Disclosure of Invention
In order to solve the problems existing in the technical proposal; the invention aims to provide a rotenone-containing solenopsis invicta killing bait and a preparation and application method thereof. The aim of the invention can be achieved by the following technical scheme: the rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: the self-made rotenone comprises, by weight, 0.3-1.8 parts of a self-made rotenone killing active ingredient, 58-65 parts of starch, 4-8 parts of diatom powder, 4-8 parts of butter, 8-12 parts of honey, 0.5-1 part of a preservative and the balance of water.
The self-made rotenone has the following killing active components: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
the starch is one or the mixture of wheat starch and corn starch;
the mesh number of the diatom powder is 200 meshes;
The preservative is potassium sorbate.
The preparation method of the rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate comprises the following steps: 2g of carboxymethyl chitosan is dissolved in 100ml of deionized water to form a first solution; 2.5g of sodium dodecyl polyoxypropylene ether phosphate is dissolved in 200ml of ethanol, then 2.5g of carbodiimides and 1.5g of N-hydroxysuccinimide are added, and stirring is continued for 1h to obtain a second solution; then heating the first solution to 80 ℃, and then slowly dripping the second solution containing the dodecyl polyoxypropylene ether sodium phosphate while stirring; after the dripping is completed, continuously stirring the mixture for 5 hours at 80 ℃; then cooling the mixed solution to 25 ℃; subsequently 1g of rotenone was dissolved in 200ml of dimethyl sulfoxide solution; slowly dripping the rotenone-containing solution into the aqueous solution of dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan, continuously stirring the mixture at 25 ℃ for 12 hours after the dripping is completed, and dialyzing the stirred mixture for 48 hours; finally, the dialysate is freeze-dried, and the dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate loaded with rotenone is prepared.
Furthermore, light shielding is needed in the dripping, stirring and dialysis processes in the preparation process;
further, deionized water needs to be replaced every 12 hours during the dialysis process.
A preparation method of a rotenone-containing solenopsis invicta killing bait comprises the following steps: dissolving the self-made rotenone killing active ingredient with acetone, and then fully and uniformly mixing the mixed solution with honey and butter; and after mixing uniformly, adding starch, diatom powder and preservative into the mixed solution, standing until acetone is completely volatilized after the mixed solution is fully and uniformly mixed, and finally adding the rest of water, and uniformly mixing to obtain the rotenone-containing solenopsis invicta killing bait.
The application method of the rotenone-containing solenopsis invicta killing bait comprises the following steps:
S1, physically blending clean sand and cycloxaprid;
s2, placing the prepared bait in sand treated by cycloxaprid, so that the surface of the bait is uniformly adhered and covered with sand with the thickness of 2-4 mm;
s3, applying the bait agent wrapped with sand to the vicinity of the solenopsis invicta nest in a ring mode.
Further, in the step S1, 0.0025g cycloxaprid powder is blended per 1kg sand.
Further, in the step S2, the bait is spherical bait with the diameter of 1.5-3 cm.
The invention has the beneficial effects that:
1. According to the invention, the dodecyl polyoxypropylene ether sodium phosphate is introduced to modify carboxymethyl chitosan, so that on the basis of ensuring water solubility, the contact area of the modified chitosan to oil is increased, the aim of high solubilization is fulfilled, and the modified chitosan is more salt-resistant and high-temperature-resistant, so that the lipophilicity and biocompatibility of the chitosan are greatly enhanced, and the modified chitosan can be distributed in the bait more uniformly; the compound soil can be used for a long time after being invaded by solenopsis invicta, and presents a scene with more complex soil physicochemical properties; therefore, the method has wider use scenes aiming at the invasion of solenopsis invicta;
2. The modified chitosan has a crosslinked structure, so that the stability and mechanical strength of the modified chitosan are greatly enhanced; after being matched with the rotenone, the rotenone has better rotenone controlled release performance in a longer time dimension, has longer lasting effect, and does not need secondary application in the process of killing the solenopsis invicta;
3. according to the application method, the prepared bait is uniformly covered on the surface with the sand treated by the cycloxaprid and the sand treated by the low concentration, so that the digging behavior of the solenopsis invicta can be promoted, the environment is friendly, and the coated bait has larger particles and can be normally used in a windy day; in addition, after the sand and the bait are compounded, the bait has excellent effect even in rainy days, so that the whole bait has longer service life.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" indicated in the examples below are parts by weight.
Example 1
The rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: 0.3 part of self-made rotenone killing active ingredient, 58 parts of starch, 4 parts of diatom powder, 4 parts of butter, 8 parts of honey, 0.5 part of preservative and the balance of water;
Wherein, the self-made rotenone kills the active ingredients as follows: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
Wherein the starch is a mixture of wheat starch and corn starch, and the weight of the wheat starch accounts for 30% of the total starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
Wherein the water of specific example 1 was 25.2 parts.
Synthesis of sodium dodecyl polyoxypropylene ether phosphate: 75g of dodecanol and 0.6g of potassium hydroxide were added to an autoclave,
After uniformly mixing, 70g of propylene oxide is added dropwise, and the whole dropwise addition process is carried out under the nitrogen atmosphere; controlling the pressure of the reaction kettle to be not more than 0.4MPa, and aging to constant pressure at 130 ℃ after the dripping is completed; neutralizing with glacial acetic acid, and vacuum drying at 70deg.C to obtain intermediate dodecyl polyoxypropylene ether; then 8g of dodecyl polyoxypropylene ether and 4g of pyrophosphoric acid are added into a three-neck flask at normal temperature, the temperature is raised to 50 ℃, and the reaction is carried out for 12 hours under mechanical stirring; then heating to 70 ℃, and adding 0.5g of deionized water for hydrolysis for 12 hours; and separating and purifying by column chromatography; and then neutralizing the product by using a sodium hydroxide absolute ethanol solution with the mass fraction of 1% until the pH value is 7, filtering to remove inorganic salts, steaming to remove the solvent, and finally drying in vacuum for 6 hours at 50 ℃ to obtain the light yellow product of the dodecyl polyoxypropylene ether sodium phosphate.
The preparation method of the rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate comprises the following steps: 2g of carboxymethyl chitosan is dissolved in 100ml of deionized water to form a first solution; 2.5g of sodium dodecyl polyoxypropylene ether phosphate is dissolved in 200ml of ethanol, then 2.5g of carbodiimides and 1.5g of N-hydroxysuccinimide are added, and stirring is continued for 1h to obtain a second solution; then heating the first solution to 80 ℃, and then slowly dripping the second solution containing the dodecyl polyoxypropylene ether sodium phosphate while stirring; after the dripping is completed, continuously stirring the mixture for 5 hours at 80 ℃; then cooling the mixed solution to 25 ℃;
Subsequently 1g of rotenone was dissolved in 200ml of dimethyl sulfoxide solution; slowly dripping a rotenone-containing solution into an aqueous solution of dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan in a dark place, continuously stirring the mixture at 25 ℃ in a dark place for 12 hours after dripping, and then carrying out dark dialysis on the stirred mixture for 48 hours, wherein deionized water is replaced every 12 hours in the dialysis process; finally, the dialysate is freeze-dried, and the dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate loaded with rotenone is prepared.
A preparation method of a rotenone-containing solenopsis invicta killing bait comprises the following steps: dissolving the self-made rotenone killing active ingredient with acetone, and then fully and uniformly mixing the mixed solution with honey and butter; and after mixing uniformly, adding starch, diatom powder and preservative into the mixed solution, standing until acetone is completely volatilized after the mixed solution is fully and uniformly mixed, and finally adding the rest of water, and uniformly mixing to obtain the rotenone-containing solenopsis invicta killing bait.
Example 2
The rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: 0.6 part of self-made rotenone killing active ingredient, 60 parts of starch, 5 parts of diatom powder, 5 parts of butter, 8 parts of honey, 0.5 part of preservative and the balance of water;
Wherein, the self-made rotenone kills the active ingredients as follows: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
wherein the starch is 100% wheat starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
In example 2, the preparation method of rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate and rotenone-containing solenopsis invicta killing bait is the same as that of example 1.
Example 3
The rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: 1 part of self-made rotenone killing active ingredient, 62 parts of starch, 6 parts of diatom powder, 6 parts of butter, 10 parts of honey, 1 part of preservative and the balance of water;
Wherein, the self-made rotenone kills the active ingredients as follows: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
wherein the starch is 100% corn starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
In example 3, the preparation method of rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate and rotenone-containing solenopsis invicta killing bait is the same as that of example 1.
Example 4
The rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: 1.4 parts of self-made rotenone killing active ingredient, 63 parts of starch, 7 parts of diatom powder, 6 parts of butter, 10 parts of honey, 1 part of preservative and the balance of water;
Wherein, the self-made rotenone kills the active ingredients as follows: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
wherein the starch is a mixture of wheat starch and corn starch, and the two starch accounts for 50% of the total weight of the wheat starch and the corn starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
In example 4, the preparation method of rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate and rotenone-containing solenopsis invicta killing bait is the same as that of example 1.
Example 5
The rotenone-containing solenopsis invicta killing bait comprises the following components in parts by weight: 1.8 parts of self-made rotenone killing active ingredient, 65 parts of starch, 8 parts of diatom powder, 8 parts of butter, 12 parts of honey, 1 part of preservative and the balance of water;
Wherein, the self-made rotenone kills the active ingredients as follows: sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan aggregate loaded with rotenone;
wherein the starch is a mixture of wheat starch and corn starch, and the two starch accounts for 50% of the total weight of the wheat starch and the corn starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
wherein, the water of the specific example 5 is 4.2 parts;
In example 4, the preparation method of rotenone-loaded dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan aggregate and rotenone-containing solenopsis invicta killing bait is the same as that of example 1.
Comparative example 1
The killing bait comprises the following components in parts by weight: 1 part of self-made active ingredient, 62 parts of starch, 6 parts of diatom powder, 6 parts of butter, 10 parts of honey, 1 part of preservative and the balance of water;
wherein, the homemade active ingredients are: dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan;
wherein the starch is 100% corn starch;
wherein the mesh number of the diatom powder is 200 meshes;
wherein the butter is edible salt-free butter;
wherein the preservative is potassium sorbate;
The synthesis method of the dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan comprises the following steps: 2g of carboxymethyl chitosan is dissolved in 100ml of deionized water to form a first solution; 2.5g of sodium dodecyl polyoxypropylene ether phosphate is dissolved in 200ml of ethanol, then 2.5g of carbodiimides and 1.5g of N-hydroxysuccinimide are added, and stirring is continued for 1h to obtain a second solution;
then heating the first solution to 80 ℃, and then slowly dripping the second solution containing the dodecyl polyoxypropylene ether sodium phosphate while stirring; after the dripping is completed, continuously stirring the mixture for 5 hours at 80 ℃;
Then cooling the mixed solution to 25 ℃, continuing stirring for 12 hours, then precipitating with ethanol, and centrifuging to obtain an intermediate product; and finally, dissolving the intermediate product in water, dialyzing in deionized water for 48 hours, and freeze-drying the dialyzed solution to obtain the final product of dodecyl polyoxypropylene ether sodium phosphate-carboxymethyl chitosan.
A preparation method of a killing bait comprises the following steps: dissolving homemade active ingredients with acetone, and then fully and uniformly mixing the mixed solution with honey and butter; after uniform mixing, adding starch, diatom powder and preservative into the mixed solution, standing until acetone is completely volatilized after full mixing, and finally adding the rest of water, and after uniform mixing, obtaining the killing bait;
Comparative example 2
A commercial red solenopsis invicta killing bait (containing 2.15% imidacloprid) is granular.
The application method of the rotenone-containing solenopsis invicta killing bait comprises the following steps:
s1, physically blending clean sand and cycloxaprid; wherein 0.0025g cycloxaprid powder is blended per 1kg sand;
s2, placing the prepared bait in the sand treated by the cycloxaprid to enable the surface of the bait to be uniformly adhered and covered with sand with the thickness of 2-4mm, wherein the bait is spherical bait with the diameter of 1.5-3 cm;
s3, applying the bait agent wrapped with sand to the vicinity of the solenopsis invicta nest in a ring mode.
In specific practice, the baits prepared in examples 1 to 5 were subjected to the operations of S1 to S3 described above, respectively, to prepare examples 6 to 10, respectively.
Wherein the bait of example 6, i.e. example 1 having performed the above steps S1-S3; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Wherein the bait of example 7, i.e. example 2 having performed the above steps S1-S3; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Wherein the bait of example 8, example 3 in which the above steps S1 to S3 were performed; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Wherein the bait of example 9, example 4 of steps S1-S3 above, is performed; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Wherein the bait of example 10, example 5 of steps S1-S3 above, is performed; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Wherein the bait of comparative example 3, comparative example 1 in which the above steps S1 to S3 were performed; except the above-mentioned differences, the formulation components and the preparation methods are identical.
Example 11
This example 11 is based on example 8, except that the bait of example 11 is used after being placed in a cool, dry and ventilated place for 7d after being prepared.
Test examples
Referring to part 149 of the national standard GBT 17980.149-2009 pesticide field efficacy test guidelines (two): performing a field trapping test on the pesticide for controlling solenopsis invicta; after the bait is applied, 7d, 14d, 21d and 28d are used for investigating the situation of the live formicary, after the formicary is found, an iron rod is used for inserting the formicary into the formicary, if more than 3 workers appear in 60s, the live formicary is judged, and if less than 3 workers or no workers appear, the non-live formicary is judged; and according to the investigation statistical results, the control effect of each example and comparative example is calculated, and the test results are shown in table 1.
TABLE 1
And (3) analyzing results of field trapping and killing tests:
examples 6 to 11 are examples coated with sand treated with a low concentration of cycloxaprid, and the control effect of the sand after the treatment is over 90 percent, so that the killing of the solenopsis invicta in the test area is basically completed;
for the habit of solenopsis invicta, which tends to bury food with soil particles after continuous feeding until saturation, and workers in solenopsis invicta also tend to handle food buried with soil particles;
Examples 6-11, however, further help the solenopsis invicta to find and handle food by manually covering the bait surface with soil particles; the habit of solenopsis invicta is utilized, and the killing effect of the bait is enhanced.
The grease and the honey in the formula can also increase the viscosity of the surface of the bait, and more uniform sand can be adhered by the cooperation of the grease and the honey; and is less prone to failure in severe weather conditions.
Example 11 is an example in which sand is covered, and after the sand is left for 7 days in a cool, dry and ventilated place, the sand is used for field killing, and the test result shows that the sand and the bait are compounded, and the sand and the bait are different from the conventional bait on the market; the bait is kept stand for a period of time, the killing effect of the bait is not affected, and the bait after the sand is compounded has a longer service period.
The comparative example 1 is a comparative example without rotenone, and only sodium dodecyl polyoxypropylene ether phosphate-carboxymethyl chitosan is added, and test results show that after the chitosan is eaten by the solenopsis invicta, the intestinal tract of the solenopsis invicta swells within about one week, so that the death of the solenopsis invicta is induced, and the diatom powder added as an auxiliary material can also cause the death of the solenopsis invicta after being eaten, so that the comparative example 1 has a certain killing capacity in an objective way even though the rotenone is not added; in comparative example 3 in which sand treated with cycloxaprid at a low concentration was coated, the killing rate was also improved to some extent because of the habit of solenopsis invicta, but both did not exceed 50%, and the killing of solenopsis invicta group was insufficient.
However, examples 6 to 11, which act synergistically with each other, have excellent killing effect against the targeted solenopsis invicta, probably because: the dodecyl polyoxypropylene ether sodium phosphate is introduced to modify carboxymethyl chitosan, so that on the basis of ensuring water solubility, the contact area of the modified chitosan to oil is increased, the aim of high solubilization is fulfilled, and the modified chitosan is more salt-resistant and high-temperature-resistant, so that the lipophilicity and biocompatibility of the chitosan are greatly enhanced, and the modified chitosan can be distributed more uniformly in the bait; the modified chitosan has a cross-linked structure, so that the stability and mechanical strength of the modified chitosan are greatly enhanced; after the rotenone is loaded, the rotenone and the bait cooperate, so that the bait has better rotenone controlled release performance in a longer time dimension, has longer lasting effect, and does not need secondary application in the process of killing the solenopsis invicta; the compound soil can be used for a long time after being invaded by solenopsis invicta, and presents a scene with more complex soil physicochemical properties; therefore, the method has wider use scenes aiming at invasion of solenopsis invicta.
Comparative example 2 is a commercial particulate solenopsis invicta killing bait containing 2.15% imidacloprid; the killing effect of the red fire ant reaches 44% in the initial stage of field trapping and killing, but the number of the red fire ants in the field is not effectively controlled; the possible reasons are: after the first few days of the killing activity, the bait of the comparative example 2 fails due to environmental factors such as strong wind, rainfall and the like, so that the subsequent killing effect on the solenopsis invicta is not achieved, and the better killing effect can be achieved only by manually and secondarily applying the pesticide.
Examples 1-5, without sand coating, showed substantially no reduction in the number of killing of solenopsis invicta during the period of 21d-28d, and the baits of examples 1-5 could fail due to environmental factors during the period of 21d-28 d; however, the overall disposable solenopsis invicta killing rate was also higher than comparative example 2;
In conclusion, when the bait is applied, the application method of the application has the best killing effect on the solenopsis invicta.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.