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Asymmetric 1,4‐Addition of Diarylphosphine Oxides to α,β‐Unsaturated 2‐Acyl Imidazoles Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Lirong Chen, Guiyong Wang, Xiufei Nong, Wendi Shao, Jiuling Li, Yafei Guo, Baomin Fan
Here we introduce a metal‐free, catalytic and enantioselective strategy from α,β‐unsaturated 2‐acyl imidazoles to the chiral phosphorous 2‐acyl imidazoles. Interestingly, this methodology was catalyzed by the classical and commercial oxazaborolidine under mild conditions. This strategy features a wide range of substrates scope with good yields and excellent enantioselectivities. The possible mechanism
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Detection and Characterization of Hydride Ligands in Copper Complexes by Hard X‐ray Spectroscopy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Lorena Fritsch, Pia Rehsies, Wael Barakat, Deven P. Estes, Matthias Bauer
Transition metal complexes, particularly copper hydrides, play an important role in various catalytic processes and molecular inorganic chemistry. This study employs synchrotron hard X‐ray spectroscopy to gain insights into the geometric and electronic properties of copper hydrides as potential catalysts for CO2 hydrogenation. The potential of high energy resolution X‐ray absorption near‐edge structure
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Electrophotocatalysis versus Indirect Electrolysis: Electrochemical Selenocyclization of 3‐Aza‐1,5‐dienes Facilitated by Energy Transfer, Direct Photolysis or N‐Hydroxyphthalimide Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Dongyin Wang, Li Zeng, Jifu Shi, Shulin Gao, Lou Shi, Shaoguang Sun, Deqiang Liang
Three hybrid electrochemical protocols, which involve the energy transfer, direct photolysis and N‐hydroxyphthalimide catalyst, respectively, are presented for the selenylation/cyclization of the fragile substrates of 3‐aza‐1,5‐dienes with diorganyl diselenides to afford 3‐selenomethyl‐4‐pyrrolin‐2‐ones. The two electrophotocatalytic reactions and the indirect electrolysis one are both regioselective
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Application of Mono and Trinuclear Cyclometalated Iridium (III) Complexes in Differential Bacterial Imaging and Antimicrobial Photodynamic therapy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Bishnu Das, Prakash Biswas, Amirul Islam Mallick, Parna Gupta
The application of transition metal complexes for antimicrobial photodynamic therapy (PDT) has emerged as an attractive alternative in mitigating a broad range of bacterial pathogens, including multidrug‐resistant pathogens. In view of their photostability, long excited‐state lifetimes, and tunable emission properties, transition metal complexes also contribute as bioimaging agents. In the present
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Efficient Synthetic Access to Stable Isotope Labelled Pseudouridine Phosphoramidites for RNA NMR Spectroscopy Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 David Glänzer, Martin Pfeiffer, Andrej Ribar, Ricarda Zeindl, Martin Tollinger, Bernd Nidetzky, Christoph Kreutz
Here we report the efficient synthetic access to 13C/15N‐labelled pseudouridine phosphoramidites, which were incorporated into a binary H/ACA box guide RNA/product complex comprising 77 nucleotides (nts) in total and into a 75 nt E. coli tRNAGly. The stable isotope (SI) labelled pseudouridines were produced via a highly efficient chemo‐enzymatic synthesis. 13C/15N labelled uracils were produced via
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Optical Upconversion in Mononuclear Lanthanide Co‐crystal Assemblies Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Yuxin Wang, Guotao Sun, Qichen Su, Yao Xie, Feifei Xing, Hongjie Zhang, Lining Sun
In this work, we developed two kinds of co‐crystal assemblies systems, consisting of discrete mononuclear Yb3+ and Er3+ and mononuclear Yb3+ and Pr3+, which can achieve Er3+ and Pr3+ upconversion luminescence, respectively, by Yb3+ sensitization under 980 nm excitation. The structure and composition of two co‐crystal assemblies were determined by single crystal X‐ray diffraction. By investigation of
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Dual Basicity and Nucleophilicity of Organosodium Reagents in Benzylic C‐H Additions of Toluenes to Diarylethenes and Ketones Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 David Anderson, Alex Truong, Eva Hevia
Profiting from the dual high basicity and nucleophilicity of organosodium complexes, here we report the stepwise lateral metalation of a wide range of alkyl arenes (MeAr), mediated by hydrocarbon‐soluble NaCH2SiMe3.PMDETA (PMDETA = N,N,N’,N’’,N’’‐pentamethyldiethylenetriamine), followed by nucleophilic addition to olenfins of the newly generated NaCH2Ar.PMDETA complexes. This method grants access to
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Molybdenum Sulfide Nanoflowers as Electrodes for Efficient and Scalable Lithium‐Ion Capacitors Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Rameez Ahmad Mir, Amir Hoseini Ahmadian Hoseini, Evan J Hansen, Li Tao, Yue Zhang, Jian Liu
Hybrid supercapacitors (HSCs) bridge the unique advantages of batteries and capacitors and are considered promising energy storage devices for hybrid vehicles and other electronic gadgets. Lithium‐ion capacitors (LICs) have attained particular interest due to their higher energy and power density than traditional supercapacitor devices. The limited voltage window and the deterioration of anode materials
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Front Cover: Combined Covalent and Supramolecular Polymerization to Reinforce Perylenebisimide Photosynthetic “Quantasomes” (Chem. Eur. J. 23/2024) Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Alisa Ranscht, Francesco Rigodanza, Thomas Gobbato, Ilaria Crea, Elsje Alessandra Quadrelli, Jerome Canivet, Marcella Bonchio
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Charge‐transfer complexes: halogen‐doped anthracene as a case of study Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-23 Simone Gilioli, Roberto Giovanardi, Andrea Gemelli, Andrea Severini, Fabrizio Roncaglia, Alberta Carella, Francesco Rossella, Davide Vanossi, Andrea Marchetti, Raanan Carmieli, Claudio Fontanesi, Luca Pasquali, Monica Montecchi, Camilla Ferrari
Charge transfer (CT) crystals exhibit unique electronic and magnetic properties with interesting applications. We present a rational and easy guide which allows to foresee the effective charge transfer co‐crystal production and that is based on the comparison of the frontier molecular orbital (MO) energies of a donor and acceptor couple. For the sake of comparison, theoretical calculations have been
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Solution‐State Structure of a Long‐Loop G‐quadruplex Formed within Promoters of Plasmodium falciparum B var Genes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Marina Juribašić Kulcsár, Valérie Gabelica, Janez Plavec
We report the high‐resolution NMR solution‐state structure of an intramolecular G‐quadruplex with a diagonal loop of ten nucleotides. The G‐quadruplex is formed by a 34‐nt DNA sequence, d[CAG3T2A2G3TATA2CT3AG4T2AG3T2], named UpsB‐Q‐1. This sequence is found within promoters of the var genes of Plasmodium falciparum, which play a key role in malaria pathogenesis and evasion of the immune system. The
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A Single Terminal [NiII‐OH] Catalyst for Direct Julia‐Type Olefination and α‐Alkylation Involving Sulfones and Alcohols Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Prabhakar K. Pandey, Moumita Patra, Prabodh Ranjan, Nilay Kumar Pal, Sanjay Choudhary, Jitendra K. Bera
A terminal [NiII‐OH] complex 1, supported by triflamide‐functionalized NHC ligands, showed divergent reactivity for the reaction of sulfone with alcohol, contingent on base concentration, temperature, and time. Julia‐type olefination of alcohols with sulfones was achieved using one equiv. of base, whereas lowering base loading to 0.5 equiv. afforded α‐alkylated sulfones. Besides excellent substrate
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High‐Intensity Circular Dichroism of Head‐to‐tail Regioregular Poly(1,4‐phenylene)s in the Aggregated State Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Rikuya Tanaka, Seiha Yamaoka, Shuichi Ikeda, Kentaro Okano, Masaki Horie, Hideto Minami, Nozomu Suzuki, Atsunori Mori
Circular dichroism (CD) studies on poly(1,4‐phenylene)s bearing a chiral side chain in the aggregated conditions were carried out. Little CD was observed in a solution form, while addition of a poor solvent into the polyphenylene solution induced aggregation and a strong CD was observed, accordingly. Applying the controlled degree of polymerization (DP) of poly(1,4‐phenylene) in the use of bidentate
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High pressure promotes binding of the allosteric inhibitor Zn2+‐cyclen in crystals of activated H‐Ras Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Eric Girard, Pedro Lopes, Michael Spoerner, Anne-Claire Dhaussy, Thierry Prangé, Hans Robert Kalbitzer, Nathalie Colloc'h
In this work, we experimentally investigate the potency of high pressure to drive a protein toward an excited state where an inhibitor targeted for this state can bind. Ras proteins are small GTPases cycling between active GTP‐bound and inactive GDP‐bound states. Various states of GTP‐bound Ras in active conformation coexist in solution, amongst them, state 2 which binds to effectors, and state 1,
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Mechanochemical C−H Arylation and Alkylation of Indoles Using 3 d Transition Metal and Zero‐Valent Magnesium Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Chongyang Wu, Jin Lv, Hangqian Fan, Weike Su, Xinjun Cai, Jingbo Yu
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Photo/mechanical/acidic multi‐stimuli responses and information encryption design of acylhydrazone derivative Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Yang Ye, Dechen Wang, Yaru Zhang, Xiaomeng Zhou, Haowen Du, Sen Yang, Ying Bao, Hongxun Hao, Chuang Xie
Stimuli‐responsive crystalline materials have received much attention for being potential candidates of smart materials. However, the occurrence of polymorphism‐driven stimuli responses in crystalline materials remains interesting but rare. Herein, three polymorphs of an acylhydrazone derivative, N'‐[(E)‐(1‐benzofuran‐2‐yl) methylidene] pyridine ‐4‐carbohydrazide (BFMP) were prepared. Form‐1 undergoes
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A Case‐Study on the Photophysics of Chalcogen‐Substituted Zinc(II) Phthalocyanines Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Sergio D. Ezquerra Riega, Matías E. Gutierrez Suburu, Hernán B. Rodríguez, Beatriz Lantaño, Martin Kleinschmidt, Christel M. Marian, Cristian A. Strassert
Singlet dioxygen has been widely applied in different disciplines such as medicine (photodynamic therapy or blood sterilization), remediation (wastewater treatment) or industrial processes (fine chemicals synthesis). Particularly, it can be conveniently generated by energy transfer between a photosensitizer's triplet state and triplet dioxygen upon irradiation with visible light. Among the best photosensitizers
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The Role of Alkalis in Orchestrating Uranyl‐Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Ana Arteaga, Trevor Arino, Guy C. Moore, Jenna L. Bustos, Matthew K. Horton, Kristin A. Persson, Jun Li, William F. Stickle, Tsuyoshi A. Kohlgruber, Robert G. Surbella, May Nyman
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Breaking Cycles: Saponification‐Enhanced NMR Fingerprint Matching for the Identification and Stereochemical Evaluation of Cyclic Lipodepsipeptides from Natural Sources Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Penthip Muangkaew, Durga Prasad, Vic De Roo, Yentl Verleysen, Lu Zhou, René De Mot, Monica Höfte, Annemieke Madder, Niels Geudens, Jose Martins
We previously described NMR based fingerprint matching with peptide backbone resonances as a fast and reliable structural dereplication approach for Pseudomonas cyclic lipodepsipeptides (CLiPs). In combination with total synthesis of a small library of configurational CLiP congeners this also allows unambiguous determination of stereochemistry, facilitating structure‐activity relationship studies and
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Pathway Selection in Temporal Evolution of Supramolecular Polymers of Ionic π‐systems: Amphiphilic Organic Solvent Dictates the Fate of Water Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Srinu Kotha, Rahul Sahu, Aditya Chandrakant Yadav, Karteek K. Bejagam, Sandeep K. Reddy, Kotagiri Venkata Rao
Understanding solvent‐solute interactions is essential to designing and synthesising soft materials with tailor‐made functions. Although the interaction of the solute with the solvent mixture is more complex than the single solvent medium, solvent mixtures are exciting to unfold several unforeseen phenomena in supramolecular chemistry. Here we report two unforeseen pathways observed during the hierarchical
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Solvent‐Free Mechanosynthesis of Oligopeptides by Coupling Peptide Segments of Different Lengths – Elucidating the Role of Cesium Carbonate in Ball Mill Processes Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Aneta Wroblewska, Irena Bak-Sypiei, Piotr Paluch, Ewelina Wielgus, Justyna Zajac, Agata Jeziorna, Slawomir Kazmierski, Marek Potrzebowski
We report an idea for the synthesis of oligopeptides using a solvent‐free ball milling approach. Our concept is inspired by block play, in which it is possible to construct different objects using segments (blocks) of different sizes and lengths. We prove that by having a library of short peptides and employing the ball mill mechanosynthesis (BMMS) method, peptides can be easily coupled to form different
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Improving Fatigue Resistance and Autonomous Switching of pH Responsive Hydrazones by Pulses of a Chemical Fuel Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Pankaj Maity, Harekrushna Pradhan, Asesh Das, Monotosh Dalapati, Dipak Samanta
The chemically triggered reversible switching of pH‐responsive hydrazones involves rotary motion‐induced configurational changes, serving as a prototype for constructing an array of molecular machines. Typically, the configurational isomerization of such switches into two distinct forms (E/Z) occurs through the alteration of the pH the medium, achieved by successive additions of acid and base stimuli
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Quest for Double Möbius Aromaticity Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Kangkan Sarmah, Ankur K. Guha
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Generation, Characterization and Reactivity of a High‐valent Mononuclear Cobalt(IV)‐diazide Complex Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Michael Kayne, Patrick S Murphy, Yubin M Kwon, Yuri Lee, Timothy A Jackson, Dong Wang
High‐valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high‐valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)‐dinitrate complex (1‐NO3) that activates sp3 C‐H bonds up to 87 kcal/mol. In this work, we have shown that the
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TEMPO/O2 Synergistically Mediated BiBrO‐Photocatalyzed Decarboxylative Phosphorylation of N‐Arylglycines Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Wen-Tao Ouyang, Hong-Tao Ji, Yuan-Yuan Liu, Ting Li, Yan-Fang Jiang, Yu-Han Lu, Jun Jiang, Wei-Min He
With both TEMPO and O2 (in air) as the homogeneous redox mediators, BiBrO as the heterogeneous semiconductor photocatalyst, the first example of semi‐heterogeneous photocatalytic decarboxylative phosphorylation of N‐arylglycines with diarylphosphine oxides was established. A series of α‐amino phosphinoxides were efficiently synthesized
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Thermal Equilibrium between Quinoid/Biradical Forms Enhancing Electrochemical Amphotericity Chem. Eur. J. (IF 4.3) Pub Date : 2024-04-22 Yusuke Ishigaki, Shin-ichi Mizuno, Kazuma Sugawara, Takumi Hashimoto, Shuichi Suzuki, Takanori Suzuki
Upon dibenzo annulation on Thiele’s hydrocarbon (tetraphenyl‐p‐quinodimethane), the quinoid form and the biradical form adopt quite different geometries, and thus are no longer resonance structures. When these two forms can interconvert rapidly due to the small energy barrier (ΔG‡), the equilibrated mixture contains both forms in a ratio that is determined by the energy difference (ΔGo) between the
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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