Exciton binding energy ( E b) has been regarded as a critical parameter in charge separation during photovoltaic conversion. Minimizing the E b of the photovoltaic materials can facilitate the exciton dissociation in low-driving force organic solar cells (OSCs) and thus improve the power conversion efficiency (PCE), nevertheless, diminishing the E b with deliberate design principles remains a significant challenge. Herein, bulky side chain as steric hindrance structure was inserted into Y-series acceptors to minimize the E b by modulating the intra- and inter-molecular interaction. Theoretical and experimental results indicate that steric hindrance-induced weaker intra-molecular interactions but stronger inter-molecular interaction can strengthen the molecular polarizability, increase the overlap of electronic orbitals between molecules and facilitate delocalized pathway charge transfer, thereby resulting in a low E b. The conspicuously reduced E b obtained in Y-ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low-driving-force OSCs, achieving a remarkable PCE of 19.1% with over 95% internal quantum efficiency. Our study provides a new molecular design rationale to reduce the exciton binding energy.

The poor prognosis of triple-negative breast cancer (TNBC) resulting from its high metastasis, whereas inflammation accompanied by excessive reactive oxygen species (ROS) is prone to aggravate tumor metastasis. Although photothermal therapy (PTT) has extremely high therapeutic efficiency, the crafty tumor cells allow increase the expression of heat shock proteins to limit its effect, and PTT induced inflammation is also thought to be a potential trigger for tumor metastasis. Herein, myricetin, iron ions and polyvinylpyrrolidone were utilized to develop nanomedicines by self-assembly strategy for the treatment of metastatic TNBC. The nanomedicines with marvellous water solubility and dispersion can inhibit glucose transporter 1 and interfer with mitochondrial function to block the energy supply of tumor cells, achieving starvation therapy on TNBC cells. Nanomedicines with excellent photothermal conversion properties allow down-regulate the expression of HSPs to enhance the effect of PTT. Interestingly, the broad spectrum of ROS scavenging ability of nanomedicines successfully attenuat PTT induced inflammation as well as regulate metastasis-related proteins through glycometabolism inhibition to reduce tumor cell metastasis. Moreover, the nanomedicines have negligible side effects and good clinical application prospect, which provides a valuable paradigm for the treatment of metastatic TNBC through glycometabolism interference, anti-inflammation, starvation and photothermal synergistic therapy.

Synergistic changes between tumor-associated macrophages (TAMs) and tumor-associated fibroblasts (CAFs) aggravated immune evasion of hepatocellular carcinoma (HCC), however, the underlying molecular mechanisms remain elusive. Their continuous and dynamic interactions are subject to bioactive molecule changes. A real-time and in-situ monitoring method suitable for in vivo research of these processes would be indispensable but is scarce. In this study, a dual imaging strategy that tracing the TAMs and CAFs simultaneously was developed using a new arginase-specific probe and established CAFs-specific probe. The emerging roles of arginase in mediating CAFs activation in mice were explored. Results showed arginase up-regulation in TAMs, followed by proline increase. Subsequently, proline produced by TAMs initiated the activation of CAFs. Through the JAK-STAT signaling, CAFs up-regulated the PD-L1 and CTLA-4, ultimately promoting immune evasion of HCC. This study revealed a new mechanism by which TAMs and CAFs collaborate in immune evasion, providing new targets for HCC immunotherapy.

Highly sensitive stimuli-responsive multifunctional luminescent materials are crucial for applications in optical sensing, high-level security, and anticounterfeiting. Here, we report two zero-dimensional (0D) hybrid copper(I) halides, (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6, which are comprised of isolated [Cu 2Br 4] 2- and [Cu 4Br 6] 2- inorganic cluster units, respectively, separated by TEP + (TEP = tetraethylphosphonium) cations. (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 demonstrate ultrabright greenish-white and orange-red emissions, respectively, with near unity photoluminescence quantum yields. Optical spectroscopy measurements and density-functional theory (DFT) calculations reveal that photoemissions of these compounds originate from the formation of self-trapped excitons (STEs) due to the excited-state distortions in the copper(I) halide units. Single crystals of both compounds are radioluminescence (RL) active at room temperature under both X- and γ-rays exposure. The excellent energy resolution values and light yields up to 15,800 ph/MeV under 662 keV γ-rays of 137Cs suggest their potential for scintillation applications. Remarkably, (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 are interconvertible through external chemical stimuli or reverse crystallization. In addition, both compounds demonstrate luminescence on-off switching upon thermal stimuli. The sensitivity of (TEP) 2Cu 2Br 4 and (TEP) 2Cu 4Br 6 to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for practical applications such as solid-state lighting, sensing, information storage, and anticounterfeiting.

In this work, we demonstrate a chiral dual-core strategy for the design of high-performance organic circularly polarized aggregation-induced emission luminogens (AIEgens), which features of connecting two thermally activated delayed fluorescence (TADF) luminophore with chiral linkage that allows efficient through-space coupling (TSC) to occur. Using this strategy, a pair of dual-core enantiomers, R/S-DNKP, were designed and synthesized by linking two benzophenone derivatives with a 1,1’-bi-2-naphthol unit. Compared to the mono-core counterpart NKP, the dual-core emitters exhibited a much higher photoluminescence quantum yields of 94%. Moreover, benefited from their chiral helical folding configurations, the R/S-DNKP enantiomers exhibited a high luminescence dissymmetry factor (|glum|) value up to 1.3×10-3 in film states. Notably, the electroluminescence devices based on the R/S-DNKP enantiomers achieved external quantum efficiency values of 21.5% and 19.7% with little roll-off. It is believed that this molecular design strategy will pave new routes for the development of high-performance chiral emitters for future organic photonic devices.

Fluorescence imaging, a key technique in life science research, frequently utilizes fluorogenic probes for precise imaging in living systems. Tetrazine is an effective emission quencher in the design of fluorogenic probes, which can be selectively damaged upon bioorthogonal click reactions, leading to considerable emission enhancement. Despite significant efforts to increase the emission enhancement ratio upon click reaction (IAC/IBC) of tetrazine-functionalized fluorogenic probes, the influence of molecular aggregation on the emission properties has been largely overlooked in the design of these probes. In this study, we reveal that an ultrahigh IAC/IBC can be realized in the aggregate system when tetrazine is paired with aggregation-induced emission (AIE) luminogens. Tetrazine can increase its quenching efficiency upon aggregation and drastically reduce background emissions. Subsequent click reactions damage tetrazine and trigger significant AIE, leading to considerably enhanced IAC/IBC. We further showcase the capability of these ultra-fluorogenic systems in selective imaging of multiple organelles in living cells. We propose the term “Matthew Effect” in Aggregate Emission to describe the unique fluorogenicity of these probes, potentially providing a universal approach to attain ultrahigh emission enhancements in diverse fluorogenic aggregate systems.

The high curing temperatures required for traditional benzocyclobutene (BCB) materials have posed limitations on their applicability in high-temperature-sensitive fields. To address this challenge, our work focuses on the synthesis of a novel tetraphenylethylene (TPE)-functionalized BCB monomer, TPE-BCB, achieved through the introduction of an ether bond onto the BCB’s four-membered ring via Williamson reaction. TPE-BCB demonstrates remarkable low-temperature curing properties, characterized by a ring-opening peak temperature of 190 °C, representing a 25% reduction compared to conventional BCBs. Fully cured TPE-BCB resins exhibit exceptional dielectric and mechanical properties, coupled with minimal water absorption. Additionally, the incorporation of TPE with aggregation-induced emission (AIE) characteristics enhances the resins’ luminescence and photolithographic capabilities. Notably, our TPE-BCB resins achieve impressive photolithography performance with a resolution ratio of up to 10 µm. In contrast to conventional BCB-functionalized resins, TPE-BCB offers the dual advantage of low-temperature curing and luminescence. This development marks a significant step in the advancement of low-temperature curing BCB materials and serves as a pioneering example in the realm of multi-layer wafer bonding materials.

Melt electrowriting (MEW) is a solvent-free (i.e., no volatile chemicals), high-resolution 3D printing method that enables the fabrication of semi-flexible structures with rigid polymers. Despite its advantages, the MEW process is sensitive to changes in printing parameters (e.g., voltage, printing pressure, and temperature), which can cause fluid column breakage, jet lag, and/or fiber pulsing, ultimately deteriorating the resolution and printing quality. In spite of the commonly used error-and-trial method to determine the most suitable parameters, here, we present a machine learning (ML)-enabled image analysis-based method for determining the optimum MEW printing parameters through an easy-to-use graphical user interface (GUI). We trained 5 different ML algorithms using 168 MEW 3D print samples, among which the gaussian process regression ML model yielded 93% accuracy of the variability in the dependent variable, 0.12329 on root mean square error for the validation set and 0.015201 mean square error in predicting line thickness. Integration of ML with control feedback loop and MEW can reduce the error-and-trial steps prior to the 3D printing process, decreasing the printing time (i.e., increasing the overall throughput of MEW) and material waste (i.e., improving the cost-effectiveness of MEW). Moreover, embedding trained ML model with the feedback control system in a GUI facilitates a more straightforward use of ML-based optimization techniques in the industrial section (i.e., for users with no ML skills).

Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics, including water-solubility, biocompatibility and environmental friendliness, and have shown potential applications in diverse fields. As an indispensable branch of nonconventional luminescent materials, polysiloxanes which consist of electron-rich auxochromic groups, have exhibited outstanding photophysical properties due to the unique silicon atom. The flexible Si-O bonds benefit the aggregation, and the empty 3d orbitals of Si atom can generate coordination bonds like N → Si and O → Si, altering the electron delocalization of the material and improving the luminescent purity. Herein, we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives. With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions, the role of Si atoms played in the nonconventional luminophores is highlighted. This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing, biomedicine, lighting devices, etc.

In biological systems, molecular assembly primarily relies on the assistance of molecular chaperones. Inspired by nature, strategies like ‘chaperone-assisted assembly’ and ‘catalyzed assembly’ have been proposed towards the sophisticated control of molecular assembly. Nonetheless, significant challenges remain in the rational design of such systems, calling for a deep understanding of underlying principles. Herein, we demonstrate an artificial chaperone serves a dual role, i.e. catalyst in low dosages and inhibitor in high dosages, in regulating the supramolecular polymerization of peptides. Low dosages of carboxymethyl cellulose, as the chaperones, catalyse the assembly of Aβ16-22 peptides into fibrils through multi-step phase separation, while high dosages trap the peptides into coacervate intermediates and therefore inhibit the fibrillation. Consequently, the quantity of chaperone does not follow the intuition that ‘more is better’ for catalyzing assembly, but instead has an optimal molar ratio. Investigation reveals that the interplay and evolution of electrostatic and hydrophobic interactions between chaperones and peptides are the keys to achieving these processes. This study provides insights into the multifaceted roles artificial chaperones may play in a dosage-dependent manner, and enriches the toolkit for efficient and controllable construction of complex assembly systems.