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PD-L1 is an immune checkpoint molecule mediating cancer immune escape, and its expression level in the tumor has been used as a biomarker to predict response to immune checkpoint inhibitor (ICI) therapy. Our previous study reveals that an 11 amino acid-long ANXA1-derived peptide (named A11) binds and degrades the PD-L1 protein in multiple cancers and is a potential peptide for cancer diagnosis and treatment. Near-infrared fluorescence (NIF) optical imaging of tumors offers a noninvasive method for detecting cancer and monitoring therapeutic responses. In this study, an NIF dye Cy5.5 was conjugated with A11 peptide to develop a novel PD-L1-targeted probe for molecular imaging of tumors and monitor the dynamic changes in PD-L1 expression in tumors. In vitro imaging studies showed that intense fluorescence was observed in triple-negative breast cancer MDA-MB-231, nonsmall cell lung cancer H460, and melanoma A375 cells incubated with Cy5.5-A11, and the cellular uptake of Cy5.5-A11 was efficiently inhibited by coincubation with unlabeled A11 or knockdown of cellular PD-L1 by shRNA. In vivo imaging studies showed accumulation of Cy5.5-A11 in the MDA-MB-231, H460, and A375 xenografts with good contrast from 0.5 to 24 h after intravenous injection, indicating that Cy5.5-A11 possesses the strong ability for in vivo tumor imaging. Moreover, the fluorescent signal of A11-Cy5.5 in the xenografts was successfully blocked by coinjection of unlabeled A11 peptide or knockdown of cellular PD-L1 by shRNA, indicating the specificity of Cy5.5-A11 targeting PD-L1 in tumor imaging. Our data demonstrate that Cy5.5-A11 is a novel tool for tumor imaging of PD-L1, which has the potential for detecting cancer and predicting ICI therapeutic responses., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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 Eu 3+ -TFPB-Bpy is synthesized by grafting Eu 3+ 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 Eu 3+ -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 Eu 3+ . More significantly, Eu 3+ -TFPB-Bpy is a highly efficient probe for sensing UO 2 2+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO 2 2+ with Eu 3+ . The turn-on sensing capability was derived from the resonance energy transfer occurring from UO 2 2+ to the Eu 3+ -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 UO 2 2+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.

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.

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 UO 2 2+ . The presence of UO 2 2+ 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 UO 2 2+ . 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.

Femtosecond and nanosecond lasers were compared for ablating brass alloys. All operating parameters from both lasers were equal except for the pulse duration. The ablated aerosol vapor was collected on silicon substrates for particle size measurements or sent into an inductively coupled plasma mass spectrometer. The diameters and size distribution of particulates were measured from scanning electron microscope (SEM) images of the collected ablated aerosol. SEM measurements showed that particles ablated using nanosecond pulses were single spherical entities ranging in diameter from several micrometers to several hundred nanometers. Primary particles ablated using femtosecond ablation were approximately 100 nm in diameter but formed large agglomerates. ICPMS showed enhanced signal intensity and stability using femtosecond compared to nanosecond laser ablation.