Luminogens with aggregation-induced emission characteristics (AIEgens) are intriguing due to its rapid expansion in various high-tech applications. However, there is still in high demand on the development of novel AIEgens with easy preparation and functionalization, stable structures, tunable emissions, and high quantum efficiency. In this contribution, three AIEgens based on diphenyl isoquinolinium (IQ) derivatives are reported. They can be facilely synthesized and possess high structural stability, favorable visible light excitation, large Stokes shifts, high quantum yields, tunable colors, and sufficient two-photon absorption of near-infrared light. Importantly, they exhibit multifunctionalities. They exhibit mechanochromic property, making them capable to be applied for rewritable papers. They can also be applied in mitochondrial imaging with high specificity, cell permeability, brightness, biocompatibility, and photostability. They are promising for the applications in evaluation of mitochondrial membrane potential and image-guided cancer cell ablation. Last, they are able to stain bacteria in a wash-free manner. All these intriguing results suggest such readily accessible and multifunctional diphenyl IQ-based AIEgens provide a new platform for construction of advanced materials for practical applications.

Jiang Meijuan    Xinggui Gu    Ryan tsz kin Kwok    Li Ying    Herman ho yung Sung    Zheng Xiaoyan    Yilin Zhang    林荣业    Ian Williams    黄旭辉    Kam sing Wong    唐本忠    

Advanced Functional Materials

2018

Conjugated polymers (CPs) have drawn great attention due to their excellent optical and electronic properties for decades. Among the varieties of CPs, polyacetylenes (PAs) triggered a revolution in polymer science due to their conductivity in highly doped state. Yet, the unstability and unprocessability of the pristine polyacetylene led researchers exploring their derivatives with substituents. Luckily, greatly improved stability and processability have been achieved by poly(disubstituted polyacetylene)s or PDSAs, that show efficient fluorescence emission in both solution and solid state and excellent circular polarized luminescence. This review summarizes recent research regarding PDSAs, beginning with the novel achievements of the discovery of the Pd-based catalyst systems for the polymerization of disubstituted acetylene monomers (DSAms), followed by a description of the effect of polymerization catalysts on the stereochemistry of obtained polymers and the effect of the stereochemistry on functional properties. Then, an updated summary of alternative synthetic routes to PDSAs, that is, post-polymerization modifications is contributed. This strategy has shown strong vitality due to the highly efficient reaction tools furnished by organic chemists such as click chemistry and activated esters. PDSAs usually possess intrinsically porous structure, exhibiting significant and variable fluorescent responses to exotic species such as solvents with different polarities, metal cations and explosives, and these properties indicate that PDSAs are promising candidates for fluorescent sensors and probes. Their reversible responses to applied fields such as stress and fluid gradient allow PDSAs to be active components of actuators. Moreover, due to the unique conjugated polyene main-chain and metathesis polymerization mechanism, PDSAs pronounced chirality transfer capacity and outstanding circular polarized luminescent property. Finally, an outlook of the application and suggestions of the synthetic efforts are forwarded.

Wang Xiao    Jingzhi Sun    唐本忠    

Progress in Polymer Science

2018

Development of new aggregation-induced emission (AIE) luminogens has been a hot research topic because they thoroughly solve the notorious aggregation-caused quenching effect confronted in conventional fluorogens and their promising applications in, for example, organic light-emitting diodes, chemo- and biosensors and bioimaging. Many AIE luminogens (AIEgens) have been prepared but most of them are silole, tetraphenylethene, distyrylanthracene, and their derivatives. In this work, based on the skeleton of tetraphenylpyrazine (TPP), a new AIEgen, named TPP-PDCV, is generated by functionalizing TPP with malonitrile group. TPP-PDCV can serve as a sensitive ratiometric fluorescent probe for detecting hydrogen sulfide with high speciality and low detection limit of down to 0.5 × 10m. The mechanism for such detection is fully investigated and deciphered. Unlike most reported mechanochromic AIEgens, which undergo turn-off or -on emission or emission bathochromic shift in the presence of external stimuli, TPP-PDCV exhibits an abnormal and reversible mechanochromism with hypsochromic effect. These indicate that TPP-PDCV possesses a huge potential for high-tech applications through rational modification of TPP core.

Chen Ming    Chen Rui    Shi Yang    Wang Jianguo    Cheng Yanhua    Li Ying    Gao Xuedong    Yun Yan    Jingzhi Sun    Anjun Qin    Ryan tsz kin Kwok    林荣业    唐本忠    

Advanced Functional Materials

2018

Transferrin receptor (TfR) is overexpressed on the surface of many cancer cells due to its vital roles in iron circulation and cellular respiration. Soluble transferrin receptor (sTfR), a truncated extracellular form of TfR in serum, is an important marker of iron deficiency anemia (IDA) and bone marrow failure in cancer patients. More recently, sTfR level in urine has been related to a specific kidney disease of Henoch-Schönlein purpura nephritis (HSPN). Despite the universal significance of sTfR, there is still a lack of a simple and sensitive method for the quantification of sTfR. Furthermore, it is desirable to have a probe that can detect both TfR and sTfR for further comparison study. In this work, we developed a water-soluble AIE-peptide conjugate with aggregation-induced emission (AIE) characteristics. Taking advantage of the negligible emission from molecularly dissolved tetraphenylethene (TPE), probe TPE-2T7 was used for the light-up detection of sTfR. The probe itself is nonemissive in aqueous solution, but it turns on its fluorescence upon interaction with sTfR to yield a detection limit of 0.27 μg/mL, which is much lower than the sTfR level in IDA patients. Furthermore, a proof-of-concept experiment validates the potential of the probe for diagnosis of HSPN by urine test.

Zhang Ruoyu    Sung Simon H. P.    Guangxue Feng    Chongjing Zhang    Kenry    唐本忠     Bin Liu   

Analytical Chemistry

2018

Structurally simple chalcone derivatives 1–2 are prepared and their diversified emission behaviors are deeply investigated. Two polymorphs (1G: λ = 536 nm, Φ = 0.08, τ = 1.81 ns; 1O: λ = 573 nm, Φ = 0.19, τ = 10.82 ns) with distinctively different emission behaviors are constructed by finely controlling the crystallization conditions of compound 1. 1G exhibits typical amplified spontaneous emission while 1O shows an interesting blue shift under smashing process (1O-S: λ = 562 nm, Φ = 0.23, τ = 6.42 ns), which is ascribed to their different molecular packing structures and intermolecular interactions. Notably, simply introducing a fluorine substituent effectively endows the crystal with red emission (crystal 2: λ = 598 nm, Φ = 0.16, τ = 18.77 ns). Thus multicolor emissions including green, yellow, orange, and red emissions are obtained based on this simple chalcone skeleton.

Xiao Cheng    Wang Zhaoyang    Tang Baolei    Hongyu Zhang    Anjun Qin    Jingzhi Sun    唐本忠    

Advanced Functional Materials

2018

Currently, the development of aggregation-induced emission (AIE) luminogens (AIEgens) has enabled us to “see” never before seen scenery. However, not all AIEgens exhibit the impressive emission efficiency in aggregated states. Moreover, the emission color of AIEgens can be seriously affected when their performance is improved. Therefore, to overcome this limitation, an efficient method is proposed here through the tailored alkyl linkages to greatly improve the emission efficiency of tetraphenylethene (TPE)-based AIEgens but retain their emission color. Encouragingly, significantly enhanced emission efficiency is achieved with the quantum yield up to 68.19% and 65.20% for BTPE-C4 and BTPE-C8, respectively, in contrast to that of TPE (25.32%), demonstrating the proverb that one plus one is much larger than two (1 + 1 >> 2). Interestingly, when alkyl linkages in skeletons are fine-tuned, self-assembled nanorods, nanosheets, and nanofibers are successfully achieved for BTPE-C1, BTPE-C4, and BTPE-C8 in tetrahydrofuran and water system. Also, these developed emissive AIEgens not only exhibit impressive response to the environmental stimuli of mechanical force, viscosity, temperature, and light, but can also be used to dynamically monitor and control the phase-separated morphology in polymeric blends.

Dang Dongfeng    Qiu Zijie    Ting Han    Liu Yong    Chen Ming    Ryan tsz kin Kwok    林荣业    唐本忠    

Advanced Functional Materials

2018

We report the design and synthesis of a novel cationic AIE-gen, i.e., (E)-TPEDEPy-DBz, which can be derived from a facile synthetic route. (E)-TPEDEPy-DBz is a stereo-pure isomer and shows evident AIE properties with yellow-greenish emission in the solid state (Φ = 43.7%). Distinct from most of the ionic AIE-gens reported in the literature, which are usually exemplified by their water solubility and the capacity for interaction with charged biological species, (E)-TPEDEPy-DBz demonstrated moderate solvatochromism and evident mechanoluminochromism behaviours. The emission of (E)-TPEDEPy-DBz can be switched between yellow-greenish in the crystalline state to red-orange in the amorphous state by grinding and fuming treatments. Due to the AIE-characteristics, cationic modification and the thus-acquired water solubility, (E)-TPEDEPy-DBz performed as a sensitive fluorescent probe to detect DNA in Tris-HCl buffer solution. More importantly, (E)-TPEDEPy-DBz showed good membrane permeability and cell viability, and the potentiality to be used as a mitochondria-specific probe working in a fluorescence turn-on mode.

Wang Zhaoyang    Gu Yuan    Liu Junyuan    Xiao Cheng    Jingzhi Sun    Anjun Qin    唐本忠    

Journal of Materials Chemistry B

2018

A theranostic drug delivery system composed of tetraphenyl-ethene (AIEgen), benzyl boronic ester (trigger), and doxorubicin (drug) was designed and synthesized; its utilities for cell imaging, drug delivery tracking, and cancer cell cytociding were evaluated.

Gao Xiaoying    Cao Jie    Song Yinuo    Shu Xiao    Jianzhao Liu    Jingzhi Sun    Bin Liu    唐本忠    

RSC Advances

2018

The development of a new polymerization methodology affords polymer materials with new structures and functionalities. Multicomponent polymerizations (MCPs) as a facile tool for preparing multifunctional polymers with complicated structures have attracted increasing attention from polymer scientists, owing to their high efficiency, high atom economy, simple procedure, structural diversity, and environmental benefit. In this work, a series of efficient one-pot multicomponent polymerizations of diynes, disulfonyl azides, and N-protected isatins are developed to afford oxindole-containing poly(N-Acylsulfonamide)s with advanced properties. After optimization of the polymerization conditions, the MCP can proceed smoothly at room temperature or 30 °C in dichloromethane/t-BuOH with CuI as the catalyst and LiOH as the base, generating poly(N-Acylsulfonamide)s with high molecular weights of up to 30600 g mol in excellent yields of up to 98%. This MCP enjoys general applicability of a series of electron-rich or electron-deficient alkynes and alkyl group or aromatic group-substituted isatins, generating six poly(N-Acylsulfonamide)s from different combination of monomers, and nitrogen gas as the only byproduct, demonstrating high atom economy and environmental benefit. The obtained poly(N-Acylsulfonamide)s can be dissolved in alcohol or alcohol/water mixtures, but cannot be dissolved in THF or dichloromethane, which show opposite solubility after the polymers are acidified with HCl, indicating reversibly tunable hydrophilicity of the polymers. Furthermore, water can participate in the MCP as the fourth component when the MCP is conducted in DMF with CuI as the catalyst and NaCO as the base, generating random copolymers consisting of 3-Alkenyloxindole moieties and two chiral center-containing 3-hydroxyindole moieties in the backbone. Some of the oxindole-containing poly(N-Acylsulfonamide)s exhibit yellow to red emission in their solid state. These MCPs provide an efficient approach for the synthesis of functional polymers with unique structures, which directly build the oxindole and N-Acylsulfonamide moieties in situ, demonstrating high synthetic efficiency.

Xu Liguo    Zhou Fan    Liao Min    胡蓉蓉    唐本忠    

Polymer Chemistry

2018

Silver staining, which exploits the special bioaffinity and the chromogenic reduction of silver ions, is an indispensable visualization method in biology. It is a most popular method for in-gel protein detection. However, it is limited by run-to-run variability, background staining, inability for protein quantification, and limited compatibility with mass spectroscopic (MS) analysis; limitations that are largely attributed to the tricky chromogenic visualization. Herein, we reported a novel water-soluble fluorogenic Ag probe, the sensing mechanism of which is based on an aggregation-induced emission (AIE) process driven by tetrazolate-Ag interactions. The fluorogenic sensing can substitute the chromogenic reaction, leading to a new fluorescence silver staining method. This new staining method offers sensitive detection of total proteins in polyacrylamide gels with a broad linear dynamic range and robust operations that rival the silver nitrate stain and the best fluorescent stains.

Xie Sheng    Wong Alex Y.H.    Ryan tsz kin Kwok    Li Ying    Su Huifang    林荣业    Sijie Chen    唐本忠    

Angewandte Chemie - International Edition

2018