ACS Publications最新文献

Lipid membrane phase separation, which is a thermodynamic physical process, has attracted attention as a dynamic function of cellular interfaces. As membrane tension influences the phase separation of cellular membranes under isothermal conditions, it is essential to clarify the physicochemical mechanism involved. Living cells contain numerous macromolecules that can generate osmotic pressure across the membrane due to the semipermeable nature of the lipid bilayer. In this research, we examined how macromolecular surroundings and the transmembrane osmotic pressure influence membrane phase separation, utilizing model membranes like giant lipid vesicles. We generated osmotic pressure across the membrane using dextran (molecular weights 40,000 and 200,000) and polyethylene glycol (molecular weight 6,000) as model macromolecules. Microscopic observations represented the changes in the percentage of phase-separated vesicles and miscibility temperature caused by osmotic tension, indicating that macromolecular surroundings tend to suppress membrane phase separation, while macromolecular osmotic pressure across the membrane markedly induces phase separation. Lipid membrane phase separation can be regulated by the macromolecular concentration and osmotic pressure across the membrane. This finding offers new insights into the formation and regulation of membrane domains within the macromolecularly crowded environments of living cells.

The asymmetric total synthesis of (+)-subincanadine F has been achieved in only 9 steps from commercial tryptamine. A key step involves an Organo-SOMO-catalyzed α-arylation of aldehydes to construct the azepino[4,5-b]indole core. Finally, a subsequent intramolecular aza-Michael addition process leads to the formation of the 1-azabicyclo[4.3.1]decane framework. In addition, this Organo-SOMO catalytic strategy features a broad substrate scope, with diverse functionalized products afforded in generally moderate to good yields and good to excellent enantioselectivities.

1,2,4-Triazole is a ubiquitous heterocycle of significance for pharmaceuticals, materials, and ligand design. A convergent, atom-economical strategy for the construction of this important moiety has been developed, leveraging functionalized heteroaryl hydrazonimides and carbaldehydes via iodine-mediated oxidative annulation in an efficient, scalable, and metal-free manner, providing completely chemoselective 1H- or 2H-3,5-disubstituted-1,2,4-triazoles of relevance to separation science and medicinal chemistry. The twenty-nine-example substrate scope is highlighted by rapid access to sp²- and sp³-hybridized substituents through carbaldehyde selection. Diversely functionalized pyridyl- and heteroaryl components were incorporated through a hydrazonimide synthon with several examples having relevance to unsymmetric, soft-N-donor complexant scaffolds utilized in minor actinide extraction in support of improving the sustainability of the nuclear fuel cycle. Single-crystal X-ray diffraction experiments confirmed the presence of 1H- and 2H-tautomers. Density functional theory computations provided support of a proposed mechanistic hypothesis. Method optimization, substrate scope, scale-up experiments, and a preliminary reaction mechanism are reported herein.

The occurrence and accumulation of novel perfluoroalkyl and polyfluoroalkyl substances (PFAS) have emerged as a scientific concern in recent years. While numerous studies have identified elevated concentrations of certain emerging PFAS, the sources and environmental accumulation differences of many homologues remain insufficiently characterized. In this study, we employed suspect and nontarget screening to characterize both legacy and emerging PFAS across environmental matrices, including water, sediment, and soil, surrounding an industrial park with predominant perfluoroalkyl carboxylic acids (PFCAs) contamination. A total of 32 classes comprising 112 compounds were identified, including 80 emerging PFAS detected through the screening approach. In addition to PFCAs, emerging PFAS, including perfluoroalkyl ether carboxylic acids (PFECAs), perfluoroalkyl alcohols (PFAs), and PFA derivatives, were frequently detected in the study area, primarily in water and sediment samples. In contrast, the contamination profile was less complicated in soil samples, where PFCAs were the predominant homologues. The median total concentrations of target PFAS in water, sediment, and soil samples were 427 ng/L, 4.17 ng/g of dw, and 3.92 ng/g of dw, respectively. Predicted risk assessment further indicated that these emerging PFAS with high concentrations pose non-negligible risks to both ecological and human health, underscoring the need for further investigation into their potential impacts.

Fluoroethylene carbonate (FEC), as a key electrolyte component, has been extensively employed across diverse electrolyte systems owing to its excellent compatibility with different anode materials. However, its mechanistic role on the cathode side remains under debate due to the strong electron-withdrawing nature of the fluorine incorporation. Here, we demonstrate that lithium difluoro(oxalate)borate (LiDFOB) can effectively trigger the latent cathode-side functionality of FEC through a rationally designed dual-additive electrolyte. At the LiNi_0.9Co_0.05Mn_0.05O₂ cathode, oxidative cleavage of LiDFOB generates BOF₂ intermediates that activate FEC and direct its decomposition toward LiF and B-O/B-F-rich inorganic species, constructing a compact and resilient cathode-electrolyte interphase (CEI). Simultaneously, the coupled reduction of FEC and DFOB^- at the lithium metal anode yields a boron-rich, LiF-enriched solid electrolyte interphase (SEI) that enhances interfacial compatibility and suppresses dendrite growth. These LiDFOB-enabled, FEC-mediated interfacial pathways significantly improve ion transport and durability, delivering 73.4% capacity retention of Li||NCM9055 full cells after 1000 cycles at 4.7 V, versus 55.1% for the base electrolyte.

Onychomycosis is a common fungal nail infection, causing nail thickening and discoloration. Tavaborole, a topical antifungal, has fewer side effects but requires long treatment periods and often results in low cure rates. In this study, we developed a Zn²⁺-driven tavaborole-adenosine (AT-Zn²⁺) hydrogel to improve its therapeutic effect. The hydrogel enhanced tavaborole's solubility, drug loading, and antifungal activity. Characterization by nuclear magnetic resonance (NMR), ultraviolet-visible (UV-vis) spectroscopy, and transmission electron microscopy (TEM) confirmed its successful synthesis and nanofiber structure. In vitro release tests showed that about 65% of tavaborole was released in PBS at pH 5.5 over 24 h, indicating pH-sensitive drug release for targeted therapy. Permeation studies using a bovine hoof model showed effective tavaborole penetration through keratinized tissues with a steady-state flux of 162 μg/cm²/h. The AT-Zn²⁺ hydrogel demonstrated lower minimum inhibitory concentrations (MICs) for C. albicans (0.00156 mM) and A. fumigatus (0.025 mM) compared to those of tavaborole alone. In a bovine onychomycosis model, the hydrogel showed stronger antifungal effects than the tavaborole solution. Cytotoxicity assays on RAW 264.7 cells indicated good biocompatibility with >85% cell viability. These findings suggest that the AT-Zn²⁺ hydrogel holds significant potential as a clinically effective antifungal agent.

Electrochemical nitrogen reduction reaction (eNRR) under ambient conditions offers a promising route for ammonia synthesis, although it currently suffers from slow kinetics and competing hydrogen evolution. Transition metal nitrides (TMNs) enable efficient nitrogen activation via the Mars-van Krevelen mechanism; however, effectively suppressing nitrogen leaching under electrochemical conditions remains challenging. Here, we report a nanostructured ruthenium nitride (RuN) catalyst synthesized via magnetron sputtering, demonstrating its application for eNRR for the first time. Structural characterization confirms a zincblende-like RuN phase, while surface properties (i.e., roughness and wettability) are tuned by the deposition duration. The optimal catalyst achieved an ammonia yield of 3.0 × 10^-10 mol cm^-2 s^-1 at -0.3 V vs RHE and a Faradaic efficiency of 6.1% at -0.1 V vs RHE in a 0.1 mol L^-1 KOH electrolyte, surpassing most reported ambient TMN catalysts. These findings underscore the promise of metal nitride-based electrocatalysts and provide insights into the rational design of next-generation catalysts for sustainable nitrogen fixation.

The electrochemical nitrate reduction to ammonia (NO₃RR) has garnered considerable interest as a highly promising route for value-added nitrate conversion. However, the efficiency of NO₃RR is often limited by the inadequate supply of active hydrogen species (H*) and their preferential consumption via the competing hydrogen evolution reaction (HER), both of which stem from the lack of precise management of H*. Herein, we report a rationally designed ternary catalyst Pt@ZIF@Cu to achieve precise control and targeted utilization of H*. The spatially separated Pt and Cu sites serve as independent centers for H* generation and consumption, respectively. A ZIF layer is introduced as a hydrogen buffer, facilitating the efficient migration of H* from Pt sites to Cu sites with a reduced energy barrier, which ultimately enhances the NO₃RR performance on the Cu surface while simultaneously suppressing HER at the Pt sites. The ternary Pt@ZIF@Cu exhibits superior NO₃RR performance with an ammonia yield rate of up to 4.6 mmol h^-1 mg_cat^-1 at -0.8 V (vs RHE) through meticulous H* management. Furthermore, it demonstrates enhanced performance (8.34 mmol h^-1 mg_cat^-1) in a membrane electrode assembly (MEA) under ampere-level current densities, and enables the convenient preparation of high-purity solid ammonium products via Ar-stripping.

Aqueous zinc-iodine (Zn-I₂) batteries, owing to their compelling combination of environmental friendliness, cost-effectiveness, and enhanced safety features, are regarded as promising candidates for large-scale energy storage systems. Nevertheless, the limited I₂/2I^- two-electron redox chemistry and nonuniform Zn deposition critically impair the energy density and cycling stability of aqueous Zn-I₂ batteries, hindering their practical deployment. Herein, multifunctional cyclohexylamine hydrochloride (CHAH) additive is introduced into the ZnSO₄ electrolyte, which synergistically enables a dendrite-free Zn anode for extended cyclability and simultaneously activates a stable four-electron 2I⁺/I₂/2I^- redox chemistry at the I₂ cathode. Combined experimental characterization and theoretical calculations reveal that the cyclohexylamine (CHA) reconstructs the Zn²⁺ solvation structure by displacing active H₂O, while fostering a nitrogen-rich solid electrolyte interphase on the Zn anode at the same time. It suppresses parasitic reactions and enables excellent Zn plating/stripping cycling for 2150 h at 1 mA cm^-2/1 mAh cm^-2. Furthermore, nucleophilic amine groups in CHA act synergistically with Cl^- to coordinate I⁺ by forming (2CHA)ICl, which improves four-electron 2I⁺/I₂/2I^- redox kinetics and achieves exceptional Zn-I₂ battery performances (256.3 mAh g^-1 at 10 A g^-1). This bilateral nitrogen interface chemistry mechanism offers key insights into the development of high-performance Zn-I₂ batteries.

RNA interference (RNAi) represents a promising approach for insect pest management; however, its application in Lepidoptera is constrained by double-stranded RNA (dsRNA) instability, limited cellular uptake, and inefficient RNAi machinery. In this study, we developed a bacteriophage MS2 virus-like particle (VLP)-based delivery platform for hairpin RNA (hpRNA) targeting the invasive pest Hyphantria cunea. When expressed in Escherichia coli, MS2 VLPs efficiently encapsulate hpRNA, markedly enhancing its resistance to nuclease activity and environmental degradation. In addition, surface display of the HIV trans-activator of transcription (TAT) peptide on MS2 VLPs significantly improved cellular internalization of hpRNA, resulting in robust RNAi-mediated gene silencing in H. cunea at low hpRNA doses. Importantly, no adverse effects were detected in three nontarget organisms: Clostera restitura, Plagiodera versicolora, and the parasitoid Chouioia cunea. Together, these results demonstrate that the MS2-hpRNA system represents a scalable, effective, and environmentally safe strategy for RNA-based pest control.