CN1053558C - Combined use of Chemicals and microbials in termite control - Google Patents

Combined use of Chemicals and microbials in termite control Download PDF

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CN1053558C
CN1053558C CN93100386A CN93100386A CN1053558C CN 1053558 C CN1053558 C CN 1053558C CN 93100386 A CN93100386 A CN 93100386A CN 93100386 A CN93100386 A CN 93100386A CN 1053558 C CN1053558 C CN 1053558C
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termite
soil
fungi
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CN1080474A (en
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W·M·泽克
D·E·西蒙内特
D·A·普赖斯
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Bayer AG
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Abstract

A composition for termite treatment composed of an effective amount of (1) a chemical termiticide selected from pyrethroids, pyrazolines, nitroguanidines and nitromethylenes and (2) an entomopathogenic fungus or bacterium preferably a fungus selected from either the Conidiobolus genus or the Paecilomyces genus or the Veauveria genus or the Metarhizium genus. The chemical termiticide is applied at a site where termites have been observed or are suspected to be present. The fungus or bacterium need not be applied to the site where the termites have been observed if the fungus or bacterium is already present at that site.

Description

Go out and remove the composition of termite and go out except that the method for termite
The present invention relates to a kind of going out except that the method and the composition that is used for this eliminating method that goes out of termite.
Known have many chemicals can kill termite under particular concentration, the instantiation of such chemicals comprises that cyfloxylate (is disclosed in for example United States Patent (USP) 4,218, in 469), unden (is disclosed in for example United States Patent (USP) 3,111, in 539), nitrile chlorobenzene phenothrin (is disclosed in for example United States Patent (USP) 4,061, in 664), isofenphos (for example be disclosed in United States Patent (USP) 3,621,082 in), Fenvalerate (is disclosed in for example United States Patent (USP) 4,024, in 163) and 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine (for example be disclosed in United States Patent (USP) 4,742,060 in).
Known certain micro-organisms, particularly some insect pathomycete and bacteriums, the relevant adverse effect that also causes under certain conditions with the termite colony.Referring to, for example, Ko, W.H., et al, " TheNature of Soil Pernicious to Coptotermes Formosanus ", JournalofInvertebrate Pathology, the 39th volume, 38-40 page or leaf (1982).
But various known termiticides, bacterium and fungi all have some characteristics, and these characteristics make it industrial undesirable.For example, many known chemicals and microorganism must be used with very big rate of application, so that uneconomical, also be that environment is unallowed.Also usually effect is too slow for known termiticide, can not guarantee its successfully application in practice.The effect of many known termiticides depends on the specific environment of using them, and therefore many uncontrollable factors may have a negative impact to it.
Have now found that, with the chemicals of specific type be selected from the fungi of Special Category or bacterium combines when being used for handling the place that termite haunts, produced the synergy of beyond thought control termite.When being used in combination, the rate of application when rate of application is significantly less than chemical termiticide and each independent use of microorganism.The chemicals of combination of the present invention and fungi or bacterium act on a couple of days rather than in several weeks as seen.This combination make people may realize stronger, have more meaning and the control of more economical termite.
Advantageous particularly part of the present invention is that it does not use chlorinated hydrocarbon, and the latter is the one group of chemicals of controlling termite that uses the most widely.The present invention control during termite based on a kind of so new notion, promptly be used in combination the residual action chemical reagent littler, and use and handle the haunt application technique in place of termite that drug effect reduces again than known termiticide with biological agent.
An object of the present invention is to provide the bond of chemical reagent and biological substance, this bond can go out except that termite effectively.
Another object of the present invention provides a kind of composition, the environmental problem that there is not chlorinated hydrocarbon in said composition and is caused, and do not need a large amount of uses just can be effective.
A further object of the invention provides a kind of method of controlling termite effectively.
These and other conspicuous purposes concerning the professional of this area realize by a kind of composition, described composition comprises the nitrofuanidine that is selected from of (1) effective dose, the nitromethane class, the fungi that the chemicals of pyrazolines and pyrethroid and (2a) insect pathomycete, preferred ear mould (Conidiobolus) entomophthora belong to (Entomophthora) or green muscardine fungus (Metarhizium) belongs to or goitre mite Paecilomyces varioti (Paecilomyces) or white muscardine fungi (white muscardine fungi (Beauveria)) or radiation trichobacteria (radiation trichobacteria (Actinomucor)) are planted or (2b) carnivorism bacterium such as Serratia (Serratieae (Serratia)).The consumption of chemicals should make it be 1ppm for 0.01ppm at least or in bait usually in handled medium (as soil).The consumption of fungi or bacterium should make usually when contacting with termite, has at least 100 spores, preferably at least 1000 spores in the handled medium of every gram.The optimised quantity of fungi or bacterium depends on used concrete fungi or the kind of bacterium.This processing method can be to use with the same way as that is used to use other known chemical termiticides.Composition of the present invention also can be used for the bait formula neutralization and is used for handling the place of having handled again.
The present invention relates to the termiticide be made up of following component, described component is (1) at least a chemicals that is selected from following material: (a) nitrofuanidine such as 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine; (h) nitromethane class such as 1-(2-chloro-5-pyridylmethyl)-2-(Nitromethylene) imidazolidine; (c) pyrazolines; (d) pyrethroid such as cyfluthrin, and or (2a) insect pathomycete such as ear mould (Conidiobolus) be (Entomophthora) or the fungi that belongs to of green muscardine fungus (Matarhizium) or goitre mite Paecilomyces varioti (Paecilomyces) or white muscardine fungi (Beauveria) or radiation trichobacteria (Actinomucor) or (2b) carnivorism bacterium such as Serratieae (Serratia).
The termiticide chemicals that is used for the present invention's practice is a known substance, can be by any known technology preparation.For example disclose some concrete nitrofuanidines and nitromethane compounds and preparation method thereof in following disclosed application and patent: EP 464,830; EP 428,541; EP 425,978; DE 36 39 877; DE 37 12 307; US 5,034, and 524; EP 386,565; EP 383,091; EP 375,907; EP 364,844; JP 02.207 083; EP 315,826; EP 259,738; EP 254,859; JP 63307,857; JP 63 287, and 764; EP 235,725; EP 212,600; EP 192,060; EP163,855; EP 154,178; EP 136,636; US 4,948, and 798; EP 303,570; EP302,833; US 4,918, and 086; EP 306,696; FR 2,611, and 114; EP 183,972; EP455,000; JP A3 279,359; JP A3,246,283; WO91/17,650; WO91/104,965; US 5,039, and 686; EP 135,956; US 5,034, and 404; EP 471,372; EP 302,389; JP 3,220, and 176; Brazil 8,803, and 621; JP 3,246, and 283; JP A92/9371; And JP 3,255,072.
For example, United States Patent (USP) 4,742,060 discloses, and 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine can be by at room temperature being prepared by the toluene solution and the cyanogen bromide reaction of N-(2-chloro-5-pyridylmethyl) ethylenediamine.1-(2-chloro-5-the pyridylmethyl)-2-imido imidazolyl alkane hydrobromate of formation like this is reacted with sulfuric acid and fuming nitric aicd again.Remove dichloromethane solvent, reclaim desired 1-(2-chloro-5-pyridylmethyl) 2-(nitro imino group) imidazolidine.
Be applicable to that the chemical termiticide of the present invention in putting into practice represent with following formula:
Figure C9310038600091
In the formula, R represents acyl group, the alkyl of hydrogen, acyl group, replacement, alkyl, aryl, aryl, the heterocyclic radical of replacement or the heterocyclic radical that replaces of replacement;
A representative or (1) are selected from the monofunctional group of following groups: the aryl of the acyl group of hydrogen, acyl group, alkyl, aryl, replacement, the alkyl of replacement, replacement, perhaps (2) double functional group of being connected with Z;
E represents electron withdraw group;
X represents N or CH; And
Z representative or (1) are selected from the monofunctional group of following groups: the heterocyclic radical of the aryl of the alkyl of the acyl group of hydrogen, acyl group, replacement, alkyl, replacement, aryl, replacement, heterocyclic radical, replacement, OR, NR 2, SR, perhaps (2) double functional group of being connected with A or X.
The acyl group of preferred acyl group and replacement comprises the aryl phosphoryl of alkyl phosphoryl, aryl phosphoryl and replacement of aryl sulfonyl, alkyl phosphoryl, the replacement of alkyl sulphonyl, aryl sulfonyl, the replacement of aryl carbonyl, alkyl sulphonyl, the replacement of alkyl-carbonyl, aryl carbonyl, the replacement of alkyl-carbonyl, replacement.
Preferred alkyl substituent comprises: any C-C alkyl that replaces, the particularly C that replaces arbitrarily 1-C 4Alkyl, most preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl or the tert-butyl group.
Preferred aryl groups comprises: phenyl and naphthyl, the most preferably phenyl that can replace arbitrarily.
Preferred heterocyclic radical comprises: have maximum 10 atoms wherein to have the aromatic ring of N, an O or S (particularly N) at least on the ring.Particularly preferred heterocycle is thienyl, furyl, thiazolyl, imidazole radicals, pyridine radicals and benzothiazolyl.
For above-mentioned acyl group, alkyl, aryl and heterocyclic radical, suitable substituents comprises: alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and the tert-butyl group with 1-4, preferred 1 or 2 carbon atom; Alkoxyl such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy with 1-6, preferred 1 or 2 carbon atom; Alkylthio group such as methyl mercapto, ethylmercapto group, positive rosickyite base, different rosickyite base, positive butylthio, isobutyl sulfenyl and uncle's butylthio with 1-4, preferred 1 or 2 carbon atom; Have 1-4, preferred 1 or 2 carbon atom and 1-5, the haloalkyl of preferred 1-3 halogen atom, halogen atom wherein can be identical or different, particularly F, Cl or Br (most preferably fluorine), for example trifluoromethyl; Hydroxyl; Halogen such as fluorine, chlorine, bromine and sulphur, particularly fluorine, chlorine and bromine; Cyano group; Nitro; Amino; The alkyl monosubstituted amino and the dialkyl amido that contain 1-4, preferred 1 or 2 carbon atom in the alkyl are as methylamino, methyl-ethyl-amino, n-propylamine base, isopropylamino and methyl-normal-butyl-amino; Carboxyl; Alkoxy carbonyl group such as methoxycarbonyl group and carbethoxyl group with 2-4, preferred 2 or 3 carbon atoms; Sulfo group (SO 3H-); Alkyl sulphonyl such as mesyl and ethylsulfonyl with 1-4, preferred 1 or 2 carbon atom; And the aryl sulfonyl such as the benzenesulfonyl that on aromatic ring, have 6-10 carbon atom.
In formula I, A and Z can form together have 5-7 in the ring, the saturated or unsaturated heterocycle of preferred 5 or 6 atoms.This ring can contain 1 or 2 hetero atom such as O, S, N or N-alkyl.If in the ring two atoms being arranged is not carbon, these two atoms can identical (as two N) or difference (as a N, an O).
The instantiation of the electron withdraw group of E representative comprises NO, CN and halogenated alkyl carbonyl as 1 among the formula I, 5-halo-C 1-C 6Alkyl-carbonyl.
In formula I, Z and X can form together 5-7 in the ring, the heterocycle of preferred 5 or 6 atoms, this ring can contain 1 or 2 heteroatom such as O, S, N or N-alkyl, and heteroatom can be identical or different.The instantiation of preferred heterocycle comprises pyrrolidines, piperidines, piperazine, hexamethylene imine, morpholine and N methyl piperazine.
Preferred compound is following compound in the formula I scope, wherein
A and Z respectively represent hydrogen, can substituted alkyl, can substituted acyl group, can substituted phosphate or NR ' R " group; wherein R ' and R " respectively represent hydrogen or alkyl or 5 or 6 yuan of rings replacing arbitrarily of representative together; this ring can contain N or S as one of its ring person
E represents electron withdraw group such as NO 2, CN or COCF 3,
X represents N or CH, and
R represent hydrogen, can substituted pyridine radicals, pyridyl alkyl, thiazolyl alkyl, alkylthio alkyl or 5 or 6 yuan of rings, this ring contains O, N or S as one of its ring person, this ring can be replaced by one or more halogens, alkyl, haloalkyl or nitro.
Particularly preferred compound comprises following formula I compound, wherein,
Z represents NH, CH or NR ' R ", wherein R ' and R " is alkyl one of at least,
A represents alkyl,
A and Z represent nitrogenous 5 or 6 yuan of sulfur-bearing 5 or the 6 yuan of rings that encircle or replaced by alkylthio arbitrarily that replaced by alkylthio arbitrarily together,
E represents CN or NO 2,
X represents N or CH, and
R represents 5 or 6 yuan of rings, and this ring contains O, N or S as its at least one ring person, and this ring is at random replaced by halogen or alkyl; With the compound of formula II representative,
Figure C9310038600111
In the formula,
N represents 1 or 2,
Above the Y representative as suitable substituents to the described any substituting group of the acyl group among the formula I, alkyl, aryl and heterocyclic radical, be preferably halogen, chlorine most preferably,
A, Z, X and E have the meaning in formula I, and formula (III) compound: A, Z, X, E, Y and n have the meaning in formula I and II in the formula.
The instantiation that can be used for nitrofuanidine of the present invention and nitromethane compounds and their related analogs comprises:
3-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) thiazolidine;
1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine;
1-(2-chloro-5-pyridylmethyl)-2-(Nitromethylene) imidazolidine;
Figure C9310038600122
Figure C9310038600131
R represents the aryl of alkyl, aryl or the replacement of hydrogen, alkyl, replacement in the formula,
Figure C9310038600141
Figure C9310038600151
Figure C9310038600152
With
Figure C9310038600161
Particularly preferred nitrofuanidine and nitromethane compounds are 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidines.
When using with the form of bait, the consumption of nitroguanidine and nitromethane compounds should account at least 0.0001% (weight) of total bait component usually, is preferably about 0.001~10.0% (weight), most preferably is about 0.01~1.0% (weight).When nitroguanidine or nitromethane compounds directly being mixed soil or directly are applied to handled surface, its consumption should make it contain 0.01ppm (1,000,000 umber) at least in soil or on the handled surface usually, preferred about 0.1~1000ppm most preferably is about 1~300ppm.
The pyrethroid that can be used in the present composition is known.Naturally occurring and synthetic chrysanthemum ester all is suitable for.The example of suitable pyrethroid comprises: cinerins, the cinerin class, the jasmolin class, allethrin [2-methyl-4-oxo-3-(2-acrylic)-2-cyclopentene-1-base-2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropanecarboxylcompound], dextrorotation counter-propylene chrysanthemum ester (D-trans-allethrin), barthrin [6-chloro-1,3-Ben Bing Er Evil penta ring-5-yl) methyl 2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropanecarboxylcompound], tetramethyl chrysanthemum ester [(1,3,4,5,6,7-six hydrogen-1,3-dioxo-2H-iso-indoles-2-yl) methyl 2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropanecarboxylcompound], alkynes sugar chrysanthemum ester [[5-(2-propynyl)-2-furyl] methyl 2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropane carboxylic acid ester ester], resmethrin [[5-(phenyl methyl)-3-furyl] methyl 2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropanecarboxylcompound], bioethanomethrin[[5-(phenyl methyl)-yl)-3-furyl] methyl 3-(ring pentylidene methyl)-2,2-dimethyl cyclopropane carboxylic acid ester], phenothrin [(3-Phenoxyphenyl) methyl 2,2-dimethyl-3-(2-methyl isophthalic acid-acrylic) cyclopropanecarboxylcompound], fenpropathrin [cyano group (3-Phenoxyphenyl) methyl 2,2,3,3-4-methyl cyclopropane carboxylic acid ester], Permanone [(3-Phenoxyphenyl) methyl 3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, cyfloxylate [cyano group (4-fluoro-3-Phenoxyphenyl) methyl-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], Fenvalerate [cyano group (3-epoxy and phenyl) methyl 3-(2, the 2-dichloroethylene)-2,2-dimethyl-cyclopropanecarboxylcompound], decis [cyano group (3-Phenoxyphenyl) methyl 3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester], nitrile chlorobenzene phenothrin [cyano group (3-Phenoxyphenyl) methyl 4-chloro-α-(1-Methylethyl) phenylacetate, and cyfloxylate [cyano group (3-Phenoxyphenyl) methyl 3-(2-chloro-3,3,3-three fluoro-1-acrylic)-2,2-dimethyl cyclopropane carboxylic acid ester].Particularly preferred pyrethroid is cyfloxylate and nitrile chlorobenzene phenothrin.
The consumption of pyrethroid in the bait composition should use it to account at least 0.0001% (weight) of bait composition weight, preferred about 0.001-10.0% (weight) usually, most preferably is about 0.01~1.0% (weight).When pyrethroid directly is added in the soil or directly is applied to handled when surface, its consumption should make it have preferred about 0.1~1000ppm, most preferably about 1.0~300ppm with the concentration of 0.01ppm at least usually.
Also can use any known pyrazoline compounds and analog thereof of the present invention in going out except that the termite composition.Such pyrazoline compounds and analog thereof are disclosed in for example disclosed european patent application 0,438,690.The suitable pyrazoles miaow compound and the example of analog thereof comprise those pyrazoline compounds and the analog thereof of following various representative:
Figure C9310038600191
α represents halogen atom, alkyl, halogen or nitro in the formula.
The consumption of pyrazoline in the bait composition should make it account at least 0.0001% (weight) of bait composition weight, preferred about 0.001-10.0% (weight) usually, most preferably is about 0.01~1.0% (weight).When pyrazoline directly is added in the soil or directly is applied to handled when surface, its consumption should make it have preferred about 0.1~1000ppm, most preferably about 1.0~300ppm with the concentration of 0.01ppm at least usually.
Of the present invention go out except that the termite composition in used natural being present in the soil of fungi, and can be at an easy rate from wherein separating.Ear mould (Entomophthora) the genus fungi that can be used in the termiticide of the present invention comprises that Conidiobolus coronatus (Conidiobolus coronatus), Conidiobolus virulenta and Conidiobolus obscura. particularly preferably are Conidiobolus coronatus.
Can be used for green muscardine fungus of the present invention and belong to that fungi is natural to be present in the soil, and can be at an easy rate from wherein separating.Various green muscardine funguss (Metarhizium anisopliae) bacterial strain all can be used for the present invention.Most preferably F52 bacterial strain of green muscardine fungus (BIO 1020, DSM Number 3884) and MADA bacterial strain (deriving from the University of Florida) (CBS Number326, Baarn, Netherlands).
Can be used for goitre mite Paecilomyces varioti (Paecilomyces) in the termiticide of the present invention and belong to fungi and comprise paecilomyces farinograph (Paecilomyces farinosus), this fungi is natural to be present in the soil and can easily to separate from soil or from the back and forming the termite of spore of causing a disease by the known method of this area professional.
Preferred Beauveria fungi is the stiff bacterium (Beauveria bassiana) of ball spore, its also natural being present in the soil, and can easily from soil or the termite after causing a disease and that form spore, separate by the known method of this area professional.
Fungi also can be used in the practice of the present invention the radiation trichobacteria.
Can be used for bacterium of the present invention and comprise the Serratieae bacterial classification, these bacterial classifications are natural to be present in the soil, and can easily separate from soil or from the back and forming the termite of sporozoite of causing a disease by the known method of this area professional.
Content of described fungi or bacterium and existence form should make in every gram medium usually at least 100 spores, preferably at least 1000 spores.Certainly optimised quantity depends on used bacterial classification.
Termiticide of the present invention can use with following form: natural and synthetic that powder, solution, suspension, emulsion, foam, cream, particle, aerosol, usefulness reactive compound and fungi were handled and the tiny capsule in polymer.When with powder or particle form, fungi can be added in soil-nitroguanidine, nitromethane, pyrazoline or the pyrethroid Recipe with suitable amount.Can comprise at random that in final composition other additives known of using for termiticide are as expanding agent, attractant, the analeptic of looking for food, pheromones.The example of suitable dust carrier comprises clay, talcum, lime and pyrophyllite.
Termiticide of the present invention also can use with various liquid forms.The suitable liquid-carrier of using for termiticide comprises water and atent solvent.Usually other additives such as the emulsifier that can be used in the insecticidal liquid agent formulation also can be included in the liquid formulations of termiticides of the present invention.The liquid preparation of chemicals and/or fungi preparation also can comprise lignin, hydrocellulose, bentonite, pectin or use after preparation is solidified any other material.
Chemical compound and fungi or bacterium can be applied in the medium successively.When this technology of use, can apply chemical compound earlier, also can apply fungi earlier.The time interval that applies chemical compound and fungi can be as short as a few minutes, also is a couple of days even several weeks.If suitable fungi or bacteria culture have been present in the medium to be processed as the naturally occurring material with essential spore density, then do not need to add fungi or bacterium, only need add chemical compound.These processing also can be carried out to guarantee long-acting with well-regulated or random intermittence repeatedly.
Termiticide of the present invention can resist all types of termites effectively, and found that they are to underground cave termite eastern subterranean termite (Reticulitermes flavipes) and Chamaecyparis formosensis formosanus) termite, (Coptotemes formosanus) is effective especially for coptotermes formosanus.
Below just understand beat all synergy in conjunction with the given tables of data of the effect of using chemicals and biological agent.If these medicaments are used to separately go out except that termite, reach and use identical the going out that is obtained by combination of the present invention and remove the termite effect, then their rate of application want high ten times several powers doubly.
The present invention described above, the following example is used for illustrating the present invention.Except as otherwise noted, otherwise all umbers that provide in these embodiments and percentage all are parts by weight and weight percent.
Embodiment
Embodiment 1-5 explanation with the chemical termiticide of independent usefulness or go out with fungi separately and compare except that termite, reaches high termite at short notice with chemical termiticide binding to fungal and goes out except that degree.The interaction of embodiment 6 and 7 explanation Conidiobolus coronatus and the agent of various pest control with insecticide ant in going out except that termite.Embodiment 8,9 and 10 illustrates the interaction of two fungal pathogens that 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidines and Conidiobolus and green muscardine fungus belong to.Embodiment 11 explanation 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidines and three kinds of other fungi kinds and the synergy of a kind of bacterium.Embodiment 12 explanation in bacterium soil is arranged microorganism and the synergy between various nitromethane class and the nitrofuanidine.
Embodiment 1
In described each sample of table 1, use the 100g sterile soil.Control sample A does not handle with nitroguanidine, nitromethane, pyrethroid, pyrazoline or fungi.1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine is directly added in the soil among sample B, C, D, E and the F with various concentration (shown in the table 1).In the soil of these samples, do not add fungi.The filter paper disk that soaked in the solution of the 1-with concentration shown in the table 1 (2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine is placed on above the soil among sample G, H and the I.In the soil of sample G, H or I, there is not fungi.In the soil of sample J, do not add nitroguanidine, but sample J comprises the soil that is obtained by used container in the previous test that wherein has the fungi Conidiobolus coronatus naturally, in soil pattern K, use the soil that wherein has the previous test of fungi Conidiobolus coronatus naturally, but in addition, will add to termite with the filter paper that 0.01% nitroguanidine soaks.
Then, 1g subteranean termites eastern subterranean termite is added in each of soil pattern A-K.Observed result in 18 days is listed in the table 1 afterwards.
Can obviously see by the data in the table 1,, in soil, must have the 1ppm nitroguanidine in order to reach obvious effect and last (after exposing 18 days) 100% lethality to termite.(nitroguanidine as 10~100ppm) can obviously not change this result to use higher proportion in soil.
When using nitroguanidine with the form (promptly on the filter paper of handling) of poison bait, more a spot of nitroguanidine (promptly 0.001%; 0.003% and 0.010%) has same effect with the big consumption that is used to handle soil.
Data in the table 1 show that also when only applying fungi (promptly not using nitroguanidine) in soil, the gained result is the same with the result who observes in undressed control sample.That is, observe strong tunnel-effect and location in sample container bottom.Yet when the filter paper disk of existing 0.01% nitroguanidine was placed on the soil that has fungi on it, the termite of 100% in the sample died in two days.
Table 11-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine is handled PPM/% to the effect sample of termite and is observed (18 days)
Nitroguanidine A comparison-----strong tunnel, termite all is
Healthy and in the bottom 8 soil 100ppm termites get lost 80-90%
From the teeth outwards, do not take food 14
Gradually hungryly after it partly get lost to the identical E soil with sample B of the dead C soil 10ppm 1ppm of identical D soil with sample B 0.1ppm; Only has fungi in the upper earth of the identical G filter paper 0.01% identical H filter paper 0.003% identical I filter paper 0.001% identical J with sample B with sample B with sample B with Sample A of part tunnel F soil 0.01ppm----identical K goes up after fungi in the earth adds 0.01% 2 days with Sample A; 100% death
Nitroguanidine mycelium in the filter paper is grown fully
Embodiment 2
Repeat the method for embodiment 1, but the soil pattern that uses the sterile soil sample and wherein be added with Conidiobolus coronatus with the form of a thick spore suspension.This thick spore suspension is to make by the spore with a Petri dish medium of 50cc rinsed with sterile water.1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine directly is added in the soil with various concentration (shown in the table 2).The results are shown in the table 2 of these tests.
Data in the table 2 show, at first observe the variation of termite situation in the sterile soil sample when 1ppm nitroguanidine content.Yet the nitroguanidine that needs 100ppm could produce suitable high mortality after 6 days.Have in the soil of fungi in transplanting, when 1ppm content, reached quite high lethality, and when 3ppm, reach whole lethality of termite.If do not handle, then transplant the termite of activity in undressed control sample of the termite in the soil that fungi is arranged with nitroguanidine.
Table 2
The lethality of termite (%) is handled soil with nitroguanidine (ppm) and transplant Conidiobolus coronatus in sterile soil after 6 days
Soil edge
0 0 0
0.1 0 0
0.3 0 25+
1.0 0+ 75++
3.0 0 100
10.0 25++ 100
100.0 80+++ 100
+ many termites are got lost
++ most of termite is subjected to grievous injury
+++all termites are subjected to grievous injury
Embodiment 3
In described each sample of table 3, use 100g soil.The soil pattern of half is made with sterile soil.Second half is to be made by the sterile soil of the thick spore suspension of transplanting one/sample Conidiobolus coronatus.Thick spore suspension is by accompanying the spore of Ti Shi medium to make with the 50cc rinsed with sterile water.The filter filter disc with have concentration shown in the table 3 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine is saturated.1g subteranean termites eastern subterranean termite is directly added each sample.Then the termite in each sample was observed 6 days.The termite lethality of each sample is listed in the table 3.
The result: if do not use any nitroguanidine, the viewing duration at 6 days, termite has the soil of Conidiobolus coronatus without any reaction to transplanting.When the filter paper poison bait that will handle is added in the soil that does not have fungi, first disease million that behavior changes appears in 0.001% handles, but even when 100 times of high degree (0.1%), lethality still very low (8%).Yet, have in the soil of fungi in transplanting, when 0.001% nitroguanidine content, the lethality after 6 days is 95%.
The lethality (%) of nitroguanidine processing (%) termite after 6 days of table 3 filter paper disk poison bait
Filter disc bait IN% transplants Conidiobolus coronatus in sterile soil
Soil edge
0 0 0
0.00001 0 0
0.00003 0
0.0001 0 0(+)
0.0003 50+
0.001 2+ 95+++
0.003 100
0.01 5++ 100
0.1 8+++ 100
Some reduction of (+) activity
+ many termites are got lost
++ most of termite is subjected to grievous injury
+++all termites are subjected to grievous injury
Embodiment 4
Research directly is exposed to termite the effect of the fungi of automatic growth under the situation that has or do not exist 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine.In these experiments, with an agar plate that does not have fungi and do not have nitroguanidine thing as a comparison.A sample is the agar plate (0.01% active component) that has with 1-(2-chloro-5-pyridylmethyl)-filter paper disk that 2-(nitro imino group) imidazolidine was handled.The 3rd agar plate transplanted to be had Conidiobolus coronatus and uses the filter paper plate that contains 0.01% nitroguanidine to handle.Be added to the termite eastern subterranean termite on each agar plate and observed 4 days.The results are shown in the table 4 of these tests.
In the control sample of not transplanting, the normal phenomenon that termite expands the tunnel immediately takes place.Do not observe lethality after 4 days.In the plate of only handling with fungi, observe 25% lethality after 4 days, in the plate of only handling with the nitroguanidine poison bait, termite seriously poisons, and does not exist with the road.For the agar of handling with fungi and nitroguanidine, 100% lethality in 1 day, occurs, and, a large amount of sporulations in 4 days, occurs for the termite of death.
Table 4
After invading and harassing agar plate, observed several days with termite
---per cent death loss is handled had only agar plate 000 that agar plate+nitroguanidine poison bait 0* 0* 20* is only arranged in 1 day 2 days 4 days, (0.01%AI) at the fungi 100% cause of disease+nitroguanidine poison bait of 05 25 cause of diseases of the fungi on the agar on agar, (0.01%AI) the * termite poisons.
Embodiment 5
4 kilograms of sands are sterilized with autoclave.Soil with sterilization is divided into two equal portions then.In a soil, water content is transferred to 10% by in every 100g soil, adding 10ml distilled water.Second part of sterilization soil mud is implanted with the thick slurry of Conidiobolus coronatus spore and mycelia.This slurry is to make by being scraped in the 50ml distilled water by the fungi of the growth of the medium on the Petri dish.Then slurry is added in the soil of sterilization with the ratio that every 100g soil adds 10ml.Each 2 kilograms a collection of soil are divided in 20 plastic cups so that contain 100g soil in each cup again.Ten cups of every batch accept to have used the filter paper disk that 0.01%1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine was handled.The filter paper disk that remaining sample acceptance had been soaked in distilled water.The eastern subterranean termite that about 1g is lived is added in each sample.Per two, three days observations lethality, activity and conks in the time in a week.The results are shown in the table 5 of these tests.
The result: as might be expected, in control sample, termite is acted normally at 7 days viewing durations.Actual in the processing of only carrying out with fungi is same situation, but observes 20% final lethality.Only handle the lethality reach same degree, but observe the poisoning effect in early days in research with chemical agent.Fungi added the chemical agent processing and reached 100% lethality in 2 day.
Table 5
Fungal pathogen is to the mutual work (the conspicuous hypothesis of section) of sterile soil
Lethality % handle 2 days 4 days 7 days comparison (no fungi does not have chemicals) 000 fungi is only arranged 10 10 20 only have chemicals 20 *0 *20 *Fungi 1+ chemicals 3100 100 3100 4 1Conidiobolus coronatus 21-(2-chloro-5-pyridylmethyl)-2-nitro imido imidazolyl alkane 3Mycelium/spore obviously appears at wall of cup and cup 4Termite changes in quality, fully sporeization *Termite moves to the surface *The termite lackluster, torpescence
Embodiment 6
The interaction of research fungi Conidiobolus coronatus and various known termiticide (listing in the table 6).In these trials, use the 100g soil pattern.According to said method among the embodiment 2 Conidiobolus coronatus is added in half soil pattern.Do not add fungi in second half sample.Then chemical termiticide is added each sample (promptly transplanted the sample of fungi and do not transplanted the sample of fungi), its addition is enough to reach ratio listed in the table 6.Then, 1g subteranean termites eastern subterranean termite is added in each sample.Observe these samples with 7 days time.Observed result is listed in the table 6.The carbamates and the organophosphorus compounds that are used for this test almost do not influence termite, and perhaps they are same to the reacting phase that does not have fungi and the soil that is added with fungi.On the contrary, used pyrethroid (cyfluthrin) does not kill termite when not having fungi, but reaches 100% lethality when adding fungi in soil.
Table 6
Conidiobolus coronatus and various chemicals
Interaction aspect termite activity
Effect after several days and termite lethality %
2 days 4 days 7 days compounds content ppm do not have the fungi fungi in the soil does not have the fungi fungi and does not have fungi fungi carbamate 21.0 000000 synthetic pyrethroids 3
1.0 0 ** 95 0 ** 100 1 0 ** 100
0.3 0 *10 0 *95 0 100 organophosphorus esters 4
1.0 0 * 0 * 0 0 0 0
0.3 0 0 0 0 0 0Phostebupirin 5 0.3 0 0 20 60 98 100
0.1 0 0 0 0 0 0
0.03 00000 0*: slight behavior changes * *: seriously poison 1: mycelium/spore 2 obviously occurs: residual worm fear (Propoxur) 3: cyfloxylate (Cyfluthrin) 4: isofenphos (Isofenphos) 5 0-[2-(1, the 1-dimethyl ethyl)-5-pyrimidine radicals]-0-ethyl-0-(1-Methylethyl) thiophosphate
Embodiment 7
Only repeat the method for embodiment 6 with the pyrethroid termiticide.The results are shown in the table 7.
The result: used three kinds of pyrethroid cyfloxylates (cyfluthrin), sumicidin and cypermethrin is for not having fungi and transplanting to have the soil of fungi all to have sizable active difference.Cyfloxylate is that the most active compound and all three observed data show that all the termite control in being added with the soil of fungi is higher 10 times than the soil that does not have fungi.
Table 7
Conidiobolus coronatus and various synthetic plan deinsectization
The interaction of chrysanthemum ester aspect termite activity
The content ppm of 2 days 4 days 6 days compounds does not have the fungi fungi in effect after several days and the termite lethality % soil does not have the fungi fungi and does not have fungi fungi cyfloxylate
3.0 60 100 1) 100 100 1) 100 100 1)
1.0 0 100 1) 15 * 100 1) 15 100 1)
0.3 0 60 0 *100 1)0 *100 1)Sumicidin
10.0 80 100 1) 95 100 1) 95 100 1)
3.0 0 * 95 0 * 100 1) 0 * 100 1)
1.0 0 * 40 0 * 60 1) 0 93 1)
0.3 000000 cypermethrins
3.0 80 98 1) 95 100 1) 95 100 1)
1.0 0 60 0 100 0 100
0.3 0 10 0 60 0 100*: slight behavior changes 1): mycelium/spore obviously appears
Embodiment 8
With listed result of the test among this embodiment of following grade evaluation and the embodiment 10.
Grade lethality % subjective assessment
1 98-100 is excellent
2 90-97 are fine
3 80-89 are good
4 65-79 are satisfied
5 45-64 are dissatisfied
6 30-44 are dissatisfied
7 20-29 are poor
8 3-19 are poor
9 0-2 are imitated
In this test, use the 100g soil pattern.Some samples add the spore of Conidiobolus coronatus, and some samples add the spore of green muscardine fungus (MADA strain, CBS Number 326).The concrete added spore quantity of sample is listed among table 8A and the 8B.Use the filter paper disk that in the 1-of variable concentrations (2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine solution, had soaked to handle these samples then.For concrete sample, the concentration that is used for preparing the solution of filter paper disk is listed in table 8A and 8B.Then 1g termite eastern subterranean termite is added in each sample.After 7 days, with these samples of above-mentioned grade evaluation.Gained the results are shown among table 8A and the 8B.Their explanations are for ear mould own (table 8A), every gram soil 10 5Spore density to almost not influence of termite.Yet, only use 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine poison bait with the soil that is generally invalid concentration and handles in, the spore concentration in soil is low to moderate 10 1The time reach 100% lethality.This means, when the poison bait that nitroguanidine is handled also adds in the soil pattern, 4 powers of required spore concentration low at least 10.When adding green muscardine fungus in the soil pattern (table 8B), under situation about the poison bait of nitro processing also being added in the soil pattern, spore concentration can hang down several powers of 10.
Table 8A
Nitroguanidine poison bait that applies and various fungal pathogen are to the interaction grade of termite activity
Nitroguanidine % 0 10 in the spore count of every gram soil Conidiobolus coronatus/grade maceration extract 110 210 310 410 5
0 9 - - 9 8 7
0.0001 9 - ① ① ② ①
0.001 9 - ① ① ① ①
0.018 8 ① ① ① ① ①
The strong synergistic symbol of zero expression
Table 8B
The stiff bacterium of every gram soil chlorine
Nitroguanidine % 0 10 in the spore count of MADA strain/grade dipping solution 510 7
0 9 9 6
0.0001 9 5 ①
0.001 9 ① ①
0.01 8 ① ①
The strong synergistic symbol of zero expression
Embodiment 9
Step with two different green muscardine fungus strain-MADA strains (CBS Number 326) and BIO 1020 strains (DSM Number 3384) and Conidiobolus coronatus repetition embodiment 8.Yet, be not to use the nitroguanidine of various concentration, and with filter paper disk in distilled water or 0.001%1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine solution soaking.Observe 10 days the results are shown in the table 9.
Nitroguanidine poison bait that table 9 is used and the various fungal pathogens (strain) in sterile soil are to the interaction of termite activity
Lethality % after several days
The spore count of 3 days 6 days 10 days every gram soil
0.0001% 0.001% 0.001%
Water nitroguanidine water nitroguanidine water nitroguanidine green muscardine fungus 10 717
Figure C9310038600411
99 99 100MAOA-strains 10 60
Figure C9310038600413
3
Figure C9310038600414
68
Figure C9310038600415
10 5-23 52
Figure C9310038600417
10 4-40 37
Figure C9310038600419
10 3-10 43 22 56 green muscardine fungus 10 750
Figure C93100386004110
99 98 95 100BIO1020-strains 10 6031
Figure C93100386004111
53 10 5-41
Figure C93100386004113
45
Figure C93100386004114
10 4-00
Figure C93100386004115
23
Figure C93100386004116
10 3-10
Figure C93100386004117
13
Figure C93100386004118
Conidiobolus coronatus 10 40 1
Figure C93100386004120
40
Figure C93100386004121
10 31 12 1
Figure C93100386004122
43
Figure C93100386004123
10 50007 33 62 10 1-20 36 25 60 10 0The synergistic symbol that the expression of-0 0 12 10 37 comparison-0 15 0 23 0 57 zero is strong
Embodiment 10
With the green muscardine fungus (MADA strain, CBS Number 326) of consumption shown in the table 10 and the step of 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) imidazolidine repetition embodiment 8.Observed the results are shown in the table 10 after 5 days adopted and identical grade described in the embodiment 8.
Result among the embodiment 9 and 10 confirms, by adding 1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) the imidazolidine poison bait of low concentration, can be reduced to many 10 4 powers with the irrelevant spore concentration of fungi kind or strain, and compare with the soil that the poison bait that only is soaked in water is handled, will reach more effective termite control.
Table 10
Synergy with bait processing of nitroguanidine soil and fungal pathogen
Grade effect (1-9) based on average termite lethality after 5 days
Nitroguanidine % 0 10 in spore count/grade (CBS NO.326) dipping solution of the stiff bacterium of every gram soil chlorine-MADA strain 110 310 510 7
0 9 9 9 9 5
0.00001 9 9 9 9 5
0.0001 9 9 9 8 ②
0.001 8 8 6 ④ ①
0.01 7 6 4 ③ ①
The strong synergistic symbol of zero expression
Embodiment 11
With fungi radiation trichobacteria sp., stiff bacterium of paecilomyces farinograph and ball spore and bacterium Serratieae (Serratia) sp repeat the step of embodiment 5.Filter paper disk is immersed in distilled water or 0.001%1-(2-chloro-5-pyridylmethyl)-2-(nitro imino group) the imidazolidine solution.Observe 7 days the results are shown in the table 11.
In table 11, the listed hierarchical system in hurdle, each frame left side is as follows:
-normal: relatively do not change with untreated control sample.
+ slight: some termites are arranged from the teeth outwards, perhaps feed and some variations are arranged with the road.
++ medium: as many termites to be arranged from the teeth outwards, feed and significantly reduce with the road; Poisoning symptom
(torpescence, inharmonious).
+++serious: all termites all from the teeth outwards, not feed and with the road; Poisoning symptom increases
By force.
++ ++ cause death: the termite of 95-100% is dead or be about to dead.
Listed numeral is the % lethality in the right hurdle of each frame in table 11.
Table 11 just derives from the pathogenic evaluation to eastern subterranean termite of other fungi of dead termite and bacterium chorista
The conspicuous hypothesis of section
After processing in shown in each day termite the behavior variation and the transplanting filter paper disk of lethality soil handle and do not have-0-0-0 in 2 days 4 days 6-7 days and do not have 0.001% ++ 2 ++ (+) 7 ++ (+) 34 1)The radiation trichobacteria does not have-0-0-0 radiation trichobacteria 0.001% ++ (+) 2 ++ and+14 ++ ++ 99 opaques do not have-0-0-0 and intend blue or green bacterium 0.001% ++ and 12 ++ ++ 95 ++ ++ 100
Table 11 is continuous
The conspicuous hypothesis of section
After processing in shown in each day termite behavior variation and the transplanting filter paper disk of death rate soil process the 2 days 4 days stiff bacterium of 6-7 celestial sphere spore and do not have-1+18 ++ stiff bacterium 0.001%+(+) 1 of 18 ball spores +++75 +++89 Serratieaes do not have-3-14-16 Serratieae 0.001%+(+) 4 ++ 53 +++68
1) though soil the termite on autoclaving and surface be killed (being immersed in the Chlorox solution), from the green muscardine fungus of termite itself to accepting 1-(2-chloro-5-) pyridylmethyl)-termite of 2-(nitro imino group) imidazolidine shows partial lethal.
Embodiment 12
Step with the filter paper disk in several different nitromethane compound that is immersed in various concentration and two kinds of soil repetition embodiment 5.A kind of soil be take from the field bacterium soil arranged.Second kind of soil is autoclaving soil.The concentration of every kind of nitromethane and observed the results are shown in the table 12 after 4 days.
Used in this embodiment nitromethane class and analog thereof are as follows:
Compound
Figure C9310038600471
Degree of intoxication is listed in the table 12, uses the hierarchical system identical with table 11.
Table 12
Lethality % nitromethane nitromethane % initial stage degree sterile soil 1 after 4 days) bacterium soil is arranged
A 0.001 + 10?FF 100FF
B 0.1 ++++ 99?FF 100?FF
0.01 +++ 25?FF 100?FF
C 0.1 +++ 62?FF 100?FF
0.01 +++ 59?FF 100?FF
0.001 ++ 35?FF 100?FF
D 0.1 ++++ 96?FF 100?FF
0.01 +++ 74?FF 100?FF
E 0.1 ++++ 74?FF 100?FF
0.01 +++ 42?FF 100?FF
0.001 +++ 24?FF 100?FF
F 0.1 +++ 22?FF 100?FF
0.01 ++ 28?FF 100?FF
G 0.1 ++++ 41?FF 100?FF
0.01 +++ 21FF 100?FF
H 0.1 ++ 12?FF 100?FF
0.01 + 6?FF 100?FF
0.001 - 0 7?FF
I 0.1 +++ 18?FF 100?FF
0.01 +++ 13?FF 100?FF
0.001 +++20 FF 100 FF comparison 0.1% aqueous solvent-0 40.1% aqueous solvent water-0 01) sterilizing methods of soil obviously is not enough." F " expression is owing to exist entomophthora to belong to fungi, and major part is that green muscardine fungus and ear are mould, the minimizing naturally of termite number.Each F represents one of twice parallel determination.
Though, described the present invention above in detail, should be appreciated that this details only is in order to illustrate that those skilled in the art can do some variations therein but not break away from spirit of the present invention and exceed scope of the present invention in order to describe.

Claims (16)

1. one kind goes out except that the composition of termite, comprising a kind of following formula: compound and the insect pathomycete of effective dose,
Figure C9310038600021
Wherein:
R represents H or alkyl;
Z represents at least one heteroatomic heterocyclic group that contains of 5-or 6-unit, and described hetero atom is selected from O, S or N, and described heterocyclic radical can be replaced by halogen atom, alkyl, haloalkyl, nitrogen-atoms;
A represents NH or S; With
X represents N or CH.
2. according to the composition of claim 1, wherein R represents H, and Z represents 6 yuan of heterocyclic radicals, a nitrogen-atoms is wherein arranged on ring.
3. according to the composition of claim 1, wherein the insect pathomycete is a Conidiobolus coronatus.
4. according to the composition of claim 1, wherein the insect pathomycete is that green deadlock is mould.
5. one kind goes out except that the method for termite, and comprising has termite to use the step of the mixture of a kind of following formula: compound of effective dose and insect pathomycete where to observing termite or suspection,
Figure C9310038600031
Wherein:
R represents H or alkyl;
Z represents at least one heteroatomic heterocyclic group that contains of 5-or 6-unit, and described hetero atom is selected from O, S or N, and described heterocyclic radical can be replaced by halogen atom, alkyl, haloalkyl, nitrogen-atoms;
A represents NH or S; With
X represents N or CH.
6. according to the method for claim 5, wherein R represents H, and Z represents 6 yuan of heterocyclic radicals, a nitrogen-atoms is wherein arranged on ring.
7. according to the method for claim 5, wherein the insect pathomycete is a Conidiobolus coronatus.
8. according to the method for claim 5, wherein the insect pathomycete is that green deadlock is mould.
9. one kind goes out except that the method for termite, and comprising has termite to use a kind of following formula: compound of effective dose and the step of insect pathomycete where successively to observing termite or suspection, Wherein:
R represents H or alkyl;
Z represents at least one heteroatomic heterocyclic group that contains of 5-or 6-unit, and described hetero atom is selected from O, S or N, and described heterocyclic radical can be replaced by halogen atom, alkyl, haloalkyl, nitrogen-atoms;
A represents NH or S; With
X represents N or CH.
10. according to the method for claim 9, wherein R represents H, and Z represents 6 yuan of heterocyclic radicals, a nitrogen-atoms is wherein arranged on ring.
11. according to the method for claim 9, wherein the insect pathomycete is a Conidiobolus coronatus.
12. according to the method for claim 9, wherein the insect pathomycete is that green deadlock is mould.
13. one kind goes out except that the method for termite, be included in to observe termite or suspection has termite where, and to a kind of following formula: compound of the soil application effective dose that has the insect pathomycete naturally,
Figure C9310038600051
Wherein:
R represents H or alkyl;
Z represents at least one heteroatomic heterocyclic group that contains of 5-or 6-unit, and described hetero atom is selected from O, S or N, and described heterocyclic radical can be replaced by halogen atom, alkyl, haloalkyl, nitrogen-atoms;
A represents NH or S; With
X represents N or CH.
14. according to the method for claim 13, wherein R represents H, Z represents 6 yuan of heterocyclic radicals, a nitrogen-atoms is wherein arranged on ring.
15. according to the method for claim 13, wherein the insect pathomycete is a Conidiobolus coronatus.
16. according to the method for claim 13, wherein the insect pathomycete is that green deadlock is mould.
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