CN111084186B - Method for preventing and controlling entomophthora in grains - Google Patents

Method for preventing and controlling entomophthora in grains Download PDF

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CN111084186B
CN111084186B CN201811234052.XA CN201811234052A CN111084186B CN 111084186 B CN111084186 B CN 111084186B CN 201811234052 A CN201811234052 A CN 201811234052A CN 111084186 B CN111084186 B CN 111084186B
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grains
fumigation
hours
fumigant
mould
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CN111084186A (en
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姜标
张琛
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B9/00Preservation of edible seeds, e.g. cereals
    • A23B9/16Preserving with chemicals
    • A23B9/24Preserving with chemicals in the form of liquids or solids
    • A23B9/26Organic compounds; Microorganisms; Enzymes

Abstract

The invention discloses a method for preventing and controlling entomophthora in grains, which utilizes a general formula I:
Figure DDA0001837798710000011
the compound with the chemical structure is used as a fumigant, grains in the granary are fumigated for 1-24 hours at 15-65 ℃, then air is pumped out under reduced pressure for 1-36 hours, and air is replaced by ventilation for 1-36 hours; r in the general formula I is selected from C2‑C4Alkylene radical, C2‑C4Alkynyl, phenyl, benzyl, C3‑C8Cycloalkyl, pyrazolyl, imidazolyl, C3‑C8Any one of cyclic olefin groups. The invention not only realizes the safe and effective control of common entomomycete diseases of grains, but also can realize the safe and effective control of large-harm but difficult-control pests of storehouse flat and house mite, has no problem of fumigant residue, does not influence grain materials and human health, and has the advantages of environmental protection.

Description

Method for preventing and controlling entomophthora in grains
Technical Field
The invention relates to a method for preventing and controlling entomophthora in grains, and belongs to the technical field of grain preservation.
Background
According to the introduction of Liuyang by researchers of agricultural product processing institute of Chinese academy of agricultural sciences: "China invests billions of yuan in full force every year to strive for 1% of grain yield increase, but the grain postpartum loss caused by mildew every year is up to 2100 million tons, which accounts for 4.2% of the total grain yield in China, and the direct economic loss caused is about 180 hundred million to 240 million yuan. "
In addition, mycotoxin pollution also severely restricts foreign trade in China. In recent years, safety events caused by food polluted by mycotoxin frequently occur, so that the health of people and livestock in China is seriously threatened, and the outward trade of agricultural products in China is also restricted. After the illegal event of the edible agricultural products exported from the European Union in the last 10 years of 2002-2011 is statistically analyzed, the following findings are found: among the factors restricting foreign trade in China, such as heavy metal, pesticide and veterinary drug residue, the overproof mycotoxin is the most main reason, and the illegal events caused by the mycotoxin reach 28.6%. It is understood that mycotoxins are the most dangerous food pollutants occurring in nature, whereas aflatoxins, which are 10 times as toxic as potassium cyanide and 68 times as toxic as arsenic, are one of the most prominent causes of liver cancer. The mycotoxin is mainly generated in the process of grain storage after production, and in the process of grain storage in China, the mould mainly comprises aspergillus flavus, fusarium asia and fusarium graminearum; in European and American countries, besides Aspergillus flavus and Fusarium graminearum, there are also Aspergillus parasiticus and Fusarium flavum. Meanwhile, compared with the characteristics of short storage period, single source, small quantity and the like of grain storage in Europe and America, the grain storage in China is mainly characterized by high bacteria carrying capacity, long storage period, wide source, various varieties, impurity and large quantity. In addition, the grains lost due to insect damage in the granary and the transportation process are not small and varied, and after the grains are eaten by the insect damage, the broken grains are increased, and the germination rate of the seeds is reduced; in addition, the pests can block the grains when spinning. The odor liquid secreted by the insect feces, the insect corpses and some pests pollutes the grains and even generates toxin, so that the grains are heated and mildewed. Common barn pests include elephants, khaki, clothiantus, clotheshorse, gelechiid moths, tobacco beetles, cockroaches, indian meal moth, barn pans, barn mites and the like. At present, most grain depots adopt modes such as grain surface pesticide application, bag burying, pipe probing fumigation and insect killing, the used fumigants mainly comprise phosphine, ethylene oxide, methyl bromide and sulfuryl fluoride, and along with the improvement of environmental protection and safety consciousness of people, the limitations of the fumigants are gradually reflected, such as: phosphine is strongly toxic, damages lung, heart, liver, kidney, central nervous system and skeleton, causes asthma, pneumonia or pulmonary fibrosis diseases due to over exposure, and is easy to burn by itself; the denaturing and explosive nature of ethylene oxide; the destructive nature of methyl bromide to atmospheric stratospheric ozone and the direct generation of toxic effects on humans have attracted a great deal of attention. Since the ninth Montreal protocol of 1997 was the meeting of contracting countries, developed countries have agreed to stop using methyl bromide disinfectant gradually from 2005, and China officially signed the Montreal protocol of Copenhagen amendment in 4 months of 2003, and agreed to stop using methyl bromide in agriculture, storage, tobacco and other industries before 1 day of 1 month of 2015. Of course, this promise will also be implemented in food sterilization; sulfuryl fluoride is colorless, toxic and strong irritant gas at normal temperature and pressure, and acute toxicity mainly damages the central nervous system to cause convulsion; in addition, it is deposited in human bone and has accumulated poisoning risk. The latest research finds that the chemical fumigant sulfuryl fluoride becomes a strong greenhouse gas after being emitted into the air, and the effect of one kilogram of sulfuryl fluoride discharged into the atmosphere on global warming is 4800 times that of one kilogram of carbon dioxide; although sulfuryl fluoride is present in air in very small quantities, about 1.5 ppm, i.e., only 1.5 sulfuryl fluoride per million air molecules, it is increasing at a rate of 5% per year, and the atmospheric greenhouse effect caused by the use of sulfuryl fluoride as a substitute for methyl bromide will be a sufficient value!
In summary, how to safely and effectively prevent and control entomophthora in grains has become an urgent problem to be solved in grain storage.
Disclosure of Invention
Aiming at the problems and the requirements in the prior art, the invention aims to provide a method for preventing and controlling food entomophthora in a green, environment-friendly, safe and effective manner.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preventing and controlling entomophthora in grains utilizes a general formula I:
Figure BDA0001837798700000021
the compound with the chemical structure is used as a fumigant, grains in the granary are fumigated for 1-24 hours at 15-65 ℃, then air is pumped out under reduced pressure for 1-36 hours, and air is replaced by ventilation for 1-36 hours; r in the general formula I is selected from C2-C4Alkylene radical, C2-C4Alkynyl, phenyl, benzyl, C3-C8Cycloalkyl, pyrazolyl, imidazolyl, C3-C8Any one of cyclic olefin groups.
Preferably, R in the general formula I is selected from C2-C4Alkylene radical, C2-C4Any one of alkynyl, phenyl, benzyl, pyrazolyl and imidazolyl.
As a further preferred embodiment, R in formula I is selected from C2-C4Any one of alkenyl, phenyl, benzyl and pyrazolyl.
As a further preferred scheme, the fumigant is
Figure BDA0001837798700000022
Figure BDA0001837798700000023
At least one compound of (a).
As a further preferred scheme, the fumigant is
Figure BDA0001837798700000031
A compound is provided.
Compared with the prior art, the invention has the following beneficial effects:
the compound of the general formula I is selected as the fumigant, so that the safe and effective control of common entomophthora diseases of grains is realized, the disposable treatment of various grains and various mildews, bacteria and pests in the same fumigation environment can be realized, the grains subjected to fumigation treatment can be placed in a barn environment or under transportation conditions for at least more than half a year without the entomophthora diseases, the problem of fumigant residue is avoided, the grain material and the human health are not influenced, and the fumigant has the advantage of environmental protection; in particular, when the fumigant is
Figure BDA0001837798700000032
The compound or containing
Figure BDA0001837798700000033
When the compound is used, the compound can simultaneously prevent and control the pests of the granary and the granary mites which are more harmful and difficult to prevent and control, and has important value and profound and remote significance for realizing the safe and long-term preservation of the grains.
Detailed Description
The technical solution of the present invention is further described in detail by examples below.
Example 1
Grain variety: corn, rice, wheat, soybean;
disease: aspergillus, Penicillium, Trichoderma, Rhizopus cereus, Rhizopus, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, bark beetle, Guthei, Binam and Binam mite;
fumigant: vinyl radicalSulfonyl fluorides
Figure BDA0001837798700000034
(CAS:667-25-8);
The treatment method comprises the following steps:
placing the fumigant and the grain sample in a fumigation chamber, sealing the fumigation chamber, controlling the temperature in the fumigation chamber to be 15 ℃, carrying out fumigation for 24 hours, carrying out reduced pressure air exhaust for 1 hour, then carrying out air replacement for 1 hour, finishing the fumigation, taking out the insect cage, and showing that the bark beetle and the grain beetle die but the flat grain and the grain mites do not die.
The following were detected by microscope: the grain sample treated by the fumigation has no mould growth;
and the detection and analysis of a gas chromatograph and mass spectrometer (GC-Ms) show that: the grain sample treated by the fumigation has no fumigant residue.
The grain sample after the fumigation treatment of the embodiment is subjected to mould and insect pest tracking detection at regular intervals in a storage environment, and the detection result is shown in the following table:
storage time 0 month 1 month 3 months old 6 months old 12 months old
Growth of mold Without any mould Without any mould Without any mould Without any mould Without any mould
Rate of killing disease 100% 100% 100% 100% 100%
In addition, the color of the grain sample after the fumigation treatment is observed by a color difference meter without obvious change.
Example 2
Grain variety: corn, rice, wheat, potato;
disease: aspergillus, Penicillium, Trichoderma, Rhizopus cereus, Rhizopus, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, Rhynchosia globerulea, Geotrichum album, Bisph Pan and Bispyri;
fumigant: phenylsulfonyl fluorides
Figure BDA0001837798700000041
(CAS:368-43-4);
The treatment method comprises the following steps:
and (3) placing the fumigant and the grain sample in a fumigation bin, sealing the fumigation bin, controlling the temperature in the fumigation bin to be 20 ℃, carrying out fumigation for 12 hours, carrying out reduced pressure air extraction for 36 hours, ventilating for 36 hours again, finishing the fumigation, and taking out the insect cage, wherein the kholderia and the khapra are seen to die, but the chupan and the chufa are not seen to die.
The following were detected by microscope: the grain sample treated by the fumigation has no mould growth;
and the detection and analysis of a gas chromatograph and mass spectrometer (GC-Ms) show that: the grain sample after the fumigation treatment has no fumigant residue;
the grain sample after the fumigation treatment of the embodiment is subjected to mould and insect pest tracking detection at regular intervals in a storage environment, and the detection result is shown in the following table:
storage time 0 month 1 month 3 months old 6 months old 12 months old
Growth of mold Without any mould Without any mould Without any mould Without any mould Without any mould
Rate of killing disease 100% 100% 100% 100% 100%
In addition, the color of the grain sample after the fumigation treatment is observed by a color difference meter without obvious change.
Example 3
Grain variety: corn, rice, wheat, soybean, sweet potato;
disease: aspergillus, Penicillium, Trichoderma, Rhizopus cerealis, Rhizopus, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, bark beetle, booklice, granary and granary mites;
fumigant: benzylsulfonyl fluorides
Figure BDA0001837798700000051
(CAS:329-98-6);
The treatment method comprises the following steps:
putting the fumigant and the grain sample into a fumigation bin, sealing a fumigation box, controlling the temperature in the fumigation bin to be 30 ℃, carrying out fumigation for 1 hour, carrying out reduced pressure air extraction for 24 hours, ventilating for 24 hours, finishing the fumigation, taking out the insect cage, and observing that the bark beetle and the booklice die, but the flat grain and the bin mites do not die.
The following were detected by microscope: the grain sample treated by the fumigation has no mould growth;
and the detection and analysis of a gas chromatograph and mass spectrometer (GC-Ms) show that: the grain sample after the fumigation treatment has no fumigant residue;
the grain sample after the fumigation treatment of the embodiment is subjected to mould and insect pest tracking detection at regular intervals in a storage environment, and the detection result is shown in the following table:
storage time 0 month 1 month 3 months old 6 months old 12 months old
Growth of mold Without any mould Without any mould Without any mould Without any mould Without any mould
Rate of killing disease 100% 100% 100% 100% 100%
In addition, the color of the grain sample after the fumigation treatment is observed by a color difference meter without obvious change.
Example 4
Grain variety: corn, rice, wheat, soybean, broad bean, potato and sweet potato;
disease: aspergillus, Penicillium, Trichoderma, Rhizopus cereus, Rhizopus, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, Guteer beetle, bark beetle, Chlamydomonas, Bidens and Bismin;
fumigant: 2-methylpropan-2-enyl-1-sulfonyl fluoride
Figure BDA0001837798700000052
(CAS:847661-06-7);
The treatment method comprises the following steps:
putting a fumigant and a grain sample into a fumigation bin, sealing the fumigation bin, controlling the temperature in the fumigation bin to be 25 ℃, performing fumigation for 24 hours, performing reduced pressure air extraction for 24 hours, ventilating for 24 hours, finishing the fumigation, and taking out the insect cage, wherein the pests such as the rice beetle, the bark beetle, the clotheshfish and the clothespin die but the mites in the bin are not die.
The following were detected by microscope: the grain sample treated by the fumigation has no mould growth;
and the detection and analysis of a gas chromatograph and mass spectrometer (GC-Ms) show that: the grain sample after the fumigation treatment has no fumigant residue;
the grain sample after the fumigation treatment of the embodiment is subjected to mould and insect pest tracking detection at regular intervals in a storage environment, and the detection result is shown in the following table:
storage time 0 month 1 month 3 months old 6 months old 12 months old
Growth of mold Without any mould Wuren-freeWhat kind of mould Without any mould Without any mould Without any mould
Rate of killing disease 100% 100% 100% 100% 100%
In addition, the color of the grain sample after the fumigation treatment is observed by a color difference meter without obvious change.
Example 5
Grain variety: corn, rice, wheat, soybean, broad bean, potato and sweet potato;
disease: aspergillus, Penicillium, Trichoderma, Rhizopus cerealis, Rhizopus, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, bark beetle, booklice, granary and granary mites;
fumigant: 1H-pyrazole-1-sulfonyl fluoride
Figure BDA0001837798700000061
(CAS:666-97-7);
The treatment method comprises the following steps:
putting the fumigant and the grain sample into a fumigation bin, sealing a fumigation box, controlling the temperature in the fumigation bin to be 65 ℃, carrying out fumigation for 2 hours, carrying out reduced pressure air extraction for 24 hours, ventilating for 36 hours, finishing the fumigation, taking out the insect cage, and showing that the bark beetle, the booklice, the bin flat and the bin mites all die.
The following were detected by microscope: the grain sample treated by the fumigation has no mould growth;
and the detection and analysis of a gas chromatograph and mass spectrometer (GC-Ms) show that: the grain sample after the fumigation treatment has no fumigant residue;
the grain sample after the fumigation treatment of the embodiment is subjected to mould and insect pest tracking detection at regular intervals in a storage environment, and the detection result is shown in the following table:
storage time 0 month 1 month 3 months old 6 months old 12 months old
Growth of mold Without any mould Without any mould Without any mould Without any mould Without any mould
Rate of killing disease 100% 100% 100% 100% 100%
In addition, the color of the grain sample after the fumigation treatment is observed by a color difference meter without obvious change.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention should be covered by the scope of the present invention.

Claims (1)

1. A method for preventing and controlling grain bin flat or/and bin mites comprises the steps of fumigating grains in a grain bin for 1-24 hours at 15-65 ℃ by using a fumigant, then carrying out reduced pressure air extraction for 1-36 hours, and then carrying out air replacement for 1-36 hours by using air; the method is characterized in that: the fumigant is
Figure DEST_PATH_IMAGE002
A compound is provided.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106343013A (en) * 2015-07-19 2017-01-25 中国科学院上海有机化学研究所 Grain storage method
CN106973990A (en) * 2016-01-19 2017-07-25 中国科学院上海有机化学研究所 A kind of fumigating method for being used to prevent and treat grain entomophthora

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106343013A (en) * 2015-07-19 2017-01-25 中国科学院上海有机化学研究所 Grain storage method
CN106973990A (en) * 2016-01-19 2017-07-25 中国科学院上海有机化学研究所 A kind of fumigating method for being used to prevent and treat grain entomophthora

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