CN108752356A - 一种石墨烯增强酞菁光敏化效应的绿色杀虫剂及其应用 - Google Patents
一种石墨烯增强酞菁光敏化效应的绿色杀虫剂及其应用 Download PDFInfo
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- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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- A—HUMAN NECESSITIES
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- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
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- A—HUMAN NECESSITIES
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
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Abstract
本申请涉及一种石墨烯增强酞菁光敏化效应的绿色杀虫剂及其应用,其中所述光敏剂具有如下所示的结构:该光敏化杀虫剂与现有化学杀虫剂和其他光敏杀虫剂相比,具有高效率、不含重金属、绿色环保可降解为无毒物质的有益效果。
Description
技术领域
本申请涉及绿色农药新技术领域,具体涉及一种石墨烯增强酞菁光敏化效应的绿色杀虫剂及其应用。
背景技术
2018年5月,第二十届中国科协年会发布了重大科学前沿问题和重大工程技术难题,其中农业领域入选的就包括绿色农药这一技术难题。杀虫剂的滥用在中国已经造成了广泛严重的问题,我国冷冻蔬菜等农产品在出口时经常被外国检验检疫机构查验出杀虫剂或农药残留超标;作为茶叶的故乡,我国的茶叶出口也受到杀虫剂残留超标的困扰,以致国际上绝大部分原料茶叶都由斯里兰卡和印度提供。
然而杀虫剂是防治病虫害保证农业丰收的重要科技手段,现代农业离不开各种类型的杀虫剂,目前杀虫方式或杀虫剂的类型主要包括生物型,化学型和物理型,其中因为稳定性和成本原因,化学型杀虫剂的使用量远远超过生物杀虫剂和物理杀虫工具。
光敏化杀虫剂是一类特殊的化学杀虫剂,主要利用化学光敏剂在光照下产生的单线态氧的光毒性实现杀虫,特定的光敏剂可以在自然光照下发生敏化效应,而单线态氧可以在非常低的氧分压情况下产生,对生物细胞有着复杂的光损伤能力来实现对害虫的杀灭效应。因为不需要直接对生物细胞产生毒理效应,光敏化合物的毒性和环境危害性比化学农药要小很多,某些光敏剂能够在自然光照下分解为低毒化合物,因此光敏化杀虫剂被认为是潜在的绿色农药。
光敏化杀虫效应的发现已有近半个世纪,染料赤藓红已经在美国被作为商业光敏杀虫剂用于杀灭家蝇幼虫。我国对光敏化杀虫剂也有相关研究,扬州大学的研究人员报道了芳香取代噻吩对夜蛾类昆虫的光敏化杀虫效应,浙江农业大学的研究人员也对竹红菌素类化合物的光敏化杀虫能力进行了研究,发现实验条件下,其对桃树害虫桃蚜虫和黄粉虫致死率在40%左右。而专利201110223237.2和201110223235.3则公开了赤藓红B和虎红对伊蚊的光敏化杀虫效果,但赤藓红一类的染料会使部分植物被染色,不适用于瓜果蔬菜等直接入口的农产物;专利201210024453.9则公开了一种从蓝藻中提取的藻蓝蛋白作为光敏化杀虫剂的应用,其实例声明在0.75mg/ml的剂量下,48小时后对果蝇的杀灭率接近90%,专利公开的藻蓝蛋白来源于引发藻华的蓝藻,且藻蓝蛋白作为生物产品的稳定性不及化学品,这都对这种产品的广泛应用带来限制。现有的光敏化杀虫剂也受到光敏化单线态氧量子产率这一量子化学原理性指标的限制,单一使用光敏化合物已无法使得杀灭效率得到实质性改善。
发明内容
因此,本申请的目的是提供一种光敏剂及包含该光敏剂的光敏化杀虫剂及其制备方法和应用,该光敏化杀虫剂具有高效、绿色、环境友好以及易降解的优良特性。
本申请是通过下述技术方案实现的:
首先,本申请提供一种光敏剂,其具有如下所示的结构:
其中,R1、R2、R3或R4各自独立地选自C1-C5直链或支链烷基。
进一步地,在一个或多个实施方式中,所述R1、R2、R3或R4各自独立地为C3-C5直链或支链烷基;
进一步地,在一个或多个实施方式中,所述R1、R2、R3或R4相同;
进一步地,在一个或多个实施方式中,所述R1、R2、R3或R4为异戊烷基;
进一步地,所述光敏剂为四异戊氧基磷酞菁。
其次,本申请提供了一种制备上述光敏剂的方法,所述方法包括:
将4-烷氧基邻苯二腈溶于正戊醇,氩气的保护下,加入金属锂条,回流反应,反应完成后以乙醇水解锂酞菁为无金属酞菁,通过硅胶柱分离后得到纯产品四烷氧基无金属酞菁;随后在氩气保护下,取得到的四烷氧基无金属酞菁与三溴氧磷在吡啶溶液中混合,加热进行反应,反应完成后,干燥除去溶剂,通过硅胶柱分离后得到四烷氧基磷酞菁;
其中,所述烷氧基为C1-C5直链或支链烷氧基,
进一步地,在一个或多个实施方式中,所述烷氧基为C3-C5直链或支链烷氧基,更进一步为异戊烷氧基。
进一步地,所述回流为在160℃条件下回流4h;
进一步地,所述方法中第一次使用硅胶柱进行分离时,所用洗脱剂为氯仿-甲醇,其体积比为10:1;
进一步地,所述加热进行反应为加热至70℃反应2h;
进一步地,所述方法中第二次使用硅胶柱进行分离时,所用洗脱剂为氯仿-吡啶,其体积比为10:1。
再次,本申请提供一种光敏化杀虫剂,其包含或由上述光敏剂、碳纳米材料、分散剂、葡萄糖和水组成;
进一步地,所述光敏剂的质量体积浓度为0.1-2%,优选为0.2-2%,更优选为0.5-1%,最优选为0.5%;
进一步地,所述石墨烯的质量体积浓度为0.2-5%,优选为0.2-1%,更优选为0.5-1%,最优选为2%;
进一步地,所述分散剂的质量体积浓度为0.1-3%,优选为0.2-2%,更优选为0.2-1,最优选为0.5%;
进一步地,所述葡萄糖的质量体积浓度为1-10%,优选为10%;
进一步地,所述光敏剂为四异戊氧基磷酞菁;
进一步地,所述分散剂为Triton X-100;
进一步地,碳纳米材料选自石墨烯、氧化石墨烯、氧化还原石墨烯、氮杂石墨烯、碳纳米管和含碳量子点;优选为石墨烯。
进一步地,所述光敏化杀虫剂可在自然光或人工光照下降解;
进一步地,所述光敏化杀虫剂在自然光照下或模拟自然光照的人工光照下累积18小时(相当于春秋自然光照2-3天)的降解率为90%;
进一步地,所述光敏化杀虫剂在人工光照6小时内,照射能量在30-60J/cm2时的降解率为98%。
再次,本申请还提供了一种制备上述光敏化杀虫剂的方法,所述方法包括室温下按处方量将光敏剂、石墨烯和分散剂混合于葡萄糖溶液中,剪切45-60min后得到混合均匀的乳浊液。
进一步地,所述剪切包括两个阶段,所述第一阶段为低速剪切阶段,使用50-150转/min的速率剪切15-20min,所述第二阶段为高速剪切阶段,使用2000-4000转/min的速率剪切30-45min;
进一步地,所述第一阶段使用100-150转/min的速率剪切15min,所述第二阶段使用3000-4000转/min的速率剪切30min;
进一步地,所述第一阶段使用100转/min的速率剪切15min,所述第二阶段使用3000转/min的速率剪切30min。
在一个或多个实施方式中,所述光敏化杀虫剂按照如下方法制备得到:
室温下按处方量将光敏剂、石墨烯和分散剂混合于葡萄糖溶液中,定容,先使用50-150转/min的速率剪切15-20min,然后使用2000-4000转/min的速率剪切30-45min,得到混合均匀地乳浊液,如有需要可稀释得到所需浓度。
制备得到的光敏化杀虫剂,如不立即使用,可避光保存。
此外,本申请提供了一种防治害虫的方法,所述方法包括采用喷雾法将权利要求5中所述的光敏化杀虫剂直接或经稀释后施用到作物上;
进一步地,所述方法包括采用喷雾法将光敏化杀虫剂在晚间施用到作物上,次日进行日照或者人工光照,累计日照或光照时间不小于4小时;
进一步地,进行人工光照时,所述人工光照模拟自然日照;
进一步地,所述作物为种植在温室大棚内的作物或种植在开放的室外的作物;
进一步地,所述害虫包括白菜螟幼虫、果蝇幼虫和果蝇卵;
进一步地,防治白菜螟幼虫的施用剂量为每100条幼虫/2-50毫升光敏杀虫剂,优选为100条幼虫/10毫升光敏杀虫剂;
进一步地,防治果蝇幼虫的施用剂量为每100只幼虫/1-50毫升光敏杀虫剂,优选为每100只幼虫/5毫升光敏杀虫剂;
进一步地,所述防治包括预防和杀虫。
与现有技术相比,本申请具有以下有益效果:
本申请的光敏化杀虫剂绿色环保高效,可在施用后累积光照(自然光或人工光照)不少于2小时可实现对白菜螟幼虫的高达90%的致死率,以及在施用后累积光照(自然光或人工光照)不少于4小时可实现对白菜螟幼虫及果蝇的最高达95%的致死率;并且可在自然光或人工光照下降解,其中,在自然光照下累积18小时(相当于春秋自然光照2-3天),降解率可达90%;在人工光照6小时内,照射能量在30-60J/cm2时,降解率可达98%;这一特性能够有利于降低杀虫剂在入口农作物上的残留量;同时该杀虫剂不会分解出锌和铝等重金属原子,符合绿色环保特征;此外,石墨烯等碳纳米材料的加入可以使得磷酞菁能够更高效的产生单线态氧,杀虫效果高于单独使用光敏化合物作为杀虫剂。
附图说明
以下,结合附图来详细说明本申请的实施方案,其中:
图1为本申请的实施方式中光敏化杀虫剂对白菜螟幼虫的杀灭效果图。
具体实施方式
下面结合具体实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。实施例中所用试剂中未注明制备方法的均可通过公开渠道采购获得。
除非另行定义,文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外,任何与所记载内容相似或均等的方法及材料皆可应用于本申请方法中。文中所述的较佳实施方法与材料仅作示范之用。
实施例1光敏剂的合成
磷酞菁光敏剂的合成如下:4-异戊氧基邻苯二腈(2.0g,0.05mol)溶于正戊醇(25ml),在氩气的保护下,加入金属锂条0.05g,回流(温度为160℃)4h,反应后以乙醇水解锂酞菁为无金属酞菁,通过硅胶柱(洗脱剂:氯仿-甲醇,v/v=10:1)分离后得到纯产品四异戊氧基无金属酞菁。随后氩气保护下,四异戊氧基无金属酞菁与三溴氧磷在吡啶溶液中混合加热70℃,反应2小时后,干燥除去溶剂,通过硅胶柱(洗脱剂:氯仿-吡啶,v/v=10:1)分离后得到四异戊氧基磷酞菁,即为本申请的光敏化合物。采用MOLDI-TOF质谱进行结构确认,结果显示:分子离子峰923.2,理论计算分子离子峰923.13,元素分析结果:C,67.9%;H,6.8%;N,12.05%;P,3.3,理论计算值:C52H60N8O6P,C,67.59%;H,6.54%;N,12.13%;O,10.39%;P,3.35%。
实施例2-7光敏化杀虫剂的制备
按照如下所示方法制备光敏化杀虫剂:
室温下,将四异戊氧基磷酞菁、石墨烯和TritonX-100混合于葡萄糖溶液中,定溶到100ml,先使用100转/min低速剪切15min,然后使用3000转/min高速剪切30min,得到混合均匀的乳浊液,其中,光敏化杀虫剂中各成分的浓度如表1中所示。
表1
实施例8光敏化杀虫剂的制备
室温下,将四异戊氧基磷酞菁、石墨烯和TritonX-100混合于葡萄糖溶液中,定容后,先使用50转/min低速剪切15min,然后使用2000转/min高速剪切30min,得到混合均匀的乳浊液,其中,光敏化杀虫剂中各成分的浓度与实施例7相同。
实施例9光敏化杀虫剂的制备
室温下,将四异戊氧基磷酞菁、石墨烯和TritonX-100混合于葡萄糖溶液中,定容后,先使用150转/min低速剪切15min,然后使用4000转/min高速剪切30min,得到混合均匀的乳浊液,其中,光敏化杀虫剂中各成分的浓度与实施例7相同。
实施例10温室大棚作物上害虫的防治
防治方法:将实施例2-9中制备得到的光敏化杀虫剂分散液采用喷雾法在晚间直接施用到作物上,次日进行自然光照或人工光照(冬季可配合使用加温灯),自然光照时间累积不小于4小时,晚间可观察施药效果;如果日光不足或天气不好,可配合使用人工光照。
(1)对白菜螟幼虫杀虫效果测试
实验分为光照组、对照组(避光条件)和空白组,取白菜螟幼虫(体长小于0.5cm),取实施例7中制备的光敏化杀虫剂按照每100条幼虫/10毫升光敏杀虫剂乳化液的剂量喷洒(诱食),喷洒后避光条件下诱食2小时。随后将光照组暴露于60W卤素灯下2小时,避光组不进行光照,空白组不进行光照和杀虫剂喷洒,各组平行进行,从喷洒(诱食)开始每小时观察幼虫死亡情况,实验重复三次,按照统计学方法计算其致死率。
按照实施实例7得到的实验结果如图1显示,结果显示:喷洒(诱食)后4小时(即光照2小时后),光照组的白菜螟幼虫的致死率达到90%以上,致死率在喷洒(诱食)后2小时给光后迅速增加,对照组的白菜螟致死率一直低于20%且随着时间的推移白菜螟致死率没有变化,空白组的致死率一直低于5%,这三组数据经过Student-T方法统计分析,存在明显差异(p<0.05),说明光敏化杀虫剂在光照下对白菜螟有着明显的毒杀效果。
此外,本申请对比了不同浓度组成以及不同工艺制备的光敏化杀虫剂的杀虫效果,其中,空白组、对照组如图1所示,实施例2-9的杀虫效果如表2所示:
表2
(2)对果蝇幼虫和卵的杀虫效果测试
实验分为光照组、对照组(避光条件)和空白组,每组各取未经清洗的杨梅果实10粒,置于温暖潮湿的瓶子中自然繁殖,使果蝇得到繁殖,第三天取出杨梅,简单计数保证瓶子里的果蝇数不低于100只,向各个瓶子中加入每100只幼虫/5毫升光敏杀虫剂乳化液的剂量进行喷洒,避光2小时后,在日光下进行光照4小时后,核实生存果蝇数量计算其致死率,继续避光放置24小时。通过手工核实各组瓶中最后生存的果蝇数量来评估其对果蝇成虫和幼虫的杀灭抑制作用,结果如表3所示。
表3光敏化杀虫剂对果蝇及其卵的杀灭效果测试结果
经过4小时照射,光照组的果蝇致死率在95%,经过放置24小时后,剩余数不足起始计数时的10%;而在对照组,4小时候果蝇致死率只有25%,且经过24小时后,果蝇继续繁殖了400%,本实验表明光敏化杀虫剂可以通过喷洒方式杀灭果蝇卵并抑制其继续繁殖。
此外,按照上述实验,本申请对比了不同浓度组成以及不同工艺制备的光敏化杀虫剂对果蝇及其幼虫的杀虫效果,其中,杀虫效果如表4所示:
表4
实施例 | 光照4小时致死率 | 避光24小时的繁殖率 |
2 | 80±3% | 18±1% |
3 | 90±3% | 12±4% |
4 | 85±2% | 13±2% |
5 | 78±4% | 16±3% |
6 | 89±4% | 15±4% |
7 | 95±2% | 10±2% |
8 | 82±5% | 18±4% |
9 | 86±3% | 20±2% |
实施例11光敏化杀虫剂的降解测试
取实施例7的光敏化杀虫剂10毫升,置于自然阳光下照射,测试时间为北纬35度的春季,白天每隔6小时取样,晚上隔夜取样,记录光照时间,样品使用紫外可见光谱仪测试四异戊氧基磷酞菁在705nm处的特征吸收峰,通过吸收峰衰减的情况来评估降解情况;同时平行试验以60W卤素灯作为光源,在光敏化杀虫剂正上方50厘米处进行光照,每隔半小时取样一次,测试光敏剂四异戊氧基磷酞菁特征吸收峰值变化情况。
实验结果显示累计自然光照18小时可以使得光敏化杀虫剂中的四异戊氧基磷酞菁降解90%,大约相当于春秋季节自然光照2-3天;使用人造光源照射能量相当于30-60J/cm2,则在6小时内可以降解掉98%,这表明残留在植物叶面果实表面的光敏化杀虫剂可以快速有效的被降解掉,保证了其使用的安全绿色和环保特性。
此外,本申请同时测定了实施例2-6和实施例8-9的光敏化杀虫剂的降解速率,其中,实施例2-6与实施例7的光敏化杀虫剂具有相近的降解率,而实施例8-9的光敏化杀虫剂则需要更多的时间完成降解。
Claims (8)
1.一种光敏剂,其具有如下所示的结构:
其中,R1、R2、R3或R4各自独立地选自C1-C5直链或支链烷基。
2.根据权利要求1所述的光敏剂,其特征在于,所述R1、R2、R3或R4各自独立地为C3-C5直链或支链烷基;
进一步地,所述R1、R2、R3或R4相同;
进一步地,所述R1、R2、R3或R4为异戊烷基;
进一步地,所述光敏剂为四异戊氧基磷酞菁。
3.一种制备权利要求1或2中所述光敏剂的方法,所述方法包括:
将4-烷氧基邻苯二腈溶于正戊醇,氩气的保护下,加入金属锂条,回流反应,反应完成后以乙醇水解锂酞菁为无金属酞菁,通过硅胶柱分离后得到纯产品四烷氧基无金属酞菁;随后在氩气保护下,取得到的四烷氧基无金属酞菁与三溴氧磷在吡啶溶液中混合,加热进行反应,反应完成后,干燥除去溶剂,通过硅胶柱分离后得到四烷氧基磷酞菁;
其中,所述烷氧基为C1-C5直链或支链烷氧基,优选为C3-C5直链或支链烷氧基,更优选为异戊烷氧基。
4.根据权利要求3所述的方法,其特征在于,所述回流条件为160℃回流4h;
进一步地,所述方法中第一次使用硅胶柱进行分离时,所用洗脱剂为氯仿-甲醇,其体积比为10:1;
进一步地,所述加热进行反应的条件为加热至70℃下反应2h;
进一步地,所述方法中第二次使用硅胶柱进行分离时,所用洗脱剂为氯仿-吡啶,其体积比为10:1。
5.一种光敏化杀虫剂,其包含或由权利要求1或2中所述的光敏剂、碳纳米材料、分散剂、葡萄糖和水组成;
进一步地,所述光敏剂的质量体积浓度为0.1-2%,优选为0.2-2%,更优选为0.5-1%,最优选为0.5%;
进一步地,所述石墨烯的质量体积浓度为0.2-5%,优选为0.2-1%,更优选为0.5-1%,最优选为2%;
进一步地,所述分散剂的质量体积浓度为0.1-3%,优选为0.2-2%,更优选为0.2-1%,最优选为0.5%;
进一步地,所述葡萄糖的质量体积浓度为1-10%
进一步地,所述光敏剂为四异戊氧基磷酞菁;
进一步地,所述分散剂为Triton X-100;
进一步地,碳纳米材料选自石墨烯、氧化石墨烯、氧化还原石墨烯、氮杂石墨烯、碳纳米管和含碳量子点;优选为石墨烯。
6.一种制备权利要求5中所述光敏化杀虫剂的方法,所述方法包括室温下按处方量将光敏剂、石墨烯和分散剂混合于葡萄糖溶液中,剪切45-60min后得到混合均匀的乳浊液。
7.根据权利要求6所述的方法,其特征在于,所述剪切包括两个阶段,所述第一阶段为低速剪切阶段,使用50-150转/min的速率剪切15-20min,所述第二阶段为高速剪切阶段,使用2000-4000转/min的速率剪切30-45min;
进一步地,所述第一阶段使用100-150转/min的速率剪切15min,所述第二阶段使用3000-4000转/min的速率剪切30min;
进一步地,所述第一阶段使用100转/min的速率剪切15min,所述第二阶段使用3000转/min的速率剪切30min。
8.一种防治害虫的方法,所述方法包括采用喷雾法将权利要求5中所述的光敏化杀虫剂直接或经稀释后施用到作物上;
进一步地,所述方法包括采用喷雾法将光敏化杀虫剂在晚间施用到作物上,次日进行日照或者人工光照,累计日照或光照时间不小于4小时;
进一步地,所述作物为种植在温室大棚内的作物或种植在开放的室外的作物;
进一步地,所述害虫包括白菜螟幼虫、果蝇幼虫和果蝇卵;
进一步地,防治白菜螟幼虫的施用剂量为每100条幼虫/2-50毫升光敏杀虫剂,优选为100条幼虫/10毫升光敏杀虫剂;进一步地,防治果蝇幼虫的施用剂量为每100只幼虫/1-50毫升光敏杀虫剂,优选为每100只幼虫/5毫升光敏杀虫剂;
进一步地,所述防治包括预防和杀虫。
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