CN107200790A - A kind of chitosan oligosaccharide derivative and its preparation method and application - Google Patents
A kind of chitosan oligosaccharide derivative and its preparation method and application Download PDFInfo
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- CN107200790A CN107200790A CN201710581760.XA CN201710581760A CN107200790A CN 107200790 A CN107200790 A CN 107200790A CN 201710581760 A CN201710581760 A CN 201710581760A CN 107200790 A CN107200790 A CN 107200790A
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- C—CHEMISTRY; METALLURGY
- 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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/02—Heterocyclic radicals containing only nitrogen as ring hetero atoms
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- Agronomy & Crop Science (AREA)
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- Pest Control & Pesticides (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of chitosan oligosaccharide derivative and its preparation method and application.Chitosan oligosaccharide derivative is that chitosan oligosaccharide dithia ring analog derivative is shown in formula I, the present invention is using active substructure splicing principle, using nontoxic, degradable chitosan oligosaccharide as lead compound, the bio-active group of dithia ring derivatives is incorporated into natural products chitosan oligosaccharide skeleton, prepare and kill line activity and be improved, there is the new chitosan oligosaccharide derivative of induction of resistance simultaneously, simultaneously synthesizing derivative can keep chitosan oligosaccharide good water solubility, Nantural non-toxic, degradable, good biocompatibility characteristic.The consumption of chemical pesticide, reduction are reduced with this to remain, reduce pollution, and new way is opened for exploitation novel biopesticide.In formula,
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of chitosan oligosaccharide derivative and preparation method thereof and should
With.
Background technology
China is a large agricultural country, to improve grain yield, tackles population pressure, and China is long-term big in agricultural production
The use chemical pesticide of amount, thus brings the environmental problem being becoming increasingly acute, ecological problem.Meanwhile, with people's environmental consciousness
And the raising of Consciousness of food security, people's food-safety problem that also growing interest residues of pesticides are brought.China is by environment
Top-priority status when protection, food security are placed on formulation national policy, to ensure public food securities, protection is certainly
It is so ecological, the strategy of sustainable development has even more been formulated, therefore it is extremely urgent to develop the biological pesticide of efficient, low toxicity, low-residual.
China is also an ocean big country simultaneously, using abundant living marine resources, develops novel sea biological source agriculture
Medicine, is a new research field having a extensive future.Chitin from the arthropod such as shrimp, crab, insect (Crustachia,
Insecta) shell or molluscan shell and fungi, the cell membrane of lower algae.Its rich content, it is renewable, it is to contain
Amount is only second to the second largest natural biological polysaccharide of cellulose.Chitin can obtain chitosan through deacetylated, and it is special that chitosan passes through
Biological enzyme technology, chemical degradation or microwave degradation technology to can obtain the degree of polymerization be the chitosan oligosaccharide between 2-20.Chitosan oligosaccharide, has
Nontoxic, good water solubility, good biocompatibility, can natural degradation the features such as.
There are some researches show chitosan, chitosan oligosaccharide can adjust microbial populations in soil, stimulate the microorganism in soil to produce
Kill the amount and the extent of injury of nematode in line material, reduction corresponding soils.In addition, research also shows that oligosaccharides can promote plant callus
Organize the formation of, activate plant cell, promote plant growth, improve biomass.Meanwhile, chitosan oligosaccharide can promote plant polyose enzyme, mistake
The multiple beneficial enzyme activation such as hydrogen oxide enzyme, induction plant produces antitoxin or protective plant protecting agent, to resist cause of disease invasion, improves immune
Power.At present, appeared on the market using chitosan, oligosaccharides as the existing multiple products of the marine organisms source pesticide of raw material development.However, because shell is few
Sugar be natural products, itself do not kill line activity, its kill indirectly line activity with chemical pesticide compared with gap it is very big, so promote compare
It is more difficult, limit its application.
Element sulphur is the important element for constituting life, and many sulfur-containing compounds have a variety of important physiologically actives.Planting
In thing protection, many efficient Insecticides (tech) ＆ Herbicides (tech)s, bactericide, nematode killing agent are all sulfur-containing compounds.Dithiocarbamate
(salt) class compound is the widely used efficient agricultural bactericide of a class, nematode killing agent.Such as killed with dithiocarbamate
Nematode agent, can be in degraded in soil into the performance fumigation action of isothiocyanic acid ester methyl ester, by suppressing biological cell division and biology
The synthesis of macromolecular and cause biological breathing to be obstructed, can effectively kill root-knot nematode.However, there is skin poison in such nematode killing agent
Property, commercialization species poisonous to plants grown it is few and expensive, and then be badly in need of a kind of good nematode killing agent of environment.
The content of the invention
The present invention aiming above mentioned problem there is provided a kind of structure it is novel, kill the good chitosan oligosaccharide derivative of line activity and
Its preparation method and application.
In order to realize the present invention above-mentioned purpose, the present invention adopt the following technical scheme that for：
A kind of chitosan oligosaccharide derivative, chitosan oligosaccharide derivative is that chitosan oligosaccharide dithia ring analog derivative is shown in formula I,
In formula,N=2-20.
A kind of preparation method of chitosan oligosaccharide derivative, chitosan oligosaccharide is in the miscible fluid of alcohol and water, in the presence of base, normal temperature
5-6h is first reacted with carbon disulfide, then 6-12h is reacted with bromomethane or 1,2- Bromofume, reactant is shown in Formulas IThe sulphur butane Hete rocyclic derivatives of chitosan oligosaccharide two or Formulas I shown inThe sulphur pentane heterocyclic derivatives of chitosan oligosaccharide two
Thing；Wherein, on the basis of a chitosan oligosaccharide, the mol ratio of chitosan oligosaccharide, alkali, carbon disulfide and bromomethane or 1,2- Bromofume is 1:
1.5-2:1.5-2:1.5-2。
Product is washed through water-soluble, alcohol precipitation with alcohol after the reaction, then water-soluble, is freezed, and it is shown in Formulas I to produce purifyingThe sulphur butane Hete rocyclic derivatives of chitosan oligosaccharide two or Formulas I shown inThe sulphur pentane heterocyclic derivatives of chitosan oligosaccharide two
Thing.
The molecular weight of the chitosan oligosaccharide is 320-3200.
The mixed liquor volume is 25 with chitosan oligosaccharide mass ratio:1-2；Wherein, mixed solution is alcohol and water, alcohol and water
Volume ratio is 4:0.5-1.
The alcohol is methanol or ethanol.
The alcohol washes middle alcohol for methanol or ethanol.
Application of the chitosan oligosaccharide dithia ring derivatives in nematicide is prepared shown in the formula I.
Principle：The amino of chitosan oligosaccharide molecule, can occur necleophilic reaction with carbon disulfide, generate Aminodithioformate,
In the presence of small molecule list bromide or many bromides, further occur parental materials, ultimately generate two sulphur of 2 substitutions
Ring.
Advantages of the present invention：Dithiocarbamates class agricultural chemicals be agriculturally a major class desinsection, sterilize class agricultural chemicals, its
Two sulphur active groups, with higher activity, and dithia ring is exactly one of derivatization direction of dithiocarbonic acid esters；This hair
It is bright that principle is spliced using active substructure, using nontoxic, degradable chitosan oligosaccharide as lead compound, by dithia ring derivatives
Bio-active group is incorporated into natural products chitosan oligosaccharide skeleton, is prepared and is killed line activity and be improved, while having induction anti-
The new chitosan oligosaccharide derivative of property, simultaneously synthesizing derivative can keep chitosan oligosaccharide good water solubility, Nantural non-toxic, degradable, raw
The good characteristic of thing compatibility.Reduce the consumption of chemical pesticide, reduction with this to remain, reduce pollution, for exploitation new bio agriculture
Medicine opens new way.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of chitosan oligosaccharide provided in an embodiment of the present invention, and its infrared signature absorbs (cm-1)：1650,
1589,1374,1315,1024,893.
Fig. 2 provides the infrared spectrogram of chitosan oligosaccharide derivative 1 for the embodiment of the present invention, and its infrared signature absorbs (cm-1)：
1633,1556,1533,1372,1311,1205,938,594,576.
Fig. 3 provides the infrared spectrogram of chitosan oligosaccharide derivative 2 for the embodiment of the present invention, and its infrared signature absorbs (cm-1)：
1574,1506,1373,1311,1021,895,849,588,571.
Embodiment
With reference to Figure of description, the invention will be further described, and protection scope of the present invention is not only limited to
Following examples.
The preparation of the derivative 1 of embodiment 1
2g molecular weight is added in 20ml ethanol for 1500 chitosan oligosaccharide, 5ml deionized waters, stirring, slow drop is added
Plus 2ml 45%NaOH solution, completion of dropping, alkalize 1h；By 1.035ml carbon disulfide, above-mentioned reaction system is slowly dropped to
In, normal-temperature reaction 5h；1.5ml bromomethanes are added in above-mentioned reaction system, normal-temperature reaction 6h；Reaction is finished, suction filtration, filter cake
10ml deionized water dissolvings are added, 20ml absolute ethyl alcohols is added and separates out yellow solid, collect solid, 2 are washed with absolute ethyl alcohol
It is secondary, freeze, obtain 2.2g, as red-brownish coloured particles, derivative 1：The sulphur butane of chitosan oligosaccharide -2- imines -1,3- two.Structure see formula I (N=2-20)
Infrared spectrum shows：The infrared spectrum (Fig. 2) of chitosan oligosaccharide derivative 1 compared with the infrared spectrum (Fig. 1) of chitosan oligosaccharide,
Positioned at 1589cm-1NH characteristic absorption peak weaken, show that NH2 has occurred and that reaction；And 1533cm-1Place occurs for C=N spies
Levy absworption peak；1205cm-1There are S-C-S characteristic absorption peaks in place；To sum up, it was demonstrated that derivative 1 is synthesized successfully.
The preparation of the derivative 2 of embodiment 2
2g molecular weight is added in 20ml ethanol for 1500 chitosan oligosaccharide, 5ml deionized waters, stirring, slow drop is added
Plus 2ml 48%NaOH solution, completion of dropping, alkalize 1h；By 2.5ml 1,3- Bromofumes are slowly dropped to above-mentioned reactant
In system, normal-temperature reaction 6h；Reaction is finished, suction filtration, and filter cake adds 10ml deionized water dissolvings, adds the precipitation of 20ml absolute ethyl alcohols
Yellow solid, collects solid, wash with absolute ethyl alcohol 2 times, lyophilized, obtains 2.2g, and red brown solid, as chitosan oligosaccharide -2- imines -
The sulphur pentanes of 1,3- bis-.As derivative 2：The sulphur pentanes of chitosan oligosaccharide -2- imines -1,3- two.Structure see formula I (N=2-
20)
Infrared spectrum shows：The infrared spectrum (Fig. 3) of chitosan oligosaccharide derivative 1 compared with the infrared spectrum (Fig. 1) of chitosan oligosaccharide,
Positioned at 1589cm-1NH characteristic absorption peak weaken, show that amino has occurred and that reaction；And 1506cm-1Place occurs for C=N spies
Levy absworption peak；895cm-1There are C=S-C characteristic peaks in place.To sum up, it was demonstrated that derivative is 2-in-1 into success.
Kill line determination of activity
Line activity is killed to Meloidogyne incognita (Meloidogyne incognita) using dip method determination sample.Survey
Try under 3 sample concentrations i.e.：0.25mg/ml, 0.13mg/ml, 0.063mg/ml, to the inhibition of Meloidogyne incognita.
Experiment is using the ivermectin medicament of same concentrations as positive control, using distilled water as negative control.Method is with reference to agriculture
Industry ministerial standard NY/T 1833.1-2009, are comprised the following steps that：
From the pieces of an egg of picking root-knot nematode on live body host plant, it is placed on the wet filter paper of culture dish, is incubated at 20-25 DEG C
Change, obtain age consistent second instar larvae.Prepare 10mg/ml sample mother liquor, be diluted to successively 0.5mg/ml, 0.25mg/ml,
0.13mg/ml.With pipettor from low concentration to high concentration, decoction is drawn successively and 100 μ l of control are added separately in 24 orifice plates, so
The μ l of nematode suspension 100 prepared are drawn afterwards to be added in 24 orifice plates, are that decoction and nematode suspension mixed in equal amounts are uniform, plus
It is placed on 25 DEG C of incubated 24h.4 repetitions are often handled, in observing nematode death condition under anatomical lens, total nematode of investigation are recorded
Number and verge of death borer population.Dead nematode is stiff, is touched with hair pin and is unable to bending motion.
Root knot survey data, calculates the death rate of each processing, and unit is percentage (%).It is calculated as follows, calculates
As a result 2 significant digits are remained into：
In formula：
P --- the death rate
K --- verge of death borer population
N --- snoop bus borer population
Experimental result is shown in Table 1
Inhibitory activity of the chitosan oligosaccharide derivative of 1 partial Formula of table 1 to Meloidogyne incognita
From above-mentioned data and structural analysis：The derivative of the present invention kills line activity, is substantially obtained compared with chitosan oligosaccharide
Improve, and activity is higher than the commercialized line antibiotic ivermectin that kills, especially derivative 2, most highly active is higher than ivermectin
Go out 20 percentage points.Consider further that, according to measurement, the substitution value of disulfide group is 20% or so, when derivatives concentration is
During 0.25mg/ml, the equivalent concentration of disulfide group is 0.05mg/ml or so, this compare under concentration like this to kill line activity high
It is many.Therefore derivative has kills line activity well.Derivative of the present invention, disulfide group active group is small molecule, cuts and only connects
It is connected on 20% or so monose, steric hindrance is small, does not change chitosan oligosaccharide primary structure, therefore does not influence the plant of chitosan oligosaccharide chain
Adjustment effect.Therefore, derivative of the present invention, while specific kill line effect, and plant regulatory function, thus can play a dual role,
Improve effect.The derivative of the present invention, using chitosan oligosaccharide as matrix.Chitosan oligosaccharide is deacetylated by natural polysaccharide chitin, then has soda acid
Or enzyme is decomposed, preparation technology is simple, and source is easy to get, meanwhile, it is nontoxic, with good biocompatibility.After connection active group,
Substantial amounts of Glucosamine skeleton, has covered the toxicity of disulfide group, products therefrom low toxicity.Importantly, chitosan chain is not
It can be absorbed by the skin, therefore to skin low toxicity, this is the place of excessively general dithiocarbamate (salt) class agricultural chemicals by force.In addition,
Chitosan oligosaccharide can be by microorganism by the use of as carbon source, and derivative is degradable, can rapidly play and kill line effect, is difficult accumulation and residual
Toxicity is stayed, thus it is environmentally friendly.
Also, presently commercially available nematode killing agent, is not that toxicity is big, is exactly that water solubility is looked into.Just by taking antibioticses ivermectin as an example,
It is water insoluble although low toxicity.If using such compound, needing to be made into missible oil etc. needs the formulation of organic reagent, invisible
In cause the wasting of resources and environmental hazard.And the derivative of the present invention is dissolved in water, solubility is therefore actual in more than 2mg/ml
It is easy to use, additional contamination is not resulted in, residual, safe green is not easy to.
To sum up, the present invention is increase nematode killing agent species, for the consumption of reduction chemical pesticide, reduction residual, reduces pollution, is
That develops novel biopesticide opens new way.
Claims (8)
1. a kind of chitosan oligosaccharide derivative, it is characterised in that：Chitosan oligosaccharide derivative is that chitosan oligosaccharide dithia ring analog derivative is formula I
It is shown,
In formula,N=2-20.
2. the preparation method of chitosan oligosaccharide derivative according to claim 1, it is characterised in that：Chitosan oligosaccharide is in the mixed of alcohol and water
In solution, in the presence of base, normal temperature first reacts 5-6h with carbon disulfide, then reacts 6- with bromomethane or 1,2- Bromofume
12h, reactant is shown in Formulas IThe sulphur butane Hete rocyclic derivatives of chitosan oligosaccharide two or Formulas I shown inShell
The sulphur pentane Hete rocyclic derivatives of oligosaccharides two；Wherein, the mol ratio of chitosan oligosaccharide, alkali, carbon disulfide and bromomethane or 1,2- Bromofume
For 1:1.5-2:1.5-2:1.5:2.
3. the preparation method of chitosan oligosaccharide derivative according to claim 2, it is characterised in that：Product is through water after the reaction
Molten, alcohol precipitation is washed with alcohol, then water-soluble, is freezed, and it is shown in Formulas I to produce purifyingThe sulphur butane heterocycle of chitosan oligosaccharide two spread out
Shown in biological or Formulas IThe sulphur pentane Hete rocyclic derivatives of chitosan oligosaccharide two.
4. the preparation method of the chitosan oligosaccharide derivative according to Claims 2 or 3, it is characterised in that：Point of the chitosan oligosaccharide
Son amount is 320-3200.
5. the preparation method of chitosan oligosaccharide derivative according to claim 2, it is characterised in that：The mixed liquor volume with
Chitosan oligosaccharide mass ratio is 25:1-2；Wherein, mixed solution is alcohol and water, and the volume ratio of alcohol and water is 4:0.5-1.
6. the preparation method of the chitosan oligosaccharide derivative according to claim 2 or 5, it is characterised in that：The alcohol be methanol or
Ethanol.
7. the preparation method of chitosan oligosaccharide derivative according to claim 3, it is characterised in that：The alcohol washes middle alcohol for methanol
Or ethanol.
8. the application of chitosan oligosaccharide derivative according to claim 1, it is characterised in that：Chitosan oligosaccharide two shown in the formula I
Application of the thia ring derivatives in nematicide is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903338A (en) * | 2017-11-23 | 2018-04-13 | 中国科学院海洋研究所 | A kind of chitosan oligosaccharide derivative and its preparation method and application |
| CN114075254A (en) * | 2020-08-21 | 2022-02-22 | 佛山市海力盈生物科技有限公司 | Novel chitosan oligosaccharide derivative nematocide and preparation method and application thereof |
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| CN102718888A (en) * | 2011-11-24 | 2012-10-10 | 中国科学院海洋研究所 | Novel dithiocarbamate derivative of chitosan and preparation method thereof |
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2017
- 2017-07-17 CN CN201710581760.XA patent/CN107200790B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718888A (en) * | 2011-11-24 | 2012-10-10 | 中国科学院海洋研究所 | Novel dithiocarbamate derivative of chitosan and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 吴庆等: ""新型含硫杂环席夫碱型大环化合物的合成及其杀菌活性"", 《合成化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903338A (en) * | 2017-11-23 | 2018-04-13 | 中国科学院海洋研究所 | A kind of chitosan oligosaccharide derivative and its preparation method and application |
| CN114075254A (en) * | 2020-08-21 | 2022-02-22 | 佛山市海力盈生物科技有限公司 | Novel chitosan oligosaccharide derivative nematocide and preparation method and application thereof |
| CN114075254B (en) * | 2020-08-21 | 2024-01-30 | 佛山市海力盈生物科技有限公司 | Chitosan oligosaccharide derivative wire-killing agent and preparation method and application thereof |
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