Science China Chemistry最新文献

Cellular forces critically regulate physiology and pathology—including cell shape, proliferation, migration, and immune responses. However, conventional mechanosensing techniques lack the spatial resolution and non-invasiveness needed to monitor these forces in living cells in real time. DNA nanotechnology overcomes these limitations through programmable design, piconewton force sensitivity, and inherent biocompatibility, enabling transformative platforms for next-generation mechanical sensors. This review synthesizes a decade of progress in DNA-based molecular force sensors, examining their structural designs, mechanotransduction mechanisms, and applications in force mapping, super-resolution imaging, and dynamic tracking at membrane receptors, extracellular microenvironments, and intercellular junctions. We further highlight how these advances will catalyze mechanopharmacology and clinical diagnostics via high-throughput mechanoreceptor screening and mechanoresponsive drug delivery systems.

Antisense oligonucleotides (ASOs) hold considerable promise for cancer gene therapy through targeted mRNA degradation. However, their biomedical application is hindered by inefficient delivery and limited visualization of biodistribution. Herein, we report a novel traceable afterglow nanoparticle platform for PLK1-targeted ASO delivery, representing the first reported integration of autofluorescence-free afterglow imaging with antisense therapeutics to enable non-invasive monitoring. Afterglow nanoparticle was assembled via nanoprecipitation of afterglow molecules (triple-anthracene derivatives) with surfactants, followed by polyethylenimine functionalization to enable ASO loading through electrostatic interactions, resulting in uniform nanoparticles with a favorable size distribution and high loading efficiency. In vitro evaluations revealed efficient cellular uptake, effective lysosomal escape and pronounced PLK1 silencing with substantial mRNA and protein downregulation, leading to marked induction of apoptosis in HeLa cells compared to free ASO. In vivo afterglow imaging demonstrated preferential tumor accumulation via the enhanced permeability and retention effect, with high signal-to-background ratios. In HeLa xenograft models, afterglow nanoparticle-mediated ASO delivery induced substantial tumor growth inhibition and widespread apoptosis, without detectable systemic toxicity as indicated by stable body weights and unremarkable organ histology. These findings highlight the potential of afterglow nanoparticles as a versatile platform for imaging-guided gene therapy, providing new avenues for enhanced precision in nucleic acid-based cancer treatments.

High-capacity and cost-effective sodium (Na) metal anode receives increasing attention for constructing high-energy-density metal batteries. However, the unstable solid electrolyte interphase (SEI) that forms on Na metal anodes drives detrimental dendrite growth and capacity fade, and its formation mechanisms remain poorly understood. Herein, an accelerated on-the-fly learning (AOFL) approach is introduced to uncover the mechanistic underpinnings of SEI formation. By combining conventional on-the-fly learning with similarity structure screening, AOFL achieves 71% faster simulations than ab initio molecular dynamics while maintaining comparable accuracy. The ClO₄⁻ decomposition forms Na₂O during the interfacial reaction simulation, while proton ion from 1,2-dimethoxyethane (DME) by reactive oxygen leads to NaOH formation, both of which are identified as critical inorganic SEI components. These insights afford theoretical guidance for elucidating SEI formation mechanisms and for the rational design of advanced electrolytes.

Electrocatalytic conversion of biomass-derived compounds and nitrate pollutants offers a promising route toward sustainable chemical synthesis and environmental remediation. In this work, a bifunctional NiO-NiCoP catalyst with a well-defined heterogeneous interface is synthesized via a low-temperature co-precipitation, annealing and phosphidation process to enable the coupled electrocatalytic 5-hydroxymethylfurfural oxidation reaction (HMFOR) and nitrate reduction reaction (NO₃⁻RR). X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), open-circuit potential (OCP), and in-situ electrochemical impedance spectroscopy (in-situ EIS) confirm the formation of the heterogeneous interface, which facilitates electron redistribution, enhances charge transfer, and optimizes reactant adsorption. The catalyst exhibits excellent HMFOR activity, achieving 99.46% HMF conversion, 97.23% 2,5-furandicarboxylic acid (FDCA) yield, and 97.62% Faradaic efficiency (FE) at 1.40 V vs. RHE. For NO₃⁻RR, nearly 100% FE and an NH₃ yield of 8.82 mg h⁻¹ cm⁻² are obtained at −0.40 V vs. RHE. In a paired HMFOR//NO₃⁻RR electrolyzer, the NiO-NiCoP catalyst demonstrates superior current density, product selectivity, and long-term stability compared to conventional oxygen evolution reaction//hydrogen evolution reaction (OER// HER) systems. At 1.60 V, the HMFOR//NO₃⁻RR system achieved a maximum HMF conversion of 95.84%, an FDCA yield of 94.83%, and a FE of 89.53%, while at 1.90 V, it reached a maximum NH₃ yield of 32.50 mg h⁻¹ cm⁻² with an FE of 94.63%. This study underscores the catalytic advantages of heterogeneous interface engineering and provides a viable strategy for integrated biomass valorization and nitrogen-cycle remediation.

Anchoring a molecular metal complex on a solid support is becoming the most fascinating field of catalysis, as it bridges homogeneous and heterogeneous catalysis. However, owing to the spatial confinement of surface chemistry in supported catalysts, they display an inevitable loss of activity and selectivity compared to the homogeneous counterparts. Here, we propose a strategy to construct swellable supported catalysts where active metal centers are located on a swellable support for enhanced performance, where the occurrence of spontaneous swelling in the reaction medium facilitates active site exposure and reactant diffusion. The key to the strategy involves simultaneous immobilization of Al-porphyrins and quaternary ammonium salts on swellable Merrifield resin, forming swellable bifunctional supported catalysts (SBSCs), which were characterized in the swollen state by polarization microscopy and X-ray photoelectron spectroscopy. Surprisingly, SBSCs displayed a record-high activity of 2540 g g⁻¹ h⁻¹ for the cycloaddition of CO₂/propylene oxide even under low catalyst loading (1.28 × 10⁻³ mol%, based on Al), significantly outperforming the non-swellable counterpart (~0 g g⁻¹ h⁻¹). Moreover, because of the heterogeneous attribute, the repeatable synthesis of colorless cyclic carbonate was realized for over 6 cycles without significant loss of activity. An in-depth understanding of reaction kinetics and mechanisms in SBSCs can be rationally analyzed owing to the high accessibility of active sites. This swellable-supported catalyst strategy is expected to pave the way for the design of next-generation heterogeneous catalysts.

Palladium (Pd) has exceptional H₂ adsorption capacity and has been used as an adsorptive filler in mixed matrix membranes (MMMs) to enhance H₂ separation performance. However, a high Pd loading (20 wt%–60 wt%) is impractical due to cost. In this study, highly dispersed Pd nanoclusters are confined within the channels of mesoporous silica nanoparticles (MSNs), largely improving Pd atom utilization for facilitating H₂ transport while greatly reducing Pd loading content. MMMs prepared by mixing Pd@MSN with polybenzimidazole matrix, corresponding to a very low Pd loading of 0.6 wt%–3.0 wt%, exhibit much improved H₂/CO₂ separation performance. Specifically, an MMM containing only 2.5 wt% Pd shows mixed-gas separation performance of 302.6 barrer of H₂ permeability and 16.3 of H₂/CO₂ selectivity at 120 °C, largely surpassing the latest 150 °C upper bound. Our work demonstrates the enormous potential for applying Pd-based MMMs in gas separation by reducing noble metal loading by nearly two orders of magnitude.

Conventional gel polymer electrolytes based on polymers such as poly(ethylene oxide) face inherent limitations in enhancing ionic conductivity and electrochemical stability. Introducing diverse functional groups into the polymer framework enables the precise modulation of its physicochemical properties, thereby influencing the performance of lithium metal batteries. Herein, an in situ dual-crosslinked gel polymer electrolyte based on polyester and polyamide is proposed. This design enables synergistic cation-anion regulation, facilitating continuous Li⁺ transport by abundant ester groups while anchoring the anions by N–H groups. The resulting gel polymer electrolyte exhibits a high ionic conductivity of 0.58 mS cm⁻¹ and an elevated Li⁺ transference number of 0.6. The assembled Li∥LiNi_0.8Mn_0.1Co_0.1O₂ coin cells achieve 400 cycles at 0.5 C and 300 cycles at 1 C. Furthermore, a 4-layer stacked Li∥LiNi_0.8Mn_0.1Co_0.1O₂ (active material mass loading of 26.7 mg cm⁻²) pouch cell in lean electrolyte conditions (1.7 g Ah⁻¹) is assembled and sustains 45 cycles without obvious decay. This study provides a strategy of synergistic cation-anion regulation in gel polymer electrolytes, offering insights for stable lithium metal batteries.

Since their discovery, aptamers have steadily gained recognition as versatile molecular probes, with their significance further underscored by their inclusion in IUPAC’s Top Ten Emerging Technologies in Chemistry in 2024. Generated through the in vitro selection process, these oligonucleotides combine high specificity, synthetic versatility, and structural adaptability, enabling diverse applications in diagnostics, biosensing, and targeted therapeutics. While early expectations positioned aptamers as direct competitors to antibodies, practical challenges—such as susceptibility to nucleases and limited functionality in complex biological environments—have prompted a strategic shift toward specialized applications. Recent innovations highlight their unique strengths, including electrochemical biosensing, integration with dynamic DNA networks for signal amplification, and targeting membrane proteins or intracellular molecules. Rather than directly replacing antibodies, aptamers are increasingly being utilized in areas where their structural flexibility and programmability provide distinct advantages. This review discusses recent advancements in aptamer selection and explores emerging applications that harness their unique capabilities. By analyzing the evolving landscape of aptamer-based technologies, we highlight key opportunities for further development and translation into practical bioanalytical and biomedical solutions.

Despite the rapid development of organic light-emitting diodes (OLEDs) in the field of displays, obtaining deep-blue OLEDs with high efficiency, small full-width at half-maximum (FWHM), and low efficiency roll-off is still a challenge. Herein, we report a new strategy to develop an efficient and narrow-band deep-blue emitter based on tetradentate Pt(II), labeled PtKW1; this approach involved increasing the ³LE character of the lowest triplet state (T₁) by extending the π conjugation in the carbazole moiety, followed by locking the N-heterocyclic carbene (NHC) and phenyl moiety with a six-membered alkyl ring, aiming to enhance the molecular rigidity. Satisfactorily, PtKW1 showed a low Huang-Rhys factor (S_M) value of 0.285 and an FWHM of only 18.4 nm in dichloromethane at room temperature. Furthermore, a PtKW1-doped exciplex host film exhibited a quantum efficiency of up to 99% and a short excited state lifetime of 3.17 μs. A PtKW1-doped deep-blue OLED achieved an FWHM of 26 nm, Commission Internationale de l’Eclairage (CIE) coordinates of (0.125, 0.189), a maximum luminescent brightness (L_max) of up to 41074 cd/m², and a maximum external quantum efficiency (EQE_max) of 27.4%, with a low-efficiency roll-off rate of only 1.46% at 1000 cd/m². This work provides new insights for designing robust, narrow-band tetradentate Pt(II) emitters to develop highly efficient and stable deep-blue OLEDs with low efficiency roll-off and high luminescence.