Aggregation-induced emission: materials, mechanism, and applications
It has been a textbook knowledge that chromophore aggregation generally quenches light emission. The conceptualization of aggregation-induced emission (AIE) breaks this common belief and provides a new stage for the exploration of practically useful luminescent materials for optical, electronic, energy and biomedical applications.
Aggregation-induced emission (AIE) stands for an intriguing phenomenon that a series of non-emissive molecules in solutions are induced to emit strongly in the aggregate or solid state. Since the concept was first coined in 2001, the surging interest in AIE research has led to diverse AIE luminogens (AIEgens) with tunable emissions and high quantum yields approaching unity in the solid state. The weak emission of AIEgens as molecular species and their bright fluorescence as nanoscopic aggregates differentiate them from conventional organic luminophores and inorganic nanoparticles, making them ideal candidates for optical, electronic, energy and biomedical applications. AIE has been ranked #2 in research fronts for chemistry and materials science by Thomson Reuters in 2015, and the research field is expanding significantly in recent years, as evidenced by the exponentially increasing numbers of citations (e.g. 11,000 in 2014, 20,000 in 2015 and 28,000 in 2016) on this theme. In recognizing the increasing importance and activity of AIE research, we propose a symposium to focus on the development of new generations of AIEgens, understanding of the AIE mechanisms and the exploration of advanced technological applications, which will enable this exciting research area to develop further. This symposium will bring together researchers in the field to discuss the progresses, challenges and potential breakthroughs, with the hope that the booming development of AIE materials will shape the future of luminescent materials. We expect to attract around 100-120 abstracts from scientists of over twenty countries.
Hot topics to be covered by the symposium:
This Symposium will represent the latest development in the field of AIE research. To highlight the breakthrough, progress, and challenges in the design, synthesis and applications of AIEgens, we propose to focus on the following topics in this symposium: (1) fluorescent and phosphorescent AIE-based polymers, oligomers and molecules; (2) advanced AIEgens with stimuli-responsiveness (e.g., photo-, thermo-, piezo-, vapo-, acido-, chronochromisms) and the related mechanisms; (3) biocompatible AIE probes for sensing, imaging, diagnosis, therapy and other biomedical applications; and (4) applications of AIEgens in optoelectronic devices and clean energy.
Confirmed invited speakers:
- Ivan Aprahamian, Department of Chemistry, Dartmouth College
- Deqing Zhang, Institute of Chemistry, Chinese Academic of Sciences
- Nicolas Mercier, Faculté des sciences, Université d'Angers
- Gen-ichi Konishi, School of Materials and Chemical Technology Chemical Science and Engineering, Tokyo Institute of Technology
- Claudia Barolo, Dipartimento di Chimica, Università degli Studi di Torino
- Yoshinori Yamanoi, School of Science, The University of Tokyo
- Takuma Yasuda, INAMORI Frontier Research Center, Kyushu University
- Andrea Pucci, Department of Chemistry and Industrial Chemistry, University of Pisa
- Eric Rivard, Department of Chemistry, University of Alberta
- Olaf Ramstrom, KTH - Royal Institute ofTechnology, Department of Chemistry, Sweden
- Lizhen, Department of Chemistry, Wuhan University
- Zhu Weihong, Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology
- Qin Anjun, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology
- Carlo Adamo, Chimie Théorique et Modélisation - Chimie ParisTech
- Paul R. McGonigal, Department of Chemistry, Durham University
Confirmed scientific committee members:
- Tony James, Department of Chemistry, University of Bath
- Takashi Kato, Department of Chemistry and Biotechnology, University of Tokyo
- Christoph Weder, Adolphe Merkle Institute, University of Fribourg
- Christopher Chang, Department of Chemistry, University of California, Berkeley
- Wolfgang Parak, Department of Physics, Philipps University of Marburg
Accepted papers will be published in Chemistry-An Asian Journal (CAJ), Wiley-VCH.
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Aggregation-induced emission: materials, mechanism, and applications Session 1 : Chaired by Qin Anjun
Authors : Min-Hui LI
Affiliations : 1. Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France 2. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, 100029 Beijing, China.
Resume : Synthetic amphiphilic polymers have been developed since last decades for the purpose of forming self-assembled polymer vesicles (polymersomes) which mimick lipid vesicles (liposomes). Polymersomes are much more stable, more robust and less permeable than liposomes due to the high molecular weight of polymers. Another interesting feature of polymersomes is that their properties can be finely adjusted by chemical design of the amphiphilic building blocks. These nanostructures are currently studied as a means of drug delivery and biomedical imaging for their ability to entrap hydrophobic molecules in the membrane and encapsulate hydrophilic ones in the inner aqueous compartment. Our group has focussed, since several years, on the tailor-design of smart polymersomes with biocompatible and biodegradable building blocks, stimuli-responsive release functions and/or aggregation-induced-emission properties. In this talk, I will first describe some examples of stimuli-responsive polymersomes, such as photo-, reduction- and oxidation-sensitive systems. I will then present our recent efforts at the development of aggregation-induced-emission polymersomes by combining polymer nanostructures with AIE luminogens (AIEgens) in order to provide innovative approaches to cell/tissue imaging and in vivo study of drug bio-distribution.
Authors : Peifa Wei,Jing-Xuan Zhang, Zheng Zhao, Yuncong Chen, Xuewen He, Ming Chen, Junyi Gong, Herman H.-Y. Sung, Ian D. Williams, Jacky W. Y. Lam, and Ben Zhong Tang
Affiliations : The Hong Kong University of Science and Technology
Resume : Seeking new methods to obtain elaborate artificial on-demand photoswitching with multiple functionalities remains challenging. Most of the systems reported so far possess only one specific function and their non-emissive nature in the aggregated state inevitably limit their applica-tions. Herein, a tailored cyanostilbene-based molecule with aggregation-induced emission characteristic was synthesized and was found to exhibit efficient, multiple and controllable photoresponsive behaviors under different conditions. Specifically, three different reactions were involved, they were: (i) reversible Z/E isomerization under room light and thermal treatment in CH3CN, (ii) UV-induced photocyclization with a concomitant dramatic fluorescence enhancement, and (iii) regio- and stereo-selective photodimerization in aqueous medium with microcrys-tal formation. Experimental and theoretical analyses gave visible insights and detailed mechanisms of the photoreaction processes. Fluorescent 2D photopattern with enhanced signal-to-background ratio was fabricated based on the controllable ?turn-on? and ?turn-off? photo-behavior in different states. The present study thus paves an easy yet efficient way to construct smart multiphotochromes for unique applications.
Authors : C. Bloyet,1 J.-M. Rueff,1 J. Cardin,2 V. Caignaert,1 B. Raveau, 1J.-L. Doualan,2 J.-F. Lohier,3 P.-A. Jaffrès.4
Affiliations : 1 Normandie Univ, ENSICAEN, UNICAEN, CNRS, CRISMAT, 14000 Caen, France. 2 Normandie Univ, ENSICAEN, UNICAEN, CEA, CNRS, CIMAP, 14000 Caen, France. 3 Normandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France. 4 CEMCA UMR CNRS 6521, Université de Brest, IBSAM, 6 Avenue Victor Le Gorgeu, 29238 BREST, France.
Resume : Phosphonic acid group is an attractive reactive function used since the year 1978 to design hybrid materials. Its tetrahedral geometry contrasts with the one of carboxylic acid and contributes to produce hybrid materials with original topologies and properties such as luminescence. The connection of phosphonic acid function to a rigid platform and the addition of further functional group having the capacity to be involved in the formation of an inorganic network open the way to a large combination of architecture. When directly connected to the rigid backbone, the phosphonic acid groups confers to the molecule a rigidity that plays a role to organize the topology of the final materials and that guarantee some thermal stability as soon as the material is not hydrated. In the course of our investigations to synthesize luminescent materials, we found that 4-phosphonobenzoic acid engaged with europium salt under hydrothermal conditions produced a lamellar material exhibiting luminescent properties and a remarkable thermal stability (up to 500°C). The use of 1-naphthylmethyl phosphonic acid, a more flexible building block, has permitted to synthesize a zinc based lamellar material which exhibited two features never observed so far, to the best of our knowledge, in any hybrid matrix containing naphthalene ligand: excimer emission and red luminescence at room temperature. The comparison with the structure and luminescence properties of the parent phosphonic acid has shown that this remarkable behavior was due to the strong π-π interactions between the naphthalene rings and time decay measurement shows that the latter may be due to aggregation induced emission (AIE) rather than to phosphorescence.
Authors : Nicolas Mercier
Affiliations : University of Angers, MOLTECH-Anjou, UMR-CNRS 6200, 2 Bd Lavoisier, 49045 Angers, France
Resume : In this communication, we will present the luminescence and mechanochromic luminescence properties of bismuth(III) complexes based on N-oxide-bipyridine ligands. While these complexes show weak luminescence in solution, they exhibit strong luminescence in the solid state (yellow-orange region) with impressive quantum yields up to 85%. Thorough investigations of the luminescence properties (temperature range 100K-293K) combined with DFT and TDDFT calculations have revealed that the emission is of aggregation induced phosphorescence type (AIP) due to restriction of molecular motion. Moreover, we also show that these complexes are the first examples of mechanochromic phosphors based on bismuth(III) ions : upon grinding, a clear change in the emission color is observed, typically from yellow to red, as a result of a 50-100 nm shift of the emission band, while the process is fully reversible when the ground sample is heated or exposed to solvent vapor (fuming) or when a few drops of solvent are added to the ground sample and quickly evaporated. X-ray powder diffraction and thermal analysis clearly show that an amorphisation of samples occurs upon grinding while the heating, fuming or fast evaporation processes involves the re-crystallization of samples. A particular case concerns a complex crystallizing as two polymorphs, P1 and P2. Besides the red shift in emission of 100 nm between the pristine compounds and the ground sample, the very interesting feature concerns the recovery of P1 or P2 from the ground sample which can be controlled depending on the process used, heating and fuming giving the thermodynamic phase P1, while drops of ACN gives the kinetic phase P2.
Authors : Meijuan Jiang, Xinggui Gu, Ryan T. K. Kowk, Ying Li and Ben Zhong Tang*
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China. E-mail: email@example.com
Resume : To cater the practical applications, fluorescent materials with strong light emission in solid/film state are of great interest. Among them, compounds with aggregation-induced emission (AIE) characteristics have attracted great attention. Herein, we reported a series of AIE luminogens (AIEgens) based on diphenyl isoquinolinium salts with easy synthesis and high structural stability. Photophysical studies show that these compounds were AIE-active with visible light excitation, large Stokes shift, high quantum yield, tunable color from blue to red, high two-photon absorption in the near-infrared region. Theoretical optimizations and crystal structures revealed that the rotatable phenyl groups and the twisted conformations were responsible for the AIE features of these compounds. We further investigated their applications in mechanochromic rewritable paper, cell imaging and microorganism imaging. These molecules were also potential for image-guided cancer cell ablation. All these intriguing results suggest that these readily accessible and multifunctional diphenyl isoquinolinium-based AIEgens are promising candidates for high-tech applications.
Authors : Inamur Rahaman Laskara, Sheik Saleem Pashaa, Hare Ram Yadavb, Angshuman Roy Choudhuryb
Affiliations : aDepartment of Chemistry, Birla Institute of Technology and Science, Pilani Campus, Pilani, India. E-mail: firstname.lastname@example.org; bDepartment of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Sector 81, S. A. S. Nagar, Manauli PO, Mohali, India.
Resume : Syntheses of multi-functional Aggregation-Induced Emission (AIE) active molecules in a simple manner with their wide ranges of applications have been drawing great attention in current luminescence materials research1. In this report a simple diamine molecule (N1-tritylethane-1,2-diamine(1)) is reacted with salicylaldehyde using a Schiff-base technique which results in a new AIE active organic molecule [2-((2-(tritylamino)ethylideneamino)methyl)-phenol (2)]. Computational calculations support that the nature of the transition is intra-molecular charge transfer/twisted intramolecular charge transfer (ICT/TICT). The mechanism of AIE has been attributed to restricted intramolecular rotation (RIR). Packing diagrams support that the nature of the aggregation is J-aggregation. The compound, 2, exhibits an irreversible mechanoluminescence (ML) property with a drastic colour change from blue to green (λmax, 445 nm - 512 nm) upon grinding. However, it undergoes a reversible transition with the same colour change (blue - green) through applying pressure axially (using a hydraulic press). The reversible transition is observed by lowering the temperature of 2 to that of liquid nitrogen. The causes of such transitions showing variations in the emission colour upon different triggers have been investigated. In addition, 2 has been successfully tested for the sensing of Zn(II) and shows a rare turn-on luminescence change, the mechanism behind which has been explored. The detection limit for Zn(II) is determined to be 0.064 ppm. Fig. 1 Chemical structure of [2-((2-(tritylamino)ethylideneamino)methyl)-phenol (2)]; Luminescence images and PL spectra of as-synthesized and the ground sample (a and b); the maximum emission wavelength change upon repeated grinding and recrystallization cycle of 2 (c) Reference 1. (a) D. Lo, C-H. Chang , G. Krucaite, D. Volyniuk, J. V. Grazulevicius and S. Grigalevicius, J. Mater. Chem., J. Mater. Chem. C, 2017, 5, 6054-6060; (b) F. Zhang, Y. Di, Y. Li, Q. Qi, J. Qian, X. Fu, B. Xu, W. Tian, Dyes and Pigments, 2017, 142, 491.
Authors : Andrea Pucci
Affiliations : Dipartmento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, 56124 Pisa, Italy.
Resume : Today, the driving force in solar photovoltaic (PV) technologies is lowering the cost per unit of power generated. Sunlight concentration is a promising path to cost-effective PV technologies. Compared to standard concentrators based on geometrical optics, luminescent solar concentrators (LSCs) show several advantages: low weight, high theoretical concentration factors, ability to work well with diffuse light and eventually no needs for sun tracking or cooling apparatuses. The building-integrated PV market is actually set to steadily increase promoted by the EU Energy Performance of Buildings Directive. LSCs are made of plastic slabs doped with red-emitting fluorophores that are generally preferred since their fluorescence well matches the Si-based PV cells band gap. Nevertheless, LSCs are plagued by critical processes that hinder their ability to deliver light to PV cells, including fluorescence quenching due to dye aggregation. This study examines for the use of aggregation-induced emission luminogens (AIEgen) to prepare red-emitting polymers for the realization of high performance LSCs. The fluorophores are photostable red-emitting AIEgen with D-A features that are physically dispersed or covalently linked to plastic matrices whose films absorb visible light in the range between 400-600 nm, and emit fluorescence around 610-650 nm when aggregated in solution or in the solid state. Study of the LSCs performances yields optical efficiencies ever registered of 10% thanks to the superior light harvesting features of the homogeneously distributed AIEgen.
Aggregation-induced emission: materials, mechanism, and applications Session 2 : Chaired by Pucci Andrea
Authors : Wang Fujia, Yang Haitao, Zhang Chong-Jing*
Affiliations : State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Science & Peking Union of Medical College
Resume : The energy transfer between dyes and quenchers is frequently used in design of light-up fluorescent probes. Dual quenchers are more effective in offering higher turn-on ratios and lower background signals than one quencher, but such probes are less studied in practice as they need both quenchers to be within the proximity of the fluorescent core. Herein, we utilized photoinduced electron transfer (PET) and intramolecular motion as quenching mechanisms to build super-quenched light-up probes based on fluorogens with aggregation-induced emission. This strategy was successfully applied to detect not only free formaldehyde (FA) but also polymeric FA. We hope that this novel dual quenching strategy will help with development of various light-up probes for bio-imaging.
Authors : Kenta Kokado, Kazuki Sada
Affiliations : Hokkaido University
Resume : Aggregation-induced emission (AIE) has attracted great attention of materials chemists, since it can present intense emission in the aggregated state. Usually AIE luminogen (AIEgen) shows the emission in the aggregated state. In this presentation, the author will demonstrate the necessity of aggregate formation to trigger AIE, and thus mechanistic consideration of AIE.
Authors : Paul R. McGonigal
Affiliations : Durham University
Resume : Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. This presentation discusses the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from some of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. These relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission.
Authors : Ying Li, Ben Zhong Tang
Affiliations : Division of Chemistry and Biological Engineering and Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Antibiotic resistance is spreading fast due to the abuse of antibiotics, and it poses a potential threat to human beings. Multidrug-resistant (MDR) bacteria pose serious threats to public health as there is currently a lack of effective and biocompatible drugs to kill MDR bacteria. In this work, we report an aggregation-induced emission luminogen that serves as antimicrobial agents for staining, combating Gram-positive (+) and Gram-negative (-) bacteria and treating bacteria-infected wounds. TriPE-NT can be applied as an assay technique, revealing its antimicrobial activity through bacteria staining and zeta potential and microstructure or elemental analyses. TriPE-NT shows antibacterial activity and kills wild bacteria and MDR bacteria efficiently in the presence of light due to the light-regulated generation of reactive oxygen species. However, it demonstrates a low toxicity to mammalian cell. TriPE-NT can inhibit the bacteria growth of E. coli-, MDR E. coli-, S. epidermidis- and MDR S. epidermidis-infected wounds on rats, Thus, TriPE-NT shows a great potential to be a low-cost and effective antimicrobial agent and may present a weapon in combating the growing threat of MDR bacteria and treating the (MDR) bacteria-infected wounds.
Authors : Duo Mao, Bin Liu
Affiliations : Department of Chemical and Biomolecular Engineering National University of Singapore 4 Engineering Drive 4, Singapore, 117585
Resume : Bacterial infection is one of the most serious physiological conditions threatening human health. There is an increasing demand for more effective bacterial diagnosis and treatment through non-invasive theranostic approaches. Herein, we report a new strategy to achieve in vivo metabolic labeling of bacteria through the use of MIL-100 (Fe) nanoparticles (NPs) as the nanocarrier for precise delivery of 3-azido-D-alanine (D-AzAla). After intravenous injection, MIL-100 (Fe) NPs could accumulate preferentially and degrade rapidly within the high H2O2 inflammatory environment, releasing D-AzAla in the process. The D-AzAla was selectively integrated into the cell walls of bacteria, which was confirmed by fluorescent signals from clickable DBCO-Cy5. Ultrasmall photosensitizer (PS) NPs with aggregation-induced emission characteristics were subsequently designed to react with the modified bacteria through in vivo click chemistry. Through photodynamic therapy, the amount of bacteria on the infected tissue could be significantly reduced. Overall, this study has demonstrated the advantages of MOF-assisted bacteria metabolic labeling strategy for precise bacterial detection and therapy guided by fluorescence imaging.
Authors : Zhen Li
Affiliations : Department of Chemistry, Wuhan University, Wuhan 430072, China
Resume : To construct (-molecules with different structures is one of the key points in the research field of opto-electronic materials. In many cases, the molecular structure not only affects the intramolecular (-conjugation, but also the intermolecular (-( stacking, to result in the different functionalities, in addition to the electronic properties of the single molecule. In this talk, some typical examples will be presented to partially demonstrate the interesting different properties with minor or even ignorable structural difference. Furthermore, some considerations of the structure-packing-performance relationship would be discussed, for the deep thinking of the molecular design for pi-molecules with different opto-electronic properties.
Authors : Wenjing Tian*, Bin Xu, Suqian Ma
Affiliations : State key laboratory of supramolecular structure and materials, Jilin University, Changchun 130012, P. R. China.
Resume : Organic luminescent materials with aggregation-induced emission (AIE) properties have attracted concentrated interest due to their outstanding properties in solid state. Increasing attention has been paid to single crystals based on AIE molecules for their high thermo-stability, long-range ordering and unique opto-electronic properties. Hence, it is of great importance to design new organic materials via crystal engineering strategies to optimize the molecular stacking and obtain excellent opto-electronic capabilities. Here we present a successful example of achieving high solid state fluorescence efficiency and amplified spontaneous emission (ASE) via cross-dipole stacking based on BDPVB single crystals. Moreover, a novel butterfly-like molecule BDPV2T is presented to show both high fluorescence efficiency and high charge carrier mobility in its J-aggregate single crystals. Apart from these, the protonation and the fluorescence change based on BP4VA crystals has been studied, showing that the fluorescence variety comes from the difference in the aggregation structures. The investigations based on aggregation structures and opto-electronic properties can provide novel insights into developing novel AIE materials.
Authors : Dongyu Zhao
Affiliations : Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, China
Resume : Emerged as a promising alternative to conventional liquid crystal displays (LCDs), luminescent LCDs (LE-LCDs) have currently stimulated extensive research attentions for the convenient device configuration, low manufacture costing and enhanced energy efficiency. In spite of the infusive prospects, the development of LE-LCs remains a challenging issue. Recently, an original phenomenon of aggregation-induced emission (AIE) associated with chromogen aggregation was discovered in some propeller-like molecules. Although detailed analysis of the factors affecting AIE has been conducted, new mechanism triggerring AIE process as well as the novel AIE systems along with it are still to be excavated. The non-traditional systems, AIEgens, furnishing the possibility to occupy the above quenching challenge, are promising candidates for the evolution of novel LE-LCs. In this study, a new technique, which invokes trace amounts of micro Ag2S[(CH3)2S] hexagonal prisms and an AIE-active LC compound TPE-PPE into the nematic LC medium, was proposed. As a synergistic effect to activate the AIE process, the concentration increment of TPE-PPE and Ag2S-TPE-PPE interaction finally resulted in approximately 36-fold enhancement in fluorescence, which was obtained in the luminescent LC system. Exhilaratingly, it is firstly reported that AIE process was activated by the cation-π interaction. This novel approach, as well as the mechanism of cation-π interaction that trigged AIE process, are not just limited in fabricating high-luminescent meso phases for future luminescent display device, it would also inspire the design of next generation of functional inorganic-organic hybrid luminescent systems.
Aggregation-induced emission: materials, mechanism, and applications Poster Session 1 : Nil
Authors : I. S. Geisler, S. Baysec, E. Preis, U. Scherf
Affiliations : Bergische Universität Wuppertal, Macromolecular Chemistry Group, Gaußstraße 20, 42119 Wuppertal, Germany
Resume : Materials with aggregation-induced emission (AIE), so-called AIEgens, have attracted great academic and industrial attention, because of their high application potential in fluorescence biosensors and optoelectronic devices. AIEgens show a weak photoluminescence in dilute solutions, but become highly emissive upon aggregation, through a restriction of intramolecular motions. In contrast, the commonly appearing aggregation-caused quenching often limits an application in concentrated solution or solid phase. Tetraphenylethylene and corresponding polymers are well-known representatives of AIE-active materials. In previous work of our group, phenoxy side groups were introduced into a poly(tetraphenylethylene) backbone, resulting in a remarkable increase of the solid state photoluminescence quantum yield from 37% to 73%. Now, the effect of an elongation of the phenoxy into bis(phenoxy) side chains was studied. Three regioisomers were synthesized by reductive polyolefination reaction, their optical properties were investigated and compared, regarding their AIE characteristics. References:  Y. Hong, J. W. Y. Lam, B. Z. Tang, Chem. Commun. 2009, 4332-4353.  S. Baysec, E. Preis, S. Allard, U. Scherf, Macromol. Rapid Commun. 2016, 37, 1802-1806.
Authors : Yuan Gu, Ben Zhong Tang
Affiliations : Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, Division of Life Science, State Key Laboratory of Molecular Neuroscience and Institute of Molecular Functional Materials, The Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon, China
Resume : Reduced glutathione (GSH, L-γ-glutamyl-L-cysteinyl-glycine) is the most abundant non-protein thiol species in mammalian and eukaryotic cells. GSH is an essential endogenous antioxidant that plays a key role in cellular defense against toxins and free radicals. GSH can enter the blood plasma and be transferred to other cells. The concentration of GSH in blood plasma is usually in the micromolar range. Several studies have shown that plasma GSH may decrease with age. What’s more, decreased plasma GSH has been associated with several diseases, such as alcoholic cirrhosis, HIV, cystic fibrosis, and Type II diabetes. In this study, a ratiometric GSH probe with Aggregation-Induced Emission Characteristics has been designed and synthesized. The probe responds selectively to GSH with the detection limit of 0.64458 nM, which is the lowest detection limit reported so far to the best of our knowledge. Finally, the probe was applied for practical blood plasma GSH measurement. It turns out that the level of GSH in blood plasma measured by the probe agrees well with data reported by previous study.
Authors : Shouchun Yin
Affiliations : College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, Zhejiang 310036, P.R. China
Resume : Control over the fluorescence of supramolecular assemblies is crucial for the development of chemosensors and light-emitting materials. Here we constructed three exohedral functionalized rhomboidal metallacycles by phenanthrene-21-crown-7 (P21C7)-based diplatinum(II) acceptor with different colors emission. The metallacycles were further linked into emissive supramolecular oligomers by adding a fluorescent bis-ammonium linker that forms complementary host–guest interactions with the pendant P21C7 units. Notably, one ensemble, which was formed by one metallacycle with AIE property and bis-ammonium linker with ACQ property, displays a concentration-dependent emission with orange emission at high concentration and blue emission at low concentration. It is well worth mentioned that at a concentration of 29 μM the same ensemble emits white light. These results were achieved by the integration of complementary emission properties (AIE and ACQ), complementary colors (orange and blue), and complementary host–guest interactions (crown ether and ammonium salts).
Authors : Longcheng Gao
Affiliations : School of Chemistry, Beihang University, Beijing, China
Resume : Understanding of the polymer chain movement is the bridge between the microstructure and the macro-scale properties of the materials. There are many methods to monitor the chain movements. However, the direct or visual techniques are somehow difficult to realize. Here, we take advantage of the aggregation properties of AIEgens, which are conjugated with the chains movement, to see the chain movement directly. When the AIEgens are incorporated in the polymer system, the polymer chain movement would influence the vibration of the AIEgens. The emission of the molecule will change, and in return, reflect the chain movement by the fluorescent observation.
Authors : Xiaolin Liu, Zijie Qiu, Zheng Zhao, Jacky W. Y. Lam, Ben Zhong Tang*
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China
Resume : Thiophene-containing conjugated polymers have found various applications in the field of organic electronics due to their excellent photoelectric properties.1 Generally, they are synthesized by Stille or Suzuki coupling, which often require the use of palladium catalyst, inert gas protection, strict monomer stoichiometric balance, and organometallic complex.2 Herein, an efficient, one-pot tandem polymerization based on Glaser Coupling and sulfur heterocyclization of diynes was developed for the preparation of thiophene-containing conjugated polymers in high yields (up to 99%) with high molecular weights (Mn up to 130,000). This new method proceeds smoothly in air without strict stoichiometric balance and does not require palladium catalysts or organometallic complexes. By incorporating diyne monomers with, such as electron-donating property, heteroatoms, and aggregation-induced emission, polymers with tunable band gap and unique properties were obtained. References 1. Cheng, Y. J.; Yang, S. H.; Hsu, C. S. Chem. Rev. 2009, 109, 5868-5923. 2. Carsten, B.; He, F.; Son, H. J.; Xu, T.; Yu, L. Chem. Rev. 2011, 111, 1493-1528.
Authors : Yu-Bing Hu, Ting Han, Jacky W. Y. Lam and Ben Zhong Tang
Affiliations : The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : The efficient and concise construction of various heterocyclic architectures in synthetic polymers is of great significance in organic, material and medicinal chemistry. To construct novel functional polymers with well-defined structure, our group has been working on the exploration of polymerization methodology from alkyne monomers for decades. Herein we developed a facile approach towards poly(2-amino-4H-1,3-oxazine)s (PAHOs) through a one-pot A3-cycloisomerization reaction of diyne (1), dialdehyde (2) and urea (3) in the presence of trifluoroacetic acid and acetic acid mixture in reflux acetonitrile. Conjugated polymers with the oxazine moiety were formed in situ with high molecular weights (Mw up to 74 700) and narrow polydispersity indices in nearly quantitative yields (up to 96.6%). The tetraphenylethene-containing PAHOs were weakly emissive in solutions but showed intense emission in the solid state, demonstrating an obvious aggregation-induced emission behavior. The nitrogen-containing heterocycles was excepted to endow the resulting polymers with advance properties, such as sensitivity to amine vapors. Through protonation and deprotonation reaction, the fluorescence of protonated thin films of PAHOs were completely recovered by exposure to ammonia vapors. A fast responsive and reversible fluorescent polymer sensor based on PAHOs was developed to detect various amine vapors, such as triethylamine, hydrazine and spermidine. Seafood freshness detection was realized by the in-situ generated ammonia and biogenic amines from spoiled shrimps and scallops in 24 h.
Authors : Fengyan Song, Zeng Xu, Anjun Qin, Jacky W. Y. Lam, Dongge Ma*, Ben Zhong Tang*
Affiliations : Hong Kong Unversity of Science and Technology
Resume : Development of highly efficient circularly polarized organic light-emitting diodes has gained increasing interest as they show improved luminous efficiency and high contract 3D images in OLED displays. In this work a series of binaphthalene-containing luminogenic enantiomers with aggregation-induced emission (AIE) and delayed fluorescence properties were designed and synthesized. These molecules could emit from green to red light depending on the solvent polarity due to the twisted intramolecular charge transfer effect. However, their solid powders show bright light emissions, demonstrating a phenomenon of AIE. All the molecules exhibit Cotton effects and circularly polarized luminescence in toluene solution and films. Multilayer CPOLEDs using the doped and neat films of the molecules as emitting layers are fabricated, which exhibit high external quantum efficiency of up to 9.3% and 3.5% and electroluminescence dissymmetry factor (gEL) of up to 0.026/-0.021 and 0.06/-0.06, respectively. Compared with doped CPOLEDs, the non-doped ones show higher gEL and much smaller current efficiency roll-off due to the stronger AIE effect. By altering the donor unit, the electroluminescence maximum of the doped film can vary from 493 nm to 571 nm. To the best of our knowledge, this is the first example of efficient CPOLEDs based on small chiral organic molecules.
Authors : Chengcheng Zhou, Meijuan Jiang, Ryan T. K. Kwork, Jacky W. Y. Lam, Benzhong Tang*
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Pathogenic microbes are a major cause of human disease and death. Thus, the development of simple and rapid method to identify microbial pathogens would be of great value to realize the origins of infectious diseases and food contamination as well as provide guidance for antibiotics usage. Here we demonstrate that a positively-charged aggregation-induced emission luminogen, namely IQ-cm, with twisted intramolecular charge transfer property can fast discriminate E. coli, S. aureus and C. albicans effectively in a visual way. IQ-cm is weakly emissive in solution but shows strong fluorescence after electrostatically targeting the microbial surface. Due to the subtle difference in the microbial surface structure, IQ-cm senses a different polar microenvironment to show different emission colors with different microbial pathogens: orange for IQ-cm/E. coli, red for IQ-cm/S. aureus and yellow for IQ-cm/C. albicans. Thus, IQ-cm is an ideal, potential diagnostic agent for the identification of pathogens based on its simple and visual merits.
Authors : Michidmaa Khorloo, Yanhua Cheng, Jacky W. Y. Lam and Ben Zhong Tang
Affiliations : Department of Chemistry and The Hong Kong Branch of National Engineering Research Centre for Tissue Reconstruction & Restoration, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China. E-mail: email@example.com
Resume : Sensitive probing of humidity plays an important role in the control systems for industrial processes and chemical reactions. However, water vapor is gaseous and invisible. If water vapor could be endowed with color, the visualization and supervision would be drastically enhanced. Herein, we develop new stimuli-responsive material to achieve in situ gradient humidity visualization by assembling AIE-based fluorescent molecular rotors within a polyhydroxyl network. As the polymer network dynamically absorbs and desorbs water molecules in response to immediate humidity, the fluorescence color of the molecular rotors changes through the polarity variation of the local environment due to the TICT effect. The new material, which shows high sensitivity and good reversibility, changes emission color in a continuous gradient, provides linear dependence on the relative humidity, and presents a spatial imaging of the gradient humidity over a microscopic scale. The application of the material can be extended to many fields, such as food processing and storage, structural health monitoring and aerospace.
Authors : Weijiang Guan, Chao Lu, Ben Zhong Tang
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China
Resume : The use of organized surfactant molecular assemblies such as micelles, reverse micelles and microemulsions for chemiluminescence resonance energy transfer (CRET) is steadily increasing because such assemblies can greatly improve the analytical performance of chemiluminescence (CL) in terms of selectivity, sensitivity and experimental convenience. One of the challenges in this field is how to control the CRET donor-acceptor distance. Microemulsion-based CRET can confine the peroxyoxalate CL donor at oil–water interface but the position of CRET acceptors is still randomly distributed. Accordingly, great effort should be devoted to develop novel strategies to control the donor−acceptor distance, aiming at the improvement of CRET efficiency. Herein, we synthesized a new molecule, namely TPE-AOT, by integration of tetraphenylethylene (TPE), an archetypal aggregation-induced emission (AIE) luminogen, to the molecular structure of AOT. TPE-AOT can form stable microemulsion and emitted intensely upon aggregate formation in microemulsion. The distance between the oil–water interface and TPE-AOT was fixed at about 1.1 nm to result in a remarkable enhancement on the CRET efficiency (93.41%). This value is much higher than that achieved in traditional CRET (59.01%). The improved CRET efficiency enables a lower detection limit for hydrogen peroxide sensing. It is anticipated that the combination of microemulsion-based CRET and AOT-based AIE luminophors can freely adjust the CL donor-acceptor distance.
Authors : Simon H. P. Sung, Ryan T. K. Kwok and Ben Zhong Tang*
Affiliations : Department of Chemistry and The Hong Kong Branch of National Engineering Research Centre for Tissue Reconstruction & Restoration, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Resume : Lysosome is an organelle responsible for cell digestion and cell components recycling. It plays a crucial role in the autophagy, a process of breaking down cell components.  Dysfunction of lysosome has been implicated in close relationship with disorders such as inflammation, cancer, and numerous lysosomal storage diseases, etc. and loss of regeneration ability of the damaged tissue. Due to its uniqueness and importance, plenty of commercial fluorescence probes with high specificity to lysosome have been developed. These commercial lysosome trackers, however, are vulnerable to photobleaching and fluorescence quenching when these probe molecules aggregated in lysosomes. Luminogens with Aggregation-Induced emission characteristics (AIEgens), on the other hand, possessing good photostability and strong emission in aggregate state provide a direct solution for tackling the problems of commercial lysosome trackers.  In this work, as the first attempt, we report a carbazole-based AIE bioprobe with red emission for lysosome imaging and its application in monitoring autophagy during the caudal fin regeneration in the zebrafish. Reference:  S. Castro-Obregon, Nat. Educ. 2010, 3, 49  Fan, F., Nie S., Yang D., Luo M., Shi H., Zhang Y. H.; Bioconjugate Chem., 2012, 23, 1309-1317  M Varga, M Sass, D Papp, K Taka´cs-Vellai, J Kobolak, A Dinnye, DJ Klionsky, and T Vellai, Cell Death and Differentiation, 2014, 21, 547–556  Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z, Chem. Rev., 2015, 115, 11718-11940
Authors : Haozhong Wu, Zhiming Wang*, Anjun Qin and Ben Zhong Tang
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (SCUT), Guangzhou 510640, China 2. School of Petrochemical Engineering, Shenyang University of Technology (SUT), Liaoyang 111003, China 3. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
Resume : The materials with intramolecular charge transfer (ICT) characteristic have been extensively investigated in few decades as their technical applications in organic light-emitting diodes, nonlinear optical collectors, photovoltaic devices and chemosensors. These compounds are almost based on a push-pull electron-effect system, including an electron-donating moiety (Donor, D) and electron-withdrawing moiety (Acceptor, A) bonded directly or with π-bridge. The ICT characteristic strongly relying on the ability of the donor to furnish electron and the acceptor to withdraw electron impacts on the luminescent properties. The most common ICT state is twisted intramolecular charge transfer (TICT) – the donor and acceptor are coplanar in the ground state, while these two moieties are twisted and even perpendicular after excitation. As the two perpendicular orbitals located on various π moieties, the low fluorescence quantum yield (Ф) was usually observed owing to absence of efficient overlap. Another ICT process is against to the TICT, named planarized intramolecular charge transfer (PICT). The PICT-based molecules are generally twisted in the ground states whereas their conformations are apt to be flat in the excited states. The decrease of D-A dihedral angle stimulates the strong conjugation between two moieties, which generates efficient frontier orbital overlap. In addition, the planarized structure may also rigidize their conformation and reduce the non-radiative decay process by limiting molecular motion, so the high efficient luminescence is expected via PICT process. In fact, many ICT materials are constructed through D-π-A type but not the D-A type, because the π bridge can prevent seriously distortion and even transform the twisted excited conformation into planar on. For realizing the aim of constructing PICT-typed molecular, a feasible strategy is attempted by introducing more stable quinone conformation to induce the formation of PICT process in excited state. As our previous literatures depicted, the materials with aggregation-induced emission (AIE) properties are often constructed with highly twisted structures. Upon excitation, the AIE molecules tend to be flatten, which is familiar to the PICT model. Recently, we have discovered the AIE block named tetraphenylpyrazine (TPP) had larger torsion among the pyrazine centre and peripheral phenyl groups in the ground state, while it was apt to form the quinoid conformation and be flatten upon excitation, which enlarged its excited conjugation for stabilization. After employing the phenanthroimidazole as donor, the two PICT materials of TPP-PPI and TPP-PI were prepared and characterized, which exhibited the obvious red shifts in luminescent spectra and the enhancement of PLQYs with increasing solvent polarity, inferring the ICT state is belong to the PICT process, against to TICT-based materials. The theoretically calculation demonstrates that their excited conformations leaned to be more flat in polar surrounding than in the non-polar solvents i.e. the structures are more plane and rigid in the excited states, resulting in the increasing the rate of radiative decay and the decreasing the rate of non-radiative decay and rendering as the high emission efficiency. The experimental and theoretical results suggest that we got the feasibility of designing strategy for PICT molecules via forming quinone conformation in excited state, e.g. TPP block. Thanks to their high thermal and morphological stability and good luminescent efficiency in solid state, their OLED devices achieve high performance with the lower turn-on voltage, good maximum luminance, current efficiency, power efficiency and external quantum efficiency (2.9 V, 16460 cd/m2, 8.34 cd/A, 8.18 lm/W, 4.85% for TPP-PI and 2.9 V, 16890 cd/m2, 8.50 cd/A, 8.23 lm/W, 4.36% for TPP-PPI). More important, their exciton utilization ratio estimated to be 57.2% and 71.9% respectively, which exceed the 25% theoretical singlet population and TTA limitation, implying the other RISC channel is active in PICT process.
Authors : Haozhong Wu, Zhiming Wang*, Anjun Qin and Ben Zhong Tang
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (SCUT), Guangzhou 510640, China 2. School of Petrochemical Engineering, Shenyang University of Technology (SUT), Liaoyang 111003, China 3. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
Resume : The materials with intramolecular charge transfer (ICT) characteristic have been extensively investigated in few decades as their technical applications in organic light-emitting diodes, nonlinear optical collectors, photovoltaic devices and chemosensors. The most common ICT state is twisted intramolecular charge transfer (TICT), and they usually suffer from the low fluorescence quantum yield (Ф) owing to absence of efficient overlap. Against to the TICT, the planarized intramolecular charge transfer (PICT) could rigidize their conformation and reduce the non-radiative decay process by limiting molecular motion, so the high efficient luminescence is expected. Here, we proved a feasible strategy of introducing more stable quinone conformation to induce the formation of PICT process by inserting AIE block tetraphenylpyrazine (TPP), which could apt to form the quinone conformation in excited state. After employing the phenanthroimidazole as donor, the two PICT materials of TPP-PPI and TPP-PI were prepared, and their experimental and theoretical results suggest our method was correct. Their OLED devices achieve good performance with higher exciton utilization ratio of 57.2% and 71.9% respectively, which exceed the 25% theoretical singlet population and TTA limitation, implying the other RISC channel is active in PICT process.
Authors : Zheng ZHENG, Jacky W. Y. Lam, Ben Zhong Tang*
Affiliations : Department of Chemistry, Hong Kong Branch of Chinese National Engineering, Research Center for Tissue Restoration and Reconstruction, Institute of Molecular Functional Materials, State Key Laboratory of Molecular Nanoscience, Division of Life Science and Biomedical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Organic materials that exhibit aggregation-induced emission (AIE) property have received increasing attentions in recent years because of their potential applications in material science and biological techniques. In this work, a carbazole-bridged far red AIEgen (DC-In), which shows strong fluorescence in both the solid state and in organic solutions, is prepared. Interestingly, DC-In displays very strong solvatochromism effect because of the push-pull nature. The AIE property and self-assembly behavior of DC-In in acetone/water mixture solvent are investigated carefully. Impressively, three single crystals based on DC-In with different luminescence colors, yellow, red, and far red, can be obtained by controlling the crystallization conditions. The relationship between the emission properties and the crystal structure of DC-In is subsequently investigated. X-ray crystallographic analyses of the three crystals show that there are remarkable differences in the molecular conformation and the molecular packing. Moreover, one of the crystals of DC-In exhibit interesting optical waveguide property.
Authors : Han Zhang, Zhiming Wang*, Zujin Zhao and Ben Zhong Tang
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (SCUT), Guangzhou 510640, China 2. School of Petrochemical Engineering, Shenyang University of Technology (SUT), Liaoyang 111003, China 3. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
Resume : Blue emitters play a highly significant role in full-color OLEDs, and their color purity, quantum yields and exciton utilizing ratios are important parameter to evaluate their quality. Aryl-substituted phenanthroimidazoles (APIs) attract more attention because of their fluorescence performance with the characteristic of hybridized local and charge-transfer excited states. However, traditional API derivatives possess lower fluorescence quantum yields in aggregate state due to aggregation-caused quenching effect, limiting their application in high efficiency OLEDs. Here, we introduce the classic aggregation-induced emission (AIE) block to the C2 position of API with different pattern, and tune D-A effect at the N1 position with inserting cyano-phenyl group, for balancing the three index above. Six API derivatives were prepared, and they all exhibited AIE emission because of TPE inserted. Compare to para-structure of TPE binding API (p-TPI), the meta-ones gave bluer emission in aggregates and OLED performance, such as the non-doped device based on mmCTPI having deep blue emission with CIE coordinates of (0.153, 0.126), but their quantum yield were lower. By tuning cyano-phenyl group, their EUE were gradually raised with the improvement of CT component from none to para-position. We had successfully developed an effective strategy to achieve the tuning of light color and exciton utilizing efficiency in purpose, which is benefit to constructing higher efficiency blue AIE-active materials.
Authors : Bo Song, Anjun Qin, Ben Zhong Tang
Affiliations : Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China
Resume : Fixing carbon dioxide (CO2) into useful polymeric materials has attracted broad interest since carbon dioxide is an abundant, inexpensive, nontoxic, and renewable C1 resource. Polymers with aggregation-induced emission (AIE) characteristics have attracted much attention because of their good solubility, processability, high emission efficiency in the aggregate states. Nevertheless, AIE polymers have not yet constructed based on CO2 and alkynes. Herein, we synthesized AIE polymers via our established facile and efficient Ag2WO4–catalyzed polymerization of CO2, diynes and alkyl dihalides under mild reaction conditions. Soluble and thermally stable AIE poly(alkynoate)s with high molecular weights (up to 31400) were obtained in high yields (up to 95%). The resultant AIE polymers possess high absolute quantum yields up to 61% in the film state, which are much higher than those of most of AIE polymers synthesized by our group previously probably because the flexible main chains enable the AIE units to rotate freely in the solution state and pack more tightly in the aggregate state. Their containing ester linkages endow the polymers degradable under basic conditions, and the alkynoate repeating units enable them to be post-functionalized by the powerful amino-yne click reaction to generate nitrogen-containing stereo- and regio-regular polymers with 100% grafting ratio.
Authors : Fan Zhou1, Zhiming Wang1,2*, Rongrong Hu1, Benzhong Tang1,3*
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology(SCUT), Guangzhou 510640, China, 2. School of Petrochemical Engineering, Shenyang University of Technology (SUT), Liaoyang 111003, China, 3. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China.
Resume : Lipid droplets (LDs) play important roles in cellular physiological activity and combating energy crisis. Especially, the abnormity of LDs are related with some diseases, and the real time monitoring of LDs is very significant for understanding their biological functional roles. Organic fluorescence probes have attracted more and more attention in biological and biomedical applications, but some of LDs-based dyes suffer from aggregation-caused quenching (ACQ) effect. In 2001, our group provided a revolutionary solution to solve the self-quenching problem at high concentrations or in the aggregated state, and namedas aggregation-induced emission (AIE). With the widespread application of AIE fluorogens (AIEgens), many specific LDsprobes were prepared, butfew successful system was reported featuring the tuning the fluorescence color only by simple organic synthesis, because ofavoiding colors-overlapping with other organellesin practical. The AIEgens based on FAS and DPAS, whoseexcited-state intramolecular proton transfer (ESIPT) process showed typical AIE character, were reported in our previous work, and now, the developmentcover from blue to red was realized only by introducing different salicylaldehydegroups.They allexhibit a large Stokes shifts and bright emission, and adjusted their fluorescence colors freely according to desirable for LD-specific imaging.Otherwise, these probes could be used to monitor the inducing differentiation processes of 3T3-L1 preadipocyte.
Authors : Jie Zhang a), Jing Zhi Sun a) , Anjun Qin b)* and Ben Zhong Tang a, b, c) *
Affiliations : a) MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China. b) State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. Email: firstname.lastname@example.org c) Department of Chemistry ,The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China.Email:email@example.com
Resume : High refractive index (n) polymers with high optical transparency are highly required in advanced photonic devices such as high performance substrates for optical waveguides, display devices, optical adhesives or encapsulants for antireflective coatings, and microlens components for charge coupled device (CCD) or complementary metal oxide semiconductor (CMOS) image sensors. Especially, a very high-n exceeding 1.7 is frequently desired, although the typical n values of conventional optical polymers are in the range of 1.30−1.70. Herein, we reported our work on preparation of high refractive index polymers based on our established novel metal-free alkyne-based polymerization of bromoalkynes and thiophenols. Thanks to its function-tolerance, tetraphenylethene, a typical luminogen featured the aggregation-induced emission (AIE) characteristics could be facilely incorporated into the polymer, making it AIE-active, too. Furthermore, the resultant polymer possesses good film-forming ability, high n (1.72 @863 nm, 1.68 @1550 nm), and high optical transparency. Thus, it could be used as optical waveguides with relatively low propagation loss of 15.6 dB/cm.
Authors : Pai Liu, Wangyang Li, Shuai Guo, Dongrui Xu, Mengni Wang, Jianbing Shi,* Zhengxu Cai, Bin Tong, Yuping Dong*
Affiliations : The authors all worked in Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Material Science & Engineering, Beijing Institute of Technology
Resume : As is well-known, Al3+ can be severely accumulated in human body to damage nervous system, leading to lots of diseases.1 Nowadays, large numbers of fluorescent probes which were used for detecting metal ions have been reported. But, most of them can only work in single solvent (organic solvent or water) due to the influence of proteins and other components. Thus, these fluorescent probes were not suitable for the direct detection of Al3+ in biological environments, especially in the human blood1. In our research, A novel “turn-on” fluorescent bioprobe,4,4',4'',4''',4''''-(1H-pyrrole-1,2,3,4,5-pentayl)pentabenzoate (PPPNa), with an aggregation-enhanced emission (AEE) characteristic was synthesized for in-situ quantitative detection of Al3+ in the blood serum. It was found that the bioprobe showed little interference of other metal ions and components in the blood serum. The high selectivity of the probe enabled in-situ quantitative detection of Al3+ without the isolation of Al3+ from the blood serum. The limit of detection (LOD) was determined as 0.98 μmol/L in the presence of BSA and became lower with the increase of BSA concentration. The turn-on mechanism of PPPNa probe to Al3+ was forming bidentate complex between carboxylate groups on PPPNa and Al3+. Meanwhile, BSA chains can further strengthen the stacking compactness of the aggregates and thus enhance PL emission of PPPNa due to restricting the intramolecular rotation of phenyl rings. References: 1. Chereddy, N. R.; Nagaraju, P.; Raju, M. V.; Krishnaswamy, V. R.; Korrapati, P. S.; Bangal, P. R.; Rao, V. J. Biosens. Bioelectron. 2015, 68, 749-756. 2. Maniyazagan M, Mariadasse R, Nachiappan M, et al. Sensor. Actuat. B-Chem. 2017, 254, 795-804.
Authors : Nian ZHANG, Hui CHEN, Yujiao FAN, Sylvain TREPOUT, Min-Hui LI
Affiliations : (N.ZHANG,M.-H. LI)Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, 100029 Beijing, China. (H.CHEN,Y.FAN,M.-H. LI)Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris (IRCP), 75005 Paris, France (S.TREPOUT)Institut Curie, PSL Research University, INSERM U1196 and CNRS UMR9187, 91405 Orsay cedex, France
Resume : Polymer vesicles exhibit tremendously interesting properties such as high membrane elasticity and large encapsulation capacity. Fluorescent polymersomes are interesting systems for cell/tissue imaging and in vivo study of drug distribution and delivery. However, traditional fluorescent polymersomes contain generally conventional organic dyes always suffer from aggregation-caused quenching (ACQ). It will be very significant to develop novel fluorescent polymersomes composed of luminogens with aggregation-induced emission (AIE) characteristics that have emerged since last decade as a new class of fluorescent materials for organelles imaging and drug delivery monitoring. In this work we report on bright fluorescent polymersomes with aggregation induced emission, which are self-assembled by amphiphilic biodegradable tetraphenylethylene-containing block copolymers PEG-b-P(TPE-MTMC). A series of AIE amphiphilic diblock copolymers were prepared through the ring opening polymerization of a tetraphenylethylene (TPE) substituted trimethylenecarbonate monomer (TPE-MTMC) with transition-metal-free organo-catalyst. Their self-assemblies in water were prepared by nanoprecipitation using dioxane or THF as co-solvent, and the self-assembling processes were studied in detail by cryo-EM, DLS and spectrofluorometer. These AIE polymersomes can be potentially used as a stable fluorescent tool to monitor the transportation, distribution of drugs and bioconjugates in living cells, providing an innovative approache for bioimaging and theranostics.
Authors : Dan Ding
Affiliations : College of Life Sciences, Nankai University, Tianjin 300071, China
Resume : Long-term stem cell tracking is very important in the field of stem cells. Herein, we report a quantum dot-sized organic dot with aggregation-induced emission (AIE) characteristics as a promising cell tracker for noninvasive long-term tracking of adipose-derived stem cells (ADSCs) in living mice. The stem cell tracking ability of the AIE dots were evaluated and compared with the widely used commercial cell trackers of PKH26 and Qtracker 655. The in vivo stem cell tracking application of AIE dots were assessed using an ischemic hind limb-bearing mouse model. It is demonstrated that the AIE dots possess high fluorescence, strong photobleaching resistance, low in vivo toxicity, excellent retention in living ADSCs and negligible interference on the ADSC pluripotency and secretome. The AIE dots also exhibit far superior in vitro cell tracking capability as compared to the PKH26 and Qtracker 655. The in vivo studies using an ischemic hind limb-bearing mouse model reveal that the AIE dots can precisely and quantitatively report the fate of ADSCs and their therapeutic effect in vivo for 6 weeks. It is concluded that the AIE dots can serve as a new and efficient nanoprobe for long-term stem cell tracking.
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Aggregation-induced emission: materials, mechanism, and applications Session 3 : Chaired by Eric Rivard
Authors : Yingjie Liu, Bin Xu, Wenjing Tian
Affiliations : State Key Laboratory of Supramolecular Structure and Materials, Jilin University,
Resume : Organic luminescent materials have been attracted intensive interests over the past decade due to their wide potential applications in the optoelectronic and biological fields. Manipulating AIE luminogens stacking modes through the supramolecular self-assembly may provide a new potential solution to develop highly efficient luminescent supramolecular system and explore the new functions of AIE molecules. In our previous work, a series of 9,10-divinylanthracene derivatives were found to possess aggregated induced emission (AIE) and peizochromism properties. Because of steric effects around the double bond, these derivatives possess twisted conformation and loosely packing structure in the solid state, which is necessary for a stimuli-responsive feature. We have recently reported two co-crystal polymorphs of supramolecular co-assemblies (C1 and C2) that consist of BP4VA and FIB. Single-crystal X-ray diffraction analyses indicate that BP4VA contact with FIB molecules through numerous hydrogen/halogen bonds. In this, we speculate that constructing co-crystal system may be an effective design strategy for new stimuli responsive luminescent materials. Herein, we demonstrate a very rare example of single crystal – single crystal (SCSC) phase transition and multi-stimuli responsive fluorescence switching based on BP4VA-FIB co-crystals. As adopting different accumulation structures and intermolecular interactions, C1 and C2 exhibit distinct luminescence characteristics under external stimuli, such as grinding, heating, solvent fuming, hydrostatic pressure and acid fuming. The photophysical, PXRD, and DSC analysis in detail provided evidence to confirm and understand the SCSC phase transitions process. And their luminescence switching features make these co-crystal systems promising candidates for sensing and optical recording.
Authors : M. Cerón1, P. Venkatesan1, E. Pérez-Gutierrez1, S. Thamotharan2 and M. Judith Percino1*
Affiliations : 1Unidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa, Pue. México. 2Biomolecular Crystallography Laboratory, Department of Bioinformatics, School of Chemical and Biotechnology, SASTRA Deemed University, Thanjavur-613401, India
Resume : Arylacrylonitriles are important building block for the synthesis of biologically active molecules such as flavonoid pigments, sexual pheromones and vitamin A. It is also used as precursor for high electron affinity polymers, which can be used to manufacture light-emitting diodes(LED) with air-stable electrodes. Our group synthesized and characterized a series of substituted 3-phenyl-2-arylacrylonitriles derivatives earlier. Regarding of previous work, we select compounds with groups -N(CH3)2 -N(Ph)2, (Cz), (Py), Halogen atom (X), and CN, attached to arylacrylonitrile derivatives to study their physicochemical properties and supramolecular architectures using X-ray diffraction and DFT method. Hirshfeld surfaces and 2D finger print plots are constructed to identify the differences in intermolecular interactions and contacts between different crystal structures. The lattice energies of the crystal structures are calculated using PIXEL method and the energetics of various intermolecular interactions are quantified. A comparative study in the context of molecular conformation, lattice energy and Hirshfeld surface analysis for the title compound along with their analogs was carried out. The structure of the title compound is optimized in the gas phase using the M05-2X functional with 6-31+G(d) basis set. The harmonic vibrational frequencies are computed at the same level of theory to confirm the global minima, and to get a better understanding and quantified the energy of the intermolecular interactions that could contribute of crystal packing yielded. To calculate the energy of these interactions it was used PIXEL method. Moreover, intermolecular interactions in the crystal structure are visualized using Hirshfeld surface analysis and the relative contributions of various interactions are estimated using 2D fingerprint plots. Furthermore, existence of various intra- and intermolecular interactions is confirmed through Atoms-in-molecules (AIM) analysis study. Percino M. J., Cerón M., Soriano-Moro G., Castro M. E., Chapela V. M., Bonilla J., Reyes M., López-Sandoval R.. CrystEngComm. 2014, 21(4) 389. Percino M. J., Cerón M., Rodríguez O., Soriano-Moro G., Castro M. E., Chapela V. M., Siegler M. A., Pérez-Gutiérrez E., Molecules, 2016, 21(4), 389 Percino, J.; Cerón, M.; Venkatesan, P.; Ceballos, P.; Bañuelos, A.; Rodríguez, O.; Siegler, M. A.; Robles, F.; Chapela, V. M.; Soriano-Moro, G.; Pérez-Gutiérrez, E.; Bonilla-Cruz, J.; Thamotharan, S. Crystal Growth & Design 2017, 17 (4), 1679-1694 Venkatesan, P.; Rajakannan, V.; Venkataramanan, N. S.; Ilangovan, A.; Sundius, T.; Thamotharan, S. Journal of Molecular Structure 2016, 1119, 259-268. Venkatesan, P.; Thamotharan, S.; Ilangovan, A.; Liang, H.; Sundius, T Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2016, 153, 625-636.
Authors : Ben Zhong Tang
Affiliations : Department of Chemistry, Division of Biomedical Engineering, Hong Kong Branch of National Engineering Research Center for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Aggregation-induced emission (AIE) luminogens have received widespread and growing attention in many fields, such as optoelectronics, chemosensing and bioimaging and biomedicine, since the discovery of AIE phenomenon in 2001. In recent years, there are still many new breakthroughs in the field of AIE by the researchers from all around the world. Herein, I will share some advance in the novel applications of AIE luminogens and newly established strategies to construct AIE luminogens. AIE luminogens has been used for bioimaging for a long time, but we use a biocompatible, inexpensive delivery system based on the natural saponins, achieving ultrafast delivery of AIE NPs into cancer cells.1 This can be as a general method to deliver AIE luminogens with fast time. Besides, we take advantage of the twisted intramolecular charge-transfer (TICT) effect of AIE-active molecular rotors to explore a visual humidity sensor, which has excellent sensitivity and fast response/recovery time.2 This is a successful application of AIE luminoges by rational use of their photophysical properties. Usually, -bonds connected with aromatic rings is regarded as basically structures for constructing efficient fluorophores, however, we design three molecular with isolated phenyl rings emit visible light, which is due to the intramolecular through-space conjugation between the isolated phenyl rings and the the restriction of the intramolecular motions (RIM).3 This might open a new area which combines high molecular flexibility and high fluorescent efficiency. Another newly proposed strategy to construct AIE luminogens is introducing anion-+ interactions to block the detrimental - stacking. The nonionic analogue suffered from the aggregation-caused quenching (ACQ) effect effectively illustrate the effect of anion-+ interactions on the AIE characteristic.4 (1) Nicol, A.; Kwok, R. T. K.; Chen, C.; Zhao, W.; Chen, M.; Qu, J.; Tang, B. Z. J. Am. Chem. Soc. 2017, 139, 14792-14799. (2) Cheng, Y.; Wang, J.; Qiu, Z.; Zheng, X.; Leung, N. L. C.; Lam, J. W. Y.; Tang, B. Z. Adv. Mater. 2017, 29, 10.1002/adma.201703900. (3) Zhang, H.; Zheng, X.; Xie, N.; He, Z.; Liu, J.; Leung, N. L. C.; Niu, Y.; Huang, X.; Wong, K. S.; Kwok, R. T. K.; Sung, H. H. Y.; Williams, I. D.; Qin, A.; Lam, J. W. Y.; Tang, B. Z. J. Am. Chem. Soc. 2017, 139, 16264-16272. (4) Wang, J.; Gu, X.; Zhang, P.; Huang, X.; Zheng, X.; Chen, M.; Feng, H.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z. J. Am. Chem. Soc. 2017, 139, 16974-16979.
Authors : Bibhisan Roy, Mallu Chenna Reddy and Partha Hazra
Affiliations : PhD senior Research scholar
Resume : Prediction of mechanochromism of organic molecule is an appealing yet challenging puzzle, since no concrete design strategy has been developed so far. In this article, we demonstrate a potent strategy to gain a deep understanding of structure-property relationship to design multistimuli responsive mechanochromic material. To achieve our goal, a variety of new donor (D)-acceptor (A) luminogens exhibiting aggregation induced emission (AIE) has been prepared through C-H bond activation using ruthenium (Ru) metal catalyzed one pot synthetic strategy.
Authors : Samuel Guieu
Affiliations : QOPNA, CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
Resume : Organic dyes with Aggregation-Induced Emission Enhancement properties have attracted much attention for biological imaging, because they can combine several advantages when compared to conventional dyes: they only shine in targeted sub-cellular organelles, thus reducing background pollution; they can be easy to produce, easy to use, and easy to modify to fine-tune their photo-physical properties. Series of organic dyes based on a double hemi-salen or dibenzalazine core have been prepared and characterized. They are almost non emissive in dilute solution, but become highly fluorescent when they are in the crystalline or aggregate state. Their AIEE properties have been rationalized through the study of their crystal structures, and the emission wavelength of the dyes has been fine-tuned by modifying the substituents. To broaden the scope of application of these fluorophores, water soluble derivatives have been prepared, presenting the same photo-physical properties. Their interaction with cyclodextrins and DNA has been studied: upon formation of inclusion complex or interaction with DNA, the emission intensity is enhanced, in a way similar to when the dyes crystallize. These preliminary results illustrate the potential of these fluorophores for applications such as biological imaging and supramolecular detection of macromolecules.
Authors : N. Barbero (1), G. M. Paternò (2), S. Galliano (1), F. Scotognella (2,3), G. Lanzani (2,3), G. Viscardi (1), C. Barolo (1)
Affiliations : (1) Dipartimento di Chimica, NIS Interdepartmental and INSTM Reference Centre, Università degli Studi di Torino, Via Pietro Giuria 7, 10125 Torino, Italy; (2) Center for Nano Science and Technology@PoliMi, Istituto Italiano di Tecnologia, Via Giovanni Pascoli, 70/3, Milano, Italy; (3) Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Resume : The vast majority of Aggregation-Induced Emission (AIE) luminogens are blue or green emissive, while only few emit red or even NIR light. However, red/near-IR (NIR) fluorescent molecules with AIE characteristics are of great interest in a wide range of fields from optoelectronic to biological applications (i.e. solid state lightning, biosensing and bioimaging). To further enrich red-emitting AIE systems and expand the applications of AIE materials, it is meaningful to convert other conventional red/NIR-emitting dyes like polymethines, porphyrins and phthalocyanines into AIE-active materials. In this work we present the synthesis and spectral characteristics of different polymethine dyes (cyanines and squaraines) with a broad range of absorption and emission from visible to NIR region. Starting from our first experiment on a single squaraine dye aggregate, which afforded both a broad absorption spectrum and a strong and relatively narrow emission NIR (centred at 1.59 eV), with a remarkable Stokes shift, we will show a tentative structure-properties relationship useful to identify the most important molecular moieties able to enlarge the AIE characteristics both in term of large Stokes shift and quantum yield.
Authors : Wenbo Wu, Bin Liu
Affiliations : National University of Singapore
Resume : Photodynamic therapy (PDT), which relies on photosensitizers (PS) and light to generate reactive oxygen species to kill cancer cells or bacteria, has attracted much attention in recent years. PSs with both bright emission and efficient singlet oxygen generation have also been used for image-guided PDT. However, simultaneously achieving effective singlet oxygen generation, long wavelength absorption, and stable far-red (FR)/near-infrared (NIR) emission with low dark toxicity in a single PS remains challenging. In addition, it is well known that when traditional PSs are made into nanoparticles, they encounter quenched fluorescence and reduced singlet oxygen production. In 2014, PSs with aggregation-induced emission (AIE) were developed to address this issue. AIE PSs show much stronger fluorescence in the aggregated state than in solution, owing to the mechanism of restriction of intramolecular motions. More importantly, the AIE PSs also offer high singlet oxygen production efficiency in the aggregated state. To date, AIE PSs have been widely applied in image-guided PDT and bacterial killing. Herein, we want to report our recently design strategy for effective AIE PSs with FR/NIR emission, and their applications in image-guided PDT.
Authors : Shunjie Liu, Ryan T. K. Kwok, Jacky W. Y. Lam* and Ben Zhong Tang*
Affiliations : Department of Chemistry and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Resume : Polymerizations are difficult to monitor and visualize in real time unless using expensive on line instruments. In this work, we demonstrated a facile and efficient approach to in situ visualize polymerization. A group of tetraphenylethylene (TPE)-containing dithiocarbomates with potential aggregation-induced emission (AIE) characteristics were synthesized and used as agents for the reversible addition fragmentation transfer (RAFT) polymerization. The spatial-temporal control character of photochemistry enabled the RAFT polymerizations to be “frozen” and “unfrozen” under alternating visible light irradiation at room temperature. The emission of TPE was sensitive to the local viscosity change, which allowed the visualization of tricky or crosslinking reactions in real time. Quantitative information, such as molecular weight or extent of gel formation could be easily acquired by “naked eyes” without destroying the reaction system.
Authors : Jens Voskuhl
Affiliations : Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstrasse 7, D-45117, Essen (Germany),
Resume : The need of novel efficient fluorophors for the recognition and labeling of biomolecules such as proteins enzymes and cells is one of the most challenging disciplines in modern biosupramolecular chemistry. Our group uses a phenomenon called aggregation induced emission. Molecules with this ability show fluorescence, contrary to normal fluorophores, when aggregated or in the solid state. Recently we found a novel class of facile thioethers with this remarkable characteristic. Our system can be easily modified and was used for the detection of proteins and bacteria. Furthermore we investigated the formation of fluorescent micelles using hydrogen bonding. Currently different compounds were investigated concerning their fluorescence properties. A range of emission in the visible region was found ranging from 430 to 590 nm. Interestingly delayed fluorescence was observed for specific compounds leading to the assumption, that and intersystem crossing to a triplet state occurs leading to a long lived fluorescence state, termed phosphorescence.
Aggregation-induced emission: materials, mechanism, and applications Session 4 : Chaired by Tang Benzhong
Authors : Fang Hu, Youyong Yuan, Wenbo Wu, Duo Mao, Bin Liu
Affiliations : Department Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585
Resume : Metabolic glycoengineering of unnatural glycans with bioorthogonal chemical groups and subsequent click reaction with fluorescent probes have been widely used in monitoring various bioprocesses. Herein, we developed a dual-responsive metabolic precursor that could specifically generate unnatural glycans with azide groups on the membrane of targeted cancer cells with high selectivity. Moreover, a water-soluble fluorescent light-up probe with aggregation-induced emission characteristic was synthesized, which turned its fluorescence on upon click reaction with azide groups on cancer cell surface, enabling special cancer cell imaging with low background signal. Furthermore, the probe can generate 1O2 upon light irradiation, endowing its dual role as an imaging and therapeutic agent for cancer cells. Therefore, the concepts of cancer cell specific metabolic precursor cRGD-S-Ac3ManNAz and AIE light-up probe are promising in bioorthogonal labeling and cancer-specific imaging and therapy.
Authors : Deqing Zhang, Guanxin Zhang
Affiliations : Beijing National Laboratory for Molecular Science, Organic Solids Laboratory, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 P. R. China.
Resume : Normally, luminogens become weakly emissive after aggregation either in the solution or solid state. This feature limit their applications in various areas. However, there are luminogens referred as to “aggregation-induced emission” (AIE) by Tang and his coworkers exhibit abnormal fluorescence behavior; they are almost non-emissive in solution, but they show strong emission after aggregation. We and others have disclosed series of chemo/biosensors by manipulating the aggregation and deaggregation of AIE luminogens including silole and tetraphenylethylene molecules. In this presentation, I will introduce representative examples of AIE-based biosensors and utilization of AIE luminogens for fluorescence turn-on cell imaging after conjugation with appropriate targeting groups. This fluorescence imaging can be carried out without multiple washing steps with rather low background fluorescence. Moreover, pyridinium-substituted tetraphenylethylene as a red-emissive AIE luminogen can be assembled into nanoparticles which show selective toxicity toward cancer cells. In particular, I will introduce new derivatives of tetraphenylethylene which show responses to light irradiation and specific chemical reactions, and these chemical transformations have been employed for sensing, imaging and phototherapy. References 1. Huang, Y.; Zhang, G.; Hu, F.; Jin, Y.; Zhao, R.; Zhang, D. Chem. Sci., 2016, 7 (12), 7013. 2. Zhan, C.; You, X.; Zhang, G.; Zhang, D. Chem. Rec. 2016, 16, 2142. 3. Hu, F.; Huang, Y. Y.; Zhang, G. X.; Zhao, R.; Yang, H.; Zhang, D. Q. Anal. Chem. 2014, 86, 7987. 4. Huang, Y.Y.; Hu, F.; Zhao, R.; Zhang, G. X.; Yang, H.; Zhang, D. Q. Chem. Eur. J. 2014, 20, 158. 5. Zhang, G.; Hu, F.; Zhang, D. Langmuir 2015, 31(16), 4593. 6. Xu, S.; Yuan, Y.; Cai, X.; Zhang, C.; Hu, F.; Liang, J.; Zhang, G.; Zhang, D.; Liu, B. Chem. Sci., 2015, 6(10), 5824.
Authors : Paola Ceroni, Giacomo Bergamini, Marco Villa, Marc Gingras
Affiliations : Paola Ceroni; Giacomo Bergamini; Marco Villa Department of Chemistry “Giacomo Ciamician”, University of Bologna Marc Gingras CNRS, UMR 7325, Interdisciplinary Center on Nanoscience of Marseille (CINaM)
Resume : In the present paper, we will discuss a class of molecules that are not phosphorescent in deaerated fluid solution and whose room temperature phosphorescence is switched on either by rigidification of the matrix or by metal complexation. The hexathiobenzene chromophore is not phosphorescent in fluid solution and becomes highly phosphorescent upon crystallization or rigidification of the matrix. Analogously, the terpyridine appended persulfurated chromophore is non-emissive in solution, but displays a green phosphorescence emission in the solid state due to the restriction of intermolecular motion in the solid state. Upon addition of Mg2+ to an air-equilibrated THF solution of the hexaterpyridine ligand, a supramolecular polymer is formed, in which a Mg2+ ion is coordinated by two terpyridine units of two different molecules. The reduced mobility of the organic moiety in the polymeric structure is reflected by the appearance of a bright phosphorescence with band shape very similar to that of the ligand in the solid state. The light-harvesting polymeric antenna can be disassembled upon fluoride ions addition, thereby switching off luminescence and offering a new tool for fluoride ion sensing. Current studies are devoted to the use of the hexathiobenzene chromophore for oxygen sensing.  Coord. Chem. Rev. 2017, 346, 62; Chem. Commun. 2017, 53, 2081  Dyes Pigm. 2014, 110, 113; J. Mater. Chem. C. 2013, 1, 2717–2724.  J. Am. Chem. Soc. 2014, 136, 6395.
Authors : Jia-Hua Li a, Xiao-Dong Li a, Jie-Sheng Lin a, Zhen-Qiang Yu a, Ben Zhong Tang b
Affiliations : a School of Chemistry and Enviromental Engineering, Shenzhen University, China; b Department of Chemistry, The Hong Kong University of Science & Technology, Hong Kong S.A.R., China
Resume : Despite the promising prospect of luminescent liquid crystal, there exists contradicts in the design and synthesis of luminescent liquid crystals: traditional organic luminescent materials usually form aggregation caused quenching (ACQ) in their aggregated state, while molecular aggregation or self-organization is an intrinsic natural process to form mesophases. The combination of luminogens with aggregation induced emission (AIE)characteristics and traditional mesogens may generate high efficiency luminescent liquid crystals and regarded as the most promising method to solve contradicts between luminescence and liquid crystallinity on the standpoint of molecular design. Tetraphenylethene (TPE) is a typical propeller molecule with AIE characteristics and their derivatives by mini-dendron can form high efficiency luminescent liquid crystal phases with hexagonal columnar phase. In this report, TPE and 1,1,2,2-tetrakis(4-(phenylethynyl)phenyl)ethane were modified to form hexagonal columnar luminescent liquid crystals. Because of the mini-dendron, the resultant molecules can form luminescent liquid crystal or molecular liquids even at room temperature. The samples are completely free of ACQ and the quantum yield in liquid crystal state can be up to 49%. DSC, 1D WAXD and other methods were applied to characterize the phase structures of the resultant luminescent liquid crystals. Acknowledgement: The work reported in this paper was supported by National Natural Science Foundation of China (21674065) and Natural Science Foundation of Guangdong Province (2016A030312002). Keywords: aggregation-induced emission, liquid crystal, tetraphenylethene, hexagonal columnar phase
Authors : Eric Rivard*, Sarah M. Parke, Emanuel Hupf, Christina A. Braun, Bruno Luppi, Alex Brown, Gang He
Affiliations : University of Alberta, Department of Chemistry, 11227 Saskatchewan Dr., Edmonton, Alberta, Canada T6G 2G2; Center for Materials Chemistry, Frontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an, Shaanxi 710054, People’s Republic of China
Resume : Our group developed a series of tellurium-based heterocycles that exhibited aggregation-induced phosphorescence at room temperature in the presence of the known quencher oxygen.[1-4] Using a combination of experimental and computational studies, we now show that the phosphorescent character in a series of structurally related bismuth (Bi) heterocycles can be understood using a set of fundamental concepts (related to enhanced spin-orbit coupling from Bi). In addition we demonstrate that emissive bismuth-containing polymers can be prepared along with the attainment of stable red-colored phosphorescence, the latter being a key advancement from the viewpoint of developing next generation bio-imaging materials.  G. He, W. Torres Delgado, D. J. Schatz, C. Merten, A. Mohammadpour, L. Mayr, M. J. Ferguson, A. Brown, K. Shankar, E. Rivard, Angew. Chem., Int. Ed. 2014, 53, 4587-4591.  G. He, B. D. Wiltshire, P. Choi, A. Savin, S. Sun, A. Mohammadpour, M. J. Ferguson, R. McDonald, S. Farsinezhad, A. Brown, K. Shankar, E. Rivard, Chem. Commun. 2015, 51, 5444-5447.  E. Rivard, Chem. Lett. 2015, 44, 730-736.  W. Torres Delgado, C. A. Braun, M. P. Boone, O. Shynkaruk, Y. Qi, R. McDonald, M. J. Ferguson, P. Data, S. K. C. Almeida, I. de Aguiar, G. L. C. de Souza, A. Brown, G. He, E. Rivard, ACS Appl. Mater. Interfaces, 2018, DOI: 10.1021/acsami.7b11628.
Aggregation-induced emission: materials, mechanism, and applications Session 5 : Chaired by Zhang Deqing
Authors : Zhiming Wang, Ben Zhong Tang
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (SCUT), Guangzhou 510640, China 2. School of Petrochemical Engineering, Shenyang University of Technology (SUT), Liaoyang 111003, China 3. HKUST-Shenzhen Research Institute, Shenzhen 518057, China 4. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
Resume : Organic fluorescence probes have attracted more and more attention in chemical sensors and bioimaging applications due to their highly sensitive and handy features. However, most of probes with π-conjugated structure suffered from aggregation-caused quenching (ACQ) effect in high-concentration solutions or in the aggregated states, which limited their application in high performance imaging. Aggregation-induced emission (AIE), an opposite photophysical phenomenon to ACQ, is attracting intense interest because of the fundamental importance and promising practical applications. As an important AIEgens, the materials based on excited state intramolecular proton transfer (ESIPT) process attract more attentions in getting high performance imaging. In our groups, a kind of asymmetrical SAA-based compounds were developed and named as “s-SAA”. Their preparing process usually exhibited facile synthetic procedures and low cost purification from commercial raw materials. Excitingly, these materials can selectively target and accumulate in cellular LDs, and locate at lysosome of cells after inserting morpholine. Additionally, their behaviors of identifying and discriminating special bacteria or fungi are developed in further, which could not only provide more valuable information for this dynamic process in visual monitoring, but also be benefit of the development of therapeutic mechanism and pharmacology.
Authors : Xiaoding Lou
Affiliations : Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, P. R. China
Resume : Precisely targeted transportation of long-term tracing regent to nucleus with low toxicity is one of the most challenging concerns in revealing the cancer cell behaviours. In this work, a dual-targeted peptide-conjugated fluorescent probe was synthesized which contained multi-functional peptide delivery system and fluorescence imaging reagent. Thanks to the good water solubility of peptide, the fluorescence of TCNTP is initially quenched, however, turned on when bind to integrin avb3 and CD13. In terms of precisely targeting protocol, enduring staining effect and benignancy to living cells, the aggregation-induced emission based probe TCNTP has distinct advantages over the conventional dye. As a proof-of-concept, the targeting ability of TCNTP towards integrin avb3 and CD13 in living cells was monitored in real time in co-cultured MDA-MB-231&A375 cells and HT-1080&A375 cells. The colocalization experiments using commercial nucleus imaging dye Hoechst 33258 reveal that TCNTP can serve as a fluorescence light-up nuclear penetrating dye with the aid of functional peptide and AIEgens. Different from Hoechst 33258, the harmless physical internalization processes and indelible cellular staining property guarantee its long-term tumor cell tracing ability. The fluorescence stains of TCNTP are carried to daughter cells with low toxicity and remain visible even after the tenth culture cycle. Moreover, its precisely targeted interaction with organelles may account for the leak-free marking inside the cells. These incredible features make TCNTP a potential vehicle for drug and nucleic acid delivery thus extends the application scope of theranostics.
Authors : Hui CHEN, Yujiao FAN, Xia YU, Sylvain TREPOUT, Vincent SEMETEY, Min-Hui LI
Affiliations : (H.Chen, Y. Fan, V. Semetey, M.-H. LI) Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris (IRCP), 75005 Paris, France. (H.Chen, X. YU, M.-H. LI) Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, 100029 Beijing, China. (S. Trepout) Institut Curie, PSL Research University, INSERM U1196 and CNRS UMR9187, 91405 Orsay Cedex, France
Resume : Different nanostructures such as spherical micelles, cylindrical micelles and vesicles are accessible by self-assembly of amphiphilic copolymers. The morphologies depend on the chemical structure of the copolymer, hydrophilic/ hydrophobic volume ratio, solvent properties, etc. Moreover, controlling the spatial configuration of amphiphilic polymer is also an interesting strategy to tune the final morphology.TPE-based derivatives show AIE which is in contrast to the ACQ observed for conventional fluorophores. Thus, the combination of polymer nanostructures with TPE provides an innovative approach to bio-imaging and drug bio-distribution. Meanwhile, (Z)- and (E)-isomers could be prepared from bi-functionalized TPE. It will be relevant to study the influence of spatial configuration in morphology and photoluminescence, as well as the effect of photo-stimulated Z/E isomerization on the stability of nanostructures. Here we report on a series of TPE-containing amphiphilic polymers with cholesterol as a hydrophobic block and PEG as the hydrophilic part. The results have revealed that (Z)- and (E)- amphiphilic polymers self-assembled into nanostructures with different morphologies and showed different AIE properties. In addition, we report that the prepared TPE-containing polymersomes could be opened and release encapsulated molecules under UV-illumination. These polymersomes could be potentially used to combine the cell imaging and drug carrier in the same system.
Authors : Anirban Bose, Sanhita Ray, Tapas Mitra, Anjan Kr Dasgupta*
Affiliations : Department of Biochemistry, University of Calcutta 35, Ballygunge Circular Road Kolkata - 700019 West Bengal, India
Resume : We have recently reported an “AIEgen” like behavior of a photosynthetic complex (PC) excreted by purple non-sulfur bacteria Rhodobacter capsulatus SB1003 . AIEgens are fluorogen that exhibit aggregation induced fluorescence emission . The PCs which are supposedly porphyrin derivatives show aggregation-induced emission enhancement , critical to variations in concentration, temperature, and static magnetic field. The present report shows that the AIEgen like behavior of the PC is drastically altered when the bacterial growth medium contains graphene. The presence of graphene, however, attenuates the temperature or static magnetic field induced aggregation switches as reported in our previous study . Though graphene quenches the fluorescence intensity of the PC, the emission enhancement by PCs become more intense with increasing dose of graphene indicating a gradual increase in the quantum yield of the AIEgen. In the present study, we report the fluorescence enhancement dynamics of the PCs in presence of different types and forms of graphene, as well as the graphene defect density sensitive extent of fluorescence enhancement. We infer that graphene may alter the dynamics of aggregation pattern of the porphyrin rings present in the PC, changing the efficiency of enhanced emission . The sensitivity of this differential amplification to the defect-density of the graphene flakes may be a consequence of this graphene catalyzed porphyrin aggregation. The amplified emission of this AIEgen even at low concentration may be a consequence of aggregation enhancing property of graphene. References: 1. Bose, Anirban, et al. "BistabilityIn Fluorescence From A Purple Non-Sulfur Bacteria." bioRxiv (2017): 132498. 2. Kwok, Ryan TK, et al. "Biosensing by luminogens with aggregation-induced emission characteristics." Chemical Society Reviews 44.13 (2015): 4228-4238. 3. Biel, ALAN J. "Control of bacteriochlorophyll accumulation by light in Rhodobacter capsulatus." Journal of bacteriology168.2 (1986): 655-659. 4. Xu, Yuxi, et al. "Chemically converted graphene induced molecular flattening of 5, 10, 15, 20-tetrakis (1-methyl-4-pyridinio) porphyrin and its application for optical detection of cadmium (II) ions." Journal of the American Chemical Society131.37 (2009): 13490-13497.
Authors : Alexander Nicol and Ben Zhong Tang
Affiliations : Department of Chemistry, Institute of Molecular Functional Materials and Division of Biomedical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, NT, Hong Kong.
Resume : Saponins are a class of naturally occurring bioactive and biocompatible glycosides produced by plants. Saponins are amphiphilic composed of one or more hydrophilic sugar moieties and a lipophilic steroid group. Some saponins such as α-hederin exhibit unique cell membrane interactions. At concentrations above their critical micelle concentration, α-hederin will interact and aggregate with membrane cholesterol to form transient pores in the cell membrane. In this project, we utilized the unique cell membrane permeabilization properties of α-hederin to deliver AIEgens into both mammalian and plant cells. For mammalian cells, we used α-hederin as a micelle to encapsulate and stabilize large red emitting AIE nanoparticles of varying sizes. We were able to successfully deliver these nanoparticles into cells in under 5 min. This is around 20x faster than previously reported nanoparticle delivery systems since this delivery method is diffusion rather than endocytosis dependent. We found this method to be biocompatible, inexpensive, ultrafast and applicable to deliver a wide variety of AIEgens into mammalian cells. For plant cells, bioimaging has been a persistent challenge because the cell wall is extremely difficult for most fluorescent probes to traverse. This is a particular issue for AIEgens which has limited their application in plant cell biology. In this study, we developed several techniques to permeabilize the cell wall using saponin allowing AIEgens to enter and stain plant cells. We confirmed the entry of our AIEgen probes by performing a series of plasmolysis experiments. Arabidopsis thaliana was used to demonstrate that our AIEgens could be used to stain a variety of plant tissues including xylem, phloem and meristematic tissues. We found that this method was compatible with both wild type and mutant GFP transgenic Arabidopsis thaliana plants. The photostability and resolution of our AIEgens was higher than that of commercially used dyes like propidium iodide.
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Aggregation-induced emission: materials, mechanism, and applications Session 6 : Chaired by Ivan Aprahamian
Authors : Wenbo Dai, Yunxiang Lei, Zhengxu Cai,* Yuping Dong
Affiliations : Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Material Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
Resume : Recently, AIEgens with various cores and functional groups have been widely developed. However, most of them including the double bonds (C=C, C=N, N=N, etc) showed highly chemical reactivity and low photostability.1 Therefore, it would be favorable to develop new AIEgens with the well-defined structures and stable aromatic cores.2 Quinoline and its derivatives are useful in diverse applications, such as quinine for the treatment of malaria. The luminogens with the quinoline moiety could be potentially explored as both the probes and the biomedicines. Recently, we designed and synthesized a series of triphenylquinoline (TPQ) based luminogens via one-pot multicomponent reaction. All the luminogens are highly emissive in solid states and their AIE characters could be converted by the subtly structural modification . The solid-state quantum yield could further promote to 50 % by incorporating the donor group on one end of the molecule. The intramolecular donor-acceptor interaction allows us to fine tune quantum yields, the emissive colors as well as the molecular packing. We believe TPQ-based AIEgens provides a new platform for the construction of novel organic solid luminogens from both fundamental and practical viewpoints. References: 1. Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z., 2015, 115, 11718-11940. 2. Jiang, M.; Gu, X.; Kwok, R. T. K.; Li, Y.; Sung, H. H. Y.; Zheng, X.; Zhang, Y.; Lam, J. W. Y.; Williams, I. D.; Huang, X.; Wong, K. S.; Tang, B. Z., DOI: 10.1002/adfm.201704589
Authors : Yuanjing Cai, David Lee Phillips, Anjun Qin, Ben Zhong Tang
Affiliations : Center for Aggregation-Induced Emission, NSFC Center for Luminescence from Molecular Aggregates, SCUT-HKUST Joint Research Institute, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China.
Resume : The general mechanism RIM (restriction of intramolecular motion) of AIE originally refers to the enhanced restriction of the molecular motion from a single molecule to its aggregated state. However, RIM can be also realized by making the compound’s structure more rigid through structural modification. According to the RIM mechanism, we expect that a more rigid structure should fluoresce in solution and thus result in non-AIE property. Follow this original speculation and our struggling perseverance to figure out the deep mechanism of AIE, here we combine computational method and ultrafast time-resolved spectroscopy to study a series of TPE derivatives with increased structural rigidity and different AIE properties.
Authors : Ivan Aprahamian
Affiliations : Department of Chemistry Dartmouth College 6128 Burke Laboratory Hanover, NH 03755
Resume : For the past few years we have been developing structurally simple, easy to make, modular, and tunable hydrazone-based functional materials (e.g., switches, sensors and fluorophores).1 This presentation will deal with our recent advances with these systems, with an emphasis on hydrazone-based fluorescent molecular rotors (viscometers),2,3 and switchable solid-state emitters. Representative references: 1. I. Aprahamian Chem. Commun. 2017, 53, 6674–6684 2. H. Qian, M. E. Cousins, E. H. Horak, A. Wakefield, M. D. Liptak, I. Aprahamian Nature Chem. 2017, 9, 83–87 3. Y. Yang, X. Su, C. Carroll, I. Aprahamian Chem. Sci. 2012, 3, 610–613.
Authors : Tao He 1, Yusheng Jiang 1, Yuncong Chen 2, Weixin Ou 1, Ni Xie 3, Ben Zhong Tang 2, Jianguang Qin 1, Youhong Tang 1
Affiliations : 1 College of Science and Engineering, Flinders University, Tonsley 5042, Australia 2 Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, China 3 AIEgen Biotech Co. Ltd, Hong Kong, China
Resume : This study uses a specially designed aggregation-induced emission fluorogen (AIEgen) to in vivo track the dynamics of Hg2+ and MeHg+ in a common species of freshwater zooplankton Daphnia carinata (D. carinata) by two methods, direct Hg2+ absorption and ingestion of Hg2+ contaminated food. The response of D. carinata to Hg2+ and MeHg+ via environment absorption differed distinctly from the response through food intake of Hg2+ contaminated algae Euglena gracilis. Meanwhile, the response of D. carinata to Hg2+ and MeHg+, especially through the food intake are completely different. The D. carinata suffered much higher mortality through direct Hg2+ and MeHg+ absorption than through food intake with significantly different mortality mechanisms. Fluorescent image analysis showed that the major recipient organs of Hg2+ in D. carinata were the compound eyes and carapace, but not the brain or heart. However, MeHg+ preferred to accumulate in the compound as well the intestine and shell gland. In the first time, the AIEgen provides an easy way to understand the toxicological pathway of the small aquatic organism leading to death under toxic substances.
Authors : Xiang Ma* and He Tian
Affiliations : Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science & Technology, Shanghai, P.R. China.
Resume : Stimuli-responsive functional supramolecular machines and polymers are attracting broad attention. Multicolor photoluminescence, including especially white-light emission, were achieved based on a siingle host-guest supramolecular systems. Room temperature phosphorescence induced by cyclodextrin (CD-RTP) and cucurbituril (CB-RTP) is provided with the advantages of good selectivity, long life, large Stokes shifts and consequently application in the area of molecular recognition. Another supramolecular polymeric hydrogel based on the host-guest recognition between α-CD and α-BrNp polymer is constructed, which can self-heal within only about one minute in natural atmosphere. Moreover, this Stimuli-responsive functional supramolecular machines and polymers are attracting broad attention. Multicolor photoluminescence, including especially white-light emission, were achieved based on a siingle host-guest supramolecular systems. Room temperature phosphorescence induced by cyclodextrin (CD-RTP) and cucurbituril (CB-RTP) is provided with the advantages of good selectivity, long life, large Stokes shifts and consequently application in the area of molecular recognition. Another supramolecular polymeric hydrogel based on the host-guest recognition between α-CD and α-BrNp polymer is constructed, which can self-heal within only about one minute in natural atmosphere. Moreover, this supramolecular polymer system can be excited to engender CD-RTP signals. A pH-switchable molecular shuttle encoded by RTP emission change was also constructed by complexation of CB and 6-bromoisoquinoline derivative. A RTP encoding rotaxane shuttle and photo-responsive supramolecular polymers with morphology adjustment were also developed.[5-6] Amorphous, efficient, room-temperature phosphorescent metal-free polymers were facilely prepared and their applications as encryption ink explored as well. A seriouos of amorphous metal-free room-temperature phosphorescent small cyclodextrin derivative molecules were prepared and there multicolor photoluminescence realized via a host-guest and dual-emission strategy. The construction of these supramolecular shuttles and polymer and their RTP function investigation would be of significant importance for the development of switchable smart materials. References . X. Ma, H. Tian. Acc. Chem. Res.47, (2014), 1971. . Q.-W. Zhang, X. Ma, H. Tian et al. J. Am. Chem. Soc., 138, (2016), 13541. . H. Chen, X. Ma, H. Tian et al. Angew. Chem. Int. Ed, 53, (2014), 14149. . X. Ma et al. Chem. Sci. 7, (2016), 4582. . T. Li, X. Ma, H. Tian et al. Adv. Opt. Mater., 4, (2016), 840-847.  R. Sun, X. Ma, H. Tian, Q. Li et al. J. Am. Chem. Soc., 135, (2013), 5990-5993.  H. Chen, X. Ma, H. Tian et al. Adv. Opt. Mater., 4, (2016), 1397.  D. Li, F. Lu, J. Wang, W. Hu, X.-M. Cao, X. Ma and H. Tian. J. Am. Chem. Soc., (2018), DOI: 10.1021/jacs.7b12800.  X. Yao, X. Ma et al.Adv. Opt. Mater., 4, (2016), 1322.
Authors : Takuma Yasuda
Affiliations : INAMORI Frontier Research Center, Kyushu University, Japan
Resume : Thermally activated delayed fluorescence (TADF) has been proposed as a new strategy to achieve a high external quantum efficiency in organic light-emitting diodes (OLEDs). Luminescent organic molecules with a small energy gap (ΔEst) between the lowest excited singlet and triplet states enable nonradiative triplet excitions to convert to emissive singlet excitons, leading to an increase in the fluorescence intensity. In order to realize a small ΔEst, it is necessary to separate the highest molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the molecule. By combining electron-donating and electron-withdrawing units, the HOMO and LUMO distributions can be separated in a molecule. Carborane is a class of boron-clusters, and possesses a strong electron-withdrawing property originating from its three-center two-electron bonds. In this study, we designed and synthesized new carborane-based luminescent molecules. Owing to the strong electron-withdrawing property of the carborane units, these molecules have a small ΔEst and exhibited efficient TADF emissions as well as high photoluminescence quantum yields in their aggregated states. We fabricated OLEDs using these molecules as TADF emitters, which showed high external quantum efficiencies.
Authors : Zikai He
Affiliations : School of Science, Harbin Institute of Technology Shenzhen, HIT Campus of University Town of Shenzhen, Nanshan, Shenzhen 518055, China
Resume : The photophysical process of organic optoelectronic materials has always been the cornerstone of organic electronics, in which the properties and the controllability of excited states are the key factors tuning the performance of materials. Recently, several triplet-related photophysical processes have led to many revolutionary developments to the research area, providing numbers of organic optoelectronic functional materials such as TADF, TTA, and SF. Meanwhile, aggregation-induced emission (AIE), as an intriguing photophysical phenomenon that a series of non-emissive molecules in solutions are induced to emit strongly in the aggregate or solid state coined by Prof Ben Zhong Tang in 2001, provides a new stage for the exploration of practically useful luminescent materials for optical, electronic, energy and biomedical applications. As an efficient triplet promoter, nitrobenzene can transfer singlet states to non-luminescent triplet states through rapid intersystem crossing process. On the other hand, nitrobenzene ring can also provide abundant intermolecular interactions including the weak hydrogen bonds. In this talk, we will firstly investigate the role of nitrobenzene in the construction of novel triplet-involved AIE systems and the development of highly sensitive stimulus response materials.
Authors : Qiuming Liu†,‡,§, Qing Xia†, Shuo Wang†, Bing Shi Li*,†, Ben Zhong Tang*,‡, §,║
Affiliations : †Department of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060, China. ‡Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. §The Hong Kong University of Science & Technology (HKUST)-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen 518057, China. ║Department of Chemistry, Institute for Advanced Study, Institute of Molecular Functional Materials and State Key Laboratory of Molecular Neuroscience, HKUST, Clear Water Bay, Kowloon, Hong Kong, China
Resume : This work provides a novel strategy for the construction and characterization of novel luminescent architectures with high efficiency fluorescence and optical activity through self-assembling of aggregation-induced emission (AIE) polymers. By introducing chiral amino acid pendent into AIE scaffolds, we have prepared chiral polytriazole with the backbone of tetraphenylethene (TPE) and amino acid attachment by Cu(I)-catalyzed click polymerization. The chiral polymer products emit weak fluorescence in their good solvent, but show intensive luminescence as nano aggregation suspensions upon addition of water, demonstrating a typical AIE property. By tuning the water content of the poor solvent, the polymer can self-assemble into various nanostructures such as vesicles, “pear-necklace” to helical nanofibers and microfibers. Their self-assembly and morphology transition processes can be observed by fluorescence microscopy, which provides a higher-contrast visualized images that directly correlate the assemblies with their fluorescence. Moreover, this series of polymers also have efficient solid-state emission, excellent optical transparency and good film-forming ability also exhibits aggregation-induced circular dichroism (AICD) and aggregation-induced circularly polarized luminescence (AICPL), demonstrating the great potential for fabricating novel functional materials which have versatile optical and electronic properties with promising applications in optoelectronic devices.
Authors : Anjun Qin, Ben Zhong Tang
Affiliations : Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. E-mail: firstname.lastname@example.org (A.J.Q.); Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China. E-mail: email@example.com (B.Z.T.)
Resume : The aggregation-induced emission (AIE), conceptually coined in 2001 by our group , refers to a unique phenomenon that a kind of luminogens are weakly or non-emissive when molecularly dissolved but induced to emit intensely upon aggregation. The research on AIE has drawn tremendous interests among the scientists worldwide and become one of the hottest research topics in chemistry and materials sciences. Currently, hundreds of low-mass AIE luminogens have been prepared. However, the research on AIE-active polymers, which inherently possess good film-forming ability and amplification effect in sensing, have paid little attention . In this talk, we will first present our recent efforts on preparing AIE-active polymers by our developed alkyne-based click polymerizations . The unique properties and potential applications of resultant polymers, such as photo-cross-linked and fluorescent patterns, high light refractivity, sensitive detection of explosives, will also be reported. Moreover, non-aromatic maleic anhydride-based AIE-active polymers will be presented, and their clusteroluminescence mechanism will also be briefly discussed . This work was supported by the National Natural Science Foundation of China(21788102, 21525417 and 21490571). References:  (a) Luo, J.; Xie, Z.; Lam, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Commun. 2001, 37, 1740. (b) Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z.Chem. Rev. 2015, 115, 11718.  (a) Qin, A.; Lam, J. W. Y. Tang, B. Z. Prog. Polym. Sci. 2012, 37, 182. (b) Hu, R.; Leung N. L. C.; Tang, B. Z. Chem. Sov. Rev. 2014, 43, 4494.  (a) Li, H.; Sun, J. Z.; Qin, A.; Tang, B. Z. Chinese J. Polym. Sci. 2012, 30, 1. (b) Yao, B.; Hu, T.; Zhang, H.; Li, J.; Sun, J. Z.; Qin, A.; Tang, B. Z. Macromolecules, 2015, 48, 7782. (c) Dong, W.; Wu, H.; Chen, M.; Shi, Y.; Sun, J. Z.; Qin, A.; Tang, B. Z. Polym. Chem. 2016, 7, 5835.  Zhou, X.; Luo, W.; Nie, H.; Xu, L.; Hu, R.; Zhao, Z.; Qin, A.; Tang, B. Z. J. Mater. Chem. C. 2017, 5, 4775.
Aggregation-induced emission: materials, mechanism, and applications Session 7 : Chaired by Tang Youhong
Authors : Shidang Xu, Youyong Yuan, Bin Liu
Affiliations : Department of Chemical and Biomolecular Engineering, National University of Singapore
Resume : The efficiency of the intersystem crossing process can be improved by reducing the energy gap between the singlet and triplet excited states (DEST), which offers the opportunity to improve the yield of the triplet excited state. Herein, we demonstrate that modulation of the excited states is also an effective strategy to regulate the singlet oxygen generation of photosensitizers. Based on our previous studies that photosensitizers with aggregation-induced emission characteristics (AIE) showed enhanced fluorescence and efficient singlet oxygen production in the aggregated state, a series of AIE fluorogens such as TPDC, TPPDC and PPDC were synthesized, which showed DEST values of 0.48, 0.35 and 0.27 eV, respectively. A detailed study revealed that PPDC exhibited the highest singlet oxygen efficiency (0.89) as nanoaggregates, while TPDC exhibited the lowest efficiency (0.28), inversely correlated with their DEST values. Due to their similar optical properties, TPDC and PPDC were further encapsulated into nanoparticles (NPs). Subsequent surface modification with cell penetrating peptide (TAT) yielded TAT?TPDC NPs and TAT?PPDC NPs. As a result of the stronger singlet oxygen generation, TAT?PPDC NPs showed enhanced cancer cell ablation as compared to TAT?TPDC NPs. Fine-tuning of the singlet-triplet energy gap is thus proven to be an effective new strategy to generate efficient photosensitizers for photodynamic therapy.
Authors : Pengfei Zhang, Zheng Zhao, Ryan T. K. Kwok, Jacky Wing Yip Lam, Ben Zhong Tang
Affiliations : Department of Chemistry, Division of Biomedical Engineering and The Hong Kong Branch of National Engineering Research Centre for Tissue Reconstruction & Restoration, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Resume : Cancer has been one of the major threats to human health for a long time. With the advantages of relatively small size, lack of immunogenicity, ease of synthesis and various modifications, aptamer has been a powerful candidate to replace monoclonal antibodies for cancer imaging and therapy. Herein, a facile and simple one-step method to fabricate aptamer-targeting organic dots based on self-assembling method has been developed. As-prepared aptamer organic-dots, which integrated the advantages of AIEgens with the cell-targeting capabilities of aptamers, showed specific targeting ability, highly stability, and good biocompatibility. Based on this general method, a variety of biocompatible highly bright organic fluorescent nanoprobes with specific recognition and highly sensitivity could be facilely constructed for long-term, real-time sensing and biomedical imaging.
Aggregation-induced emission: materials, mechanism, and applications Poster Session 2 : Nil
Authors : Die Huang, Anjun Qin, Ben Zhong Tang
Affiliations : Die Huang and Anjun Qin*: Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. E-mail: firstname.lastname@example.org (A.J.Q.); Ben Zhong Tang*: Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong. E-mail: email@example.com (B.Z.T.)
Resume : Nowadays, aggregation-induced emission (AIE) has been a hot research topic. Massive endeavors of scientists were devoted to study the structure-property relationship of low-mass molecules.1 However, the work on AIE-active polymers has been rarely reported.2 Recently, we has established a Ru(II)-catalyzed click polymerization (RuAACP), and 1,4- and 1,5-regioregular polytriazoles (1,4- and 1,5-PTAs) could be produced by simple control of ligands. In this work, using this effective polymerization, we successfully obtained tetraphenylethene (TPE)-containing 1,4- and 1,5-PTAs with similar molecular weights and small variation in the linking manner. It was found that 1,4-PTA exhibited a longer conjugation and redder luminescence compared to its 1,5-PTA counterparts. Thanks to the typical AIE luminogen of TPE moiety, both of 1,4- and 1,5-PTAs showed AIE characteristics. However, they had very different performances when they were used as fluorescent chemosensors to detect Pd2+. 1,5-PTA showed very high sensitivity (Kq up to 587785 L/mol) and selectivity. In contrast, 1,4-PTA doesn’t work. We surmised that the difference coordination ability between 1,5-triazole ring and 1,4-triazole ring with Pd2+ is primary reason.
Authors : Zhiyang Liu, Haixiang Liu, Ryan T. K. Kwok, Jacky W. Y. Lam, Ben Zhong Tang
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology
Resume : Monitoring of biological processes and diagnosis of diseases are important for the physiological functions of living organisms and related to the health. Fluorescent techniques play a great role in recognizing the mechanism of life and pathogenesis of diseases, guiding therapeutic effect in theranostics. The conventional organic fluorophores unavoidably face a problem of aggregation-caused quenching (ACQ), where their fluorescence is quenched at high concentrations due to the formation of strong π-π stacking, leading to quick photo-bleaching for bioimaging. Luminogens with aggregation-induced emission characteristic (AIEgens) could serve as superior agents for biological process monitoring and disease theranostics with the advantages of high brightness, large Stokes shift and excellent photostability compared to commercial dyes. Herein, we synthesized a series of AIEgens as aldose reductase inhibitors to treat Diabetes mellitus. The AIEgens not only could target mitochondrion and aldose reductase for imaging and therapy but also possess the performance of two-photon excitation (from 700 nm to 1000 nm). Two-photon imaging has the merits of a higher 3D resolution, lesser photobleaching, a reduced autofluorescence and deeper penetration in tissue. The AIEgens with the imaging and therapy abilities are beneficial to understanding the mechanism of diseases and directing the drug design for the human health.
Authors : Hui-Qing Peng, Ben Zhong Tang
Affiliations : Hong Kong University of Science and Technology
Resume : Stereochemistry involves the study of spatial configurations of one molecule and their characteristic properties. This research area has been widely explored due to their potential applications such as asymmetric catalysis, stereoselective synthesis, drug discovery and so on. (Z)- and (E)-isomers of carbon-carbon double bonds represent one class of the most indispensable configurations in stereochemistry. Numerous (Z)- and (E)-derivatives have been exploited to learn their distinct biological roles and pharmic properties in life and material sciences.the development of novel stereoisomers with very different properties is not only helpful to understand biological processes but also expected to create new functional materials. In this study, we employed oligoethylene glycol monomethyl ether (OEG) as polar unit to synthesize amphiphiles of TPE. Pure stereoisomers of OEG-functionalized tetraphenylethene ((Z)-TPEOEG and (E)-TPEOEG) were easily separated by high-performance liquid chromatography (HPLC) and their geometric structures were validated by 2D COSY and NOESY spectroscopies. Both (Z)- and (E)-isomers inherit AIE features of TPE. (Z)-TPEOEG self-assemblies into vesicles while its (E)-counterpart forms micelles in water. Furthermore, the (Z)-isomer exhibits a lower critical solution temperature (LCST) of 39.0 C, but no such behavior was observed for (E)-TPEOEG even at high temperature of 52.0 C. These macroscopic differences are undoubtedly resulted from configuration differences in (Z)- and (E)-TPEOEG. Our findings add families of (Z)- and (E)-derivatives and will guide further construction of AIE materials based on TPE stereoisomers.
Authors : Jianlei Shen,Yiru Zhang, Rong Hu,Ryan T. K, Zhiming Wang, Anjun Qin*, Benzhong Tang*
Affiliations : State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China
Resume : Developing of simple, robust and reliable nucleic acids detection strategy holds tremendous promise for cancers or pathogens’ diagnostic. Here, a versatile “seesaw” strategy was proposed for dual mode detection of nucleic acids with naked eye. In this design, aggregation-induced emission (AIE) based fluorometric assay and gold nanoparticles based colorimetric assay were combined to construct an aqueous “seesaw”, whose balance was determined by the quantity of target nucleic acid. After intergating with hybridization chain reaction (HCR) technique, we achieved a reliable detection of DNA and microRNA from two signal channels with detection limit of 100 fM and 10 nM, respectively. The proposed seesaw strategy that integrates fluorometric and colorimetric assay holds great potentials for nucleic acids point-of-care testing.
Authors : Yuanyuan Li, Shunjie Liu, Ryan T. K. Kwok, Jacky W. Y. Lam and Ben Zhong Tang*
Affiliations : Department of Chemistry and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Photosensitizers (PSs) are materials that are capable of generating reactive oxygen species (ROS) that causing oxidative damage to target cells or tissues. So far, the structure-property relationship of PSs is not fully established. In this work, we demonstrate a facile method for improving the ROS generation of the materials. The common small molecular aggregation-induced emission (AIE) dyes with donor-acceptor structure displaying low ROS generation can be changed into highly efficient PSs by making them into conjugated polymers. The resulting polymers can induce efficiency cancer cell death both in vitro and in vivo under light irradiation. Meanwhile, the brightness of the AIE polymers made it act as fluorescence probe for accurate diagnosis of tumor in vivo. Our approach provided a facile and efficiency theranostic combined photodynamic therapy and fluorescence imaging with AIE characteristics.
Authors : Shijie Zhen, Shaowei Wang, Zujin Zhao, Bin Liu, and Ben Zhong Tang
Affiliations : Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China; Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117585, Singapore; Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Luminogens with aggregation-induced emission (AIE) characteristics have attracted much attention because of their broad applications in optoelectronics, bioprobes and environmental monitoring. Amongst them, red/near-infrared AIE luminogens are especially desired in the field of biological applications, but most of them are far from satisfactory. Herein, a series of novel red/near-infrared fluorophores based on an electron-withdrawing benzo[1,2-b:4,5-b']dithiophene 1,1,5,5-tetraoxide (BDTO) core are synthesized and characterized and their crystallographic, spectroscopic, electrochemical properties are investigated. These BDTO-based fluorophores possess both AIE and hybridized local and charge-transfer (HLCT) characteristics, and show greatly red-shifted emission wavelength, enhanced emission efficiency, enlarged two-photon absorption cross section and increased reactive oxygen species (ROS) generation efficiency in comparison with the dyes based on benzo[1,2-b:4,5-b']dithiophene (BDT). The nanoparticles (NPs) with strong red/near-infrared emission are fabricated using BDTO-based fluorophores, and their biological applications are systematically investigated. The results reveal that the NPs show good performance in targeted photodynamic ablation of cancer cells and in vivo two-photon fluorescence imaging of blood vessels in mouse brain
Authors : Yasuhiro Kubota, Kazumasa Funabiki, Masaki Matsui
Affiliations : Gifu University
Resume : Organoboron complexes are among the most important fluorescent dyes. Especially, boron dipyrromethene (BODIPY) dyes have gained prominence. BODIPY dyes can be tuned the fluorescence wavelength from blue to near infrared by modifying the substituent groups or annulation of an aromatic ring in solution. However, most BODIPY dyes lose their excellent fluorescence properties in the solid-state. BODIPY dyes generally exhibit limited fluorescence in the solid-state due to their high planarity, which easily leads to π–π interactions between neighboring fluorophores, and their small Stokes shift (5–20 nm, in most cases) which causes serious self-quenching at high concentration. Therefore, considerable effort has been devoted to the development of novel fluorescent boron complexes. Recently, we reported boron complexation using ligands based on quinone, pyrimidine, pyrazine, benzothiazole, pyridomethene and squarylium. Some synthesized boron complexes exhibited aggregation-induced emission properties. In this conference, we will report the aggregation-induced emission properties of boron complexes.
Authors : Xuewen He, Feng Yin, Ling-Hong Xiong, Zheng Zhao, Ganglin Wang, Ryan T. K. Kwok, Jacky W. Y. Lam, Nan Ma, Ken-Tye Yong, Zigang Li, Ben Zhong Tang
Affiliations : Xuewen He, Ling-Hong Xiong, Zheng Zhao, Ryan T. K. Kwok, Jacky W. Y. Lam and Ben Zhong Tang: Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration and Reconstruction, Institute for Advanced Study, Institute of Molecular Functional Materials, State Key Laboratory of Molecular Neuroscience, Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong; Feng Yin and Zigang Li: School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055, China; Ganglin Wang and Nan Ma: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China; Ken-Tye Yong: School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798, Singapore.
Resume : RNA interference (RNAi) is emerging as one of the most powerful technologies for sequence-speciﬁc suppression of genes and presents a great potential in biomedical applications ranging from gene analysis to diseases therapeutics. Considering the drawbacks of current siRNA delivery vehicles in biocompatibility and efficacy, the development of high efficient siRNA delivery nanocarrier associated with self-monitoring functionality is of great significance. Herein, by taking advantage of aggregation-induced emission luminogens (AIEgens), a new generation of inorganic/organic core@shell nanocarrier that allowed efficient delivery and real-time monitoring of siRNA in living cells had been developed. The phenoxy and amine groups in the nanocarriers behaved as a proton-absorber and promoted the release of siRNA from endosome. The AIE properties provided a unique fluorescence imaging modality for long-term tracking and intracellular localization of siRNA during transfection. Comparing to the commercial siRNA transfection reagents, the present system displayed a pretty higher efficiency and reproducibility in terms of intracellular transfection and target down regulation with a much lower cytotoxicity.
Authors : Shun-Wen Cheng, Ting Han, Teng-Yung Huang, Yu-Hsin Chang Chien, Cheng-Liang Liu,* Ben Zhong Tang,* and Guey-Sheng Liou*
Affiliations : Institute of Polymer Science and Engineering National Taiwan University Department of Chemistry The Hong Kong University of Science and Technology Department of Chemical and Materials Engineering, National Central University
Resume : A novel AIE-acitive TPA-CN-TPE polyamide was successfully synthesized and introduced as electret layer in the organic phototransistor-type memory device. The strong green PL emitted from TPA-CN-TPE under UV illumination could increase the memory window of the device ranging from 20 to 42 V caused by photo-induced charges from pentacene layer. The high photoresponsivity and photosensitivity of the resulted devices manifest great potential for multinary data storage and photodetector within single device. With the significant photo-induced charge trapping in the TPA-CN-TPE electret layer, the device reveals a high DR up to 14 bits. Therefore, this facile concept offers the efficient fabrication of highly UV-responsive phototransistors for UV sensors and nonvolatile memory devices on data storage application.
Authors : Guangle Niu, Ruoyao Zhang, John P. C. Kwong, Jacky W. Y. Lam, Xiaoqiang Yu, Ben Zhong Tang
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong 999077, China
Resume : Lipid droplets (LDs) are highly associated with obesity, diabetes, inflammatory disorders and cancer. Therefore, direct and selective LDs visualization and monitoring in biological samples is particularly important. Reliable two-photon dye at ultra-low concentration for specific LDs imaging in live cells and live tissues has rarely been reported. Here, we synthesized a new family of AIEgens, namely NAPCNs for specific two-photon LDs staining. Their photophysical properties were investigated by one- and two-photon fluorescence spectroscopy, DFT calculations and single-crystal X-ray diffraction. The NAPCNs exhibited large Stokes shift (>110 nm), high solid fluorescence quantum yield of up to 30%, good two-photon absorption cross section (45–100 GM at 860 nm), high biocompatibility and good photostability. They could specifically stain the LDs at ultra-low concentration (50 nM) in 15 min. In vitro and ex vivo two-photon imaging of LDs in live cells and live mice liver tissues were successfully demonstrated. In addition, selective visualization of LDs in live mice liver tissues could be achieved at the depth of about 70 μm. The NAPCNs showed higher hydrophobicity than the commercial LDs dyes, which were responsible for their high specificity to target the LDs. These excellent photophysical and two-photon imaging properties render the present molecules as promising candidates for investigating LDs-associated physiological and pathological processes in biological samples.
Authors : Qing Wan, Zhiming Wang*, Benzhong Tang*
Affiliations : 1. SCUT-HKUST Joint Research Institute, Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology (SCUT), Guangzhou 510640, China 2. Department of Chemistry, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China
Resume : In past three decades, organic light-emitting devices (OLED) have made great progresses in material preparation, process optimization and relevant theoretical researches, where the aromatic conjugated material plays an important role. As a representative, anthracene and its heterocyclic derivatives (such as phenothiazine, acridine and so on) have a pretty good performance in device efficiency owing to their high quantum yield and good transfer capacity, which origin from their relative planar and rigid chemical structure. While, recent studies have shown that the distribution of molecular dipoles exhibited a significant effect on their performance. Taking anthracene as an example, its dipole has two orientation (long and short axis effect) in the two-dimensional space, leading to the increase of energy gap between T1 and T2, their RISC process is tuned in high energy level and their exciton utilization ratio would be affected. Here, we choose the acridone (a class of anthracene heterocyclic derivatives) group as core, and construct multidirectional dipole distribution by introducing the donor (TPA or Cz) and accepter (Cyano group). After employing CT and RIR mechanism, one-armed and two-armed products are prepared, whose dipole orientations locate two and three form in 2D space respectively. A series of spectral characterization and device results display that one-armed products give good performance and controllable regulatory properties. By locking the RIR process in different pattern, its importance is reflected in improving the efficiency of the solid state and improving the utilization of the exciton.
Authors : Yuanhang Wang, Xiaoling Pan, Zhe Peng, Yahui Zhang, Pai Liu, Zhengxu Cai,* Bin Tong, Jianbin Shi, Yuping Dong*
Affiliations : Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Material Science & Engineering ,Beijing Institute of Technology, Beijing 100081, China.
Resume : Cerium (Ce) shows a great potential application in biocatalysis, drug release and biomedical science.1 As a result of its enormous usage, there is a growing demand to study the environmental, medical and biological effects of cerium. To date, the photometric detection for Ce ion is still rarely reported. Recently, luminogens with aggregation-induced emission (AIE) properties have attracted great interests. It is practically non-emissive or faintly emissive in the solution state, but becomes highly emissive as aggregates in poor solvents. Due to this unique effect, a wide range of AIEgens have been developed and utilized in detecting metal cations.2 In our research, we synthesized a tetraphenylbutadiene (TPBD) derivative with two carboxyl groups as substituents (TPBD-COOH), which remarkably exhibited the AIE property. TPBD-COOH as a novel fluorescent probe was designed for the detection of Ce3+. It shows a real-time and time-stable detection of Ce3+ with a detection limit of 2.27 μmol/L. The interaction mechanism was deducted by DLS analysis, XRD analysis, NMR and FT-IR measurements, suggesting that the Ce3+ probably binds the carboxyl group on TPBD-COOH. Moreover, Ce4+ could also be distinguished and detected in the presence of 1,2-propanediol as a reducing agent. 1. T. Pirmohamed, J. M. Dowding, S. Singh, B. Wasserman, E. Heckert, A. S. Karakoti, J. E. S. King, S. Seal, W. T. Self, Chem. Commun. 2010, 46, 2736-2738. 2. J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam, B. Z. Tang, 2015, 115, 11718-11940.
Authors : Jin Dan, Yuncong CHEN, Jacky W. Y. Lam, Ben Zhong Tang*
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Aggregation-induced emission (AIE) materials have recently been intensively explored for bioimaging applications owing to their outstanding optical feature compared with conventional organic materials. Near-infrared fluorescence has superior features in vivo, such as deep penetration, weak auto-fluorescence, minimal photo-bleaching. Thus, far red/near-infrared aggregation induced emission luminogens are in high demand. Here, we report a high efficient Far red/Near-infrared fluorescent compounds with aggregation-induced emission (AIE) properties. A new near-infrared aggregation-induced emission luminogen, namely NZA2TPE, with high brightness, good biocompatibility and excellent photostability was synthesized for bioimaging. NZA2TPE exhibits a high photoluminescence quantum yield of 78.7 % in hexane (650 nm) and 21.5% in the solid state (685 nm). It has been fabricated into nanoparticles for bioimaging. Different methods have been used to encapsulate the dye molecules to generate stabilized nanoparticles. The size of the nanoparticles can be controlled in the range from 20 nm to 150 nm. The emission maximum falls at 685 nm to 693 nm. DSPE-PEG-folate (DSPE-PEG-FA) based NZA2TPE NPs have been prepared through a simple one-pot self-assembly route, which shows high brightness and low cytotoxicity. More importantly, it exhibited specific targeting for cancer cells. Such fluorescent nanoparticles are expected to be potential for an array of biological applications.
Authors : Yuan Kang, Rongrong Hu,* Ben Zhong Tang*
Affiliations : 1.State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. 2.Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Resume : Pure organic room-temperature phosphorescence (RTP) materials have attracted much attention recently with its growing reports in aggregation-induced emission field. The development of organic RTP compounds remain to be a challenging work due to the instability of triplet excited states at room temperature, which has long been limited to cryogenic and inert conditions. Herein, a series of dibenzofuran derivatives was designed and synthesized through facile Friedel-Crafts acylation reaction. The compounds generally contain one or two carbonyl groups on the dibenzofuran core with an unsymmetric or symmetric structures, and halogen atoms are also introduced in the structures, which is designed to promote the intersystem crossing from S1 state to T1 state. These dibenzofuran derivatives are non-emissive or weakly emissive in their solution or amorphous state. Their crystals, however, generally exhibit dual emission of fluorescence and room-temperature phosphorescence, demonstrating typical crystallization-induced emission phenomenon. Photophysical study suggests that their phosphorescence lifetime can be up to 69 ms and their phosphorescence quantum yield can be up to 4.3%. One of the dibenzofuran derivatives without any halogen atom emits white light under UV irradiation. The prompt and delayed photoluminescence spectra suggest the coexistence of a fluorescence emission at 437 nm, and a phosphorescence emission at ~575 nm, suggesting that it's a single molecular fluorescence/phosphorescence hybrid white light emitter.
Authors : Michelle M. S. Lee, Dong Wang and Ben Zhong Tang*
Affiliations : Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Imaging-guided therapy is a promising strategy in biomedical research. In contrast to the existing bioimaging dyes with aggregation-caused quenching effect, luminogens with aggregation-induced emission characteristics (AIEgens) are better candidates for such application. AIEgens show no emission in the solution state but they are induced to emit intensely by aggregate formation. This feature is exact opposite of ACQ and is beneficial to biomedical application. Deep tissue penetration and high spatial resolution become the ultimate goals for IGT. In this regard, the combination of two-photon excitation and NIR emissive dyes help achieve low autofluorescence, low scattering, deep tissue penetration and high spatial resolution. However, NIR AIEgens that can be excited by two-photon are limited and their synthetic routes are quite complicated. In this work, three NIR-emissive AIEgens were facilely synthesized. All the compounds were characterized by 1H NMR, 13C NMR and HRMS spectroscopies. They show absorption maximum at 520560 nm and emit at 680720 nm. Their specificity to target the lipid droplets is demonstrated in cancer cell line. Two-photon imaging of lipid droplets using these dyes are carried out to achieve deep tissue imaging.
Authors : Jingjing Guo, Jiajie Zeng, Zujin Zhao, Ben Zhong Tang
Affiliations : Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China, E-mail: firstname.lastname@example.org; Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China, E-mail: email@example.com
Resume : Purely organic materials with aggregation-induced delayed ﬂuorescence (AIDF) exhibit tremendous potential in fabricating high-performance nondoped organic light-emitting diodes (OLEDs) with low efficiency roll-off. Herein, we have developed a new series of AIDF materials with unsymmetrical D-A-D′ structures, where benzoyl serves an electron acceptor, and 10H-phenoxazine and fluorene derivatives as electron donors. These AIDF emitters can be readily synthesized so that they are applicable for the large-scale commercial applications. Interestingly, they exhibit weak emissions without delayed ﬂuorescence in THF solutions but strong emissions with obvious delayed components upon aggregate formation or in neat films, exhibiting the typical AIDF characteristics. Through combining the photophysical measurements and theoretical calculations, this phenomenon can be ascribed to the suppression of internal conversion channels of the first singlet excited state in the aggregate state, which is induced by restriction of intramolecular motion. Due to the unique AIDF properties, their nondoped OLEDs achieved excellent EL performance of up to 14.3%, 41.7 cd A-1 and 45.0 lm W-1 with extremely negligible efficiency roll off at 1000 cd m-2.
Authors : Xinggui Gu, Ben Zhong Tang
Affiliations : Beijing Advanced Innovation Center for Soft Matter Science and Engineering (BAIC-SM) Beijing University of Chemical Technology, Room 101, Science and Technology Building North Third Ring Road East 15, Chaoyang District, Beijing, 100029, P. R. China. E-mail: firstname.lastname@example.org Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China. E-mail: email@example.com
Resume : Fluorophores, whose emission can be activated and switchable by light irradiation, are of paramount importance for single-molecule localization microscopy and are promising for constructing super-resolved images in nanometer scale.[1,2] Herein, we report a new fluorescent turn-on photoactivatable fluorophore, abbreviated as o-TPE-ON+. This luminogen undergoes an unconventional photocyclodehydrogenation reaction in the presence of light irradiation, turning it from a weak fluorophore to a strong emitter (c-TPE-ON+) with high quantum yield, long excitation wavelength of above 500 nm and fluorescence insensitive to pH or environmental change. o-TPE-ON+ not only is highly cell permeable and biocompatible but also can spontaneously undergo blinking in the absence of any additives. The feasibility of applying o-TPE-ON+ to super-resolution imaging of mitochondrion is demonstrated in both fixed and live cells under physiological conditions, which enables the investigation of the dynamics of mitochondria in nanometer scale. It is anticipated that the strategy described here will open up new avenues to develop more photoactivatable small organic fluorophores for super-resolution imaging under physiological condition with organelle specifity.
Authors : Rong Hu, Anjun Qin, Ben Zhong Tang
Affiliations : firstname.lastname@example.org; email@example.com; firstname.lastname@example.org
Resume : A conjugated polymer showing aggregation-induced emission (AIE) characteristic was prepared, and displays relatively high selectivity towards viable cells over apoptotic and dead cells as well as microbes. This polymeric probe show tremendous advantages over low-mass organic probes, such as better biocompatibility, higher selectivity and stronger tracing ability. We figure out that the negatively charged side-chain of the polymer and the endocytosis process play crucial roles in this discrimination behavior. As far as we know, this is the first example that using AIE polymer to identify viable mammalian cells with high specificity. This work is expected to serve as a powerful tool for precise cancer therapy.
Authors : Qiguang Zang, a Jiayi Yu, a Wenwen Luo,a Jun Qian,b Wenbin Yu,b Rongrong Hu,*a and Ben Zhong Tang*a,c
Affiliations : a.State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. b.State Key Laboratory of Modern Optical Instrumentation, Centre for Optical and Electromagnetic Research, Zhejiang Provincial Key Laboratory for Sensing Technologies, Zhejiang University, Hangzhou, China. c.Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong.
Resume : Aggregation-induced emission (AIE) materials has proved to be efficient fluorescent dyes as photosensitizers in photodynamic therapy, owing to their strong aggregated state emission, high photostability, and high ROS production yield. Herein, a series of electron-deficient 7H-naphtho[1,8-gh]quinolin-7-one derivatives with diphenylamino group and tetraphenylethene moiety were designed and synthesized with efficient aggregated state emission. The strong electron donor and electron acceptor structures endow these compounds red or near-infrared emission with the emission maxima up to 658 nm. Among them, 3-(diphenylamino)-7H-naphtho[1,8-gh]quinolin-7-one with emission maximum at 635 nm enjoys the highest emission quantum efficiency of 22.8% at solid state, which is also the smallest compound in terms of volumn size and molecular weight. This compound can be enternalized in HeLa cell in lysosome and possess high photostability, which also shows good photo-induced reactive oxygen species (ROS) production efficiency. Under the irradiation of visible white light with a light intensity of 1.67 mW·cm-2 for 20 min, cell viability decreased dramatically with the treatment of the dye and significant photo-induced cytotoxicity was observed with the IC50 value to be 6.2×10-7 M. Moreover, deep tissue penetration down to 280 μm depth is realized through two-photo imaging of mouse brain vessels with the AIE compounds under the excitation of 1040 nm laser.
Authors : Xinfeng Tao, Sylvain Trepout, Min-Hui Li*
Affiliations : Xinfeng Tao, Min-Hui Li, Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, UMR8247, 11 rue Pierre et Marie Curie, 75231 Paris, France; Sylvain Trepout, Institut Curie, PSL Research University, INSERM U1196 and CNRS UMR9187, 91405 Orsay cedex, France
Resume : Nanoparticles composed of amphiphilic copolymers are widely used in bioimaging and drug delivery areas. Among them, polymersomes have attracted special attention due to their vesicular cell- and virus-mimicking structures. Recently, luminogens with aggregation-induced emission (AIE) characteristics have emerged as a new class of fluorescent materials for organelles imaging and drug delivery monitoring. The combination of AIE luminogens (AIEgens) with polymer nanostructures, especially polymersomes, will provide innovative approaches to cell/tissue imaging and to in vivo study of drug distribution. Polypeptoids have a N-substituted pseudo-peptide structure, and have been rediscovered with interesting properties and great potential in biomedical field. By applying the ring-opening polymerization of N-thiocaboxyanhydride (NTA), polypeptoids could be conveniently prepared with controlled manners. In our study, novel amphiphilic block copolypeptoids based on polysarcosine and poly(allyl glycine) are synthesized with AIEgens attached on side chains through click chemistry. Polymer nanoparticles with AIE properties are prepared and their stimuli-responsivity are analyzed in detail.
Authors : Xianglong Hu, Ben Zhong Tang
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Aggregation-induced emission (AIE) is a kind of photophysical phenomenon associated with chromophore aggregation. The concept of AIE was coined by Prof. Benzhong Tang and coworkers in 2001. In a typical AIE process, non-emissive luminogens are induced to emit by the aggregate formation. The AIE luminogens (AIEgens) are practically non-emissive when they are molecularly dissolved in a solvent as the free intramolecular rotations of molecules serve as a relaxation channel for the excited states to deactivate. However, in the aggregated state, such rotational motions are restricted due to the physical constraint. This blocks the non-radiative pathway and thus the molecules become highly fluorescent. By utilizing the state-dependent emission property, high photostability, and facile functionalization of AIEgens, many innovative AIE bioprobes have been developed as AIEgen conjugates and ultra-bright AIE nanoparticles in biomedicine for long-term theranostics. On the other hand, polymers have shown promising applications as nanocarriers of therapeutic drugs/proteins, and imaging/contrast agents due to their unique core–shell nanostructures. The aqueous self-assembly of amphiphilic polymers often afford micelles, rod, vesicles, and some unknown nanostructures. The hydrophobic moieties of the assembles can solubilize hydrophobic drugs and serve as a repository. Furthermore, the presence of hydrophilic parts in polymer such as poly(ethylene oxide) can effectively protect hydrophobic cargoes against the external milieu, minimizing non-specific protein adsorption during blood circulation and capture by the reticuloendothelial system (RES). Since the size of polymer nanocarriers is typically above the threshold for kidney filtration, polymeric delivery systems demonstrate prolonged circulation duration following intravenous injection and possess passive targeting capabilities to tumor tissues via the enhanced permeability and retention (EPR) effect. Among many parameters of polymers, polymer topology has shown potentially significant impact on the in vitro/in vivo trafficking and fate of nanocarriers and the formulated drugs. Typically, previous work has demonstrated that branched polymers exhibit remarkably extended blood circulation based on magnetic resonance imaging (MRI). However, further exploration in biomedicine concerning the polymer topology, distinct topology-regulated self-assembly, blood circulation, biodistribution, pharmacokinetics and the theranostic capability is immature. Herein, it is extremely meaningful to study AIE-featured polymer delivery systems with optimized topology for long-term theranostics in biomedicine, which takes advantage of the high photostability and long-term monitoring potency of AIEgens as well as the smart fabrication of drug-tethered polymers with flexible topology.
Authors : Ryan T. K. Kwok, Ji Qi, Dan Ding, Ben Zhong Tang
Affiliations : Institute for Advanced Study, Department of Chemistry, The Hong Kong University of Science and Technology
Resume : Near-infrared (NIR)-absorbing organic small molecules hold great promise as the phototheranostic agents for clinical translation by virtue of their intrinsic advantages such as well-defined chemical structure, high purity, and good reproducibility. However, most of the currently available ones face the challenges in varying degrees in terms of photothermal instability, and photobleaching/reactive oxygen nitrogen species (RONS) inresistance, which indeed impair their practical applications in precise diagnosis and treatment of diseases. Herein, we developed highly stable and biocompatible organic nanoparticles (ONPs) for effective phototheranostic application by design and synthesis of an organic small molecule (namely TPA-T-TQ) with intensive absorption in the NIR window. The TPA-T-TQ ONPs with no noticeable in vivo toxicity possess better capacities in photothermal conversion and photoacoustic imaging (PAI), as well as show far higher stabilities including thermal/photothermal stabilities, and photobleaching/RONS resistances, when compared with the clinically popularly used indocyanine green. Thanks to the combined merits, the ONPs can serve as an efficient probe for in vivo PAI in a high-contrast manner, which also significantly causes the stoppage of tumor growth in living mice through PAI-guided photothermal therapy. This study thus provides an insight into the development of advanced NIR-absorbing small molecules for practical phototheranostic applications.
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Aggregation-induced emission: materials, mechanism, and applications Session 8 : Chaired by Zhao Zijun
Authors : Meng Gao
Affiliations : South China University of Technology
Resume : The distribution and movement of organelles in living cells are closely related with their biological functions. Photoactivatable fluorescent probes with a high spatiotemporal imaging ability are ideal tools for organelle study. However, conventional photo-caged pro-fluorogens suffer from drawbacks of aggregation-caused quenching (ACQ) and low photoactivation efficiency. We have developed a series of photoactivatable pro-fluorogens, which can selectively accumulate in organelles and further undergo photooxidative dehydrogenation reaction to afford the aggregation-induced emission fluorogens (AIEgens). The photoactivatable AIE pro-fluorogens for organelle-specific imaging has significant advantages in terms of simple preparation, excellent photoactivation efficiency, and high spatiotemporal resolution.
Authors : Zujin Zhao, and Ben Zhong Tang
Affiliations : 1. Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. 2. Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
Resume : Luminogens with thermally activated delayed fluorescence (TADF) can harvest singlet and triplet excitons to afford high electroluminescence (EL) efficiencies for OLEDs. However, most doped OLEDs of TADF emitters encounter a knotty problem of swift efficiency roll-off as luminance increases. In this work, we developed a series of novel luminogens with aggregation-induced delayed fluorescence (AIDF), which can easily settle the above challenge and realize nearly nil efficiency roll-off. They are composed by a carbonyl core and various electron-donating groups. Their structures and properties are investigated by crystallography, theoretical calculation, steady and transient spectroscopies, etc. They possess eximious emission with prominent delay fluorescence component in neat films, and can facilely solve the concentration or aggregation-caused emission quenching and/or exciton annihilation problem of those current TADF emitters. The nondoped OLEDs based on the neat films of these AIDF luminogens exhibit lowered turn-on voltages and increased luminance with respect to the doped OLEDs. Thanks to the excellent exciton utility, the nondoped devices furnish remarkable electroluminescence efficiencies of up to 72.9 cd A‒1, 81.8 lm W‒1 and 22.6%, and negligible efficiency roll-off. To the best of our knowledge, the present nondoped devices are the most efficient and stable devices reported so far.
Authors : Wolfgang J. Parak
Affiliations : Universität Hamburg, Hamburg, Germany; CIC Biomagune, San Sebastian, Spain
Resume : Nanoparticles can be made resposive to stimuli, such as the adsorption of proteins etc. In case such stimulus causes aggregation there is an effect on the particle, for example on plasmonic, fluorescence, or magnetic properties. This concept might be used in the future for in vivo sensing. References: M. Carril, D. Padro, P. del Pino, C. Carrillo-Carrion, M. Gallego, W. J. Parak, "In situ detection of the protein corona in complex environments", Nature Communications 8, 1542 (2017). W. G. Kreyling, A. M. Abdelmonem, Z. Ali, F. Alves, M. Geiser, N. Haberl, R. Hartmann, S. Hirn, K. Kantner, D. Jimenez de Aberasturi, G. Khadem-Saba, J.-M. Montenegro, J. Rejman, T. Rojo, I. Ruiz de Larramendi, R. Ufartes, A. Wenk, W. J. Parak, "In vivo integrity of polymer-coated gold nanoparticles", Nature Nanotechnology 10, 619–623 (2015).
Authors : Zhaoyang Wang, Xiao Cheng, Jing Zhi Sun, and Ben Zhong Tang
Affiliations : Mr. Zhaoyang Wang, Dr. Xiao Cheng, Prof. Jing Zhi Sun, Zhejiang University Prof. Ben Zhong Tang, The Hong Kong Univeristy of Science & Technology
Resume : Organic/Polymeric materials possessing aggregation-induced emission (AIE) property have attracted ever broad interests from both academic and industrial circles. One of the main-streams for AIE-relating researches is to find novel AIE-active materials with expected properties. Pyridinyl is a functional group commonlly used in modifying the structure and property of organic functional materials. Here, we report our recent investigation on the versatile properties of pyridinyl-functionalized tetraphenylethene (TPE). Due to the conjugation of pyridinyl groups with the AIE-active flurogen of TPE, the derivatives demonstrate, the following properties: (i) Intrinsic AIE behaviour since the presence of TPE unit. (ii) Acid responsive fluorescence emission as pyridinyl is an organic base or proton acceptor. (iii) Strong solvatochromism due to the electron-withdrawing nature of the pyridinyl group. (iv) Evident mechanochromism due to the enlarged and flexible structure of the pyridinyl-functionalized TPE. (v) Self-assembling behaviour because pyridinyl is a receptor for hydrogen-bond formation. (vi) Generation of cationic species upon the formation of pyridinium salt. (vii) Formation of luminescent metal-organic frameworks owing to the coordination capacity of the pyridinyl groups.
Authors : Sheng Wang*, Chengpeng Li, Liangwei Ma, Miao luo, Huan Dong, Xue Li
Affiliations : School of Chemistry and Chemical Engineering, Lingnan Normal University
Resume : Photochromic compounds display a reversible molecular structure transformation, which result in significant absorption spectra change upon the stimulation of ultraviolet (UV) and visible light. The special optical property makes them have high potential application in optical data storage, chemical sensors, optical switches, ophthalmic lenses, security documents. The fluorescent photochromic organic material is one of themost active areas. However, the fluorescence emission of most organic fluorescent molecules is quenched when it is in high concentrations or aggregated state, which is known as aggregationcaused quenching (ACQ) and commonly observed in the conventional organic dyes. Evidently, ACQ is a harmful photophysical effect in terms of light emission and practical applications，Excitedly, Tang's group discovered a new type of organic fluorescent molecules showing the aggregation-induced emission (AIE) properties in 2001, which is different from the conventional ACQ phenomenon. This interesting phenomenon provides a new way to design organic fluorescent materials with more effective emission in aggregated state. Here in，we designed and synthesized a series of new fluorescent photochromic materials with aggregation induced emission[3-6].They exhibited good AIE properties, non-emissive in the solution but good fluorescent emission in the aggregate or solid state. Meanwhile, their fluorescence intensities almost exhibit good photochromic properties when upon irradiation with UV light and visible light. They showed potential application for external stimuli-responsive materials, such as photoswitch, bioprobe and so on.
Authors : Carlo Adamo
Affiliations : Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, Paris 75005, France
Resume : Aggregation-induced emission (AIE) can be rationalized via the restriction of intramolecular rotation in the involved molecules and/or excimer formation. The enhanced luminescence recently observed for aggregates of fluorenone derivatives are a clear example of this phenomenon. In order to have deeper insights on these mechanism and on their interplay we have applied use a recently developed excited-state electrostatic embedding  to study AIE in 2,7 diphenylfluorenone crystals. Our results suggest that the observed enhanced emission can be easily rationalized by considering a single-molecule process, in which the field induced by the crystalline environment at the excited state enhances the relative brightness of otherwise poorly emissive states, resulting in both enhanced fluorescence and a substantial bathochromic shift in comparison with emission in dilute solution . References Yuan, M.-S.; Wang, D.-E.; Xue, P.; Wang, W.; Wang, J.-C.; Tu, Q.; Liu, Z.; Liu, Y.; Zhang, Y.; Wang, J. Fluorenone Organic Crystals: Two-Color Luminescence Switching and Reversible Phase Transformations between Π−π Stacking-Directed Packing and Hydrogen Bond-Directed Packing. Chem. Mater. 2014, 26, 2467−2477. Wilbraham, L.; Adamo, C.; Labat, F.; Ciofini, I. Electrostatic Embedding To Model the Impact of Environment on Photophysical Properties of Molecular Crystals: A Self-Consistent Charge Adjustment Procedure. J. Chem. Theory Comput. 2016, 12, 3316−3324.  Presti,D.; Wilbraham, L, Targa, C.; Labat, F.; Pedone, A.; Menziani, M.C.; Ciofini, I.; Adamo, C. Understanding Aggregation-Induced Emission in Molecular Crystals: Insights from Theory J. Phys. Chem. C 2017, 121, 5747−5752
Authors : Dongxia Zhu, Guangfu Li, Yang Jiang, Martin R Bryce
Affiliations : Northeast Normal University; Durham University
Resume : A series of dinuclear Ir( III )complexes have been synthesized and shown to exhibit both aggregation induced emission (AIE) and piezochromic luminescence (PCL) behaviour. We employed highly flexible Schiff base ligands to construct an AIE-active molecule with strong intermolecular interactions between the aryl rings in the aggregated or crystal state. The multifunctional dinuclear Ir(III) complexes are applied in second-level anti-counterfeit trademark, data encryption device and reversible monitoring device for volatile organic compounds.
Authors : Hai-Bo Yang
Affiliations : East China Normal University
Resume : Tetraphenylethene (TPE)-based functional metallosupramolecular through coordination-driven self-assembly have proven to be novel scaffolds to construct various fluorescent materials with aggregation-induced emission (AIE) properties. For example, from TPE-based ligands, a series of metal-organic frameworks (MOFs) with AIE properties have been successfully prepared. Afterwards, Stang group successfully constructed a library of TPE-based discrete organoplatinum(II) metallosupramolecular structures with rich optical properties.Recently, based on our previous research on well-defined functional metallacycles, we have expanded our related investigation towards the construction of TPE-based functional materials. Firstly, we successfully prepared a new family of tris-TPE metallacycle via coordination-driven self-assembly, which could aggregate into the ordered linear nanostructures upon threading the heparin through the metallacycles driven by multiple electrostatic interaction, thus allowing for the detection of heparin at the clinical dosage level. In addition, with the aim to build novel water-soluble TPE-based functional metallosupramolecular materials, we have developed a facile approach for synthesis of fluorescent supra-amphiphilic star polymers possessing well-defined metallacycles as the core via post-assembly polymerization. The obtained amphiphilic fluorescent star polymers presented high dispersibility in water and good biocompatibility, thus allowing for bioimaging applications.
Authors : Gen-ichi Konishi, Shunsuke Sasaki
Affiliations : Department of Chemical Science and Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan
Resume : Fluorescent molecules are sensitive to their steric environments, such as local viscosities, aggregations, binding to macromolecules and encapsulations to cavities. These fluorescent molecular systems have recently been emerged as versatile imaging/detection materials. Fluorescent molecular rotors and aggregation-induced emission luminogens (AIEgens) are representative types of steric-environment sensitive fluorophores, as they exhibit sizable changes in fluorescence intensity, lifetime, and spectral shape in response to subtle steric restrictions. Commonly used fluorophores undergo straightforward emission from an excited state, while fluorescent molecular rotors and AIEgens are designed to involve much more complicated relaxation paths. Their surrounding steric environments affect the excited-state equilibrium and/or internal conversion rate. Several AIEgens possess strong donor-acceptor structures to utilize their excited-state equilibrium, often called the “twisted intramolecular charge transfer” (TICT) state. In sterically restricted environments, interconversion between a weakly fluorescent TICT state and highly fluorescent states (e.g. locally excited (LE) or “coplanar” ICT states) is hampered, resulting enhanced fluorescence intensity and deformed spectral shape. On the other hand, inhibition of internal conversion, by restricting intramolecular motions (RIM), is the principal design strategy of AIEgens. Fast internal conversion can be induced by vibration in solution, but is suppressed in solid states. Since isomerizable double bonds and multiple aryl-aryl bonds often dominate such vibrations, these structures have been adopted in many AIEgens. In spite of recent advances in the area, it is still challenging to develop fluorophores from simple aromatic hydrocarbons that are sensitive to steric environments. Simple aromatic hydrocarbons, do not undergo any excited-state reaction within lower singlet manifolds, and introduction of either donor or acceptor on these hydrocarbons do not improve this problem. Therefore, development of novel strategies that modifies the potential energy surfaces (PESs) of the aromatic hydrocarbons to undergo excited-state reactions becomes critical. In this presentation, we report the steric-environment sensitivity of fluorescence of 9,10-bis(N,N-dialkylamino)anthracenes (BDAAs) in experimentally and theoretically. A new design strategy to tune simple aromatic hydrocarbons as efficient aggregation-induced emission (AIE) luminogens and molecular rotors is proposed. For a variety of BDAAs, prominent Stokes shifts and efficient solid-state fluorescence were observed. Calculations on BDAA-methyl suggested that in the ground state (S0) conformations, the pyramidal amine groups are highly twisted, so that their lone-pair orbitals cannot conjugate with the anthracene π orbitals. Fluorescence takes place from the S1 minima, in which one or both amine groups are planarized. The stability of the S1 excited state minima as well as destabilization of the S0 state is the origin of large Stokes shift. Experimental measurement of the non-adiabatic transition rate suggests that para disubstitution by dialkylamino (or strongly electron-donating) groups is a key for fast internal conversion. Minimum energy conical intersection (MECI) between S1 and S0 states was found to have a Dewar-benzene like structure. Although this can be reached efficiently in liquid phase for fast internal conversion, a large amplitude motion is required to reach this MECI, which is prohibited in the solid state and caused efficient AIE. This strategy is used to find experimentally that naphthalene analogues are also efficient AIE luminogens. The flexibility of alkyl chains on amino groups is also found to be important for allowed charge-transfer transition. Thus, three points (1. highly twisted N,N-dialkylamines, 2. substitution at the para positions 3. with flexible alkyl groups) were proposed for activation of small aromatic hydrocarbons. We also present some application of the AIEgens.
Authors : Haoke Zhang, Jacky W. Y. Lam and Ben Zhong Tang
Affiliations : The Hong Kong University of Science and Technology
Resume : π-Bonds connected with aromatic rings were generally believed as the standard structures for constructing highly efficient fluorophores. Materials without these typical structures, however exhibited only low fluorescence quantum yields and emitted in the ultraviolet spectral region. In this work, three molecules, namely bis(2,4,5-trimethylphenyl)methane, 1,1,2,2-tetrakis(2,4,5-trimethylphenyl)ethane and 1,1,2,2-tetraphenylethane, with non-conjugated structures and isolated phenyl rings were synthesized and their photophysical properties were systematically investigated. Interestingly, the emission spectra of these three molecules could be well extended to 600 nm with high solid-state quantum yields of up to 70%. Experimental and theoretical analyses proved that intramolecular through-space conjugation between the “isolated” phenyl rings played an important role for this abnormal phenomenon.
Authors : Zhaoyu Wang, Pengfei Zhang, Haixiang Liu, Ben Zhong Tang
Affiliations : Department of Chemistry, The Hong Kong University of Science and Technology; Division of Biomedical Engineering, The Hong Kong University of Science and Technology; Division of Biomedical Engineering, The Hong Kong University of Science and Technology; Department of Chemistry, The Hong Kong University of Science and Technology
Resume : Crime scene investigators (CSI) never stop being in need of novel forensic methods and technologies to help them detect and collect more useful information in crime scene, including but not limited to latent bloodstain, fingerprint, etc. Since the late 1970s, advancements in the technology of luminescence detection have greatly aided the hunt for many types of forensic evidence. Currently, aggregation-induced emission luminogens (AIEgens) have been widely applied in biological imaging, medical diagnosis and therapy, and optoelectronic materials, but rarely appear in forensic science. Bloodstains are traditionally detected and enhanced by a chemiluminescent reagent, luminol, but the observation window, namely emitting time, is comparatively short, often on the order of a few seconds. Thus, we propose to use Tetraphenylethene maleimide (TPE-MI), an AIEgen that can specifically react with thiol group in human serum albumin from blood and become yellow-emissive under ultraviolet light, to detect and enhance bloodstain in both visible and invisible type. The method is rapid and sensitive which can provide CSI with long-lasting emissive and high-resolution bloodstain visualization. As another example apart from bloodstain detection, fingerprints also play irreplaceable role in crime scene to identify criminal suspects. Here, we combine cyanoacrylate fuming with a series of AIEgens to design a novel fluorescent fingerprint development method. Even third-level minutiae (sweat pore and ridge edges) information can be clearly collected from a latent fingerprint. Besides these work, there remains large potential for AIEgens in forensic applications.
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