CN107668195A - Fludioxonil combines application of the cinnamic acid in preventing and treating fruit, vegetable storage disease - Google Patents

Abstract

The invention discloses the application of fludioxonil combined with cinnamic acid in preventing and controlling diseases of fruit and vegetable storage, and the diseases are botrytis cinerea and garlic cinerea caused by Botrytis cinerea. For specific applications, fludioxonil and cinnamic acid are compounded into a fungicidal composition, diluted with water, sprayed or dipped on the surface of fruits and vegetables, and after drying, they can be stored in a cold storage routinely; in the fungicidal composition, fludioxonil The weight ratio to cinnamic acid is 1-5:1-3, preferably 1-3:1, more preferably 3:1, 2:1, 1:1. An antiseptic and fresh-keeping agent is also disclosed: 0.5%-50% of fludioxonil, 0.5%-15% of cinnamic acid, and the balance is allowed and acceptable auxiliary materials in pesticide science. The present invention has the following advantages: (1) obvious synergistic effect; (2) reducing the amount and frequency of use of chemical fungicides; (3) combined use of medicaments with different action mechanisms to delay the generation of fungicide resistance; (4) The anti-corrosion and fresh-keeping effect of fruit and vegetable products is more significant.

Description

Application of Fludioxonil Combined with Cinnamic Acid in the Prevention and Control of Storage Diseases of Fruits and Vegetables

technical field

The invention relates to the application of fludioxonil combined with cinnamic acid in preventing and curing diseases of fruits and vegetables during storage, and belongs to the field of prevention and treatment of post-harvest diseases of fruits and vegetables.

Background technique

With the development of science and technology, people's living standards are gradually improving, and the demand for fruits and vegetables produced in different seasons and regions is increasing. However, after fresh fruits and vegetables are harvested, they still undergo complex physiological, biological and physical changes. The cells and tissues of fruits and vegetables continue to respire and transpirate, which is prone to rot, wilting, deterioration and other phenomena, which affects the quality of fruits and vegetables. and sales. Therefore, preservation of fruits and vegetables is a very important issue in the production, storage and sales of fruits and vegetables. Botrytis cinerea is an important pathogen that causes postharvest rot and deterioration. It can harm many fruits and vegetables such as cherries, strawberries, peaches, apples, pears, tomatoes, cucumbers, eggplants, and leeks. It causes serious harm and is also an important disease during storage.

Commonly used chemical fungicides for the prevention and control of Botrytis cinerea in production, such as carbendazim, dimethocarb, iprodione, pyrimethanil, etc., but Botrytis cinerea has the characteristics of rapid reproduction, large genetic variation, and high suitability, so continuous use of the same Chemicals are easy to produce drug resistance, which brings great difficulties to the prevention and control. Only by increasing the dosage or frequency of application to control the rot and deterioration of fruit and vegetable products is not good for improving the antiseptic effect or ensuring the quality of fruits and vegetables. At the same time, as people pay more attention to food safety issues, the residual toxicity of fungicides has been paid more and more attention. It is necessary to look for safer, broad-spectrum, and less-used fungicide combinations to reduce the use of chemical fungicides and delay the development of drug resistance. Production is the research hotspot of antisepsis and fresh-keeping after harvesting fruits and vegetables, and is also a technical problem to be solved in the present invention.

Fludioxonil (fludioxonil) is a non-systemic phenylpyrrole fungicide, which is a secondary metabolite produced by different species of Pseudomonas pyrrocinia (Pseudomonas pyrrocinia) ( pyrrolnitrin), because it is more resistant to photolysis than the natural product nitropyrrolnitrin, and can specifically inhibit molds and is widely used in the prevention and treatment of fungal diseases in agricultural production. Fludioxonil can not only inhibit spore germination, bacterial germ tube elongation, Botrytis cinerea mycelium growth, but also effectively resist Streptococcus (Monilinia spp.), Sclerotinia spp. Mold (Penicillium expansum) and other fungi have good control effects on pathogenic bacteria such as Ascomycetes, Basidiomycetes, and Deuteromycetes.

Cinnamic acid, also known as β-phenylacrylic acid, 3-phenyl-2-acrylic acid, is an organic acid isolated from cinnamon bark or benzoin. Mainly used in flavors and fragrances, food additives, medicine, beauty and so on. Cinnamic acid can be widely added to all foods, and it is already an ingredient allowed to be added in my country's food standard GB2760. At the same time, it has strong fresh-keeping and anti-corrosion capabilities, and can be widely used in the fresh-keeping and anti-corrosion of grain, vegetables, and fruits. It is an environmentally friendly and pollution-free fresh-keeping preservative.

The Chinese patent of CN 103947746 B discloses a method for keeping grapes fresh or making grapes resistant to gray mold. The cinnamic acid solution includes cinnamic acid and water, the final concentration of the cinnamic acid in the cinnamic acid solution is 1-10 mM; the soaking time is 30 seconds.

At present, there is no report about the combination of fludioxonil and cinnamic acid to prevent and control diseases of fruits and vegetables during storage.

Contents of the invention

Aiming at the above-mentioned prior art, the present invention provides a new method for preventing and controlling diseases of fruits and vegetables during storage—combined application of fludioxonil and cinnamic acid.

The present invention is achieved through the following technical solutions:

Application of fludioxonil combined with cinnamic acid in the control of stored diseases of fruits and vegetables.

Preferably, the fruit is selected from grapes, cherries, blueberries, strawberries, peaches, apples, and pears; and the vegetables are selected from tomatoes, cucumbers, eggplants, leeks, and garlic sprouts.

Preferably, the disease is a disease caused by Botrytis cinerea, such as Botrytis cinerea and Botrytis cinerea.

Further, for specific applications, fludioxonil and cinnamic acid are compounded into a bactericidal composition, diluted with water, sprayed or dipped on the surface of fruits and vegetables, and after drying, conventional storage in a cold storage is sufficient; in the bactericidal composition, The weight ratio of fludioxonil to cinnamic acid is 1-5:1-3, preferably 1-3:1, more preferably 3:1, 2:1, 1:1.

Preferably, the bactericidal composition is composed of the following components in parts by weight: 0.5% to 50% of fludioxonil, 0.5% to 15% of cinnamic acid, and the balance is allowed and acceptable excipients in pesticide science; When used, dilute 1000-2000 times with water.

Further, during specific application, the preparation with fludioxonil as active ingredient (during specific application, can be obtained by diluting fludioxonil preparation on site), the preparation with cinnamic acid as active component (during specific application, can be obtained through on-site Dilute cinnamic acid preparation), spray or dip on the surface of fruits and vegetables, after drying, store in cold storage routinely.

An anti-corrosion and fresh-keeping agent, used for anti-corrosion and fresh-keeping of fruits and vegetables during storage, is composed of the following components in parts by weight: 0.5%-50% of fludioxonil, 0.5%-15% of cinnamic acid, and the balance is pesticide The allowed and acceptable excipients in the study.

Allowing to use and acceptable adjuvant is selected from solvent, dispersant, diffusion agent, disintegrant, emulsifier, adsorbent, stabilizer, wetting agent, defoamer, antifreeze etc. and other helpful The use of auxiliaries is allowed for the stability and exertion of the efficacy of the active ingredients.

The antiseptic and antistaling agent can be prepared into any dosage form suitable for agricultural production using known processing methods in the prior art, and the preferred dosage form is: wettable powder, suspending agent, water emulsion, water dispersible granule, microemulsion .

A fresh-keeping method for fruits and vegetables (a method for preventing and controlling diseases during storage of fruits and vegetables): fludioxonil and cinnamic acid are compounded into a fungicidal composition, diluted with water, sprayed or dipped on the surface of fruits and vegetables, and dried in the air Finally, conventional storage in cold storage can be done; in the bactericidal composition, the weight ratio of fludioxonil to cinnamic acid is 1～5:1～3, preferably 1～3:1, more preferably 3:1, 2:1, 1:1 1;

Or: during specific application, the preparation with fludioxonil as active ingredient (during specific application, can be obtained by on-site dilution of fludioxonil preparation), the preparation with cinnamic acid as active ingredient (during specific application, can be obtained by on-site dilution Cinnamic acid preparation), spray or dip on the surface of fruits and vegetables, after drying, store in cold storage routinely.

Preferably, the bactericidal composition is composed of the following components in parts by weight: 0.5%-50% of fludioxonil, 0.5%-15% of cinnamic acid, and the balance is allowed and acceptable auxiliary materials in pesticide science.

The inventors of the present invention have found through tests that the compounding of fludioxonil and cinnamic acid has the following advantages: (1) obvious synergistic effect, the composition has improved the bactericidal activity of fludioxonil to Botrytis cinerea ; (2) Reduce the amount and frequency of use of chemical fungicides, reduce the use cost of fludioxonil, and improve the quality and safety of food; (3) The combined use of medicaments with different mechanisms of action delays the generation of fungicide resistance; (4) The anti-corrosion and fresh-keeping effect of fruit and vegetable products is more significant, which greatly prolongs the shelf life of fruit and vegetable products and improves the economic value of fruit and vegetable products.

detailed description

The present invention will be further described below in conjunction with embodiment.

The instruments, reagents, materials, etc. involved in the following examples, unless otherwise specified, are conventional instruments, reagents, materials, etc. in the prior art, and can be obtained through formal commercial channels. The experimental methods, detection methods, etc. involved in the following examples, unless otherwise specified, are conventional experimental methods, detection methods, etc. in the prior art.

Experimental control effect of combination of fludioxonil and cinnamic acid

1. Test agent: 95% cinnamic acid standard (Shanghai Merrill Chemical Technology Co., Ltd.), 95% fludioxonil technical product (Swiss Syngenta Crop Protection Co., Ltd.), and cinnamic acid is dissolved in DMSO to prepare 100mmol /L of the mother solution, the original drug of fludioxonil was dissolved in acetone, and made into a 10000 μg/mL mother solution, and the emulsifier Tween-80 was added at a volume fraction of 0.2%, stored in the refrigerator at 4°C for later use, and used without Bacterial water was diluted to an appropriate concentration.

2. Pathogenic bacteria for testing: the pathogenic bacteria (Botrytis cinerea) of botrytis cinerea of cherries and garlic sprouts.

3. Indoor toxicity determination method:

The toxicity of fludioxonil, cinnamic acid and their combinations in different ratios was determined by mycelium growth rate method, and the co-toxicity coefficient (CTC) was calculated.

Single-dose toxicity assay method:

First prepare the test agent into 5 concentration gradients (fludioxonil: 0.5, 1.0, 2.0, 4.0, 8.0 mg/kg, etc.; cinnamic acid: 7.5, 15.0, 30.0, 60.0, 120.0 mg/kg, etc. 5 concentration gradients), Botrytis cinerea was pre-cultured on PDA medium at 26°C for 3 days, and a hole punch with a diameter of 7mm was used to punch the fungus cake on the same circle near the edge of the colony, and inoculate it into the medium containing different drug concentrations One piece per dish was placed on a plate and cultured in a 26°C incubator for 3 days. The colony growth diameter of each treatment was measured by the cross method, and water was used as a control, and each concentration treatment was repeated 4 times. Measure the radial linear growth of the colony to determine the inhibitory rate of the agent on the growth of the colony. Through the linear regression analysis between the mycelia growth inhibition probability value and the logarithmic value of the drug concentration, the effective inhibitory concentration (EC ₅₀ value) of each drug to the strain was obtained.

Mixture joint toxicity test:

On the basis of the single-dose toxicity test, the doses of fludioxonil and cinnamic acid for mixing were set according to their EC ₅₀ values in volume ratios of 10:1, 5:1, 3:1, 2:1, and 1, respectively. :1, 1:2, 1:3, 1:5, 1:10, 1:15, a total of 10 ratios, according to different ratios, the final mass concentration is 0.25, 0.5, 1.0, 2.0, 4.0mg/kg 5 serial concentrations of drug-containing PDA medium were used to determine the inhibitory rate of the drug on mycelia growth. Each treatment (per concentration level per strain) was repeated 4 times. Through the linear regression analysis between the mycelia growth inhibition probability value and the logarithmic value of the drug concentration, the _EC50 value and CTC value of the effective inhibitory medium concentration of the mixed drug on the strain were obtained, and the PDA medium without the drug was used as a control.

4. Statistical analysis of data

The experimental data were statistically analyzed by Microsoft Excel 2013 and DPS data processing work platform, and the EC ₅₀ value and 95% confidence limit of each drug were calculated. Use Sun Yunpei's method (1960) to calculate the co-toxicity coefficient of the mixture, and evaluate the synergistic effect of the mixture according to the co-toxicity coefficient.

The inhibition rate of each drug was calculated according to the following formula.

Growth inhibition rate (%)=[(control inhibition zone diameter-treatment inhibition zone diameter)/(control inhibition zone diameter-5mm punching diameter)]×100.

Growth inhibition rate (%)=[(control colony diameter-treated colony diameter)/(control colony diameter-bacteria cake diameter)]×100.

Toxicity index TI=(standard drug EC ₅₀ /test drug EC ₅₀ )×100.

The actual toxicity index ATI of the mixture=(standard drug EC ₅₀ /mixed preparation EC ₅₀ )×100.

Theoretical toxicity index TTI of the mixture = TI of single agent A × PA + TI × PB of single agent B (PA and PB are the percentages of active ingredients in the mixture, respectively).

Co-toxicity coefficient CTC = actual toxicity index ATI of the mixture/theoretical toxicity index TTI of the mixture × 100.

Judgment of synergistic effect: CTC ≥ 120, it has synergistic effect; 80 < CTC < 120, it is additive effect; CTC ≤ 80, it is antagonistic effect.

5. Results and Analysis

Table 1 The toxicity test results of fludioxonil and cinnamic acid mixed in different proportions against Botrytis cinerea

It can be seen from Table 1 that fludioxonil, cinnamic acid and their mixed preparations have a good inhibitory effect on Botrytis cinerea, and when the ratio of fludioxonil to cinnamic acid is between 5:1 and 1:3 , the co-toxicity coefficients to the tested pathogenic bacteria are all above 120, indicating that the two compositions have a good synergistic effect under this ratio, especially when the ratio is between 2:1 and 1:1. The co-toxicity coefficient (CTC) value of the preparation reaches 148.07-151.88, and the synergistic effect is more significant.

Formulation Example 1 16% Fludioxonil · Cinnamic Acid Suspension Concentrate

Components are composed as follows (each component is by weight percentage):

Water topped up to 100%.

The preparation method is as follows: fully mix the above-mentioned active ingredients, various additives and water in proportion, put them into a sand mill, grind to a particle size of 5 μm, and prepare a 16% fludioxonil·cinnamic acid suspension concentrate.

Formulation example 2 12% fludioxonil · cinnamic acid wettable powder

Components are composed as follows (each component is by weight percentage):

Bentonite (filler) makes up to 100%.

The preparation method is as follows: the above-mentioned active components, various auxiliary agents and fillers are fully mixed in proportion, and the mixture is pulverized by an ultrafine pulverizer to obtain a 12% fludioxonil·cinnamic acid wettable powder.

Formulation Example 3 20% Fludioxonil·Cinnamic Acid Emulsion in Water

Components are composed as follows (each component is by weight percentage):

Water topped up to 100%.

The preparation method is as follows: fully mix the above-mentioned active ingredients and various auxiliary agents in proportion to dissolve into a uniform oil phase, and mix the oil phase with the water phase under high-speed stirring to obtain 20% fludioxonil·cinnamic acid water emulsion.

Formulation example 4: 15% fludioxonil·cinnamic acid water dispersible granules

Components are composed as follows (each component is by weight percentage):

Calcium carbonate (filler) made up to 100%.

The preparation method is as follows: fully mix the above-mentioned active ingredients, sodium lauryl sulfate, wetting agent, disintegrant, and filler in proportion, and pulverize them to a particle size of 5 μm in a jet mill to obtain mother powder, and mix the mother powder with alkane The calcium salt of phenylbenzenesulfonate is fully mixed, then granulated, dried and sieved to obtain 15% fludioxonil·cinnamic acid water-dispersible granules.

Formulation example 5: 12% fludioxonil·cinnamic acid microemulsion

Components are composed as follows (each component is by weight percentage):

Water topped up to 100%.

The preparation method is as follows: fully mix the above-mentioned active ingredients and various auxiliary agents in proportion to dissolve into a uniform oil phase, and mix the oil phase with the water phase under high-speed stirring to obtain 12% fludioxonil·cinnamic acid microemulsion.

Biological Example 1: Efficacy Test of Chemical Control on Cherry Postharvest Botrytis

On May 6, 2016, the experiment was carried out in the cherry orchard of Xiazhang Town, Daiyue District, Tai'an City, and the variety was Hongdeng. 15 days before the ripe cherry was picked, each agent was processed (2000 times, 1500 times, 1000 times of 16% fludioxonil cinnamic acid suspension concentrate prepared in embodiment 1; 2000 times of 50% fludioxonil wettable powder, 400 grams/ liter pyrimethanil suspension concentrate 1500 times) and clear water control whole tree spraying once. On May 21st, on the day of picking, select fruits without rot and mechanical damage in each treatment plot, and conduct a fruit dipping test at the same concentration. The fruit dipping time is 1 min, and then placed on sterilized filter paper laid under the trees in the field to dry in the shade. Then transport it back to the Shandong Provincial Fruit Tree Research Institute, pre-cool it in the fresh-keeping warehouse (temperature 0±0.5°C) for 24 hours, then weigh 1.0kg/bag and carefully put it into a PE fresh-keeping bag, and then put it neatly into a plastic fruit packaging box that can be turned over , put 2 bags in each case, 84 cases in total, put into fresh-keeping warehouse (temperature: 0±0.5 ℃, relative humidity: 90%～95%) at last for storage. Three boxes of fruit were taken out from each treatment every 15 days, and the rot rate survey was carried out, and the weight loss rate survey and the determination of the pulp hardness were carried out at 60 days. The peeled fruit hardness was measured with a GY-B hardness tester, and 20 fruit pieces were randomly selected for each treatment. The treatment method at room temperature at 25°C is the same as above.

Statistical analysis method of drug effect: Calculate the drug control effect according to the following formula; use DPS software to perform Duncan's new multiple range test for the difference (P≤0.05).

a.

b.

c.

Table 2 Survey results of various indicators during storage of cherries

Table 3 The efficacy results of 16% fludioxonil·cinnamic acid suspension concentrate in the control of cherry gray mold

It can be seen from Table 2 and Table 3 that after 1500 times and 1000 times of pre-harvest spraying and post-harvest fruit dipping with 16% fludioxonil·cinnamic acid suspending agent, the cherries were stored for 50 days and left the warehouse to investigate various quality indicators, such as decay rate, The weight loss rate was significantly better than 50% fludioxonil wettable powder by 2000 times, 400 g/L pyrimethanil suspension concentrate by 1500 times, and water control. Under refrigerated conditions, before 50 days, the control effect of 16% fludioxonil·cinnamic acid suspension concentrate 1000 times against Botrytis cinerea has been above 90%, and the effect is significantly better than other treatments. At room temperature of 25°C, when stored for 25 days, the 1000-fold treatment of 16% fludioxonil·cinnamic acid suspension concentrate has a control effect of more than 85% on Botrytis cinerea, which is significantly better than other treatments. Therefore, preharvest spraying with 16% fludioxonil·cinnamic acid suspension concentrate and postharvest fruit dipping to treat cherries can inhibit the occurrence of Botrytis cinerea during storage, thereby prolonging the storage period and improving the commerciality of storage.

Biological Example 2: 15% Fludioxonil·Cinnamic Acid Water Dispersible Granules Controlling Garlic Sprout Diseases During Storage Period

On May 1, 2016, the experiment was conducted in the cold storage dedicated to garlic sprouts for farmers in Yushan Town, Jinxiang County. Before garlic sprouts are harvested into the warehouse, add 1500 times and 1000 times to 15% fludioxonil·cinnamic acid water-dispersible granules (prepared in Example 4), 1500 times to 50% fludioxonil WP, and 250 times to 25% prochloraz aqueous emulsion. In the clean water control, soak the garlic sprouts and moss tips for 30 seconds, drain the water and store them in storage. After the garlic sprouts are pre-cooled to -0.3°C±0.2°C, put them into silicon window bags for storage, and manage them in a normal cold storage together with other garlic sprouts. The experimental observation period is 240 days. Each treatment has 4 replicates, and each replicate has 2 bags (approximately 19kg garlic sprouts per bag). The indicators such as the rot rate of garlic sprouts and the color of moss tips were investigated on 90d, 120d, 150d, 180d, 210d and 240d respectively. The results are shown in Table 4.

a.

b.

Table 4 The efficacy results of 15% fludioxonil·cinnamic acid water dispersible granules in the control of gray mold of garlic scape

It can be seen from Table 4 that after 1500 times of 15% fludioxonil·cinnamic acid 1500 times and 1000 times of postharvest soaking treatment, the control effect of garlic sprouts stored for 240 days was above 90%, and the color of the moss was normal, and there was no dehydration phenomenon, showing Good anti-corrosion and fresh-keeping effect, significantly better than 50% fludioxonil wettable powder 1500 times, 25% prochloraz aqueous emulsion 250 times. Therefore, after garlic sprouts are harvested, dipping moss moss with 15% fludioxonil·cinnamic acid water dispersible granule can significantly inhibit the occurrence of gray mold during the storage of garlic sprouts, thereby prolonging the storage period and improving the commerciality of storage.

Claims (10)

1. fludioxonil combines application of the cinnamic acid in preventing and treating fruit, vegetable storage disease.

2. application according to claim 1, it is characterised in that：The fruit be selected from grape, cherry, blueberry, strawberry, peach, Apple, pears；The vegetables are selected from tomato, cucumber, eggplant, leek, garlic stems.

3. application according to claim 1, it is characterised in that：The disease is the microbial disease of Botrytis cinerea, such as Grape grey mould, garlic stems gray mold.

4. application according to claim 1, it is characterised in that：During concrete application, fludioxonil and cinnamic acid compounding are made Bactericidal composition, after being diluted with water, sprinkling or dipping are in fruit, vegetable surface, after drying, freezer normal storage；Sterilization In composition, the weight ratio of fludioxonil and cinnamic acid is 1~5:1~3, preferably 1~3:1, more preferably 3:1、2:1、1:1；

Or：During concrete application, it will be sprayed respectively by the preparation of active component, the preparation using cinnamic acid as active component of fludioxonil Or dipping is in fruit, vegetable surface, after drying, freezer normal storage.

5. application according to claim 4, it is characterised in that：The bactericidal composition is the component group by following parts by weight Into：Fludioxonil 0.5%~50%, cinnamic acid 0.5%~15%, surplus are to allow in Pesticide Science using auxiliary with acceptable Material.

A kind of 6. antisepsis antistaling agent for water fruits and vegetables, it is characterised in that：It is made up of the component of following parts by weight：Cough up Bacterium nitrile 0.5%~50%, cinnamic acid 0.5%~15%, surplus are to allow to use and acceptable auxiliary material in Pesticide Science.

7. antisepsis antistaling agent according to claim 6, it is characterised in that：Allow to use and can receive in the Pesticide Science Auxiliary material be selected from solvent, dispersant, diffusant, disintegrant, emulsifying agent, adsorbent, stabilizer, wetting agent, defoamer, antifreezing agent Deng and other stabilizations for contributing to active ingredient drug effect and performance allow use auxiliary agent.

8. the antisepsis antistaling agent according to claim 6 or 7, it is characterised in that：The formulation of the antisepsis antistaling agent is selected from can WP, suspending agent, aqueous emulsion, water dispersible granules, microemulsion；

When for suspending agent when, be made up of the component of following percetage by weight：

When for wettable powder when, be made up of the component of following percetage by weight：

When for aqueous emulsion when, be made up of the component of following percetage by weight：

When for water dispersible granules when, be made up of the component of following percetage by weight：

When for microemulsion when, be made up of the component of following percetage by weight：

A kind of 9. preservation method of water fruits and vegetables, it is characterised in that：Bactericidal composition is made in fludioxonil and cinnamic acid compounding, After being diluted with water, sprinkling or dipping are in fruit, vegetable surface, after drying, freezer normal storage；In bactericidal composition, fludioxonil Weight ratio with cinnamic acid is 1~5:1~3, preferably 1~3:1, more preferably 3:1、2:1、1:1；

Or：Respectively by using fludioxonil be active component preparation, using cinnamic acid as active component preparation sprinkling or dipping in water Fruits and vegetables surface, after drying, freezer normal storage.

10. the preservation method of water fruits and vegetables according to claim 9, it is characterised in that：The bactericidal composition be by with The component composition of lower parts by weight：Fludioxonil 0.5%~50%, cinnamic acid 0.5%~15%, surplus are to allow to make in Pesticide Science With with acceptable auxiliary material.