CN114539443B - Acylated marine organism polysaccharide derivative and preparation method and application thereof - Google Patents
Acylated marine organism polysaccharide derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the ocean chemical engineering technology, and particularly relates to an acylated marine organism polysaccharide derivative, and a preparation method and application thereof. The derivative is shown as a formula I or a formula II, wherein R is pyridin-3-yl, pyridin-4-yl or 2-chloropyridin-3-yl; n=2-20. The pyridine formyl chitosan oligosaccharide derivative prepared by the invention has good solubility, can be dissolved in various solvents, expands the application field, has antibacterial activity and metal ion adsorption function, and can not only kill agricultural pathogenic bacteria, but also remove heavy metal ions enriched in cultivated lands. Has potential application value in the pesticide field.
Description
Technical Field
The invention belongs to the ocean chemical engineering technology, and particularly relates to an acylated marine organism polysaccharide derivative, and a preparation method and application thereof.
Background
Chemical pesticides make an important contribution to reducing agricultural plant diseases and insect pests and increasing crop yield. However, unreasonable use of chemical pesticides also brings a series of problems such as pesticide residue, drug resistance, environmental pollution, ecological balance destruction and the like, and seriously threatens the agricultural product safety and the agricultural ecological environment safety of China. Therefore, there is a need to develop a powerful green, efficient, low-toxicity biopesticide to promote the green development of agricultural disease control.
Chitosan (Chitosan), the only natural cationic polymer found at present, is prepared from Chitin (Chitin) extracted from shrimp and crab shells through deacetylation treatment, and has excellent bioactivity and physicochemical properties. Chitosan oligosaccharide (chitosan) is a small molecular polysaccharide obtained by degrading chitosan, and has the molecular weight of generally lower than 2000Da, safety, no toxicity, good biocompatibility, good affinity with human cells and no immunogenicity. The chitosan oligosaccharide and its derivatives have broad-spectrum antibacterial function on various bacteria and fungi due to their unique biological activities.
Pyridine acyl chloride is used as an analogue of natural vitamin B3 nicotinic acid, the synthesis method and the biological activity of the pyridine acyl chloride are widely focused by scientists, and the changeable structural types of the pyridine acyl chloride lay a foundation for continuously synthesizing new compounds. Opens up a new way for developing novel biological pesticides.
Disclosure of Invention
The invention aims at the problems and provides an acylated marine organism polysaccharide derivative, 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:
an acylated marine organism polysaccharide derivative, the derivative is shown as a formula I or a formula II,
in the formula I or the formula II, R is pyridin-3-yl, pyridin-4-yl or 2-chloropyridin-3-yl; n=2-20.
A preparation method of an acylated marine organism polysaccharide derivative:
1) Dissolving chitosan oligosaccharide in excessive solvent A, then adding trimethylchlorosilane and imidazole, and reacting at room temperature to generate O-trimethylsilyl chitosan oligosaccharide; wherein, the mol ratio of the chitosan oligosaccharide to the trimethylchlorosilane is 1:1-3;
the molecular weight of the chitosan oligosaccharide is 1000-1500.
2) Dissolving O-trimethylsilyl chitosan oligosaccharide in excessive solvent B, adding pyridine acyl chloride and an acid binding agent, and reacting at room temperature to obtain O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide; wherein the mol ratio of the O-trimethylsilyl chitosan oligosaccharide to the pyridine acyl chloride is 1:1-3;
3) Dissolving the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide in an excessive solvent C, and then adding a tetrahydrofuran solution of tetrabutylammonium fluoride to react at room temperature to obtain the N-pyridine formyl chitosan oligosaccharide shown in the formula I;
4) Dissolving the N-pyridine formyl chitosan oligosaccharide shown in the formula I in an excessive solvent D, and then adding copper acetate monohydrate to react under stirring at room temperature to obtain a complex pyridine formyl chitosan oligosaccharide copper complex shown in the formula II; wherein the mass ratio of the N-pyridine formyl chitosan oligosaccharide to the copper acetate monohydrate is 1:1-2.
The step 1) chitosan oligosaccharide is dissolved in a solvent A, and then trimethylchlorosilane and imidazole are added to react for 12-16 hours at room temperature to generate O-trimethylsilyl chitosan oligosaccharide; wherein the mass ratio of the volume of the solvent A to the chitosan oligosaccharide is 10-20:1; the mass ratio of the chitosan oligosaccharide to the imidazole is 1:1; solvent A is N, N-dimethylformamide and/or N-methylpyrrolidone.
The O-trimethylsilyl chitosan oligosaccharide obtained in the step 2) is dissolved in excessive solvent B, and pyridine acyl chloride is added to react for 12-24 hours at room temperature, so that O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is obtained; wherein the mol ratio of the O-trimethylsilyl chitosan oligosaccharide to the pyridine acyl chloride is 1:1-3; the mass ratio of the volume of the solvent B to the chitosan oligosaccharide is 10-20:1; the pyridine acyl chloride is nicotinyl chloride hydrochloride, isonicotinyl chloride hydrochloride or 2-chloronicotinyl chloride; the acid binding agent is pyridine and/or triethylamine; the solvent is N, N-dimethylformamide and/or N-methylpyrrolidone.
The step 3) is to dissolve the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide in excessive solvent C, then add tetrahydrofuran solution of tetrabutylammonium fluoride to react for 6-12 hours under the condition of room temperature, and obtain N-pyridine formyl chitosan oligosaccharide shown in the formula I; wherein the mass ratio of the volume of the solvent C to the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is 10-20:1; the mass ratio of the tetrahydrofuran solution of tetrabutylammonium fluoride to the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is 10-20:1; solvent C is water and/or tetrahydrofuran.
Dissolving the obtained N-pyridine formyl chitosan oligosaccharide shown in the formula I in an excessive solvent D, adding copper acetate monohydrate, stirring at room temperature, reacting for 6-12 hours, filtering after the reaction, washing a filter cake with the solvent, and drying at 50-80 ℃ to obtain a complex pyridine formyl chitosan oligosaccharide copper complex shown in the formula II; wherein the mass ratio of the volume of the solvent to the N-pyridine formyl chitosan oligosaccharide is 40-100:1.
The application of the acylated marine organism polysaccharide derivative is that the derivative shown in the formula I is applied to the preparation of agricultural bactericides.
The derivative shown in the formula I is applied to preparation of agricultural fungus bactericides.
Principle of: the chitosan oligosaccharide structure contains-NH 2 The pyridine formyl can be introduced into the chitosan oligosaccharide structure through nucleophilic substitution reaction with pyridine acyl chloride, so that synergistic effect is generated with chitosan oligosaccharide, and the biological activity of the derivative is obviously improved; and simultaneously, the carbonyl coordinated copper ions with high electron density in the pyridine formyl chitosan oligosaccharide are used to generate a synergistic effect with the chitosan oligosaccharide, so that the biological activity of the derivative is obviously improved.
The invention has the advantages that:
1. according to the invention, the pyridine formyl is introduced into the chitosan oligosaccharide structure, and the pyridine formyl and the chitosan oligosaccharide produce a synergistic effect, so that the antibacterial activity of the chitosan oligosaccharide is obviously improved; at the same time, pyridine formyl and copper ions are further introduced into the chitosan oligosaccharide structure, and the three produce a synergistic effect, so that the antibacterial activity of the chitosan oligosaccharide is remarkably improved.
2. The pyridine formyl chitosan oligosaccharide derivative prepared by the invention has good water solubility, improves the antibacterial effect, simultaneously avoids the residue of heavy metal ions in soil, expands the application field of the derivative, and has potential application value in the pesticide field.
Drawings
FIG. 1 is an infrared spectrum of chitosan oligosaccharide, which has infrared characteristic absorption (cm) -1 )：3259,2884，1520,1410，1068。
FIG. 2 shows an embodiment of the present inventionInfrared spectrum of chitosan oligosaccharide derivative 1, its infrared characteristic absorption (cm) -1 )：3357,1725,1652,1555,1421,1288。
FIG. 3 is an infrared spectrum of chitosan oligosaccharide derivative 2 according to the embodiment of the invention, which shows the characteristic absorption (cm) -1 )：3294,1732,1651,1541,1410,1282。
FIG. 4 is an infrared spectrum of chitosan oligosaccharide derivative 3 according to the embodiment of the invention, which has infrared characteristic absorption (cm -1 )：3364,1733,1653,1562,1404,1297。
FIG. 5 is an infrared spectrum of chitosan oligosaccharide derivative 4 according to the embodiment of the invention, which shows the characteristic absorption (cm) -1 )：3275,1728,1647,1558,1421,1286。
FIG. 6 is an infrared spectrum of a chitosan oligosaccharide derivative 5 according to an embodiment of the invention, which has an infrared characteristic absorption (cm -1 )：3272,1734,1649,1558,1412,1284。
FIG. 7 is an infrared spectrum of a chitosan oligosaccharide derivative 6 according to an embodiment of the invention, which shows the characteristic absorption (cm) -1 )：3290,1735,1655,1561,1403,1296。
Detailed Description
The present invention will be further described with reference to the drawings, and the scope of the present invention is not limited to the following examples.
In the invention, trimethyl chlorosilane is firstly adopted to protect the 6-hydroxyl of oligosaccharide, and pyridine acyl chloride and chitosan oligosaccharide C are then adopted 2 in-NH at position 2 O-trimethyl silicon base-N-pyridine formyl chitosan oligosaccharide is generated by reaction, trimethyl silicon base is removed under the action of tetrabutylammonium fluoride to generate N-pyridine formyl chitosan oligosaccharide derivative, oxygen in carbonyl on the chitosan oligosaccharide derivative is coordinated with copper ions of copper acetate to generate pyridine formyl chitosan oligosaccharide copper complex derivative, the structure of the obtained derivative is determined by infrared spectrum analysis, and the chitosan oligosaccharide and an accessed group are effectively combined to generate the pyridine formyl chitosan oligosaccharide derivative, and meanwhile, the derivative is obtained by copper coordination.
Example 1 preparation of derivative 1
15 g of chitosan oligosaccharide with molecular weight of 1000 (see figure 1), 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide, the mixture is reacted for 12 hours at 35 ℃, three times of ethyl acetate is added into the reactant, the mixture is filtered by suction to obtain precipitate, the precipitate is washed by absolute ethyl alcohol, and the precipitate is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.12g of nicotinyl chloride hydrochloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N-nicotinyl chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N-nicotinoyl chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture under stirring to react for 4 hours at 25 ℃, ethanol is added for precipitation, the precipitation is filtered by suction, absolute ethanol is used for washing, and the mixture is dried at 50 ℃ to obtain yellow powder, namely the pyridine formyl chitosan oligosaccharide derivative 1, the structure of which is shown as a general formula I (R is pyridine-3-yl; n=2-20).
The infrared spectrum shows that: the infrared spectrum of the pyridine formyl chitosan oligosaccharide derivative 1 (figure 2) is compared with the infrared spectrum of the full chitosan oligosaccharide (figure 1) and is located at 1725cm -1 Carbonyl characteristic absorption peak of (C) and 1652cm -1 、1555cm -1 1288cm -1 Is characterized by a secondary amide characteristic absorption peak; 1594cm -1 Is characteristic absorption of pyridine ring; the eyesight improving derivative 1 was successfully synthesized.
Example 2 preparation of derivative 2
15 g of chitosan oligosaccharide with molecular weight of 1000, 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide for reaction for 12 hours at 35 ℃, three times of ethyl acetate is added into reactants, precipitation is obtained by suction filtration, the solution is washed by absolute ethyl alcohol, and the solution is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.12g of isonicotinyl chloride hydrochloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N-isonicotinyl chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N-isonicotinyl chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture to react for 4 hours at 25 ℃, ethanol precipitation is added, the precipitate is filtered by suction, the mixture is washed by absolute ethanol and dried at 50 ℃ to obtain yellow powder, namely the pyridine formyl chitosan oligosaccharide derivative 2, and the structure is shown as a general formula I (R is pyridine-4-yl; n=2-20).
The infrared spectrum shows that: the infrared spectrum of the pyridine formyl chitosan oligosaccharide derivative 2 (figure 3) is compared with the infrared spectrum of the full chitosan oligosaccharide (figure 1) and is positioned at 1732cm -1 Carbonyl characteristic absorption peak of 1651cm -1 、1541cm -1 1282cm -1 Is characterized by a secondary amide characteristic absorption peak; 1603cm -1 Is characteristic absorption of pyridine ring; the synthesis of derivative 2 proved successful.
EXAMPLE 3 preparation of derivative 3
15 g of chitosan oligosaccharide with molecular weight of 1000, 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide for reaction for 12 hours at 35 ℃, three times of ethyl acetate is added into reactants, precipitation is obtained by suction filtration, the solution is washed by absolute ethyl alcohol, and the solution is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.04g of 2-chloronicotinyl chloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N- (2-chloronicotinyl) chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N- (2-chloronicotinyl) chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture under stirring to react for 4 hours at 25 ℃, ethanol is added for precipitation, the precipitation is filtered by suction, the mixture is washed by absolute ethanol and dried at 50 ℃ to obtain yellow powder, namely the pyridine formyl chitosan oligosaccharide derivative 3, and the structure is shown as a general formula I (R is 2-chloropyridine-3-yl; n=2-20).
The infrared spectrum shows that: an infrared spectrum of pyridine formyl chitosan oligosaccharide derivative 3 (figure 4) and an infrared spectrum of full chitosan oligosaccharide (figure 1)) In comparison, a position at 1733cm appears -1 Carbonyl characteristic absorption peak of 1653cm -1 、1562cm -1 1297cm -1 Is characterized by a secondary amide characteristic absorption peak; 1579cm -1 Is characteristic absorption of pyridine ring; the eyesight improving derivative 3 is successfully synthesized.
Example 4 preparation of derivative 4
15 g of chitosan oligosaccharide with molecular weight of 1500 (see figure 1), 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide, the mixture is reacted for 12 hours at 35 ℃, three times of ethyl acetate is added into the reactant, the mixture is filtered by suction to obtain precipitate, the precipitate is washed by absolute ethyl alcohol, and the precipitate is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.12g of nicotinyl chloride hydrochloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N-nicotinyl chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N-nicotinoyl chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture under stirring to react for 4 hours at 25 ℃, ethanol precipitation is added, the precipitation is filtered by suction, absolute ethanol is used for washing, and the mixture is dried at 50 ℃ to obtain yellow powder, namely the N-nicotinoyl chitosan oligosaccharide.
0.5 g of N-nicotinoyl chitosan oligosaccharide was dissolved in 20mL of water, 0.38 g of Cu (OAc) 2 ·H 2 O is dissolved in 5mL of water, copper acetate aqueous solution is dropwise added into N-nicotinoyl chitosan oligosaccharide aqueous solution under stirring at room temperature, reaction is carried out for 6 hours, absolute ethyl alcohol is added for precipitation, centrifugation, absolute ethyl alcohol washing and drying at 50 ℃ are carried out, and dark green powder is obtained, namely the pyridine formyl chitosan oligosaccharide copper complex derivative 1, the structure of which is shown as the general formula I (R is pyridine-3-yl; n=2-20).
The infrared spectrum shows that: the infrared spectrum of the pyridine formyl chitosan oligosaccharide copper complex derivative 4 (figure 5) is compared with the infrared spectrum of the full chitosan oligosaccharide (figure 1) and is located at 1728cm -1 Is characterized by a carbonyl characteristic absorption peak of 1647cm -1 、1558cm -1 1286cm -1 Is a secondary amide of (2)Characteristic absorption peaks; 1590cm -1 Is characteristic absorption of pyridine ring; the eyesight improving derivative 1 was successfully synthesized.
Example 2 preparation of derivative 5
15 g of chitosan oligosaccharide with molecular weight of 1500, 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide for reaction for 12 hours at 35 ℃, three times of ethyl acetate is added into reactants, precipitation is obtained by suction filtration, the solution is washed by absolute ethyl alcohol, and the solution is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.12g of isonicotinyl chloride hydrochloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N-isonicotinyl chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N-isonicotinyl chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture under stirring to react for 4 hours at 25 ℃, ethanol precipitation is added, the precipitation is filtered by suction, absolute ethanol is used for washing, and the mixture is dried at 50 ℃ to obtain yellow powder, namely the N-isonicotinyl chitosan oligosaccharide.
0.5 g of N-isonicotinyl chitosan oligosaccharide was dissolved in 20mL of water, 0.38 g of Cu (OAc) 2 ·H 2 O is dissolved in 5mL of water, the copper acetate aqueous solution is dropwise added into the N-isonicotinyl chitosan oligosaccharide aqueous solution under stirring at room temperature, the reaction is carried out for 6 hours, absolute ethyl alcohol is added for precipitation, the mixture is centrifuged, the absolute ethyl alcohol is used for washing, and the mixture is dried at 50 ℃ to obtain dark green powder, namely the pyridine formyl chitosan oligosaccharide copper complex derivative 2, the structure of which is shown as a general formula I (R is pyridine-4-yl; n=2-20).
The infrared spectrum shows that: the infrared spectrum of the copper pyridine formyl chitosan oligosaccharide complex derivative 5 (figure 6) appears to be at 1734cm compared with the infrared spectrum of the full chitosan oligosaccharide (figure 1) -1 Is characterized by a carbonyl characteristic absorption peak of 1649cm -1 、1558cm -1 1284cm -1 Is characterized by a secondary amide characteristic absorption peak; 1590cm -1 Is characteristic absorption of pyridine ring; the synthesis of derivative 2 proved successful.
EXAMPLE 3 preparation of derivative 6
15 g of chitosan oligosaccharide with molecular weight of 1500, 12.1 g of trimethylchlorosilane and 15 g of imidazole are added into 100mL of N, N-dimethylformamide for reaction for 12 hours at 35 ℃, three times of ethyl acetate is added into reactants, precipitation is obtained by suction filtration, the solution is washed by absolute ethyl alcohol, and the solution is dried at 50 ℃ to obtain the O-trimethylsilyl chitosan oligosaccharide.
Adding 4g of O-trimethylsilyl chitosan oligosaccharide into 30mLN, N-dimethylformamide and 30mL of pyridine, adding 6.04g of 2-chloronicotinyl chloride into the mixture under stirring, reacting for 24 hours at 35 ℃, adding acetone for precipitation, filtering the precipitate, washing the precipitate with acetone, and drying the precipitate at 50 ℃ to obtain yellow powder, namely the O-trimethylsilyl-N- (2-chloronicotinyl) chitosan oligosaccharide.
1.5 g of O-trimethylsilyl-N- (2-chloronicotinyl) chitosan oligosaccharide is added into 15mL of water, 15mL of tetrahydrofuran solution (1 mol/L) of tetrabutylammonium fluoride is added into the mixture under stirring to react for 4 hours at 25 ℃, ethanol is added for precipitation, the precipitation is filtered by suction, the mixture is washed by absolute ethanol, and the mixture is dried at 50 ℃ to obtain yellow powder, namely the N- (2-chloronicotinyl) chitosan oligosaccharide.
0.5 g of N- (2-chloronicotinyl) chitosan oligosaccharide was dissolved in 20mL of water, 0.38 g of Cu (OAc) 2 ·H 2 O is dissolved in 5mL of water, the copper acetate aqueous solution is dropwise added into the N- (2-chloronicotinyl) chitosan oligosaccharide aqueous solution under stirring at room temperature, the reaction is carried out for 6 hours, absolute ethanol is added for precipitation, the solution is centrifuged, the solution is washed by absolute ethanol and dried at 50 ℃ to obtain dark green powder, namely the pyridine formyl chitosan oligosaccharide copper complex derivative 3, the structure of which is shown as a general formula I (R is 2-chloropyridin-3-yl; n=2-20).
The infrared spectrum shows that: the infrared spectrum of the copper pyridine formyl chitosan oligosaccharide complex derivative 6 (figure 7) appears to be at 1735cm compared with the infrared spectrum of the full chitosan oligosaccharide (figure 1) -1 Carbonyl characteristic absorption peak of 1655cm -1 、1561cm -1 1296cm -1 Is characterized by a secondary amide characteristic absorption peak; 1578cm -1 Is characteristic absorption of pyridine ring; the eyesight improving derivative 3 is successfully synthesized.
Determination of bacteriostatic Activity
And determining the antibacterial activity of the sample on phytophthora capsici by adopting a growth rate method. The test was performed at 2 sample concentrations: 0.04mg/mL, and 0.08 mg/mL.
The experiment uses the same concentration of thiabendazole (commercially available as 20% suspension) as a positive control and distilled water as a negative control. The medium was poured evenly into 1 petri dish with a diameter of 9cm, and after complete solidification, 3 cakes with a diameter of 5mm were inoculated into each petri dish. After incubation at 27℃for 72 hours, colony diameters were measured and the antibacterial rate of the samples was calculated. Each treatment was performed by providing 1 dish, inoculating 3 colonies per dish, and measuring the maximum diameter (D max ) And minimum diameter (D min ) Average value is taken as diameter D of the sample inhibition zone Sample of All experiments were repeated once. The antibacterial ratio was calculated according to the following formula (see table 1).
Antibacterial ratio (%) = (D) Blank- D Sample of )/(D Blank- 5)×100
TABLE 1 inhibition Activity of Chitosan oligosaccharide derivatives of formula 1 on Phytophthora capsici
The experimental results in the table 1 show that the pyridine formyl chitosan oligosaccharide derivative and the pyridine formyl chitosan oligosaccharide copper complex derivative have good antibacterial effect on phytophthora capsici at high concentration, and are better than the existing thiabendazole copper products.
Claims (8)
1. An acylated marine organism polysaccharide derivative characterized by: the derivative is shown as a formula II,
in the formula II, R is pyridin-3-yl, pyridin-4-yl or 2-chloropyridin-3-yl; n=2-20;
the preparation method comprises the following steps:
1) Dissolving chitosan oligosaccharide in excessive solvent A, then adding trimethylchlorosilane and imidazole, and reacting at room temperature to generate O-trimethylsilyl chitosan oligosaccharide; wherein, the mol ratio of the chitosan oligosaccharide to the trimethylchlorosilane is 1:1-3;
2) Dissolving O-trimethylsilyl chitosan oligosaccharide in excessive solvent B, adding pyridine acyl chloride and an acid binding agent, and reacting at room temperature to obtain O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide; wherein the mol ratio of the O-trimethylsilyl chitosan oligosaccharide to the pyridine acyl chloride is 1:1-3;
3) Dissolving the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide in an excessive solvent C, and then adding a tetrahydrofuran solution of tetrabutylammonium fluoride to react at room temperature to obtain the N-pyridine formyl chitosan oligosaccharide shown in the formula I;
4) Dissolving the N-pyridine formyl chitosan oligosaccharide shown in the formula I in an excessive solvent D, and then adding copper acetate monohydrate to react under stirring at room temperature to obtain a complex pyridine formyl chitosan oligosaccharide copper complex shown in the formula II; wherein the mass ratio of the N-pyridine formyl chitosan oligosaccharide to the copper acetate monohydrate is 1:1-2;
the compound of formula I is:
in the formula I, R is pyridin-3-yl, pyridin-4-yl or 2-chloropyridin-3-yl; n=2-20.
2. A process for the preparation of an acylated marine polysaccharide derivative as claimed in claim 1, wherein:
1) Dissolving chitosan oligosaccharide in excessive solvent A, then adding trimethylchlorosilane and imidazole, and reacting at room temperature to generate O-trimethylsilyl chitosan oligosaccharide; wherein, the mol ratio of the chitosan oligosaccharide to the trimethylchlorosilane is 1:1-3;
2) Dissolving O-trimethylsilyl chitosan oligosaccharide in excessive solvent B, adding pyridine acyl chloride and an acid binding agent, and reacting at room temperature to obtain O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide; wherein the mol ratio of the O-trimethylsilyl chitosan oligosaccharide to the pyridine acyl chloride is 1:1-3;
3) Dissolving the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide in an excessive solvent C, and then adding a tetrahydrofuran solution of tetrabutylammonium fluoride to react at room temperature to obtain the N-pyridine formyl chitosan oligosaccharide shown in the formula I;
4) Dissolving the N-pyridine formyl chitosan oligosaccharide shown in the formula I in an excessive solvent D, and then adding copper acetate monohydrate to react under stirring at room temperature to obtain a complex pyridine formyl chitosan oligosaccharide copper complex shown in the formula II; wherein the mass ratio of the N-pyridine formyl chitosan oligosaccharide to the copper acetate monohydrate is 1:1-2;
the compound of formula I is:
in the formula I, R is pyridin-3-yl, pyridin-4-yl or 2-chloropyridin-3-yl; n=2-20.
3. The method for preparing the acylated marine organism polysaccharide derivative according to claim 2, wherein: the step 1) chitosan oligosaccharide is dissolved in a solvent A, and then trimethylchlorosilane and imidazole are added to react for 12-16 hours at room temperature to generate O-trimethylsilyl chitosan oligosaccharide; wherein the mass ratio of the volume of the solvent A to the chitosan oligosaccharide is 10-20:1; the mass ratio of the chitosan oligosaccharide to the imidazole is 1:1; solvent A is N, N-dimethylformamide and/or N-methylpyrrolidone.
4. The method for preparing the acylated marine organism polysaccharide derivative according to claim 2, wherein: the O-trimethylsilyl chitosan oligosaccharide obtained in the step 2) is dissolved in excessive solvent B, and pyridine acyl chloride is added to react for 12-24 hours at room temperature, so that O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is obtained; wherein the mol ratio of the O-trimethylsilyl chitosan oligosaccharide to the pyridine acyl chloride is 1:1-3; the mass ratio of the volume of the solvent B to the chitosan oligosaccharide is 10-20:1; the pyridine acyl chloride is nicotinyl chloride hydrochloride, isonicotinyl chloride hydrochloride or 2-chloronicotinyl chloride; the acid binding agent is pyridine and/or triethylamine; the solvent is N, N-dimethylformamide and/or N-methylpyrrolidone.
5. The method for preparing the acylated marine organism polysaccharide derivative according to claim 2, wherein: the step 3) is to dissolve the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide in excessive solvent C, then add tetrahydrofuran solution of tetrabutylammonium fluoride to react for 6-12 hours under the condition of room temperature, and obtain N-pyridine formyl chitosan oligosaccharide shown in the formula I; wherein the mass ratio of the volume of the solvent C to the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is 10-20:1; the mass ratio of the tetrahydrofuran solution of tetrabutylammonium fluoride to the O-trimethylsilyl-N-pyridine formyl chitosan oligosaccharide is 10-20:1; solvent C is water and/or tetrahydrofuran.
6. The method for preparing the acylated marine organism polysaccharide derivative according to claim 1, wherein: dissolving the obtained N-pyridine formyl chitosan oligosaccharide shown in the formula I in an excessive solvent D, adding copper acetate monohydrate, stirring at room temperature, reacting for 6-12 hours, filtering after the reaction, washing a filter cake with the solvent, and drying at 50-80 ℃ to obtain a complex pyridine formyl chitosan oligosaccharide copper complex shown in the formula II; wherein the mass ratio of the volume of the solvent to the N-pyridine formyl chitosan oligosaccharide is 40-100:1.
7. Use of an acylated marine polysaccharide derivative according to claim 1, characterized in that: the derivative shown in the formula II is applied to preparation of agricultural bactericides.
8. The use of an acylated marine polysaccharide derivative as claimed in claim 7, wherein: the derivative shown in the formula II is applied to preparation of agricultural fungus bactericides.
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| CN101054397A (en) * | 2007-04-27 | 2007-10-17 | 大连中科格莱克生物科技有限公司 | N-nicotinoyl chitosan oligosaccharide and preparation method thereof |
| CN101781374A (en) * | 2010-02-04 | 2010-07-21 | 聊城大学 | Preparation method and application of copper compound with chitosan and/or derivatives thereof |
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| CN100360036C (en) * | 2005-04-30 | 2008-01-09 | 武汉大学 | Preparation method of chitin/metal copper composite antibactericidal agent |
| CN105801722A (en) * | 2016-03-28 | 2016-07-27 | 中国科学院海洋研究所 | Marine organism polysaccharide copper compound and preparation method and application thereof |
| CN105887242A (en) * | 2016-06-22 | 2016-08-24 | 天津中盛生物工程有限公司 | Preparation method of chitosan copper fibers |
| CN107936229A (en) * | 2017-12-22 | 2018-04-20 | 西南交通大学 | Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method |
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