Zijie Qiu

Multiscale Humidity Visualization by Environmentally Sensitive Fluorescent Molecular Rotors

Building humidity sensors possessing the features of diverse-configuration compatibility, and capability of measurement of spatial and temporal humidity gradients is of great interest for highly integrated electronics and wearable monitoring systems. Herein, a visual sensing approach based on fluorescent imaging is presented, by assembling aggregation-induced-emission (AIE)-active molecular rotors into a moisture-captured network; the resulting AIE humidity sensors are compatible with diverse applications, having tunable geometries and desirable architectures. The invisible information of relative humidity (RH) is transformed into different fluorescence colors that enable direct observation by the naked eyes based on the twisted intramolecular charge-transfer effect of the AIE-active molecular rotors. The resulting AIE humidity sensors show excellent performance in terms of good sensitivity, precise quantitative measurement, high spatial-temporal resolution, and fast response/recovery time. Their multiscale applications, such as regional environmental RH detection, internal humidity mapping, and sensitive human-body humidity sensing are demonstrated. The proposed humidity visualization strategy may provide a new insight to develop humidity sensors for various applications.

In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene‐Containing Agents with Aggregation‐Induced Emission Characteristics

A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)-containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial-temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation-induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process.

Facile Multicomponent Polymerizations toward Unconventional Luminescent Polymers with Readily Openable Small Heterocycles

Heterocyclic polymers have gained enormous attention for their unique functionalities and wide applications. In contrast with the well-studied polymer systems with five- or six-membered heterocycles, functional polymers with readily openable small-ring heterocycles have rarely been explored due to their large synthetic difficulty. Herein, a facile one-pot multicomponent polymerization to such polymers is developed. A series of functional polymers with multisubstituted and heteroatom-rich azetidine frameworks are efficiently generated at room temperature in high atom economy from handy monomers. The four-membered azetidine rings in the polymer skeletons can be easily transformed into amide and amidine moieties via a fast and efficient acid-mediated ring-opening reaction, producing brand-new polymeric materials with distinctive properties. All the as-prepared azetidine-containing polymers exhibit intrinsic visible luminescence in the solid state under long-wavelength UV irradiation even without conventionally conjugated structures. Such unconventional luminescence is attributed to the clusteroluminogens formed by through-space electronic interactions of heteroatoms and phenyl rings. All the obtained polymers show excellent optical transparency, high and tunable refractive indices, low optical dispersions and good photopatternability, which make them promising materials in various advanced electronic and optoelectronic devices. The ring-opened polymers can also function as a lysosome-specific fluorescent probe in biological imaging.

Recent New Methodologies for Acetylenic Polymers with Advanced Functionalities

Polymers synthesized from acetylenic monomers often possess electronically unsaturated fused rings and thus show versatile optoelectronic properties and advanced functionalities. To expand the family of acetylenic polymers, development of new catalyst systems and synthetic routes is critically important. We summarize herein recent research progress on development of new methodologies towards functional polymers using alkyne building blocks since 2014. The polymerizations are categorized by the number of monomer components, namely homopolymerizations, two-component polymerizations, and multicomponent polymerizations. The properties and applications of acetylenic polymers, such as aggregation-induced emission, fluorescent photopatterning, light refraction, chemosensing, mechanochromism, chain helicity, etc., are also discussed.

A Highly Sensitive Bimodal Detection of Amine Vapours Based on Aggregation Induced Emission of 1,2-Dihydroquinoxaline Derivatives

The detection of food spoilage is a major concern in food safety as large amounts of food are transported globally. Direct analysis of food samples is often time-consuming and requires expensive analytical instrumentation. A much simpler and more cost-effective method for monitoring food fermentation is to detect biogenic amines generated as a by-product during food decomposition. In this work, a series of 1,2-dihydroquinoxaline derivatives (DQs) with aggregation-induced emission (AIE) characteristics were synthesised and their protonated forms, that is, H+ DQs, can be utilised for the sensitive detection of biogenic amines. For example, upon exposure to amine vapours, deprotonation occurs that converts the red-coloured, non-emissive H+ DQ2 back to its yellow-coloured, fluorescent parent form. The bimodal absorption and emission changes endow the system with high sensitivity, capable of detecting ammonia vapour at a concentration of as low as 690 ppb. Taking advantage of this, H+ DQ2 was successfully applied for the detection of food spoilage and was established as a robust and cost effective technique to monitor food safety.

The Marriage of Aggregation-Induced Emission with Polymer Science

Aggregation-induced emission (AIE) is a novel photophysical phenomenon coined in 2001 by our group and describes the enhanced light emission of some luminogens in the aggregate or solid state. The combination of AIE research and polymer science is a smart approach to produce functional luminescent materials with mechanical strength and excellent processability for real-world applications. In this feature article, recent progress in AIE polymeric systems, including chemical synthesis and physical blending strategies, is summarized. Through chemical synthesis, various AIE-active polymers, such as covalently bonded polymers, supramolecular polymers, and nonconjugated luminescent polymers, can be obtained. Serving as environmentally sensitive probes, AIE luminogens can also be physically doped into polymers to generate interesting systems. Finally, outlooks and perspectives on the future direction of AIE polymeric systems are discussed.

Dynamic Visualization of Stress/Strain Distribution and Fatigue Crack Propagation by an Organic Mechanoresponsive AIE Luminogen

Stress exists ubiquitously and is critically important for the manufacturing industry. Due to the ultrasensitive mechanoresponse of the emission of 1,1,2,2,-tetrakis(4-nitrophenyl)ethane (TPE-4N), a luminogen with aggregation-induced emission characteristics, the visualization of stress/strain distributions on metal specimens with a pure organic fluorescent material is achieved. Such a fluorescence mapping method enjoys the merits of simple setup, real-time, full-field, on-site, and direct visualization. Surface analysis shows that TPE-4N can form a nonfluorescent, crystalline uniform film on the metal surface, which cracks into fluorescent amorphous fragments upon mechanical force. Therefore, the invisible information of the stress/strain distribution of the metal specimens are transformed to visible fluorescent signals, which generally matches well but provides more details than software simulation. Remarkably, fatigue crack propagation in stainless steel and aluminum alloy can be observed and predicted clearly, further demonstrating the ultrasensitivity and practicability of TPE-4N.