CN109400754A - A kind of chitosan-active acid complex salt and its preparation method and application - Google Patents
A kind of chitosan-active acid complex salt and its preparation method and application Download PDFInfo
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- CN109400754A CN109400754A CN201811307288.1A CN201811307288A CN109400754A CN 109400754 A CN109400754 A CN 109400754A CN 201811307288 A CN201811307288 A CN 201811307288A CN 109400754 A CN109400754 A CN 109400754A
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- 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
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Abstract
The present invention relates to daily chemicals field and pharmaceuticals industry, a kind of chitosan-active acid complex salt and its preparation method and application is provided.Using chitosan as raw material, by-the NH of chitosan2Group and the-H of various active acid by ionic bond in conjunction with, obtain chitosan-active acid complex salt.This method have the advantage that: the active acid selected has good antioxidant activity, after being modified on chitosan, resulting chitosan-active acid complex salt antioxidant activity is significantly stronger than chitosan raw material, and water-soluble good, can be widely applied to the fields such as medicine and functional food.
Description
Technical field
The present invention relates to marine chemical industry field of engineering technology, can be applied to medicine or functional food field, and in particular to one
Kind chitosan-active acid complex salt preparation method and application.
Background technique
Chitosan (Chitosan) one of as the most abundant natural polysaccharide, have biodegradability, biocompatibility,
A series of excellent biochemical characteristics such as nontoxic, anti-inflammatory, anti-oxidant, antibacterial, can be applied to biotechnology, pharmacy, waste water, change
The fields such as cosmetic, agricultural, Food Science, textile.However due to chitosan oxidation resistance itself and commercial antioxidant phase
It is weaker, therefore the antioxidant activity for further increasing chitosan is critical issue urgently to be resolved.It is anti-that chitosan is improved at present
The method of oxidability is mainly to carry out chemical modification by amino to chitosan and hydroxyl to introduce active antioxidant groups,
Change the physical and chemical performance of chitosan itself, and achievees the effect that enhance oxidation resistance by active principle of stacking.Cause
This, we have chosen the preferable active acid of several antioxidant activities, such as: ascorbic acid, chlorogenic acid, gallic acid make in acid
- H and chitosan in-NH2It is combined by ionic bond, is desirably to obtain the preferable chitosan-active acid of several antioxidant activities
Complex salt.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of chitosan-active acid complex salt and preparation method thereof and
Using.Using chitosan as raw material, by-NH2 the group of chitosan and the-H of various active acid by ionic bond in conjunction with, it is poly- to obtain shell
Sugar-active acid complex salt.
Specific technical solution is as follows:
A kind of chitosan-active acid complex salt, chitosan-active acid complex salt structural formula are as follows:
Wherein the average value range of n is 10-1242.
The chitosan-active acid complex salt can be applied to medicine and functional food.
A kind of preparation method of chitosan-active acid complex salt, includes the following steps:
It takes a certain amount of chitosan to be scattered in deionized water, stirs 1 hour, sequentially add corresponding proportion active acid, in
The reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-active acid complex salt.
The active acid is followed successively by citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid or citric acid, Vitamin C
Acid, niacin, malic acid and chlorogenic acid or citric acid, ascorbic acid, gallic acid, malic acid and niacin.
The chitosan, deionized water, citric acid, ascorbic acid, gallic acid, malic acid, chlorogenic acid, niacin dosage
Are as follows: the deionized water of 1g chitosan 50mL, 0.08g citric acid, 0.22g ascorbic acid, 0.21g gallic acid, 0.09g apple
Acid, 0.44g chlorogenic acid, 0.15g niacin.
This method have the advantage that:
(1)-the NH of the invention by chitosan2Group is combined with-the H of various active acid by ionic bond mode, and will
Several preferable active acids of antioxidant activity are introduced into chitosan, and it is multiple to obtain the stronger chitosan-active acid of oxidation resistance
Salt is closed, and chitosan-active acid complex salt removing superoxide anion ability is significantly stronger than chitosan itself.
(2) chitosan is combined with active acid with ionic means in the present invention, therefore preparation condition is milder, and simple
It is easy to operate.
(3) research shows that the derivative is water-soluble good, there is good antioxidant activity, can be widely applied to medicine
With the fields such as functional food.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of chitosan；
Fig. 2 is chitosan-active acid complex salt infrared spectrogram prepared by the embodiment of the present invention 1；
Fig. 3 is chitosan-active acid complex salt infrared spectrogram prepared by the embodiment of the present invention 2；
Fig. 4 is chitosan-active acid complex salt infrared spectrogram prepared by the embodiment of the present invention 3.
Specific embodiment
The following describes the present invention in detail with reference to examples, but protection scope of the present invention is not limited by embodiment.
Embodiment 1:
The preparation of chitosan-active acid (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt: 1g is taken
Chitosan is scattered in 50mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.21g
Gallic acid, 0.15g niacin and 0.44g chlorogenic acid, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-work
Property sour (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt.
Embodiment 2:
The preparation of chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt: 1g shell is taken
Glycan is scattered in 50mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.15g cigarette
Acid, 0.09g malic acid and 0.44g chlorogenic acid, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-active acid
(citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt.
Embodiment 3:
The preparation of chitosan-active acid (citric acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt: 1g is taken
Chitosan is scattered in 50mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.21g
Gallic acid, 0.09g malic acid and 0.15g niacin, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-work
Property sour (citric acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt.
Embodiment 4:
The preparation of chitosan-active acid (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt: 1g is taken
Chitosan is scattered in 60mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.21g
Gallic acid, 0.15g niacin and 0.44g chlorogenic acid, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-work
Property sour (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt.
Embodiment 5:
The preparation of chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt: 1g shell is taken
Glycan is scattered in 60mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.15g cigarette
Acid, 0.09g malic acid and 0.44g chlorogenic acid, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-active acid
(citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt.
Embodiment 6:
The preparation of chitosan-active acid (citric acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt: 1g is taken
Chitosan is scattered in 60mL deionized water, is stirred 1 hour, is sequentially added 0.08g citric acid, 0.22g ascorbic acid, 0.21g
Gallic acid, 0.09g malic acid and 0.15g niacin, the reaction was continued at 40 DEG C 24 hours, is then lyophilized to get chitosan-work
Property sour (citric acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt.
Fig. 1 be chitosan infrared spectrogram, Fig. 2 be the embodiment of the present invention 1 prepare chitosan-active acid (citric acid,
Ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt infrared spectrogram, as seen from the figure, compared with chitosan raw material,
In 1718cm-1There is the vibration absorption peak of C=O in active acid in place, in 1527cm-1And 759cm-1Place occur ascorbic acid,
Niacin, chlorogenic acid, in gallic acid aromatic rings vibration absorption peak, the above analysis data, it was demonstrated that chitosan-active acid (lemon
Acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt synthesizes.
Fig. 3 be the embodiment of the present invention 2 prepare chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid with it is green
Ortho acid) complex salt infrared spectrogram, as seen from the figure, compared with chitosan raw material, in 1725cm-1There is C in active acid in place
The vibration absorption peak of=O, in 1525cm-1And 758cm-1Place occur ascorbic acid, niacin, in chlorogenic acid aromatic rings vibration
Absorption peak, the above analysis data, it was demonstrated that chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) is multiple
Close salt synthesis.
Fig. 4 is chitosan-active acid (citric acid, ascorbic acid, gallic acid, malic acid prepared by the embodiment of the present invention 3
With niacin) infrared spectrogram of complex salt, as seen from the figure, compared with chitosan raw material, in 1724cm-1Place occurs in active acid
The vibration absorption peak of C=O, in 1534cm-1And 756cm-1Place occur ascorbic acid, niacin, in gallic acid aromatic rings vibration
Dynamic absorption peak, the above analysis data, it was demonstrated that chitosan-active acid (citric acid, ascorbic acid, gallic acid, malic acid and cigarette
Acid) complex salt synthesis.
Chitosan-active acid complex salt prepared by embodiment 1,2,3 is purged superoxide anion oxidation resistance
Measurement.It is compound that chitosan, chitosan-active acid (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) are measured respectively
Salt, chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt and chitosan-active acid (lemon
Lemon acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt removing superoxide anion ability.
By chitosan-active acid in experiment chitosan, embodiment 1 (citric acid, ascorbic acid, gallic acid, niacin with
Chlorogenic acid) complex salt, chitosan-active acid (citric acid, ascorbic acid, niacin, malic acid and chlorogenic acid) is compound in embodiment 2
Chitosan-active acid (citric acid, ascorbic acid, gallic acid, malic acid and niacin) complex salt vacuum is cold in salt and embodiment 3
Be lyophilized dry to after constant weight, be respectively 0.2 with trishydroxymethylaminomethane-HCl buffer preparation concentration, 0.4,0.8,1.6,
The solution of 3.2mg/mL.It is slow to sequentially add 1.5mL trishydroxymethylaminomethane-HCl for the sample solution for taking 1.5mL various concentration
Rush solution, 0.5mL Reducing Coenzyme I (468 μM), 0.5mL nitro blue tetrazolium (300 μM) and 0.5mL phenazine methosulfate (60
μM), after mixing in test tube, the ultimate density of sample is 0.1,0.2,0.4,0.8,1.6mg/mL, 5min is stood at room temperature,
Absorbance A is measured at 560nm, control group 0.5mL trishydroxymethylaminomethane-HCl buffer solution replaces Reducing Coenzyme I, empty
White group of 1.5mL trishydroxymethylaminomethane-HCl buffer solution replaces sample solution, and sample is surveyed three times, is averaged, and calculates
Superoxide anion ability is removed, superoxide anion ability (%)=[1- (A is removedSample-AControl)/ABlank]×100.Chitosan, shell are poly-
Sugar-active acid (citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid) complex salt, chitosan-active acid (citric acid,
Ascorbic acid, niacin, malic acid and chlorogenic acid) complex salt and chitosan-active acid (citric acid, ascorbic acid, gallic acid,
Malic acid and niacin) complex salt removing superoxide anion capability result it is as shown in table 1.
1 chitosan of table, chitosan-active acid complex salt removing superoxide anion ability (%)
The experimental results showed that chitosan-active acid complex salt synthesized by the present invention and chitosan remove superoxide anion
Ability is as shown in table 1, since selected active acid has stronger oxidation resistance, passes through ionic bond combination,
Several active acids are introduced into chitosan, have obtained the stronger chitosan of oxidation resistance-active acid complex salt, and shell is poly-
Sugar-active acid complex salt removing superoxide anion ability is significantly stronger than chitosan itself.
Claims (5)
1. a kind of chitosan-active acid complex salt, it is characterised in that: chitosan-active acid complex salt structural formula are as follows:
Wherein the average value range of n is 10-1242.
2. chitosan as described in claim 1-active acid complex salt, it is characterised in that: the chitosan-active acid complex salt
It can be applied to medicine and functional food.
3. chitosan as described in claim 1-active acid complex salt preparation method, which comprises the steps of:
It takes a certain amount of chitosan to be scattered in deionized water, stirs 1 hour, corresponding proportion active acid is sequentially added, in 40 DEG C
Lower the reaction was continued 24 hours, is then lyophilized to get chitosan-active acid complex salt.
4. chitosan as claimed in claim 3-active acid complex salt preparation method, it is characterised in that: the active acid according to
Secondary is citric acid, ascorbic acid, gallic acid, niacin and chlorogenic acid or citric acid, ascorbic acid, niacin, malic acid and green original
Acid or citric acid, ascorbic acid, gallic acid, malic acid and niacin.
5. chitosan as claimed in claim 3-active acid complex salt preparation method, it is characterised in that: the chitosan is gone
Ionized water, citric acid, ascorbic acid, gallic acid, malic acid, chlorogenic acid, niacin dosage are as follows: 1g chitosan is with 50~60mL's
Deionized water, 0.08g citric acid, 0.22g ascorbic acid, 0.21g gallic acid, 0.09g malic acid, 0.44g chlorogenic acid,
0.15g niacin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256607A (en) * | 2019-08-14 | 2019-09-20 | 中国科学院烟台海岸带研究所 | A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105191940A (en) * | 2015-08-25 | 2015-12-30 | 江苏科技大学 | Application of chitosan derivative in bacterial wilt prevention and treatment |
| CN106893004A (en) * | 2017-03-17 | 2017-06-27 | 广西大学 | A kind of preparation method of shitosan phenolic acid conjugates |
| CN107586800A (en) * | 2017-10-09 | 2018-01-16 | 泰兴市东圣生物科技有限公司 | A kind of chitosan derivatives preparation method and its application in food fresh keeping |
| CN108623708A (en) * | 2018-06-01 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids |
| CN108727516A (en) * | 2018-09-19 | 2018-11-02 | 中国科学院烟台海岸带研究所 | A kind of chitosan chlorogenic acid salt and its preparation method and application |
-
2018
- 2018-11-05 CN CN201811307288.1A patent/CN109400754A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105191940A (en) * | 2015-08-25 | 2015-12-30 | 江苏科技大学 | Application of chitosan derivative in bacterial wilt prevention and treatment |
| CN106893004A (en) * | 2017-03-17 | 2017-06-27 | 广西大学 | A kind of preparation method of shitosan phenolic acid conjugates |
| CN107586800A (en) * | 2017-10-09 | 2018-01-16 | 泰兴市东圣生物科技有限公司 | A kind of chitosan derivatives preparation method and its application in food fresh keeping |
| CN108623708A (en) * | 2018-06-01 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids |
| CN108727516A (en) * | 2018-09-19 | 2018-11-02 | 中国科学院烟台海岸带研究所 | A kind of chitosan chlorogenic acid salt and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 德）沃尔特 著: "《德国足球队队医的完全健康手册》", 30 April 2010, 安徽教育出版社 * |
| 李金凤 等: "多糖-酚酸缀合物的合成及特性研究进展", 《食品与发酵工业》 * |
| 海春旭: "《自由基医学》", 31 December 2006, 第四军医大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256607A (en) * | 2019-08-14 | 2019-09-20 | 中国科学院烟台海岸带研究所 | A kind of anionic 2- hydroxypropyltrimethylammonium chloride chitosan and preparation method and application |
| CN110256607B (en) * | 2019-08-14 | 2022-03-08 | 中国科学院烟台海岸带研究所 | Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof |
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