CN105578881B - 包含溴硝丙二醇、棉隆或4‑(2‑硝基丁基)吗啉与4，4′‑(2‑乙基‑2‑硝基三亚甲基)二吗啉的混合物的杀微生物组合物 - Google Patents
包含溴硝丙二醇、棉隆或4‑(2‑硝基丁基)吗啉与4，4′‑(2‑乙基‑2‑硝基三亚甲基)二吗啉的混合物的杀微生物组合物 Download PDFInfo
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- A01N—PRESERVATION 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
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- Agronomy & Crop Science (AREA)
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Abstract
一种协同杀微生物组合物，其具有两种组分。所述第一组分是具有以下结构的非离子表面活性剂：R2O(CH2CH(CH3)O)3(CH2CH2O)5H，其中R2是C8‑C14直链烷基的混合物。所述第二组分是2‑溴‑2‑硝基丙‑1，3‑二醇(溴硝丙二醇)、四氢‑3，5‑二甲基‑2H‑1，3，5‑噻二嗪‑2‑硫酮(棉隆)或4‑(2‑硝基丁基)吗啉与4，4′‑(2‑乙基‑2‑硝基三亚甲基)二吗啉的混合物。
Description
技术领域
本发明涉及杀微生物组合物，其含有2-溴-2-硝基丙-1，3-二醇(BNPD)、四氢-3，5-二甲基-2H-1，3，5-噻二嗪-2-硫酮(棉隆)或BIOBAN P-1487(4-(2-硝基丁基)吗啉与4，4′-(2-乙基-2-硝基三亚甲基)二吗啉的分别约81∶5混合物)和表面活性剂。
背景技术
美国专利第4,295,932号中公开一种组合物，其含有5-氯-2-甲基异噻唑啉-3-酮、2-甲基异噻唑啉-3-酮和非离子分散剂。所述组合物含有5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的3∶1混合物，以及环氧乙烷与环氧丙烷的共聚物，其看起来具有与PLURONIC L61或TERGITOL L61分散剂相同的组成。然而，需要对多种微生物菌株具有协同活性的杀微生物剂的组合来提供对微生物的有效控制。此外，出于环境和经济益处，需要含有低含量的个别杀微生物剂的此类组合。由本发明解决的问题是提供杀微生物剂的此类协同组合。
发明内容
本发明针对一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)2-溴-2-硝基丙-1，3-二醇；其中所述非离子表面活性剂与2-溴-2-硝基丙-1，3-二醇的重量比是1∶0.08到1∶0.12或1∶0.2到1∶1.8286。
本发明进一步针对一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)四氢-3，5-二甲基-2H-1，3，5-噻二嗪-2-硫酮；其中所述非离子表面活性剂与四氢-3，5-二甲基-2H-1，3，5-噻二嗪-2-硫酮的重量比是1∶0.0024到1∶0.4571。
本发明进一步针对一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
其中R1是C8烷基；和(b)81∶5重量比的4-(2-硝基丁基)吗啉与4，4′-(2-乙基-2-硝基三亚甲基)二吗啉的混合物；其中所述非离子表面活性剂与所述混合物的重量比是1∶0.0006到1∶0.2743。
本发明进一步针对用于抑制微生物在水性介质中的生长的方法，其通过向水性介质中添加本文所述的比率的如本文所述的非离子表面活性剂和2-溴-2-硝基丙-1，3-二醇、四氢-3，5-二甲基-2H-1，3，5-噻二嗪-2-硫酮或4-(2-硝基丁基)吗啉与4，4′-(2-乙基-2-硝基三亚甲基)二吗啉的约81∶5混合物来进行。
具体实施方式
“BNPD”是2-溴-2-硝基丙-1，3-二醇，“棉隆”具有四氢-3，5-二甲基-2H-1，3，5-噻二嗪-2-硫酮(CAS第533-74-4号)作为活性成分，并且“BIOBAN P-1487”是4-(2-硝基丁基)吗啉与4，4′-(2-乙基-2-硝基三亚甲基)二吗啉的约81∶5(重量)混合物。如本文所用，除非上下文另外明确指示，否则以下术语具有所指定的定义。术语“杀微生物剂”是指能够抑制微生物生长或控制微生物生长的化合物；杀微生物剂包括杀细菌剂、杀真菌剂和除藻剂。术语“微生物”包括例如真菌(例如酵母和霉菌)、细菌和藻类。本说明书通篇使用以下缩写：ppm＝重量百万分率(重量/重量)，mL＝毫升。除非另外规定，否则温度以摄氏度(℃)为单位，提到百分比是重量百分比(重量％)并且量和比率以活性成分(即BNPD、棉隆或BIOBANP-1487活性成分和非离子表面活性剂的总重量)计。环氧丙烷或环氧乙烷的聚合单元的数目是数目平均值。
优选地，具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物，与BNPD的重量比是1∶0.2286到1∶1.18286。
本发明进一步针对一种用于抑制霉菌、优选白假丝酵母(C.albicans)在水性介质中的生长的方法，其通过添加以下各物来进行：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)BNPD；其中所述非离子表面活性剂与BNPD的重量比是1∶0.08到1∶0.12或1∶0.2到1∶1.8286、优选1∶0.2286到1∶1.18286。
优选地，具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物，与棉隆的重量比是1∶0.0114到1∶0.4571。
本发明进一步针对一种用于抑制金黄色葡萄球菌(S.aureus)在水性介质中的生长的方法，其通过添加以下各物来进行：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)棉隆；其中所述非离子表面活性剂与棉隆的重量比是1∶0.0114到1∶0.4571。
优选地，具有以下结构的非离子表面活性剂：
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
其中R1是C8烷基，与BIOBAN P-1487的重量比是1∶0.0160到1∶0.2743。
本发明进一步针对一种用于抑制真菌、优选黑曲霉(A.niger)在水性介质中的生长的方法，其通过添加以下各物来进行：(a)具有以下结构的非离子表面活性剂：
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
其中R1是C8烷基，与BIOBAN P-1487的重量比是1∶0.0160到1∶0.2743。
R2是C8-C14直链烷基的混合物。优选地，C8-C14直链烷基包含50到85重量％C8-C10直链烷基和15到50重量％C12-C14直链烷基，优选60到75重量％C8-C10直链烷基和25到40重量％C12-C14直链烷基，优选约70重量％C8-C10直链烷基和约30重量％C12-C14直链烷基。优选地，直链烷基源自种子油。优选地，R1是2-乙基己基。
优选地，每一种组合物实质上不含除非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487以外的杀微生物剂，即，其具有以活性成分的总重量计少于1重量％、优选少于0.5重量％、优选少于0.2重量％、优选少于0.1重量％的除非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487以外的杀微生物剂。优选地，当非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487添加到水性介质中时，介质实质上不含其它杀微生物剂，即，其具有以活性成分的总重量计少于1重量％、优选少于0.5重量％、优选少于0.2重量％、优选少于0.1重量％的除非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487以外的杀微生物剂。
本发明的组合物可含有其它成分，例如消泡剂和乳化剂。本发明的杀微生物组合物可用以通过向经受微生物攻击的水性介质中引入杀微生物有效量的组合物来抑制微生物或更高等形式水生生物(例如原生动物、无脊椎动物、苔藓虫类、沟鞭藻类、甲壳动物、软体动物等)的生长。适合水性介质见于例如：工业处理水；电涂膜沉积系统；冷却塔；空气洗涤器；洗气器；矿浆；废水处理；观赏喷泉；逆渗透过滤；超滤；压载水；蒸发冷凝器；热交换器；纸浆和纸加工流体和添加剂；淀粉；塑料；乳液；分散液；油漆；胶乳；涂料，例如清漆；建筑产品，例如填补剂、填缝剂和密封剂；建筑粘合剂，例如陶瓷粘合剂、地毯背衬粘合剂和层压粘合剂；工业或消费者用粘合剂；摄影化学品；印刷流体；家居产品，例如浴室和厨房清洁剂；化妆品；厕所用品；洗发剂；皂类；个人护理产品，例如擦拭巾、洗剂、防晒霜、护发素、乳霜和其它免洗式应用；洗涤剂；工业清洁剂；地板抛光剂；洗衣漂洗水；金属加工流体；传送带润滑剂；液压流体；皮革和皮革产品；织物；纺织产品；木材和木材产品，例如胶合板、木屑板、刨花板、层压梁、定向刨花板、硬纸板和芯板材；石油加工流体；燃料；油田流体，例如注射水、压裂流体和钻井泥浆；农业辅助保存；表面活性剂保存；医疗装置；诊断试剂保存；食品保存，例如塑料或纸食品包装；食品、饮料和工业处理巴氏消毒器；抽水马桶；娱乐用水；水池；以及矿泉。
在应用中抑制或控制微生物生长所必需的本发明杀微生物组合物的具体量将变化。本发明组合物的量基于活性成分(即，非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487)给出。对于纸应用中所用的BNPD/表面活性剂，优选浓度是2到50ppm、优选5到40ppm。对于油气钻探应用中所用的BNPD/表面活性剂，优选浓度是10到500ppm、优选20到350ppm。对于金属加工流体中所用的BNPD/表面活性剂，优选浓度是150到2000ppm、优选300到1500ppm。对于金属加工流体中所用的BIOBAN P-1487/表面活性剂，优选浓度是600到1800ppm、优选800到1500ppm。对于燃料应用中所用的BIOBAN P-1487/表面活性剂，优选浓度是300到4000ppm、优选500到3000ppm。燃料应用包括燃料用烃类的保存，例如生物乙醇应用、柴油储罐保存和通用油箱保存。在本发明方法中，通过一起或分别添加将产生上文所指出的浓度的量的非离子表面活性剂和BNPD、棉隆或BIOBAN P-1487来处理组合物从而抑制微生物生长。
实例
通过确定组合的协同指数(synergy index，S.I.)来评价表面活性剂和杀生物剂的协同作用。基于单独和组合的两种抗微生物化合物(A和B)的最小抑制浓度(MIC)来计算协同作用指数。测试生物是革兰氏阴性(Gram negative)细菌(绿脓假单胞菌(Pseudomonasaeruginosa)ATCC编号15442)、革兰氏阳性(Gram positive)细菌(金黄色葡萄球菌ATCC编号6538)、酵母(白假丝酵母ATCC编号10203)和霉菌(黑曲霉ATCC编号16404)。细菌的接触时间是24和48小时，酵母是48和72小时，并且霉菌是3和7天。在96孔微量滴定板中进行测试。
表面活性剂A R1O(CH2CH(CH3)O)5(CH2CH2O)9H，其中R1是2-乙基己基
表面活性剂D R2O(CH2CH(CH3)O)3(CH2CH2O)5H
表面活性剂E R2O(CH2CH(CH3)O)3(CH2CH2O)7H
在表面活性剂D和表面活性剂E中，R2是C8-C14直链烷基的混合物(70％C8-C10直链烷基和30％C12-C14直链烷基)
所用接种物
表4.所用介质
胰酶大豆培养液的pH是7.3，并且马铃薯右旋糖培养液的pH是5.1。
用于证明MIC组合的协同作用的测试结果展示于下表中。各表显示针对用培育时间测试的微生物的两种组分的组合的结果；通过MIC测量的单独化合物A(CA)、单独组分B(CB)和混合物(Ca)和(Cb)的以ppm为单位的终点活性；SI计算值；以及所测试的各组合的协同比率的范围。SI如下计算：
Ca/CA+Cb/CB＝协同作用指数(“SI”)
其中：
CA＝化合物A单独作用时产生终点的以ppm为单位的浓度(化合物A的MIC)。
Ca＝化合物A在混合物中时产生终点的以ppm为单位的浓度。
CB＝化合物B单独作用时产生终点的以ppm为单位的浓度(化合物B的MIC)。
Cb＝化合物B在混合物中时产生终点的以ppm为单位的浓度。
当Ca/CA和Cb/CB的总和大于1时，指示拮抗作用。当总和等于1时，指示加合作用，并且当小于1时，证实协同作用。
测试BNPD、棉隆或BIOBAN P-1487与界面活性剂所处的比率范围如下表中所概述：
A：表面活性剂A
B：BNPD
介质：1/10TSB
接种物大小：8.134E+07CFU/ml
无协同作用：黑曲霉、白假丝酵母、金黄色葡萄球菌
A：表面活性剂D
B：BNPD
介质：PDB
接种物大小：1.156E+06
A：表面活性剂D
B：BNPD
介质：PDB
接种物大小：5.726E+05CFU/ml
A：表面活性剂D
B：BNPD
介质：1/10TSB
接种物大小：1.16E+08
A：表面活性剂D
B：BNPD
介质：1/10TSB
接种物大小：1.808E+05
A：表面活性剂E
B：BNPD
介质：PDB
接种物大小：1.808E+06CFU/ml
A：表面活性剂E
B：BNPD
介质：1/10TSB
接种物大小：5.727E+07CFU/ml
A：表面活性剂E
B：BNPD
介质：1/10TSB
接种物大小：1.808E+06CFU/ml
无协同作用：黑曲霉
A：表面活性剂A
B：棉隆
介质：1/10TSB
接种物大小：8.13E+07
金黄色葡萄球菌ATCC 6538无协同作用
A：表面活性剂A
B：棉隆
介质：PDB
接种物大小：1.156E+06
A：表面活性剂A
B：棉隆
介质：PDB
接种物大小：1.156E+06
A：表面活性剂A
B：棉隆
介质.：1/10TSB
接种物大小：8.134E+07
A：表面活性剂E
B：棉隆
介质：PDB
接种物大小：1.156E+06
白假丝酵母ATCC 102031无协同作用
A：表面活性剂E
B：棉隆
介质：1/10TSB
接种物大小：5.7E+07
绿脓假单胞菌ATCC 15442无协同作用
A：表面活性剂E
B：棉隆
介质：1/10TSB
接种物大小：1.8E+06
A：表面活性剂E
B：棉隆
介质：PDB
接种物大小：1.156E+06
A：表面活性剂D
B：棉隆
介质：PDB
接种物大小：1.16E+08
绿脓假单胞菌ATCC 15442无协同作用
A：表面活性剂D
B：棉隆
介质：PDB
接种物大小：5.72E+05
A：表面活性剂D
B：棉隆
介质：PDB
接种物大小：1.56E+06
A：表面活性剂D
B：棉隆
介质：1/10TSB
接种物大小：5.72E+05
A：表面活性剂A
B：BIOBAN P-1487
介质：PDB
接种物大小：1.156E+06CFU/ml
A：表面活性剂A
B：BIOBAN P-1487
介质：PDB
接种物大小：1.156E+06CFU/ml
A：表面活性剂A
B：BIOBAN P-1487
介质：1/10TSB
接种物大小：8.134E+07CFU/ml
无协同作用：金黄色葡萄球菌
A：表面活性剂E
B：BIOBAN P-1487
介质：PDB
接种物大小：1.156E+06CFU/ml
A：表面活性剂E
B：BIOBAN P1487
介质：PDB
接种物大小：1.808E+06
A：表面活性剂E
B：BIOBAN P-1487
介质：1/10TSB
接种物大小：5.727E+07CFU/ml
A：表面活性剂E
B：BIOBAN P-1487
介质：1/10TSB
接种物大小：1.808E+06CFU/ml
A：表面活性剂D
B：BIOBAN P-1487
介质：PDB
接种物大小：1.156E+06
A：表面活性剂D
B：BIOBAN P-1487
介质：PDB
接种物大小：5.726E+05CFU/ml
A：表面活性剂D
B：BIOBAN P-1487
介质：1/10TSB
接种物大小：1.808E+05
绿脓假单胞菌
以下杀生物剂当与以下表面活性剂配对时对测试的任何生物不具协同作用：
表面活性剂A
苯甲酸钠、Tris Nitro
表面活性剂E
DMDMH
表面活性剂D
CS-1246、OPP、DMDMH
在以下组合中，观察到协同作用的表面活性剂与杀生物剂的比率不是商业相关的，即1∶0.2或更大的比率(相对于表面活性剂，杀生物剂较少)。在这些比率下，配制产品中的杀生物剂含量将太低而不实用：
表面活性剂A
DIDAC、IPBC
表面活性剂E
CMIT/MIT、IPBC、OIT、TTPC、WSCP
表面活性剂D
CMIT/MIT、OIT、DIDAC
(MBIT、IPBC、WSCP仅在1∶0.05下协同作用或更糟，仅一个数据点除外)
Claims (3)
1.一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)2-溴-2-硝基丙-1,3-二醇；其中所述非离子表面活性剂与2-溴-2-硝基丙-1,3-二醇的重量比是1:0.08到1:0.12或1:0.2到1:1.8286；其中，所述C8-C14直链烷基的混合物包含60到75重量％C8-C10直链烷基和25到40重量％C12-C14直链烷基。
2.一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R2O(CH2CH(CH3)O)3(CH2CH2O)5H
其中R2是C8-C14直链烷基的混合物；和(b)四氢-3,5-二甲基-2H-1,3,5-噻二嗪-2-硫酮；其中所述非离子表面活性剂与四氢-3,5-二甲基-2H-1,3,5-噻二嗪-2-硫酮的重量比是1:0.0024到1:0.4571；其中，所述C8-C14直链烷基的混合物包含60到75重量％C8-C10直链烷基和25到40重量％C12-C14直链烷基。
3.一种协同杀微生物组合物，其包含：(a)具有以下结构的非离子表面活性剂：
R1O(CH2CH(CH3)O)5(CH2CH2O)9H
其中R1是C8烷基；和(b)81:5重量比的4-(2-硝基丁基)吗啉与4,4'-(2-乙基-2-硝基三亚甲基)二吗啉的混合物；其中所述非离子表面活性剂与所述混合物的重量比是1:0.0006到1:0.2743；其中，R1是2-乙基己基。
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- 2014-10-03 EP EP14790421.3A patent/EP3027024B1/en active Active
- 2014-10-03 CN CN201480052682.9A patent/CN105578881B/zh not_active Expired - Fee Related
- 2014-10-03 RU RU2016117115A patent/RU2653763C2/ru not_active IP Right Cessation
- 2014-10-03 CA CA2926623A patent/CA2926623A1/en not_active Abandoned
-
2017
- 2017-07-28 US US15/662,457 patent/US9808001B1/en active Active
- 2017-07-28 US US15/662,460 patent/US9832992B1/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647703A (en) * | 1970-01-02 | 1972-03-07 | Betz Laboratories | Synergistic composition and its use |
| US3759828A (en) * | 1971-07-12 | 1973-09-18 | Texaco Inc | Soluble oil compositions |
| WO1990007273A1 (en) * | 1988-12-24 | 1990-07-12 | Laporte Industries Limited | Absorbent material |
| WO2008031087A1 (en) * | 2006-09-08 | 2008-03-13 | Delaval Holdings Ab | Compositions comprising a c2-c14 carboxylic acid and a surfactant for treating hoof diseases |
Non-Patent Citations (1)
| Title |
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| 土壤消毒防治西洋参、人参土传根病的研究;王丽华 等;《特产科学实验》;19861001(第3期);第17-20,22页 * |
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|---|---|
| EP3027024A1 (en) | 2016-06-08 |
| US20170325450A1 (en) | 2017-11-16 |
| AU2014329443B2 (en) | 2017-12-21 |
| CN105578881A (zh) | 2016-05-11 |
| US9775343B2 (en) | 2017-10-03 |
| AU2014329443A1 (en) | 2016-05-05 |
| US20160227769A1 (en) | 2016-08-11 |
| RU2016117115A3 (zh) | 2018-02-28 |
| BR112016006598A2 (pt) | 2017-08-01 |
| WO2015051205A1 (en) | 2015-04-09 |
| EP3027024B1 (en) | 2017-07-26 |
| US20170325449A1 (en) | 2017-11-16 |
| US9832992B1 (en) | 2017-12-05 |
| JP2016532636A (ja) | 2016-10-20 |
| RU2016117115A (ru) | 2017-11-10 |
| RU2653763C2 (ru) | 2018-05-14 |
| US9808001B1 (en) | 2017-11-07 |
| JP6527856B2 (ja) | 2019-06-05 |
| BR112016006598B1 (pt) | 2020-09-15 |
| CA2926623A1 (en) | 2015-04-09 |
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