Tetraphenylpyrazine-based AIEgens: facile preparation and tunable light emission

Research on aggregation-induced emission (AIE) has been a hot topic. Due to enthusiastic efforts by many researchers, hundreds of AIE luminogens (AIEgens) have been generated which were mainly based on archetypal silole, tetraphenylethene, distyrylanthracene, triphenylethene, and tetraphenyl-1,4-butadiene, etc. To enlarge the family of AIEgens and to enrich their functions, new AIEgens are in high demand. In this work, we report a new kind of AIEgen based on tetraphenylpyrazine (TPP), which could be readily prepared under mild reaction conditions. Furthermore, we show that the TPP derivatives possess a good thermal stability and their emission could be fine-tuned by varying the substituents on their phenyl rings. It is anticipated that TPP derivatives could serve as a new type of widely utilized AIEgen, based on their facile preparation, good thermo-, photo- and chemostabilities, and efficient emission.     

Responsive hyperbranched poly(formyl-1,2,3-triazole)s toward quadruple-modal information security protection

Science China Chemistry - Secrecy has received tremendous attention in modern information society. Innovative polymer-based fluorescent materials with multiple mode emission are quite desirable to...     

Click polymerization: The aurora of polymer synthetic methodology

As an emerged efficient polymerization methodology, the click polymerization plays a significant role in the area of polymer and materials sciences. Similar to the click reaction, the click polymerization enjoys the advantages of high efficiency, mild reaction conditions, and high regio- and stereo-selectivity etc. In this highlight, we summarize the recent progress on click polymerizations, with focus on the alkyne-based ones. The challenges and opportunities in this area are also briefly discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 616–621     

绿色单体二氧化碳参与的新型聚合反应

二氧化碳（CO₂）是一种丰富、廉价、无毒以及可再生的一碳资源,也是一种可用于聚合的绿色单体.基于CO₂的聚合是近年来的研究热点之一.目前广泛报道的是CO₂和环氧单体的聚合反应,经过几十年的发展已经成功实现工业化生产.最近几年,一些CO₂参与的新型聚合反应被陆续报道,这些工作大都通过两种途径实现从CO₂到高分子材料的转变.第一个途径是先将CO₂转化为可以聚合的单体,例如：内酯、环状碳酸酯和2,5-二呋喃甲酸等,再利用开环或者逐步聚合将单体转化为聚合物;另一个途径是直接以CO₂为单体和其他类型单体共聚得到聚合物.这两种途径对于发展CO₂参与的新型聚合反应,拓展CO₂基聚合物种类都具有重要意义.本综述按照CO₂直接还是间接参与聚合反应分类总结了近年来在CO₂制备高分子材料方面的进展,并对未来发展方向进行了简单阐述.     

磷手性中心的不对称构建

对由非光学活性底物不对称构建磷手性中心的方法进行综述,根据底物的结构以及机理的不同分为两类介绍,分别是前对映异构体的去对称化以及不同取代底物的化学拆分.     

ELASTO-PLASTIC COUPLED ANALYSIS OF BURIED STRUCTURE AND SOIL MEDIUM BY PERTURBATIONAL SEMI-ANALYTIC METHOD

I.IntroductionMoreandmoreelasto-plasticanalysesareusedinCivilEngineering.TheMohr-Coulombyieldconditionisoftenappliedtorockandsoilmediumtostudythesituationofdestruction.Theperturbationalmethodwasfirstusedinthestudyofcelestialmechanics,thenithasbeenusedinsolidmechanicstocarryoutthegeometricallyandphysicallynonlinearanalysis[']'12].Forlarge?scalcproblems,thegeneralnumericalmethodsmaynotbeapttothiscomplexcalculation,butsemi-analyticalmethodscandoitwell.Touseanalyticalfunctionsinoneortwodirectio…     

AuCl3催化炔酮分子内环化反应的机理

采用密度泛函理论的B3LYP方法研究炔酮发生分子内环化生成菲衍生物的反应机理.结果表明：在无催化剂和AuCl₃催化剂作用下,反应均可通过[2+2]和[6+2]途径生成产物.无催化剂时,两条途径控制步骤的能垒都较高,但是[2+2]途径的能垒比[6+2]途径的低32.01 kJ·mol^-1,故反应主要通过[2+2]途径进行.在AuCl₃催化作用下,反应的优势途径为[2+2]途径,其能垒为137.05 kJ·mol^-1.比较活化能发现,AuCl₃催化剂明显地降低了反应能垒,使反应能够顺利进行.     

含四苯基乙烯的炔酮衍生物的设计合成、聚集诱导发光性质及其对Pd2+的选择性荧光检测

聚集诱导发光（AIE）材料吸引了许多光电器件和生物荧光技术领域的科学家的关注.对聚集诱导发光化合物构效关系的深入理解对于设计新材料至关重要.在本工作中,基于经典的AIE基元四苯基乙烯,设计并合成了一系列具有AIE性质,含不同电子给体/受体取代基的炔酮衍生物.对这一系列化合物的光物理性质进行了系统研究并分别探讨了取代基团对发光波长、发光效率和AIE性质的影响.它们的聚集态最大发射波长位于511～565 nm,在四氢呋喃/水混合溶液中的荧光量子产率可达31%.在末端苯环上的电子给体/受体取代基团会降低聚集态的发光效率,而引入硝基取代基则会在发射波长红移的同时,显著猝灭荧光.最为重要的是,这些化合物结构中的炔酮基元可以在一系列金属离子中选择性地与Pd²⁺配位,猝灭纳米聚集体的发光,并有望作为一个有效的Pd²⁺荧光传感器.     

Lab-in-cell based on spontaneous amino-yne click polymerization

Unnatural reaction in the living cells is a powerful tool for biological research. However, the polymerization inside cells is rarely reported. In this work, a lab-in-cell is illustrated based on our developed spontaneous amino-yne click polymerization. Carbonyl group activated terminal diyne can spontaneously polymerize with tetraphenylethene(TPE)-containing primary diamine inside cells, and polymer with weight-average molecular weight of 7,300 was yielded. By utilizing this in vivo amino-yne click polymerization and taking advantage of the aggregation-induced emission feature of TPE, a "turn-on" cell imaging was realized,and in-situ killing of cells was also acquired by destroying the structures of actin and tubulin, which cannot be realized by preprepared polymer. This strategy provides a useful platform and holds great promise in biochemistry and therapy applications.     

含非典型性生色团的发光聚合物

发光聚合物一般是由具有大p电子系统的共轭基元作为发光单元, 通过共价键连接而成的高分子. 近年来, 研究者发现: 另一类仅含有脂肪胺、羰基、酯基、酰胺等传统意义上的助色团的聚合物在适当条件下也能发射强的荧光. 树枝状聚酰胺胺(PAMAM)和超支化聚酰胺胺(hb-PAMAM)是最早和最广泛被研究的含非典型性荧光生色团的聚合物. 最近, 这类聚合物被扩展到含有叔胺基元的聚氨酯、聚醚酰胺、聚脲体系. 这些体系的生色团被认定为其结构中的叔胺基元, 叔胺的氧化是荧光产生的根源. 同时, 也有文献报道马来酸酐与醋酸乙烯酯交替共聚物、异丁烯与顺丁烯二酸酐共聚物、聚多糖动态高分子、聚酰腙以及通过RAFT试剂制备的含聚三硫碳酸酯的多嵌段共聚物等也可以发射荧光. 这些聚合物的一个共同特点是结构中不含叔胺基元, 而仅含羰基和酯基, 其发光机理通常用多个羰基聚集效应或羰基和苯环之间的相互作用来解释.