蒽-N，N-二甲基苯胺二元体系的荧光开关行为研究

通过Curtius重排反应,将高荧光量子产率的葸基团通过脲基连接在N,N-二甲基苯胺单元上,合成了二元给受电子体系9-（4-N,N-二甲胺基苯基）脲基葸（DMA—An）。选择性激发蒽单元,该二元体系发生从N,N-二甲基苯胺到蒽的光诱导电子转移反应（photoinduced electron transfer PET）,导致葸荧光猝灭。酸化使N,N-二甲基苯胺基质子化,PET过程受阻,DMA-An的荧光恢复。此时,向该体系中加入三乙胺可使DMA-An的荧光恢复至初始的猝灭状态。多次实验证明此荧光猝灭-增大过程是可逆的,即DMA—An的荧光随酸碱变化呈光开关on／off行为。     

基于蒽酰亚胺基团的新型Fe~(3+)和Hg~(2+)化学敏感器

含蒽酰亚胺基团的化合物N-(2-(6-氨基吡啶))-9-蒽酰亚胺(L1)对Fe3+表现出灵敏的荧光增强响应.L1的衍生物N,N-′(2,6-吡啶基)-二(9-蒽酰亚胺)(L2)对Hg2+在紫外-可见吸收光谱和荧光光谱上显示了良好的识别性.即使在其它金属阳离子存在下,L1和L2分别对于Fe3+和Hg2+仍然表现出较好的选择性.     

N-甲基-2-（4’-双噻吩基）-[60]富勒烯吡咯烷的合成及荧光特征

合成了N-甲基-2-(4'-双噻吩基)-[60]富勒烯吡咯烷,以1H NMR,13C NMR,FTIR,FAB-MS和UV进行了结构表征.测量其在甲苯溶液中的荧光发射光谱,并在此最大发射波长下测得其荧光寿命为6.03 ns,而C60在室温的荧光寿命大约是1.2 ns.表明N-甲基-2-(4'-双噻吩基)-[60]富勒烯吡咯烷在激光激发下,加成基团双噻吩环与母体C60之间发生了分子内能量转移和电荷传递,有可能产生长寿命的电荷分离态,为下一步制备聚噻吩富勒烯及太阳能电池的组装提供了光电等基本参数.     

新型菲醌类染料的合成及性能

设计合成了以含有丙二腈基团的菲醌结构为电子受体、三苯胺或N,N-二(4-正丁基苯基)苯胺结构为电子给体的D-A-D型纯有机功能染料(Ⅳ和Ⅴ)。利用紫外-可见吸收光谱、荧光发射光谱、循环伏安曲线及理论计算对该类染料及其前体的光学、电化学性质进行了研究。结果表明,染料Ⅳ和Ⅴ在可见光区域均有较宽的吸收带和发射带,其最大吸收波长分别为581和605 nm,最大发射波长分别为442和472 nm;相对于HOMO能级,丙二腈基团的引入对LUMO能级的影响更大。     

新型希夫碱铜三元配合物与DNA相互作用的研究

合成了铜(Cu)-噻吩-2-甲醛缩L-蛋氨酸亚胺-1,10-邻菲啰啉(phen)三元配合物,并通过元素分析、红外光谱、紫外-可见光谱、核磁共振及TG-DTG等手段对其结构和化学组成进行表征,确定其化学组成为[CuL(Phen)(H2O)].Ac.2H2O(L:C10H12NO2S2)。利用紫外-可见吸收光谱、荧光光谱、粘度测试研究了配合物与DNA的相互作用,结果表明,配合物与DNA之间通过插入作用结合。     

8-羟基喹啉的丙烯酸酯及其聚合物的荧光光谱研究

在同一分子中既含有电子给体基团,又含有电子受体基团的单体,如甲基丙烯酸二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基)代丙烯酰胺(DMAPAA)及其聚合物的荧光光谱颇为有趣。在这类单体中,由于同时有电子给体二甲氨基苯基和电子     

靛红希夫碱衍生物的合成及金属离子识别研究

以靛红、水合肼、2-羟基-1-萘甲醛为原料,经缩合及还原反应合成出主体分子,3-((2-羟基萘)亚甲基)亚肼基-2-吲哚酮(HNHI)。通过1H NMR、13C NMR和元素分析等方法对其结构进行了表征。研究了不同金属离子对主体分子HNHI紫外-可见吸收光谱和荧光光谱的影响。结果表明,Cu2 、Co2 和Ni2 对HNHI的紫外吸收光谱有影响,在长波区有新峰出现,溶液由无色变成粉色;并且这三种金属离子对HNHI的荧光光谱也有影响,荧光明显增强。     

柔性链修饰三苯胺氨基衍生物的构建策略

以4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}苯甲醛为原料,首先经过缩合反应,得到系列带有含氮基团的还原底物,再利用金属硼氢化试剂对极性双键的选择性还原特征,合成了系列饱和柔性烷基链修饰的三苯胺氨基衍生物(Ⅱb~d)。通过控制反应时间和加料顺序、梯度增强还原剂还原能力等方式对合成路线进行了优化。实验结果表明,硼氢化钠在-5℃下能够对硝基相邻双键进行高效还原,而氰基相邻双键极性较小需要采用硼氢化锂在80℃下回流10h进行还原。最后将得到的氨基衍生物与均三嗪基团相连,得到系列给体-受体(D-A)化合物(Ⅲb~d),利用核磁氢谱、碳谱、高分辨质谱以及红外吸收光谱对其进行了结构表征。通过分析紫外-可见吸收,荧光发射光谱,并结合相关电化学数据可知,此系列化合物可产生光诱导长寿命电荷分离态,在有机光电领域具有一定的应用前景。     

氰基富勒烯[60]和1,2-二氰基富勒烯[60]的合成和表征

亲核加成是Fullerene[60]典型、特征的反应,由于富勒烯分子有很多反应活性点,大多数亲核取代发生多元加成,生成难分离的混合物。Fullerene[60]和氰化钠的加成反应证明:以N,N-二甲基甲酰胺和邻二氯苯为混合溶剂,氰基负离子(CN-)与C60能发生可控的一元亲核加成反应,生成[C60(CN)]-,不分离此中间体,直接加入三氟乙酸得到产物C60(CN)H;如果在C60(CN)-的溶液中加入对甲苯磺酰氰,可高收率地得到C60(CN)2。利用1H NMR、质谱、元素分析对产物的组成和结构进行了确认和鉴定。     

水杨醛缩对氯苯胺Co(Ⅱ)配合物的合成、表征及其荧光性质研究

以水杨醛和对氯苯胺为原料合成了水杨醛缩对氯苯胺(HL),将其作为主要配体与1,4-对苯二酚以及氯化钴(CoCl2·6H2O)反应生成了Co(Ⅱ)的配合物[Co(C6H4O2)(L)2]n,用元素分析、红外吸收光谱、紫外可见吸收光谱对其结构进行了表征,并通过荧光光谱对配体、配合物荧光发光性质进行了研究。结果表明,配体水杨...     

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.     

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.     

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。     

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.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.