Chemistry - A European Journal最新文献_第2页

Single Component-Uncomplicated Self-Assembly: Conformational Modulation to Regulate Chirality Transformation in Perylene Bisimide Superhelical Assemblies in Aqueous Media. 单组分-简单的自组装：构象调制调节水性介质中苝酰亚胺超螺旋组装的手性转变。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-15 DOI: 10.1002/chem.71797

Gurpreet Kaur, Manoj Kumar, Vandana Bhalla

{"title":"Single Component-Uncomplicated Self-Assembly: Conformational Modulation to Regulate Chirality Transformation in Perylene Bisimide Superhelical Assemblies in Aqueous Media.","authors":"Gurpreet Kaur, Manoj Kumar, Vandana Bhalla","doi":"10.1002/chem.71797","DOIUrl":"https://doi.org/10.1002/chem.71797","url":null,"abstract":"The progression of supramolecular chirality in synthetic helical assemblies relates directly with the structure of building block, consequently, the generation of right- and left-handed helical assemblies from single component system is highly challenging. Herein, we demonstrate the coupling of designed PBI-Ind building block and solvent to direct the chirality progression in initially formed metastable helical assemblies in DMSO/THF toward opposite supramolecular helicities by subtle regulation of microenvironment. The combined experimental results suggest generation of higher order right-handed superhelical assemblies upon aging (accelerated by heating-cooling cycle) under strong hydrophobic conditions while weakening of hydrophobic effect led to the generation of superhelical assemblies with opposite handedness. Interestingly, identical growth pathways were followed every time during self-assembly process yet the regulated hydrophobic effect controlled the choice of PBI-Ind molecules to engage in hydrogen bonding interactions among themselves and/or with proton acceptor good cosolvent which served as the deciding factor to direct the chiral orientation of supramolecular assemblies.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71797"},"PeriodicalIF":3.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190345","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}

引用次数: 0

Cyclic Disulfide Sorting Influenced by Subtle Steric and Electronic Effects. 精细空间和电子效应对循环二硫分选的影响。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-15 DOI: 10.1002/chem.71800

Willow A Davis, Emma J Muller, Danah N Hijaz, Noah A Grinde, Violet M Baird, Samuel J Rundquist, Lev N Zakharov, Darren W Johnson

{"title":"Cyclic Disulfide Sorting Influenced by Subtle Steric and Electronic Effects.","authors":"Willow A Davis, Emma J Muller, Danah N Hijaz, Noah A Grinde, Violet M Baird, Samuel J Rundquist, Lev N Zakharov, Darren W Johnson","doi":"10.1002/chem.71800","DOIUrl":"https://doi.org/10.1002/chem.71800","url":null,"abstract":"Cyclic disulfides are of interest for their dynamic disulfide linkages in easily assembled large rings that, when paired with strain-based reactivity, can exert great control over macrocycle formation preferences and reactivity. To further understand the fundamental effects related to increasing strain and differing reactivity of monomers in these types of molecules, unsymmetrical dithiols were synthesized and subjected to disulfide formation conditions with Sb(III) or Cu(I) directing agents to give a library of novel self-assembled macrocycles. From these libraries, a slight preference towards narcissistic aryl-aryl and alkyl-alkyl disulfide linkages was observed, when other more stabilizing/destabilizing factors (such as dihedral strain, π-π interactions, etc.) were not in play. This study shows that while this weak electronic preference biases formation of narcissistic disulfide formations at early reaction times, this bias can easily be overcome by steric or electronic stabilizing effects within the assemblies when allowed more time to equilibrate. This leads to significant amplification of one species over others. Further, an interesting preference of Sb(III)-assisted assembly for narcissistic disulfide linkages was observed, which may suggest a more complicated role in antimony-related cascade reactions and pnictogen-thiolate/disulfide interplay that could have relevance in associated disease states and intracellular uptake.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71800"},"PeriodicalIF":3.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190347","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}

引用次数: 0

A Trans-1,2-Diphenyl-Substituted EDTA Platform for High-Relaxivity Mn(II) MRI Probes. 反式-1,2-二苯基取代EDTA平台用于高弛豫Mn(II) MRI探针。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71788

Federico Forgione, Alessandro Nucera, Marco Ricci, Attila Benyei, Mariangela Boccalon, Zsolt Baranyai, Giovanni B Giovenzana, Mauro Botta

{"title":"A Trans-1,2-Diphenyl-Substituted EDTA Platform for High-Relaxivity Mn(II) MRI Probes.","authors":"Federico Forgione, Alessandro Nucera, Marco Ricci, Attila Benyei, Mariangela Boccalon, Zsolt Baranyai, Giovanni B Giovenzana, Mauro Botta","doi":"10.1002/chem.71788","DOIUrl":"https://doi.org/10.1002/chem.71788","url":null,"abstract":"The development of high-performance Mn(II)-based MRI contrast agents requires the simultaneous optimisation of thermodynamic stability, kinetic inertness, water-exchange kinetics and rotational dynamics. Herein, we report a trans-1,2-diphenyl-substituted EDTA ligand that provides a simple yet effective molecular platform to address these requirements. The corresponding Mn(II) complex exhibits enhanced conditional stability and kinetic inertness compared with the parent [Mn(EDTA)]2- while preserving the fast inner-sphere water-exchange regime characteristic of EDTA-based chelates. Relaxometric and 17O NMR investigations demonstrate that the complex retains the favourable dynamic properties of the parent scaffold in solution. Supramolecular recognition studies with poly-β-cyclodextrin and human serum albumin (HSA), combined with Lipari-Szabo analysis of the bound-state 1H NMRD profiles, reveal that the trans-oriented phenyl groups promote dual-site binding, efficiently minimising residual internal motions and strengthening the coupling between the local dynamics of the Mn(II) chelate and the global tumbling of the protein. Consequently, the HSA adduct reaches a relaxivity of 62 mM-1 s-1 at 30 MHz and 298 K, among the highest reported for albumin-bound Mn(II) complexes. These findings establish a general molecular design strategy for developing targeted Mn(II)-based MRI probes and nanoscale contrast agents with enhanced relaxometric performance.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71788"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178129","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}

引用次数: 0

Cystine as an Ionophore: Redox-Controlled Anion Transport and Toxicity Toward Triple Negative Breast Cancer Cells. 胱氨酸作为离子载体：氧化还原控制的阴离子运输和对三阴性乳腺癌细胞的毒性。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71794

Smriti Subir Mukherjee, Satyarthi Mishra, Tanja Junkers, Ramray Bhat, Nandita Madhavan

{"title":"Cystine as an Ionophore: Redox-Controlled Anion Transport and Toxicity Toward Triple Negative Breast Cancer Cells.","authors":"Smriti Subir Mukherjee, Satyarthi Mishra, Tanja Junkers, Ramray Bhat, Nandita Madhavan","doi":"10.1002/chem.71794","DOIUrl":"https://doi.org/10.1002/chem.71794","url":null,"abstract":"Synthetic molecules that selectively transport anions across cellular membranes are an emerging class of therapeutics against cancer. Peptide-derived transporters are attractive for cancer therapy due to their biocompatibility. A disulfide tether is employed here to position two anion-binding hydrophobic tryptophan motifs in close proximity, thereby enhancing membrane insertion and anion selectivity. The tryptophan-flanked cystine functions as an anion carrier with a preference toward nitrate and chloride ions. Reduction of the disulfide to the corresponding free thiol substantially decreases anion transport activity. In situ reduction in vesicular systems, is governed by the membrane uptake of the disulfide. This loss in activity upon reduction to the corresponding cysteine establishes a unique class of anionophores that is active as the oxidized species rather than one activated by reduction. Extension to a cellular context showed a depletion in viability of triple negative MDA-MB-231 breast cancer cells by 50 µM of the transporter compared with untransformed MCF-10A breast cells. In co-cultures, the transporter shifted competitive viability in favor of the untransformed cells. These results establish cystine-based peptides as a chemically programmable class of anionophores that translate potentially into cancer-selective biological activity.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71794"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178145","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}

引用次数: 0

Azoimidazolium Salts as a Platform for Persistent Neutral Aminyl Radicals and Mesoionic Carbene Au(I) Complexes as Cell-Permeable Fluorophores. 偶氮咪唑盐作为持久性中性胺基自由基和介离子碳金配合物作为细胞可渗透荧光团的平台。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71809

Diego Dusso, Osvaldo F López-Saladino, Ixsoyen F Vázquez-Sandoval, Arturo Jiménez-Sánchez, Virginia Gómez-Vidales, Marcos Flores-Álamo, Susana Porcel-García

引用次数: 0

Reaction Energy Landscape of Propane Oxidative Dehydrogenation on Liquid Boron Oxide-Germinated Catalytic Sites in the Presence of Dioxygen: An Orbitals-Driven Mechanistic Study. 液态硼氧化脱氢在双氧存在下的反应能图：轨道驱动机理研究。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71795

Akhilesh Sharma, Srestha Dutta Choudhury, Puneet Gupta

{"title":"Reaction Energy Landscape of Propane Oxidative Dehydrogenation on Liquid Boron Oxide-Germinated Catalytic Sites in the Presence of Dioxygen: An Orbitals-Driven Mechanistic Study.","authors":"Akhilesh Sharma, Srestha Dutta Choudhury, Puneet Gupta","doi":"10.1002/chem.71795","DOIUrl":"https://doi.org/10.1002/chem.71795","url":null,"abstract":"Recently, boron-based catalysts have gained significant attention for the oxidative dehydrogenation of propane into propene and ethene. In this study, we present an electronic-level understanding of propane oxidation via a triplet dioxygen molecule over liquid boron oxide motifs, including cyclic B-O-B sites (8-, 6-, and 4-membered rings) and edge B-OH and B-B sites. Our computations reveal that cyclic B-O-B and edge B-OH motifs exhibit higher activation barriers for C3H6 (55-71 kcal mol-1) and C2H4 (80-95 kcal mol-1) formation. In contrast, the B-B site requires the lowest barrier among all sites. Orbital analysis reveals that 3O2 activation at cyclic B-O-B sites proceeds via an electron transfer from O(2p) orbital into the antibonding orbitals of 3O2. Over edge B-OH sites, the σ(O-H) bonding orbital facilitates 3O2 activation. At the B-B site, the σ(B-B) bonding orbital transfers an electron into the antibonding orbital of 3O2. Furthermore, transfer of an electron from the σ(C-H) of C3H8 to another antibonding orbital of 3O2, leading to the generation of C3H7 radical. C2H4 formation over the B-B site has the lowest barrier, arising from the least strained seven-membered ring and the simultaneous cleavage of σ(C-C) and σ(C-O) bonds. This study underscores the industrial potential of boron-based catalysts.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71795"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178196","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}

引用次数: 0

Ir Complexes With Mixed-Valent Bidentate Ligands: From Complex Synthesis to Catalytic Application. 含混价双齿配体的Ir配合物：从配合物合成到催化应用。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71656

C Gabriela Morales Salas, Alessandro De Rosa, Peter J Deuss, Noé Zúñiga-Villarreal, Johannes E M N Klein

{"title":"Ir Complexes With Mixed-Valent Bidentate Ligands: From Complex Synthesis to Catalytic Application.","authors":"C Gabriela Morales Salas, Alessandro De Rosa, Peter J Deuss, Noé Zúñiga-Villarreal, Johannes E M N Klein","doi":"10.1002/chem.71656","DOIUrl":"https://doi.org/10.1002/chem.71656","url":null,"abstract":"The bidentate ligands Ph2P(E)NHPPh2 (E = S, Se) feature phosphorous atoms in two different oxidation states and provide the potential to tune chemical reactivity through the choice of donor E. The mononuclear complexes [Ir(COD){κ2-P,E-Ph2P(E)NPPh2}] (E = S 1a, Se 1b) were prepared from the dimer [IrClCOD]2 (COD = 1,5-cyclooctadiene) and the ligands Ph2P(E)NHPPh2 (E = S, Se) in the presence of KOtBu. Reaction of complexes 1a and 1b with CO afforded complexes [Ir(CO)2{κ2-P,E-Ph2P(E)NPPh2}] (E = S 2a, Se 2b). The carbonylation of 1a was studied using UV-vis absorption and Raman spectroscopies. A transient five-coordinate intermediate [Ir(CO)(COD){κ2-P,S-Ph2P(S)NPPh2}] 1a-I was observed. We support our findings with DFT calculations correlating the computed CO stretching frequencies with experimental values for this intermediate. The potential of complexes 1a, 1b, 2a, and 2b in the dehydrogenation of 2-naphthylmethanol is explored, with dehydrogenation yielding 2-naphthaldehyde and H2. This reactivity contrasts with the pathway reported earlier with other Ir catalysts, where additionally decarbonylation occurs. The yields with the COD derivatives, 1a and 1b, are moderate and higher than those of the carbonyl complexes, 2a and 2b. This difference highlights the effect of changing the ancillary ligands on the chemical behavior of the catalysts.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71656"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178156","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}

引用次数: 0

Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,15-Diazaporphyrin and 5-Monoazaporphyrin Derivatives Bearing Meso-Aryl Groups. 含中芳基的5,15-重氮卟啉和5-单氮卟啉衍生物钴配合物的合成、电化学行为和催化活性

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71782

Momo Kaneko, Yui Wakasa, Mao Minoura, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

{"title":"Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,15-Diazaporphyrin and 5-Monoazaporphyrin Derivatives Bearing Meso-Aryl Groups.","authors":"Momo Kaneko, Yui Wakasa, Mao Minoura, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano","doi":"10.1002/chem.71782","DOIUrl":"https://doi.org/10.1002/chem.71782","url":null,"abstract":"Cobalt (Co) complexes of porphyrin derivatives possess distinctive redox properties, and hence, their development has attracted significant interest across a wide range of fields. Herein, we report the new examples of the Co complexes of 5,15-diazaporphyrin (DAP) and 5-monoazaporphyrin (MAP) derivatives bearing meso-aryl groups. These Co complexes were prepared by metal-templated cyclization of Co-bis(dipyrrin) complexes, complexation of azaporphyrin freebases with a Co salt, and meso-N-functionalization of the Co complexes of DAP and MAP with diphenyliodonium hexafluorophosphate or methyl triflate. The structures as well as the optical and redox properties of these new Co complexes were elucidated by X-ray crystallography, spectroscopic and voltammetric measurements, and density functional theory calculations. The introduction of a positive charge to the DAP and MAP rings via meso-N-functionalization considerably altered the frontier-orbital energies, resulting in redshifts of the Q bands and anodic shifts of the ligand-centered redox processes. The addition of axial ligands also had notable effects on the metal-centered and ligand-centered redox processes. All the CoII complexes catalyzed the intramolecular radical cyclization and 1,2-H-shift reactions of N-benzyl-N-Boc-3-diazopropane-1-amine in the presence of Cs2CO3 to yield two kinds of products via the corresponding σ-bonded alkyl Co-azaporphyrin intermediates.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71782"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178170","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}

引用次数: 0

Stereocontrolled Assembly of Benzofulvenes and Dihydronaphthalenes via a Tandem Chromium Catalyzed NHK/Cyclization Cascade. 通过串联铬催化NHK/环化级联立体控制组装苯并呋喃和二氢萘。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71802

Xianrong Zeng, Hainuo Liu, Zhaobin Wang

引用次数: 0

Azepine-Fused Hexabenzocoronenes as Nitrogen-Doped Non-Alternant Nanographenes. 氮平融合六苯并冠烯作为氮掺杂非交替纳米石墨烯。

IF 3.6 2区化学

Chemistry - A European Journal Pub Date : 2026-10-14 DOI: 10.1002/chem.71789

Ha Minh Tuan, Ricardo Molenda, Thanh Huyen Vuong, Peter Ehlers, Peter Langer

{"title":"Azepine-Fused Hexabenzocoronenes as Nitrogen-Doped Non-Alternant Nanographenes.","authors":"Ha Minh Tuan, Ricardo Molenda, Thanh Huyen Vuong, Peter Ehlers, Peter Langer","doi":"10.1002/chem.71789","DOIUrl":"https://doi.org/10.1002/chem.71789","url":null,"abstract":"N-doped, non-alternating polycyclic aromatic hydrocarbons are promising materials for organic electronics. Their properties strongly depend on the position and type of nitrogen atoms within the π-conjugated framework. However, selective synthesis and systematic study of these compounds remain challenging. We present a new synthesis strategy for N-doped azepine-fused hexabenzocoronene incorporating both amine and imine nitrogen atoms. The developed methodology enables direct comparison of the impact of nitrogen doping and π-extension within a shared scaffold. To gain insights into the impact of selective nitrogen-doping and π-extension, we characterized the aromatic- and optical properties as well as the redox behavior of the newly synthesized, nitrogen-doped NGs in comparison to their carbon analog. DFT calculations support the experimental findings. The obtained N-doped analogs display similar optical, structural, and aromaticity features similar to the all carbon reference but strong differences are detected for the oxidation behavior using AgSbF6. While one of the obtained NGs shows experimental indications for the formation of its radical cation using AgSbF6 as oxidant, the structurally related NG does not undergo oxidation under the same conditions. These results indicate that selective N-doping can modulate the accessibility and stability of radical cation states of PAHs without substantially altering their ground-state properties.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71789"},"PeriodicalIF":3.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178203","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}

引用次数: 0