Advanced Science最新文献

Specific ions can be intercalated into functional materials using the electrolyte gating technique, which has been widely used to regulate channel conductance in transistors and develop low-power neuromorphic devices. However, in these devices, fundamental exploration of ion intercalation-induced structural phase transitions remains largely overlooked and rarely explored. Here, the lithium-based electrolyte gating technique is used to probe the collective interactions between ions, lattices, and electrons in a van der Waals ferroelectric semiconductor α-In₂Se₃. Using a polymer electrolyte as the lithium-ion reservoir and α-In₂Se₃ as the channel material, the intercalated lithium concentration via a gate electric field is modulated. This manipulation drives a phase transition in α-In₂Se₃ from a ferroelectric semiconductor to a dirty metal and finally to a metal, accompanied by a structural transformation. Concurrently, with enhanced intercalation, the ferroelectric hysteresis window progressively narrows and eventually disappears, indicating the evolution from switchable to non-switchable polarization. This study represents a promising platform for the artificial construction of correlated material systems, enabling a systematic investigation into the interaction of ferroelectricity and electronic conduction using ion intercalation.

Elastocaloric polymers, whose performance typically relies on phase transformation between amorphous chains and crystalline domains, offer a promising alternative to traditional refrigeration technologies. While engineering polymer-network architecture has shown the potential to boost elastocaloric performance, the role of topological defects remains unexplored despite their prevalence in real polymers. This study reports a defect-engineering approach in end-linked star polymers (ELSPs) that enables an adiabatic temperature change of up to 8.14 ± 1.76 °C at an ambient temperature above 65 °C, showing an enhancement of 39% compared to ELSPs with negligible defects. This defect-regulated solid-state cooling is attributed to two competing effects of dangling-chain defects on strain-induced crystallization (SIC) and temperature-induced crystallization (TIC), synergistically regulating the adiabatic temperature change. Specifically, increasing dangling-chain defects monotonically lowers ELSPs' mechanical performance at high temperatures due to suppressed SIC, but nonmonotonically impacts the mechanical performance at low temperatures due to the competition between suppressed SIC and enhanced TIC.

Colorectal cancer liver metastasis (CRLM) involves complex molecular mechanisms. By integrating The Cancer Genome Atlas (TCGA) data and employing Cox regression, Weighted Gene Co-expression Network Analysis (WGCNA), and single-cell RNA sequencing, this study identifies RNF32 as a key gene linking poor prognosis to metastasis. Functional assays demonstrate that RNF32 promotes tumor cell proliferation, invasion, and epithelial-mesenchymal transition (EMT) in vitro, and drives tumor growth and liver metastasis in vivo. Mechanistically, RNF32 catalyzes K48-linked ubiquitination at the K60 site of GSK3β, stabilizing β-catenin and activating the Wnt signaling pathway, thereby upregulating CCL2. Mass cytometry and other experiments further reveal that RNF32 recruits SPP1⁺ macrophages via CCL2 to remodel the metastatic niche, a process dependent on the CCR2/FABP1/PPARG axis. Macrophage depletion abrogates metastasis, while the FABP1 inhibitor orlistat reverses SPP1 upregulation in macrophages. Moreover, SPP1⁺ macrophages interact with tumor cell CD44, synergizing with RNF32 to enhance cancer stemness via Wnt signaling. Importantly, virtual screening identifies indole-3-acetic acid (IAA) as an RNF32 inhibitor that suppresses liver metastasis and reverses immunosuppression in vivo. This study establishes RNF32 as a dual-functional driver of metastasis and proposes IAA as a promising therapeutic agent, offering new hope for targeting both tumor-intrinsic EMT and the immune microenvironment in CRC liver metastasis.

The development of mechano-responsive room-temperature phosphorescent (RTP) materials with reversibility and durable memory stress-recording capability remains a critical challenge, particularly under extreme operational conditions where covalent bond-dependent systems often suffer from irreversible degradation. Herein, a hydrogen-bond-induced dynamic supramolecular confinement framework is constructed to achieve cyclodextrin-trapped carbon nanodots (CNDs) with reversible and memorable mechano-responsive RTP. Mechanical stress disrupts the metastable hydrogen-bond network and weakens phosphorescence via enhanced non-radiative decay of triplet excitons. Remarkably, the system exhibits a recovery of RTP intensity through ultrasonic reconstruction of the rigid cyclodextrin matrix. When deployed in aerospace structural health monitoring, the CND-embedded film visualizes stress distribution in wings under sudden stress events through RTP weakening. This work establishes a non-destructive monitoring paradigm for an extreme aerospace environment.

Biotin is an essential cofactor for central metabolic pathways in all organisms. The newly identified BioE-BioL module constitutes a new biotin biosynthesis pathway, yet its mechanisms remain incompletely characterized. Phylogenetic analyses reveal widespread distribution of the bioE, including obligate intracellular Chlamydia, despite the genus lacking its cognate repressor BioL. Structural modeling and biochemical characterization of Elizabethkingia meningoseptica BioE (EmBioE) and Chlamydia psittaci BioE (CpBioE) reveal a conserved diiron oxygenase catalytic core but divergent oligomeric structure state and substrate preferences. EmBioE forms a homodimer capable of recognizing both long-chain acyl-ACP and acyl-CoA, whereas CpBioE functions as a monomer restricted to acyl-ACP. Heterologous overexpression of EmBioE, but not CpBioE, induces a fitness cost in Escherichia coli. Genetic ablation of bioL leads to biotin auxotrophy in Elizabethkingia, mainly attributed to the unregulated EmBioE pathway exhausting long-chain fatty acids and depleting ATP/SAM metabolic pools. This highlights EmBioE's biphasic role: initiating biotin synthesis to sustain viability while inducing stress upon overexpression, requiring BioL regulation for metabolic homeostasis. Virtual screening uncovers compound 466982 as a selective BioE inhibitor with dose-dependent antibacterial activity against Elizabethkingia. Balanced BioE expression is critical for bacterial viability, positioning BioE as a druggable target for antimicrobial discovery against multidrug-resistant pathogens.

Real-time observation of molten droplet-driven crystal growth provides an unprecedented in situ window into the formation of atomically thin transition metal dichalcogenides (TMDCs). Materials such as MoS₂ and WS₂ exhibit remarkable optoelectronic properties arising from their monolayer structures, enabling advanced applications that exploit valley degrees of freedom. Among various synthetic approaches, vapor-liquid-solid (VLS) growth from a low-melting molten source containing alkali, transition metal, halide, and oxygen atoms has proven highly effective for producing large single-crystal monolayer TMDCs, while also yielding distinct growth regimes including molten particle-driven nanoribbon formation. A chemical vapor deposition method is recently developed that integrates VLS growth with the spatial confinement provided by a substrate-stacked microreactor; however, the precise role of confinement and droplet dynamics remains unclear. Here, in situ the VLS growth of TMDCs inside such microreactors is directly captured using an infrared heating furnace. The microreactor, formed by sealing a transparent sapphire substrate with a Na₂WO₄-coated SiO₂/Si wafer, enables continuous observation of growth mode transitions governed by the balance of sulfur and Na₂WO₄ supply. The findings demonstrate that fine control over precursor supply rates is essential for engineering the size, morphology, and crystallinity of monolayer TMDCs in the VLS regime.

Screening and identification of novel small-molecule have proven to be effective strategies in addressing the growing threat of cancer to human health. In this study, a novel natural terpenoid compound, Halorotetin B, is identified from the edible ascidian Halocynthia roretzi. Halorotetin B is shown to significantly inhibit tumor growth both in vitro and in vivo. Mechanistically, the E2 ubiquitin-conjugating enzyme C (UBE2C) is identified as a direct binding target of Halorotetin B through a combination of the peptide-centric local stability assay and the omics-based target enrichment and ranking. Further investigations reveal that Halorotetin B binding to UBE2C induced M phase cell cycle arrest by inhibiting the ubiquitin-mediated degradation of key cell cycle regulators, including cyclin B1 and securin, ultimately leading to tumor cell senescence. These findings suggest that Halorotetin B, as a novel cell cycle inhibitor targeting UBE2C, holds strong potential for development into ascidian-derived therapeutics for cancer treatment.

Transition metal (i.e., Mn, Fe, Cr) and chalcogen (Se) substituents are introduced into single-crystalline NiPS₃, and the evolution of the two emergent quasi-particle excitations characteristic to the XXZ correlated antiferromagnetism of NiPS₃ (i.e., spin orbit entangled exciton (SOX) and two-magnon scattering (2M )) are investigated as functions of substituent concentration through comprehensive room- and low-temperature photoluminescence (PL) and Raman spectroscopy studies. These findings are further correlated with the magnetic properties of the same set of compounds reported in prior studies. The work revealed that the SOX emission intensities and linewidths are mainly controlled by the magnetic anisotropy and spin orientations, and are strongly suppressed by the introduction of substituents. The suppression depends on the type of substituent, with Fe affecting the SOX emission more than Mn and Cr. The 2 m scattering is linked to short-range correlations and exhibits greater resiliency against metal atom substitution. While the 2M  peak at low temperature gets suppressed and red-shifted in frequency with increasing concentrations of all the substituents, Fe induces the weakest suppression compared to all other substituents. Altogether, these findings revealed the introduction of substituents as a powerful route to control the emergent collective excitations in NiPS₃ and mixed-MPX₃ materials.

Catalytic DNA circuits hold significant promise for nucleic-acid-based diagnostics, yet they remain hindered by slow reaction kinetics and the non-universal nature of one-pot approaches. Here, a universal catalytic DNA circuits termed TACTIC (Thermus thermophilus Argonaute (TtAgo) protein-driven autocatalytic circuit) is developed for one-pot detection of DNA and RNA in multiple clinical samples. TACTIC employs the heat-activated cleavage activity of TtAgo to accelerate reaction kinetics of rolling circle amplification (RCA) by producing an efficient circular template with Gibbs free energy approaching zero at 70. Combined with TtAgo cleavage-mediated explosive regeneration and accumulation of target mimics, an autocatalytic positive-feedback circuit is successfully constructed for universal and sensitive detection of nucleic acid biomarkers. Efficient TACTIC is developed by increasing 381% amplification efficiency and achieved detection sensitivity at the attomolar (aM) level. TACTIC enables rapid one-pot detection of bacterial DNA, mutant mRNA, and four extracellular vesicle-derived miRNAs (EV miRNAs) within 30 min. Integrated with machine learning, the distinct expression patterns of four EV miRNAs across different biofluids are accurately profiled, and machine learning-driven diagnostic and staging models for breast cancer are established within a clinical cohort. TACTIC offers new insights for advancing higher-order catalytic circuits and expanding the toolbox for accurate nucleic acid detection.

Strongly alkaline electrolytes are typically used for electrochemical 5-hydroxymethylfurfural oxidation (HMFOR) to selective 2,5-furandicarboxylic acid (FDCA) production, despite HMF degradation. Although HMF remains stable in weakly alkaline media, slow kinetics due to limited OH^- concentration hinder active FDCA formation. Herein, unlike the CuO or NiOOH catalyst, significantly improved direct aldehyde oxidation is demonstrated via the utilization of adsorbed OH (^*OH) on the CuO/NiOOH interface surface, enabling complete conversion to FDCA even at mild pH. Operando measurements reveal that the CuO/NiOOH interface serves as a synergistic active site: Cu sites enhance ^*OH adsorption and utilization, while Ni sites promote HMF dehydrogenation through rapid Ni(OH)₂/NiOOH redox cycling. The synergistic effect promotes highly selective FDCA production while preventing premature desorption of intermediates, which leads to outperforming activity compared with individual CuO and Ni(OH)₂. The interface-enriched CuO@NiOOH catalyst delivers >95% FDCA yield and Faradaic efficiency, and maintains long-term stability for 32.8 h under large-volume operation, owing to the enhanced HMF stability at pH 12. Water structure investigation further supports that the electrolyte microenvironment significantly affects HMFOR kinetics alongside the intrinsic activity of the interface. These insights provide a strategy for designing catalysts capable of efficient biomass-to-FDCA conversion across a broader pH range.