Chemistry - A European Journal最新文献_第6页

Hydrophobic And Polarized Aromatic Residues Promote Internalization Of Arg-Rich Cell Penetrating Peptides Through Ionpair-π Interactions. 疏水和极化芳香残基通过离子对-π相互作用促进富精细胞穿透肽的内在化。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501138

Sonia Khemaissa, Antonio Bauzá, Émilie Lesur, Françoise Illien, Sandrine Sagan, Antonio Frontera, Astrid Walrant

{"title":"Hydrophobic And Polarized Aromatic Residues Promote Internalization Of Arg-Rich Cell Penetrating Peptides Through Ionpair-π Interactions.","authors":"Sonia Khemaissa, Antonio Bauzá, Émilie Lesur, Françoise Illien, Sandrine Sagan, Antonio Frontera, Astrid Walrant","doi":"10.1002/chem.202501138","DOIUrl":"10.1002/chem.202501138","url":null,"abstract":"Cell penetrating peptides (CPPs) are small sequences that can cross cell membranes. Arg and Trp are highly prevalent amino-acids in natural and synthetic efficient CPP sequences. In particular, Trp is essential and cannot be substituted by other hydrophobic or aromatic amino-acids. The aim of the present study is to decipher the role of Trp in synthetic Arg/Trp CPP sequences. To do so, a small peptide library in which this residue was substituted by other natural or non-natural amino-acids was designed. Internalization of these peptides in cells was evaluated and it appeared that combining aromaticity and hydrophobicity in the presence of Arg residues leads to enhanced internalization. The study of the interaction of these peptides with model lipid membranes revealed that the modulation of hydrophobicity promoted insertion in bilayers, but had little impact on the binding affinity. On the other hand, more hydrophobic substitutes of Trp led to more favorable binding enthalpies to heparin. With DFT analysis, we suggest that ion-pair···π interactions between the aromatic ring and the ion pair formed by the positively charges Arg and the negatively charged cell surface groups can be established, and could be at the origin of the unique internalization properties of Trp-containing Arg-rich CPPs.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501138"},"PeriodicalIF":3.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144332189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Benzo-Extended Thiaquasi[7]Circulenes: Strategic Scholl-Type Synthesis, Tunable Electronic, and Stimuli-Responsive Properties. 苯并扩展的噻唑烷环：战略性合成、可调电子和刺激响应特性。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501471

Raseswari Dash, Sudhakar Maddala, Prabhakar Chetti, Venkatakrishnan Parthasarathy

{"title":"Benzo-Extended Thiaquasi[7]Circulenes: Strategic Scholl-Type Synthesis, Tunable Electronic, and Stimuli-Responsive Properties.","authors":"Raseswari Dash, Sudhakar Maddala, Prabhakar Chetti, Venkatakrishnan Parthasarathy","doi":"10.1002/chem.202501471","DOIUrl":"10.1002/chem.202501471","url":null,"abstract":"Thia-quasi[7]circulenes (TQCs) are a novel class of π-conjugated molecules exhibiting unique electronic, optical, and electrochemical properties. We report a highly efficient bottom-up synthesis of TQCs via Scholl oxidative cyclization, achieving exceptional yields and structural precision. Single-crystal X-ray analysis confirms their negatively curved geometry, featuring a central antiaromatic heptagonal core and a surrounding aromatic rim, leading to bifacial electronic properties. TQCs demonstrate stable redox behavior with tunable Highest Occupied Molecular Orbital (HOMO)-Lowest Unoccupied Molecular Orbital (LUMO) energy levels. Their remarkable electrochemical stability highlights potential as redox-active materials. TQCs exhibit blue-shifted fluorescence compared to carbo-quasi[7]circulenes, with enhanced quantum yields upon benzoannulation. Additionally, they display mechanochromic luminescence upon grinding, revealing tunable molecular characteristics. These findings establish TQCs as versatile molecular frameworks, bridging fundamental chemistry and next-generation functional materials, making them promising candidates for organic electronics, energy storage, and optoelectronic applications.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501471"},"PeriodicalIF":3.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144332184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chemoenzymatic synthesis and in vitro selection of de novo thiazole-containing macrocyclic peptides. 化学酶合成及含新噻唑大环肽的体外筛选。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501355

Akihiro Saito, Hiroyuki Kimura, Hiroyasu Onaka, Hiroaki Suga, Yuki Goto

{"title":"Chemoenzymatic synthesis and in vitro selection of de novo thiazole-containing macrocyclic peptides.","authors":"Akihiro Saito, Hiroyuki Kimura, Hiroyasu Onaka, Hiroaki Suga, Yuki Goto","doi":"10.1002/chem.202501355","DOIUrl":"10.1002/chem.202501355","url":null,"abstract":"Backbone thiazole moieties prevail in bioactive peptidic natural products and play important roles in their biological functions. However, the de novo discovery of artificial thiazole-containing peptide ligands remains challenging. Here, we report an mRNA display-based selection platform for thiazole-containing macrocyclic peptides (ThzteMP), established through a dedicated posttranslational chemoenzymatic transformation. This method exploits the unique reactivity of ribosomally incorporated thioamides, enabling enzyme-free spontaneous heterocyclization to form thiazoline, which is further oxidized using the substrate-tolerant azoline dehydrogenase (GodE) to yield a thiazole moiety. By integrating this chemoenzymatic process with chloroacetyl-mediated thioether macrocyclization and mRNA display, we have successfully discovered thiazole-containing macrocyclic peptide ligands with high binding affinities against p-21 activated kinase 4 (PAK4). This study establishes a robust system to expedite ligand discovery of pseudo-natural peptides and to investigate the functional benefit of their backbone thiazoles.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501355"},"PeriodicalIF":3.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144339709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electrochemical Oxidative Radical Polar Crossover Route to 1,4-Keto Carboxylates Mediated by Anchimeric Assistance. 电化学氧化自由基极性交叉途径介导的1,4-酮羧酸的辅助。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501779

Ian MacLean, Laura Blanco, Elena Echávarri, Alba Collado, Leyre Marzo, José Alemán

引用次数: 0

Hybrid Tuning in NHC Ligands: Synergistic Effects of BIAN π -Conjugation and Aryl σ -Modulation in Gold(I) Complexes. NHC配体的杂化调谐：金(I)配合物中BIAN π -共轭和芳基σ -调制的协同效应。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501647

Roman Pankov, Aliya Khanipova, Alexandra Son, Darya Prima, Andrey Kolesnikov, Nina Ivanova, Artem Fakhrutdinov, Mikhail Minyaev, Valentine P Ananikov

{"title":"Hybrid Tuning in NHC Ligands: Synergistic Effects of BIAN π -Conjugation and Aryl σ -Modulation in Gold(I) Complexes.","authors":"Roman Pankov, Aliya Khanipova, Alexandra Son, Darya Prima, Andrey Kolesnikov, Nina Ivanova, Artem Fakhrutdinov, Mikhail Minyaev, Valentine P Ananikov","doi":"10.1002/chem.202501647","DOIUrl":"10.1002/chem.202501647","url":null,"abstract":"In this study, we explore extended design of metal-NHC complexes that relies on dual strategies for tuning ligand properties: (i) electronic modulation through π-extended frameworks such as bis(imino)acenaphthene (BIAN), and (ii) systematic aryl substitution to influence σ-donor strength and steric environment. We report the first integrated exploration of these two strategies on a unified ligand platform. A series of Au(I)/BIAN-NHCX complexes were synthesized by introducing electron-withdrawing substituents (X = F, Cl, Br, CF₃) at the ortho-, meta-, and para-positions of the N-aryl groups. This hybrid tuning approach allowed us to probe the synergistic and antagonistic effects arising from π-σ interplay across multiple dimensions. Each complex was thoroughly characterized with respect to synthetic yield, structural features (including X-ray structure and dynamics in solution), photophysical properties (UV-Vis and luminescence), catalytic performance in hydroamination of phenylacetylene, and cytotoxicity in HEK293T cells. Structure-property correlations revealed distinct cooperative and counteractive regimes depending on the substituent type and position. These findings demonstrate that combining orthogonal electronic control elements enables a more predictive and fine-grained design of NHC-based metal complexes, with future implications for catalysis, materials science, and biomedical applications.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501647"},"PeriodicalIF":3.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144332188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

What Can be Learned From the Electrostatic Environments Within Nitrogenase Enzymes? 我们可以从氮酶内部的静电环境中学到什么？

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-20 DOI: 10.1002/chem.202501616

Thijs Stuyver, Olena Protsenko, Davide Avagliano, Thomas Ward

{"title":"What Can be Learned From the Electrostatic Environments Within Nitrogenase Enzymes?","authors":"Thijs Stuyver, Olena Protsenko, Davide Avagliano, Thomas Ward","doi":"10.1002/chem.202501616","DOIUrl":"10.1002/chem.202501616","url":null,"abstract":"Nitrogen fixation is a fundamental, and yet challenging, chemical transformation due to the intrinsic inertness of dinitrogen. Whereas industrial ammonia synthesis relies on the energy-intensive Haber-Bosch process, nitrogenase enzymes achieve this transformation under ambient conditions-yet at the expense of a remarkably high ATP demand. Understanding their mode of operation could inspire the development of more efficient synthetic catalysts. In this study, we scrutinize the electrostatic environment surrounding nitrogenase's active site, the so-called M-cluster. Strikingly, we observe that all types of M-clusters exhibit similar trends, with distinct patterns around the individual metal sites that have been proposed as potential N2-coordination sites. Specifically, a strong local electric field pointing away from the Fe2 site is identified, as well as a minor field pointing toward the Fe6 sites. Furthermore, a significant oriented long-range field along the Fe2-Fe6 axis is computed across the entire family of nitrogenases. In the final part of the manuscript, we discuss how the observed electrostatic patterns may impact chemical reactivity, and how they can be connected to previously made mechanistic hypotheses. Overall, this study provides further evidence for the ubiquitousness of local electric fields in enzyme catalysis, even when substrates that seemingly have only limited electrostatic susceptibility are involved.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501616"},"PeriodicalIF":3.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144332191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Design and Synthesis of Bimetallic Cu(II) Compounds as Potent Antibacterial and Antibiofilm Agents with Metallo- β -Lactamase Inhibitory Activityagainst Multidrug Resistant Pseudomonas aeruginosa. 具有金属β -内酰胺酶抑制多重耐药铜绿假单胞菌活性的双金属Cu（II）化合物的设计与合成

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-19 DOI: 10.1002/chem.202501313

Samik Biswas, Sujan Sk, Sangita Das, Indrajit Das, Shrabasti Bandyopadhyay, Soma Mondal, Sk Imran Ali, Supratim Mandal, Manindranath Bera

{"title":"Design and Synthesis of Bimetallic Cu(II) Compounds as Potent Antibacterial and Antibiofilm Agents with Metallo- β -Lactamase Inhibitory Activityagainst Multidrug Resistant Pseudomonas aeruginosa.","authors":"Samik Biswas, Sujan Sk, Sangita Das, Indrajit Das, Shrabasti Bandyopadhyay, Soma Mondal, Sk Imran Ali, Supratim Mandal, Manindranath Bera","doi":"10.1002/chem.202501313","DOIUrl":"https://doi.org/10.1002/chem.202501313","url":null,"abstract":"In this research, a novel class of biologically active bimetallic Cu(II) compounds have been discovered as cutting-edge antibiofilm agents with metallo-β-lactamase (MBL) inhibitory activity against the clinically isolated multidrug resistant (MDR) gram-negative bacterium, Pseudomonas aeruginosa (Pa-CI-1). Thus, the 2,6-bis[N-{N-(carboxymethyl)-N-(pyridylmethyl)amine}methyl]-4-methylphenol (H3L)-incorporated three bimetallic Cu(II) compounds, [Cu2L(H2O)(Cl)]∙H2O (1), [Cu2L(H2O)(NO3)]∙H2O (2) and [Cu2L(H2O)(CH3CO2)]∙H2O (3) have been strategically designed and synthesized with unsymmetrical coordination arrangement that synergistically modifies the electronic environment of Cu centres for the enhancement of antibacterial and antibiofilm activity. The standard nitrocefin assay disclosed that 1-3 significantly inhibited the activity of MBLs produced by Pa-CI-1 at their 1/2 MIC doses. Molecular docking study revealed an excellent propensity of these Cu compounds for binding with different MBL-producing proteins. All three Cu(II) compounds displayed significantly high antibacterial and antibiofilm activity as established by multiple bioassays, including ex-vivo applicability studies. They showed an exceptional combinatorial activity when examined with commercially accessible five different β-lactam-based antibiotics such as amoxicillin (AMX), chloramphenicol (CHL), cefotaxime (CTX), ceftriaxone (CTR) and Cefoxitin (CX) against Pa-CI-1. Our study disclosed that 1-3 could be the emergent drug leads and attract great attention to the inorganic, material and biological chemists, combating antimicrobial resistance.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501313"},"PeriodicalIF":3.9,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of Siphonazole B Through Domino Cycloisomerization-Oxazolonium Ion Rearrangements. 通过多米诺环异构化-恶唑鎓离子重排法合成Siphonazole B。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-19 DOI: 10.1002/chem.202501394

Filip Paulsen, Sebastian Clementson, Henrik von Wachenfeldt, Michał Antoszczak, Simon Fridolf, Daniel Strand

引用次数: 0

Investigating the Site-Specific Impact of Fluorine Substitution on Aromatic Interactions in a Tryptophan Zipper Peptide. 研究氟取代对色氨酸拉链肽中芳香相互作用的位点特异性影响。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-19 DOI: 10.1002/chem.202501263

David Reiter, Ferhat Mutlu, Dominik Ebert, Marceline Noutio, Joachim Heberle, Mario Schubert, Beate Koksch

引用次数: 0

Scandium-Catalyzed Highly Selective Deoxygenation of Alcohols by Using Hydrosilanes as Reductants. 以氢硅烷为还原剂钪催化醇的高选择性脱氧。

IF 3.9 2区化学

Chemistry - A European Journal Pub Date : 2025-06-19 DOI: 10.1002/chem.202501596

Ruqaya Buhaibeh, Neethu Thyagarajan, Guillaume Bousrez, Louis Monsigny, Thibault Cantat, Emmanuel Nicolas

引用次数: 0