Sensing analysis is significantly important for human health and environmental safety, and has gained increasing concern. As a promising material, porous organic polymers (POPs) have drawn widespread attention due to the availability of plentiful building blocks and their tunable structures, porosity and functions. Moreover, the permanent porous nature could provide a micro-environment to interact with guest molecules, rendering POPs attractive for application in the sensing field. In this review, we give a comprehensive overview of POPs as a platform for sensing applications. POP-based sensors are mainly divided into five categories, including fluorescence turn-on sensors, fluorescence turn-off sensors, ratiometric fluorescent sensors, colorimetric sensors and chemiresistive sensors, and their various sensing applications in detecting explosives, metal ions, anions, small molecules, biological molecules, pH changes, enantiomers, latent fingerprints and thermosensation are summarized. The different structure-based POPs and their corresponding synthetic strategies as well as the related sensing mechanisms mainly including energy transfer, donor-acceptor electron transfer, absorption competition quenching and inner filter effect are also involved in the discussion. Finally, the future outlook and perspective are addressed briefly.

Porous organic polymers as a platform for sensing applications.

Very bright mechanoluminescence and remarkable mechanochromism using a tetraphenylethene derivative with aggregation-induced emission

Enantiopure molecules based on macrocyclic architecture are unique for applications in enantioselective host-guest recognition, chiral sensing and asymmetric catalysis. Taking advantage of the chiral transfer from the intrinsically planar chirality of pillar[5]arenes, we herein present an efficient and straightforward approach to achieve early examples of highly luminescent chiral systems (P5NN and P5BN). The optical resolution of their enantiomers has been carried out via preparative chiral HPLC, which was ascribed to the molecular functionalization of pillar[5]arenes with π-conjugated, sterically bulky triarylamine (Ar3 N) as an electron donor and triarylborane (Ar3 B) as an acceptor. This crucial design enabled investigations of the chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL) in the solid state. The intramolecular charge transfer (ICT) nature in P5BN afforded an interesting thermochromic shift of the emission over a wide temperature range.

/pdf/planar-chiral-organoboranes-with-thermoresponsive-emission-2t1qdwkapp.pdf

Planar Chiral Organoboranes with Thermoresponsive Emission and Circularly Polarized Luminescence: Integration of Pillar[5]arenes with Boron Chemistry

Co-MOF@MXene-carbon nanofiber-based freestanding electrodes for a flexible and wearable quasi-solid-state supercapacitor

Molecular aggregates are self-assembled from multiple molecules via weak intermolecular interactions, and new chemical and physical properties can emerge compared to their individual molecule. With the development of aggregate science, much research has focused on the study of the luminescence behaviour of aggregates rather than single molecules. Pyrene as a classical fluorophore has attracted great attention due to its diverse luminescence behavior depending on the solution state, molecular packing pattern as well as morphology, resulting in wide potential applications. For example, pyrene prefers to emit monomer emission in dilute solution but tends to form a dimer via π-π stacking in the aggregation state, resulting in red-shifted emission with quenched fluorescence and quantum yield. Over the past two decades, much effort has been devoted to developing novel pyrene-based fluorescent molecules and determining the luminescence mechanism for potential applications. Since the concept of "aggregation-induced emission (AIE)" was proposed by Tang et al. in 2001, aggregate science has been established, and the aggregated luminescence behaviour of pyrene-based materials has been extensively investigated. New pyrene-based emitters have been designed and synthesized not only to investigate the relationships between the molecular structure and properties and advanced applications but also to examine the effect of the aggregate morphology on their optical and electronic properties. Indeed, new aggregated pyrene-based molecules have emerged with unique properties, such as circularly polarized luminescence, excellent fluorescence and phosphorescence and electroluminescence, ultra-high mobility, etc. These properties are independent of their molecular constituents and allow for a number of cutting-edge technological applications, such as chemosensors, organic light-emitting diodes, organic field effect transistors, organic solar cells, Li-batteries, etc. Reviews published to-date have mainly concentrated on summarizing the molecular design and multi-functional applications of pyrene-based fluorophores, whereas the aggregation behaviour of pyrene-based luminescent materials has received very little attention. The majority of the multi-functional applications of pyrene molecules are not only closely related to their molecular structures, but also to the packing model they adopt in the aggregated state. In this review, we will summarize the intriguing optoelectronic properties of pyrene-based luminescent materials boosted by aggregation behaviour, and systematically establish the relationship between the molecular structure, aggregation states, and optoelectronic properties. This review will provide a new perspective for understanding the luminescence and electronic transition mechanism of pyrene-based materials and will facilitate further development of pyrene chemistry.

Aggregation behaviour of pyrene-based luminescent materials, from molecular design and optical properties to application.

Precise Probe Design Based Esipt Coupled Aie Mechanism Toward Endogenous Cyanide in Food Detection and Bioimaging

Herein, a novel strategy was proposed for identifying carbon monoxide (CO), which plays a crucial part in living systems. For the first time, we have managed to design, synthesize, and characterize successfully this new Cu2+-assisted fluorescent probe (DPHP) in detecting CO. Compared with the commonly adopted Pd0-mediated Tsuji-Trost reaction recognition method, such a new strategy did not engage costly palladium (II) salt and generated no leaving group, indicating a satisfactory anti-interference ability. The recognition mechanism was confirmed by IR, 1H NMR titration, HR-MS, cyclic voltammetry, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and optical properties. Surprisingly, it was found that the new method achieved high selectivity and rapid identification of CO with a lower limit of detection (1.7 × 10-8 M). More intriguingly, it could recognize endogenous and exogenous CO in HeLa cells. The cytotoxicity of this new method was so low that it allowed the detection of CO in mice and zebrafish. Basically, our results trigger a novel viewpoint of rationally designing and synthesizing advanced materials for CO detection with unique features, impelling new research in detection chemistry.

Strategy for Detecting Carbon Monoxide: Cu2+-Assisted Fluorescent Probe and Its Applications in Biological Imaging.

Peptide bond, the amide bond formed between α-amino acids, constitutes the backbone of peptides and proteins. Although peptide bonds can be constructed efficiently under mild reaction conditions in nature, their...

Active ester-based peptide bond formation and its application in peptide synthesis

As one of the most toxic heavy metals to human beings and the environment, how to simultaneously achieve fluorescence detection and removal of mercury in wastewater is still a challenge and rarely reported. Here, we for the first time synthesize a sulfur-modified covalent organic polymer (COP-108-S) by using facile Ni-catalyzed Yamamoto coupling reactions, and achieve the bifunctional application of COP-108-S for Hg2+ fluorescence detection with a detection limit of 1.44 mM and simultaneous removal with a capacity of 241 mg g−1. On the contrary, the corresponding counterpart (COP-108) without sulfur-modification does not possess the bifunctional property, which means that the sulfur-modification is the key to the bifunctional property of COP-108-S. In addition, COP-108-S also shows good recycle use performance with 99% removal efficiency after five cycles. In short, sulfur-modification may be a useful strategy to develop bifunctional COP materials for simultaneous removal and detection of toxic heavy metal ions.

Sulfur-modified porous covalent organic polymers as bifunctional materials for efficient fluorescence detection and fast removal of heavy metal ions

The surface grafting of electro-negative cyano groups on polymer carbon nitrides (PCNs) is an effective way to tail their electronic structure. Despite the significant progress in the synthesis of cyano group-enriched PCN, developing a simple and efficient method remains challenging. Here, we describe a facile strategy for fabricating surface cyano-rich PCN (PCN-DM) with a porous structure via chemical vapor modification using diaminomaleonitrile. The cyano groups of diaminomaleonitrile substituted the amino groups on PCN surface via a deamination. The hydrogen production rate of the PCN-DM was approximately 17 times higher than that of pristine PCN. This significant increase in photocatalytic performance can be assigned to the fusion of cyano groups in the surface of PCN, forming new gap states that broaden the visible-light harvesting and accelerate charge separation for photoredox reactions. This study unveils a promising approach for incorporating functional units in the design of novel photocatalysts for efficient hydrogen production.

Facile chemical vapor modification strategy to construct surface cyano-rich polymer carbon nitrides for high efficient photocatalytic H2 evolution.

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