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The triplet benzene dianion is predicted to be aromatic based on Baird's rule. However, it has remained elusive due to the Jahn-Teller distortion. Herein, we report isolation of a benzene dianion with a triplet ground state in an inverse-sandwich europium benzene complex. Combined experimental and theoretical studies unveil that the strong antiferromagnetic coupling between the benzene dianion and 4f 7 Eu 2+ ions is pivotal to the stabilization of the triplet state of the benzene dianion with Baird aromaticity. In addition, a comparison with analogous ytterbium benzene and europium para -xylene complexes further reveals that the spin state of the benzene dianion depends on the spin-spin interaction and local symmetry. These results accomplish the isolation of the long-sought triplet benzene dianion and illustrate the effectiveness of spin modulation using lanthanide ions.

The Topological Hall effect (THE) is a fascinating physical phenomenon related to topological spin textures, serving as a powerful electrical probe for detecting and understanding these unconventional magnetic orders and skyrmions. Recently, the THE has been observed in strontium ruthenate (SrRuO 3 , SRO) thin films and its heterostructures, which originates from the disruption of interfacial inversion symmetry and Dzyaloshinskii-Moriya interaction (DMI). Here, we demonstrate a practically pure proton doping effect for controlling the DMI and THE in the SRO epitaxial films using the Pt electrode-assisted hydrogenation method. The hydrogenation process can realize approximately 0.8 protons per unit cell incorporating into the SRO films (thickness >10 nm) without causing significant lattice expansion and oxygen vacancies. Consistent with first-principles calculations, atomic-scale observations confirm that the proton doping induces a vertical displacement of Ru and O atoms in hydrogenated SRO (H-SRO), which remarkably enhances the DMI and leads to the emergence of the THE. More importantly, the proton doping drives two distinct topological signals in the ferromagnetic H-SRO, exhibiting greater THE values but no occurrence of structural transition. Our study has demonstrated that catalysis-assisted hydrogenation is an efficient strategy for manipulating the emerging THE and magnetic textures in correlated oxide thin films.

Vibrio strains, identified by 16S rDNA, were isolated from the marine environment surrounding Taiwan, revealing diverse bioactive effects, such as iron-chelating and antimicrobial activities. Notably, the hierarchical clustering dendrogram of mass spectrum profiles (MSP) of the Vibrio strains using MALDI-TOF, in contrast to the phylogenetic tree based on 16S rDNA sequencing analysis, exhibited a strong correlation with their observed bioactivities. Within this set, GNPS molecular network analysis by LC-HRMS/MS highlighted that three strains, Vibrio tubiashii DJW05-1, V. japonicas DJW05-8, and V. fortis DJW21-4 shared similar bioactive pseudopeptides in the same cluster. Subsequent chromatographical isolation and purification yield an unprecedented unsaturated diketopiperazine, (Z)-3-(2-methylpropylidene)-2,3-dihydropyrrolo[1,2-a]pyrazine-1,4-dione (1), along with a series of diketopiperazines, and a potential new annotated pseudopeptide 2, as well as three pseudopeptides, including andrimid (10), moiramide B (11), and moiramide C (12), and several alkaloids from V. tubiashii DJW05-1. Further investigation into the combined applications of the major antimicrobial compound and commercial antibiotics revealed that andrimid (10) displayed significant inhibitory effects against Gram-positive Staphylococcus aureus, and Gram-negative Escherichia coli, Salmonella typhimurium, and Acinetobacter baumannii, except for Pseudomonas aeruginosa. Nevertheless, the potential for synergistic and additive effects of andrimid (10) with certain antibiotics remains, presenting valuable prospects for medicinal applications., Competing Interests: The authors declare that they have no conflict of interest., (Thieme. All rights reserved.)

RNA-binding motif 47 (RBM47) is a recently identified RNA-binding protein involved in early vertebrate development, immune homeostasis, and cancer development. This study examined the biological functions of RBM47 in thyroid-associated ophthalmopathy (TAO). Orbital fibroblasts (OFs) were obtained from the control (n = 6) and TAO groups (n = 6). Protein and gene expression in the obtained samples were investigated using immunohistochemistry, western blotting (WB), and RT-PCR. OFs with RBM47 knockdown were established using small interfering RNA. Subsequently, Oil Red O staining, WB, and RT-PCR were performed to assess adipogenesis in the OFs. The IL-1β-induced expression of proinflammatory molecules and hyaluronan (HA) was determined using enzyme-linked immunosorbent assay and RT-PCR. Moreover, TGF-β-induced fibrosis was evaluated using scratch assays, RT-PCR, and WB. RBM47 expression was markedly increased in orbital tissues and OFs obtained from individuals with TAO. RBM47 knockdown decreased adipogenesis and fibrosis in OFs, and downregulated the levels of insulin-like growth factor 1 receptor (IGF-1R), proinflammatory molecules, and HA. Furthermore, low RBM47 expression downregulated IGF-1R, which subsequently inhibited adipocyte differentiation by decreasing extracellular signal-regulated kinase signalling. These findings indicate that RBM47 may be involved in the regulation of adipogenesis, inflammation, HA production, and fibrosis, highlighting its potential of RBM47 as a therapeutic target for TAO., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Since ancient times, plants have provided humans with important bioactive compounds for the treatment of various diseases. Nine compounds were isolated from the roots and rhizomes of Caulophyllum robustum (a plant in the family Panaxaceae), including two new saponins C. Spanion A and C. Spanion B (1-2) and seven known saponins (3-9). The cytotoxicity of these compounds on human cancer cell lines was analyzed using MTT method. Compounds 6 and 9 exhibit cytotoxicity towards these three types of human cancer cells (<10 μM). By utilizing the SEA platform for target prediction, a common tumor related target CD81 was identified. The molecular docking of saponins 1, 2, 6, and 9 with CD81 protein showed strong binding affinities ranging from -4.5 to -7.1 kcal/mol. Research has shown that these compounds can become potential anti-tumor drugs. Further research is still recommended to understand its exact molecular mechanism and toxicological effects., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2025 Zhang, Wang, Qiu, Feng, Wang, Cao, Wei, Zhou, Tang, Lu and Zhang.)

Electron spin plays a critical role in chemical processes, particularly in reactions involving metal complexes with unpaired electrons. However, more definitive state-to-state experiments are needed to better elucidate the role of electronic spin. Herein, we chose nickel (II) 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin 1 as a catalyst, which allows switching from a low spin to a high spin state of Ni (II) center through an axial pyridine coordination, for electrocatalytic hydrogen evolution reaction (HER). When pyridine is present, we observed β-hydrogenation of porphyrin through electron transfer followed by proton transfer. In contrast, hydrogen evolution mainly occurs via the concerted proton-coupling electron transfer without pyridine coordination. Similar distinct spin-dependent selectivity was also observed in chemical reduction of 1 by CoCp 2 with subsequent addition of pyridinium p-toluenesulfonate. Computational calculations using density functional theory demonstrated that the transition from low spin to high spin state enriches the ligand's electron density after one-electron reduction, leading to preferential protonation of β-periphery rather than meso-position or metal center., (© 2024 Wiley-VCH GmbH.)

A new single-molecule magnet (SMM) complex [K(18-crown-6)][(COT)Er(µ-Cl) 3 Er(COT)] (Er 2 Cl 3 , COT = cyclooctatetraenide dianion) is obtained by the reaction of [(COT)Er(µ-Cl)(THF)] 2 (Er 2 Cl 2 , THF = tetrahydrofuran) with an equivalent of KCl in the presence of 18-crown-6. The two COT-Er units in the newly formed complex are triply bridged by µ-Cl ligands, leading to the "head-to-tail" alignment of the magnetic easy axes distinctly different from the "staggered" arrangement in the precursor complex. This structural transformation has led to significantly enhanced intramolecular dipolar interactions and a reduced transverse component of the crystal fields, increasing the energy barrier from 150(8) K for Er 2 Cl 2 to 264(4) K for Er 2 Cl 3 and extending its magnetic relaxation time at 2 K by 2500 times with respect to Er 2 Cl 2 . More importantly, the blocking temperature increased from lower than 2 K for Er 2 Cl 2 to 8 K for Er 2 Cl 3 , and the magnetic hysteresis loops at 2 K changed from butterfly-shaped for Er 2 Cl 2 to open hysteresis loop with coercive force of 7 kOe for Er 2 Cl 3 . These results suggest that the properties of SMMs can be effectively tuned and improved by rationally arranging magnetic spins via molecular engineering., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)