Aggregation-induced Quenching Research Articles

RhB intercalated Zr(VI)-bipyridine architecture for efficient ratiometric fluorescent response toward Cr(VI) analyte and decontamination of Cr(VI) and reactive dye via photochemical REDOX

It is extremely‌ imperative to enhance the sensing accuracy of water-stable Zr-MOFs for Cr(VI), because the single emission signal in a sole Zr-MOF is rather vulnerable to external factors. Interpolation of guest luminous species into Zr-MOF crystals presents a feasible way to achieve dual-emission signals. In this contribution, a highly water-stable Zr-MOF (Zr-bcu-22bipy44dc) which emits bright-blue fluorescence was deployed as matrix to intercalate fluorochrome Rhodamine B (RhB), creating a novel dual-emission (at 410 and 580 nm) luminescent platform, RhB@Zr-MOF. Then, it was utilized as a fluorescence probe to accurately detect trace-level Cr(VI) ions, by assessing the relative fluorescence intensity (IR) difference between the host Zr-MOF (I410) and the guest RhB (I580). Interestingly, the septal interpolation of luminescent species within Zr-MOF matrix effectively suppresses aggregation-induced quenching (ACQ), which tends to occur easily for RhB molecules. Moreover, its determined detection limits (DL) for CrO42- (6.13 ppb) and Cr2O72- (10.04 ppb) ions have been remarkably enhanced by approximately 4.92-fold and 3.66-fold, respectively, compared to the initial Zr-MOF (30.11 and 36.76 ppb). DFT and TD-DFT calculations have confirmed that the orange-yellow photoluminescence exhibited by RhB@Zr-MOF should be attributed to the PET process inherent to the intercalated RhB molecules, rather than the commonly accepted intermolecular Förster resonance energy transfer (FRET) mechanism or the photo-induced electron transfer (PET) effect previously identified by us. Efficient antenna effect of RhB module synergizes with Zr-MOF's appropriate band structure, also enables RhB@Zr-MOF convincing ability to photochemically deoxidize Cr(VI) and bleach reactive dark blue K-R (K-R)

Leading edge biosensing applications based on AIE technology

Luminescent materials provide a unique method for biological imaging. Luminescent probes can label molecules of interest and present luminescent signals. Bioluminescence bioimaging has shown great efficacy in environmental, live cell and animal studies. Light-emitting materials play a very wide role in the field of light-emitting devices and biosensing. Luminescent materials are usually used as solid films or aggregate states. However, it is difficult to monitor the selectivity and sensitivity of various ions and small molecules in living cells with ordinary luminescent materials due to the changes in various aspects of analytes. Organic luminescent materials exhibit aggregation-induced quenching (ACQ) on molecular aggregation, and the ACQ effect is very common, which greatly limits the application of luminescent materials in chemical sensing, especially in biological imaging. Academician Tang Benzhong proposed “aggregation-induced emission (AIE)" as a powerful method to solve the ACQ problem for the first time. In this paper, the working principle of AIE is reviewed, and the research on the core working mechanism of AIE technology is not only of great fundamental significance, but also can pave the way for practical innovation of AIE technology applications. In this review, we outline the current basic understanding of the working mechanism of AIE, collate the cutting-edge biosensing applications based on AIE technology, including applications based on AIE in substance detection, biological detection, and disease detection. At last, we discuss the future development of AIE research.

NIR-Sensitive Squaraine Dye-Peptide Conjugate for Trypsin Fluorogenic Detection.

Trypsin enzyme has gained recognition as a potential biomarker in several tumors, such as colorectal, gastric, and pancreatic cancer, highlighting its importance in disease diagnosis. In response to the demand for rapid, cost-effective, and real-time detection methods, we present an innovative strategy utilizing the design and synthesis of NIR-sensitive dye-peptide conjugate (SQ-3 PC) for the sensitive and selective monitoring of trypsin activity by fluorescence ON/OFF sensing. The current research deals with the design and synthesis of three unsymmetrical squaraine dyes SQ-1, SQ-2, and SQ-3 along with a dye-peptide conjugate SQ-3-PC as a trypsin-specific probe followed by their photophysical characterizations. The absorption spectral investigation conducted on both the dye alone and its corresponding dye-peptide conjugates in water, utilizing SQ-3 and SQ-3 PC respectively, reveals enhanced dye aggregation and pronounced fluorescence quenching compared to observations in DMSO solution. The absorption spectral investigation conducted on dye only and corresponding dye-peptide conjugates in water utilizing SQ-3 and SQ-3 PC, respectively, reveals not only the enhanced dye aggregation but also pronounced fluorescence quenching compared to that observed in the DMSO solution. The trypsin-specific probe SQ-3 PC demonstrated a fluorescence quenching efficiency of 61.8% in water attributed to the combined effect of aggregation-induced quenching (AIQ) and fluorescence resonance energy transfer (FRET). FRET was found to be dominant over AIQ. The trypsin-mediated hydrolysis of SQ-3 PC led to a rapid and efficient recovery of quenched fluorescence (5-fold increase in 30 min). Concentration-dependent changes in the fluorescence at the emission maximum of the dyes reveal that SQ-3 PC works as a trypsin enzyme-specific fluorescence biosensor with linearity up to 30 nM along with the limit of detection and limit of quantification of 1.07 nM and 3.25 nM, respectively.

Advances in the study of AIE polymers

Aggregation-induced emission (AIE) can exhibit different properties in different situations, such as non-emission and highly fluorescent in the dissolved state of the molecule and in the aggregate or solid state, respectively. This property of AIE is distinguished from aggregation-induced quenching (ACQ) or even the opposite. Combining the AIE phenomenon with different polymers yields different polymers with corresponding AIE properties. In this paper, the mechanism, synthesis, branching and application of AIE in the fields of optoelectronic functional materials, sensors, biology, and environment are reviewed. It is hoped that this review will stimulate more research on molecular aggregates and promote further cross-fertilisation and greater development in the disciplines of materials, chemistry and biomedicine.

Rare-Earth-Metal-Free Solid-State Fluorescent Carbonized-Polymer Microspheres for Unclonable Anti-Counterfeit Whispering-Gallery Emissions from Red to Near-Infrared Wavelengths.

Colloidal carbon dots (CDs) have garnered much attention as metal-free photoluminescent nanomaterials, yet creation of solid-state fluorescent (SSF) materials emitting in the deep red (DR) to near-infrared (NIR) range poses a significant challenge with practical implications. To address this challenge and to engineer photonic functionalities, a micro-resonator architecture is developed using carbonized polymer microspheres (CPMs), evolved from conventional colloidal nanodots. Gram-scale production of CPMs utilizes controlled microscopic phase separation facilitated by natural peptide cross-linking during hydrothermal processing. The resulting microstructure effectively suppresses aggregation-induced quenching (AIQ), enabling strong solid-state light emission. Both experimental and theoretical analysis support a role for extended π-conjugated polycyclic aromatic hydrocarbons (PAHs) trapped within these microstructures, which exhibit a progressive red shift in light absorption/emission toward the NIR range. Moreover, the highly spherical shape of CPMs endows them with innate photonic functionalities in combination with their intrinsic CD-based attributes. Harnessing their excitation wavelength-dependent photoluminescent (PL) property, a single CPM exhibits whispering-gallery modes (WGMs) that are emission-tunable from the DR to the NIR. This type of newly developed microresonator can serve as, for example, unclonable anti-counterfeiting labels. This innovative cross-cutting approach, combining photonics and chemistry, offers robust, bottom-up, built-in photonic functionality with diverse NIR applications.

A disaggregation-driven BODPIY-based probe for ratiometric detection of G4 DNA

In conventional systems, fluorescent probes with planar structures usually experience the phenomenon of aggregation-induced quenching (ACQ) that limits their practical applications in bio-medical sensing. To confront such problem, an attractive way is to develop a disaggregation-induced emission (DIE) sensing strategy, where the quenched fluorescence is recovered via a disaggregation process. Currently most of the fluorescent probes designed based on DIE mechanism are signal off-on type with the fluorescent intensity changed at a single wavelength. On the other hand, ratiometric fluorescent probes have the advantage of having two distinct emission wavelengths, effectively avoiding environmental interference. The DIE probes with a ratiometric fluorescence response still poorly established. Herein, we report a BODIPY-based probe BODPA, where a 2,2′-dipicolylamine group was introduced to the meso-position of BODIPY core, for the selective ratiometric detection of G-quadruplex (G4) DNA. This probe in buffer solution formed aggregates with weak fluorescence at 508 nm. In the presence of G4 DNA, bright fluorescence was emitted at 518 nm through DIE mechanism. Taking advantage of the ratiometric manner, probe BODPA exhibited selectivity for G4 DNA over duplex DNA. The binding details between probe BODPA and G4 DNA were assessed by spectroscopic and molecular modeling methods, which suggested the ability of this probe could coordinate with G4 structure via end stacking and partial groove binding mode.

Nanoscale Covalent Organic Framework with Staggered Stacking of Phthalocyanines for Mitochondria-Targeted Photodynamic Therapy.

Phthalocyanine photosensitizers (PSs) have shown promise in fluorescence imaging and photodynamic therapy (PDT) of malignant tumors, but their practical application is limited by the aggregation-induced quenching (AIQ) and inherent photobleaching of PSs. Herein, we report the synthesis of a two-dimensional nanoscale covalent organic framework (nCOF) with staggered (AB) stacking of zinc-phthalocyanines (ZnPc), ZnPc-PI, for fluorescence imaging and mitochondria-targeted PDT. ZnPc-PI isolates and confines ZnPc PSs in the rigid nCOF to reduce AIQ, improve photostability, enhance cellular uptake, and increase the level of reactive oxygen species (ROS) generation via mitochondrial targeting. ZnPc-PI shows efficient tumor accumulation, which allowed precise tumor imaging and nanoparticle tracking. With high cellular uptake and tumor accumulation, intrinsic mitochondrial targeting, and enhanced ROS generation, ZnPc-PI exhibits potent PDT efficacy with >95% tumor growth inhibition on two murine colon cancer models without causing side effects.

Discovery of a near-infrared fluorescent probe for G-quadruplexes by exploiting the concept of unfolding-intramolecular-aggregation-induced emission

In the very recent years, the concept of disaggregation-induced emission (DIE) has been applied to design G4 probes, thereby rendering several fluorophores that may suffer from aggregation-induced quenching (ACQ) to develop into desirable G4-selective probes. However, the design idea based on DIE was often limited by the instability and irreversibility of the “intermolecular” aggregation/disaggregation process. In this study, a self-folded, near-infrared fluorescent probe for selectively illuminating G4s was engineered. This probe restored its fluorescence via unfolding of its intramolecular aggregation (UIA) mediated by distinctive G4 binding, which may display more controllable background emission as well as more promising ability to track G4 forming dynamics as compared to the reported DIE probes. Altogether, this study provided insights into the development of new types of applicable G4 selective fluorescent probes.

"Off/On” Fluorescent Probe based on Aggregation-Induced Quenching of ZnO-Quantum dots for Determination of Ara-C: Pharmacokinetic Applications, Adsorption Kinetics & Green Profile Assessment

Herein, a turn “Off/On” fluorescence probe based on ZnO quantum dots (ZnO-QDs) has been proposed and successfully utilized for the determination of Ara-C (cytarabine) using ceric ions (Ce4+) as quencher and ethylenediamine (ED) as a linker. The probe is based initially on the quenching effect of Ce4+ ions on the strong native fluorescence of ZnO-QDs forming the Turn Off system (Ce@ZnO-QDs) that believed to occur due to the aggregation-induced quenching (AIQ) mechanism. The second step is the addition of Ara-C in the presence of ethylenediamine (ED) that encourages the formation of Ara-C/ED/Ce4+ as well as the release of the free ZnO-QDs, leading to the recovery of the fluorescence intensity. The developed sensing platform shows a linear response towards Ara-C over the range of 10 to 1000 ng mL−1 giving a limit of detection (LOD) and limit of quantitation (LOQ) of 1.22 ng mL−1 and 3.70 ng mL−1, respectively. A dispersive magnetic solid phase micro-extraction (dMSPE) method was developed and optimized for the extraction of Ara-C in spiked human plasma using thiol-modified magnetite nanoparticles (S-MNPs). The proposed platform exhibits good sensitivity toward Ara-C in the presence of different interfering substances. Excellent recoveries are obtained after spiking different concentrations of Ara-C into rabbit plasma samples. The validated experimental parameters have been successfully applied to monitor the pharmacokinetic profile of Ara-C in rabbit plasma. A detailed adsorption kinetics study has been carried out to provide a deep insight into the adsorption behavior of Ara-C on the thiol-doped-magnetite nanoparticles. The greenness assessment of the proposed method was achieved and compared with other reported methods using two tools of greenness; the green analytical procedure index (GAPI) and the analytical greenness calculator AGREE.

Design and Synthesis of Novel Squaraine Dye with Highly Enhanced Far‐Red Fluorescence and its Interaction with a Model Protein

Novel amine‐functionalized symmetrical squaraine (SQ)‐dye and fluorescein isothiocyanate (FITC)–SQ–FITC dye conjugate are designed and successfully synthesized, followed by their structural and photophysical characterizations. Symmetrical SQ dye exhibits complete fluorescence quenching in polar solvents, which is explained by considering photoinduced electron transfer (PET) as a dominant quenching pathway. In contrast, FITC–SQ–FITC dye conjugate results in a decrease in an aggregation of both SQ and FITC units and about 47 times enhancement in the far‐red fluorescence appearing at 674 nm. This profound enhancement in the far‐red fluorescence is explained by the synergistic influence of suppression of aggregation‐induced quenching (ACQ) and PET. This newly designed FITC–SQ–FITC dye conjugate shows complete quenching of the far‐red fluorescence in phosphate buffer saline (PBS) owing to very strong dye aggregation, as confirmed by spectral absorption investigation. In PBS, it strongly interacts with bovine serum albumin (BSA) (Ka = 1.1 × 104 m−1) used as a model protein breaking the dye aggregation by BSA and increasing far‐red fluorescence associated with SQ as a function of increasing BSA concentration. A profound 117 times increase in fluorescence at 674 nm with 25 times of BSA concentration suggests that the designed FITC–SQ–FITC is an excellent far‐red probe for dye‐protein interaction.

Unraveling the Mechanism of ACQ-to-AIE Transformation of Fluorescein Derivatives.

Although fluorescein derivatives have excellent properties and strong practicability, they are typical aggregation-induced quenching (ACQ) molecules, which are not conducive to working in the solid state. Recently, the fluorescein derivative Fl-Me with aggregation-induced emission (AIE) property was synthesized, which brought a new dawn for the research and development of fluorescein-based materials. In this study, the AIE mechanism of Fl-Me was investigated based on time-dependent density functional theory and the ONIOM method. The results revealed that an effective dark-state deactivation pathway leads to the fluorescence quenching of Fl-Me in a solution environment. Accordingly, the AIE phenomenon originates from the closure of the dark-state quenching channel. It is worth emphasizing that we found that the carbonyl group of molecular Fl-Me has intermolecular hydrogen bonding interaction with the adjacent molecules, which caused the increase of the dark-state energy in the crystalline state. Moreover, the restriction of the rotational motion and the nonexistence of the π-π stacking interaction are beneficial to the enhancement of fluorescence upon aggregation. Finally, the ACQ-to-AIE transformation mechanisms of fluorescein derivatives have been discussed. This work provides deeper insight into the photophysical mechanism for the fluorescein derivatives Fl-Me with AIE feature and eventually is expected to help researchers to develop more fluorescein-based AIE materials with remarkable properties for various fields.

Fluorescent Probes Based on Metal and Aggregation-induced Luminescent Organic Molecule Complexes for Bioimaging and Sensing Applications

Metal-Organic Coordination polymer (MOCPs) is an emerging class of inorganic-organic porous hybrid materials with infinite coordination polymers (CPs) or metal-organic backbones (MOFs) formed by the interaction between metal ions and organic ligands and ligand functional groups. The molecular structure of the organic ligands composing MOCPs is rich in variation, while inorganic metal ions generally have good photoelectromagnetic properties. Therefore, MOCPs have diverse structural variations, adjustable pore size, high stability and controllable synthesis, and have received wide attention in gas storage, multiphase catalysis, chemical sensing and biological applications. Fluorescence properties are one of the most widely used techniques for bioimaging and sensing detection. However, conventional luminescent groups are usually affected by aggregation-induced quenching (ACQ) effects. Aggregation-induced luminescence molecules (AIEs) based on metal-organic coordination polymers combine the advantages of organic AIEs and transition metal centers to improve photophysical properties and therapeutic effects.

Debut of a novel AIE-based fluorescent probe as tyrosinase tracer to image skin pigmentary disorders

Tyrosinase (TYR) functions as the critical enzyme in biosynthesis of melanin, and its abnormality is an important hallmark for skin pigmentary disorders. This renders the visualization of tyrosinase dynamics a strategically vital way to facilitate clinical diagnostic and monitoring. However, the use of small molecule fluorescent probes to assess tyrosinase levels and evaluate related therapeutics and drugs has been limited. This is mainly due to the aggregation-induced quenching (ACQ) effects of existing fluorescent probes. In this study, we introduce the first aggregation-induced emission (AIE) small molecule fluorescent probe, BTFTYR, for simple, highly sensitive, and effective detection of tyrosinase activity. The specific fluorescence signal generated by tyrosinase catalytic reaction enables the imaging of pigment cells. We demonstrate its application in visualizing tyrosinase with high contrast in living vertebrates, benefiting from the inherent photobleaching resistance of AIE materials, large Stokes shift, and considerable tissue permeability. We also show the outstanding skin penetration capability of BTFTYR in a skin model. Moreover, we present the first comprehensive evaluation of relevant clinical therapeutic approaches or drugs, including ultraviolet B (UVB) irradiation, kojic acid, and α-MSH, by interpreting the tyrosinase variation with BTFTYR. Finally, our studies confirm that BTFTYR neither causes skin inflammation nor produces visceral toxicity, making it a promising chemical tool for medical diagnosis and drug screening. This tool may further help elucidate the pathomechanisms associated with tyrosinase.

Synergism of Photo-Induced Electron Transfer and Aggregation-Induced Quenching Mechanisms for Highly Sensitive Detection of Silver Ion and Captopril.

Carbon-based nanoprobes, with excellent physicochemical performance and biocompatibility, are a kind of ideal nanomaterial for biosensing. Herein, we designed and prepared novel oxygen-doped nitrogen-enrichment carbon nanoribbons (ONCNs) with an excellent optical performance and uniform morphology, which could be used as a dual-mode fluorescence probe for the detection of Ag+ ion and captopril (Ctl) based on the synergism of photo-induced electron transfer and aggregation-induced quenching mechanisms. By recording the changes in fluorescent intensities of ONCNs, the Ag+ ion and Ctl concentrations can be easily tested in real samples. The results displayed that two good linear relationships existed between the change in fluorescent intensity of ONCNs and the concentrations of Ag+ ion and Ctl in the ranges of 3 μM to 30 μM and 1 μM to 30 μM, with the detection limit of 0.78 µM and 74 nM, respectively. The proposed sensing platform has also been successfully applied for the Ctl analysis in commercial tablet samples based on its high selectivity, proving its value in practical applications.

Fluorescent N-CQDs uniformly implanted into sponge-like PVDF-HFP piezoelectric film by facile two-step process for multifunctional pressure sensor

To meet the diversified demands for the booming intelligent systems, a multifunctional pressure sensor with two basic capabilities of ultraviolet excited fluorescence and force-electricity response has been proposed, and named as fluorescent pressure sensor (FPS). Carbon quantum dots (CQDs) are being rapidly developed as an reasonable photoluminescence materials. However, the CQDs were utilized in the solid-state film along with serious aggregation-induced quenching (AIQ). Here, we developed a two-step method instead of the typical one-step method to overcome the AIQ of the CQDs in the representative piezoelectric polymer. The sponge-like poly (vinylidene) fluoride-hexafluoropropylene (PVDF-HFP) film with high porosity formed based on nonsolvent-induced phase separation was selected as the host matrix of the guest nitrogen-doped CQDs (N-CQDs). The impressive bright blue fluorescence with enhanced intensity derived from the N-CQDs is successfully implanted into the obtained N-CQDs/PVDF-HFP piezoelectric hybrid film, attributing to two key factors: (i) the sponge-like matrix supported uniform distribution of the N-CQDs and (ii) the hydrogen bonding between the N-CQDs and the matrix chains. Meanwhile, the hybrid film used in the FPS still keeps a sensitivity of 92.7 mV N−1, thanks to the β piezoelectric phase formation in the matrix. Since the hybrid film based FPS has multiple features, such as ultraviolet excited fluorescence, force-electricity response, self-powered capability and flexibility, it will show a great potential in the intelligent systems used as the multifunctional sensor and energy harvester.

Enhancing electrochemiluminescence by assembling ACQ ligands into Hf-based metal-organic framework nanosheet: A novel ECL emitter for fabricating ultrasensitive biosensor

Polycyclic aromatic hydrocarbons (PAHs) are classic electrochemiluminescence (ECL) materials. However, the ECL performance of PAHs aggregates in water phase is limited owing to the aggregation-induced quenching (ACQ) effect of PAHs. To surmount this shortcoming, we proposed an innovative strategy for enhancing the ECL performance by assembling PAH derivative ligands into metal-organic framework nanosheets (MONs), which can separate ACQphores to eliminate the ACQ effect. Gratifyingly, the ECL intensity of Hf-DEADB MON (DEADB = 4,4′-(diethylanthracene-9,10-diyl)dibenzoate) prepared according to the strategy was 5.71-fold higher than that of H2DEADB aggregates. This improvement occurred not only because the distance between the ACQphores in the Hf-DEADB MON was enlarged to surmount the ACQ effect but also because the ultrathin porous Hf-DEADB MON could shorten the diffusion pathways of ion/electron and co-reactant, which boosted electrochemical activation of DEADB luminophores. Given the prominent ECL performance of Hf-DEADB MON, it was used to fabricate a hypersensitive biosensor for detecting microRNA-21, displaying a broad response range (100 aM–10 nM) with an ultralow detection limit (24 aM). Overall, our work developed a promising strategy to eradicate the ACQ effect of PAHs for ECL enhancement, thus pointing out a new direction to design high-efficient ECL materials for constructing ultrasensitive ECL sensors.

Using azaacene as an acceptor unit to construct an ultraefficient red fluorophore with an EQE over 40.

Azaacenes, which have been known for a long time, are of scientific and practical importance in organic electronics. Azaacenes once shone as the luminophore in organic light-emitting diodes (OLEDs). However, due to the low exciton utilization efficiency and/or the aggregation induced quenching (ACQ) effect, N-heteroacene based OLEDs generally showed inferior device performance. In this work, azaacene has been revisited and applied as an acceptor for a red fluorophore (AZA-TPA), where the judicious connection pattern between donor and acceptor maximized the harvest of singlet and triplet excitons, resulting in a high photoluminescence efficiency of 94.6% in doped films (3 wt%). In addition, the linearly-fused polycyclic structure contributed to a high horizontal emitting dipole ratio (Θ‖ = 90%). As a result, an AZA-TPA-based OLED achieved an unprecedented external quantum efficiency of 41.30% at 610 nm. This work will pave a new path for the development of efficient N-heteroacene-based fluorophores.

Dual-binding domain electrochemiluminescence biosensing platform with self-checking function for sensitive detection of synthetic cathinone in e-cigarettes

Current single signal electrochemiluminescence (ECL) sensors are susceptible to false positive or false negative phenomena due to experimental conditions. Therefore, sensors with “self-checking” function are attracting democratic attention. In quick succession, a highly sensitive single-cathode dual ECL signal aptasensor with self-checking function to improve the shortcomings mentioned above was designed. This aptasensor used In-based metal-organic framework (MIL-68) as load and stabilizer to effectively attenuate the aggregation-induced quenching (ACQ) effect of porphyrin derivatives (Sn-TCPP) while improve ECL stability. The introduction of cooperative-binding split-aptamers” (CBSAs) aptamers increased the specificity of the aptasensor and its unique double-binding domains detection accelerated the detection efficiency. When analyzing 3,4-methylenedioxypyrovalerone (MDPV), we could calculate two concentrations based on the strength of ECL 1 and ECL 2. If the concentrations are the same, the result would be obtained; if not, it should be retested. Depending on the above operation, the results achieve self-check. It was found that the designed aptasensor could quantify the concentration of MDPV between 1.0 × 10−12 g/L and 1.0 × 10−6 g/L with the limit of detection (LOD) of 1.4 × 10−13 g/L and 2.0 × 10−13 g/L, respectively (3 σ/slope). This study not only improves the detection technology of MDPV, but also explores the dual-signal detection of porphyrin for the first time and enriches the definition of self-checking sensor.

A Novel 3D-Morphology Pyrene-Derived Conjugated Fluorescence Polymer for Picric Acid Detection.

Aggregation-induced quenching (ACQ) is a hard problem in fluorescence material, leading to a poor utilization rate of fluorophores. In this work, 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) was synthesized and used as a precursor to build two kinds of fluorescence polymer. The TFFPy molecule with D2h symmetry can easily form polymers with C3 symmetry amines through the Schiff base reaction, making the resulting polymer a 3D amorphous material. Thus, ACQ of fluorophore can be reduced to minimum, making the most usage of the fluorescence of pyrene core. Fluorescence titration and DFT calculation can clearly prove this conclusion. The resulting CPs showed a highly sensitivity to picric acid, down to 3.43 ppm in solution, implying its potential in explosive detection.

Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations.

Photo-catalysis by small-molecules is often limited by catalyst degradation and low electron-transfer efficiency. Herein we report a stable N-phenyl-phenothiazine (PTH)-derived porous coordination cage (PCC) as a highly efficient photocatalyst. By the incorporation of the photocatalytic PTH moiety into a PCC, aggregation-induced quenching (AIQ) was shown to be reduced. An improvement in catalyst stability was discovered, ascribed to the synergistic effects of the PTH moieties. The catalyst, operating through a photolytic single-electron transfer, was utilized for photo-catalyzed dehalogenation and borylation. Evaluation of the catalytic mechanism in the borylation reaction showed that the improved performance results from the more efficient formation of the electron donor-acceptor (EDA) complex with the cage. This discovery provides a potential strategy to improve the photophysical properties and stabilities of small-molecule organic photocatalysts via supramolecular chemistry.