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Aromaticity in semi‐condensed figure‐eight molecules Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Albert Artigas, Yannick Carissan, Denis Hagebaum-Reignier, Harald Bock, Fabien Durola, Yoann Coquerel
Electron delocalization and aromaticity was comparatively evaluated in recently synthesized figure‐eight molecules made of two condensed U‐shaped polycyclic aromatic hydrocarbon moieties connected either by two single bonds or by two para‐phenylene groups. The selected examples include molecules that incorporate eight‐membered and sixteen‐membered rings, as well as a doubly [5]helicene‐bridged (1,4)cyclophane
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A Bis‐Porphyrin Cavitand Breathing‐In to Constrict Bucky Balls Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Anupam Kumari, Pradip Kumar Mondal, Preetika Verma, Paritosh Mahato, Sujesh S, Koushik Mandal, Mauri Polentarutti, Adithya Lakshmanna Yapamanu, Jeyaraman Sankar
Bis‐porphyrin cages have long been exploited to bind fullerenes selectively for various applications. The major consideration for an effective binding here had been the cavity size. Herein, we structurally demonstrate that a bis‐Ni‐porphyrin cavitand having even a smaller cavity can host a larger fullerene by a breathing and ruffling mechanism. It has also been shown that both the electronic and steric
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Alared: Solvatochromic and Fluorogenic Red Amino Acid for Ratiometric Live‐cell Imaging of Bioactive Peptides Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Antoine Mirloup, Yann Berthomé, Stéphanie Riché, Patrick Wagner, Fabien Hanser, Arthur Laurent, Xavier Iturrioz, Catherine Llorens-Cortes, Julie Karpenko, Dominique Bonnet
To fill the need for environmentally sensitive fluorescent unnatural amino acids able to operate in the red region of the spectrum, we have designed and synthesized Alared, a red solvatochromic and fluorogenic amino acid derived from the Nile Red chromophore. The new unnatural amino acid can be easily integrated into bioactive peptides using classical solid‐phase peptide synthesis. The fluorescence
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Determining Structures of Layer‐by‐Layer Spin‐Coated Zinc Dicarboxylate‐Based Metal‐Organic Thin Films Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Jan C. Fischer, Robbin Steentjes, Dong-Hui Chen, Bryce S. Richards, Egbert Zojer, Christof Wöll, Ian A. Howard
Thin films of crystalline solids with substantial free volume from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn‐based SBUs are especially relevant in this case because they avoid quenching the chromophore’s luminescence. We find that layer‐by‐layer spin‐coating using Zn acetate
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A Comprehensive Review on Reductive Recycling of Cathode Materials of Spent Lithium‐Ion Batteries Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Yiran Li, Junhui Cai, Jiayu Wang, Shengnv Xu, Yanjuan Li, Wei He, Zhanzhan Wang, Shun Yang, Xiao Yan
The prosperity of the lithium‐ion battery market is inevitably accompanied by the depletion of corresponding resources and the accumulation of spent batteries in a dialectical manner. Spent lithium‐ion batteries are harboring the characteristics of hazardous waste and high‐value resources, so efficient recycling is of great significance. The cathode material is considered as an interesting target for
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Classical versus Collective Interactions in Asymmetric Trigonal Bipyramidal Alkaline Metal‒Boron Halide Complexes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-20 Zahra Badri, Cina Foroutan-Nejad
Collective interactions are a novel type of chemical bond formed between metals and electron‐rich substituents around an electron‐poor central atom. So far only a limited number of candidates for having collective interactions are reported. In this work, we extend the newly introduced concept of collective bonding to a series of neutral boron complexes with the general formula M2BX3 (M = Li, Na, and
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Hollow UiO‐66‐NH2 encapsulated Pd catalysts for highly selective hydrogenation of furfural to furfuryl alcohol Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Bo Zhao, Yao Yao, Kexin Huang, Jiaxin Li, Minjie Chen, Chao Liu, Hongjian Xu, Xinyu Zhao, Ganggang Chang
The selective hydrogenation of furfural (FFA) to furfuryl alcohol (FA) is regarded as attractive transformation to achieve the sustainable synthesis of value‐added chemicals from biomass resources. However, the conventional supported catalysts are significantly restricted by their narrow pore size, ununiform dispersion and easy leaching or aggregation of catalytic sites. Herein, we designed hollow
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A Magnesium Binding Site And The Anomeric Effect Regulate The Abiotic Redox Chemistry Of Nicotinamide Nucleotides Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Lorenzo Sebastianelli, Harpreet Kaur, Ziniu Chen, Ramanarayanan Krishnamurthy, Sheref S. Mansy
Nicotinamide adenine dinucleotide (NAD+) is a redox active molecule that is universally found in biology. Despite the importance and simplicity of this molecule, few reports exist that investigate which molecular features are important for the activity of this ribodinucleotide. By exploiting the nonenzymatic reduction and oxidation of NAD+ by pyruvate and methylene blue, respectively, we were able
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Metal‐(Acyclic Diaminocarbene) Complexes Demonstrate Nanomolar Antiproliferative Activity against Triple‐Negative Breast Cancer Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Svetlana A. Katkova, Alexander S. Bunev, Rovshan E. Gasanov, Dmitry A. Khochenkov, Andrey V. Kulsha, Oleg A. Ivashkevich, Tatiyana V. Serebryanskaya, Mikhail A. Kinzhalov
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HFIP‐mediated Desulfinative Friedel–Crafts Cyclobutenylation Reaction Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Hikaru Yanai, Shota Kurogi, Shoki Hoshikawa, Takashi Matsumoto
In 1,1,1,3,3,3‐hexafluoroisopropyl alcohol (HFIP), gem‐bis(triflyl)cyclobutenes, which can be prepared by the (2+2) cycloaddition reaction of Tf2C=CH2 with alkynes, underwent desulfination to generate the corresponding cyclobutenyl cation. This unique reactivity was successfully applied to the Friedel–Crafts type cyclobutenylation reaction of several (hetero)aromatic compounds.
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Benzoselenadiazole‐Functionalized H‐bonded Arylamide Foldamers: Solvent‐Responsive Properties and Helix Self‐Assembly Directed by Chalcogen Bonding in Solid State Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Chuanzhi Liu, Chi Zhang, Chang-Gen Li, Hui-Bin Chen, Wen Yang, Zhong-Yi Li, Zhi-Yuan Hu, Liang Xu, Bin Zhai, Zhan-Ting Li
In this study, a series of H‐bonded arylamide foldamers bearing benzoselenadiazole ends with solvent‐responsive properties have been synthesized. In dichloromethane or dimethyl sulfoxide solvents, the molecules exhibit meniscus or linear structures, respectively, which can be attributed to the unique intramolecular hydrogen bonding behavior evidenced by 1D 1H NMR and 2D NOESY spectra. UV‐vis spectroscopy
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Exploration of Vitamin B6‐Based Redox‐Active Pyridinium Salts towards the Application in Aqueous Organic Flow Batteries Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Anton A. Nechaev, Gabriel Gonzalez, Prachi Verma, Vsevolod A. Peshkov, Anton Bannykh, Arsalan Hashemi, Jenna Hannonen, Andrea Hamza, Imre Papai, Kari Laasonen, Pekka Peljo, Petri M. Pihko
Pyridoxal hydrochloride, a vitamin B6 vitamer, was synthetically converted to a series of diverse redox‐active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory‐scale redox flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery
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Calcium‐Based Metal‐Organic Framework: Detection and Idiosyncratic Removal of Copper by Nano‐particle Deposition Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-19 Pallav Mondal, Bhaskar K. Brahma, Khasim Vali Dudekula, Joydeep Ray, Jyothirlatha V. N. Kasu, Avishek Gangopadhyay, Sourav Laha, Utpal Adhikari
A novel calcium‐based metal‐organic framework (CaMOF@LSB) was designed and synthesized, exhibiting dual functionality for both selective detection and removal of Cu2+ ions from aqueous solutions. The framework's stability, including solvent and pH variations, was established with notable thermal resilience. Colorimetric Cu2+ detection (≥ 5 ppm) with a high capture capacity of 484.2 mg g‐1 by CaMOF@LSB
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Redox‐Active Triazole‐Derived Mesoionic Imines with Ferrocenyl Substituents and their Metal Complexes: Directed Hydrogen‐Bonding, Unusual C‐H Activation and Ion‐Pair Formation Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Richard Rudolf, Derman Batman, Niklas Mehner, Robert. R. M. Walter, Biprajit Sarkar
We present herein the synthesis, characterization and complexation of ferrocenyl‐substituted MIIs (mesoionic imines) and their metal complexes. In the free MIIs, strong hydrogen bonding interactions are observed between the imine‐N and the C‐H bonds of the ferrocenyl substituents both in the solid state and in solution. The influence of this hydrogen bonding is so strong that complexation of the MIIs
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Novel Types of Phyllobilins in a Fern ‐ Molecular Reporters of the Evolution of Chlorophyll Breakdown in the Paleozoic Era Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Theresia Erhart, Christian Nadegger, Stefan Vergeiner, Christoph Kreutz, Thomas Müller, Bernhard Kräutler
Breakdown of chlorophyll (Chl), as studied in angiosperms, follows the pheophorbide a oxygenase/phyllobilin (PaO/PB) pathway, furnishing linear tetrapyrroles, named phyllobilins (PBs). In an investigation with fern leaves we have discovered iso‐phyllobilanones (iPBs) with an intriguingly rearranged and oxidized carbon skeleton. We report here a key second group of iPBs from the fern and on their structure
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Mimicking Ozonolysis via Mechanochemistry: Internal Alkynes to 1,2‐Diketones using H5IO6 Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Pravat Nayek, Prasenjit Mal
Utilizing periodic acid as an environmentally benign oxidizing agent, this study introduces a novel mechanochemical method that mimics ozonolysis to convert internal alkynes into 1,2‐diketones, showcasing effective emulation of ozone's reactivity. Notably, this oxidation occurs at room temperature in aerobic conditions, eliminating the need for toxic transition metals, hazardous oxidants, or expensive
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Comparison of Classical and Green RPLC Methods in the Determination of pKa Values of Some Piperazine Group Antihistamines Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 İkbal Demet Nane, Ebru Çubuk Demiralay, Yaşar Doğan Daldal
In this study, protonation constant values and liquid chromatographic behaviors of hydrophobic cyclizine, chlorcyclizine, hydroxyzine, cinnarizine, cetirizine, meclizine, and buclizine in some water‐organic solvent binary mixtures were examined for the first time using classical and green reverse phase liquid chromatography methods. In the isocratic study, the relationship of the retention time and
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Use of Unprecedented Intramolecular 1,3‐Dipolar Cycloaddition Reaction in meso‐Nitrile Oxide‐Containing BODIPY as a New Pathway for the Preparation of Fused NIR Platforms Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Yuriy V. Zatsikha, Dijo Prasannan, Briana Scharge, David E. Herbert, Nikolay N. Gerasimchuk, Matthew Zeller, Victor N. Nemykin
Meso‐nitrile oxide group in 1,7‐Diphenyl‐containing BODIPYs can be involved in highly unusual [3+2] intramolecular cycloaddition reaction with the formation of the dihydrobenzo[d]isoxazole‐containing BODIPYs. Oxidation of these compounds results in the formation of unprecedented either benzisoxazole‐ or benzo[b]azepine‐fused fully conjugated NIR absorbing BODIPYs. The photophysical properties and electronic
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Engineering Amino Acid and Peptide Supramolecular Architectures through Fluorination Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Eleonora Veronese, Pierangelo Metrangolo, Valentina Dichiarante
Fluorinated non‐natural amino acids are attracting considerable research interest, especially in the biomedical field and in materials science, thanks to their ability to self‐assemble into peculiar supramolecular structures. The conformational changes induced by the presence of fluorine atoms obviously affect their functions, as well as the biological activity of the deriving peptides and proteins
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A Triply Linked Copper(III) Dicarbacorrole Dimer Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Ruijuan Jiao, Ningchao Liu, Zhaohui Zong, Xian-Sheng Ke
A triply linked dicarbacorrole dimer (7) was synthesized from a new meso‐meso singly linked dicarbacorrole dimer precursor (6) via an oxidative fusion reaction by 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) in the presence of trifluoromethanesulfonic acid (TfOH). Single crystal X‐ray structure of 7 adopts a flat conformation with a length as ca. 15.946 Å and a width as 6.903 Å, which can be regarded
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Organophotocatalytic Remote Thiocyanation Reaction via Ring‐Opening Functionalization of Cycloalkanols Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-18 Ruirui Hua, Qing Wang, Hongquan Yin, Fu-Xue Chen
The remote C(sp3)‐SCN bond formation via ring‐opening functionalization of cycloalkanols with N‐thiocyanatosaccharin as the precursor of SCN radicals and pyrylium salt as the organic photocatalyst under visible light has been developed. Thus, various terminal keto thiocyanates were prepared without transition metals and oxidants in moderate to good yields. The simplicity, wide substrate scope and mild
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Structural Chemistry of Titanium (IV) Oxo Clusters, Part 2: Clusters Without Carboxylate or Phosphonate Ligands Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Ulrich Schubert, Berthold Stöger
Homometallic titanium oxo clusters (TOC) are one of the most important groups of metal oxo clusters. In a previous article, TOC structures with carboxylato and phosphonato ligands were reviewed and categorized. This work is now extended to clusters with other ligands. Comparison of the different cluster types shows how the interplay between condensation of the titanium polyhedra by means of bridging
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Directly‐Fused Ni(II)Porphyrin Conjugated Polymers with Blocked meso‐positions: Impact on Electrocatalytic Properties Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Deepak BANSAL, Hadi Ghahramanzadehasl, Drialys Cardenas-Morcoso, Jessica Desport, Gilles Frache, Giuseppe Bengasi, Nicolas D. Boscher
The oxidative coupling reaction of two Ni(II) porphyrins meso‐substituted with three and four phenyl groups, Ni(II) 5,10,15‐(triphenyl)porphyrin (NiPh3P) and Ni(II) 5,10,15,20‐(tetraphenyl)porphyrin (NiPh4P) respectively, was investigated in a oxidative chemical vapor deposition (oCVD) process. Irrespective of the number of meso‐substituents, high‐resolution mass spectrometry evidences the formation
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Perfect Polar Alignment of Parallel Beloamphiphile Layers: Improved Structural Design Bias Realized in Ferroelectric Crystals of the Novel “Methoxyphenyl Series of Acetophenone Azines” Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Harmeet Bhoday, Nathan Knotts, Rainer Glaser
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Understanding the Remarkable Stability of Well‐defined Dinuclear Copper(I) Carbene Complexes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Roel Bienenmann, Marianne de Vries, Martin Lutz, Daniel Broere
The synthesis of a well‐defined dicopper carbene complex supported by the PNNP (2,7‐bis(di‐tert‐butylphosphaneyl)methyl‐1,8‐naphthyridine) expanded pincer ligand is reported. This carbene complex is remarkably stable, even in the presence of air and water. The reactivity of this complex was explored towards typical carbene transfer substrates and its electronic structure was investigated. Using a combination
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Enantioselective Synthesis of α‐Quaternary Isochromanes by Oxidative Aminocatalysis and Gold Catalysis Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Philipp Waser, Jonas Faghtmann, Marta Gil-Ordóñez, Anne Kristensen, Esben B. Svenningsen, Thomas B. Poulsen, Karl Anker Jørgensen
A novel strategy that combines oxidative aminocatalysis and gold catalysis allows the preparation of chiral α‐quaternary isochromanes, a motif that is prevalent in natural products and synthetic bioactive compounds. In the first step, α‐branched aldehydes and propargylic alcohols are transformed into α‐quaternary ethers with excellent optical purities (>90% ee) via oxidative umpolung with DDQ and an
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Opportunity of Patterning in Chemistry Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Denis Gentili, Massimiliano Cavallini
Patterning offers an efficient way to quantitatively enhance and enlarge material properties and functionalities, offering unprecedented opportunities for innovation in various scientific domains. By precisely controlling the spatial arrangement of materials at the micro‐ and nanoscale, patterning enables the exploitation of inherent material properties in novel ways. In addition, it generates new
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Steric effects on single‐molecule conductance in flat‐lying phenanthrene Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Kevin Batzinger, Qinghai Zhou, Xiang Ye, Eric Borguet, Shengxiong Xiao, Manuel Smeu
A previous combined experimental and theoretical study found that the position of anchoring groups on a phenanthrene (PHE) backbone played a large role in determining the single‐molecule conductance of the PHE derivative. However, a consistent 0.1 G0 feature was found across all PHE derivatives. To understand this, the previously investigated PHE derivatives were placed flat on a simulated Au substrate
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Fluorescence and Lifetime Imaging of Endoplasmic Reticulum Polarity Change During Ferroptosis Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Mingfeng Li, Yuncong Chen, Weijiang He, Zijian Guo
As a new form of regulated cell death, ferroptosis is closely related to various diseases. Tracing ferroptosis related biological behavior is helpful to better understand this process and its related biology. Considering that ferroptosis is featured with remarkable lipid peroxidation which can easily change the membranes’ compositions and structures, it is potential to detect intracellular environmental
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Energy Barrier and Gaps between Two Excited States in a Dual‐Emissive Carborane Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Xueyuan Zhao, Xining Zhang, Xin Li, Lin Wu, Lei Ji
A thorough understanding of the internal conversion process between excited states is important for designing ideal multiple emissive materials. However, it is hard to experimentally measure both the energy barrier and energy gaps between the excited states of a compound. For a long time, it is dubious if what was measured is the energy gap or energy barrier between two excited states. In this paper
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Post‐formation of fused pentagonal structure on fjord region of polyaromatic hydrocarbons under hydrothermal conditions Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Naoto Hamaguchi, Takumi Kubota, Masaaki Yamada, Hikaru Kimura, Hayato Tsuji
This study explores the synthesis of cyclopenta‐fused polyaromatic hydrocarbons (CP‐PAHs) via Pt‐catalyzed cyclization in water, focusing on the formation of fused pentagonal rings within heavily fused PAH frameworks. Utilizing platinum catalysts at lower temperatures (200‐260°C) in water, led to the successful synthesis of singly cyclized CP‐PAHs. The reaction conditions facilitated the mono‐cyclization
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Selective B(3)‐H activation without auxiliary reagents affording multinuclear Ir(III) complexes with (o‐carboranyl)dithioester ligands Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Yong-Xiao Zhu, Run-Ze Yuan, Hai-Ning Zhang, Guo-Xin Jin
A method was developed to link two or three o‐carborane moieties to form a series of carboranyl dithioester bridging ligands via in situ substitution of haloalkanes by tetraphenylphosphonium carboranyldithiocarboxylates. Based on these ligands, direct B‐H activation without the assistance of Ag(I) and alkali was successfully achieved with half‐sandwich Ir(III) substrate [Cp*IrCl2]2 to yield corresponding
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Ion Mobility Mass Spectrometry‐based Disaccharide Analysis of Glycosaminoglycans Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Lukasz Polewski, Eunjin Moon, Andreas Zappe, Michael Götze, Gergő Péter Szekeres, Christian Roth, Kevin Pagel
Glycosaminoglycans (GAGs) are linear and acidic polysaccharides. They are ubiquitous molecules, which are involved in a wide range of biological processes. Despite being structurally simple at first glance, with a repeating backbone of alternating hexuronic acid and hexosamine dimers, GAGs display a highly complex structure, which predominantly results from their heterogeneous sulfation patterns. The
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A Structure‐Activity Investigation of the Fungal Metabolite (‐)‐TAN‐2483B: Inhibition of Bruton’s tyrosine kinase. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Jordan McCone, Paul H. Teesdale-Spittle, Jack U. Flanagan, Joanne E. Harvey
The natural product (‐)‐TAN‐2483B is a fungal secondary metabolite which displays promising anti‐cancer and immunomodulatory activity. Our previous syntheses of (‐)‐TAN‐2483B and sidechain analogues uncovered inhibitory activity against Bruton’s tyrosine kinase (Btk), an established drug target for various leukaemia and immunological diseases. A structure‐based computational study using ensemble docking
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Current Developments in Emerging Lanthanide‐doped persistent luminescent scintillators and their applications Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Huiru Ye, Yantao Li, Xukai Chen, Weidong Du, Longfei Song, Yu Chen, Qiuqiang Zhan, Wei Wei
Lanthanide‐doped scintillators have the ability to convert the absorbed X‐ray irradiation into ultraviolet (UV), visible (Vis), or near‐infrared (NIR) light. Lanthanide‐doped scintillators with excellent persistent luminescence are emerging as a new class of persistent luminescent materials recently. They have attracted great attention due to their unique "self‐luminescence" characteristic and potential
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Pyrene Functionalized Norbornadiene‐Quadricyclane Fluorescent Photoswitches: Characterization of their Spectral Properties and Application in Imaging of Amyloid Beta Plaques Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Shima Ghasemi, Monika Shamsabadi, Axel Olesund, Andreas Erbs Hillers-Bendtsen, Francisco Najera, Fredrik Edhborg, Adil S. Aslam, Wera Larsson, Zhihang Wang, Francoise M. Amombo Noa, Rebecca J. Salthouse, Lars Öhrström, Helen Hölzel, Ezequiel Perez-Inestrosa, Kurt V. Mikkelsen, Jörg Hanrieder, Bo Albinsson, Ambra Dreos, Kasper Moth-Poulsen
This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aβ) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization
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Continuous Synthesis of a Macrocyclic Sulfite of Polyethylene Glycol by Cascaded Continuous Stirred Tank Reactors (CSTRs) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Jichang Wei, Yinli Liu, Yuchen Sun, Jun Bai, He Gao, Zhaojun Yang, Long Pan
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Fagopyrins from Buckwheat Flowers: Structural and Stereochemical Characterization through Combined NMR/CD Spectroscopy and Theoretical Calculations. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-17 Valerio Galbusera, Benedetta Lattuada, Andrea Pinto, Alberto Barbiroli, Gigliola Borgonovo, Enzio Maria Ragg
Fagopyrins are phenantroperylenequinones present in the flowers of Fagopyrum esculentum (buckwheat) endowed with photodynamic activity. It has been reported that fagopyrin extracts actually contain a complex mixture of closely related compounds, differing only on the nature of the perylenequinone substituents. We report our systematic and detailed study on the chemical composition of fagopyrin extracts
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Tetraanionic Oligo‐Dioxaborines: Strongly Absorbing Near‐Infrared Dyes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Vladyslav Polishchuk, Andrii Kulinich, Mykola Shandura
Polymethine dyes of tetraanionic nature comprising 1,3,2‐dioxaborine rings in the polymethine chain and end‐groups of different electron‐accepting abilities have been synthesized. They can be considered as oligomeric polymethines, where a linear conjugated π‐system passes through three 1,3,2‐dioxaborine units and a number of tri‐ and dimethine π‐bridges between two end‐groups. The obtained dyes exhibit
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Engineering Modular DNA Reaction Networks for Signal Processing Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Shuang Cui, Xin Liu, Xun Zhang, Peijun Shi, Yanfen Zheng, Bin Wang, Qiang Zhang
Diversified molecular information‐processing methods have significant implications for nanoscale manipulation and control, monitoring and disease diagnosis of organisms, and direct intervention in biological activities. However, as an effective approach for implementing multifunctional molecular information processing, DNA reaction networks (DRNs) with numerous functionally specialized molecular structures
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A Highly Sterically Encumbered Boron Lewis Acid Enabled by a Organotellurium‐based Ligand Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Daniel Wegener, Alberto Pérez-Bitrián, Niklas Limberg, Anja Wiesner, Kurt F. Hoffmann, Sebastian Hasenstab-Riedel
Lewis acidic boron compounds are ubiquitous in chemistry due to their numerous applications, yet tuning and optimizing their properties towards different purposes is still a challenging field of research. In this work, the boron Lewis acid B[OTeF3(C6F5)2]3 was synthesized by reaction of the teflate derivative HOTeF3(C6F5)2 with BCl3 or BCl3·SMe2. This new compound presents a remarkably high thermal
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Synthesis Strategies, Preparation Methods, and Applications of Chiral Metal‐Organic Frameworks Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Hui Zhang, Qingsong Cheng, Hebing Pei, Simin He, Ruibin Guo, Nijuan Liu, Zunli Mo
: Chiral metal‐organic framework (CMOFs) is a kind of material with great application value in recent years. Formed by the coordination of metal ions or metal clusters with organic ligands. It is widely used in chemistry, biology, medicine and materials science because of its ordered and adjustable pores, multi‐dimensional network structure, large specific surface area and excellent adsorption properties
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14‐Membered Macrocyclic β‐Diiminato Gold(II) – A New Member for the Gold(II) Complex Family? Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Lukas Sorge, Julian Link, Katja Heinze
The chemistry of molecular gold compounds is dominated by the oxidation states +I and +III. For the intermediate oxidation state +II with 5d9 electron configuration, dimerization or disproportionation of the gold(II) radicals is favoured, so that only a few mononuclear gold(II) complexes have been isolated to date. The present study addresses the one‐electron reduction of the macrocyclic gold(III)
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Exploring the Magnetic Interactions in Two Novel Cyanide‐bridged Homo‐ and Heterometallic Hexadecanuclear Complexes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Jyoti Yadav, Arindam Gupta, Arpan Mondal, Florian Daumann, Gerald Hörner, Birgit Weber, Sanjit Konar
Two novel isostructural cyanide‐bridged hexadecanuclear complexes with the general formula {[Fe(CN)6]6[M{en(Bn)py}]10}2+ [M = Fe (12+), Ni (22+)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 12+ whereas all the Fe centres share a conserved oxidation state in complex 22+. The DC magnetic study revealed antiferromagnetic
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One‐Pot Synthesis of Nanoflower‐Like Bimetallic Sulfides of Zn2SnS4 as Nanozymes for Highly Sensitive Sensing of H2O2 Released by Living Cells Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Xia Wen, Jiancong Ni, Shunmu Zeng, Zhiping Song, Weiwei Qiu
The sensitive and reliable nanozyme‐based sensor enables the detection of low concentrations of H2O2 in biological microenvironments, it has potential applications as an in‐situ monitoring platform for cellular H2O2 release. The uniformly dispersed bimetallic sulfide (Zn2SnS4) nanoflowers were synthesized via a one‐pot hydrothermal method and the two kinds of metal ions can serve as morphology and
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Effect of Co‐adsorbed Guest Adsorbates on the Separation of Ethylene/Ethane Mixtures on Metal‐Organic Frameworks with Open Metal Sites Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Yuqing Xiao, Shenhui Li, Bin Jiang, Xinmiao Liang, Yueying Chu, Feng Deng
Direct determination of the equilibrium adsorption and spectroscopic observation of adsorbent‐adsorbate interaction is crucial to evaluate the olefin/paraffin separation performance of porous adsorbents. However, the experimental characterization of competitive adsorption of various adsorbates at atomic‐molecular level in the purification of multicomponent gas mixtures is challenging but rarely conducted
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Application of Sublimation in the Synthesis and Crystal Growth of Organosulfones Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Lamis Alaa Eldin Refat, Jolanta Karpinska, Saidulu Konda, John M. Simmie, Paul Vincent Murphy, Patrick McArdle, Andrea Erxleben
The solvent‐free elimination of sulfinic acid and aromatization of 1,6‐trans‐substituted bis(arylsulfone) trienes is reported. It is shown that sublimation can be used as a ‘green’ method to combine the thermal transformation of six trienes and the crystal growth of the resulting 4‐(phenylsulfonyl)biphenyls. When the sublimation conditions are carefully controlled, high quality single crystals of the
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Catalytic Cascade: Efficient Synthesis of Cyclohepta[b]indoles and Cyclohepta[b]indole‐Indoline Conjugates via RCM, Hydrogenation, and Acid‐Catalyzed Ring Expansion Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Nabin Parui, Tirtha Mandal, Sandip Maiti, Jyotirmayee Dash
Cyclohepta[b]indoles, prevalent in natural products and pharmaceuticals, are conventionally accessed via metal or Lewis acid‐mediated cycloadditions with prefunctionalized substrates. Our study introduces an innovative sequential catalytic assembly for synthesizing cyclohepta[b]indoles from readily available isatin derivatives. The process involves three catalytic sequences: ring‐closing metathesis
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Variation in Catalytic Efficacies of a 2D pH‐stable MOF by Altering Activation Methods Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Janaki Behera, Arun Pal, Rupam Sahoo, Madhab C. Das
Although it is well‐known that the Lewis acidity of Metal‐Organic Frameworks (MOFs) can effectively enhance their catalytic activity in organic transformations, access to these Lewis‐acidic sites remains a key hurdle to widespread applications of Lewis‐acidic catalysis by MOFs. Easy accessibility of strong Lewis acidic sites onto 2D MOFs by using proper activation methods can be a cornerstone in attaining
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Multiple Bonding in AeN‐ (Ae = Ca, Sr, Ba) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Li-juan Cui, Yu-qian Liu, Meng-hui Wang, Bing Yan, Sudip Pan, Zhong-hua Cui, Gernot Frenking
Quantum chemical calculations using ab initio methods at the MRCI+Q(8,9)/def2‐QZVPPD and CCSD(T)/def2‐QZVPPD levels as well as density functional theory are reported for the diatomic molecules AeN‐ (Ae = Ca, Sr, Ba). The nature of the bonds is analyzed with a variety of methods. The anions CaN‐ and SrN‐ have electronic triplet (3Π) ground states with nearly identical bond dissociation energies De ~57
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Selective Lattice Doping Enables a Low‐cost, High‐capacity and Long‐lasting Potassium Layered Oxide Cathode for Potassium and Sodium storage Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Ruopeng Ai, Xinyuan Zhang, Shuyue Li, Zhixuan Wei, Gang Chen, Fei Du
Layered transition metal oxides are highly promising host materials for K ions, owing to their high theoretical capacities and appropriate operational potentials. To address the intrinsic issues of KxMnO2 cathodes and optimize their electrochemical properties, a novel P3‐type oxide doped with carefully chosen cost‐effective, electrochemically active and multi‐functional elements is proposed, namely
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Synthesis of Calix[4]arene‐Based Porous Organic Cages and Their Gas Adsorption Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Qidi Kong, Lei-Lei Liu, Zhongyue Li
Two crystalline large‐sized porous organic cages (POCs) based on conical calix[4]arene (C4A) were designed and synthesized. The four‐jaw C4A unit tends to follow the face‐directed self‐assembly law with the planar triangular building blocks such as tris(4‐aminophenyl)amine (TAPA) or 1,3,5‐tris(4‐aminophenyl)benzene (TAPB) to generate a predictable cage with a stoichiometry of [6+8]. The formation of
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Reductions of Arenes using a Magnesium‐Dinitrogen Complex Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Matthew J. Evans, Jeremy Mullins, Rahul Mondal, Cameron Jones
In this contribution, we present “Birch‐type”, and other reductions of simple arenes by the potassium salt of an anionic magnesium dinitrogen complex, [{K(TCHPNON)Mg}2(μ‐N2)] (TCHPNON = 4,5‐bis(2,4,6‐tricyclohexylanilido)‐2,7‐diethyl‐9,9‐dimethyl‐xanthene), which acts as a masked dimagnesium(I) diradical in these reactions. This reagent is non‐hazardous, easy‐to‐handle, and readily provides access
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Dynamics of Coordinated Phosphonate Group Directly Observed by 17O‐NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue. Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Adam Svítok, Jan Blahut, Peter Urbanovský, Petr Hermann
Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of the exchange (“phosphonate rotation”) in model Ln(III) complexes of monophosphonate H4dota analogue which alters phosphorus atom chirality of coordinated
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Classification and identification of perfume scents by an enantioselective colorimetric sensor array of chiral metal‐organic‐framework‐based Fabry‐Pérot films Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Kuo Zhan, Anemar Bruno Kanj, Lars Heinke
Many odors, like perfumes, are complex mixtures of chiral and achiral molecules where the cost‐efficient (enantio‐)selective sensing represents a major technical challenge. Here, we present a colorimetric sensor array of surface‐mounted metal‐organic‐framework (SURMOF) films in Fabry–Pérot (FP) cavities. The optical properties of the FP‐SURMOF films with different chiral and achiral structures are
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In Silico Design and Characterization of a New Molecular Electride: Li@Calix[3]Pyrrole Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Ranajit Saha, Bastian Bjerkem Skjelstad, Sudip Pan
Electrides, in which anionic electrons are localized independent of the atoms in the compound, have shown promise especially as catalysts and optoelectronic materials. Here, we present a new computationally designed molecular electride, Li@calix[3]pyrrole (Li@C3P). Electron density and electron localization function analyses unequivocally confirm the existence of localized electride electron density
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Azophosphines: Synthesis, Structure and Coordination Chemistry Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Emma J. Jordan, Ethan D. E. Calder, Holly V. Adcock, Louise Male, Martin Nieger, J. Chris Slootweg, Andrew R. Jupp
The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus‐containing analogues of triazenes are underexplored but offer great potential as flexible and small bite‐angle ligands. This manuscript explores the synthesis and characterisation of a family of air‐stable azophosphine‐borane complexes, and their subsequent
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Conformational and Electronic Variations in 1,2‐ and 1,6‐Cyclophellitols and Their Impact on Retaining α‐Glucosidase Inhibition Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Tim P. Ofman, Jurriaan J. A. Heming, Alba Nin-Hill, Florian Küllmer, Elisha Moran, Megan Bennett, Roy Steneker, Anne-Mei Klein, Gijs Ruijgrok, Ken Kok, Zach W. B. Armstrong, Johannes M. F. G. Aerts, Gijsbert A. van der Marel, Carme Rovira, Gideon J. Davies, Marta Artola, Jeroen D. C. Codée, Hermen S. Overkleeft
: Glycoside hydrolases (glycosidases) take part in myriad biological processes and are important therapeutic targets. Competitive and mechanism‐based inhibitors are useful tools to dissect their biological role and comprise a good starting point for drug discovery. The natural product, cyclophellitol, a mechanism‐based, covalent and irreversible retaining β‐glucosidase inhibitor has inspired the design
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B(C6F5)3/CPA‐Catalyzed Aza‐Diels–Alder Reaction of 3,3‐Difluoro‐2‐Aryl‐3H‐indoles and Unactivated Dienes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-16 Xing-Pin Wei, Xin-Chun Wang, Tao Ma, Xiu-Xiu Qiao, Ganpeng Li, Yonghui He, Xiao-Jing Zhao
Here we report B(C6F5)3/CPA‐catalyzed enantioselective aza‐Diels–Alder reaction of 3,3‐difluoro‐2‐Aryl‐3H‐indoles with unactivated dienes to access chiral 10,10‐difluoro‐tetrahydropyrido[1,2‐a]indoles. This protocol allows the formation of pyrazole‐based C2‐quaternary indolin‐3‐ones with high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis of the 10,10‐difluoro‐tetrahydropyrido[1
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Boosting Excited‐State Energy Transfer by Anchoring Dipole Orientation in Binary Thermally Activated Delayed Fluorescence/J‐Aggregate Assemblies Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-15 Zhuoming Ma, Zilong Guo, Yixuan Gao, Yaxin Wang, Min Du, Yandong Han, Zheng Xue, Wensheng Yang, Xiaonan Ma
Förster resonance energy transfer (FRET) has been widely applied in fluorescence imaging, sensing and so on, while developing useful strategy of boosting FRET efficiency becomes a key issue that limits the application. Except optimizing spectral properties, promoting orientation factor (κ2) has been well discussed but rarely utilized for boosting FRET. Herein, we constructed binary nano‐assembling