基于苝酰亚胺衍生物荧光探针的研究进展

苝酰亚胺衍生物(perlenediimide derivatives, PDIs)又称为苝四羧酸二酰亚胺衍生物,结构中具有平面共轭大π键,苝湾骨架和羧基的存在使其具备亲脂性和亲水性。作为一类性能优异的新型光电材料,由于其良好的光电性能、较强的化学稳定性和可修饰性,在荧光探针、传感材料等方面有着极其广泛的应用。近年来,荧光光谱测定技术得到了迅速发展,荧光分析方法也成为了较热门的现代分析技术,在医疗卫生、环境勘测、分析等众多领域都受到了广泛关注。荧光分子探针是基于荧光分析和分子识别的一种新兴技术,可将化合物分子的识别信息转变为光信号,具有成本低、荧光信号变化剧烈、灵敏度高、实时分析等优点,苝酰亚胺衍生物显示出了越来越重要的实际利用价值。     

苝酰亚胺衍生物金属离子荧光探针的研究进展

苝酰亚胺衍生物(perlenediimide derivatives,PDIs)是具有平面共轭大π键的稠环大分子,光化学稳定性好,荧光发光性能强,是一类性能优异的纳米分子材料,已在传感材料、太阳能电池等方面引起广泛关注。由于苝酰亚胺衍生物具有良好的光电性能和强化学可修饰性,在医用荧光探针方面显示出良好的应用前景,例如可用作金属离子识别、药物载体、抗肿瘤药物、荧光示踪剂等用于疾病的诊断和治疗,也可用于环境分析中各种不同分析物的检测。这种金属离子荧光探针灵敏度高、操作简便、荧光信号变化剧烈,能准确实现金属离子识别。本文综述了近几年来国内外学者对苝酰亚胺衍生物作为金属离子荧光探针方面的研究,并对其发展做了展望。     

单边苯基苝酰亚胺的合成工艺研究

研究了以3,4,9,10-苝四羧酸二酐为原料,经过水解,酸酐化,苯胺酰亚胺化,乙酸铵条件下酰亚胺化,最终制备得到不对称的N-苯基苝酰亚胺分子。通过红外光谱分析表征了结构。     

教学研究与课程思政协同发展的药物化学实践教学——一种苝酰亚胺衍生物医用荧光探针的合成

药物化学是一门实践性很强的药学类本科专业的核心课程,灵活地将思政元素与科研实例有机融合,充分发挥教学研与思政教育的协同作用,在知识传播中增强学生的专业认同感,实现药物化学课程思政的育人功能。设计一种以四氯苝酐为原料、可选择性识别Pb²⁺的新型苝酰亚胺荧光探针,并将其与Pb²⁺配位后的荧光性能进行详细研究,准确实现Pb²⁺的识别。本实验不仅能够锻炼学生对仪器的合理使用,熟悉苝酰亚胺衍生物医用荧光探针的结构、性能和制备方法,还可以使学生进一步了解学科前沿,促进教学研与课程思政全面协同发展,从而培养科学能力,提升科学素养。     

基于苝酰亚胺席夫碱荧光探针的制备及其对镉离子的选择性识别研究

利用C=N异构机制,以苝酰亚胺为骨架设计合成了一种香草醛席夫碱荧光探针,通过红外光谱和质谱对其结构进行了表征。同时利用紫外-可见光谱仪和荧光光谱仪对其性能进行了研究,研究结果表明,当使用490 nm的激发波长对该化合物进行激发时,化合物对Cd^2+表现出良好的选择性,在530 nm处的荧光发射峰强度显著上升。干扰实验表明,Zn^2+、Cu^2+和Hg^2+对Cd^2+的识别存在干扰,大多数金属离子对识别过程影响不大。荧光实验数据分析结果表明两者之间形成了1∶1的键合关系,键合常数lgK为5.37。该荧光探针对Cd^2+的检出限为0.2 nmol/L(约22.8 ng/L),可以满足水体中镉离子的检测要求。     

含叔胺基团苝酰亚胺的合成及其自组装性能

利用苝酐为原料,合成了两种不同碳链长度叔胺基取代的苝酰亚胺分子N,N-二(N,N-二甲基乙二胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝四甲酸酰亚胺(MDI-PBI)和N,N-二(3-二甲胺基丙胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝四甲酸酰亚胺(MPI-PBI),两分子分别在两种两相溶剂体系中进行快速溶剂扩散自组装。利用SEM、UV-Vis、偏光干涉和XRD对聚集体形貌结构、光物理性能和内部分子排列情况进行了表征。结果表明,两分子在甲醇中的溶解度(S)比在正己烷中大,且S(MPI-PBI)S(MDI-PBI)。MDI-PBI和MPI-PBI在两种自组装体系中均为J型聚集,疏溶剂化作用较强时,分子形成聚集程度更高、更稳定的纳米带或纳米线;疏溶剂化作用较弱时,形成球状结构。π–π堆积作用为MDI-PBI聚集体长轴方向生长的作用力,疏溶剂作用为短轴方向生长的作用力,叔胺取代基碳链更长的MPI-PBI则刚好相反。V(甲醇)∶V(THF)=5∶1情况下MDI-PBI形成的纳米带内部分子之间π–π堆积的距离为0.37 nm,并根据此结果得到了其内部分子的堆积模型。     

吸电子基对苝酰亚胺微纳米结构传感性能的影响

在苝四酸酐的苝湾(1,7位或1,6,7,12位)位置引入—Cl或—CN,分别制备了两种苝酰亚胺衍生物N,N-双(七氟丁基)-1,6,7,12-四氯-3,4:9,10-苝二酰亚胺(PTCDI-ClF7)和N,N-双(七氟丁基)-1,7-二氰基-3,4:9,10-苝二酰亚胺(PTCDI-CNF7),探索了其在氯仿/甲醇混合溶液中的超分子自组装并测定其微/纳米结构的气敏传感性能。研究显示,两种化合物在苯肼氛围中的灵敏度变化不同,PTCDI-ClF7气敏传感器电阻下降比PTCDI-CNF7高出近2个数量级,其原因是两者占据的最低未占分子轨道(LUMO)能级值相差较大。结果表明:湾位吸电子取代基的不同对苝酰亚胺衍生物微/纳米结构的气敏传感性能影响显著。     

基于1,8-萘酰亚胺的SO_2衍生物荧光探针研究进展

根据荧光探针分子的识别机理,综述了近年来基于1,8-萘酰亚胺基团的SO_2荧光探针的研究进展,并展望了其未来发展趋势。     

苝酰亚胺衍生物抗肿瘤作用的研究进展

恶性肿瘤是人类因疾病死亡的主要因素,新型高效低毒的抗肿瘤药物已成为目前社会研究的热点。苝酰亚胺衍生物(perylenediimides derivatives, PDIs)是具有共轭大π键的大分子,荧光效率优异、稳定性高且化学可修饰性强,可作为抗肿瘤药物、药物载体、医用荧光探针等用于肿瘤疾病的诊断和治疗。本文综述了近年来国内外学者对苝酰亚胺衍生物在抗肿瘤作用方面的研究概况,并对其发展做了展望。     

邻位取代苝酰亚胺衍生物的合成及其电子迁移率的研究

以N,N'-二(3-戊胺)苝酰亚胺为底物,分别经过Ir催化剂直接催化邻位C—H的硼酸酯化和取代反应得到了2,5,8,11位含氯和含溴的苝酰亚胺衍生物Ⅲ和Ⅳ,利用1HNMR、13CNMR和HRMS对产物进行了表征。通过在苝酰亚胺的邻位引入卤原子后,相对于化合物Ⅰ,化合物Ⅲ和Ⅳ吸收光谱和荧光光谱均发生了蓝移;LUMO能级明显降低,分别为-4.18 eV和-4.16 eV。邻位引入卤原子后化合物Ⅲ和Ⅳ仍然具有良好的热稳定性,其失重5%时的温度(T d)均大于370℃。利用空间电荷限制电流(SCLC)法测试了它们的电子迁移率,发现卤原子的引入使分子间排列更加有序,其中化合物Ⅲ的迁移率最高,可以达到3.05×10-4cm2·V-1·s-1。     

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.