Europium(III) Functionalized Covalent Organic Framework as Sensitive and Selective Fluorescent Switch for Detection of Uranium.

Uranium poses severe health risks due to its radioactivity and chemical toxicity if released into the environment. Therefore, there is an urgent demand to develop sensing materials in situ monitoring of uranium with high sensitivity and stability. In this work, a fluorescent Eu3+-TFPB-Bpy is synthesized by grafting Eu3+ cation onto TFPB-Bpy covalent organic framework (COF) synthesized through Schiff base condensation of monomers 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 5,5'-diamino-2,2'-bipyridine (Bpy). The fluorescence of Eu3+-TFPB-Bpy is enhanced compared with that of TFPB-Bpy, which is originated from the intramolecular rotations of building blocks limited by the bipyridine units of TFPB-Bpy coordinated with Eu3+. More significantly, Eu3+-TFPB-Bpy is a highly efficient probe for sensing UO22+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO22+ with Eu3+. The turn-on sensing capability was derived from the resonance energy transfer occurring from UO22+ to the Eu3+-TFPB-Bpy. The developed probe displayed desirable linear range from 5 nM to 5 µM with good selectivity and rapid response time (2 s) for UO22+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.

σ-Hole Effect-Induced Electroluminescence of Halogen Cocrystals for Determination of Iodide in Seawater.

Developing new electrochemiluminescence (ECL) luminators with high stability, wide applicability, and strong designability is of great strategic significance to promote the ECL field to the frontier. Here, driven by the I···N bond, 1,3,5-trifluoro-2,4,6-triiodobenzene (TFTI) and 2,4,6-trimethyl-1,3,5-triazine (TMT) self-assembled into a novel halogen cocrystal (TFTI-TMT) through slow solution volatilization. Significant difference of charge density existed between the N atoms on TMT and the σ-hole of the I atoms on TFTI. Upon the induction of σ-hole effect, high-speed and spontaneous charge transferring from TMT to the σ-hole of TFTI occurred, stimulating exciting ECL signals. Besides, the σ-hole of the I atoms could capture iodine ions specifically, which blocked the original charge transfer from the N atoms to the σ-hole, causing the ECL signal of TFTI-TMT to undergo a quenching rate as high as 92.9%. Excitingly, the ECL sensing of TFTI-TMT toward I- possessed a wide linear range (10-5000 nM) and ultralow detection limit (3 nM) in a real water sample. The halogen cocrystal strategy makes σ-hole a remarkable new viewpoint of ECL luminator design and enables ECL analysis technology to contribute to addressing the environmental and health threats posed by iodide pollution.

Hydrogen-Bonded Cocrystals Encapsulating CsPbBr3 Perovskite Nanocrystals with Enhancement of Charge Transport for Photocatalytic Reduction of Uranium.

At present, poor stability and carrier transfer efficiency are the main problems that limit the development of perovskite-based photoelectric technologies. In this work, hydrogen-bonded cocrystal-coated perovskite composite (PeNCs@NHS-M) is easily obtained by inducing rapid crystallization of melamine (M) and N-hydroxysuccinimide (NHS) with PeNCs as the nuclei. The outer NHS-M cocrystal passivates the undercoordinated lead atoms by forming covalent bonds, thereby greatly reducing the trap density while maintaining good structure stability for perovskite nanocrystals. Moreover, benefiting from the interfacial covalent band linkage and long-range ordered structures of cocrystals, the charge transfer efficiency is effectively enhanced and PeNCs@NHS-M displays superior photoelectric performance. Based on the excellent photoelectric performance and abundant active sites of PeNCs@NHS-M, photocatalytic reduction of uranium is realized. PeNCs@NHS-M exhibits U(VI) reduction removal capability of up to 810.1 mg g-1 in the presence of light. The strategy of cocrystals trapping perovskite nanocrystals provides a simple synthesis method for composites and opens up a new idea for simultaneously improving the stability and photovoltaic performance of perovskite.

Rapid Charge Transfer Enabled by Noncovalent Interaction through Guest Insertion in Supercapacitors based on Covalent Organic Frameworks.

Covalent organic frameworks (COFs) have been proposed for electrochemical energy storage, although the poor conductivity resulted from covalent bonds limits their practical performance. Here, we propose to introduce noncovalent bonds in COFs through a molecular insertion strategy for improving the conductivity of the COFs as supercapacitor. The synthesized COFs (MI-COFs) establish equilibriums between covalent bonds and noncovalent bonds, which construct a continuous charge transfer channel to enhance the conductivity. The rapid charge transfer rate enables the COFs to activate the redox sites, bringing about excellent electrochemical energy storage behavior. The results show that the MI-COFs exhibit much better performance in specific capacitance and capacity retention rate than those of most COFs-based supercapacitors. Moreover, through simply altering inserted guests, the mode and strength of noncovalent bond can be adjusted to obtain different energy storage characteristics. The introduction of noncovalent bonds is an effective and flexible way to enhance and regulate the properties of COFs, providing a valuable direction for the development of novel COFs-based energy storage materials.

Structural Isomerism of Covalent Organic Frameworks Causing Different Electrochemiluminescence Effects and Its Application for the Detection of Arsenic.

The structural isomerism of the covalent organic framework (COF) has a significant effect on the electrochemiluminescence (ECL) performance. Herein, we report a pair of isomeric COFs, (TFPB-BD(OMe)2-H and TAPB-BD(OMe)2-H), based on the different directions of imine linkages and further conversion of the imine to the quinoline structure. The obtained two isomeric COFs with the same composition and similar structures exhibit dramatic differences in the photoelectrochemical and ECL fields. Indeed, TFPB-BD(OMe)2-H demonstrates robust ECL emission superior to that of TAPB-BD(OMe)2-H. The difference in ECL performance is due to the stronger polar interaction of TFPB-BD(OMe)2-H than that of TAPB-BD(OMe)2-H. The polarity is derived from the uneven charge distribution within the framework and enhances the electron interactions. In addition, the ordered conjugate skeleton provides high-speed charge transport channels for carrier transport. Therefore, the TFPB-BD(OMe)2-H presents a smaller band gap energy and stronger polarization interaction, which are more favorable to charge migration to achieve stronger ECL signals. Furthermore, we describe a convenient ECL sensor for detecting toxic As(V) with an outstanding detection property and ultralow detection limit. This work provides a guiding principle for the design and development of ECL organic luminophores.

Molecular Insertion: A Master Key to Unlock Smart Photoelectric Responses of Covalent Organic Frameworks.

Covalent organic frameworks (COFs) show potentials in prominent photoelectric responses by judicious structural design. However, from the selections of monomers and condensation reactions to the synthesis procedures, the acquisition of photoelectric COFs has to meet overmuch high conditions, limiting the breakthrough and modulation in photoelectric responses. Herein, the study reports a creative "lock-key model" based on molecular insertion strategy. A COF with suitable cavity size, TP-TBDA, is used as the host to load guests. Merely through the volatilization of mixed solution, TP-TBDA and guests can be spontaneously assembled via non-covalent interactions (NCIs) to produce molecular-inserted COFs (MI-COFs). The NCIs between TP-TBDA and guests acted as a bridge to facilitate charge transfer in MI-COFs, unlocking the photoelectric responses of TP-TBDA. By exploiting the controllability of NCIs, the MI-COFs can realize the smart modulation of photoelectric responses by simply changing the guest molecule, thus avoiding the arduous selection of monomers and condensation reactions required by conventional COFs. The construction of molecular-inserted COFs circumvents complicated procedures for achieving performance improvement and modulation, providing a promising direction to construct late-model photoelectric responsive materials.

Guest Molecular Assembly Strategy in Covalent Organic Frameworks for Electrochemiluminescence Sensing of Uranyl.

The application of covalent organic frameworks (COFs) in electrochemiluminescence (ECL) is promising in environmental monitoring. Developing an emerging design strategy to expand the class of COF-based ECL luminophores is highly desirable. Here, a COF-based host-guest system was constructed through guest molecular assembly to deal with nuclear contamination analysis. The efficient charge transport network was formed by inserting an electron-withdrawing guest tetracyanoquinodimethane (TCNQ) into the open space of the COF host (TP-TBDA; TP = 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde and TBDA = 2,5-di(thiophen-2-yl)benzene-1,4-diamine) with an electron-donating property; the construction of the COF-based host-guest system (TP-TBDA@TCNQ) triggered the ECL emission of non-emitting TP-TBDA. Furthermore, the dense active sites in TP-TBDA were utilized to capture the target substance UO22+. The presence of UO22+ broke the charge-transfer effect in TP-TBDA@TCNQ, resulting in the weakening of the ECL signal, thus the established ECL system integrating the low detection limit with high selectivity monitors UO22+. This COF-based host-guest system provides a novel material platform for constructing late-model ECL luminophores and creates an opportunity for the vigorous ECL technology.

Covalent Organic Frameworks as Advanced Uranyl Electrochemiluminescence Monitoring Platforms.

Electrochemiluminescence (ECL), as an advanced sensing process, can selectively control the generation of excited states by changing the potential. However, most of the existing ECL systems rely on poisonous coreactants to provide radicals for luminescence; although the ECL efficiency was improved, the athematic coreactants will cause unpredictable interference to the accurate analysis of trace targets. Herein, we realized the ECL of nonemitting molecules by performing intramolecular electron transfer in the olefin-linked covalent organic frameworks (COFs), with a high efficiency of 63.7%. Employing internal dissolved oxygen as the coreactant, it is well suitable for the analysis of various complex samples in the environment. Taking nuclear contamination analysis as the goal orientation, we further illustrated a design of a "turn-on" uranyl ion monitoring system integrating fast response, low detection limit, and high selectivity, showing that new ECL-COFs are promising to facilitate environment-related sensing analysis and structure-feature correlation mechanism exploration.

Arousing Electrochemiluminescence Out of Non-Electroluminescent Monomers within Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with stable long-range ordered arrangements are promising materials for organic optoelectronics. However, their electrochemiluminescence (ECL) from non-ECL active monomers has not been realized. Here, we report a design strategy for ECL-emitting COF family. The donors and acceptors co-crystallized and stacked into the highly aligned array of olefin-linked COFs, so that electrons can be transported freely. By this means, a tunable ECL is activated from non-ECL molecules with the maximum efficiency of 32.1% in water with the dissolved oxygen as an inner coreactant, and no additional noxious co-reactant is needed any more. Quantum chemistry calculations further demonstrate that this design reduces the COFs' band gaps and the overlap of electrons and holes in the excited state for better photoelectric properties and stronger ECL signals. This work exploits a basis to envisage the broad application potential of ECL-COFs for various biosensors and light-emitting display.

A general design approach toward covalent organic frameworks for highly efficient electrochemiluminescence.

Electrochemiluminescence (ECL) plays a key role in analysis and sensing because of its high sensitivity and low background. Its wide applications are however limited by a lack of highly tunable ECL luminophores. Here we develop a scalable method to design ECL emitters of covalent organic frameworks (COFs) in aqueous medium by simultaneously restricting the donor and acceptor to the COFs' tight electron configurations and constructing high-speed charge transport networks through olefin linkages. This design allows efficient intramolecular charge transfer for strong ECL, and no exogenous poisonous co-reactants are needed. Olefin-linked donor-acceptor conjugated COFs, systematically synthesized by combining non-ECL active monomers with C2v or C3v symmetry, exhibit strong ECL signals, which can be boosted by increasing the chain length and conjugation of monomers. The present concept demonstrates that the highly efficient COF-based ECL luminophores can be precisely designed, providing a promising direction toward COF-based ECL phosphors.

Evaluation of a novel Cardiac Peri-Operative Transfusion Trigger Scoring system in patients with coronary artery disease.

BACKGROUND: A simple and accurate scoring system to guide perioperative blood transfusion in patients with coronary artery disease (CAD) undergoing cardiac surgery is lacking. The trigger point for blood transfusions for these patients may be different from existing transfusion guidelines. This study aimed to evaluate the safety and efficacy of a new scoring strategy for use in guiding transfusion decisions in patients with CAD. METHODS: A multicenter randomized controlled trial was conducted at three third-level grade-A hospitals from January 2015 to May 2018. Data of 254 patients in a Cardiac Peri-Operative Transfusion Trigger Score (cPOTTS) group and 246 patients in a group receiving conventional evaluation of the need for transfusion (conventional group) were analysed. The requirements for transfusion and the per capita consumption of red blood cells (RBCs) were compared between groups. RESULTS: Baseline characteristics of the two groups were comparable. Logistic regression analyses revealed no significant differences between the two groups in primary outcomes (1-year mortality and perioperative ischemic cardiac events), secondary outcomes (shock, infections, and renal impairment), ICU admission, and ICU stay duration. However, patients in the cPOTTS group had significantly shorter hospital stays, lower hospital costs, lower utilization rate and lower per capita consumption of transfused RBCs than controls. Stratified analyses revealed no significant differences between groups in associations between baseline characteristics and perioperative ischemic cardiac events, except for hemofiltration or dialysis and NYHA class in I. CONCLUSIONS: This novel scoring system offered a practical and straightforward guideline of perioperative blood transfusion in patients with CAD. Trial registration chiCTR1800016561(2017/7/19).