CN114304169B - Sterilization composition containing sinomenine analogue and micromolecular phenolic compound and application thereof in preventing and controlling plant diseases - Google Patents
Sterilization composition containing sinomenine analogue and micromolecular phenolic compound and application thereof in preventing and controlling plant diseases Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 150000002989 phenols Chemical class 0.000 title claims abstract description 20
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 10
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 9
- INYYVPJSBIVGPH-QHRIQVFBSA-N Sinomenine Chemical class C([C@@H]1N(CC2)C)C3=CC=C(OC)C(O)=C3[C@@]32[C@@H]1C=C(OC)C(=O)C3 INYYVPJSBIVGPH-QHRIQVFBSA-N 0.000 title claims description 65
- 201000010099 disease Diseases 0.000 title claims description 7
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title claims description 7
- 241000345998 Calamus manan Species 0.000 claims abstract description 51
- 239000003513 alkali Substances 0.000 claims abstract description 51
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- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 claims abstract description 16
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000007746 carvacrol Nutrition 0.000 claims abstract description 16
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
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- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical group CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims abstract 9
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical group CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000005844 Thymol Substances 0.000 claims abstract 9
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- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical group CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 claims abstract 5
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- INYYVPJSBIVGPH-UHFFFAOYSA-N 14-episinomenine Natural products C1CN(C)C2CC3=CC=C(OC)C(O)=C3C31C2C=C(OC)C(=O)C3 INYYVPJSBIVGPH-UHFFFAOYSA-N 0.000 claims description 63
- RARWEROUOQPTCJ-RBUKOAKNSA-N cepharamine Natural products C1CC2=CC=C(OC)C(O)=C2[C@@]2(CCN3C)[C@]13C=C(OC)C(=O)C2 RARWEROUOQPTCJ-RBUKOAKNSA-N 0.000 claims description 63
- 229930002966 sinomenine Natural products 0.000 claims description 63
- -1 phenol compound Chemical class 0.000 claims description 15
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- 239000004480 active ingredient Substances 0.000 abstract description 13
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
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- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
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- VLEUZFDZJKSGMX-UHFFFAOYSA-N pterostilbene Natural products COC1=CC(OC)=CC(C=CC=2C=CC(O)=CC=2)=C1 VLEUZFDZJKSGMX-UHFFFAOYSA-N 0.000 description 2
- ZGVSETXHNHBTRK-OTYSSXIJSA-N solanine Chemical compound O([C@H]1[C@@H](O)[C@@H](CO)O[C@H]([C@@H]1O[C@@H]1[C@@H]([C@H](O)[C@@H](O)[C@H](C)O1)O)O[C@@H]1CC2=CC[C@H]3[C@@H]4C[C@@H]5N6C[C@@H](C)CC[C@@H]6[C@H]([C@@H]5[C@@]4(C)CC[C@@H]3[C@@]2(C)CC1)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O ZGVSETXHNHBTRK-OTYSSXIJSA-N 0.000 description 2
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Abstract
The invention discloses a sterilization composition containing white leaf rattan alkali or neowhite leaf rattan alkali and small molecular phenol compounds, wherein the active ingredients are white leaf rattan alkali, neowhite leaf rattan alkali and thymol, carvacrol, 6-tertiary butyl m-cresol, 2-isopropyl phenol, 2-tertiary butyl phenol, 2, 4-di-tertiary butyl phenol, and the mass part ratio of white leaf rattan alkali or neowhite leaf rattan alkali to small molecular phenol compounds is 1:1, 1:10, 1:20, 1:50, 1:100; the bactericidal composition can be used for preventing and treating rhizoctonia solani, sclerotinia rot of colza, gray mold of tomato, scab of wheat, rice blast and fusarium wilt of cotton.
Description
Technical Field
The bactericidal composition takes the sinomenine or the sinomenine and the micromolecular phenolic compound as the active ingredients, and is suitable for the application in preventing and controlling plant diseases caused by rhizoctonia solani, sclerotinia rot of colza, gray mold of tomato, wheat scab, rice blast and cotton wilt.
Background
Among a plurality of measures for preventing and controlling plant pathogenic fungi, chemical prevention and control are still the mainstream prevention and control means at present, and high-efficiency prevention and control effects can be generally obtained at the early stage of prevention and control. However, due to the unreasonable use for a long time, bacteria and fungi generate different degrees of resistance to the chemical bactericides, so that the ideal sterilizing effect can be achieved only by increasing the dosage, and further, the medicine residues are increased and the toxic and side effects are enhanced. In order to cope with the drug resistance, the dosage of the chemical bactericide is reduced, and the combined use or the compounding is particularly important, so that the dosage of the medicine can be reduced, the sensitivity of bacteria to the bactericide is increased, the antibacterial spectrum is enlarged, the environmental pollution is reduced, and more importantly, the occurrence of the drug resistance of the bactericide can be slowed down.
The sinomenine and neosinomenine are alkaloids in the medicinal plant sinomenine (C.sanguinolentena) of western medicine. The compound has various biological activities including cytotoxicity, antibacterial, antifungal, antiparasitic and the like, and is one of the hot spots of the current natural medicine research due to novel structure and various activities.
The phenolic compounds are relatively common bioactive small molecular compounds, are important secondary metabolites in plants in nature, and the simple phenols, flavones, quinones and the like in the phenolic compounds are reported to have an inhibiting effect on the hypha growth and spore germination of plant pathogenic fungi in vitro, have a certain regulating effect on the plant growth and development in plants, and also have important effects on plant disease resistance, gene induction expression, signal transduction and the like. Furthermore, studies have found that mic=200 μg/mL of Eugenol (Eugenol) to Phytophthora nicotianae (Phytophthora); pterostilbene (Pterostilbene) can completely inhibit spore germination of Botrytis cinerea at 50 mg/L; the spore germination inhibition rate of carvacrol (carvacrol) on rhizopus stolonifer (Rhizopus Stolonifer) reaches 100% at 25 mug/mL. It is worth noting that although they have high antibacterial and insecticidal efficacy, they have low toxicity to warm-blooded animals, so that phenolic compounds have good application prospects in terms of antibacterial activity.
A large number of experiments show that the combination application of the sinomenine or the neosinomenine and the micromolecular phenol compound has obvious synergistic effect in preventing and treating rhizoctonia solani, sclerotinia rot of colza, gray mold of tomato, scab of wheat, rice blast and cotton wilt. The pesticide composition has the advantages of improving the control effect, reducing the dosage and meeting the requirement of 'zero increase of pesticide'. And at present, related reports of the compounding of the sinomenine or the sinomenine and the micromolecular phenolic compound are not related.
Disclosure of Invention
The invention aims to provide a bactericide composition containing white leaf rattan alkali or neowhite leaf rattan alkali and a micromolecular phenolic compound, which is used for preventing and treating rhizoctonia solani, sclerotinia rot of colza, gray mold of tomato, wheat scab, rice blast and cotton wilt.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a bactericide composition containing white leaf rattan alkali or neowhite leaf rattan alkali and small molecular phenolic compounds comprises an active component A and an active component B, wherein the active component A is white leaf rattan alkali or neowhite leaf rattan alkali, the active component B is small molecular phenolic compounds, and the weight ratio of the active component A to the active component B is 1:1,1:10,1:20,1:50,1:100.
The bactericide composition provided by the invention has the following beneficial effects:
1) The bactericidal composition provided by the invention has obvious synergism within a certain proportion range, and the control effect of the bactericidal composition is obviously improved compared with that of a single agent.
2) The bactericidal composition provided by the invention has different effective component action mechanisms, is expected to delay or overcome the generation of disease drug resistance, prolongs the service life of the medicament, and is favorable for comprehensive treatment of diseases.
Detailed Description
For a better understanding of the essence of the present invention, the following examples are further illustrative, but the present invention is not limited to these examples. In these examples, all percentages are by weight unless otherwise indicated.
Example 1: a bactericide composition containing white leaf rattan alkali or neowhite leaf rattan alkali and small molecular phenolic compound comprises an active component A and an active component B (shown as a structural formula 1), wherein the active component A is white leaf rattan alkali or neowhite leaf rattan alkali, and the active component B is small molecular phenolic compound.
Example 2: indoor activity determination of colza sclerotinia by mixing sinomenine and active component B
The plant pathogenic bacteria used in the experiment are strains preserved at the temperature of 4 ℃ in a laboratory, and the adopted culture medium is potato agar glucose culture medium (PDA for short). PDA culture medium formula: 200g of potato (peeled), 20g of glucose, 15g of agar and 1000mL of distilled water, and the natural PH.
Compounding synergy of bactericides the synergy coefficient of different medicaments after mixing is calculated according to the Wadley (1967) formula:
wherein a and B represent the ratio EC of the two agents of the sinomenine or the sinomenine (A) and the micromolecular phenolic compound (B) in the mixture 50 (A)，EC 50 (B) Respectively represent the actual observation EC 50 Value, EC 50 (Exp) represents the theoretical EC of a and B two drugs mixed according to a: B 50 Value, EC 50 (Obs) is A, actual observation EC of two medicaments B mixed according to a: B 50 Values. SR (SR)>1.5 is synergy; SR (SR)<0.5 is antagonism; an SR between 0.5 and 1.5 indicates an additive effect.
The synergistic effect of the sinomenine and the active component B on indoor toxicity of sclerotinia rot of colza is shown in table 1.
TABLE 1 synergistic effect of sinomenine and active ingredient B in combination with indoor virulence of sclerotinia rot of colza
From Table 1, the blending mass ratio of the sinomenine to the active component B is 1:1,1:10,1:20,1:50 and 1:100, and the composition has obvious synergism on the sclerotinia rot of colza, especially the mass ratio of the sinomenine to the P4 is 1:50, and the SR is as high as 39.75.
Example 3: indoor activity determination of sinomenine and active component B mixed with rhizoctonia solani
The synergistic effect of indoor toxicity of sinomenine and active component B in Rhizoctonia solani is shown in Table 2.
TABLE 2 synergistic action of indoor toxicity of sinomenine and active ingredient B
From Table 2, the blending mass ratio of the sinomenine to the active component B is 1:1,1:10,1:20,1:50 and 1:100, and the sinomenine and the active component B have obvious synergistic effect on rhizoctonia solani, and especially the SR is as high as 9.75 when the mass ratio of the sinomenine to the P1 is 1:1.
Example 4: indoor activity determination of wheat scab by mixing sinomenine and active component B
The synergistic effect of the sinomenine and the active component B on the indoor toxicity of wheat scab is shown in Table 3.
TABLE 3 synergistic action of the mixture of white leaf rattan alkali and active component B on wheat scab in indoor toxicity
As can be seen from table 3, the synergy of the white leaf rattan alkali and the active component B is not obvious when the mass ratio of the white leaf rattan alkali to the active component B is 1:1,1:10,1:20,1:50, and 1:100, and sr=1.53 only when the mass ratio of the white leaf rattan alkali to the active component B is 1:50; when the mass ratio of the sinomenine to the P5 is 1:100, SR=1.52. The remaining compositions are more indicative of additive effects, followed by antagonistic effects.
Example 5: indoor activity determination of tomato gray mold by mixing sinomenine and active component B
The synergistic effect of the combination of the sinomenine and the active component B on the indoor toxicity of the tomato gray mold is shown in Table 4.
TABLE 4 synergistic effect of the mixture of white leaf rattan alkali and active ingredient B on indoor virulence of Botrytis cinerea
From Table 4, the compounding mass ratio of the sinomenine to the active component B is 1:1,1:10,1:20,1:50 and 1:100, and the composition has obvious synergism on the gray mold of tomatoes, and especially the SR is as high as 14.44 when the mass ratio of the sinomenine to the P6 is 1:10.
Example 6: indoor activity determination of rice blast by mixing sinomenine and active component B
The synergistic effect of the combination of solanine and active ingredient B on indoor virulence against rice blast is shown in Table 5.
TABLE 5 synergistic effect of the mixture of white leaf rattan alkali and active ingredient B on indoor virulence of Pyricularia oryzae
From Table 5, the mixing mass ratio of the sinomenine to the active component B is 1:1,1:10,1:20,1:50 and 1:100, and the composition has obvious synergism on the gray mold of tomatoes, especially when the mass ratio of the sinomenine to the P1 is 1:1, the SR is as high as 2.52.
Example 7: indoor activity determination of cotton wilt by mixing sinomenine and active component B
The synergistic effect of the combination of solanine and active component B on indoor virulence of cotton wilt is shown in Table 6.
TABLE 6 synergistic effect of the indoor toxicity of the mixture of white leaf rattan alkali and active component B on cotton wilt
As can be seen from table 6, the synergism of the white leaf rattan alkali and the active component B to the cotton wilt is not obvious when the mass ratio of the white leaf rattan alkali to the active component B is 1:1,1:10,1:20,1:50,1:100, but sr= 2.01,1.86 when the mass ratio of the white leaf rattan alkali to the active component B is 1:1, 1:10. The remaining compositions are more indicative of additive effects, followed by antagonistic effects.
Example 8: indoor activity determination of sclerotinia rot of colza by mixing sinomenine and active component B
The synergistic effect of the combination of neowhite leaf cambogine and active component B on indoor virulence of sclerotinia rot of colza is shown in Table 7.
TABLE 7 indoor toxicity potentiating action of Sinomenine and active component B in combination on Sclerotinia sclerotiorum
As shown in Table 7, the synergistic effect of the neowhite leaf rattan alkali and the active component B on the sclerotium disease of rape is obvious when the mixing mass ratio of the neowhite leaf rattan alkali to the active component B is 1:1,1:10 and 1:20, and especially when the mass ratio of the neowhite leaf rattan alkali to the active component P4 is 1:1, the SR is as high as 3.93.
Example 9: indoor activity determination of rhizoctonia solani compounded by neowhite leaf rattan alkali and active component B
The indoor virulence potentiating effect of the blending of the sinomenine and the active component B on the rhizoctonia solani is shown in table 8.
TABLE 8 indoor toxicity potentiating action of Sinomenine and active component B compounding against Rhizoctonia solani
As can be seen from table 8, the synergism of the rhizoctonia solani is not obvious when the compounding mass ratio of the neowhite leaf rattan alkali to the active component B is 1:1,1:10 and 1:20, and sr=1.65 only when the mass ratio of the neowhite leaf rattan alkali to the active component B is 1:20. The remaining compositions are more indicative of additive effects, followed by antagonistic effects.
Example 10: indoor activity determination of wheat scab by mixing neowhite leaf gamboge and active component B
The synergistic effect of the combination of neowhite leaf cambogine and active component B on wheat scab in indoor toxicity is shown in Table 9.
TABLE 9 indoor toxicity potentiation of wheat scab by blending neowhite leaf gamboge with active ingredient B
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As can be seen from Table 9, the prevention and treatment of wheat scab at a mass ratio of 1:1,1:10,1:20 of neowhite leaf camboge and active ingredient B did not have a synergistic effect, mostly additive effect, while several groups of antagonism also existed.
Example 11: indoor activity determination of mixing of sinomenine and active component B on tomato gray mold
The synergistic effect of the combination of neowhite leaf cambogine and active component B on the indoor virulence of tomato gray mold is shown in Table 10.
TABLE 10 synergistic effect of Sinomenine and active ingredient B in combination on indoor virulence of tomato gray mold
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From Table 10, the synergy of the neowhite leaf rattan alkali and the active component B is obvious when the mixing mass ratio of the neowhite leaf rattan alkali to the active component B is 1:1,1:10 and 1:20, and especially when the mass ratio of the neowhite leaf rattan alkali to the active component P1 is 1:1, the SR is as high as 5.61.
Example 12: indoor activity determination of rice blast by mixing neowhite leaf gamboge and active component B
The synergistic effect of the combination of neowhite leaf cambogine and active ingredient B on indoor virulence against rice blast is shown in table 11.
TABLE 11 indoor toxicity potentiation of Rice blast by mixing Sinomenine and active ingredient B
As can be seen from Table 11, the prevention and treatment of rice blast at the mass ratios of 1:1,1:10,1:20 of neowhite leaf cambogine and active component B were not synergistic, mostly antagonistic, while there were several groups of additive effects.
Example 13: indoor activity determination of cotton wilt by mixing neowhite leaf gamboge and active component B
The synergistic effect of the combination of neowhite leaf cambogine and active component B on indoor virulence of cotton wilt is shown in Table 12.
TABLE 12 indoor toxicity potentiating effect of New white leaf rattan alkali and active component B mixture on cotton Fusarium wilt
As can be seen from Table 12, the prevention and treatment of cotton wilt at the mass ratios of 1:1,1:10,1:20 of neowhite leaf cambogine and active ingredient B did not have a synergistic effect, mostly additive effect, and several groups of antagonism also existed.
Taken together, it can be seen that the antibacterial activity of the combination of the sinomenine and the small-molecule phenolic compound is better than that of the sinomenine composition, especially the sinomenine: p4=1:50, SR is as high as 39.75 when resistant to sclerotinia rot of colza. This is much higher than the conditions that produce synergy (SR > 1.5). In the control of sclerotinia rot of colza, many synergistic combinations occur, for example in the case of white leaf gamboges: p1, white leaf rattan alkali: p2 and sinomenine: when P3 is 1:1, the SR is 12.42, 11.74 and 13.09 respectively.
Claims (6)
1. An application of an agricultural sterilization composition containing sinomenine or neosinomenine and a small molecular phenol compound in preventing and treating sclerotinia rot of colza, wherein the small molecular phenol compound is thymol, carvacrol, 6-tert-butyl m-cresol, 2-isopropylphenol, 2-tert-butylphenol or 2, 4-di-tert-butylphenol; in the bactericidal composition, the mass part ratio of the white leaf rattan alkali to the thymol is 1:1,1:10,1:20,1:50 or 1:100;
or the mass part ratio of the sinomenine to the carvacrol is 1:10,1:20 or 1:50;
or the mass part ratio of the sinomenine to the 6-tertiary butyl metacresol is 1:10,1:20 or 1:50;
or the mass part ratio of the white leaf rattan alkali to the 2-isopropyl phenol is 1:10,1:20 or 1:50;
or the mass part ratio of the sinomenine to the 2-tertiary butyl phenol is 1:10,1:20 or 1:50;
or the mass part ratio of the sinomenine to the 2, 4-di-tert-butylphenol is 1:10,1:20 or 1:50;
or the mass part ratio of the neowhite leaf rattan alkali to the carvacrol is 1:1;
or the mass part ratio of the sinomenine to the 6-tertiary butyl metacresol is 1:1 or 1:20;
or the mass part ratio of the neowhite leaf rattan alkali to the 2-isopropyl phenol is 1:1;
or the mass ratio of the neowhite leaf rattan alkali to the 2-tertiary butyl phenol is 1:1.
2. An application of an agricultural sterilization composition containing sinomenine or neosinomenine and a small molecular phenol compound in preventing and treating diseases caused by rhizoctonia solani, wherein the small molecular phenol compound is thymol, carvacrol, 6-tertiary butyl m-cresol or 2-isopropyl phenol; in the bactericidal composition, the mass part ratio of the white leaf rattan alkali to the thymol is 1:1,1:10,1:20 or 1:50;
or the mass part ratio of the sinomenine to the carvacrol is 1:1,1:10 or 1:20;
or the mass part ratio of the sinomenine to the 6-tertiary butyl metacresol is 1:1,1:10,1:20 or 1:50;
or the mass part ratio of the white leaf rattan alkali to the 2-isopropyl phenol is 1:1,1:10 or 1:20;
or the mass part ratio of the sinomenine to the 6-tertiary butyl m-cresol is 1:20.
3. Application of agricultural sterilization composition containing sinomenine or neosinomenine and small molecular phenol compound in preventing and treating wheat scab, wherein the small molecular phenol compound is carvacrol, 2-tert-butylphenol or 2.4-di-tert-butylphenol; in the bactericidal composition, the mass part ratio of the sinomenine to the carvacrol is 1:50;
or the mass part ratio of the sinomenine to the 2-tert-butylphenol is 1:100;
or the mass part ratio of the neowhite leaf rattan alkali to the 2-tertiary butyl phenol is 1:1;
or the mass part ratio of the neowhite leaf rattan alkali to the 2, 4-di-tert-butylphenol is 1:1.
4. An application of an agricultural sterilization composition containing white leaf rattan alkali and small molecular phenolic compounds in preventing and treating gray mold of tomatoes, wherein the small molecular phenolic compounds are thymol, carvacrol, 6-tertiary butyl m-cresol, 2-isopropyl phenol, 2-tertiary butyl phenol or 2.4-di-tertiary butyl phenol; in the bactericidal composition, the mass part ratio of the white leaf rattan alkali to the thymol is 1:1, 1:20,1:50 or 1:100;
or the mass part ratio of the sinomenine to the carvacrol is 1:1, 1:50 or 1:100;
or the mass part ratio of the sinomenine to the 6-tertiary butyl metacresol is 1:50 or 1:100;
or the mass part ratio of the white leaf rattan alkali to the 2-isopropyl phenol is 1:10 or 1:50;
or the mass part ratio of the sinomenine to the 2-tertiary butyl phenol is 1:10, 1:50 or 1:100;
or the mass part ratio of the sinomenine to the 2, 4-di-tert-butylphenol is 1:10, 1:50 or 1:100.
5. An application of an agricultural sterilization composition containing white leaf rattan alkali and small molecular phenol compounds in preventing and treating rice blast, wherein the small molecular phenol compounds are thymol, carvacrol or 6-tertiary butyl m-cresol; in the bactericidal composition, the mass part ratio of the white leaf rattan alkali to the thymol is 1:1,1:10,1:20 or 1:100;
or the mass part ratio of the sinomenine to the carvacrol is 1:10;
or the mass part ratio of the sinomenine to the 6-tertiary butyl metacresol is 1:10,1:20 or 1:100.
6. An application of an agricultural sterilization composition containing sinomenine and a small molecular phenol compound in preventing and treating cotton wilt, wherein the small molecular phenol compound is carvacrol; in the bactericidal composition, the mass part ratio of the sinomenine to the carvacrol is 1:1 or 1:10.
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| CN103800928A (en) * | 2014-03-06 | 2014-05-21 | 苏州爱德芬生物科技有限公司 | Antibiotic deodorant |
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| JPS5576802A (en) * | 1978-12-05 | 1980-06-10 | Ajinomoto Co Inc | Volatile anti-bacterial and anti-fungal agent |
| CN103800928A (en) * | 2014-03-06 | 2014-05-21 | 苏州爱德芬生物科技有限公司 | Antibiotic deodorant |
| CN109090123A (en) * | 2018-06-21 | 2018-12-28 | 兰州大学 | Application of the new cryptolepine derivative in prevention and treatment plant source germ |
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