CN102382206A - Chitooligosaccharide quaternary ammonium salt and preparation method thereof - Google Patents
Chitooligosaccharide quaternary ammonium salt and preparation method thereof Download PDFInfo
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- CN102382206A CN102382206A CN2010102658440A CN201010265844A CN102382206A CN 102382206 A CN102382206 A CN 102382206A CN 2010102658440 A CN2010102658440 A CN 2010102658440A CN 201010265844 A CN201010265844 A CN 201010265844A CN 102382206 A CN102382206 A CN 102382206A
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Abstract
The invention provides chitooligosaccharide quaternary ammonium salt shown in the following formula and a preparation method thereof. In the formula, n is equal to 2-10.
Description
Technical field
The present invention relates to pesticide field, specifically, is chitosan quaternary ammonium salt and preparation method thereof.
Background technology
Oligochitosan is to be passed through by 2～10 GSs
β-1, the oligosaccharide that the 4-glycosidic link is formed by connecting is the alkaline polysaccharide of the unique a large amount of existence of occurring in nature---the degraded product of chitosan.It has advantages such as good water solubility, safety non-toxic, easy absorption.At present; Oligochitosan is as a kind of novel plant growth hormones, has the activation of the vegetable cell of promotion, inducing plant is disease-resistant and improves effect [Zhang Fuyun, Zhao Xiaoming such as soil microenvironment; Bai Xuefang; Zhang Yukui, Du Yuguang. oligochitosan inducing plant disease resistance progress [J]. the Chinese biological control. 2008,24 (2): 174-178].Oligochitosan will can produce sensitization the susceptible pre-treatment plant of plant when inducing plant is disease-resistant.If plant contacts large-area serious pathogenic bacteria, single use oligochitosan is spreading of disease controlling effectively.Therefore,, make oligochitosan promptly have the inducing anti-disease effect, have pair plant pathogenic fungi to have direct repression preferably again, even reach the effect of quick kill pathogens for the biological activity of improving oligochitosan has the needs of opening up a kind of new approach.This area is improved its biological property for oligochitosan as biological pesticide has exigence.
From the structure of oligochitosan, the hydroxyl in its structural unit on C6 and C2 position all is the reactive group of strong nucleophilic group with amino, is prone to take place nucleophilic addition(Adn) or nucleophilic substitution reaction.Because the nucleophilicity of C2 bit amino is greater than the nucleophilicity of C6 position hydroxyl, can obtain having only the amino derivatize product that reacts so control reaction conditions well.For example: acidylate, alkylation, quaternized and sulfonation etc.It is generally acknowledged that the amino on the oligochitosan C2 plays a crucial role in bacteriostatic activity; It can change the permeability of microorganism cells film; Thereby the leakage that can stop material to get into cell or cause cell to be formed makes microbial death; Micromolecular quaternary ammonium salt also can get in the cell paste through cytolemma, thereby kill pathogens [Yang Yuhong. oligochitosan is to colibacillary restraining effect [J]. Chinese Tissue Engineering Study and clinical rehabilitation. 2008,13 (16): 3101-3104].When keeping the inducing anti-disease activity of oligochitosan to plant, strengthening oligochitosan through chemical modification will be the novel direction that the oligochitosan verivate is used on agricultural to directly antibiotic, the fungicidal activity of plant pathogenic fungi.
In the art when preparation oligochitosan quaternary ammonium salt; All be employed in 50 ℃ of long-time higher temperatures (>) reaction [Kim Ji Young under the condition; Lee Jong Keun; Lee Taek Seung; Park Won Ho. Synthesis of chitooligosaccharide derivative with quaternary ammonium group and its antimicrobial activity against Streptococcus mutans [J]. International Journal of Biological Macromolecules, 2003,32 (1-2): 23-27].Under this condition, oligochitosan can produce side reaction, and its C2 amino is oxidized easily, amino on the sugared ring structure and hydroxyl generation aldol condensation with
β-1, the bond rupture of 4-nucleosides makes the final product molecular weight reduce, the structure heterogeneity, thus influence biotic induce activity and sterilization, the fungistatic effect of oligochitosan quaternary ammonium salt.
Therefore, this area needs a kind of preparation oligochitosan quaternary ammonium salt, keeps its bioactive method simultaneously.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of active oligochitosan quaternary ammonium salt of good biological that has.
In one aspect of the invention, a kind of oligochitosan quaternary ammonium salt is provided, it is a following formula:
n=2～10。
Another object of the present invention provides the preparation method that a kind of preparation has the active oligochitosan quaternary ammonium salt of good biological.
Aspect second of the present invention, a kind of method for preparing chitosan quaternary ammonium salt is provided, through following prepared in reaction oligochitosan quaternary ammonium salt:
N=2～10 wherein;
The deacetylation of wherein said chitosan is 85%-100%, and molecular weight is 500-2000Da, and said being reflected at below 50 ℃ carried out.The pH value of preferred reaction is controlled between the 7-10.Preferred reaction is carried out under 25-45 ℃.
In an embodiment aspect this, chitosan process before reaction is selected from the one or more step process in dissolving, suction filtration, alcohol precipitation and the lyophilize.
In another embodiment aspect this, this preparation method also comprises the spissated step of reaction back dialysis.
In another embodiment aspect this, after dialysis concentrates, also comprise the one or more steps that are selected from solvent deposition and suction filtration.Preferred solvent is acetone-alcohol mixed solvent.
Description of drawings
Curve a is the infrared spectrum of oligochitosan raw material among Fig. 1; Curve b is that substitution value is the infrared spectrum of 60% oligochitosan quaternary ammonium salt; Curve c is that substitution value is the infrared spectrum of 30% oligochitosan quaternary ammonium salt.
Fig. 2 is the 1H NMR spectrogram of oligochitosan quaternary ammonium salt.
Embodiment
The present invention has overcome oligochitosan and in organic synthesis, has been prone to oxidized weakness, provide a kind of simple, cost is low, the oligochitosan quaternary ammonium salt compound method of structure homogeneous, different degree of substitution.The oligochitosan quaternary ammonium salt has not only kept characteristics such as oligochitosan activation vegetable cell, promotion plant-growth, and has strengthened the direct sterilizing ability of oligochitosan to rice Pyricularia grisea.
1. prepare the oligochitosan quaternary ammonium salt:
Reaction formula of the present invention is following:
N=2-10 wherein, the deacetylation of said chitosan is 85%-100%, and molecular weight is 500-2000Da, and said being reflected at below 50 ℃ carried out.
The deacetylation of raw material oligochitosan of the present invention is 85%～100%, molecular weight is 500～2000 Da, and raw material oligochitosan (available from the big health biological products in Shanghai ltd) is refining through steps such as dissolving, suction filtration, alcohol precipitation, lyophilizes.These purification step all do not have influence to the structure and the chemical property of oligochitosan.Concrete process for purification visible [Zhang Wenqing. the research [D] of the preparation of different molecular weight chitosan and inducing plant resistance reaction. Shanghai: East China University of Science, 2003].
R is COCH
3Compound be chitin, its deacetylated product is a chitosan.Generally speaking, the N-ethanoyl is sloughed and just can be described as chitosan more than 55%.As the chitosan of industrial goods, the N-deacetylation is usually more than 70%.Ultimate analysis shows, has 12.5% amino not have the N-acetylize in the natural chitin molecule approximately, with acid, alkali separation and Extraction the time, has some N-ethanoyl to be removed again, and therefore the chitin of preparation is gone up in industry, has been removed the N-ethanoyl of 15%-20% in fact.This shows that chitosan is the different of deacetylation with the difference of chitin.
The quaternary ammonium salt that reacts with oligochitosan is 2, and 3-epoxypropyl trimethylammonium chloride ammonium (available from Sigma-Aldrich China) is reflected under the weak basic condition and carries out, and the pH scope can be 7-10, preferred 8.
Oligochitosan and 2, the reaction mol ratio of 3-epoxypropyl trimethylammonium chloride ammonium is 1:1.Preferred adopt excessively 2,3-epoxypropyl trimethylammonium chloride ammonium makes quaternization fully carry out.
Temperature of reaction of the present invention is to be higher than 0 ℃, to being lower than 50 ℃, is preferably 25 ℃-45 ℃, and under such temperature, the side reaction of chitosan is very little, and C2 amino is not easy oxidized, thereby can better react.
After reaction, can carry out further purifying and separating treatment to the oligochitosan quaternary ammonium salt prepared product that obtains, make it meet the needs of agricultural chemicals or other preparation scale requirement.These separate and purifying for example comprises, dialysis, concentrated, mixed solvent deposition, suction filtration, drying etc.
2. experiment and detection:
(1) adopt the specific conductivity volumetry to detect the quaternization degree of oligochitosan.This method such as Huang Jinyuan, Wu Ruofeng, Sun Ying. the Study on Preparation of water-soluble chitosan quaternary ammonium salt [J]. chemical science and technology, 2008,16 (3): described in the 26-31.
(2) rice blast pathogen control scab experiment
The rice blast grade scale is following:
0 grade: anosis;
1 grade: leaf spot lesion is below 5;
3 grades: leaf spot lesion is at 6～15;
5 grades: leaf spot lesion is at 16～30;
7 grades: leaf spot lesion accounts for about 50% of leaf area;
9 grades: scab is covered with, and the blade volume is withered.
From the examination result get a haircut everywhere disease index or scab number and blank relatively, calculate control effect.
3. major advantage of the present invention
Through choosing suitable quaternary ammonium salt, and improve reaction conditions, realized that molecular weight is bigger, the C2 activity still keeps, and has the oligochitosan quaternary ammonium salt of the active and bactericidal and bacteriostatic effect of desirable biotic induce.
Embodiment
To do further elaboration to the present invention among the following embodiment, but the invention is not restricted to this.
Embodiment 1
The oligochitosan aqueous solution (available from the big health biological products in Shanghai ltd) of 30 mL10% is placed 100 mL there-necked flasks, use the aqueous sodium hydroxide solution regulator solution pH value of 1 mol/L to be 7-10.Get 4.0 mL 2 then, 3-epoxypropyl trimethylammonium chloride aqueous ammonium (available from Sigma-Aldrich China, 0.5 g/mL) divides three droppings, drips half a hour at every turn, and temperature of reaction is 25 ℃～45 ℃, and at N
2Protection is reaction 3 h down.After reaction finishes; Behind dialysis tubing (available from U.S. combinating carbide company) dialysis 24 h～72 h with molecular weight cut-off 3000, concentrate the acetone-alcohol mixed solvent of 5～10 times of volumes (V/V=1:1) deposition three times; Suction filtration; Filter cake more than 30 ℃ of vacuum-drying 10 h, the khaki color solid, product through FT-IR with
1H NMR carries out structural characterization.It is 30% that the specific conductivity volumetry records the substitution value of quaternary ammonium salt on amino.
Embodiment 2
In 100 mL there-necked flasks, use the aqueous sodium hydroxide solution regulator solution pH value of 1 mol/L to be 7-10 oligochitosan (available from the big health biological products in the Shanghai ltd) aqueous solution of 30 mL10%.Get 8.0 mL 2 then, 3-epoxypropyl trimethylammonium chloride aqueous ammonium (available from Sigma-Aldrich China, being made into 0.5 g/mL) divides three droppings, drips half a hour at every turn, and temperature of reaction is 25 ℃～45 ℃, and at N
2Protection is reaction 3 h down.After reaction finishes; Behind dialysis tubing (available from U.S. combinating carbide company) dialysis 24 h～72 h with molecular weight cut-off 3000, concentrate the acetone-alcohol mixed solvent of 5～10 times of volumes (V/V=1:1) deposition three times; Suction filtration; Filter cake more than 30 ℃ of vacuum-drying 10 h, the khaki color solid, product through FT-IR with
1H NMR carries out structural characterization.It is 60% that the specific conductivity volumetry records the substitution value of quaternary ammonium salt on amino.
Shown in embodiment 1 and 2, visible use reaction of the present invention, quaternised degree only is directly proportional with the quaternary ammonium salt that uses, therefore, and easy and simple to handle and easiness in handling, side reaction is very little.
Embodiment 3
Under 25 ℃, select the rice seedling (from biology portion of Shanghai Nanfang Pesticide Research Centre) of 3～4 leaf periods, growing way homogeneous for use, by the inoculation rice blast pathogen (
Pyricularia oryzae071402-2 is the physiological strain of pathogenic fungus strain by force; Biology portion of Shanghai Nanfang Pesticide Research Centre) preceding 14 d, 7 d, 3 d and 1 d distinguish the chitosan quaternary ammonium salt of embodiment 1 resulting 500 mg/L of even sprinkling and 1000 mg/L oligochitosan quaternary ammonium salt (DS=30%) aqueous solution and identical substitution value, deacetylation in advance on rice seedling, are treated to contrast not spray medicine.The laggard pedestrian worker's inoculation of medication 24 h the last time.Elder generation adds pure water during inoculation in covering with the substratum ware of spore, scrapes gently with the flat spoon of stainless steel and gets surperficial spore, filters through double gauze, counts through the blood counting plate and processes spore suspension, and control magnaporthe grisea spore concentration is 3 * 10
5Individual/mL～5 * 10
5Individual/mL.Use WM-4 oil-free gas compressor (building appearance experiment equipment ltd) then available from the Wuxi; Connect the throat spray shower nozzle through pressure-resistant conduit; The even spraying inoculation carefully moves to (temperature: 26 ℃～28 ℃ in the climatic chamber immediately after the inoculation on the paddy rice seedling; Humidity: RH100%) bring out 24 h, after 6 days blank contrast scabs are stable, how much carry out the classification investigation according to scab.The preventive effect of the inducing paddy rice blast resisting of oligochitosan quaternary ammonium salt reaches 77.2%, and the preventive effect of the inducing paddy rice blast resisting of chitosan quaternary ammonium salt only reaches 46.9%.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition after having read above-mentioned teachings of the present invention, those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (9)
1. oligochitosan quaternary ammonium salt, it is a following formula:
n=2～10。
2. the preparation method of the described oligochitosan quaternary ammonium salt of claim 1 is characterized in that, through following prepared in reaction oligochitosan quaternary ammonium salt: n=2～10 wherein;
The deacetylation of wherein said chitosan is 85%-100%, and molecular weight is 500-2000Da, and said being reflected at below 50 ℃ carried out.
3. method as claimed in claim 2 is characterized in that said reaction pH value is controlled between the 7-10.
4. method as claimed in claim 2 is characterized in that, carries out under the said 25-45 of being reflected at ℃.
5. method as claimed in claim 2 is characterized in that, said chitosan process before reaction is selected from the one or more step process in dissolving, suction filtration, alcohol precipitation and the lyophilize.
6. method as claimed in claim 2 is characterized in that, this preparation method also comprises the spissated step of reaction back dialysis.
7. method as claimed in claim 6 is characterized in that, after dialysis concentrates, also comprises the one or more steps that are selected from solvent deposition and suction filtration.
8. method as claimed in claim 7 is characterized in that said solvent is acetone-alcohol mixed solvent.
9. method as claimed in claim 8 is characterized in that, acetone and alcoholic acid volume ratio are 1:1 in the said solvent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN110240664A (en) * | 2019-07-01 | 2019-09-17 | 北京化工大学 | A kind of preparation method and product of antibacterial chitosan quaternary ammonium salt |
| CN117903520A (en) * | 2024-03-15 | 2024-04-19 | 汕头市汇诚包装材料实业有限公司 | Antibacterial modified polyethylene film and preparation method and application thereof |
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| US4985410A (en) * | 1985-08-14 | 1991-01-15 | Etablissement Texcontor | Quaternary ammonium salts of polysaccharides, prossessing hypocholesterolemic activity |
| CN1544480A (en) * | 2003-11-25 | 2004-11-10 | 武汉大学 | Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method |
| CN1752111A (en) * | 2004-09-24 | 2006-03-29 | 樊木 | Industrial production method of chitin quaternary ammonium salt |
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Patent Citations (4)
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| US4985410A (en) * | 1985-08-14 | 1991-01-15 | Etablissement Texcontor | Quaternary ammonium salts of polysaccharides, prossessing hypocholesterolemic activity |
| CN1544480A (en) * | 2003-11-25 | 2004-11-10 | 武汉大学 | Quaternised chitosan resin and chitosan-carried boron hydrogen anion reductant and its making method |
| CN1752111A (en) * | 2004-09-24 | 2006-03-29 | 樊木 | Industrial production method of chitin quaternary ammonium salt |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN103012619B (en) * | 2013-01-11 | 2015-04-08 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN110240664A (en) * | 2019-07-01 | 2019-09-17 | 北京化工大学 | A kind of preparation method and product of antibacterial chitosan quaternary ammonium salt |
| CN117903520A (en) * | 2024-03-15 | 2024-04-19 | 汕头市汇诚包装材料实业有限公司 | Antibacterial modified polyethylene film and preparation method and application thereof |
| CN117903520B (en) * | 2024-03-15 | 2024-05-24 | 汕头市汇诚包装材料实业有限公司 | Antibacterial modified polyethylene film and preparation method and application thereof |
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Inventor after: Zhang Wenqing Inventor after: Xia Wei Inventor after: Feng Huafeng Inventor after: Zuo Pingping Inventor after: Pan Chen Inventor before: Zhang Wenqing Inventor before: Xia Wei Inventor before: Feng Huafeng Inventor before: Zuo Pingping |
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