This work introduces a scalable strategy for fabricating monodisperse cluster-luminescent polymer microspheres via functional group engineering. The microspheres exhibit broad emission (400–700 nm) and low fluorescence coefficient of variation (CV < 3%), fulfilling requirements for routine flow cytometer calibration. More importantly, kilogram-scale synthesis could be achieved facilely, demonstrating industrial potential (e70176).
Zhang et al. developed a novel direct deaminative functionalization strategy based on N-nitroamine intermediates, overcoming the explosiveness of traditional diazonium salts to achieve safe and efficient transformation. This method covers over 170 substrates, supports gram-scale preparation and one-pot cross-coupling, provides a new avenue for the synthesis of organic optoelectronic materials. And its N-nitroamine intermediate mechanism supplements the theoretical framework of deaminative reactions.
Agents to combine functions simultaneously are highly needed but still challenging in synergistic therapy. Particularly, capabilities to deplete glutathione (GSH) in tumors and monitor their process are also important. Therefore, platinum(II) metallacycles are prepared by using aggregation-induced emission active ligands. Despite their similar structures, high emission for Mh1 is obtained (PLQY = 49.2%) in solids, but a PLQY of only 6.8% is recorded for Mh2. NIR emission in Mh2 can be turned-on in depleting GSH by releasing emissive ligands. Also, both type I and type II reactive oxygen species (ROS) are obtained in Mh2 nanoparticles. Due to the depletion of GSH and generation of ROS, oxidative stress in immunogenic cell death can be induced. By combining chemotherapy and photoimmunotherapy, synergistic therapy in vivo is obtained for Mh2-NPs to well inhibit the tumor growth, also showing antitumor immune effects in distant tumors. The work here provides some guidelines in designing the multi-functional agents, showing the great potentials in efficient cancer therapy.
As environmental concerns and the transition to a carbon-neutral society gain importance, proton exchange membrane fuel cells (PEMFCs) using hydrogen as a fuel have attracted significant attention as eco-friendly energy technology. Although Pt is the primary catalyst for PEMFC anodes, its high cost and limited availability pose major barriers to commercialization. To address these challenges, non-Pt catalysts, alloy catalysts, and core-shell structured catalysts have been extensively studied; nevertheless, performance degradation and structural instability remain significant issues. In this study, we design Pt-lean Pt1Co4 alloy nanoparticles encapsulated with an ultrathin carbon shell derived from the carbon sources of the metal precursor ligands. Notably, after synthesizing the carbon-incorporated alloy nanoparticles, heat treatment under a carbon monoxide (CO) atmosphere induces selective surface segregation of Pt atoms due to their strong CO binding affinity, occurring before the carbonization temperature is reached for carbon shell formation, resulting in a Pt-enriched surface structure. The carbon shell imparts a nano-confinement effect that effectively suppresses particle growth and aggregation during heat treatment, thereby significantly enhancing electrochemical stability. Remarkably, despite a 55% reduction in Pt content, the combination of surface segregation and near-surface alloying allows the Pt-lean alloy catalyst to maintain hydrogen oxidation reaction activity comparable to a bare Pt catalyst while providing superior durability. Owing to this dual function of heat treatment, the design of the Pt-lean alloy catalyst structure offers a promising strategy for developing highly efficient and cost-effective anode catalysts for PEMFCs.
Confinement effect, by strengthening interactions between structural components, provides an effective strategy for precisely regulating functional units, which is critical for properties associated with microscopic accumulation effects, such as second harmonic generation (SHG) and ferroelectricity. Here, we propose a molecular dipole management strategy through confinement effect to enhance the SHG and ferroelectricity properties in a new hybrid germanium perovskite system. Utilizing the cyclohexylammonium (Cy) cation, we successfully synthesize three polar phases, including one-dimensional (1D) hexagonal (Cy)GeI3, a step-like two-dimensional (2D) (Cy)4Ge3I10 phase, and a 2D (CyF)2GeI4 phase (CyF = 4,4-difluorocyclohexanammonium). All three phases exhibit photoresponses, characteristic of semiconductors. The metastable 1D (Cy)GeI3 phase has the highest local dipole moment (LDM) of 14.07 Debye along the c-axis, resulting in a strong SHG response, and a high octahedral distortion parameter (Di = 0.10). The step-like 2D (Cy)4Ge3I10 phase exhibits ferroelectric properties, where the remanent polarization of 0.34 µC/cm2 has been confirmed by PFM and P-E hysteresis loop measurements. To achieve both high phase stability and SHG intensity, we introduce a fluorine group into the organic cation, forming strong C─H···F─C hydrogen bonds that align polar units uniformly, increasing Di to 0.11. The 2D (CyF)2GeI4 phase achieves a high SHG of 4 × KH2PO4. Furthermore, its phase transition temperature also increases by 88 K compared to the (Cy)4Ge3I10 phase. Raman spectra and DFT calculations further reveal intensified confinement effect in the (CyF)2GeI4 phases, consistent with its stronger structural rigidity. Our work provides comprehensive perspective and design strategies for tuning and optimizing hybrid perovskite-based nonlinear optical materials.
High-performance circularly polarized organic light-emitting diodes (CP-OLEDs) with ultraviolet and deep-blue circularly polarized electroluminescence (CP-EL) are important for 3D displays, but designing short-wavelength circularly polarized luminescence (CPL) materials remains a significant challenge. Herein, a series of ultraviolet and deep-blue CPL materials was developed, successfully integrating high photoluminescence quantum yields with efficient high-level reverse intersystem crossing (hRISC) properties. Efficient ultraviolet and deep-blue CP-OLEDs are created by utilizing these chiral materials as emitters, providing maximum external quantum efficiencies (ηext,maxs) of 6.7% at 398 nm (full-width at half-maximum [FWHM] = 44 nm) and 10.8% at 454 nm (FWHM = 68 nm) with obvious CP-EL. Furthermore, by adopting these chiral materials as sensitizers or functional layers, well-developed achiral multi-resonance thermally activated delayed fluorescence green and yellow emitters are enabled to generate obvious CP-EL with large dissymmetry factors and excellent EL performance (ηexts = 34.5% and 35.3%, FWHM = 42 and 40 nm). These results demonstrate that the developed new ultraviolet and deep-blue chiral materials can be used not only as emitters for ultraviolet and deep-blue CP-OLEDs, but also as sensitizers and functional layers to furnish a simple and universal way of achieving efficient narrow-spectrum CP-OLEDs with achiral emitters.
Aggregation-induced emission luminogens (AIEgens) have become a vital class of functional materials for optoelectronic and biomedical applications. Extending AIE behavior from single-component to two-component systems opens a new avenue for modulating emission through intermolecular interactions, yet it also introduces substantial complexity in understanding and controlling the aggregation process. In particular, elucidating how multicomponent molecular packing governs macroscopic photophysical behavior remains a central challenge. Herein, we constructed four distinct charge-transfer (CT) cocrystals through the coassembly of electron-rich dibenzo-heterocyclic donors and electron-deficient 1,2,4,5-tetracyanobenzene (TCNB) acceptors. The cocrystallization process allows precise manipulation of the dynamic aggregation pathway by tuning the DMSO/H2O ratio. Intriguingly, the morphology evolves from amorphous aggregates to rod-like and finally to needle-like microcrystals, showing a nonmonotonic size variation with increasing water content, accompanied by a gradual enhancement of fluorescence intensity. The four CT complexes exhibit wide emission tunability from green to orange-red, and notably, the AIE-active DBT/TCNB pair enables a practical demonstration in water-jet rewritable encryption paper. Overall, this work establishes a simple yet effective paradigm for designing high-performance solid-state emitters, while unveiling fundamental principles that govern the controllable molecular assembly in multicomponent luminescent systems.
The hypoxic tumor microenvironment severely limits the effectiveness of photodynamic therapy (PDT) in hepatocellular carcinoma (HCC). To overcome this limitation, we designed and synthesized a dual-functional photosensitizer, PorRu, by conjugating a porphyrin unit with a ruthenium(II) polypyridyl complex through a flexible alkyl chain. PorRu is engineered to achieve specific accumulation in HCC cells and “dual-lock” binding with G-quadruplex DNA (G4 DNA). It demonstrated approximately 3–6 folds higher photocytotoxicity against HCC cells compared to its individual components, owing to enhanced tumor targeting and improved Type I photochemical reactivity. Unlike conventional oxygen-dependent PDT, PorRu efficiently generates reactive oxygen species (ROS) under near-infrared irradiation, directly oxidizing guanine bases in G4 DNA and causing extensive oxidative damage under both normoxic and hypoxic conditions. The ROS burst induces severe oxidative stress, mitochondrial dysfunction, and the release of mitochondrial DNA (mtDNA), ultimately activating the inflammasome and triggering pyroptosis. In vivo studies validated the potent tumor-suppressive capability of PorRu, highlighting its potential to circumvent hypoxia-induced therapy resistance. This work not only presents PorRu as a promising agent for precise HCC targeting but also offers a novel strategy to enhance PDT efficacy against hypoxic tumors.
Colorectal cancer (CRC) is the third most commonly diagnosed cancer in the world, exhibiting persistently high mortality rates due to delayed diagnosis and imprecise lesion localization. Leveraging the prevalent hypoxic microenvironment characteristic of CRC lesions, this study innovatively developed a PEGylated iridium-based near-infrared (NIR) hypoxia nanoprobe, Ir-PEG. This nanoprobe can be activated in situ under hypoxic conditions, providing high-contrast imaging of colonic lesions, even though the intestine is inherently a low oxygen environment. In vitro evaluation demonstrated that Ir-PEG had excellent oxygen sensitivity, water solubility, and deep tissue penetration capability. These properties enabled Ir-PEG to achieve precise imaging of CRC in the native colonic microenvironment. Remarkably, in both in vitro and in vivo models, Ir-PEG achieved highly sensitive detection of cancer cell populations, and could detect as few as 104 CT26 cells in vivo. In addition, the nanoprobe could successfully identify different tumor types based on differential oxygen consumption rates across various cancer cells, suggesting its potential to identify intratumoral heterogeneity. As a molecular imaging tool, Ir-PEG enabled early non-invasive detection of CRC with high sensitivity and specificity, and holding significant promise for clinical translation.
Cooperative self-assembly based on multiple non-covalent interactions is ubiquitous in nature, yet the rational design of artificial cooperative systems remains challenging. Here we synthesize two carbazole derivatives, CbzE (with an ester group) and CbzA (with amide groups), to investigate how hydrogen bonding (HB) and halogen bonding (XB) jointly guide self-assembly into nanotubular supramolecular polymers. Using 1,4-diiodotetrafluorobenzene (DITFB) as XB donor or diplatinum(II) as linker, two types of [4 + 4] macrocycles are constructed and characterized by high-resolution mass spectrometry, ultraviolet-visible, infrared, and atomic force microscopy. CbzA, benefiting from strong HB, cooperatively assembles with DITFB into nanofibers and nanotubes, whereas CbzE, lacking amide groups, forms only disordered aggregates. Pt(II) coordination disrupts HB networks and redirects CbzA toward lateral aggregation, underscoring the sensitivity of assembly pathways to the balance of interactions. Remarkably, nanotubular CbzA + DITFB structures disassemble rapidly under trifluoroacetic acid vapor but are restored by triethylamine, demonstrating a reversible gel–sol–gel transition. This orthogonal acid/base responsiveness highlights the tunable and dynamic features of cooperative HB/XB systems. Overall, these results reveal the critical role of HB and XB cooperativity in directing ordered architectures and provide new design principles for intelligent supramolecular polymers with stimuli-responsive functions.
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