炔烴的多組分環化反應選擇性合成非芳香五元含硫雜環

雜環,特別是五元含硫雜環,在天然產物、醫藥分子和材料化學等領域廣泛存在.例如艾沙托立賓,一種新型的鳥苷類似物,可作為TLR7激動劑;法羅培南鈉是一種可有效殺死結核分枝桿菌的口服可吸收培南類抗生素;苯并草硫醇衍生物BOT-64也是一種NF-kB抑制劑

異腈單體的聚合及在功能高分子材料制備中的應用

作為一類重要的三鍵單體,異腈單體的聚合可產生含氮原子的新型聚合物,并賦予其特殊的功能和應用,因而這一領域的研究引起了越來越多的關注并已經取得了長足的進展。但是,目前鮮有文獻對該領域進行較全面的綜述。本專論較系統地總結了近年來基于異腈單體的單組分、雙組分以及多組分聚合反應,并較詳細介紹了其在制備光電和生物等功能高分子材料方面的應用,最后對其未來可能的發展方向進行了展望。 Thanks to the highly efficient of isocyanide-based organic reaction, the isocyanide-involved polymerizations have also been developed and used to prepare nitrogen-containing novel polymers with remarkable functions have been constructed. At present, the new polymerizations based on isocyanide have been reported continuously, but few articles have been published to review these new polymerizations. In this review, we briefly summarized the recent progresses in the development of isocyanide-involved polymerizations and their applications in preparation of functional polymers. The polymerizations were classified by the number of monomers, i.e. single component, double component and multicomponent polymerizations. Moreover, the properties and applications of the polymeric materials were also introduced in detail. It is anticipated that with the efforts paid by the polymer scientists, more efficient isocyanide-involved polymerizations will be established and new applications of the resultant polymeric materials will be developed. © 2021, Editorial Board of Polymer Materials Science & Engineering. All right reserved

聚集誘導發光探針分子在熒光傳感中的應用

熒光傳感作為化學傳感領域中的一項重大技術,具有靈敏度高、選擇性好和響應快等優點,但是傳統有機發光分子在高濃度或者聚集狀態下,容易發生熒光強度的降低或是完全消失,這在一定程度上不利于其在應用中發揮最佳效果.聚集誘導發光（AIE）概念的提出為解決聚集導致發光猝滅（ACQ）的難題提供了方案,實現了發光分子在聚集態下的高熒光量子產率.具有AIE特性的發光分子被用作熒光傳感器不僅具有高亮度的熒光信號,而且不必擔心由于分子聚集導致的熒光信號的降低或猝滅.同時,由于某些分子聚集程度的增強導致的熒光顏色和強度的變化,可以被用來實現對靶標物的定性和定量分析.本文簡述了近幾年來AIE分子在熒光傳感方面的應用,如離子檢測、氣體、有機小分子、爆炸物、蛋白質及酶等化學/生物傳感器,同時對基于AIE分子的熒光傳感器在設計和應用前景做了展望. Fluorescent probes that exhibit distinct advantages of high sensitivity, good selectivity, fast response speed, etc., have been widely applied in diverse sensing areas. However, the fluorescence of traditional organic probes tends to decrease or be quenched at high concentration or in aggregate state due to the aggregation-caused quenching (ACQ) effect, which limits their application in sensing areas. In 2001, our group coined the concept of aggregation-induced luminescence (AIE), which is exactly opposite to the ACQ effect and refers to a unique phenomenon that a kind of non- or weakly emissive luminogens in dilute solutions are induced to emit intensely upon aggregation or in solid state. Thus, the AIE-active luminogens (AIEgens) provide an alternative to solve this difficulty. Thanks to their intrinsic advantages, the fluorescent sensors based on AIEgens show lower background, higher signal-to-noise ratio and more outstanding resistance to photobleaching etc. Moroever, the AIE probes not only could overcome the problem encountered by ACQ ones, but also achieve faster and more sensitive detection of the targets. Thus, using AIE probes to detect a wide varity of targets is one of the hot research areas. To highlight the progress in this area, herein, we briefly summarize the sensing applications of AIEgens. First, we introduced the AIE probes used in the detection of ions, including K+, Hg2+, Fe3+, CN-, ClO-, PO43-, etc. Notably, the fluorescent probes based on AIEgen could realize the selective detection of various ions not only in the organic solutions, but also in aqueous solutions. Next, we discussed the detection of low mass molecules using AIE probes for they play a very important role in life activities and their content can reflect the health status and life information of an organism. The used low mass molecules include gas (NH3, CO2, H2S), explosive (PA, TNT), biothiol (Gys, GSH), and ATP and so on. Third, we summarized the qualitative and quantitative sensing of biomacromolecules, such as DNA, proteins, enzyme, by AIE probes, which is critical to the life sciences, biotechnology, and pharmaceutical industries. Fourth, the application of AIE probes in the fields like pH response, cell membrane imaging, mitochondrial imaging and fungal detection are reviewed. Finally, the prospects for the design and application of AIE probes are presented. We hope that this review will stimulate interests in AIE-based sensors and provide some new ideas for researchers working in this area. © 2020, Science Press. All right reserved

聚集誘導發光探針用于線粒體靶向和癌細胞識別研究進展

聚集誘導發光（Aggregation-induced emission, AIE）探針由于其極高的靈敏度和極佳的光穩定性在癌癥診斷和治療等方面具有不可估量的應用前景。線粒體作為所有細胞共有的重要細胞器,在癌細胞和正常細胞中顯示出明顯的性質區別,因此可作為線粒體靶向AIE探針區分癌細胞與正常細胞的靶標。本文介紹了線粒體靶向AIE探針的設計方法、成像機理以及它們對癌細胞與正常細胞、循環腫瘤細胞與白細胞以及癌細胞和相關細菌與正常細胞的區別成像。這些熒光探針在癌癥診斷、手術導航、癌癥治療的效果評估和后續復發監測以及細胞污染評估等方面具有廣闊的應用前景。通過本文的介紹,能夠讓更多讀者了解AIE探針在癌細胞識別方面的顯著優勢,激發開發性能更為豐富的探針材料和開展更為深入的研究,從而促進生物醫學領域的快速發展,造福人類。 Aggregation-induced emission(AIE) probes have shown great potential in cancer diagnosis and therapy due to their excellent sensitivity and photo-stability. Mitochondria, which is regarded as one of the most important organelles in cells, has obvious difference between cancer cells and normal cells. Thus, it is reliable to utilize mitochondria-targeted AIE probes to distinguish cancer from normal cells. In this review, we exhibit the design principle and imaging mechanism of AIE probes for mitochondria target, and their distinguishing imaging between cancer cells and normal cells, circulating tumor cells and leukocyte, and dual identification imaging of cancer cells and related bacteria. The probes show remarkable advantages in cancer diagnosis, surgical navigation, cancer treatment assessment and recurrence monitoring, and cell pollution evaluation. We hope, this review will motivate to develop more AIE probes with rich properties and conduct deeper researches to promote the rapid development of biomedical field and maintain human health. © 2021, Science Press. All right reserved

含硫聚合物、其製備方法及其應用

本發明提供含硫大分子以及製備該含硫大分子的方法，所述方法包括聚合步驟，其中，所述含硫大分子含有內部單元... ...，所述聚合步驟為：... ... 其中，n大於1，所述前體包含具有一個或多個炔基的炔烴、以及具有一個或多個巰基的硫醇；R為所述硫醇中除巰基以外的剩餘部分，R'為所述炔烴中除炔基以外的剩餘部分，並且R和R'選自有機基團或有機金屬基團。A sulfur-containing macromolecule and a method of preparing the sulfur-containing macromolecule comprising a polymerization step are provided, where the sulfur-containing macromolecule contains internal units of ... ... and the polymerization step is: ... ... wherein n is greater than 1, said precursor comprises alkyne having one or more acetylene groups and thiol having one or more thiol groups; and R is remainder of said thiol excluding said thiol groups, R’ is remainder of said alkyne excluding said acetylene groups, and R and R’ are selected from organic or organometallic groups

含非典型性生色团的发光聚合物

發光聚合物一般是由具有大π電子系統的共軛基元作為發光單元,通過共價鍵連接而成的高分子.近年來,研究者發現:另一類僅含有脂肪胺、羰基、酯基、酰胺等傳統意義上的助色團的聚合物在適當條件下也能發射強的熒光.樹枝狀聚酰胺胺(PAMAM)和超支化聚酰胺胺(hb-PAMAM)是最早和最廣泛被研究的含非典型性熒光生色團的聚合物.最近,這類聚合物被擴展到含有叔胺基元的聚氨酯、聚醚酰胺、聚脲體系.這些體系的生色團被認定為其結構中的叔胺基元,叔胺的氧化是熒光產生的根源.同時,也有文獻報道馬來酸酐與醋酸乙烯酯交替共聚物、異丁烯與順丁烯二酸酐共聚物、聚多糖動態高分子、聚酰腙以及通過RAFT試劑制備的含聚三硫碳酸酯的多嵌段共聚物等也可以發射熒光.這些聚合物的一個共同特點是結構中不含叔胺基元,而僅含羰基和酯基,其發光機理通常用多個羰基聚集效應或羰基和苯環之間的相互作用來解釋. Luminescent polymers are referred to as conjugated polymers, which are constructed by pi-aromatic building blocks functioning as emitting units. But in recent years, it has been found that a few kinds of polymers only containing auxochromophores or unconventional chromophores such as aliphatic tertiary amine, carbonyl, ester, and amide demonstrate strong luminescence under proper conditions. Poly(amido amine) (PAMAM) dendrimers and hyperbranched poly(amido amine)s are the first reported and most investigated luminescent polymers containing unconventional chromophores. Lately, this kind of polymers have been extended to hyperbranched poly(amino ester)s (hb-PAEs), hyperbranched poly(ether amide)s (hb-PEAs), and polyurea dendrimers (PUREs) containing tertiary amine moieties. The luminogen of PAMAMs, hb-PAEs, hb-PEAs and PUREs is associated with the N-branched tertiary amine moiety and the oxidation of the tertiary amine is assigned to the emitting source. Meanwhile, some distinct polymers had been also reported to be luminescent. Poly[(maleic anhydride)-alt-(vinyl acetate)], polyisobutene succinic anhydrides, glycodynamer analogues of poly(acrylhydrazone)s and multiblock polymer derived by poly(trithiocarbonate) mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropyl-acrylamide. A common feature of these polymers is that only carbonyl and ester groups rather than tertiary amine are involved in the polymer structure. Aggregation of multiple carbonyl groups induced emission is usually adopted to explain the mechanism of the emission, and the interaction between carbonyl and phenyl groups was also used to explain the unconventional emission

含硫大分子及其製備方法

本發明提供含硫大分子和製備含硫大分子的方法，其中所述方法包括聚合步驟，並且其中所述含硫大分子包含由式(I)表示的內部單元，並且所述聚合步驟如式(II)所示，其中n大於1；所述前體包含具有一個或多個炔基的炔，和具有一個或多個巰基的硫醇；R是所述硫醇中除所述巰基之外的殘餘基團，R'是所述炔中除所述炔基之外的殘餘基團，R和R'選自有機基團或有機金屬基團。A sulfur-containing macromolecule and a method of preparing the sulfur-containing macromolecule comprising a polymerization step are provided, where the sulfur-containing macromolecule contains internal units of formula (I) and the polymerization step is formula (II) wherein n is greater than 1, said precursor comprises alkyne having one or more acetylene groups and thiol having one or more thiol groups; and R is remainder of said thiol excluding said thiol groups, R' is remainder of said alkyne excluding said acetylene groups, and R and R' are selected from organic or organometallic groups

含有手性和发光官能团侧基的聚1-苯基-1-辛炔的合成与性能研究

設計并合成了一系列含手性和發光生色團側基的聚(1-苯基-1-辛炔)衍生物{-[(C6H13)C=C(C6H4-p-CO2-R)]n-,R=[(1S)-endo]-(-)-冰片基(P3),(1R,2S,5R)-(-)-薄荷基(P4),-C6H4-p-(1R,2S,5R)-(-)-薄荷基(P5),2-萘基(P6),4-聯苯基(P7)}.用WCl6-Ph4Sn作催化劑,成功地制備了這些具有中等產率和高分子量(Mw高達64000)的聚合物.聚合物的結構和性能通過NMR,TGA,UV,CD,PL和EL等分析方法進行了表征.所有聚合物都表現出良好的熱穩定性,在N2保護條件下,其失重5%的溫度在300～416℃之間.所有聚合物的帶隙約為3.0eV.聚合物P4和P5表現出與聚合物鏈段螺旋性相對應的CD吸收.在UV輻照下,P3～P7的THF溶液均發射強烈藍光,其最大發射波長位于485nm左右,量子效率均高于20%.聚合物薄膜發射與其溶液發射在相同的光譜區域,并表現出輕微的聚集誘導猝滅.制備了ITO/聚合物:PVK/BCP/Alq3/LiF/Al多層聚合物EL器件,其最大發射波長為487nm.隨著側基的改變,器件的最大亮度和外量子效率也隨之發生變化,其中P6表現出最高的外量子效率(0.16%).EL器件均具有良好的光譜穩定性,其EL最大發射峰幾乎不隨外加電壓的變化而改變

聚集诱导发光

聚集诱导发光(AIE)是唐本忠院士于2001年提出的一个科学概念,是指一类在溶液中不发光或者发光微弱的分子聚集后发光显著增强的现象。高效固态发光的AIE材料有望从根本上解决有机发光材料面临的聚集导致发光猝灭难题,具有重大的实际应用价值。从分子内旋转受限到分子内运动受限,从聚集诱导发光到聚集体科学,AIE领域已经取得了许多原创性的成果。在本综述中,我们从AIE材料的分类、机理、概念衍生、性能、应用和挑战等方面讨论了AIE领域最近取得的显著进展。希望本综述能激发更多关于分子聚集体的研究,并推动材料、化学和生物医学等学科的进一步交叉融合和更大发展。 Aggregation-induced emission (AIE), conceptually coined by Prof. Ben Zhong Tang in 2001, refers to a unique photophysical phenomenon non- or weakly emissive luminogens in dilute solutions emit intensely upon aggregation. AIE can solve the aggregation-caused quenching problem that traditional fluorophores are suffering from and hold great technological values for practical applications. The past 20 years have witnessed the rapid development of AIE research, from the restriction of intramolecular rotations to restriction of intramolecular motions, and from AIE to aggregate science, and many original results have been achieved. In this review, we summarize the advances in the field of AIE and its related areas. We specifically discuss the recent progress in AIE area, including material classification, mechanism, concept derivation, property, applications, and challenges. It is hoped that this review will inspire more research into the molecular aggregate level and make significant advances in materials, chemistry and biological sciences