Chemistry - A European Journal最新文献

{"title":"Modulation of O₂ Affinity and Enzymatic Activity of Core‒Shell Structured Hemoglobin Nanoparticles.","authors":"Ryo Hoshiya, Tomoka Araki, Teruyuki Komatsu","doi":"10.1002/chem.71327","DOIUrl":"10.1002/chem.71327","url":null,"abstract":"<p><p>Hemoglobin-based O₂ carriers (HBOCs) are promising substitutes for red blood cells (RBCs), but their performance depends critically on optimized O₂ affinity and stability of oxygenated hemoglobin (oxy Hb). In this study, we report the precise modulation of both O₂ affinity and enzymatic (antioxidant) activity in core-shell structured stroma-free Hb nanoparticles (X-SFHbNPs, X = human serum albumin (HSA) or poly(2-ethyl-2-oxazoline) (POx)). Low-affinity nanoparticles (X-SFHbNP^Ls) were prepared from deoxy Hb (T-state), and circular dichroism (CD) analysis indicated that the core Hb retains a T-state-like structure even under oxygenated conditions. Blending high- and low-affinity nanoparticles enabled fine tuning of O₂ affinity. POx-SFHbNP preserved the intrinsic catalase (Cat), superoxide dismutase (SOD), and carbonic anhydrase (CA) activities of the parent SFHb. Moreover, POx-Hb(Cat/SOD/CA)NPs, prepared by incorporating elevated levels of these enzymes into purified Hb, exhibited enhanced enzymatic activities. Both X-SFHbNPs and X-Hb(Cat/SOD/CA)NPs showed excellent resistance to oxidation, with negligible metHb formation after 2 h in aqueous H₂O₂. These multifunctional Hb nanoparticles provide a versatile platform for advanced HBOCs with tunable O₂ transport and antioxidant capabilities. Furthermore, X‒SFHbNPs showed reduced binding affinities toward haptoglobin, a Hb-binding plasma protein.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71327"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148389607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Selectfluor-based Polonovski Rearrangement Leading to Novel Entities for Synthetic and Medicinal Applications.","authors":"Jakob Kuhn, Susanne Gradl, Vanessa Osterloh, Peter Gmeiner, Harald Hübner, Markus R Heinrich","doi":"10.1002/chem.71318","DOIUrl":"10.1002/chem.71318","url":null,"abstract":"<p><p>The classical Polonovski reaction starting from N-oxides of tertiary amines and acid chlorides, or anhydrides, offers manifold synthetic options. This large preparative potential is now broadened by a novel, unusual version of the Polonovski reaction based on Selectfluor and carboxylic acids, through which new chemical entities for synthetic and medicinal applications become readily accessible under particularly mild conditions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71318"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13660494/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148366340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lewis Acidity and Anion-Complexation Ability of Oxo- and Phenylimino-Bridged Planar Triphenylboranes as Lithium-Ion-Conducting Solid-State Electrolytes","authors":"Yuichi Kitamoto,&nbsp;Daiki Tsuji,&nbsp;Shunsuke Yamamoto,&nbsp;Yohei Kitani,&nbsp;Maiko Akiba,&nbsp;Kyota Sampei,&nbsp;Tetsutaro Hattori","doi":"10.1002/chem.71572","DOIUrl":"10.1002/chem.71572","url":null,"abstract":"<div>\u0000 \u0000 <p>Boron-containing π-conjugated molecules are promising candidates for the development of advanced Lewis-acidic materials. Planar triphenylboranes containing heteroatoms instead of the methylene groups at the 8-, 14-, and 22-positions of 1-borahexacyclodocosanonaene are particularly interesting because they are stable in the absence of sterically protecting groups around the boron center. However, further investigation of their complexation behavior is required to gain insight into their Lewis acidity and to develop functional materials. Here, the Lewis acidity and anion-complexation ability of oxo- and aza-bridged planar triphenylboranes are reported. UV–vis titration experiments showed that oxo- and aza-bridged planar triphenylboranes exhibit higher binding constants with fluoride ions than trimesitylborane, a conventional triarylborane bearing a sterically protecting group on the boron center. Density-functional-theory (DFT) studies indicated that the sterically less crowded environment around the boron center in planar triphenylboranes is most likely responsible for their high binding constants, and that the six-membered bridging structure does not hinder complexation. The oxo-bridged planar triphenylborane, which shows the highest binding constant toward fluoride ions among the three analogs evaluated, also exhibits high complexation ability toward diverse soft halide anions and molecular anions. A solid-state electrolyte prepared using the oxo-bridged planar triphenylborane and lithium triflate possesses very high lithium-ion conductivity.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 38","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148719846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-Support Synergy in Nitrogen-Doped Carbon-Supported Ru Nanoparticles Enables Base-Free Aerobic Oxidation of Isononanol to Isononanoic Acid.","authors":"Jingyi Chen, Shuangfeng Ren, Zizheng Liu, Xiaoling Mou, Ping Fang, Ronghe Lin","doi":"10.1002/chem.71347","DOIUrl":"10.1002/chem.71347","url":null,"abstract":"<p><p>Selective aerobic oxidation of long-chain primary aliphatic alcohols to the corresponding carboxylic acids remains a fundamental yet industrially challenging transformation, particularly under base-free conditions. Herein, we report a systematic investigation of Ru nanoparticles supported on nitrogen-doped carbon (Ru/NC) for the oxidation of isononanol to isononanoic acid using molecular oxygen as the sole oxidant. By tailoring the thermal treatment atmosphere and temperature, the particle size and surface oxidation state of Ru were precisely regulated. Among the catalysts examined, Ru/NC reduced in H₂ at 523 K exhibited optimal performance, affording 98% conversion and 88% selectivity to isononanoic acid at 393 K and 0.8 MPa O₂ after 24 h without any added base. Structure-activity correlation reveals a volcano-type dependence of activity on Ru particle size with an optimum around 1.3 nm, and a strong positive correlation between surface Ru° fraction and catalytic performance. The N-doped carbon support not only stabilizes highly dispersed Ru nanoparticles but also modulates their electronic structure via metal-support interactions. Catalyst deactivation is primarily attributed to Ru leaching and nanoparticle sintering. This study provides mechanistic insight into Ru-catalyzed oxidation of high-carbon aliphatic alcohols and highlights the critical role of controlled reduction in achieving efficient, base-free oxidation systems.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71347"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148337067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Decoding Heptazine Architectures: From Molecular Association to Structural Insight.","authors":"Silvia Del Moral, Daniel Barrena-Espés, Julen Munarriz, Matthias Lehmann, Pilar Romero, José Luis Serrano","doi":"10.1002/chem.71350","DOIUrl":"10.1002/chem.71350","url":null,"abstract":"<p><p>Heptazine (Hpz) derivatives display remarkable supramolecular organization governed by noncovalent interactions. Here, we explore how molecular chirality and structural variation influence the self-association and organization of three Hpz derivatives (two chiral and one nonchiral) in solution and in the condensed phase. Variable-temperature and concentration-dependent NMR studies allowed the determination of dimerization and supramolecular aggregation constants, as well as the calculation of the thermodynamic parameters of these processes. Computational studies -including conformational analysis and molecular dynamics-corroborated the experimental findings, confirming the energetic stability and geometry of the proposed dimers. Moreover, photophysical studies showed aggregation-induced emission (AIE) behavior, with blue light emission upon molecular association. Additionally, the introduction of chiral chains resulted in mirror-image circular dichroism (CD) responses for the two Hpz enantiomers, demonstrating retention of chirality in bulk. In contrast, the nonchiral analogue displayed liquid crystalline (LC) behavior at high temperatures, characterized by a smectic mesophase. These results reveal how subtle structural variations modulate the supramolecular, optical, and mesomorphic properties of Hpz derivatives, highlighting the versatility of the heptazine core for multifunctional supramolecular and optoelectronic materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71350"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13660486/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148381336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid Assembly of a Covalently Locked Organic Cage Revealing Symmetry-Matched Guest Recognition.","authors":"Melvin Raulin, Arnaud Tillet, Vincent Barbier, Flavien Bourdreux, Régis Guillot, Jérôme Marrot, Olivier R P David","doi":"10.1002/chem.71335","DOIUrl":"10.1002/chem.71335","url":null,"abstract":"<p><p>Robust organic cages featuring convergent hydrogen-bonding cavities constitute attractive platforms for confined molecular recognition. Here, we report a rapid four-step synthesis of a well-defined pyridyl hexa-amide cage based on a readily accessible benzylic tris-aniline platform. Microwave-assisted imine condensation enables fast cage assembly, while subsequent Pinnick oxidation converts the dynamic architecture into a permanently locked C₃-symmetric host. Single-crystal x-ray diffraction reveals a rigid cavity lined with six inward-oriented N-H donors, generating a confined hydrogen-bonding environment suitable for anion recognition. In DMSO, mono- and dicarboxylate guests bind in a fast-exchange regime with comparable apparent affinities. In contrast, a symmetry-matched tricarboxylate (nitrilotripropionate, NTP) induces the formation of a discrete 1:1 host-guest complex displaying distinct titration behavior and confirmed crystallographically. Control experiments with a more rigid tricarboxylate (aluminon) revealed no detectable binding under comparable conditions, suggesting that guest conformational adaptability also contributes to complex formation. These observations highlight how rigidification and geometric complementarity within a confined cavity can influence host-guest recognition behavior in solution.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71335"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148343449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Perfect in-Plane [5555] Metallo-Annulene Frameworks and Nonmetallo-Annulene Complexes: A Theoretical Prediction","authors":"Qin-Wei Zhang,&nbsp;Qiang Chen,&nbsp;Xiao-Ni Zhao,&nbsp;Rui Wei,&nbsp;Si-Dian Li","doi":"10.1002/chem.71322","DOIUrl":"10.1002/chem.71322","url":null,"abstract":"<div>\u0000 \u0000 <p>Inspired by the newly discovered in-plane [55555] metallo-annulene frameworks in 3D [Os]C₁₅H₁₀ ([Os] = OsL¹L² and L represents PPh₃, CO, or PEt₃ σ-ligands in axial direction) and recently proposed perfect 2D in-plane [55555] metallo-annulene complexes <i>D</i>₅<i>_h</i> MC₁₅H₁₀ (M = Pt, Pd, Ni), based on extensive first-principles theory calculations, we predict herein a series of perfect in-plane [5555] metallo-annulene frameworks in 3D <i>D</i>₄<i>_h</i> [Fe]C₁₂H₈ (<b>1</b>, [Fe] = Fe(CO)₂) and <i>D</i>₄<i>_h</i> [Co]C₁₂H₈⁺ (<b>2</b>, [Co] = Co(CO)₂) and perfect 2D in-plane [5555] nonmetallo-annulene complexes including <i>D</i>₄<i>_h</i> PC₁₂H₈^– (<b>3</b>), <i>D</i>₄<i>_h</i> SC₁₂H₈ (<b>4</b>), and <i>D</i>₄<i>_h</i> ClC₁₂H₈⁺ (<b>5</b>). Detailed bonding pattern and ring current analyses indicate that planar tetracoordinate metal or nonmetal centers participate in the delocalized π-bonding systems of the annulene complexes, rendering π-aromaticity and extra stability to the systems. Such species with a planar [12]C₁₂H₈ annulene ligand can be enlarged in 2D to form the <i>C</i>₄<i>_v</i> [Fe]C₃₆H₁₆ (<b>6</b>), <i>D</i>₄<i>_h</i> [Co]C₃₆H₁₆⁺ (<b>7</b>), <i>D</i>₄<i>_h</i> PC₃₆H₁₆^– (<b>8</b>), <i>D</i>₄<i>_h</i> SC₃₆H₁₆ (<b>9</b>), and <i>C_s</i> ClC₃₆H₁₆⁺ (<b>10</b>) and expanded in 3D to generate the tubular nanobelt <i>C</i>₂<i>_v</i> (SC₁₂H₄)₁₂ (<b>11</b>) via partial dehydrogenations. The NMR, IR, and UV-vis spectra of the most concerned species <b>1–5</b> are computationally simulated to facilitate their future experimental characterizations.</p>\u0000 </div>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"32 38","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148366292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Expanding Cyanide-Bridged Weakly Coordinating Anions Through the Brominated Silver Salt Ag[BCNB^Br].","authors":"Amina L Moshtaha, Tim-Niclas Streit, Joshua Parche, Robin Sievers, Moritz Malischewski","doi":"10.1002/chem.71310","DOIUrl":"10.1002/chem.71310","url":null,"abstract":"<p><p>Weakly coordinating anions (WCAs) composed of a cyanide unit bridging two triarylborane Lewis acids are an attractive but largely unexplored complement to established tetraarylborates such as [B(C₆F₅)₄]^- (BArF₂₀). Here, we report the brominated representative [μ-(CN)(B(C₆F₄Br)₃)₂]^- ([BCNB^Br]^-) through its readily accessible silver salt Ag[BCNB^Br], prepared from AgCN and two equivalents of B(C₆F₄Br)₃ in CH₂Cl₂. Ag[BCNB^Br] provides convenient access to [BCNB^Br]^- in weakly coordinating media and enables the introduction of this WCA through oxidation or halide abstraction. Its utility is demonstrated by the synthesis of a range of [BCNB^Br]^- salts containing oxidizing and electrophilic cations. These results show that [BCNB^Br]^- is stable under strongly oxidizing conditions, including systems reaching at least +1.14 V vs. FeCp₂/FeCp₂ ⁺. [BCNB^Br]^- represents a bromine-substituted WCA whose heavier bromine substituents enhance X-ray scattering and facilitate crystal structure analysis of its salts.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71310"},"PeriodicalIF":3.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13660483/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148337021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling Methane Selectivity on Cu-Based Single-Atom Alloys for CO₂ Electroreduction via Synergistic DFT and Machine Learning.","authors":"Bicheng Zhang, Jiawen Liu, Huiyang Zhang, Haitao Zhao, Xiuyun Zhang, Yixin Ouyang, Li Shi","doi":"10.1002/chem.71784","DOIUrl":"https://doi.org/10.1002/chem.71784","url":null,"abstract":"<p><p>Electrochemical CO₂ reduction offers a sustainable route for converting CO₂ into value-added fuels and chemicals, yet achieving efficient methane production remains challenging because of the complex reaction network and insufficient catalyst selectivity. Herein, density functional theory combined with interpretable machine learning were employed to investigate the structure-activity relationship of Cu-based single-atom alloys constructed by incorporating 13 transition-metal atoms into Cu(100)/(111) surfaces. The calculations reveal that isolated metal atoms effectively regulate the electronic structures of both the dopant and neighboring Cu atoms, thereby altering the energetics of HCOO* formation. More importantly, the synergistic interaction between the isolated metal atom and adjacent Cu sites stabilizes the CH₂OO*, redirecting the reaction pathway toward highly selective CH₄, in sharp contrast to pristine Cu surfaces. Among all investigated catalysts, Ge₁/Cu(100) is most active, with a limiting free energy as low as 0.24 eV while effectively suppressing the hydrogen evolution reaction. Machine learning analysis further identifies electron affinity and catalyst-support charge transfer as the two dominant descriptors governing catalytic activity, providing quantitative insight into the origin of the structure-activity relationship. This combined DFT-ML framework establishes descriptor-guided design principles for methane-selective CO₂ reduction and offers a general strategy for the rational development of high-performance single-atom alloy electrocatalysts.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71784"},"PeriodicalIF":3.6,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boron Monofluoride Complexes Bearing π-Expanded Coumarin Subunits: Facile Synthesis, Crystal Structure, and Solid-State Enhanced Emission.","authors":"Amine Assel, Fausto Puntoriero, Mohamed Chellegui, Antonio Santoro, Francesco Nicolò, Mayssa Zayene, Hichem Ben Jannet, Alessandro Auditore, Tianhong Yan, Alessandro Amadeo, Frédéric Labat, Ilaria Ciofini, Sebastiano Campagna","doi":"10.1002/chem.71756","DOIUrl":"https://doi.org/10.1002/chem.71756","url":null,"abstract":"<p><p>Boron-containing compounds have received special interest over the last few years owing to their favorable photophysical characteristics, stimulating their use as fluorescent sensors, in bioimaging and mechanofluorochromic materials. However, their synthesis is often time-consuming and requires specialized protocols. Here, we report the design and synthesis of a novel class of monofluoroborate compounds featuring π-expanded coumarin subunits, with simple access in relatively high yields, and investigate, by computational and experimental approaches, their photophysical properties in solution and in the solid state. These compounds exhibit intense absorption in the 350-450 nm range and show fluorescence in the solid state, while are not luminescent in solution. The absence of emission in fluid solution is ascribed to ultrafast radiationless decay via conical intersection, as suggested by computational data. Ultrafast pump-probe transient absorption spectroscopy in fluid solution confirms the excited-state computed data, indicating that the excited state decays within few picoseconds to the ground state. The structural rearrangement needed for reaching the conical intersection is inhibited in the solid state thanks to the presence of dimers with restricted geometrical flexibility, as evidenced by crystallographic studies and calculations, giving rise to solid-state emission.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71756"},"PeriodicalIF":3.6,"publicationDate":"2026-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149147171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}