 5 times (the purpose of ethanol washing was to remove the excess unreacted propane-1, 2, 3-tricarboxylic acid because propane-1, 2, 3-tricarboxylic acid was readily soluble in ethanol, the chitosan-propane-1, 2, 3-tricarboxylic acid derivative was insoluble in ethanol), and then freeze-dried, and ground again into a powder, to obtain the chitosan-5-oxolane 2, 3-dicarboxylic acid derivative, i.e., the chitosan-tricarboxylic acid derivative.
FIG. 1 is a diagram of natural chitosan 1 H-NMR (hydrogen nuclear magnetic resonance) spectrum (the abscissa "f" of FIG. 1 represents chemical shift); FIG. 2 is a schematic illustration of 5-oxolane 2, 3-dicarboxylic acid 1 H-NMR (nuclear magnetic resonance hydrogen spectrum) spectrum; FIG. 3 is a schematic diagram of a chitosan-5-oxolane 2, 3-dicarboxylic acid derivative obtained in example 2 of the present invention 1 H-NMR (the abscissa "f1" in FIGS. 2 and 3 indicates chemical shift, and Arabic numerals in FIGS. 2 and 3 indicate the numbers for protons directly connected to C). The peak signals of fig. 3 represent protons in different electron environments and thus can be used to identify specific chemical groups, as well as changes in electron density.
In fig. 2 and 3, both spectra have the same characteristic peak of the solvent at 4.7ppm, and different protons are also noted in the figures.
In FIG. 3, the area ratio of proton characteristic peak number 5 (from adjacent carbon of chitosan amino group) to proton characteristic peak number 4 (from 5-oxolane 2, 3-dicarboxylic acid) is 1:0.94, indicating 94% chitosan deacetylation amino group, salt formation with 5-oxolane 2, 3-dicarboxylic acid.
Meanwhile, it can be seen that in FIG. 3, protons No. 3 and No. 4 of the carboxyl group on 5-oxolane 2, 3-dicarboxylic acid, electron cloud shift occurs, proton No. 3 shifts from the initial 3.79ppm in FIG. 2 to 3.67ppm in FIG. 3; proton No. 4, from the initial 5.22ppm in fig. 2, moved to 5.08ppm in fig. 3. The proton electron clouds of numbers 1 and 2 were not shifted. The proton cloud environments of No. 3 and No. 4 in FIG. 3 are changed, and the salt formation reaction of the carboxyl group on the 5-oxolane 2, 3-dicarboxylic acid and the amino group on the chitosan is proved.
Comparative example 1
Comparative example 1 differs from example 1 only in that the propane-1, 2, 3-tricarboxylic acid in example 1 was replaced with acetic acid in an amount 3 times by mole, and the remaining production method was the same as in example 1. Comparative example 1 chitosan-acetic acid was prepared.
Comparative example 2
Comparative example 2 differs from example 1 only in that the propane-1, 2, 3-tricarboxylic acid in example 1 was replaced with 3-fold molar amount of lactic acid, and the remaining production method was the same as in example 1. Comparative example 2 chitosan-lactic acid was prepared.
Product effect test
1. Antibacterial effect test
The chitosan-tricarboxylic acid derivatives prepared in examples 1-2, the chitosan-acetic acid prepared in comparative example 1, the chitosan-lactic acid prepared in comparative example 2, the chitosan, propane-1, 2, 3-tricarboxylic acid, 5-oxolane 2, 3-dicarboxylic acid were taken as samples to be tested, and the samples to be tested were tested against bacteria (including gram-positive bacteria including staphylococcus aureus, bacillus cereus, lactobacillus plantarum, gram-negative bacteria including escherichia coli, pseudomonas aeruginosa), yeast (candida albicans), and mold (aspergillus niger) with a Minimum Inhibitory Concentration (MIC) (concentration gradient of the samples to be tested was 2000ppm, 1000ppm, 500ppm, 250ppm, 125 ppm).
The cultured system was a commercially available nutrient broth (model 022010, available from Guangdong CycloKai microorganism technology Co., ltd.) and had a pH of 6, the bacteria were cultured at 36℃for 7 days, and the yeasts and molds were cultured at 28℃for 7 days, and the results are shown in Table 1.
Table 1: antibacterial Effect (data in Table 1 indicate MIC in ppm)
Remarks: in Table 1 "/" indicates no bacteriostatic effect.
As can be seen from Table 1, the chitosan-tricarboxylic acid derivatives prepared in examples 1-2 of the present invention have significantly better inhibitory effects on yeasts and molds than comparative examples 1-2. The chitosan-tricarboxylic acid derivatives prepared in examples 1-2 of the present invention have significantly better inhibitory effect on gram-negative bacteria than comparative example 2. Taken together, the antibacterial effect of the chitosan-tricarboxylic acid derivatives prepared in examples 1-2 of the present invention is significantly better than that of comparative examples 1-2.
2. High temperature stability test
2.1 high temperature stability test of the chitosan-tricarboxylic acid derivative prepared in example 1
The chitosan-tricarboxylic acid derivative obtained in example 1 was tested for antibacterial effect after being treated under different temperature conditions (the different temperature conditions are specifically divided into treatment at normal temperature of 25 ℃ for 1 hour, high-pressure wet heat treatment for 15 minutes (101 KPa,121 ℃) and treatment at normal pressure of oil bath of 121 ℃ for 1 hour), and further the high-temperature stability of the chitosan-tricarboxylic acid derivative obtained in example was found, and the results are shown in Table 2.
The culture system used in the antibacterial effect test was a commercially available nutrient broth (model 022010, supplied by Guangdong CycloKai Biotechnology Co., ltd.) and the pH of the culture system was 6, the culture conditions of the bacteria were that of the bacteria at 36℃for 7 days, and the culture conditions of the yeasts and the mold were that of the bacteria at 28℃for 7 days.
Table 2: antibacterial Effect (data in Table 2 indicate MIC in ppm)
As can be seen from table 2, even though the chitosan-tricarboxylic acid derivative prepared in example 1 was subjected to high temperature treatment under different conditions, the antibacterial property of the chitosan-tricarboxylic acid derivative prepared in example 1 after the high temperature treatment was not impaired, indicating that the chitosan-tricarboxylic acid derivative prepared in example 1 had high temperature stability.
2.2 high temperature stability test of the chitosan-tricarboxylic acid derivative prepared in example 2
The chitosan-tricarboxylic acid derivative prepared in example 2 was tested for high temperature stability according to the procedure of "high temperature stability test of chitosan-tricarboxylic acid derivative prepared in example 1", and the results are shown in Table 3.
Table 3: antibacterial Effect (data in Table 3 indicate MIC in ppm)
As can be seen from table 3, even though the chitosan-tricarboxylic acid derivative prepared in example 2 was subjected to high temperature treatment under different conditions, the antibacterial property of the chitosan-tricarboxylic acid derivative prepared in example 2 after the high temperature treatment was not impaired, indicating that the chitosan-tricarboxylic acid derivative prepared in example 2 had high temperature stability.
3. Solubility test
The chitosan-tricarboxylic acid derivatives prepared in examples 1-2, as well as chitosan were used as a control, and the solubility in water at a temperature of 20℃was tested, and the results are shown in Table 4.
Table 4: solubility test results
| Solubility (g/100 g water) | Solubility of | |
| Chitosan | ＜0.01 | Insoluble/poorly soluble |
| Example 1 | 10.5 | Is easily dissolved |
| Example 2 | 11 | Is easily dissolved |
As can be seen from Table 4, the chitosan-tricarboxylic acid derivatives prepared in examples 1-2 of the present invention had better water solubility than chitosan, which had very important effects on the application and effect of the chitosan-tricarboxylic acid derivatives.
4. Food preservative application
The chitosan-tricarboxylic acid derivative, chitosan, propane-1, 2, 3-tricarboxylic acid, 5-oxolane 2, 3-dicarboxylic acid and potassium sorbate prepared in examples 1-2 were used as samples to be tested, and the content of the samples to be tested in the spiced beef food was tested in the non-vacuum refrigerated shelf life test of the spiced beef pieces and is shown in Table 5.
Table 5: experimental group conditions
The procedure for the non-vacuum refrigerated shelf life test of the marinated beef pieces is as follows:
(1) Thawing frozen beef, cutting into blocks, wherein each block is about 350g;
(2) Preparing 2% saline solution (the sample to be tested is added into saline solution, the potassium sorbate group records the original pH value of the saline solution, citric acid is added to adjust the pH value to 5.0, then potassium sorbate is added and uniformly stirred), heating in a pot, adding 2 pieces of beef, stewing with low fire for about 1h after boiling with high fire, and the beef is soft but not scattered when the beef is in a specific condition;
(3) Cutting cooked beef into small pieces of about 20g, filling each 2 small pieces into a bag, directly heat-sealing, and sealing each group into 14 bags;
(4) Refrigerated placement, D0 (D0 represents day 0) test colony count, taking 2 replicates per test, and then monitoring colony count daily;
(5) The test was repeated for two rounds and the final results were calculated and analyzed by taking the average of the data from the two independent tests and the results are shown in table 6 (D1 represents day 1 and D7 represents day 7).
Table 6: antibacterial results (number units in Table 6 are log cfu/mL)
As can be seen from Table 6, the chitosan-tricarboxylic acid derivatives prepared in examples 1-2 have good antiseptic and antibacterial effects on spiced beef.
5. Cosmetic antiseptic challenge experiment
The chitosan-tricarboxylic acid derivative, chitosan, propane-1, 2, 3-tricarboxylic acid and 5-oxolane 2, 3-dicarboxylic acid prepared in examples 1-2 are taken as samples to be tested, the samples to be tested are respectively added into an essence according to the content standard of 0.2% by mass, and the components of the essence are shown in table 7. A blank group is additionally arranged, namely the blank group replaces the sample to be detected by equal amount of water.
Table 7: essence component
| Component (A) | Mass fraction (%) |
| Water and its preparation method | Added to 100 |
| Glycerol | 3 |
| Trehalose | 1 |
| Carnosine (carnosine) | 0.5 |
| Sodium hyaluronate | 0.2 |
| Nicotinamide | 0.5 |
| Xanthan gum | 0.15 |
| Sample to be measured | 0.2 |
The results of counting the log total number of colonies in the serum for 28 days are shown in table 8 (D0 represents day 0, D28 represents day 28).
Table 8: log cfu/mL of total colony count log value for 28 days
As can be seen from Table 8, the chitosan-tricarboxylic acid derivatives prepared in examples 1-2 have good antiseptic and antibacterial effects.
In addition, the chitosan-tricarboxylic acid derivatives prepared by the preparation method of reference example 1 or example 2 also have similar antibacterial effects by changing technical characteristics such as 1-hydroxypropane-1, 2, 3-tricarboxylic acid, 2-hydroxypropane-1, 2, 3-tricarboxylic acid, 1, 2-dihydroxypropane-1, 2, 3-tricarboxylic acid, 1,2, 3-trihydroxypropane-1, 2, 3-tricarboxylic acid, 2-hydroxy-5-oxolane 2, 3-dicarboxylic acid, 3-hydroxy-5-oxolane 2, 3-dicarboxylic acid, within the technical proposal claimed in the present invention.
Claims (6)
1. A chitosan-tricarboxylic acid derivative, characterized in that its structure comprises a chitosan or chitosan derivative structure, and a tricarboxylic acid substance or tricarboxylic acid derivative structure, wherein an ionic bond is formed between an amino group of the chitosan or chitosan derivative structure and a carboxyl group of the tricarboxylic acid substance or tricarboxylic acid derivative structure;
the tricarboxylic acid substance or tricarboxylic acid derivative has a structure of 5-oxolane 2, 3-dicarboxylic acid.
2. The method for producing a chitosan-tricarboxylic acid derivative as defined in claim 1, comprising the steps of:
mixing chitosan or chitosan derivative, tricarboxylic acid substance or tricarboxylic acid derivative for reaction to obtain the chitosan-tricarboxylic acid derivative;
the temperature of the reaction is 65-75 ℃;
the pH value of the mixture formed by mixing the chitosan or the chitosan derivative, the tricarboxylic acid substance or the tricarboxylic acid derivative is 2.8-3.7.
3. The method according to claim 2, wherein the chitosan derivative is at least one selected from carboxymethyl chitosan, carboxybutyl chitosan, hydroxyethyl chitosan and hydroxypropyl chitosan.
4. The method of claim 2, wherein the chitosan has a molecular weight of 1-1000kDa.
5. The method of claim 2, wherein the chitosan has a degree of deacetylation of 60% -99%.
6. Use of the chitosan-tricarboxylic acid derivative of claim 1 in the preparation of cosmetics, foods, or medicines.
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| CN109667186A (en) * | 2018-12-24 | 2019-04-23 | 山东太阳生活用纸有限公司 | A kind of tissue and preparation method thereof |
| CN113336870A (en) * | 2021-05-21 | 2021-09-03 | 珠海市自然之旅生物技术有限公司 | Tropolone-chitosan derivative and preparation method and application thereof |
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| CN109667186A (en) * | 2018-12-24 | 2019-04-23 | 山东太阳生活用纸有限公司 | A kind of tissue and preparation method thereof |
| CN113336870A (en) * | 2021-05-21 | 2021-09-03 | 珠海市自然之旅生物技术有限公司 | Tropolone-chitosan derivative and preparation method and application thereof |
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