Browse Articles

Angularly Resolved Tip‐Enhanced Raman Spectroscopy

Abstract Despite intensive research in tip‐enhanced Raman spectroscopy (TERS), the angular distribution of Raman scattering in the TERS gap remains experimentally unreported leaving its relevance to the TERS signal formation to be seldomly discussed. Here, we investigate the angular distribution of the tip‐enhanced Raman signal in the Fourier plane using a model system composed of flat‐lying cobalt (II) hexadecafluoro‐phthalocyanine (CoPcF 16 ) molecules physically adsorbed on a smooth gold surface. Both in‐plane and out‐of‐plane vibrational modes are observed, where the out‐of‐plane Raman modes at about 678 and 740 cm −1 have different angular intensity distributions than those of in‐plane Raman modes at 1309 and 1373 cm −1 . We interpret the angular spectrum of the TERS signal considering the molecular vibrational modes computed with density functional theory (DFT) for the free and gold‐deposited molecule, and the directed Raman scattering by the gap‐mode predicted by finite‐difference time‐domain (FDTD) simulations. We contend that the TERS gap directs the Raman vibrational modes differently, leading to distinct angularly distributed Raman scattering intensities. These findings emphasize the nonnegligible role of the TERS detection scheme in understanding spectral features, such as the relative peak intensity ratio variations for studying molecular orientations, or for monitoring chemical reactions.

Signal mining and risk analysis of tisotumab vedotin adverse events based on the FAERS database

Cyclo‐Octasulfur Crystals as Light‐Controlled Molecular Muscles

Abstract Here, we describe the synthesis and photo‐responsive properties of 2D cyclo‐octasulfur microcrystals (α‐ S8 MCs), produced using a quick, simple, cost‐effective, and environmentally friendly hydrothermal method. Controlled 385‐nm irradiation of these crystals induces an immediate, reversible, and sustained bending effect. The time required for the crystals to return to their initial shape is significantly reduced when exposed to 475‐nm light, completing the entire excitation‐relaxation cycle in less than 2 s. Moreover, this process can be repeated up to 50 times as long as the crystals remain in water. The dependence of recovery time on light wavelength is rationalized qualitatively via highly correlated quantum‐chemical calculations of the absorption spectra of S8 chains. The underlying mechanism involves a combination of ring‐to‐chain and chain‐to‐ring transformations: the breaking of α‐ S8 rings by 385‐nm radiation induces bending in the α‐ S8 MCs, while the excitation of the chains with 475‐nm light facilitates an accelerated recovery process, allowing the S8 molecules to swiftly regain their ring shape. Thus, our study demonstrates that α‐ S8 MCs represent intelligent actuators as light‐controlled molecular muscles with the simplest inorganic composition reported to date.

The nature of phantom dark energy and its relation to time crystals

To select the optimal immunohistochemical staining method for pigmented melanoma

The psychometric network of individual flourishing across nationally representative samples from 22 countries

Abstract To effectively promote human flourishing, it is important to understand how the different dimensions of flourishing might be related to one another in different sociocultural contexts. Applying a systems perspective to flourishing, this study uses nationally representative survey cross-sectional data from 22 geographically and culturally diverse countries included in the Global Flourishing Study (N = 202,898) to explore the interrelatedness of the components of individual flourishing captured by the Secure Flourish Measure. A meta-analytic gaussian network aggregation (MAGNA) model was applied to investigate similarities and differences among the interrelations of individual flourishing components across countries. Results revealed a network of mostly positive interrelations among the 12 components, although there was substantial heterogeneity in the strength of associations, especially between life satisfaction, happiness, and mental health. Understanding cross-country differences in light of socio-contextual peculiarities will be crucial for informing the development of targeted interventions to promote flourishing.

MXene‐Supported Ru–Ni: A Common Active Site for Hydrolysis, Hydrogen Oxidation, and Hydrogenation

Abstract Insights into the activation and conversion of hydrogen using a single‐mode catalyst are crucial for advancing fuels and fine chemical production. In this paper, the activation and conversion of H 2 molecules in hydrogen production and application were investigated on RuM (M = Ni, Co, Cu, Fe)‐MXene catalysts. RuM (M = Ni, Co, Cu, Fe) bimetallic nanoclusters were uniformly distributed on Ti 3 C 2 MXene. The optimal Ru 2.5 Ni 2.5 ‐Ti 3 C 2 exhibits the highest turnover frequency (TOF) value of 1833 min −1 toward ammonia borane (AB, NH 3 BH 3 ) hydrolysis. Meanwhile, the catalysts also showed good catalytic activity in hydrogen oxidation reaction (HOR) and phenylacetylene hydrogenation. The high activity originates from the acceleration of the catalytic process by RuNi clusters‐Ti 3 C 2 and the promotion of H 2 molecular transport by the special interface of RuNi cluster‐MXene. The RuNi clusters—Ti 3 C 2 with multisites provide a dependable platform for the regulated activation and conversion of H 2 molecules and various reaction intermediates. The competitiveness of nanocluster‐MXene catalytic material is showcased for activation and conversion of hydrogen. This research of reaction‐inducing adaptation uncovered the pathway to explore multifunctional catalysts in energy, chemistry, and materials applications.

Atorvastatin exhibits anticancer effects by inhibiting YAP/TAZ activity in mesenchymal-like non-small cell lung cancer

Abstract Non-small cell lung cancer (NSCLC) accounts for most lung cancer diagnoses. Statins preferentially inhibit the proliferation of mesenchymal- over epithelial-like cells in various types of cancer, including NSCLCs. However, the mechanisms underlying the differential statin sensitivity of mesenchymal and epithelial cancer cells remain unknown. Statins inhibit YAP/TAZ, effectors of the Hippo pathway, via depletion of geranylgeranyl pyrophosphate. Here, we aimed to elucidate the mechanisms underlying statin sensitivity in mesenchymal cancer. We explored the anticancer effects of atorvastatin and its association with YAP/TAZ activity in NSCLC cell lines with different epithelial-mesenchymal phenotypes. Atorvastatin significantly reduced the proliferation, migration, and invasion of mesenchymal-like cells, while showing negligible effect on epithelial-like cells. Atorvastatin also inhibited YAP/TAZ nuclear localization and downstream gene expression in mesenchymal cells but did not affect epithelial cells. Small interfering (si) RNA-mediated inhibition of both YAP and TAZ reduced the proliferation of all NSCLC cell lines tested, regardless of phenotype, indicating that sensitivity to YAP/TAZ inhibition and statins differ. In summary, our results suggest that inhibited YAP/TAZ nuclear localization by statins differs between epithelial and mesenchymal NSCLC cell lines, resulting in differential statin sensitivity.

Sustainable Closed‐Loop Recycling of Polyester Waste Using Reconstructed Defective‐Metal–Organic Frameworks

Abstract Chemical recycling of polyester waste presents a promising strategy for achieving a sustainable circular economy. However, the development of efficient, low‐cost recycling methods that minimize energy consumption and carbon emissions remains challenging. Here, we report an approach for depolymerization polyester waste to bis (hydroxyethyl)terephthalate (BHET) using a reconstructed metal–organic framework ( r ‐Zn–MOF74–NT) catalyst under mild conditions. The r ‐Zn–MOF74–NT exhibited a space‐time yield of 1035.8 g BHET g cat −1  h −1 at 190 °C. Importantly, this is an order of magnitude higher than that reported for similar MOF‐based catalysts. In situ spectroscopy combined with theoretical calculations revealed that the depolymerization pathway involves the activation of oxygen and ethylene glycol adsorbed on r ‐Zn–MOF74–NT, forming nucleophilic intermediates. These intermediates then facilitate the cleavage of the polyester C─O bond through nucleophilic attack, thereby gradually generating the BHET product. Sustainability evaluation results validated the circular economy feasibility of the recycling approach, with a minimum sales price (MSP) of 498 $/ton, much lower than the MSP of the traditional petroleum‐based production route (1000 $/ton). The approach also achieved a 61% reduction in energy use and a 52% decrease in greenhouse gas emissions. This work provides a sustainable solution for managing polyester waste accumulation.

Surface texture dependency of photocatalytic behavior of facile synthesized mesoporous ZnS-ZnO heterostructure under LED illumination

Sulfasalazine induces ferroptosis in osteosarcomas by regulating Nrf2/SLC7A11/GPX4 signaling axis

Controlled Electrocatalytic Glycerol Upgrading to Glyceraldehyde in Near Neutral Media by Cobalt Oxide Lattice Activation

Abstract Electrocatalytic upgrading of biomass‐derived glycerol driven by renewable electricity offers a greatly attractive green way to produce value‐added chemicals at much reduced global carbon footprint. However, achieving both the enhanced activity and selectivity for the most‐valuable C3 product‐glyceraldehyde (GAD) of glycerol oxidation reaction (GOR) in neutral media, though of great importance, is extremely challenging. In this work, we propose a Co 3 O 4 lattice activation mechanism by introducing single atom Ru (0.36 wt%) into the tetrahedral sites (Co Td ) of Co 3 O 4 lattice to significantly elevate the GOR activity and the GAD selectivity. The as‐constructed Ru‐Co 3 O 4 /NF only needs 1.16 V to achieve the current density of 10 mA cm −2 during GOR and maintains ∼60% GAD selectivity (∼90% for C3 products) over a broad potential window, which are the highest reported in near neutral media. This excellent performance has been demonstrated to originate from the introduction of Ru atoms, which activates the lattice active sites of Co 3 O 4 by promoting the rapid reconstruction of the catalyst to generate sufficient Co 3+ ‐(OH) ads electrophilic oxygen species, resulting in not only the accelerated GOR kinetics, also largely enhanced selectivity of GAD by the adsorption configuration regulation of glycerol primary alcohols (C α ‐OH) favoring the primary alcohol oxidation pathway.

Callerya Atropurpurea shells derived nitrogen doped carbon quantum dots of electrodes for symmetrical and asymmetrical supercapacitors

Abstract Callerya Atropurpurea shells were utilized as activated carbon precursors in a one-stage activation process at 700 °C using H2SO4, NaOH and KOH as activating agents. Herein, carbon quantum dots (CQDs) were produced via self-doping using urea as a nitrogen source. The structural, functional, and morphological properties of the doped active materials were examined using X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. The elemental composition was conducted using energy-dispersive X-ray spectroscopy, and surface sensitivity was determined using X-ray photoelectron spectroscopy techniques. The surface properties showed that the nitrogen-doped CQDs produced good crystallinity with an abundance of nitrogen heteroatoms attached to the surface, facilitating the conductivity of the devices. The electrodes of NCQDs-1, NCQDs-2 and NCQDs-3 were prepared and used for the fabrication of asymmetric and symmetric supercapacitor electrodes. The NCQDs-3 electrode used in the asymmetric and symmetrical devices showed a higher specific capacitance of 22 F/g at a current density of 0.5 A/g. Also, the NCQDs-3 electrode achieved the highest coulombic efficiency of 98% and a capacitive retention of 99% even after 1000 GCD cycles.

Liposomal ellagic acid enhances the regenerative potential of ADMSC-laden nanofibrous PCL scaffolds in a rat model of spinal cord injury

Abstract Spinal cord injury (SCI) leads to myelin breakdown and extensive neuronal loss around the injury site due to increased oxidative stress. This study aims to develop a comprehensive platform incorporating scaffolds, therapeutic agents, and stem cells to restore structures and pathways in SCI. Scaffolds were created through the electrospinning of a PCL/functionalized multi-walled carbon nanotube (f-MWCNTs) composite, which was then coated with liposomal ellagic acid (EA@lip) and seeded with adipose-derived mesenchymal stem cells (ADMSCs). The optimal drug concentration was determined by conducting MTT and DPPH assays through three different time points. After assessing the biocompatibility and anti-inflammatory properties of the scaffolds for ADMSCs, the implant was tested in a rat model of dorsal hemisection. The female Wistar rats were divided into six groups ( n  = 10): Sham, SCI, SCI + PCL/f-MWCNTs (PCs), SCI + scaffolds + EA@lip (PC/N), SCI + scaffolds + ADMSCs (PC/C), and SCI + scaffolds + EA@lip + ADMSCs (PC/N/C). In the second week, biochemical analyses were conducted to evaluate oxidative stress in the animals’ blood. Throughout the study, the motor function of the animals was monitored. After six weeks, the rats were subjected to real-time PCR and histological analysis, utilizing Cresyl Violet/Luxol Fast Blue staining and evaluating the expression of the genes COX2, GPX1, MBP, and Slc17a6/7. Liposomal encapsulation efficiency was measured to be 33%. The results revealed that EA@lip had the desired size, zeta potential, and lipid concentration. Transmission electron microscopy revealed that f-MWCNTs were well-aligned along nanofibers. EA@lip dramatically enhanced the hydrophilicity of the scaffolds. The MTT assay, DAPI staining, and FE-SEM images confirmed the successful implantation, proliferation, adhesion, and survival of ADMSCs on the liposome-coated scaffold. Additionally, in vitro oxidative stress tests indicated that this platform exhibited superior antioxidant and anti-inflammatory effects for ADMSCs. Histological assessments revealed that the hybrid platform facilitated the regeneration of myelin and neurons, correlating with improved blood levels of oxidative markers. Furthermore, real-time PCR results demonstrated a decrease in COX2 expression and an increase in GPX1, MBP, and Slc17a6/7 expression due to the platform. The findings suggest that the combination of ADMSCs with EA@lip-coated PCL/f-MWCNT scaffolds hold significant promise for applications in spinal cord regeneration.

Reactivity of a Methylene‐Bridged 1,3‐Bis(germylene) in Dynamic Equilibrium with Its Dimer

Abstract We report the properties and reactivity of an unprecedented methylene‐bridged 1,3‐bis(germylene) derivative. In the solid state, it undergoes dimerization to afford a 1,2,4,5‐tetragermacyclohexa‐1,4‐diene derivative (Ge 4 CHD). Moreover, theoretical calculations on Ge 4 CHD reveal σ*–π interactions between the two π orbitals (Ge═Ge) and the CH σ* orbital. This interaction is confirmed by a significant red shift in the solid‐state UV–vis spectrum. In contrast to the behavior in the solid state, the Ge 4 CHD derivative dissociates in solution into a methylene‐bridged 1,3‐bis(germylene) derivative. The resultant 1,3‐bis(germylene) derivative reacted with S 8 to form a novel cage compound containing three S and two Ge atoms. On the other hand, in the reaction with triphenylphosphine sulfide, the in situ generated 2‐thia‐1,3‐digermabicyclo[1.1.0]butane derivative activated the benzene solvent, leading to the formation of a [2 + 2] cycloaddition product. Additionally, the 1,3‐bis(germylene) derivative reacted with 4‐dimethylaminopyridine (DMAP) to form a three‐membered ring. Its structural parameters and the results of theoretical calculations indicated the zwitterionic character.

A Transformer-LSTM-SVR hybrid model for AI-driven emotional optimization in NEV embedded interior systems

Tunable Thermally Activated Delayed Fluorescence from Supramolecular Polymers Toward Application in Aqueous Media

Abstract Thermally activated delayed fluorescence (TADF) offers great potential for application in light emitting devices and bioimaging. Supramolecular polymers can offer intriguing properties for the same applications, such as stimuli responsiveness and self‐healing owing to their dynamic intermolecular interactions. However, merging the two has remained a formidable challenge, due to the nonplanar geometry of common TADF chromophores. Herein, we overcome this challenge by utilizing a less distorted multiple resonance TADF (MR‐TADF) chromophore connected to a polymerization inducing building block. The obtained supramolecular synthon is capable of assembling in aliphatic solvents due to combined interchromophore interactions and hydrogen bonding. Within the supramolecular ensemble the long‐lived photoluminescence properties of the chromophore are maintained. Further modification of the photoluminescence properties could be achieved by using different supramolecular modulators in a social self‐sorting approach, allowing fine‐tuning of the photoluminescence lifetime and bandwidth. Notably, the extent of intermolecular interactions can switch these assemblies from kinetically to thermodynamically controlled regimes. Finally, we employ this co‐assembly strategy to move from organic to aqueous media highlighting the potential toward biological applications.

Mucus plug and lung cancer incidence in patients with COPD

Study on fissure development law of surrounding rock in horizontal section stope of steeply dipping coal seam group

Operando XAFS Deciphering Dynamic Evolution of Heteronuclear Cu–Ni From Atomic Sites to Atomic Clusters for Enhanced CO ₂ Electroreduction

Abstract Revealing the dynamic evolution of atomic‐level active sites during catalytic reactions is critical for identifying true catalytic centers and optimizing the adsorption of reaction intermediates. However, elucidating the dynamic atomic/electronic transformation mechanisms of metal sites in multimetallic systems and achieving atomic‐level control remains challenging. Here, we report a potential‐dependent in‐plane atomic reconstruction intrinsic to Cu–Ni heteronuclear atomic sites during the electrocatalytic CO 2 reduction reaction (eCO 2 RR). Operando X‐ray spectroscopy and microscopy unveil the transformation of asymmetric Cu–Ni dimers into fully exposed Cu x –Ni atomic clusters (Cu x –Ni ACs, x = 3–7) at potentials from −0.7 to −1.2 V versus RHE, anchored on porous carbon through N/S coordination. The Cu‐rich evolution reshapes geometric structures of active sites, inducing gradual electron localization, thereby optimizing the adsorption energy of CO 2 intermediates as evidenced by operando measurements and theoretical analysis. Specifically, the tailored Cu 5 –Ni ACs formed at −0.9 V reduce the antibonding orbital occupancy between Cu 3 d and C 2 p states, facilitating CO 2 protonation and enhancing eCO 2 RR kinetics. These findings demonstrate high CO selectivity and catalytic stability, providing fundamental insights into the dynamic reconstruction and catalytic mechanism of atomic‐scale active sites.