CN107880154B - Novel chitosan derivative bactericide, and preparation method and application thereof - Google Patents
Novel chitosan derivative bactericide, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technology of ocean chemical engineering, and particularly relates to a chitosan derivative and a preparation method and application thereof. The chitosan derivative is a chitosan polyethyl amino dithiocarbamate derivative shown as a general formula I, wherein n is 20-1200, m and t is 1-5. The invention takes polyamino chitosan as a carrier, and dithiocarbamic acid ester (salt) active groups are grafted, so that the antibacterial effects of the polyamino chitosan and the dithiocarbamic acid ester (salt) active groups are exerted, the toxicity is reduced, and the green and safe biological pesticide is formed.
Description
Technical Field
The invention belongs to the technology of ocean chemical engineering, and particularly relates to a chitosan derivative and a preparation method and application thereof.
Background
China is a large population country and a large agricultural country, and in order to keep high yield and high yield of grain crops and economic crops, a large amount of chemical pesticides are used for a long time in the actual production process, so that increasingly sharp environmental problems and ecological problems are brought. Meanwhile, with the improvement of environmental awareness and food safety awareness of people, people are also paying more attention to the food safety problem caused by pesticide residues. In order to solve the problems of environmental problems, ecological problems and food safety, under the strategy of sustainable development in China, the development of efficient, low-toxicity and low-residue biopesticides is a feasible and urgent approach.
China is also a marine big country at the same time, and has abundant marine organism resource contents to be developed. The novel marine organism source pesticide developed from marine active substances has wide application prospect and is becoming a new research field. Chitin is derived from shells of arthropods (crustacean and insect) such as shrimp, crab and insect, shells of mollusks, and cell walls of fungi and lower algae. It is rich in content, renewable, and the second largest natural biological polysaccharide with the content second to cellulose. Chitosan is an alkaline polysaccharide and has the characteristics of no toxicity, good water solubility, good biocompatibility, natural degradation and the like. Research shows that chitosan has bactericidal effect and may act on protonated amino group to act on anionic group of thallus cell membrane to affect cell activity. It is presumed that the more amino groups, the stronger the positive charge, and the greater the bactericidal effect of chitosan, which has been proved by many studies.
Sulfur is an important element in life activities, many sulfur-containing compounds have various important physiological activities, for example, proteins have disulfide bonds to maintain stable protein structures, and mucopolysaccharides such as chondroitin sulfate and keratan sulfate have special effects on proteins. In agricultural production, sulfur-containing compounds also become the main active ingredient of many efficient pesticides, herbicides, bactericides and nematicides. Among these compounds, the main functional group of a broad class of fungicides is the dithiocarbamate. The bactericidal composition has dithiocarbamate bactericides, can be degraded into methyl isothiocyanate in soil to play a fumigating role, or can be directly absorbed by thalli, or can play a role by influencing the metabolism of the thalli through complex heavy metals, and the bactericidal effect is high. Such fungicides have low acute toxicity, but are irritating to the skin and mucous membranes, and therefore there is a need for safe, highly effective, green dithiocarbamate carriers, which are less toxic to such fungicides.
Disclosure of Invention
Aiming at the problems, the invention provides a chitosan derivative with novel structure and good bactericidal activity, and a preparation method and application thereof.
In order to achieve the above purpose of the present invention, the present invention adopts the following technical scheme:
a chitosan derivative is a chitosan polyethyl amino dithio carbamate derivative shown in a general formula I,
wherein n is 20-1200, m and t is 1-5.
The preparation method of the chitosan derivative comprises the following steps:
(1) dissolving the polyethylamine chitosan derivative in alcohol or a mixed solution of water and alcohol, and reacting with carbon disulfide at normal temperature for 6-12h in the presence of alkali to obtain a chitosan polyethylamine dithioformate derivative; wherein, taking chitosan monosaccharide in the polyethylene-based chitosan derivative as a reference, the molar ratio of the polyethylene-based chitosan derivative to alkali to carbon disulfide is 1:1.5-2: 1.5-2;
(2) dissolving the chitosan poly-ethylamine dithiocarbamate derivative obtained in the step (1), reacting for 2 hours at 0-5 ℃ in the presence of sulfuric acid and hydrogen peroxide, carrying out reaction and suction filtration, washing a filter cake with water and alcohol, and drying at 50-60 ℃ to obtain a chitosan poly-ethylamine thiuram disulfide serving as a chitosan poly-aminodithiocarbamate derivative shown in a formula I; wherein the molar ratio of the sulfuric acid to the hydrogen peroxide is 1:1, and the pH value of the reaction system is 2-3.
The polyethylene-based chitosan derivative is prepared by suspending chitosan in an organic solvent, and reacting with chloroethylamine hydrochloride at 60-80 ℃ for 18-24h in the presence of an acid-binding agent to obtain the polyethylene-based chitosan derivative; wherein, taking chitosan monosaccharide as a reference, the molar ratio of the chitosan to the acid-binding agent to the chloramine hydrochloride is 1:2-3: 2-10; the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, isopropanol or tetrahydrofuran; the acid-binding agent is pyridine, triethylamine or ammonia water.
In the steps (1) and (2), the alcohol is methanol or ethanol; the alkali is sodium hydroxide or potassium hydroxide.
In the step (1), the volume ratio of water to alcohol in the mixed solution of water and alcohol is 0-1: 1-10.
The molecular weight of the chitosan is 1000-200000.
The application of the chitosan derivative, namely the application of the chitosan polyethyl amino dithio carbamate derivative shown as the general formula I in the preparation of bactericides.
The principle is as follows: the hydroxyl and amino groups of the chitosan molecule can be deacidified with chloride so as to connect new groups. The introduced amino group can undergo a nucleophilic reaction with carbon disulfide to form a dithiocarbamate, and the thiol groups in two adjacent dithioformic acid groups can be oxidized to form a disulfide bond.
The invention has the advantages that:
the invention takes polyamino chitosan as a carrier, and dithiocarbamic acid ester (salt) active groups are grafted, so that the antibacterial effects of the polyamino chitosan and the dithiocarbamic acid ester (salt) active groups are exerted, the toxicity is reduced, and the green and safe biological pesticide is formed.
In addition, the aminodithioformate pesticide is a large class of agricultural pesticides for killing insects and fungi, the dithio active group of the aminodithioformate pesticide has higher activity, and the dithio heterocycle is one of the derivatization directions of dithioformates; the invention adopts an active substructure splicing method, takes natural chitosan as a lead compound, introduces a polyethylamino side chain, and then introduces a biological active group of the dithio-heterocyclic derivative onto the chitosan side chain to prepare a novel chitosan derivative with good bacteriostatic and induced disease-resistant activities. The synthesized derivative can keep the chitosan natural, non-toxic, easy to degrade and good in biocompatibility, and a new way is opened for developing novel biopesticides.
Drawings
FIG. 1 is an infrared spectrum of chitosan according to an embodiment of the present invention, wherein the spectrum has an infrared characteristic absorption (cm)-1)：1650，1589，1374，1315，1024，893。
FIG. 2 is an infrared spectrum of a polyethylenimine-based chitosan derivative having characteristic absorption in the infrared (cm) according to an embodiment of the present invention-1)：1613，1504，1455，1371，1312，1063，1025。
FIG. 3 is an infrared spectrum of chitosan polyethylene amine thiuram disulfide in the form of absorption in the infrared (cm)-1)：,1635，1496，1455，1372，1324，1232，1022。
Detailed Description
The present invention is further described with reference to the drawings attached to the specification, and the scope of the present invention is not limited to the following examples.
EXAMPLE 1 preparation of Polyethylamine-based Chitosan derivative
Taking 5g of chitosan with the molecular weight of about 150000 into a three-neck flask, adding 30ml of N, N-dimethylformamide and 7ml of pyridine, soaking for 12h for swelling, adding 11g of chloroethylamine hydrochloride, refluxing at 60 ℃ for 18h, cooling to room temperature, performing suction filtration, washing a filter cake with absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain 11g of the polyethyl-chitosan derivative.
The infrared spectrum shows that: the infrared spectrum of the chitosan polyethylene amine (figure 2) is 1589cm in comparison with that of the chitosan (figure 1)-1The characteristic absorption peak of-NH of (2) is weakened, which indicates that the in-situ amino group of the chitosan has reacted; and occurs at 1504cm-1CH of (A)2-NH-peak, 1455cm-1Of (2) a novel-NH2Peak, indicating that the grafting of the polyethylamine groups has been successful; in conclusion, the synthesis of the polyethylamine chitosan is successful, wherein n is 930, m is 1-3, and t is 1-3.
EXAMPLE 2 preparation of derivative I
1.6g of the polyethylenyl chitosan derivative obtained in the above embodiment is taken and added into a single-neck flask, 30ml of deionized water is added, 1.5ml of 4% sodium hydroxide solution is dropwise added, the mixture is stirred for a plurality of minutes, 1.8ml of carbon disulfide is slowly dropwise added, and the reaction is carried out for 10 hours at normal temperature. And (2) performing ice bath, dropwise adding a sulfuric acid/hydrogen peroxide (molar ratio is 1:1) solution, adjusting the pH to 2-3, continuously stirring for 2 hours, performing suction filtration, washing a filter cake with deionized water for 2 times, washing with 95 ethanol for 2 times, and drying at 60 ℃. 1.6g of a tan solid was obtained, namely the derivative I chitosan polyethylene amine thiuram disulfide.
The infrared spectrum shows that: infrared spectrum (figure 3) of chitosan polyethylene amine thiuram disulfide and polyComparing the infrared spectrum of ethylamine chitosan (figure 2) with 1455cm-1CH of (A)2-NH2The peak disappears, which indicates that the amino group is accessed; and 1496cm-1The peak appears as C ═ S characteristic absorption peak, 1324cm-1C ═ S stretching peak appears; 1232cm-1And an S-S characteristic peak appears. In conclusion, the synthesis of chitosan polyethylene amine thiuram disulfide proves successful, wherein n is 930, m is 1-3, and t is 1-3.
Determination of bacteriostatic Activity
The bacteriostatic activity of the sample on Botrytis cinerea (Botrytis cinerea) is determined by a growth rate method. The test was performed at 3 sample concentrations: 100. mu.g/ml, 200. mu.g/ml and 400ug/ml, and has an inhibitory effect on Phytophthora capsici.
The experiment uses good common oligosaccharide medicament (commercially available as 2% water solution) with the same concentration as a positive control and uses distilled water as a negative control. The medium was poured evenly into 2 petri dishes of 9cm diameter, and after complete coagulation, 3 cakes of 5mm diameter were inoculated into each dish. After culturing at 27 ℃ for 48 hours, the colony diameter was measured, and the bacteriostatic ratio of the sample was calculated. Every time the processing sets up 2 culture dishes, every dish inoculation 3 bacterial colonies, to every bacterial colony survey maximum diameter (Dmax) and minimum diameter (Dmin), take the average value to be sample antibacterial ring diameter D sample, all tests are repeated once. The bacteriostatic rate was calculated according to the following formula.
Bacteriostatic rate (%) - (D blank-D sample)/(D blank-5) × 100%
The results are shown in Table 1
TABLE 1 inhibitory Activity of Chitosan derivatives of general formula I on Phytophthora capsici
As shown in table 1, the chitosan polyethylenimine dithiocarbamate derivatives of the general formula i: the activity of the polyethylene amine thiuram disulfide is obviously better than that of the chitosan raw material, and is 10 percent stronger than that of the existing commercial antibacterial agent good spectrum oligosaccharide. The activity of the intermediate polyethylamine chitosan is also stronger than that of chitosan, and is equivalent to that of the control good spectrum oligosaccharide. Therefore, the polyethylene amine chitosan and the polyethylene amine thiuram disulfide have better bacteriostatic activity.
The derivative I and the intermediate of the invention take natural nontoxic chitosan as a framework and then are grafted with amino dithioformate active groups. The macromolecular chitosan can dilute the toxicity of the small molecular active group and reduce the skin toxicity of the dithiocarbamate compounds. Meanwhile, the chitosan and the chitosan derivative can be degraded by microorganisms, so that the chitosan and the chitosan derivative are harmless to the environment, stable in structure and long in acting time.
The derivative I and the intermediate of the invention take macromolecular chitosan as a matrix, do not need to be degraded into chitosan oligosaccharide, and have lower cost and high economy. In addition, the chitosan has the function of regulating the immunity of plants, so the derivative has the functions of antibacterial activity, regulating the growth of plants and integrating the functions.
In conclusion, the invention provides a new idea for reducing the use of chemical pesticides with high pollution and high toxicity and developing novel biological pesticides.
Claims (5)
1. A method for preparing a chitosan derivative is characterized in that: the chitosan derivative comprises a structural unit shown as a formula I,
wherein m, t = 1-5;
the preparation method of the chitosan derivative comprises the following steps:
(1) dissolving the polyethylamine chitosan derivative in alcohol or a mixed solution of water and alcohol, and reacting with carbon disulfide at normal temperature for 6-12h in the presence of alkali to obtain a chitosan polyethylamine dithioformate derivative; wherein, taking chitosan monosaccharide in the polyethylene-based chitosan derivative as a reference, the molar ratio of the polyethylene-based chitosan derivative to alkali to carbon disulfide is 1:1.5-2: 1.5-2;
(2) dissolving the chitosan polyethyl amino dithiocarbamate derivative obtained in the step (1), reacting for 2 hours at 0-5 ℃ in the presence of sulfuric acid and hydrogen peroxide, carrying out reaction and suction filtration, washing a filter cake with water and alcohol, and drying at 50-60 ℃ to obtain a chitosan polyethyl amino dithiocarbamate derivative containing a structural unit shown in a formula I; wherein the molar ratio of the sulfuric acid to the hydrogen peroxide is 1:1, and the pH of a reaction system is 2-3;
wherein the polyethylamino chitosan derivative is prepared by suspending chitosan in an organic solvent, and reacting with chloroethylamine hydrochloride at 60-80 ℃ for 18-24h in the presence of an acid-binding agent to obtain the polyethylamino chitosan derivative; wherein, taking chitosan monosaccharide as a reference, the molar ratio of the chitosan to the acid-binding agent to the chloramine hydrochloride is 1:2-3: 2-10; the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, isopropanol or tetrahydrofuran; the acid-binding agent is pyridine, triethylamine or ammonia water;
the molecular weight of the chitosan is 1000-200000.
2. The method for producing a chitosan derivative according to claim 1, wherein: the alcohol in the steps (1) and (2) is methanol or ethanol; in the step (1), the alkali is sodium hydroxide or potassium hydroxide.
3. The method for producing a chitosan derivative according to claim 1, wherein: in the step (1), the volume ratio of water to alcohol in the mixed solution of water and alcohol is 0-1: 1-10.
4. A chitosan derivative produced by the production method according to any one of claims 1 to 3.
5. Use of the chitosan derivative of claim 4 in the preparation of a bactericide.
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| CN114075300B (en) * | 2020-08-21 | 2023-02-28 | 佛山市海力盈生物科技有限公司 | Chitosan oligosaccharide derivative nematicide and preparation method and application thereof |
| CN115105624B (en) * | 2022-08-26 | 2022-11-08 | 广东海洋大学 | Marine polysaccharide-based efficient antibacterial film dressing and preparation method 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 |
| CN107216410A (en) * | 2017-07-17 | 2017-09-29 | 中国科学院海洋研究所 | A kind of chitosan derivatives and its preparation method and application |
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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 |
| CN107216410A (en) * | 2017-07-17 | 2017-09-29 | 中国科学院海洋研究所 | A kind of chitosan derivatives and its preparation method and application |
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| "多氨基壳聚糖衍生物的制备及抑菌活性研究";孟祥涛;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20121015;B014-403 * |
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