桃金娘烯醛基噻二唑-酰胺化合物的合成及性能

以α-蒎烯(Ⅰ)为原料,经选择性烯丙位甲基氧化反应制备了桃金娘烯醛(Ⅱ),Ⅱ再经缩合反应得到了桃金娘烯醛缩氨基硫脲(Ⅲ),进一步氧化环化得到了桃金娘烯醛基噻二唑(Ⅳ),然后与系列酰氯化合物进行N-酰化反应,以66%~81%的收率合成得到了11个桃金娘烯醛基噻二唑-酰胺化合物Ⅴa~k。采用FTIR、1HNMR、13CNMR和ESI-MS对目标化合物进行了结构表征,并测试了目标化合物的抑菌和除草活性。结果表明:在化合物Ⅴa~k的质量浓度为50 mg/L时,Ⅴa~k对测试的苹果轮纹病菌、黄瓜枯萎病菌、花生褐斑病菌、小麦赤霉病菌和番茄早疫病菌均显示不同程度的抑菌活性,其中桃金娘烯醛基噻二唑-乙酰胺(Ⅴa)、桃金娘烯醛基噻二唑-氯乙酰胺(Ⅴb)和桃金娘烯醛基噻二唑-正丙酰胺(Ⅴc)对苹果轮纹病菌的相对抑制率分别为93.0%、93.0%和98.2%,化合物Ⅴb对黄瓜枯萎病菌的相对抑制率为84.3%,表现出与阳性对照嘧菌酯(对苹果轮纹病菌和黄瓜枯萎病菌的相对抑制率分别为96.0%和87.5%)相当的抑菌活性。构效分析表明:脂肪族取代基衍生物表现出更好的抑菌活性。此外,在质量浓度为100 mg/L时,化合物Ⅴc对油菜胚根生长的相对抑制率为79.6%,显示出比阳性对照丙炔氟草胺(抑制率为63.0%)更好的除草活性。     

含嘧啶结构的三唑席夫碱衍生物的合成、抗菌活性及分子对接

[目的]在1,2,4-三唑-3-硫酮母环中引入嘧啶环及亚氨基团,以期获得具有良好生物活性的候选药物。[方法]采用亚结构拼接原理获得了含嘧啶结构的1,2,4-三唑席夫碱衍生物,并通过元素分析及光谱分析对其结构进行表征。采用菌丝生长速率法研究了化合物对小麦赤霉病菌、葡萄黑痘病菌和苹果炭疽病菌的抑制活性。利用分子对接技术将合成的化合物与受体蛋白(5E9H)进行对接。[结果]目标化合物对小麦赤霉病菌的抑制效果最为显著,其EC₅₀值介于6.15～10.31 mg/L之间,小于对照药物氟康唑,且化合物FTP3-2的抑制效果约为对照药物的1.5倍。分子对接结果表明,化合物与受体蛋白(5E9H)的对接结合能越小,对小麦赤霉病菌的抑制作用越强。[结论]合成的化合物具有抗小麦赤霉病菌的潜力,其中化合物FTP3-2可作为先导化合物进行深入研究。     

咪唑和三唑醚类化合物的合成及生物活性

以2,4-二氯-α-氯代苯乙酮、取代甲苯、咪唑、三唑为起始原料,合成了9个咪唑醚类和16个三唑醚类化合物,所有化合物结构经1HNMR、IR和元素分析进行了确证,对化合物对马铃薯晚疫病菌(Phytophthoro infestans)和秧苗枯萎病菌(Phizoctonia)的抑菌活性进行了测定,测定表明,25个化合物都有不同程度的抑菌活性,其中Ⅲa、Ⅲb、Ⅲd、Ⅳg、Ⅴb、Ⅴc等6个化合物质量浓度为50 mg/L和10 mg/L时,对两种病菌的抑菌率达80%和50%以上,初步分析了化合物抑菌活性与结构的关系。     

含苯基(糖基)和嘧啶基哌啶结构的1,2,3-三唑类化合物的设计、合成与生物活性

[目的]寻找较高活性和杀菌谱更宽的杀菌剂先导化合物并进行结构优化。[方法]设计合成了一类含有取代的苯基(糖基)和嘧啶基哌啶的1,2,3-三唑类化合物。[结果]合成12个结构新颖的含有取代的苯基(糖基)和嘧啶基哌啶的1,2,3-三唑类化合物,结构经过核磁共振氢谱(1H NMR)、高分辨质谱(HMRS)或元素分析确证,并进行杀菌活性测试研究。[结论]杀菌活性测试结果表明:部分目标化合物对对苹果轮纹菌和小麦赤霉菌表现了很好的活性,与百菌清相当。     

Click Chemistry合成1,2,3-三唑氨基酸衍生物

通过W ong叠氮转化和亲核取代反应,分别合成了叠氮苯丙氨酸、叠氮丙氨酸、苄基叠氮,采用上述叠氮化物与L-炔丙基甘氨酸进行C lick反应,合成了3个1,4-取代1,2,3-三唑氨基酸衍生物:2-氨基-3-[1-(1-羧基-2-苯乙基)-1H-1,2,3-三唑-4-基]丙酸、3,3-′(1H-1,2,3-三唑-1,4-基)双(2-氨基丙酸)和2-氨基-3-(1H-1,2,3-三唑-1-苄基-4-基)丙酸,收率分别是76%、62%和68%,产物结构经核磁共振波谱、质谱、红外光谱进行了表征。1,2,3-三唑氨基酸衍生物含双功能螯合基团,是很有潜力的fac-[188Re(CO)3(H2O)3]+放射性标记配体。     

取代吲哚-3-甲醛类化合物抑菌活性研究

拓宽取代吲哚-3-甲醛类化合物在抑制植物病原真菌活性的应用范围。首先通过Vilsmeier-Haack反应制备得到取代吲哚-3-甲醛类化合物(Ⅰ~Ⅴ);采用菌丝生长速率法分别测定化合物对5种常见植物病原真菌的室内毒力。化合物Ⅰ~化合物Ⅴ对所测5种病原真菌均表现出不同程度的毒力。其中化合物5-硝基-3-醛基吲哚(Ⅳ)和5-氰基-3-醛基吲哚(Ⅴ)对油菜菌核病菌表现出高于霉灵的活性,其相对毒力分别是霉灵的325倍和1.86倍。     

5-甲基-4-乙酰基-1-对氯苄基-1,2,3-三唑的合成研究

以对氯苄基叠氮和乙酰丙酮为原料合成5-甲基-4-乙酰基-1-对氯苄基-1,2,3-三唑,考察了催化剂类型、溶剂、配比对反应的影响,并确定了优化的工艺条件:无水碳酸钾为催化剂,乙腈和乙醇等体积混合为反应溶剂,n(对氯苄基叠氮)∶n(乙酰丙酮)=1∶1.2,反应时间2 h。产品收率达94%,目标化合物的结构经1H NMR和IR确证。     

2-取代-4-氯-5-芳基-2H-1,2,3-三唑类化合物的合成及生物活性

以芳醛、硝基甲烷及叠氮化钠为起始原料,经环化、氯化、烃化反应,以收率53%～94%合成了15个2-取代-4-氯-5-芳基-2H-1,2,3-三唑类化合物(Ⅳa～o),经核磁共振波谱、质谱和元素分析对目标化合物的结构进行确证。采用菌丝生长速率测定法,在质量浓度25mg/L下,目标化合物对小麦赤霉病菌、辣椒疫霉病菌、烟草赤星病菌、黄瓜灰霉病菌、水稻纹枯病菌及油菜菌核病菌6种作物病菌进行离体抑菌活性实验。初步的抑菌活性测试结果表明:化合物Ⅳd对小麦赤霉病菌、黄瓜灰霉病菌及油菜菌核病菌的抑制率分别为70.4%、74.1%和72.9%,化合物Ⅳk对黄瓜灰霉病菌及油菜菌核病菌的抑制率分别为87.0%及84.7%。Ⅳd对辣椒疫霉病菌的抑制率为61.4%,高于商品化品种苯醚甲环唑的42.5%。     

N-(1,4-二取代吡唑-5-基)-1,2,3-噻二唑酰胺类化合物的合成与杀菌活性研究

设计合成了9个N-(1,4-取代吡唑-5-基)-1,2,3-噻二唑酰胺类化合物,测试了化合物对小麦赤霉病菌(Gibberella zeae)、辣椒枯萎病菌(Fusarium oxysporum)和苹果腐烂病菌(Cytospora mandshurica)的抑制活性。初步结果表明,目标化合物在50μg/mL浓度下对小麦赤霉病菌、辣椒枯萎病菌和苹果腐烂病菌有一定的抑制作用,其中化合物8j对小麦赤霉病菌的抑制率达到47.6%,接近对照药剂恶霉灵;化合物8d对苹果腐烂病菌的抑制率达到56.8%,与对照药剂恶霉灵相当,具有进一步研究的价值。     

樟脑基咪唑盐类化合物合成及其抑菌活性

以天然可再生资源樟脑磺酸为原料制备了10-碘代樟脑,10-碘代樟脑再经季铵化反应、离子交换后得到16个樟脑基咪唑盐。通过HRMS、~1HNMR、~(13)CNMR和19FNMR对目标化合物结构进行了表征,采用菌丝生长速率法测定了它们对立枯丝核菌、层出镰刀菌和灰葡萄球菌的抑制率。结果表明,目标化合物对3种真菌均具有一定的抑制作用,部分目标化合物对灰葡萄球菌的抑制效果显著,3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-1-(2,4,6-三甲基)苯基-咪唑-3-鎓双三氟甲磺酰亚胺盐(Ⅲd)、1-(4-氯苯基)-3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-咪唑-3-鎓碘盐(Ⅴa)抑制率可达100%,效果优于阳性药百菌清;化合物Ⅲd、Ⅳa〔1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-咪唑-3-鎓碘盐〕对层出镰刀菌有较好的抑制活性,抑制率分别可达为66.2%、70.4%,效果与阳性药百菌清相近;目标化合物对立枯丝核菌的抑制效果整体不及百菌清。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。