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The Effect of Reactive Oxygen Species on Respiratory Complex I Activity in Liposomes Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-26 Jana Eisermann, Yuxin Liang, John Joseph Wright, Eleanor Clifford, James D.E.T. Wilton-Ely, Marina Kuimova, Maxie Roessler
Respiratory complex I (R-CI) is an essential enzyme in the mitochondrial electron transport chain but also a major source of reactive oxygen species (ROS), which are implicated in neurodegenerative diseases and ageing. While the mechanism of ROS production by R-CI is well-established, the feedback of ROS on R-CI activity is poorly understood. Here, we perform EPR spectroscopy on R-CI incorporated in
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A Data-driven Approach for Enhanced CO2 Capture with Ruthenium Complexes Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-26 Guangchao Liang, Min Zhang
To attain carbon neutrality, significant efforts have been made to capture and use CO2. The homogeneous hydrogenation of CO2 catalyzed by transition metal complexes, particularly ruthenium complexes, has demonstrated significant advantages and is regarded as a viable approach for practical application. Insertion of CO2 into the Ru-H bond, producing the Ru-formate product, is the key step in the hydrogenation
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Assessing Solid Catalysts with Ionic Liquid Layers (SCILL) from Molecular Dynamics Simulations: On the role of local charge polarization Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-26 Simon Trzeciak, Dirk Zahn
Recent developments in molecular mechanics modelling of metal catalyst surfaces with interfaces to complex ad-layers or bulk liquids enable the study of 10 nm scale systems by molecular dynamics simulations of up to microseconds. Therein, electronic polarization as otherwise benchmarked by quantum calculations is mimicked via atom-centered partial charges that are adjusted dynamically to account for
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Double Chalcogen Bonding Recognition Arrays in Solution Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-26 Deborah Romito, Hanspeter Kählig, Paolo Tecilla, Gabriele Sosso, Davide Bonifazi
N-substituted pyridino-based congeners of Ebselen, named here as Pyrselen, incorporating proximal Se and N atoms, undergo dimerization in solution and in the solid state through a dual donor-acceptor arrangement of chalcogen bonding sites. Dimerization constants were measured within the 15-50 M–1 range. Computational studies on the dimers depict a notable charge-transfer contribution to the association
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Enhanced electrochemical performance of NiMn layered double hydroxides/graphene oxide composites synthesized by one-step hydrothermal method for supercapacitors Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-26 Jun Chen, Xin Jing, Ji-chao Wang, Wan-qing Zhang, Yong Zhang
This study aims to enhance the performance of supercapacitors, focusing particularly on optimizing electrode materials. While pure NiMn layered double hydroxides (LDHs) exhibit excellent electrochemical properties, they have limitations in achieving high specific capacitance. Therefore, this paper successfully synthesized composite materials of NiMn LDHs with varying loadings of graphene oxide (GO)
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Syntheses of diarylmethanes via an oxidative benzylic functionalization of p-alkyl phenol derivatives under quaternary ammonium hypoiodite catalysis Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 David Pollheimer, Christopher Mairhofer, Mario Waser
We herein report two strategies for the quaternary ammonium hypoiodite-mediated oxidative benzylic functionalization of p-alkyl phenol derivatives. By using either dibenzoylperoxide or H2O2 in hexafluoroisopropanol in the presence of tetrabutyl ammonium iodide gives access to activated intermediates which can then be coupled with electron-rich aromatic compounds. Overall, this sequential two-step one-pot
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Helix-to-Disc Conversion of Thia[6]helicenes into Coronenes Facilitated by Sulfur Oxidation and Fluorination Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Kaito Seino, Tsubasa Okano, Koki Oya, Hiroshi Katagiri, Takashi Murase
Helicenes, with their unique helical structures, have long captured the interest of synthetic chemists, not only as end products, but also as versatile platforms for further chemical transformations. However, transforming [6]helicene into planar coronene typically requires harsh conditions and poses significant challenges. Herein, we demonstrate that replacing the terminal benzene ring of [6]helicene
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Bridging Titanium Nitrido Complexes Containing A Linear Ti–N–Ti Core with A Two-Coordinate Nitrido Ligand Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Akira Okumura, Priyabrata Ghana, Thomas P. Spaniol, Jun Okuda
A series of titanium m2-nitrido complexes supported by the triamidoamine ligand Xy-N3N (Xy-N3N = {(3,5-Me2C6H3)NCH2CH2}3N3–) is reported. The titanium azido complex [(Xy-N3N)TiN3] (1-N3), prepared by salt metathesis of the chloride complex [(Xy-N3N)TiCl] (1-Cl) with NaN3, reacted with lithium metal or with alkali metal naphthalenides (alkali metal M = Na, K, and Rb) in THF to give the corresponding
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Amorphous Strategy and Doping Copper on Metal-organic Framework Surface for Enhanced Photocatalytic CO2 Reduction to C2H4 Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Lixiao Zheng, Huayong Yang, Min Zhang, Zhongjie Guan, Qiuye Li, Jianjun Yang
Amorphous photocatalysts are characterized by numerous grain boundaries and abundant unsaturated sites, which enhance reaction efficiency from both kinetic and thermodynamic perspectives. However, amorphization strategies have rarely been used for photocatalytic CO2 reduction. Doping copper onto a metal–organic framework (MOF) surface can regulate the electronic structure of photocatalysts, promote
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Building 3D Crosslinked Graphene-MXene Nanoarchitectures Decorated with MoS2 Quantum Dots Enables Efficient Electrocatalytic Hydrogen Evolution Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Ying Feng, Ya Xue, Binfeng Shen, Lu Yang, Haiyan He, Quanguo Jiang, Guobing Ying, Huajie Huang
Although MoS2 quantum dots with abundant edge sites have been regarded as promising eletrode materials for the hydrogen evolution reaction (HER), their electrocatalytic capacity still requires improvements in actual applications. Herein. we demonstrate a controllable and robust bottom-up approach to build 3D crosslinked graphene-Ti3C2Tx MXene frameworks decorated with MoS2 quantum dots (MQD/RGO-MX)
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Chemoselectivity Switch between Enantioselective [2,3]‐Wittig Rearrangement and Conia‐Ene‐Type Reactions of Propargyloxyoxindoles Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Yu-Lin Gao, Yang Yang, Chen Wu, Ming-Sheng Xie, Hai-Ming Guo
Despite the existence of three competing reactions for propargyloxyoxindoles, we report a chemoselectivity switch between enantioselective propargyl [2,3]‐Wittig rearrangement and Conia‐ene‐type reactions, with suppression of the [1,2]‐Wittig‐type rearrangement. Using C1‐symmetric imidazolidine‐pyrroloimidazolone pyridine as the ligand and Ni(acac)2 as the Lewis acid, diverse 3‐hydroxy 3‐substituted
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A Review of Electrospun Carbon‐based Nanofibers Materials Used in Lithium‐Sulfur Batteries Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Chengbiao Wei, Xiaodong Shao, Feng Lin, Xiaoyan Liu, Wei Ding, Guoxu Wang, Hao Liu, Ruihui Gan
Commercial lithium‐ion batteries are gradually approaching their theoretical values (200‐250 Wh kg‐1), which cannot meet the fast‐growing energy storage demands. Lithium‐sulfur (Li‐S) batteries are anticipated to supersede lithium‐ion batteries as the next‐generation energy storage system owing to their high theoretical specific capacity (1675 mAh g‐1) and energy density (2600 Wh kg‐1). Nonetheless
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Copper‐mediated Synthesis of N‐Aryl‐oxamic Acids. Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Margaux Badufle, Frédéric Robert, Yannick Landais
The Cu‐catalyzed Ullmann‐Goldberg cross‐coupling between aryl iodides and oxamates is shown to afford the corresponding N‐aryloxamates with yields ranging from moderate to excellent, when the oxamate precursor incorporates a bulky tertiary alkyl group effectively preventing product degradation under the strongly basic reaction conditions. The final oxamic acids are then generated through the acid hydrolysis
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Theoretical Insight into Complexation Between Cyclocarbons and C60 Fullerene Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Zeyu Liu, Tian Lu
This work conducts the comprehensive theoretical study on the non‐covalent complexation between cyclocarbons and C60 fullerene for the first time. The binding energy between cyclocarbons and C60 fullerene is significantly stronger than that between two C18 or two C60 fullerenes, indicating a particularly strong affinity. The cyclocarbons and C60 fullerene can spontaneously assemble into complexes in
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Synthesis and Analysis of (g,g', g'', ‐ Trifluoro)neopentyl (TFNP) Aryl ethers as a Polar Aliphatic Motif Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Atsushi Tarui, Bruno A. Piscelli, Nawaf Al-Maharik, Josephine M Stewart, Patricie Niemcova, David B Cordes, Aiden P McKay, Cormac Murphy, Rodrigo Cormanich, David O'Hagan
A route is developed to (g,g’,g’’’’‐trifluoro)neopentyl (TFNP) aryl ethers to extend the methods for the introduction of the tert‐butyl group, carrying a fluorine on each of the methyl substituents. The route combines neopentyltosylate 3 with phenols and thiophenols to give efficient substitution reactions to the corresponding TFNP aryl ethers. The three C‐F bonds adopt a helical propeller conformation
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Efficient Synthesis of a C2‐Symmetric 2,2'‐Bipyridine‐α,α'‐1‐t‐butyl‐diol Ligand by Stereoselective Double Hydrogen Transfer to a 2,2'‐Bipyridine‐diketone Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Stéphany Bouzid, Antony Marcoux, Thierry Ollevier
An efficient and practical method was developed for the synthesis of C2‐symmetric 2,2'‐bipyridine‐α,α’‐1‐t‐butyl‐diol ligands. The disclosed synthesis involves the Ullmann homocoupling of a keto bromo‐pyridine under NiCl2/Zn/PPh3 conditions, followed by the stereoselective double hydrogen transfer to the obtained 2,2'‐bipyridine‐diketone using RuII Noyori–Ikariya catalysts. This approach allowed the
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Superior Tumor Cell Uptake by Mono‐ and Tri‐nuclear Rhodamine‐Gadolinium(III) Agents Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Amy G. Robertson, Andrew J. Hall, Anita Marfavi, Louis Rendina
The synthesis and characterization of a novel trinuclear rhodamine‐Gd(III) complex, along with two analogous mononuclear rhodamine‐Gd(III) complexes, are reported. All complexes displayed good selectivity in a human glioma cell line (T98G) when compared to a glial cell line (SVG p12), with low cytotoxicities. Superior tumor cell uptake for these Gd(III) complexes was observed at lower incubation concentrations
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An Effective Strategy on Synthesizing a Stable SiOx‐Based Anode for High Density Lithium‐Ion Batteries Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-25 Zhenyuan Tang, Zhengyu Zhang, Jiani Wu, Minglv Zhang, Huacheng Wu, Qian Luo, Jun Li
Silicon oxides (SiOx) have received extensive attention as an promising anode candidate for next‐generation lithium‐ion batteries (LIBs). However, their commerical applications have been seriously hindered by low conductivity, large volume expansion and unstable soild‐electrolyte interface (SEI) layer, which result in low intial coulombic efficiency, poor rate performance and short cycling lifepan
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Skeletal Editing by Hypervalent Iodine Mediated Nitrogen Insertion Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Srimanta Manna, Joydev K. Laha, Anjali Gupta, Pratibha Bhatti
Hypervalent iodine reagents are versatile and readily accessible reagents that have been extensively applied in contemporary synthesis in modern organic chemistry. Among them, iodonitrene (ArI=NR), is a powerful reactive species, widely used for a single‐nitrogen‐atom insertion reaction, and skeletal editing to construct N‐heterocycles. Skeletal editing with reactive iodonitrene components has recently
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Visible‐Light‐Induced Multi‐Component Nitrooxylation Reactions of α‐Diazoesters, Cyclic Ethers, and tert‐Butyl nitrite Leading to Organic Nitrate Esters Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Cunwei Qian, Xian Li, Meng-Qing Gu
A simple and efficient strategy has been developed for the synthesis of organic nitrate esters via visible‐light‐induced multi‐component nitrooxylation reactions of α‐diazoesters, cyclic ethers, and tert‐butyl nitrite under open air atmosphere. This transformation could be conducted under mild and metal‐free conditions to provide a number of organic nitrate esters in moderate to good yields using air
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Synthesis and Development of Inverse‐Type Nucleoside Diarylethene Photoswitches Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Christoph M. Hendrich, Martin Reinschmidt, Simon M. Büllmann, Theresa Kolmar, Andres Jäschke
Nucleosidic diarylethenes (DAEs) have evolved from an emerging class of photochromes into a well‐established option for integrating photochromic functionalities into biological systems. However, a comprehensive understanding of how chemical structure influences their photochromic properties remains essential. While structural features, such as an inverse connection between the aryl residues and the
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Halogen Impact on the Supramolecular Organization of Chiral Phthalimide EmittersDisplaying Room Temperature Phosphorescence Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Catherine Demangeat, Maxime Remond, Thierry Roisnel, Cassandre Quinton, Ludovic Favereau
Room temperature phosphorescence from organic materials has attracted an increasing attention in the recent years due to their potential application in various advancing technologies, notably in bioimaging and displays. In this context, heavy atoms such as halogen ones revealed useful tools to enhance the spin‐orbit coupling (SOC) of molecular organic phosphors. However, the effect of halogen at the
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Green Synthesis of the Triazine Derivatives and their Application for the Benign Electrocatalytic Reaction of Nitrate Reduction to Ammonia Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Olga Lebedeva, Valery Zakharov, Irina Kuznetsova, Dmitry Kultin, Leonid Kustov, Leonid Aslanov, Vladimir Chernyshev, Serguei Savilov, Sergey Dunaev, Konstantin Kalmykov
This work uses green sustainable reactions twice. Firstly, it is microwave synthesis: 2,4,6‐tribiphenyl‐4‐yl‐1,3,5‐triazine and similar compounds were prepared in a closed microwave reactor in n‐octane by the Friedel‐Crafts reaction. Second, a hybrid electrocatalyst for the highly demanded electrochemical reaction of nitrate reduction to ammonia (NO3RR) was prepared based on this material. This reaction
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Robust and Irreversible Sortase‐Mediated Ligation by Empolyment of Sarkosyl Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-24 Yihang Xiao, Mingxuan Wu
Sortase‐mediated ligation (SML) is a widely used method for peptide and protein ligation due to ease of substrate preparation and fast enzymatic kinetics. But there are drawbacks that limit broader applications. Sorting motif in substrates may not be exposed to sortase efficiently due to folding or aggregation. In addition, the ligation is reversible under transpeptidation equilibrium that restricts
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Concentration controlling of carboxylic ester‐based electrolyte for low temperature lithium‐ion batteries Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Song Gao, Kang Wang, Liying Wang, Xijia Yang, Yue Yang, Wencui Xiu, Xuesong Li, Wei Lü
Low temperature has been a major challenge for lithium‐ion batteries (LIBs) to maintain satisfied electrochemical performance, and the main reason is the deactivation of electrolyte with the decreasing temperature. To address this point, in present work, we develop a low‐temperature resistant electrolyte which includes ethyl acetate (EA) and fluoroethylene carbonate (FEC) as solvent and lithium di
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Halogen and Chalcogen Activation by Nucleophilic Catalysis Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Haripriyo Mondal
The high utility of halogenated organic compounds has prompted the development of numerous transformations that install the carbon‐halogen motif. Halogen functionalities, deemed as "functional and functionalizable" molecules due to their capacity to modulate diverse internal properties, constitute a pivotal strategy in drug discovery and development. Traditional routes to these building blocks have
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Binary Catalytic Hydrogen/Deuterium Exchange of Free α‐Amino Acids and Derivatives Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Guorong Xiao, Hong Sun, Gege Jiang, Ying Liu, Gaohan Song, Duanyang Kong
The increasing demand for deuterium‐labeled amino acids and derivatives has heightened interest in direct hydrogen/deuterium exchange reactions of free amino acids. Existing methods, including biocatalysis and metal catalysis, typically require expensive deuterium sources or excessive use of deuterium reagents and often struggle with site selectivity. In contrast, our pioneering binary catalysis system
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The Hydronaphthalide Monoanion: Isolation of the “red transient” Birch Intermediate from liquid Ammonia Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Clara A. von Randow, Günther Thiele
Birch reactions employing alkali metals in ammonia have been a well‐established method for the reduction and functionalisation of aromatic compounds for nearly 100 years. Speculations regarding intermediates in the reaction pathway have been discussed since the beginning. We hereby report the isolation of NMe4(HNaph) (1), a kinetically trapped intermediate of the Birch reaction of naphthalene and sodium
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N‐Glycosylation‐induced pathologic protein conformations as a tool to guide the selection of biologically active small molecules Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Andrea Magni, Cristiano Sciva, Matteo Castelli, Chander S Digwal, Anna Rodina, Sahil Sharma, Stefan Ochiana, Hardik Patel, Smit Shah, Gabriela Chiosis, Elisabetta Moroni, Giorgio Colombo
Post‐translational modifications such as protein N‐glycosylation, significantly influence cellular processes. Dysregulated N‐glycosylation, exemplified in Grp94, a member of the Hsp90 family, leads to structural changes and the formation of epichaperomes, contributing to pathologies. Targeting N‐glycosylation‐induced conformations offers opportunities for developing selective chemical tools and drugs
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Investigating the Catalytic Site of Human 15‐lipoxygenase‐1 via Marine Natural Products Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Ntaniela Spacho, Marcello Casertano, Concetta Imperatore, Christos Papadopoulos, Marialuisa Menna, Nikolaos Eleftheriadis
Human 15‐lipoxygenase‐1 (15‐LOX‐1) is a key enzyme that possesses an important role in (neuro)inflammatory diseases. The pocket of the enzyme plays the role of a chiral catalyst, and therefore chirality could be an important component for the design of effective enzyme inhibitors. To advance our knowledge on this concept, we developed a library of the identified chiral 15‐LOX‐1 inhibitors and applied
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Machine Learning‐Inspired Molecular Design, Divergent Syntheses, and X‐ray Analyses of Dithienobenzothiazole‐Based Semiconductors Controlled by S•••N and S•••S Interactions Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-23 Takuya Ogaki, Yasunori Matsui, Haruki Okamoto, Naoyuki Nishida, Hiroyasu Sato, Toshio Asada, Hiroyoshi Naito, Hiroshi Ikeda
Inspired by the previous machine‐learning study that the number of hydrogen‐bonding acceptor (NHBA) is important index for the hole mobility of organic semiconductors, seven dithienobenzothiazole (DBT) derivatives 1a–g (NHBA = 5) were designed and synthesized by one‐step functionalization from a common precursor. X‐ray single‐crystal structural analyses confirmed that the molecular arrangements of
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Cascade C−H Activation and Two C−C Bond Forming in Reaction of Azalutetacyclopentadiene with 2-Methylbenzonitriles Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-17 Zhengqi Chai, Ze-Jie Lv, Wei Liu, Jinxiao Yang, Junnian Wei, Wen-Xiong Zhang
Azametallacyclopentadienes are an important class of metallacycles as the key intermediates in metal-promoted or catalyzed carbon-carbon coupling reaction of nitriles and alkynes. Rare-earth azametallacyclopentadienes have shown unique reactivity toward benzonitriles. The reaction chemistry of azalutetacyclopentadienes toward 2-methylbenzonitriles has been investigated in this work, showing different
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Improving Environmental Stress Cracking Resistance of High-Density Polyethylene Grades by Comonomer Addition and Nanocomposite Approach Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-17 AmirMohammad Mansouri, Nona Ghasemi Hamedani, Chen Zou, Saber Mousavi, Hossein Ali Khonakdar, Naeimeh Bahri-Laleh, Montserrat Rodríguez-Pizarro, Artur Brotons-Rufes, Sergio Posada-Pérez, Albert Poater
The aim is to determine the effect of polymer density, correlated to the comonomer content, and nanosilica addition on the mechanical and Environmental Stress Cracking Resistance (ESCR) characteristics of high-density polyethylene (HDPE). In this regard, five HDPE samples with similar Melt Flow Index (MFI) and molar mass but various densities were acquired from a petrochemical plant. Two polymerization
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Photocatalytic Synthesis and Functionalization of Sulfones, Sulfonamides and Sulfoximines Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 José J. Garrido‐González, Katy Medrano‐Uribe, Cristian Rosso, Jorge Humbrías‐Martín, Luca Dell'Amico
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Iodine‐Catalyzed Carbonyl‐Alkyne Metathesis Reactions Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Thiemo Arndt, Martin Breugst
The reaction between aldehydes or ketones and alkynes –the carbonyl‐alkyne metathesis– constitutes a very useful strategy for the synthesis of a,b‐unsaturated carbonyls. We now demonstrate that iodine is a highly efficient catalyst for both the intra‐ and intermolecular metathesis reaction in very small concentrations (0.1–1 mol%). Our protocol outperforms other catalytic systems, is operationally
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Exohedral Diels‐Alder Reactivity of Endohedral Metallofullerene C36 Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Athul Santha Bhaskaran, Dani Romero del Blanco, Adrià Romero-Rivera, Sílvia Osuna, Marcel Swart
Understanding the exohedral reactivity of metallofullerenes is crucial for its application in various fields. By systematically controlling the trapped species inside the fullerene its reactivity can be tamed. In this work we report the preferential position of 3d metal atoms inside the C36 cage and their effect on exohedral reactivity in comparison with the neutral and the dianionic cage. The Diels‐Alder
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Advancing Optoglycomics: Two Orthogonal Azobenzene Glycoside Antennas in One Glycocluster – Synthesis, Switching Cycles, Kinetics and Molecular Dynamics Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Leon M. Friedrich, Bernd Hartke, Thisbe K. Lindhorst
Carbohydrate recognition is essential for numerous biological processes and is governed by various factors within the supramolecular environment of the cell. Photoswitchable glycoconjugates have proven as valuable tools for the investigation and modulation of carbohydrate recognition as they allow to control the relative orientation of sugar ligands by light. We have synthesized a biantennary glycocluster
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Tetrel bond affects the self‐assembly of acetylcholine and its analogues and is an ancillary interaction in protein binding Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Andrea Daolio, Miriam Calabrese, Andrea Pizzi, Cristina Lo Iacono, Nicola Demitri, Roberta Beccaria, Rosa Gomila, Antonio Frontera, Giuseppe Resnati
The ‐N+(CH3)3 residue is present in acetylcholine (ACh) and in many of its analogues which are used as selective ACh agonist or antagonists for human therapy. The X‐ray structures of four ACh derivatives show the presence of short and linear contacts between the C atoms of ‐N+(CH3)3 groups and lone pair possessing atoms. These contacts can be rationalized as tetrel bonds (TtBs) thanks to their geometric
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A New Structural Motif in Aggregation of Methylalumoxanes: Non‐hydrolytic Route by the Alkylation of Dicarboxylic Acids Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Antoni Pietrzykowski, Iwona Justyniak, Vadim Szejko, Tomasz Skrok, Tomasz Radzymiński, Kinga Suwińska, Janusz Lewiński
Alumoxanes are typically produced via controlled hydrolysis of short‐chain alkyl aluminium compounds which leads to oligomeric species that are usually difficult to obtain in crystalline form. Simultaneously, various alternative non‐hydrolytic approaches to alumoxanes have also been used. In this work, we report on a new methylalumoxane scaffold derived from the alkylation of a series of dicarboxylic
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Electrocatalytic Dinitrogen Reduction to Ammonia Using Easily Reducible N‐Fused Cobalt Porphyrins Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Ashwin Ganesan, Alireza Hajiseyedjavadi, Pinki Rathi, Alankar Kafle, Qasim Adesope, Sandeep Kumar, Vitaly Mesilov, Jeffry Kelber, Thomas Cundari, Muniappan Sankar, Francis D'Souza
Single‐site molecular electrocatalysts, especially those that perform catalytic conversion of N2 to NH3 under mild conditions, are highly desirable to derive fundamental structure‐activity relations and as potential alternatives to the current energy‐consuming Haber‐Bosch ammonia production process. Combining theoretical calculations with experimental evidence, it has been shown that easily reducible
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Rhodium‐Catalyzed Pyridylation of Alkynamides with Pyridylboronic Acids: A Route to Functionalized Enamides Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Huilong Zhu, Dingcheng Sun, Shengxiang Zhang, Junning Chen, Zhou Xu
The catalytic direct hydroarylation of alkynamides is a highly efficient approach for accessing functionalized trisubstituted arylalkenes with amide groups. Herein, we report a rhodium‐catalyzed pyridylation of alkynamides with pyridylboronic acids, yielding diverse primary, secondary, and tertiary enamides in good to excellent yields (up to 94%). This reaction demonstrates broad tolerance towards
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CaLi2PN3 – A Quaternary Chain‐Type Nitridophosphate by Medium‐Pressure Synthesis Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Reinhard M. Pritzl, Nadine Fahle, Kristian Witthaut, Sebastian Wendl, Wolfgang Schnick
Nitridophosphates are in the focus of current research interest due to their structural versatility and properties, such as ion conductivity, ultra‐incompressibility and luminescent properties when doped with suitable activator ions. Multinary representatives often require thorough investigation due to the competition with the thermodynamically more stable binary and ternary compounds. Another point
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Switchable Deep Eutectic Solvents for Sustainable Sulfonamide Synthesis Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Maristella Simone, Mara Pulpito, Filippo Maria Perna, Vito Capriati, Paola Vitale
A sustainable and scalable protocol for synthesizing variously functionalized sulfonamides, from amines and sulfonyl chlorides, has been developed using environmentally responsible and reusable choline chloride (ChCl)‐based deep eutectic solvents (DESs). In ChCl/glycerol (1:2 mol mol–1) and ChCl/urea (1:2 mol mol–1), these reactions yield up to 97% under aerobic conditions at ambient temperature within
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Unlocking Selective Anticancer Mechanisms: Dinuclear Manganese Superoxide Dismutase Mimetics Combined with Pt(II) Complexes Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Andrea Squarcina, Phipipp Maier, Laura Senft, Thibaut Vignane, Milos R. Filipovic, Ivana Ivanovic-Burmazovic
We exploration the in vitro activities of the dinuclear Mn2L2Ac and Mn2L2 complexes (where HL = 2‐{[di(2‐pyridyl)methylamino]‐methyl}phenol), possessing dual superoxide dismutase (SOD) and catalase (CAT) activity, both individually and in conjunction with various Pt(II)‐complexes, either as mixtures or as the Mn2‐Pt adducts. Our findings revealed a notable up to 50% enhancement in the viability of
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Recent Toolboxes for Chemoselective Dual Modifications of Proteins Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Yiping Zhao, Tiangmeng Zhang, Yujie Zhu, Juan Yin, Rida Omer, Xinya Hemu, Wenyi Li, Xiaobao Bi
Site‐selective chemical modifications of proteins have emerged as a potent technology in chemical biology, materials science, and medicine, facilitating precise manipulation of proteins with tailored functionalities for basic biology research and developing innovative therapeutics. Compared to traditional recombinant expression methods, one of the prominent advantages of chemical protein modification
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Tracking microenvironmental response on self‐assembled phthalocyanine systems – adaptive and non‐adaptive antibacterial photosensitization Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Anzhela Galstyan
Self‐assembly has proven to be one of the effective methods for the formation of nanoscale therapeutics without the need to use nanodelivery systems. Such minimal models of supramolecular systems formed from amphiphilic photosensitizers (PS) have recently emerged as a new class of photoactive systems, providing unique and in some cases superior activities. Although the mechanism of photogenerated reactive
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Hydrazone‐Linked Donor‐Acceptor Covalent Organic Polymer as a Heterogeneous Photocatalyst for C‐S Bond Formation Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Mohit Mohit, Sunil Kumar, K R Justin Thomas
In the realm of solar energy utilization, there is a growing focus on designing and implementing effective photocatalytic systems, for the conversion of solar energy into valuable chemical fuels. The potential of Covalent Organic Polymers (COPs) as photocatalysts for visible‐light‐driven organic transformation has been widely investigated, positioning them as promising candidates in this field. In
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THE QUEST FOR STABLE BOROZENE CORE IN MAIN‐GROUP CAPPED INVERSE SANDWICH COMPLEXES, [(HE)2B6H6]2‐ (E=B, Al, Ga, In, and Tl) Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-22 Gaurav Joshi, Eluvathingal Devassy Jemmis
The ubiquitous chemistry of benzene led us to explore ways to stabilise analogous borozene, by capping them with appropriate groups. The mismatch in overlap of ring‐cap fragment molecular orbitals in [(HB)2B6H6]2‐ is overcome by replacing the two BH caps with higher congeners of boron. We calculated the relative energies of all the polyhedral structural candidates for [(HE)2B6H6]2‐ (E = Al‐Tl) and
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Unveiling the Twisted Aromatic Donor Effect on the Nonlinear Response of D‐π‐A Type Malononitrile‐Derived Chromophores Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-20 Xiang-Zhao Zhu, Song-Hua Chen, Jia-Bei Xu, Jian-hua Huang, Jianfeng Yan, Yao-Feng Yuan
This study presents the design, synthesis, and comprehensive characterization of a novel series of D‐π‐A type malononitrile‐derived chromophores, BTC‐1 to BTC‐4. Combining various spectroscopic techniques, nonlinear Z‐scan measurements, and quantum chemical calculations, we revealed the intricate relationship between nonlinear optical properties and the interplay of molecular structure, intramolecular
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Carbon Dots in Photodynamic Therapy: The Role of Dopant and Solvent on Optical and Photo‐Responsive Properties Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-20 Agung Wibowo, Mohd Jahir Khan, Kanokwan Sansanaphongpricha, Pongtanawat Khemthong, Navadol Laosiripojana, Yu Sheng Yu, Kevin C.W. Wu, Chularat Sakdaronnarong
Carbon dots (CDs) are novel carbon‐based luminescent materials with wide‐ranging applications in biosensing, bioimaging, drug transportation, optical devices, and beyond. Their advantageous attributes, including biocompatibility, biodegradability, antioxidant activity, photostability, small particle size (< 10 nm), and strong light absorption and excitation across a broad range of wavelengths, making
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On‐Surface Stepwise Double Dehydrogenation for the Formation of a para‐Quinodimethane‐Containing Undecacene Isomer Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-20 Dolores Pérez, Suchetana Sarkar, Berta Álvarez, Kwan Ho Au-Yeung, Agustín Cobas, Roberto Robles, Nicolás Lorente, Diego Peña, Francesca Moresco
The on‐surface synthesis of an isomer of undecacene, bearing two four‐membered rings and two para‐quinodimethane moieties, starting from a tetramethyl‐substituted diepoxy precursor, is presented. The transformation implies a thermal double deoxygenation followed by a stepwise double dehydrogenation reaction on the Au(111) surface, locally induced by inelastic tunneling electrons. This results in the
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Neutral and Anion Species of Quinoidal Thienothiophene Diketopyrrolopyrroles Display a Common Aggregation Mode Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-19 Sergio Moles Quintero, Maria João Álvaro-Martins, Daniel Aranda, Yonghao Zheng, Juan Aragó, Enrique Ortí, Angela Sastre, Juan Casado
A comprehensive investigation of two new molecular triads incorporating the diketopyrrolopyrrole unit into a quinoidized thienothiophene skeleton, which is further end‐capped with dicyanomethylene (DPP‐TT‐CN) or phenoxyl groups (DPP‐TT‐PhO), has been carried out. A combination of UV‐Vis‐NIR and infrared spectroelectrochemical techniques and cryogenic UV‐Vis‐NIR absorption spectroscopy supported by
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Solvent Effect on Dative and Ionic Bond Strengths: A Unified Theory from the Potential Analysis and Valence Bond (VB) Computation Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-19 Xinru Peng, Jiayao Li, Yakun Fan, Xubin Wang, Shiwei Yin, Changwei Wang, Yirong Mo
Solvent molecules interact with a solute through various intermolecular forces. Here we employed a potential energy surface (PES) analysis to interpret the solvent‐induced variations in the strengths of dative (Me3NBH3) and ionic (LiCl) bonds, which possess both ionic and covalent (neutral) characteristics. The change of a bond is driven by the gradient (force) of the solvent‐solute interaction energy
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Aliphatic Ketone Claisen Rearrangement: Troubleshooting the Transetherification Step by Identifying a Stable Acid Catalyst Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-19 Petri M. Pihko, Kari Laasonen, Veera Karoliina Bruce, Aino Rolig, Kaveh Farshadfar
After optimization for retention of catalytic activity, 4‐chlorobenzoic acid emerged as the optimal catalyst for the aliphatic ketone Claisen rearrangement. The optimal catalyst enables a one‐pot, metal‐free, catalytic protocol from allylic alcohols to γ,δ‐unsaturated ketones. The optimized process tolerates a range of substrates, including substituents with acid‐labile protecting groups. Reaction
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A BODIPY‐Ferrocene Conjugate for the Combined Photodynamic Therapy and Chemodynamic Therapy with Improved Antitumor Efficiency Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Bin Yuan, Wenhui Zhang, Hua Wang, Jiang-Fei Xu, Xi Zhang
Photodynamic therapy (PDT) can destroy tumor cells by generating singlet oxygen (1O2) under light irradiation, which is limited by the hypoxia of the neoplastic tissue. Chemodynamic therapy (CDT) can produce toxic hydroxyl radical (•OH) to eradicate tumor cells by catalytic decomposition of endogenous hydrogen peroxide (H2O2), the therapeutic effect of which is highly dependent on the concentration
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Redox‐triggered Reversible Switching between Dynamic and Quasi‐static α‐Helical Peptides Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Naoki Ousaka, Mark J. MacLachlan, Shigehisa Akine
We report the reversible transformation between a singly stapled dynamic α‐helical peptide and a doubly stapled quasi‐static one through redox‐triggered dithiol/disulfide conversions of a stapling moiety. This process allows the rate of interconversion between the right‐handed (P) and left‐handed (M) α‐helices to be altered by a factor of approximately 103 before and after the transformation. An as‐obtained
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Synthesis and Reactivity of Masked Organic Sulfates Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Bharath K Villuri, Umesh R. Desai
Nature offers a variety of structurally unique, sulfated endobiotics including sulfated glycosaminoglycans, sulfated tyrosine peptides, sulfated steroids/bile acids/catecholamines. Sulfated molecules display a large number of biological activities including antithrombotic, antimicrobial, anticancer, anti‐inflammatory, and others, which arise from modulation of intracellular signaling and enhanced in
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Isolation, Structure Elucidation, and Biological Activity of the Selective TACR2 Antagonist Tumonolide and its Aldehyde from a Marine Cyanobacterium Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Sofia Kokkaliari, Laura Grauso, Alfonso Mangoni, Gustavo Seabra, Valerie J. Paul, Hendrik Luesch
The macrocyclic tumonolide (1) with enamide functionality and the linear tumonolide aldehyde (2) are new interconverting natural products from a marine cyanobacterium with a peptide‐polyketide skeleton, representing a hybrid of apratoxins and palmyrolides or laingolides. The planar structures were established by NMR and mass spectrometry. The relative configuration of the stereogenically‐rich apratoxin‐like
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Correspondence on “Beyond the Dimer and Trimer: Tetraspiro[2.1.25.1.29.1.213.13]hexadecane‐1,3,5,7‐tetraone – the Cyclic Tetramer of Carbonylcyclopropane” Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Venkatesan S. Thimmakondu
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α‐Selective Solid‐Phase Synthesis of Glycosyl Phosphate Repeating Structure via the Phosphoramidite Method Chem. Eur. J. (IF 3.9) Pub Date : 2024-07-18 Kazuki Kawato, Kazuki Sato, Takeshi Wada
Lipophosphoglycans (LPGs) are found on the surface of Leishmania, a protozoan parasite, and are immunologically important. Herein, disaccharide 1‐phosphate repeating units of LPGs were successfully synthesized on a solid support with high anomeric purity using a disaccharide α‐1‐phosphoramidite building block. To enhance solubility in the reaction solvent, hydroxy‐protecting groups in the form of para‐t‐butylbenzoyl