CN102399305A - Chitosan fumaroyl derivative and preparation method thereof - Google Patents
Chitosan fumaroyl derivative and preparation method thereof Download PDFInfo
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- CN102399305A CN102399305A CN2011104283576A CN201110428357A CN102399305A CN 102399305 A CN102399305 A CN 102399305A CN 2011104283576 A CN2011104283576 A CN 2011104283576A CN 201110428357 A CN201110428357 A CN 201110428357A CN 102399305 A CN102399305 A CN 102399305A
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Abstract
The invention relates to a chitosan fumaroyl derivative and a preparation method thereof and belongs to the technical field of food preservatives. A water-soluble chitosan fumaroyl derivative is prepared by performing acylation reaction on water-insoluble chitosan serving as a raw material and fumaric acid by a chemical modification technology. The chitosan fumaroyl derivative prepared by the method has high water solubility and strong bacteriostatic activity, can serve as a preservative widely applied in the fields of medicines, food and the like, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of novel chitosan fumaryl verivate and preparation method thereof, belonged to the food preservatives technical field.The present invention is a raw material with non-water-soluble chitosan, utilizes chemical modification technique to prepare chitosan fumaryl verivate.The chitosan derivatives of this invention preparation is water-soluble better, and has stronger bacteriostatic activity.This invention can be applicable to the production of the sanitas in food, the pharmaceutical industries, has broad application prospects.
Background technology
Chitosan is nontoxic, no antigen, biodegradable, and has a lot of special physiological properties.All have a wide range of applications in a plurality of fields such as medicine, chemical industry, material, biotechnology, food and nutrition, agricultural and environment protection.Particularly chitosan all has restraining effect to a series of mikrobes that comprise bacterium, fungi, is regarded as the ideal material of development of new antiseptics for natural food.Chitosan is a biomacromolecule, through amino a large amount of in the molecule and the hydrogen bond action between the hydroxyl, forms the structure of highly crystalline; Make it water insoluble; Also be insoluble to organic solvent, only be dissolved in rare organic acid soln, seriously limited its application aspect anti-corrosive antibacterial.
Through the method for chemical modification, in chitosan molecule, introduce hydrophilic radicals such as carboxyl, can destroy its intermolecular hydrogen bond action, reduce its iso-electric point, improve water-soluble.The bioactive performance of chitosan depends on the protonated of C2 position free amine group, so the introducing of water soluble group, often masks the highest C2 position free amine group of reactive behavior, causes the reduction of chitosan bacteriostatic activity.Fumaric acid also is fumaroyl, contains two carboxyls and special transconfiguration in the molecule, is acidic flavoring agent and sanitas commonly used in a kind of food.The hydroxyl generation acylation reaction of carboxyl and chitosan through the fumaric acid molecule is grafted to the fumaric acid molecule in the chitosan molecule.The existence of fumaric acid another one free carboxy can improve the water-soluble of verivate, and newly-generated fumaryl group is the unsaturated carbonyl structure with very strong bacteriostatic activity, can give verivate stronger bacteriostatic activity.
Summary of the invention
The objective of the invention is to prepare a kind of water-solubility chitosan derivative with strong bacteriostatic activity.
Technical scheme of the present invention: chitosan is a raw material, utilizes chemical modification technique to prepare water-soluble chitosan fumaryl verivate.The synthetic route of chitosan fumaryl verivate is:
Concrete technology is: a kind of preparation method of chitosan fumaryl verivate is characterized in that: with deacetylation is 95%, and the chitosan of viscosity-average molecular weight 100kDa is a raw material; Taking by weighing exsiccant chitosan 1.7g is dispersed in the 100mL deionized water; Adding is the fumaric acid of 1 ︰ 4 with GS unit's mol ratio, at room temperature in system, drips the vitriol oil of 0.5mL, and mixed system is heated to 80 ℃; Stirring reaction 4h uses 10% NaHCO
3Solution is transferred the pH to 7.0 of reaction system, and reaction finishes; Remove unreacted fumaric acid with 50mL ethanol sedimentation and washing, filter, it is chitosan fumaryl verivate that vacuum-drying 12h obtains white powder.Its ir spectra: 1597cm
-1Absorbing band is the characteristic absorbance of free amine group, 1722cm
-1For reacting the characteristic absorbance of newly-generated ester bond, 2900cm
-1Wide absorption band is the characteristic absorbance of carboxylate radical;
Its biological physicochemical characteristics is following: moisture content≤5%, substitution value 0.3-0.4, the solubleness ≈ 40g/L in the aqueous solution;
Its DSC curve display: its pyrolysis temperature is 193 ℃;
Characteristic of biological activity: it is to the minimal inhibitory concentration of intestinal bacteria, streptococcus aureus, saccharomyces cerevisiae and black-koji mould: in chitosan fumaryl verivate g/L substratum, be 0.05%, 0.05%, 0.05%, 0.05% respectively.
Effective effect of the present invention
1, the raw material of the present invention's employing is water-insoluble chitosan, and products obtained therefrom chitosan fumaryl verivate has solvability preferably in water, widened the Application of Chitosan scope.
2, the present invention adopts single stage method to prepare chitosan fumaryl verivate, has avoided the technology of amido protecting and deprotection, and easy and simple to handle, cost is low.
3, the present invention has improved the restraining effect of chitosan fumaryl verivate to mikrobe improving the water miscible while of chitosan, and it is had a good application prospect in the food and medicine field as natural base preservative.
Description of drawings
The infared spectrum of Fig. 1 chitosan (a) and chitosan fumaryl verivate (b).
Fig. 2 chitosan and chitosan fumaryl verivate DSC curve.
Specific embodiments
Embodiment 1
The 85g chitosan is dispersed in the 5000mL deionized water, and adding is 1 ︰, 4 fumaric acid with GS unit's mol ratio.The vitriol oil that at room temperature in aforementioned system, adds 25mL.Mixed system is heated to 80 ℃, and stirring reaction 4h uses 10% NaHCO
3Solution is transferred the pH to 7.0 of reaction system, and reaction finishes.The ethanol sedimentation and the washed product that add 2500mL are filtered and are collected, and vacuum-drying 12h obtains the chitosan fumaryl verivate 110g of substitution value 0.3-0.4.
The chitosan fumaryl verivate of preparation is added to respectively in intestinal bacteria, streptococcus aureus, black-koji mould and the cereuisiae fermentum substratum; The chitosan fumaryl derivatives concentration that adds is 0.05%, 0.05%, 0.05%, 0.05% (w/v) respectively; Cultivate after 24 hours; Can suppress the growth of mentioned microorganism fully, explain that this verivate has very strong bacteriostatic activity.
Claims (2)
1. the preparation method of a chitosan fumaryl verivate, it is characterized in that: with deacetylation is 95%, the chitosan of viscosity-average molecular weight 100kDa is a raw material; Taking by weighing exsiccant chitosan 1.7g is dispersed in the 100mL deionized water; Adding is the fumaric acid of 1 ︰ 4 with GS unit's mol ratio, at room temperature in system, drips the vitriol oil of 0.5mL, and mixed system is heated to 80 ℃; Stirring reaction 4h uses 10% NaHCO
3Solution is transferred the pH to 7.0 of reaction system, and reaction finishes; Remove unreacted fumaric acid with 50mL ethanol sedimentation and washing, filter, it is chitosan fumaryl verivate that vacuum-drying 12h obtains white powder.
2. with the product chitosan fumaryl verivate of the said method preparation of claim 1, it is characterized in that its ir spectra: 1597cm
-1Absorbing band is the characteristic absorbance of free amine group, 1722cm
-1For reacting the characteristic absorbance of newly-generated ester bond, 2900cm
-1Wide absorption band is the characteristic absorbance of carboxylate radical;
Its biological physicochemical characteristics is following: moisture content≤5%, substitution value 0.3-0.4, the solubleness ≈ 40g/L in the aqueous solution;
Its DSC curve display: its pyrolysis temperature is 193 ℃;
Characteristic of biological activity: it is to the minimal inhibitory concentration of intestinal bacteria, streptococcus aureus, saccharomyces cerevisiae and black-koji mould: in chitosan fumaryl verivate g/L substratum, be 0.05%, 0.05%, 0.05%, 0.05% respectively.
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| CN2011104283576A CN102399305A (en) | 2011-12-20 | 2011-12-20 | Chitosan fumaroyl derivative and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936885A (en) * | 2014-04-28 | 2014-07-23 | 华南理工大学 | O-fumarate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof |
| CN103951765A (en) * | 2014-04-28 | 2014-07-30 | 华南理工大学 | O-fumarate ester-N-chitosan quaternary ammonium salt and preparation method and application thereof |
| CN105056295A (en) * | 2015-08-11 | 2015-11-18 | 安徽省康宁医疗用品有限公司 | Anti-inflammatory, anti-bacterial and absorbable medical suture and preparation method thereof |
| CN105294257A (en) * | 2015-10-30 | 2016-02-03 | 全椒县琪悦家庭农场 | Sustained-release mixed fertilizer and preparation method thereof |
| CN105347916A (en) * | 2015-10-30 | 2016-02-24 | 全椒县琪悦家庭农场 | Sterilization soil-improvement slow-release composite fertilizer and preparation method thereof |
| CN105724429A (en) * | 2016-04-15 | 2016-07-06 | 佛山市聚成生化技术研发有限公司 | Preparing method for degradable modified chitosan bactericide and prepared degradable modified chitosan bactericide |
| WO2016159750A1 (en) * | 2015-04-01 | 2016-10-06 | Jifkins S.A. De C.V. | Post-harvest coating and production process |
| CN115399179A (en) * | 2021-05-27 | 2022-11-29 | 中国科学院化学研究所 | Application of polysaccharide-based cationic polymer in prevention and treatment of soil-borne diseases of agriculture and forestry |
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| CN101012287A (en) * | 2006-12-14 | 2007-08-08 | 上海交通大学 | Water soluble chitosan derivative and preparing method thereof |
| KR100873021B1 (en) * | 2008-04-22 | 2008-12-09 | (주)정상 엔지니어링 | Water cut-off layer composition and water cut-off layer holding the heavy metal absorption and self-healing function |
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| CN101012287A (en) * | 2006-12-14 | 2007-08-08 | 上海交通大学 | Water soluble chitosan derivative and preparing method thereof |
| KR100873021B1 (en) * | 2008-04-22 | 2008-12-09 | (주)정상 엔지니어링 | Water cut-off layer composition and water cut-off layer holding the heavy metal absorption and self-healing function |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936885A (en) * | 2014-04-28 | 2014-07-23 | 华南理工大学 | O-fumarate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof |
| CN103951765A (en) * | 2014-04-28 | 2014-07-30 | 华南理工大学 | O-fumarate ester-N-chitosan quaternary ammonium salt and preparation method and application thereof |
| CN103951765B (en) * | 2014-04-28 | 2016-04-13 | 华南理工大学 | The rich horse ester-N-chitosan quaternary ammonium salt of O-and method for making thereof and application |
| CN103936885B (en) * | 2014-04-28 | 2016-06-22 | 华南理工大学 | O-richness horse ester-N-N-trimethyl chitosan TMC quaternary ammonium salt and method for making thereof and application |
| WO2016159750A1 (en) * | 2015-04-01 | 2016-10-06 | Jifkins S.A. De C.V. | Post-harvest coating and production process |
| CN105056295A (en) * | 2015-08-11 | 2015-11-18 | 安徽省康宁医疗用品有限公司 | Anti-inflammatory, anti-bacterial and absorbable medical suture and preparation method thereof |
| CN105294257A (en) * | 2015-10-30 | 2016-02-03 | 全椒县琪悦家庭农场 | Sustained-release mixed fertilizer and preparation method thereof |
| CN105347916A (en) * | 2015-10-30 | 2016-02-24 | 全椒县琪悦家庭农场 | Sterilization soil-improvement slow-release composite fertilizer and preparation method thereof |
| CN105724429A (en) * | 2016-04-15 | 2016-07-06 | 佛山市聚成生化技术研发有限公司 | Preparing method for degradable modified chitosan bactericide and prepared degradable modified chitosan bactericide |
| CN115399179A (en) * | 2021-05-27 | 2022-11-29 | 中国科学院化学研究所 | Application of polysaccharide-based cationic polymer in prevention and treatment of soil-borne diseases of agriculture and forestry |
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Inventor after: Xia Wenshui Inventor after: Feng Yongwei Inventor after: Jiang Qixing Inventor after: Liang Shuanglin Inventor after: Yu Peipei Inventor after: Xu Yanshun Inventor before: Xia Wenshui Inventor before: Feng Yongwei Inventor before: Jiang Qixing Inventor before: Yu Peipei Inventor before: Xu Yanshun |
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Effective date of registration: 20120821 Address after: Food College of Jiangnan University No. 1800 Li Lake Avenue 214122 in Jiangsu province Wuxi City Binhu District Applicant after: Jiangnan University Applicant after: Jiangsu Shuanglin Marin Biological Phamacuetic Co., Ltd. Address before: Food College of Jiangnan University No. 1800 Li Lake Avenue 214122 in Jiangsu province Wuxi City Binhu District Applicant before: Jiangnan University |
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