Ju Mei,†,‡,∥ Nelson L. C. Leung,†,‡,∥ Ryan T. K. Kwok,†,‡ Jacky W. Y. Lam,†,‡ and Ben Zhong Tang*,†,‡,§ †HKUST-Shenzhen Research Institute, Hi-Tech Park, Nanshan, Shenzhen 518057, China ‡Department of Chemistry, HKUST Jockey Club Institute for Advanced Study, Institute of Molecular Functional Materials, Division of Biomedical Engineering, State Key Laboratory of Molecular Neuroscience, Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China Guangdong Innovative Research Team, SCUT-HKUST Joint Research Laboratory, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China

Aggregation-Induced Emission: Together We Shine, United We Soar!

Luminogenic materials with aggregation-induced emission (AIE) attributes have attracted much interest since the debut of the AIE concept in 2001. In this critical review, recent progress in the area of AIE research is summarized. Typical examples of AIE systems are discussed, from which their structure–property relationships are derived. Through mechanistic decipherment of the photophysical processes, structural design strategies for generating new AIE luminogens are developed. Technological, especially optoelectronic and biological, applications of the AIE systems are exemplified to illustrate how the novel AIE effect can be utilized for high-tech innovations (183 references).

Aggregation-induced emission

"United we stand, divided we fall."--Aesop. Aggregation-induced emission (AIE) refers to a photophysical phenomenon shown by a group of luminogenic materials that are non-emissive when they are dissolved in good solvents as molecules but become highly luminescent when they are clustered in poor solvents or solid state as aggregates. In this Review we summarize the recent progresses made in the area of AIE research. We conduct mechanistic analyses of the AIE processes, unify the restriction of intramolecular motions (RIM) as the main cause for the AIE effects, and derive RIM-based molecular engineering strategies for the design of new AIE luminogens (AIEgens). Typical examples of the newly developed AIEgens and their high-tech applications as optoelectronic materials, chemical sensors and biomedical probes are presented and discussed.

Aggregation-Induced Emission: The Whole Is More Brilliant than the Parts

During the past decade, fluorescent chemosensors have become an important research field of supramolecular chemistry and have attracted great attention because of their simplicity, high selectivity and sensitivity in fluorescent assays. In the design of new fluorescent chemosensors, exploration of new sensing mechanisms between recognition and signal reporting units is of continuing interest. Based on different photophysical processes, conventional sensing mechanisms including photo-induced electron transfer (PET), intramolecular charge transfer (ICT), metal–ligand charge transfer (MLCT), twisted intramolecular charge transfer (TICT), electronic energy transfer (EET), fluorescence resonance energy transfer (FRET), and excimer/exciplex formation have been investigated and reviewed extensively in the literature. This tutorial review will mainly focus on new fluorescent sensing mechanisms that have emerged in the past five years, such as aggregation-induced emission (AIE) and CN isomerization, which can be ascribed to fluorescence changes via conformational restriction. In addition, excited-state intramolecular proton transfer (ESIPT) has not been well reviewed yet, although a number of chemosensors based on the ESIPT mechanism have been reported. Thus, ESIPT-based chemosensors have been also summarized in this review.

New sensing mechanisms for design of fluorescent chemosensors emerging in recent years

Light emission of 2-(2,6-bis((E)-4-(diphenylamino)styryl)-4H-pyran-4-ylidene)malononitrile (TPA-DCM) is weakened by aggregate formation. Attaching tetraphenylethene (TPE) units as terminals to TPA-DCM dramatically changes its emission behavior: the resulting fluorogen, 2-(2,6-bis((E)-4-(phenyl(4′-(1,2,2-triphenylvinyl)-[1,1′-biphenyl]-4-yl)amino)styryl)-4H-pyran-4-ylidene)malononitrile (TPE-TPA-DCM), is more emissive in the aggregate state, showing the novel phenomenon of aggregation-induced emission (AIE). Formulation of TPE-TPA-DCM using bovine serum albumin (BSA) as the polymer matrix yields uniformly sized protein nanoparticles (NPs) with high brightness and low cytotoxicity. Applications of the fluorogen-loaded BSA NPs for in vitro and in vivo far-red/near-infrared (FR/NIR) bioimaging are successfully demonstrated using MCF-7 breast-cancer cells and a murine hepatoma-22 (H22)-tumor-bearing mouse model, respectively. The AIE-active fluorogen-loaded BSA NPs show an excellent cancer cell uptake and a prominent tumor-targeting ability in vivo due to the enhanced permeability and retention effect.

Biocompatible Nanoparticles with Aggregation‐Induced Emission Characteristics as Far‐Red/Near‐Infrared Fluorescent Bioprobes for In Vitro and In Vivo Imaging Applications

CO2 sensing is of great societal implications, as CO2 is a component of gas mixtures from many natural and anthropogenic processes with huge impacts on globe climate and human well-being. Herein we report a CO2 assay scheme over a wide concentration range, utilizing a fluorogen with an aggregation-induced emission feature and a liquid with tunable polarity and viscosity. The CO2 sensing process is specific, quantitative, and interferent tolerant.

Fluorescent Chemosensor for Detection and Quantitation of Carbon Dioxide Gas

Groundwater is one of the main sources of water for irrigation used worldwide. However, the application of the resource is threatened by the possibility of high saline levels, especially in low-lying coastal regions. Furthermore, the lack of readily accessible materials for successful treatment procedures makes the purification of such water a constant challenge. Based on the fact that natural zeolite is one of the easily accessible and relatively cheap filter materials, this study examined the potential use of high-salinity groundwater filtered by natural zeolite for irrigation. Zeolite-filled filters at two different depths (0.5 m and 1 m) were studied. The samples were collected from the low-lying areas of Dar es Salaam City, Tanzania. The study observed that when the raw groundwater samples were exposed to the 0.5 m column depth, sodium (Na+) had the lowest removal efficiency at 40.2% and calcium (Ca2+) had the highest removal efficiency at 98.9%. On the other hand, magnesium (Mg2+) had the lowest removal efficiency, at about 61.2%, whereas potassium (K+) had up to about 99.7% removal efficiency from the 1 m column depth treatment system. Additionally, from the salinity hazard potential analysis, most of the samples fell within C4 (based on the electrical conductivity), which is a “very high salinity” class, and based on the quality it means the water cannot be directly applied for irrigation purposes. From the 0.5 m column depth, most of the samples fell within C3 (the “high salinity” class), and from the 1 m column depth most of the samples fell within C1 (“low salinity” class). The findings of this study offer some valuable insight into the prospective use of natural zeolite for the filtration of saline groundwater before its application for irrigation.

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Natural Zeolite for The Purification of Saline Groundwater and Irrigation Potential Analysis

Constituent Composition of Essential Oil from Artemisia semiarida

Constituent Composition and Biological Activity of Essential Oil from Kalimeris incisa

5-(Benzylidene)pyrimidine-2,4,6-triones with different substituents on the phenyl rings: 5-(4’-dimethyl-aminobenzylidene) barbituric acid and 5-(4’-methoxybenzylidene) barbituric acid were synthesized, and their spectral-luminescent properties were investigated. A decreasing fluorescence efficiency in the solid-state is general and is mainly attributed to the intermolecular vibronic interactions, which induce the nonradiative deactivation process. Whereas the isolated dye molecules are virtually non-luminescent in dilute solutions, they become highly emissive upon solution thickening or aggregation in poor solvents or in the solid-state, show an increase of luminescence intensity, the phenomenon of the aggregation-induced emission (AIE phenomenon). The development of efficient luminescent materials is a topic of great current interest. The emission color is changed from red (maximum at 630 nm) to green (maximum at 540 nm) by varying the substituent on the phenyl ring from dimethylamino to the methoxy group. Theoretical calculation shows that the dye molecules' aggregation-induced emission characteristics result from intermolecular interactions. Utilizing such features, the molecules can be employed as fluorescent probes for the detection of the ethanol content in aqueous solutions.

Dinara Birimzhanova

Papers

Fluorescent Chemosensor for Detection and Quantitation of Carbon Dioxide Gas

Natural Zeolite for The Purification of Saline Groundwater and Irrigation Potential Analysis

Constituent Composition of Essential Oil from Artemisia semiarida

Constituent Composition and Biological Activity of Essential Oil from Kalimeris incisa

Aggregation-induced emission of 5-(benzylidene)pyrimidine-2,4,6-triones