Alexander R Davis, Sena Öztürk, Kushal Samanta, Louise Male, Adam A L Michalchuk, Sarah J Pike
{"title":"Solvent Effects on the Conformational Preferences of 2,6-Pyridylcarboxamide Foldamers.","authors":"Alexander R Davis, Sena Öztürk, Kushal Samanta, Louise Male, Adam A L Michalchuk, Sarah J Pike","doi":"10.1002/chem.71097","DOIUrl":"https://doi.org/10.1002/chem.71097","url":null,"abstract":"<p><p>The marked influence of organic solvents and water on the conformational preferences of a chiral, soluble 2,6-pyridylcarboxamide foldamer has been established in an array of seventeen distinct solvents/solvent mixtures. Circular dichroism (CD) spectroscopy has been used to determine the conformational behavior of the soluble PEGylated foldamer as a function of the solvent for aromatic solvents (benzene, toluene and pyridine), chlorinated solvents (chloroform, dichloromethane and tetrachloroethane), polar aprotic solvents (tetrahydrofuran, acetone, acetonitrile, nitromethane, dimethylformamide and dimethylsulfoxide) and polar protic solvents (methanol, methanol/water mixtures). In aromatic and chlorinated solvents, the foldamer displays pronounced CD signals indicating the adoption of a stable helical conformation in these environments. Notably, even in the presence of polar protic solvents containing high levels of water (of up to 35% water in methanol mixtures), a helical conformation is still adopted by the foldamer, albeit with a less well-defined helical conformation than for other less competitive solvents. These investigations provide crucial insights into the conformational preferences of this foldamer class in a wide range of organic solvents and water mixtures. It is anticipated that this solvent study will prove to be highly important for aiding the future design and operation of functional foldamers, including water compatible systems, in diverse environments.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71097"},"PeriodicalIF":3.7,"publicationDate":"2026-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831285","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}
{"title":"Synthesis and Reactivity of 3-Aminosydnones in Cycloaddition Reactions With Alkynes.","authors":"Apolline Dominic, Timothée D'anfray, Guillaume Force, David-Alexandre Buisson, Maxime Tricoire, Alexis Leblais, Davide Audisio, Frédéric Taran","doi":"10.1002/chem.71110","DOIUrl":"https://doi.org/10.1002/chem.71110","url":null,"abstract":"<p><p>We present in this article the synthesis, functionalization, and properties of 3-aminosydnones, a forgotten class of mesoionic compounds. Their capacity to react as 1,3-dipoles in cycloaddition reactions with cyclic alkynes was investigated, revealing their potential as valuable tools for bioconjugation applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71110"},"PeriodicalIF":3.7,"publicationDate":"2026-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831409","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}
{"title":"Fibrous/Sheet Nanostructures of Spin-Crossover Complexes With Glycyrrhetinic Acid Glycosides in Polar Solvents: Supramolecular Control of Mixed HS/LS State.","authors":"Keita Kuroiwa, Kouta Araki, Rara Naito, Sangeetha Srinivasa Shetty, Yasuhito Koyama, Shinya Hayami","doi":"10.1002/chem.71111","DOIUrl":"https://doi.org/10.1002/chem.71111","url":null,"abstract":"<p><p>Hybridization of [Fe(qsal)<sub>2</sub>]Cl·2H<sub>2</sub>O (qsal: N-(8-quinolinyl)salicylaldimine) with glycyrrhetinic acid glycosides affords novel magnetic materials that exhibit spin-crossover behavior with stabilization of mixed HS/LS states. The glycosides direct the self-assembly of [Fe(qsal)<sub>2</sub>]<sup>+</sup> complexes into fibrous and sheet-like nanostructures in polar solvents, particularly in water, where solvation plays a critical role. The 1:1 molar hybrids were characterized by scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy, and dynamic light scattering, confirming nanostructure formation and aggregation in methanol and aqueous media. Ultraviolet-visible spectroscopy revealed temperature-dependent spin crossover through changes in ligand-to-metal charge-transfer and d-d transitions. Superconducting quantum interference device magnetometry further confirmed spin-crossover behavior, showing distinct magnetic susceptibility changes during heating and cooling cycles, consistent with stabilization of a mixed HS/LS state (high spin:low spin ≈ 1:1). This behavior is attributed to asymmetric packing of the iron complexes within the nanostructures and partial stabilization of the high-spin state in highly polar environments. These results demonstrate that supramolecular organization in polar solvents can effectively modulate spin states, providing a new strategy for designing solution-processable and potentially biocompatible spin-crossover materials.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71111"},"PeriodicalIF":3.7,"publicationDate":"2026-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831263","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}
Haruka Yoshino, Kohei Yamagami, Yuki Imamura, Hirona Yamagishi, Sayuri Shimoda, Benjamin Le Ouay, Ryo Ohtani, Hitoshi Miyasaka, Masaaki Ohba
{"title":"Precise Control of Water Adsorption Behavior in Solid Solutions of Amorphous Coordination Polymers.","authors":"Haruka Yoshino, Kohei Yamagami, Yuki Imamura, Hirona Yamagishi, Sayuri Shimoda, Benjamin Le Ouay, Ryo Ohtani, Hitoshi Miyasaka, Masaaki Ohba","doi":"10.1002/chem.71070","DOIUrl":"https://doi.org/10.1002/chem.71070","url":null,"abstract":"<p><p>Metal-organic frameworks (MOFs) and coordination polymers (CPs) with flexible coordination networks can exhibit rapid adsorption accompanied by structural changes at a specific pressure called the gate-opening pressure (P<sub>go</sub>), making them well-suited for various water-uptake-based applications. Herein, we demonstrated the precise modulation of the water uptake behavior in the amorphous coordination polymers (Am-CPs), Co<sub>x</sub>M<sub>(1-x)</sub>[Ni(CN)<sub>4</sub>] (Co<sub>x</sub>M<sub>(</sub> <sub>1</sub> <sub>-x)</sub>; M = Mn, Fe), via a solid solution approach. All amorphous solid solutions of Co<sub>x</sub>M<sub>(</sub> <sub>1</sub> <sub>-x)</sub> showed abrupt water adsorption within the relative pressure range of P/P<sub>0</sub> = 0.5-0.9. This phenomenon was associated with an amorphous-to-crystalline transformation into the 2D Hofmann-type analog of Co<sub>x</sub>M<sub>(1-x)</sub>(H<sub>2</sub>O)<sub>2</sub>[Ni(CN)<sub>4</sub>]·4H<sub>2</sub>O (Co<sub>x</sub>M<sub>(</sub> <sub>1</sub> <sub>-x)</sub>-H<sub>2</sub>O). Systematic changes in P<sub>go</sub> for Co<sub>x</sub>M<sub>(</sub> <sub>1</sub> <sub>-x)</sub> were controlled by the type and ratio of the central metals, which were revealed using a combination of L<sub>2,3</sub>- and K-edge X-ray absorption fine structure (XAFS) techniques. Slight differences in the bond energies of bonds in the vicinity of the water-induced amorphous-to-crystalline transformation. This transformation involves a change in the coordination geometry, from tetrahedral to octahedral, through the rearrangement of CN-Co(M) bonds via cleavage/reformation, giving rise to the desirable water uptake characteristics.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71070"},"PeriodicalIF":3.7,"publicationDate":"2026-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831298","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}
Yun-Long Bai, Rui Ning, Xu-Dong Wang, Li-Xia Wang, Jie Cui, Jun-Feng Xiang, Yu-Fei Ao, De-Xian Wang, Qi-Qiang Wang
{"title":"Chiral Macrocycle-Enabled In-Situ Trapping of Catalytically Active Peroxometalate Anions for Directing Asymmetric Sulfoxidation.","authors":"Yun-Long Bai, Rui Ning, Xu-Dong Wang, Li-Xia Wang, Jie Cui, Jun-Feng Xiang, Yu-Fei Ao, De-Xian Wang, Qi-Qiang Wang","doi":"10.1002/chem.71092","DOIUrl":"https://doi.org/10.1002/chem.71092","url":null,"abstract":"<p><p>Herein, we report a strategy employing chiral macrocycles for the in situ trapping of catalytically active anions, enabling highly efficient and enantioselective catalysis. By exploiting the strong anion-binding ability of tailored bis-thiourea macrocycles, active peroxotungstate species generated from a Na<sub>2</sub>WO<sub>4</sub>/Na<sub>3</sub>PO<sub>4</sub>/H<sub>2</sub>O<sub>2</sub> system are selectively captured within a confined chiral cavity. Using only 1 mol% macrocycle, sulfide oxidation proceeds efficiently to afford sulfoxides in up to 95% yield and 91% ee. Mechanistic studies identify a macrocycle-bound phosphato-bis(oxoperoxotungstate) complex as the key catalytic species. The pronounced macrocyclic effect and the fine stereochemical modulation in response to subtle structural variations underscore the precise control conferred by the confined environment. This work demonstrates that macrocyclic anion trapping can steer the reactivity and stereoselectivity of otherwise elusive polyanionic catalysts-offering a distinct approach that operates beyond conventional cationic ion-pairing systems. The strategy is expected to be applicable to a wide range of catalytic transformations involving active anionic species.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71092"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831217","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}
Noemí Nogal, Hugo Laigle, Maxime Mansy, Sébastien Ulrich, Mathieu Surin
{"title":"Dynamic Control of Nucleic Acids Self-Assembly and Expression Using Photoswitches.","authors":"Noemí Nogal, Hugo Laigle, Maxime Mansy, Sébastien Ulrich, Mathieu Surin","doi":"10.1002/chem.71079","DOIUrl":"https://doi.org/10.1002/chem.71079","url":null,"abstract":"<p><p>Synthetic nucleic acids have become readily available and now constitute versatile building blocks in materials science-where they can be used to engineer DNA origami-and biotechnologies, where they act as bioactive entities. It has therefore become of interest to develop chemical approaches enabling an external control over their function. In this line, photoswitches have attracted a strong interest since light is a benign stimulus which can be applied with spatio-temporal precision. In this review, we showcase the recent evolution in the design of photoswitches with improved performances, and highlight selected applications of their combination with nucleic acids.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71079"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831176","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}
Yunfan Fei, Yajie Wang, Jie Zhang, Jie Liu, Zilin Zhao, Takanori Hattori, Jun Abe, Xiao Dong, Ho-Kwang Mao, Haiyan Zheng, Kuo Li
{"title":"Fused-Ring Nanothread Synthesized via High-Pressure Polymerization of Naphthalene.","authors":"Yunfan Fei, Yajie Wang, Jie Zhang, Jie Liu, Zilin Zhao, Takanori Hattori, Jun Abe, Xiao Dong, Ho-Kwang Mao, Haiyan Zheng, Kuo Li","doi":"10.1002/chem.71096","DOIUrl":"https://doi.org/10.1002/chem.71096","url":null,"abstract":"<p><p>Carbon nanothreads (CNThs) are one-dimensional saturated carbon nanomaterials with exceptional mechanical properties. Polycyclic aromatic hydrocarbons (PAHs) are anticipated to form thicker, multi-ring CNThs with improved mechanical performance under high-pressure. Herein, we systematically investigated the high-pressure polymerization of naphthalene, the simplest PAH, using multiple cutting-edge methods. Naphthalene molecules adopt a herringbone stacking along the a-b direction, and underwent reactions along this stacking direction above 20 GPa, affording one-dimensional unsaturated CNThs with the [4+2] cycloaddition reaction as the dominant reaction path. In contrast to the formation of many reported CNThs, the nucleation of the naphthalene-derived CNThs occurs during compression while their growth proceeds during decompression; this behavior is likely common among aromatics with a herringbone structure. The unit cell of the as-obtained CNTh crystal was determined, and a possible structure of the CNTh product was proposed. Our research reveals the polymerization characteristics of naphthalene under high-pressure, highlighting that the slip-angle and herringbone-angle play an important role in governing the polymerization pathway.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71096"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831310","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}
{"title":"Interfacial Chemistry in High-Voltage Ni-Mn-Based Cathodes: Understanding and Controlling Degradation Pathways.","authors":"Yongkang Shen, Haotian Rui, Weiwei Fang, Lili Liu, Xinhai Yuan, Xiangwen Gao, Kenneth I Ozoemena, Yuping Wu","doi":"10.1002/chem.71086","DOIUrl":"https://doi.org/10.1002/chem.71086","url":null,"abstract":"<p><p>Owing to its high energy density, environmental friendliness, and low cost, the high-voltage Ni-Mn-based oxides material has emerged as a highly promising cathode candidate. Nevertheless, such kind of material faces significant limitations including hydrofluoric acid (HF) corrosion, transition metal dissolution, and the Jahn-Teller effect, which substantially hinder its large-scale commercialization. This review comprehensively introduces the fundamental characteristics and limitations of LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) and LiNi<sub>x</sub>Co<sub>y</sub>Mn<sub>z</sub>O<sub>2</sub> (NCM), followed by state-of-the-art mitigation approaches of CEI regulation encompassing electrolyte additives, synergistic additive combinations, doping modifications, surface coating engineering, and particle design optimization. Future research could explore the synergistic combination of these modification approaches, potentially sparking novel research avenues.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71086"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831266","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}
{"title":"Design of Fuel-Dependent, Complex-Coacervate-Based Synthetic Cells.","authors":"Anna-Lena Holtmannspötter, Xiaoyao Chen, Yiyi Fu, Melisa Badem, Phillip S Weiß, Nicolas Glück, Chase Kanitz, Veronika Rupp, Kaige Wang, Job Boekhoven","doi":"10.1002/chem.71099","DOIUrl":"https://doi.org/10.1002/chem.71099","url":null,"abstract":"<p><p>Fuel-dependent synthetic cells are compartments that require fuel to emerge and sustain. Without fuel, they decay, serving as a selection pressure in fueling-starvation experiments. Recently, we introduced fuel-dependent synthetic cells based on droplets as a route to synthetic life. These droplets grow, divide, and decay under starvation conditions. However, which parameters influence their lifetime and their ability to divide remain unknown. Moreover, previous designs of these synthetic cells suffer from the accumulation of waste products of their chemical reactions. In this work, we offer design rules for chemically fueled complex coacervate droplets with a focus on hexapeptides. We find that incorporating tryptophan into peptide designs increases the peptides' affinity for polyanions and thus their ability to form droplets. The resulting synthetic cells are longer-lived and more waste-resistant and can produce offspring when RNA is used as the polyanion. Placing the tryptophan close to the reactive C-terminus further extends the droplet lifetime by slowing deactivation. Together, these results lead to a new series of peptides to produce waste-resistant, RNA-compatible, fuel-dependent synthetic cells.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71099"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831224","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}
{"title":"An Efficient Artificial Light-Harvesting System Constructed Based on Host-Guest Interactions in Aqueous Environment for Photocatalytic Dehalogenation Reactions.","authors":"Yuanyuan Zhang, Shicong Liu, Junqiu Liu, Chunxi Hou","doi":"10.1002/chem.71073","DOIUrl":"https://doi.org/10.1002/chem.71073","url":null,"abstract":"<p><p>In this study, a strategy for constructing an artificial light-harvesting system (LHS) in an aqueous environment through host-guest interactions is proposed. An amphiphilic anthracene derivative (MVPA), functionalized with two methylated vinylpyridine arms, was designed and synthesized. Upon sequential addition of cucurbit[6]uril (CB[6]) and cucurbit[8]uril (CB[8]), MVPA underwent supramolecular self-assembly to form well-defined polymeric structures exhibiting enhanced fluorescence properties and distinct spherical morphologies, thereby serving as efficient energy donors (MVPA-CB[6] and MVPA-CB[8]). Subsequently, the fluorescent dye Cy5 was introduced into the aqueous solutions of MVPA-CB[6] and MVPA-CB[8] as an energy acceptor. The resulting artificial LHSs demonstrated highly efficient Förster resonance energy transfer from the donor to the acceptor, with an energy transfer efficiency of 81% for the MVPA-CB[8]-Cy5 system. To harness the harvested energy further, MVPA-CB[6] and MVPA-CB[8] assemblies were employed as photocatalysts for dehalogenation reactions in aqueous solutions. At 0.12 mol%, the reaction yields improved to 51% and 68%, respectively, indicating the effective conversion of solar energy into chemical energy. This work not only presents a new approach for constructing high-performance aqueous artificial LHSs but also demonstrates their practical application in photocatalytic transformations, specifically the dehalogenation of α-bromoacetophenone, thus highlighting their potential in mimicking natural photosynthetic processes.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e71073"},"PeriodicalIF":3.7,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831187","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}