A new aggregation-induced emission (AIE) compound 1,1-dimethyl-2,5-bis[4-(isothiocyanatemethyl)phenyl]-3,4-diphenylsilole (SITC) was synthesized and used to conjugate with aminoallyl-dUTP. The SITC–dUTP can be incorporated enzymatically into DNA strands with the degree of labeling (DOL) up to the theoretic limit.

Yong Yu;Jianzhao Liu;Zujin Zhao;Ka Ming Ng;Kathy Qian Luo;本忠 唐

Chemical Communications

2012-5-30

A series of hyperbranched poly(ferrocenylenesilyne)s, [(η⁵-CC₅H₄)₂FeSi(R)]_n {R = CH ₃ [1(1)], CH=CH₂ [1(V)], n-C₈H₁₇ [1(8)], n-C₁₂H₂₅ [1(12)], n-C₁₆H₃₃ [1(16)], n-C₁₈H₃₇ [1(18)]}, was prepared in good isolation yields (up to 77 wt %) by one-pot coupling reactions of dilithioferrocene with trichlorosilanes. While the polymers which small R groups [1(1) and 1(V)] were partially soluble, those with long alkyl chains [1(m) with m ≤ 8] were completely soluble and readility film forming. The polymers exhibited diagnostic solution properties of hyperbranched macromolecules; for example, 1(18) had a high absolute molecular weight (M_w = 5 × 10⁵ Da) but a low intrinsic viscosity ([η] = 0.02 dL/g). Spectroscopic analyses revealed that the polymers possessed rigid skeleton structures with extended conjugations, with their absorption spectra tailed into the infrared region (> 700 nm). With an increase in the alkyl chain length, the polymer changed from glassy to rubbery state. The polymers lost little of their weights when heated to ∼400°C but ceramized when pyrolyzed at higher temperatures, with ceramization yield increasing with a decrease in the alkyl chain length. Sintering 1(1) and 1(V) in 700-1200°C produced ceramics in ∼50% yields. Higher temperature pyrolyses favored the formation of ceramics with bigger inorganic nanoclusters and better magnetic performances. The ceramic prepared from the calcination of 1(1) at 1200°C contained large iron silicide nanocrystals and exhibited high magnetizability (up to ∼51 emu/g) but near-zero remanence and coercivity. This ceramic is thus an outstanding soft ferromagnet with a high magnetic susceptibility and practically nil hysteresis loss.

Qunhui Sun;Kaitian Xu;Han Peng;Ronghua Zheng;Matthias Häussler;本忠 唐

Macromolecules

2003-4-8

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.

Ming Chen;Lingzhi Li;Han Nie;Jiaqi Tong;Lulin Yan;Bin Xu;Jing Zhi Sun;文晶 田;Zujin Zhao;Anjun Qin;本忠 唐

Chemical Science

2015-3-1

A series of ten 2,3,4,5-tetraphenylsiloles with different 1,1-substituents [XYSi(CPh)₄] were prepared, and three of these, i.e., 1,1,2,3,4,5-hexaphenylsilole [X = Y = Ph (3)], 1-ethynyl-1,2,3,4,5-pentaphenylsilole [X = Ph, Y = C≡CH (15)], and 1,1-bis(phenylethynyl)-2,3,4,5-tetraphenylsilole [X = Y = C≡CPh (18)], were characterized crystallographically. The ground- and excited-states of the siloles were influenced by the inductive effect of the 1,1-substituents: with an increase in their electronegativity, the absorption and emission spectra of the siloles bathochromically shifted. A simple and reliable TLC-based method was developed for measurement of the solid-state luminescence spectra of the siloles. When molecularly dissolved in common solvents at room temperature, all the siloles were practically nonemissive ("off"). When poor solvents were added, the silole molecules clustered into nanoaggregates, which turned the emission "on" and boosted the photoluminescence quantum yields by up to 2 orders of magnitude (aggregation-induced emission). The silole emission could also be greatly enhanced by increasing the viscosity and decreasing the temperature of the silole solutions. The solution thickening and cooling experiments suggest that the aggregation-induced emission is caused by the restricted intramolecular rotations of the peripheral aromatic rings upon the axes of the single bonds linked to the central silole cores.

军武 陈;Charles C.W. Law;Jacky W.Y. Lam;Yuping Dong;Samuel M.F. Lo;Ian D. Williams;道本 朱;本忠 唐

Chemistry of Materials

2003-4-8

Next generation smart coatings with the ability to signal changes in the environment are hugely anticipated in a variety of applications. For example in chemical and vapor sensing, in warning systems, corrosion inhibition and repair, and many others. Thus, in this paper a method for synthesizing a smart epoxy resin using a one-step alkaline interaction with AIEgen TPE-2CH₂Br to obtain an aggregation-induced emission (AIE), fluorescent functional epoxy coating (TPE-EPOXY) is reported. Because of the restriction of intramolecular rotation mechanism, the internal structure of the fluorescent coating during curing, organic vapor stimulation, and corrosion performance were systematically studied using fluorescence spectroscopy. The results given in this paper demonstrate the unique advantages of AIE coatings in the field of environmental responsiveness and provide a rich source of information on the interaction of AIE molecules with traditional materials.

Wei Yao;Mike Tebyetekerwa;Xuehao Bian;Weili Li;Shengyuan Yang;美芳 朱;Rong Hu;Zhiming Wang;Anjun Qin;本忠 唐

Journal of Materials Chemistry C

2018

Aggregation-induced emission (AIE) active compounds and materials have become one of the hottest research topics worldwide, due to their unprecedented merits such as ultra-high fluorescence quantum efficiencies as aggregates or in solid state. Up to now, it is still extremely crucial and fundamental to expand the AIE-genic molecular systems for this research area. Here, we prepared two fluoranthene-modified tetraphenylethene (TPE) derivatives, TPE-FA and TPE-DFA, through the Suzuki-Miyaura coupling between boronate-bearing TPE and bromo-bearing fluoranthene under mild reaction condition. The conjugation between fluoranthene and TPE moieties assures that the as-prepared TPE-FA and TPE-DFA both possess aggrega-tion-enhanced emission (AEE) characteristics. The emission maximum of TPE-FA and TPE-DFA as aggregates in THF/water mixtures is at 477 nm and 494 nm, and the absolute quantum yields of the two compounds in solid films are as high as 74.1% and 40.4%, respectively. They can be utilized as fluorescent probes for picric acid with high sensitivity. Their quenching coef-ficients can be as high as 4×10⁴ L·mol^-1, while their detection limits can be lower than 1 μg·g^-1. These AEE-active molecules are promising to act as fluorescent probes in the detection of other nitro-substituted electron-deficient molecules.

Wei Bai;Yang Shi;Chen Song;Jie He;Anjun Qin;Jing Zhi Sun;本忠 唐

Acta Chimica Sinica

2016-11-15

In recent years, photodynamic therapy (PDT) has drawn much attention as a noninvasive and safe cancer therapy method due to its fine controllability, good selectivity, low systemic toxicity, and minimal drug resistance in contrast to the conventional methods (for example, chemotherapy, radiotherapy, and surgery). However, some drawbacks still remain for the current organic photosensitizers such as low singlet oxygen (¹O₂) quantum yield, poor photostability, inability of absorption in the near-infrared (NIR) region, short excitation wavelength, and limited action radius of singlet oxygen, which will strongly limit the PDT treatment efficiency. As a consequence, the development of efficient photosensitizers with high singlet oxygen quantum yield, strong fluorescent emission in the aggregated state, excellent photostability, NIR excitation wavelength ranging in the biological transparency window, and highly specific targeting to mitochondria is still in great demand for the enhancement of PDT treatment efficiency. In this study, two new two-photon AIEgens TPPM and TTPM based on a rigid D-π-A skeleton have been designed and synthesized. Both AIEgens TPPM and TTPM show strong aggregation-induced emission (AIE) with the emission enhancement up to 290-folds, large two-photon absorption with the two-photon absorption cross section up to 477 MG, and highly specific targeting to mitochondria in living cells with good biocompatibility. They can serve as two-photon bioprobes for the cell and deep tissue bioimaging with a penetration depth up to 150 μm. Furthermore, high ¹O₂ generation efficiency with high ¹O₂ quantum yield under white light irradiation has been found for both TPPM and TTPM and high PDT efficiency to HeLa cells under white light irradiation has also been proven. To the best of our knowledge, AIEgens in this work constitute one of the strongest emission enhancements and one of the highest ¹O₂ generation efficiencies in the reported organic AIEgens so far. The great AIE feature, large two-photon absorption, high specificity to mitochondria in living cells, and high PDT efficiency to living cells as well as excellent photostability and biocompatibility of these novel AIEgens TPPM and TTPM reveal great potential in clinical applications of two-photon cell and tissue bioimaging and image-guided and mitochondria-targeted photodynamic cancer therapy.

Weihua Zhuang;莉 杨;Boxuan Ma;Qunshou Kong;Gaocan Li;Yunbing Wang;本忠 唐

ACS applied materials & interfaces

2019-6-12

With rapid development of aggregation-induced emission (AIE), AIE polymers have attracted great attention because of their outstanding properties such as intense fluorescence, easy processability, facile functionalization, structural diversity, and excellent thermal stability, which offer them with an extensive fields of applications. In this chapter, different synthetic strategies of AIE polymers will be summarized, mainly including post-functionalization and direct polymerization. After that, the widespread applications of AIE polymers in optoelectronic, sensing, and biological fields will be introduced. Although great progress has been made, more work can be done for further development of AIE polymers. As most of reported AIE polymers are based on TPE moiety, new AIE systems with various structures are highly desired, which possess high emission efficiency and broad emission spectrum.

Jiabao Gu;Anjun Qin;本忠 唐

2018-10-9

Molecular self-assembly of small molecules to ordered macromolecular structures by noncovalent interactions is well known and often found in nature (Whitesides et al. 1991), in which hollow tubular structures of molecular sizes provide various biological functions: for example, scaffolding and packaging roles played by cystoskeletal microtubules and viral coat proteins, respectively, as well as the chemical transport and screening activities of membrane channels. Organic tubular assemblies are of interest owing to their numerous possible applications, many of which are obvious from the viewpoints of mimicry of biological systems (Eisengerg, B., 1998, Voges et al., 1998, Zwickl et al., 1999, Sigler et al., 1998, Borgnia et al., 1999). Much research has been focussed on the construction of simpler synthetic tubes for applications such as specific ion sensors, tailored molecular reaction vessels, and molecular sieves.

Bing Shi Li;Kevin Ka Leung Cheuk;军武 陈;旭东 肖;春礼 白;本忠 唐

2003-1-1

We have succeeded in synthesizing soluble, stereoregular, and high molecular weight polyacetylenes containing polar cyano functional groups in high yields. Two new cyanoalkyne monomers, [4-[[[n-[(4′-cyano-4-biphenylyl)oxy]alkyl]oxy]carbonyl]phenyl]acetylenes (1; n = 6, 12), are synthesized via multistep reactions. [Rh(nbd)Cl]₂ effects the polymerization of 1, producing polymers (2) with high molecular weights (M_w up to 158 000) in high yields (up to 71%). Spectroscopic analysis reveals that the polymers possess alternating-double-bond backbones with high stereoregularity. The electronic and thermal transitions in 2 are sensitive to their stereostructures: The polymer with higher stereoregularity absorbs at longer wavelength and melts at higher temperature. The polymers prepared in DMF-based solvents are completely soluble in DMF, THF, and chloroform, although the dissolution takes quite a long time (up to a week) due to the high stereoregularity of the polyacetylene backbones and the strong electronic interaction among the push-pull mesogenic pendant groups. The polymers are thermally very stable (temperature for 5% weight loss: ca. 400 °C) and can be melt-processed in a moderate temperature range (ca. 100-150 °C).

本忠 唐;Xiangxing Kong;新华 宛;Xin De Feng

Macromolecules

1997-9-22