CN103965372B - The preparation method of a kind of chitosan-gallic acid graft copolymer - Google Patents
The preparation method of a kind of chitosan-gallic acid graft copolymer Download PDFInfo
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- CN103965372B CN103965372B CN201410152551.XA CN201410152551A CN103965372B CN 103965372 B CN103965372 B CN 103965372B CN 201410152551 A CN201410152551 A CN 201410152551A CN 103965372 B CN103965372 B CN 103965372B
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- chitosan
- gallic acid
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- acid graft
- dimethylamino
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Abstract
The present invention discloses each method of system of a kind of chitosan-gallic acid graft copolymer.Chitosan I-hydroxybenzotriazole auxiliary under be dissolved in the water, utilize 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide to be grafted on chitosan by gallic acid.Utilize the inventive method efficiently can prepare chitosan-gallic acid multipolymer, percentage of grafting can reach more than 200mg gallic acid/g multipolymer.
Description
Technical field
The invention belongs to biotechnology, Food Science and Engineering field, be specifically related to the preparation method of a kind of chitosan-gallic acid graft copolymer.
Background technology
Grafting is a kind of technique means be connected to by small molecules by covalent linkage on macromole.The advantage of the comprehensive small molecule monomer of this synthesis strategy energy and superpolymer macromole two aspect, obtains type material, is applied to specific area.Graft copolymer can be prepared by means such as chemistry, radiation, photochemistry, plasma radiation, enzymatic reactions.
Chitosan is a kind of cationic polysaccharide of Nantural non-toxic, obtains by chitin being carried out de-acetyl process.The glucosamine that it is connected by β-Isosorbide-5-Nitrae key and N-Acetyl-D-glucosamine form.In recent years, chitosan is widely used in chemical industry, food and biomedicine field.Chitosan molecule chain has very high regularity, and hydrogen bond action strong with intermolecular existence in molecule, make chitosan have larger degree of crystallinity.This structure makes chitosan be insoluble to general organic solvent and water.Chitosan has three kinds of active groups, the amino on No. two position carbon, the hydroxyl on No. three and No. six position carbon, and this is that the modification of chitosan provides possibility.
Gallic acid (Gallic Acid) is that one is present in the beverages such as plant and red wine such as tea, grape, small berries in a large number.It can affect many cell-signaling pathways, has anti-oxidant, anti-inflammatory, anti-mutation and antitumor isoreactivity, therefore, is widely used in food, medicine and makeup.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of chitosan-gallic acid graft copolymer.
For achieving the above object, technical scheme of the present invention is: the preparation method of chitosan-gallic acid graft copolymer, is characterized in that comprising the following steps:
(1) chitosan of deacetylation >=85% and I-hydroxybenzotriazole in the mol ratio of chitosan repeating unit and I-hydroxybenzotriazole be the ratio mixed dissolution of 1: 1 in pure water, stir hydrotropy;
(2) gallic acid is added in the solution obtained to step (1), after abundant dissolving, the ethanolic soln of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide is dropwise added, temperature of reaction 10-30 DEG C, reaction times 12-24 hour under stirring;
(3) hydrochloric acid dripping 0.1mol/L in the reaction product obtained to step (2) is clarified to system;
(4) be put into by the solution obtained in step (3) in dialysis tubing and dialyse 48 hours, period changes water 8 times;
(5) by the solution for vacuum lyophilize in the dialysis tubing that obtains in step (4), chitosan-gallic acid graft copolymer is obtained.
The Structural Identification of the macromolecule product obtained the results are shown in Figure of description.Product of the present invention has the following advantages: 1. percentage of grafting is high, and by the ratio of adjustment gallic acid with the relative chitosan of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide, percentage of grafting can reach more than 200mg gallic acid/g multipolymer; 2. the dissolving of chitosan is without the need to acetic acid hydrotropy.
Accompanying drawing explanation
Fig. 1 is the ultra-violet absorption spectrum of chitosan, gallic acid and chitosan-gallic acid graft copolymer.
Fig. 2 is nucleus magnetic resonance (1HNMR) collection of illustrative plates of gallic acid, chitosan, chitosan-gallic acid graft copolymer.
Embodiment
Term used in the present invention, except as otherwise noted, generally has the implication that those of ordinary skill in the art understand usually.
Below in conjunction with specific embodiment and comparable data describes in further detail the present invention.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way.
In the examples below, the various process do not described in detail and method are ordinary methods as known in the art.
Embodiment 1:
(1) be 100,000 by 0.1g molecular weight, deacetylation is chitosan and 0.095g mono-hydration I-hydroxybenzotriazole mixed dissolution in 10ml pure water of 90%, and stirring is spent the night;
(2) in step (1) solution, add 0.12g mono-hydration gallic acid be stirred to and dissolve completely;
(3) in step (2) solution, dropwise add the ethanolic soln that 2ml contains 0.12g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride while stirring, 25 DEG C are reacted 20 hours;
(4) hydrochloric acid dripping 0.1mol/L in the reaction product obtained to step (2) is clarified to system;
(5) solution that step (3) obtains being put into molecular weight cut-off is dialyse 48 hours in the dialysis tubing of 3500, changes water 8 times;
(6) by the solution for vacuum lyophilize in the dialysis tubing that obtains in step (4), chitosan-gallic acid graft copolymer is obtained.
Embodiment 2:
(1) be 200,000 by 0.3g molecular weight, deacetylation is chitosan and 0.284g mono-hydration I-hydroxybenzotriazole mixed dissolution in 40ml pure water of 90%, and stirring is spent the night;
(2) in step (1) solution, add 1.045g mono-hydration gallic acid be stirred to and dissolve completely;
(3) in step (2) solution, dropwise add the ethanolic soln that 6ml contains 1.06g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride while stirring, 25 DEG C are reacted 20 hours;
(4) with the step (4) of example 1;
(5) with the step (5) of example 1, wherein dialysis tubing molecular weight cut-off is changed into 8000;
(6) with the step (6) of example 1.
Embodiment 3:
(1) be 400,000 by 0.3g molecular weight, deacetylation is chitosan and 0.284g mono-hydration I-hydroxybenzotriazole mixed dissolution in 50ml pure water of 90%, and stirring is spent the night;
(2) in step (1) solution, add 0.35g mono-hydration gallic acid be stirred to and dissolve completely;
(3) in step (2) solution, dropwise add the ethanolic soln that 5ml contains 0.35g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride while stirring, 20 DEG C are reacted 20 hours;
(4) with the step (4) of example 1;
(5) with the step (5) of example 1, wherein dialysis tubing molecular weight cut-off is changed into 14000;
(6) with the step (6) of example 1.
Be only of the present invention in sum and goodly execute example, be not used for limiting practical range of the present invention.Namely all equivalence changes done according to the content of the present patent application the scope of the claims all should be technology category of the present invention with modification.
Claims (2)
1. a preparation method for chitosan-gallic acid graft copolymer, comprises the following steps:
(1) chitosan of deacetylation >=85% and I-hydroxybenzotriazole in the mol ratio of chitosan repeating unit and I-hydroxybenzotriazole be the ratio mixed dissolution of 1: 1 in pure water, stir hydrotropy;
(2) gallic acid is added in the solution obtained to step (1), after abundant dissolving, the ethanolic soln of 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide is dropwise added, temperature of reaction 10-30 DEG C, reaction times 12-24 hour under stirring;
(3) hydrochloric acid dripping 0.1mol/L in the reaction product obtained to step (2) is clarified to system;
(4) be put into by the solution obtained in step (3) in dialysis tubing and dialyse 48 hours, period changes water 8 times;
(5) by the solution for vacuum lyophilize in the dialysis tubing that obtains in step (4), chitosan-gallic acid graft copolymer is obtained.
2. the preparation method of chitosan-gallic acid graft copolymer as claimed in claim 1, is characterized in that step (2) described 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide comprises 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride form.
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| CN105343886B (en) * | 2015-10-30 | 2018-04-20 | 成都理工大学 | A kind of biocidal property chitin medicine carrier and preparation method thereof |
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| CN106084088A (en) * | 2016-06-06 | 2016-11-09 | 武汉艾美博特医疗用品有限公司 | The Preparation method and use of chitosan gallic acid copolymer |
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| CN108676108B (en) * | 2018-06-01 | 2021-03-26 | 陕西科技大学 | Phenolic acid grafted chitosan oligosaccharide, preparation method and application of modified waterborne polyurethane of phenolic acid grafted chitosan oligosaccharide |
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| CN112961264B (en) * | 2021-03-01 | 2022-05-03 | 华中科技大学 | Chitosan-gallic acid graft copolymer and preparation method and application thereof |
| CN113812398B (en) * | 2021-10-11 | 2022-07-29 | 章毅 | Cryogenic freezing method of scaffolds for tissue repair |
| CN113957749B (en) * | 2021-11-05 | 2023-03-07 | 泗县舒怡纸品有限公司 | Easily degradable roll paper and preparation method thereof |
| CN114306462A (en) * | 2021-12-03 | 2022-04-12 | 安徽省双辉生物科技有限公司 | Production method of prepared rehmannia root refined decoction pieces |
| CN116462863B (en) * | 2023-06-15 | 2023-09-01 | 首都医科大学附属北京口腔医院 | Contains Mg 2+ Gallic acid grafted chitosan hydrogel of tannic acid microparticles, preparation method and application |
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