CN102382206B - Chitooligosaccharide quaternary ammonium salt and preparation method thereof - Google Patents
Chitooligosaccharide quaternary ammonium salt and preparation method thereof Download PDFInfo
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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 glucosamines
βthe oligosaccharide that-Isosorbide-5-Nitrae-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 the advantages such as good water solubility, safety non-toxic, easy absorption.At present, oligochitosan is as a kind of novel plant growth hormones, have promote vegetable cell activation, inducing plant is disease-resistant and improve the effect [Zhang Fuyun such as Soil Micro-environment, Zhao little Ming, Bai Xuefang, Zhang Yukui, Du Yuguang. Advances of Plant Resistance Induced by Oligochitosan [J]. Chinese biological control. 2008,24 (2): 174-178].Oligochitosan, when inducing plant is disease-resistant,, the susceptible pre-treatment plant of plant, can produce sensitization.If the large-area serious pathogenic bacteria of plant contact, single oligochitosan that uses can not be controlled spreading of the state of an illness effectively.Therefore, for improving the biological activity of oligochitosan, there are the needs of opening up a kind of new approach, make oligochitosan there is induced resistance effect, have again pair plant pathogenic fungi to there is good direct repression, even reach the effect of quick kill pathogens.This area is improved its biological property for oligochitosan as biological pesticide exigence.
From the structure of oligochitosan, the hydroxyl in its structural unit on C6 and C2 position and amino are all the reactive groups of strong nucleophilic group, and nucleophilic addition(Adn) or nucleophilic substitution reaction easily occur.Because the nucleophilicity of C2 bit amino is greater than the nucleophilicity of C6 position hydroxyl, therefore control reaction conditions well, can obtain only having the derivatize product of amino reaction.Such as: acidylate, alkylation, quaternized and sulfonation etc.It is generally acknowledged that the amino on 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 enter cell or cause cell to form makes microbial death, micromolecular quaternary ammonium salt also can enter in cell paste by 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 reservation oligochitosan is to the inducing anti-disease activity of plant, directly antibacterial, the fungicidal activity that strengthens Chitosan-Oligosaccharides on Some Phytopathogens by chemical modification will be the novel direction that oligochitosan derivative is applied in agricultural.
In the art when preparing chitooligosaccharidequaternary quaternary ammonium salt, all adopt reaction [Kim Ji Young under long-time higher temperatures (>50 ℃) 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 easily oxidized, the amino on sugared ring structure and hydroxyl generation aldol condensation and
βthe bond rupture of-Isosorbide-5-Nitrae-nucleosides, reduces final product molecular weight, structure heterogeneity, thus affect the biotic induce activity of chitooligosaccharidequaternary quaternary ammonium salt and sterilization, fungistatic effect.
Therefore, this area needs a kind of chitooligosaccharidequaternary quaternary ammonium salt of preparing, and keeps its bioactive method simultaneously.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of chitooligosaccharidequaternary quaternary ammonium salt with good biological activity.
In one aspect of the invention, provide a kind of chitooligosaccharidequaternary quaternary ammonium salt, it is following formula:
n=2～10。
Another object of the present invention is to provide a kind of preparation method who prepares the chitooligosaccharidequaternary quaternary ammonium salt with good biological activity.
Aspect second of the present invention, a kind of method of preparing chitosan quaternary ammonium salt is provided, by following reaction, prepare chitooligosaccharidequaternary quaternary ammonium salt:
N=2～10 wherein;
The deacetylation of wherein said chitosan is 85%-100%, and molecular weight is 500-2000Da, and described reaction is carried out below at 50 ℃.The pH value of preferred reaction is controlled between 7-10.Preferred reaction is carried out at 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 lyophilize.
In another embodiment aspect this, this preparation method also comprises the concentrated step of the rear dialysis of reaction.
In another embodiment aspect this, after dialysis is concentrated, also comprise the one or more steps that are selected from solvent deposition and suction filtration.Preferred solvent is acetone-alcohol mixed solvent.
Accompanying drawing explanation
In Fig. 1, curve a is the infrared spectrum of oligochitosan raw material; Curve b is that substitution value is the infrared spectrum of 60% chitooligosaccharidequaternary quaternary ammonium salt; Curve c is that substitution value is the infrared spectrum of 30% chitooligosaccharidequaternary quaternary ammonium salt.
Fig. 2 is the 1H NMR spectrogram of chitooligosaccharidequaternary quaternary ammonium salt.
Embodiment
The present invention has overcome oligochitosan easy oxidized weakness in organic synthesis, provide a kind of simple, cost is low, the chitooligosaccharidequaternary quaternary ammonium salt synthetic method of structure homogeneous, different degree of substitution.Chitooligosaccharidequaternary quaternary ammonium salt has not only retained the characteristics such as oligochitosan activation vegetable cell, Promoting plant growth, and has strengthened the direct sterilizing ability of oligochitosan to rice Pyricularia grisea.
1. prepare chitooligosaccharidequaternary quaternary ammonium salt:
Chemical equation of the present invention is as follows:
N=2-10 wherein, the deacetylation of described chitosan is 85%-100%, and molecular weight is 500-2000Da, and described reaction is carried out below at 50 ℃.
The deacetylation of raw material oligochitosan of the present invention is 85%～100%, molecular weight is 500～2000 Da, and raw material oligochitosan (purchased from Shanghai Wei Kang biological products company limited) is refining through steps such as dissolving, suction filtration, alcohol precipitation, lyophilizes.These purification step all do not have impact to the structure of oligochitosan and chemical property.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 chitosan.Generally speaking, N-ethanoyl is sloughed and more than 55% just be can be described as chitosan.As the chitosan of industrial goods, N-deacetylation is conventionally more than 70%.Ultimate analysis shows, approximately has 12.5% amino there is no N-acetylize in natural chitin molecule, when by acid, alkali separation and Extraction, has again some N-ethanoyl to be removed, and the therefore chitin of industrial preparation has been removed the N-ethanoyl of 15%-20% in fact.As can be seen here, chitosan is the different of deacetylation from the difference of chitin.
The quaternary ammonium salt reacting with oligochitosan is 2,3-epoxypropyltrimethylchloride chloride (purchased from Sigma-Aldrich China), and reaction is carried out under weak basic condition, and pH scope can be 7-10, preferably 8.
The reaction mol ratio of oligochitosan and 2,3-epoxypropyltrimethylchloride chloride is 1:1.It is excessive 2 preferably to adopt, and 3-epoxypropyltrimethylchloride chloride, fully carries out quaternization.
Temperature of reaction of the present invention is higher than 0 ℃, to lower than 50 ℃, is preferably 25 ℃-45 ℃, and at 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 purification and separation processing to the chitooligosaccharidequaternary quaternary ammonium salt prepared product obtaining, make it meet the needs of agricultural chemicals or other preparation scale requirement.These separation and purifying for example comprise, dialysis, concentrated, and mixed solvent precipitation, suction filtration, dry etc.
2. experiment and detection:
(1) adopt specific conductivity volumetry to detect the quaternization degree of oligochitosan.The method is as Huang Jinyuan, Wu Ruofeng, Sun Ying. the Study on Preparation of Effect of Water Soluble Quaternary Ammonium Salt of Chitosan [J]. and chemical science and technology, 2008,16 (3): described in 26-31.
(2) rice blast pathogen is controlled scab experiment
Rice blast grade scale is as follows:
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 50% left and right of leaf area;
9 grades: scab is covered with, blade volume is withered.
From examination result manage everywhere disease index or scab number and blank relatively, calculate prevention effect.
3. major advantage of the present invention
By choosing suitable quaternary ammonium salt, and improve reaction conditions, realized molecular weight larger, C2 activity still retains, and has the chitooligosaccharidequaternary quaternary ammonium salt of ideal biological induced activity and bactericidal and bacteriostatic effect.
Embodiment
In the following examples, the invention will be further elaborated, but the invention is not restricted to this.
Embodiment 1
The oligochitosan aqueous solution of 30 mL10% (purchased from Shanghai Wei Kang biological products company limited) is placed in to 100 mL there-necked flasks, is 7-10 by the aqueous sodium hydroxide solution regulator solution pH value of 1 mol/L.Then get 4.0 mL 2, the 3-epoxypropyltrimethylchloride chloride aqueous solution (purchased from Sigma-Aldrich China, 0.5 g/mL), minute three droppings drip half an hour at every turn, and temperature of reaction is 25 ℃～45 ℃, and at N
2lower reaction 3 h of protection.After reaction finishes, after dialysis tubing (purchased from U.S. combinating carbide company) dialysis 24 h～72 h with molecular weight cut-off 3000, concentrated, acetone-the alcohol mixed solvent of 5～10 times of volumes (V/V=1:1) precipitation three times, suction filtration, filter cake, more than 30 ℃ of vacuum-drying 10 h, obtains khaki color solid, product by FT-IR and
1h NMR carries out structural characterization.It is 30% that specific conductivity volumetry records the substitution value of quaternary ammonium salt on amino.
Embodiment 2
By the oligochitosan of 30 mL10% (purchased from the Shanghai Wei Kang biological products company limited) aqueous solution, in 100 mL there-necked flasks, by the aqueous sodium hydroxide solution regulator solution pH value of 1 mol/L, be 7-10.Then get 8.0 mL 2, the 3-epoxypropyltrimethylchloride chloride aqueous solution (purchased from Sigma-Aldrich China, being made into 0.5 g/mL), minute three droppings drip half an hour at every turn, and temperature of reaction is 25 ℃～45 ℃, and at N
2lower reaction 3 h of protection.After reaction finishes, after dialysis tubing (purchased from U.S. combinating carbide company) dialysis 24 h～72 h with molecular weight cut-off 3000, concentrated, acetone-the alcohol mixed solvent of 5～10 times of volumes (V/V=1:1) precipitation three times, suction filtration, filter cake, more than 30 ℃ of vacuum-drying 10 h, obtains khaki color solid, product by FT-IR and
1h NMR carries out structural characterization.It is 60% that specific conductivity volumetry records the substitution value of quaternary ammonium salt on amino.
As shown in embodiment 1 and 2, use as seen reaction of the present invention, quaternised degree is only directly proportional with the quaternary ammonium salt using, and therefore, easy and simple to handle and easily control, side reaction is very little.
Embodiment 3
At 25 ℃, select the rice seedling (from biology portion of Shanghai Nanfang Pesticide Research Centre) of 3～4 leaf periods, growing way homogeneous, by inoculation rice blast pathogen (
pyricularia oryzaethe physiological strain of the strong Pathogenic Strains of 071402-2, biology portion of Shanghai Nanfang Pesticide Research Centre) front 14 d, 7 d, 3 d and 1 d distinguish the chitosan quaternary ammonium salt of resulting 500 mg/L of embodiment 1 of even sprinkling and 1000 mg/L chitooligosaccharidequaternary quaternary ammonium salt (DS=30%) aqueous solution and identical substitution value, deacetylation in advance on rice seedling, not spray medicine, are treated to contrast.The laggard row artificial inoculation of medication 24 h the last time.During inoculation, first in covering with the substratum ware of spore, add pure water, with the flat spoon of stainless steel scraping surface spore gently, through double gauze, filter, through blood counting chamber counting, make spore suspension, controlling magnaporthe grisea spore concentration is 3 * 10
5individual/mL～5 * 10
5individual/mL.Then use WM-4 oil-free gas compressor (purchased from Wuxi Jian Yi experiment equipment company limited), by pressure-resistant conduit, connect throat spray shower nozzle, on rice seedlings, even spraying inoculation, carefully moves to (temperature: 26 ℃～28 ℃ in climatic chamber immediately after inoculation; Humidity: RH100%) bring out 24 h, after 6 days blank scabs are stable, how much carry out classification investigation according to scab.The preventive effect of the inducing paddy rice blast resisting of chitooligosaccharidequaternary 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 of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. a purposes for chitooligosaccharidequaternary quaternary ammonium salt, is characterized in that, for inducing paddy rice blast resisting, described chitooligosaccharidequaternary quaternary ammonium salt is following formula:
n＝2～10；
Described chitooligosaccharidequaternary quaternary ammonium salt is prepared by following reaction:
N=2～10 wherein;
The deacetylation of wherein said oligochitosan is 85%-100%, and molecular weight is 500-2000Da, and described reaction is carried out at 25-45 ℃.
2. purposes as claimed in claim 1, is characterized in that, the pH value of described reaction is controlled between 7-10.
3. purposes as claimed in claim 1, is characterized in that, described oligochitosan process before reaction is selected from the one or more step process in dissolving, suction filtration, alcohol precipitation and lyophilize.
4. purposes as claimed in claim 1, is characterized in that, this preparation method also comprises the concentrated step of the rear dialysis of reaction.
5. purposes as claimed in claim 4, is characterized in that, after dialysis is concentrated, also comprises the one or more steps that are selected from solvent deposition and suction filtration.
6. purposes as claimed in claim 5, is characterized in that, described solvent is acetone-alcohol mixed solvent.
7. purposes as claimed in claim 6, is characterized in that, in described solvent, the volume ratio of acetone and ethanol is 1:1.
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| CN103012619B (en) * | 2013-01-11 | 2015-04-08 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
| CN110240664B (en) * | 2019-07-01 | 2020-10-30 | 北京化工大学 | Preparation method of antibacterial chitosan quaternary ammonium salt and product |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101130574A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院海洋研究所 | Chitosan quaternary ammonium salt, preparing method and application of the same |
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2010
- 2010-08-30 CN CN201010265844.0A patent/CN102382206B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101130574A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院海洋研究所 | Chitosan quaternary ammonium salt, preparing method and application of the same |
Non-Patent Citations (1)
| Title |
|---|
| 蒋挺大.壳聚糖.《壳聚糖》.化学工业出版社,2001,(第1版),9. * |
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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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