Cell Reports Physical Science最新文献

RNA secondary structures comprise double-stranded (ds) and single-stranded (ss) regions. Antisense peptide nucleic acids (asPNAs) enable the targeting of ssRNAs and weakly formed dsRNAs. Nucleobase-modified dsRNA-binding PNAs (dbPNAs) allow for dsRNA targeting. A programmable RNA-structure-specific targeting strategy is needed for the simultaneous recognition of dsRNAs and ssRNAs. Here, we report on combining dbPNAs and asPNAs (designated as daPNAs) for the targeting of dsRNA-ssRNA junctions. Our data suggest that combining traditional asPNA (with a 4-letter code: T, C, A, and G) and dbPNA (with a 4-letter code: T or s²U, L, Q, and E) scaffolds facilitates RNA-structure-specific tight binding (nM to μM). We further apply our daPNAs in substrate-specific inhibition of Dicer acting on precursor miRNA (pre-miR)-198 in a cell-free assay and regulating ribosomal frameshifting induced by model hairpins in both cell-free and cell culture assays. daPNAs would be a useful platform for developing chemical probes and therapeutic ligands targeting RNA.

Diabetes is an inflammatory disease that usually causes chronic wounds for which no satisfactory therapies currently exist. Here we report a physical approach using a cold atmospheric plasma (CAP) to target diabetic wounds locally for regulating the inflammatory phase of the wounds. In this paper, a comprehensive analysis of inflammatory factors combined with physical investigations of the helium plasma jet characteristics is conducted. The physical and biological safety and clinical application prospects of the CAP jet for the human body are also analyzed. The results demonstrate for the first time that CAP therapy can stimulate the body’s own inflammatory regulation function to achieve a normal state, rather than excessively interfere in a single target. This involves the inhibition of pro-inflammatory factors in the onset subphase and the promotion of anti-inflammatory factors in the subsequent resolution subphase. This research contributes to the development of highly effective and safe topical therapies to promote chronic wound healing.

Commercial lithium-ion battery electrodes today are manufactured by slurry casting active material powder onto a metal current collector foil. This manufacturing process has become embedded over recent decades but limits commercial cell performance. This paper presents patterning of a monolithic active material sheet as an alternative to slurry casting. The concept is proven experimentally by laser drilling a pyrolytic graphite sheet to increase the gravimetric active material capacity from 10 mA h g⁻¹ to 450 mA h g⁻¹, when used as a negative lithium-intercalation electrode. Cell-level calculations show that, without changing the chemistry, a pyrolytic graphite sheet electrode with a hexagonal array of 5 μm diameter, 20 μm pitch channels could increase the gravimetric energy density of a LGM50 cell by 22% to 322 W h kg⁻¹. By moving beyond slurry casting, patterned monolithic electrodes could enable batteries with lower cost, reduced energy intensity, and enhanced performance.

Dense bioceramics feature hierarchical microstructures with weak interfaces that endow them with strength, toughness, and structural functionalities. Conversely, most technical ceramics possess limited structural complexity and strong grain boundaries that restrict their toughness and functions. Here, we report a rational design strategy to fabricate ceramics with various bioinspired microstructural motifs, leading to strength, toughness, and locally varying properties. We employ magnetically assisted slip casting (MASC) for local orientations of alumina microplatelets and ultrafast high-temperature sintering (UHS) as a densifying method. We sequentially vary the slurry composition and sintering processes to attain high texture, relative density, and weak grain interfaces. We realize dense ceramics with horizontal, periodic, and graded motifs that exhibit direction- and site-specific properties, with flexural strengths of ∼290, 155, and 215 MPa, and fracture toughness of ∼7, 5, and 10 MPa·m^0.5, respectively. The strategy could be used to fabricate ceramic composites for tailorable local and bulk properties.

Recycling diverse waste plastics poses challenges due to complex sorting and processing, resulting in high costs and inefficiency. To tackle this, we present a metal-free catalytic sorting method for targeted deconstruction of polyester from post-consumer plastic waste, encompassing textiles, plastic mixtures, and multilayer packaging materials. This method employs N-methylpiperidine, a tertiary amine catalyst in methanol, to depolymerize polyethylene terephthalate (PET). Operating under these conditions (160°C, 1 h), we achieve 100% yields of dimethyl terephthalate and ethylene glycol. This technique also effectively breaks down other polyesters, including polylactic acid, polycarbonate, and polybutylene terephthalate, yielding high-yield monomers at relatively low temperatures. Through comprehensive nuclear magnetic resonance (NMR) analysis, we propose that N-methylpiperidine’s role is in enhancing methanol nucleophilicity and activating PET’s ester bond. Our insights advance the chemical recycling of post-consumer plastic waste, offering a potentially simple and efficient path to closing the polyester production loop.

Fusicoccane diterpenoids, originating from fungi, plants, and bacteria, constitute a diverse natural product family featuring a 5-8-5 tricyclic framework. They were restricted to plant physiology in the past. However, fusicoccanes are presently at the forefront of biomedicine and are indispensable for probing 14-3-3 protein-protein interactions (PPIs). The need for material supply and scaffold diversification encouraged their study by the synthetic community. This review highlights the total synthetic works on fusicoccane diterpenoids published in the last 5 years. Key transformations including ring-closing metathesis, metal-catalyzed cross-coupling, and carbocyclization markedly enhanced synthetic efficiency and versatility. Recently identified biosynthetic transformations inspired innovative chemoenzymatic strategies. Investigation into the functional aspects of fusicoccanes should be the future direction to realize their therapeutic potential as general 14-3-3 PPI modulators.

Reed diffusers are widely used as an indoor scenting source, in which aromatic components are thought to have sleep-improving and anxiety-relieving effects. Nevertheless, it is crucial to consider the potential health impacts associated with certain components in aromatherapy. This study aims to comprehensively explore the impact of reed diffusers on indoor air quality. We analyze the composition of gas-phase volatile organic compounds (VOCs) based on emission tests of a typical reed diffuser in a full-scale chamber. The observed top three VOCs are linalool acetate, linalool, and α-pinene, with linalool acetate accounting for 31.4%–43.6% of the total at 25°C. A physics-based model is then developed to characterize VOC emissions from a reed diffuser, and the key transport parameters are determined. Independent experiments validate the reliability of model parameters. Computational fluid dynamics simulations further demonstrate that reed diffuser position significantly impacts VOC distribution, which is essential for sophisticated exposure assessment.

The photoactivation of electron donor-acceptor complexes is a useful tool for the generation of radical species in synthetic chemistry. However, alkene difunctionalization via catalytic donor-acceptor complexes remains less developed. Herein, we report a versatile catalytic photoactivation of an electron donor-acceptor complex platform for the difunctionalization of alkenes without a need for precious transition metal catalysts or synthetically elaborate organic dyes. By taking advantage of the visible light potential of aggregates between triarylamines and S-fluoromethyldiaryl sulfonium salts, photoinduced single-electron transfer is initiated to generate a stable radical cation, which acts as an endogenous oxidant to convert the radical addition intermediate into a cationic species. Subsequent N-nucleophilic addition enables the difunctionalization of styrenes. This general photocatalyst-free protocol is applied to fluoroalkylative sulfonamidation, amidation, hydrazidation, azidation, and anilination reactions under mild conditions.

Exposome science captures the totality of environmental drivers of human health. However, the comprehensive determination of numerous exogenous and endogenous compounds remains extremely challenging, restricting the purpose of exposome science to characterize both external and internal exposure. Herein, we develop hierarchically porous polymers of intrinsic microporosity (HPPIM) films to achieve ultrahigh-throughput determination of exo/endogenous molecules in biological fluids. The film’s porous properties, including three-stage micro-submicro-nanometer architectures, large specific surface area, and appropriate pore geometry and organophilicity enable fast molecular transport and high trapping capability, therefore achieving ultrahigh-throughput determination of exo/endogenous molecules in biological fluids. Further application in a small-scale cancer study demonstrates the unique advantages of HPPIM films over existing techniques, including broad coverage of analytes, satisfactory trapping efficiency, low-volume demand on specimens, high simplicity and reusability, and drastically reduced financial cost. Our work demonstrates the great potential of HPPIM for advancing exposome science from concept to utility.

Proteolysis-targeting chimeras (PROTACs) are a powerful approach for targeted protein degradation. One of the current bottlenecks for developing PROTACs is the lack of an operationally simple linkerology to rapidly construct PROTACs with various linkers. The classic convergent synthesis strategy by coupling pre-assembled linkers with two ligands stepwise commonly needs at least four steps to give the final target PROTACs, which results in low total yields with long reaction times (several days) and tedious operations. Here, we develop an efficient photocatalytic one-pot linkerology for the rapid coupling of analogs of PROTACs containing triazole-based linkers without any linker-pre-assembled procedure. The reaction was completed within 4 h with up to 95% yields at room temperature. Easily accessible cyclic ethers are directly used as linker precursors to furnish the one-pot fashion, including alkenyl, polyethylene glycol (PEG), ketone, and cyclohexane chains. The study provides a highly efficient, step-economic, operationally simple, and environmentally friendly one-pot linkerology for PROTAC drug discovery.