Wiley最新文献

Conjugated organic molecules with open-shell diradical character (y) possess two weakly paired electron spins interacting across their constituent π-systems. These materials provide fundamental insight into the nature of electron pairing, enabling the utilization of the spin degree of freedom within emerging technologies. However, materials systems that synergistically offer high modularity, tunable y, high chemical stability, and interrelated (opto)electronic functionalities remain limited. Here, we report the facile synthesis of donor-acceptor-donor diradicaloids comprised of a central electron-deficient 6,7,8,9-tetrachloro-[1,2,5]thiadiazolo[3,4-b]phenazine acceptor flanked by electron-rich thiophene-based donors. Nuclear magnetic resonance and electron paramagnetic resonance spectroscopies, and theoretical investigations that account for the multiconfigurational nature of these species, connect a narrowing of the singlet-triplet splitting (∆E_ST), extension of π-conjugation, and electronic correlations with the evolution of diradical character. These data demonstrate that the differences in structural, electronic, spin, magnetic, physicochemical, and transport properties of the materials can be modulated, while the inherent multireference nature of the electronic structure can be predicted using optimally tuned long-range corrected Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory. These insights enable facile access to a broader range of open-shell materials and facilitate the manipulation of important properties such as electronic structure, topology, exchange, and interrelated optoelectronic and transport functionalities.

Palladium hydride is a model system for studying metal-hydrogen interactions. Yet, its bulk electronic structure has proven difficult to directly probe, with most studies to date limited to surface-sensitive photoelectron spectroscopy approaches. This work reports the first in situ ambient-pressure hard X-ray photoelectron spectroscopy (AP-HAXPES) study of hydrogen incorporation in Pd thin films, providing direct access to bulk chemical and electronic information at elevated hydrogen pressures. Structural characterization by in situ X-ray diffraction and neutron reflectometry under comparable conditions establishes a direct correlation between hydrogen loading, lattice expansion, and electronic modifications. Comparison with density functional theory (DFT) reveals how hydrogen stoichiometry and site occupancy govern the density of occupied states near the Fermi level. These results resolve long-standing questions regarding PdH and establish AP-HAXPES as a powerful tool for probing the bulk electronic structure of metal hydrides under realistic conditions.

Photothermal effect using mild light irradiation has emerged as an interesting strategy in modern synthetic chemistry due to its rapid reaction with high selectivity and spatiotemporal control over conventional heating. However, applying photothermal conversion to carry out organic reactions efficiently using carbon nanomaterials remained largely uncharted. To address this, herein, we report for the first time, graphene oxide (GO) as the photothermal agent to perform ring-closing metathesis (RCM) under 940 nm NIR LED light, as well as solar simulator and natural sunlight, using Grubbs-II catalyst to rapidly synthesize dihydro-pyrroles in high yield with excellent GO recyclability. Theoretical calculation unveiled that this photothermal RCM efficiency originated from the cumulative synergy between substrate-GO absorption energy, activation barrier, and nonradiative relaxation rate which emerged as the predominant contributor for the overall reaction outcome. The RCM product can be further functionalized through Pd-catalyzed Heck coupling to forge various fluorophores for efficient imaging of endoplasmic reticulum (ER), mitochondria, and Golgi apparatus (GA) in HCT-116 colon cancer cells. This GO-mediated photothermal RCM can open a new direction toward synthesizing complex organic molecules with ease and high yield for biomedical applications.

While smoking is a known risk factor for fractures, its precise mechanisms among older women, particularly involving physical function, bone density, and bone microarchitecture, remain incompletely understood. This prospective cohort study included 3,024 community-dwelling Swedish women aged 75-80 years, followed for a median of 7.3 years. Participants were categorized as current smokers (n = 157), former smokers (n = 1,343), and never smokers (n = 1,524). Radiographically verified fractures and all-cause mortality were assessed. Cox proportional hazards models, mediation analyses, and competing risk models evaluated associations between smoking status, fracture risk, and potential mediators, including walking speed and total volumetric bone mineral density (vBMD). Current smokers had significantly increased risks of any fracture (HR 1.35, 95% CI 1.04-1.75) and hip fracture (HR 2.23, 95% CI 1.43-3.49) compared to never smokers. Former smokers exhibited intermediate risks. Women who had ceased smoking for 5-10 years had substantially lower fracture risk than current smokers. Each year since cessation conferred an ~1% relative reduction in fracture and mortality risk. Mediation analyses revealed significant indirect effects via slower walking speed (18-28%) and lower total vBMD, suggesting these factors are key contributors to fracture risk. Importantly, competing risk models confirmed elevated fracture risk in smokers even after accounting for increased mortality. These findings demonstrate that smoking is associated with increased fracture risk in older women, partly through impairments in physical function and vBMD. Smoking cessation appears to confer meaningful skeletal benefits, indicating a need for integrated strategies targeting both behaviour change and physical function to reduce fracture burden in aging populations.

Designing coatings with a wide spectrum of functions such as self-healing, liquid repellency, anticorrosion, and a high level of mechanical robustness is crucial in engineering applications. However, simultaneously meeting two or more conflicting requirements remains a challenge. In this work, a holistic, skin-inspired tri-layer coating is proposed to resolve the conflicting requirements of self-healing, liquid repellency, and corrosion resistance in hydrophilic polymer materials. The rational design of multiple gradients in self-healing, wetting, and strength endows a sustained liquid repellency, corrosion resistance, and self-healing even under harsh environments, as well as strong adhesion with metal substrate. The skin-inspired tri-layer coating exhibits complete self-healing even in harsh aqueous environments, owing to the synergistic interaction between layers. The tri-layer structure consists of a hydrophobic epidermis-like barrier layer, a hydrophilic self-healing polymer middle layer, and a micro-arc oxidation porous base layer that provide strong interfacial adhesion and mechanical support. The hydrophilic polymer layer, composed of polyvinyl alcohol and tannic acid, rapidly repairs damaged coating regions through hydrogen bonding and diffusion, triggered by water molecules. Meanwhile, the hydrophobic outer layer acts as a sealing barrier, limiting excessive diffusion of the hydrophilic polymer. Such an integrated skin-inspired coating strategy provides new insights into design and manufacturing multifunctional polymeric coatings to tackle the critical challenges in a variety of engineering services.

Electrocatalytic carbon dioxide (CO₂) reduction reaction (CO₂RR) to valuable liquid fuels offers a promising solution for global warming. The challenges of low CO₂ delivery and poor product selectivity hinder the practical application of CO₂RR technology. This study proposes electrocatalytic CO₂-to-formic acid (HCOOH) conversion using a cypress-like carbonic anhydrase/antimony-decorated bismuth (CA/Sb-decorated Bi) biohybrid. The carbonic anhydrase (CA) as CO₂ shuttle can enrich CO₂ concentration on the electrode surface, accelerating the CO₂ hydration kinetics and reaction rate. Density functional theory (DFT) calculations indicate that the introduction of Sb can alter the adsorption energy of H* and HCOO*, which is beneficial for CO₂RR to form HCOOH. Besides, CA/Sb-decorated Bi biohybrid can suppress competitive hydrogen evolution reactions (HER). Consequently, the CA/Sb-decorated Bi biohybrid achieves the Faradaic efficiency of 93.41% and 100% selectivity for HCOOH at -1.3 V. This work demonstrates the application potential of enzyme modification and metal decorating in CO₂RR for the development of sustainable energy.

Magnetization switching plays a key role for high-density, ultrafast, non-volatile spin-based devices. Although domain modulation via interfacial or thickness effects has been studied, the impact of fabrication structures on switching remains underexplored. Here, we investigate geometric and boundary effects on magnetotransport in patterned SrRuO₃ (SRO) films made via advanced micro/nanoscale processing. Channel miniaturization to one micrometer hugely increases saturation field from 9 to 32.5 kOe. Edge magnetic anisotropy induces pronounced multi-step magnetization switching, validated by micromagnetic simulations. Non-volatile electrical modulation of magnetization is achieved in multiferroic films: 10 nm SRO exhibits a voltage-tunable high-field magnetoresistance (MR); 7.8 nm SRO shows a suppressed multi-step switching alongside a high-field modulation of MR; particularly, 2.6 nm SRO has a coercive field altered from 21.6 to 12.1 kOe by ±9 V. These results stem from ferroelectric polarization and antiferromagnetism. This switching process, regulated by geometry and external bias, enables advances in multistate memory and artificial synapses.

Wireless flow sensing technologies have attracted significant interest for enabling safe operation and performance optimization in gas-liquid two-phase flow systems. Nevertheless, the real-time quantitative monitoring of liquid flow rates without phase separation remains a considerable challenge. In this work, we present a wireless, self-powered, and real-time quantitative liquid flow measurement system utilizing a gas-liquid electricity generator (GLEG) based on the triboelectric effect. The GLEG features a dual-electrode configuration consisting of an external ring electrode and an internal porous electrode, which efficiently harvests mechanical energy from high-speed continuous gas-liquid mixed flow and converts it into usable electrical power. By integrating a sensor circuit board with a power regulation module, a microcontroller unit, and wireless transmission components, we demonstrate a fully self-sustained sensing system capable of real-time quantitative monitoring in gas-liquid mixed flow environments. Under continuous flow conditions with an air pressure of 0.6 MPa and flow speed of 30 m/s, the system achieves real-time measurement of liquid flow rates in the range of 0-90 mL/min with an accuracy of 95%. This triboelectric nanogenerator-based wireless sensing platform offers a promising approach for in situ parameter analysis and measurement in multiphase flow systems.

Strain is a proven technique for modifying the bandgap and enhancing carrier mobility in 2D materials. Most current strain engineering techniques rely on the post-growth transfer of these atomically thin materials from growth substrates to target surfaces, limiting their integration into nanoelectronics. Here, we present a new approach where strain in 2D materials is already introduced directly during their growth on grayscale-patterned topographies instead of flat surfaces. Both strain levels and orientations are deterministically engineered by controlling grayscale surface contour lengths through thermal expansion mismatches in nanostructured stacks, where the conformally grown and firmly attached 2D material is forced to match the underlying morphology change during cooling. With this method, we experimentally demonstrate precise control of localized tensile strain from 0 to 0.5% in grown MoS₂ monolayer along both uni- and multiaxial directions, while higher strain levels are shown to be theoretically possible. This strain-engineered growth of 2D material films directly on the target substrates is a generic and adaptable approach to various combinations of grayscale-thin-film/substrates and eliminates all the transfer-related limitations of previous approaches, thus paving the way for integrating strained 2D materials into next-generation nanoelectronics.

Since the discovery of YBa₂Cu₃O_7-δ (YBCO or Y123), enhancing its superconducting and mechanical properties has been a major focus. Ag doping is a promising strategy for bulk materials, but its mechanism remains debated, particularly regarding whether Ag segregates at grain boundaries or enters the lattice. The origin of the enhancement remains unclear, as conventional powder-doping methods hinder gradient formation and obscure key effects at specific doping levels. Here, we propose a dual-material co-extrusion and freeze-drying strategy to construct a macroscopic Ag-YBCO interface, where directional pores in YBCO enable Ag diffusion and compositional gradient formation at high temperatures. Experiments reveal a [001]-oriented YBa₂Cu_3-xAg_xO_7-δ solid solution with coherent interfaces with Y123, which transmit crystallographic orientation at the atomic scale and promote orientated Y123 growth. First-principles calculations reveal that Ag substitution-induced lattice relaxation plays a key role in driving texture formation. As a result, the composite exhibits a significantly enhanced critical current density (J_c) while maintaining a stable critical temperature (T_c), accompanied by a transition in the fracture behavior from intergranular to transgranular fracture. This work reveals the mechanism of solid solution-driven texture induced by Ag doping in YBCO, providing new insights into dopant-mediated texture evolution in REBCO (Re = rare earth) superconductors.