{"title":"Tag-Assisted Liquid-Phase Oligonucleotide Synthesis: Toward a Convergent Approach.","authors":"Shinnosuke Akahane, Yuki Takahashi, Eimi Morikawa, Masae Sugai, Hideaki Umemoto, Takuya Onaka, Satoshi Ito, Naoto Taki, Yuya Yoshida, Yuto Toichi, Yoshikazu Kitano, Kazuhiro Chiba, Yohei Okada","doi":"10.1002/chem.202500616","DOIUrl":"10.1002/chem.202500616","url":null,"abstract":"<p><p>Although soluble support (tag)-assisted liquid-phase methods have found practical applications in peptide synthesis, they are still in their infancy for oligonucleotide synthesis. The development of techniques for selective tag cleavage with protective groups remaining is particularly important because such techniques are necessary to realize a convergent approach. Herein, we report an effective soluble support-assisted liquid-phase oligonucleotide synthesis using a novel tag that can be prepared from commercially available methyl gallate without column chromatography. Selective tag cleavages with protective groups remaining are made possible under mild reducing conditions to prepare protected fragments, which is necessary to realize a convergent approach.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500616"},"PeriodicalIF":3.9,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143958805","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":"Anion-Mediated Charge-Transfer Assemblies Composed of Resorcin[4]arene and Viologen Salts.","authors":"Yuki Konishi, Shinnosuke Horiuchi, Shota Ogura, Kanami Sugiyama, Hikaru Sotome, Mikihiro Hayashi, Masahiro Higashi, Tsukasa Abe, Shuichi Hiraoka","doi":"10.1002/chem.202501042","DOIUrl":"https://doi.org/10.1002/chem.202501042","url":null,"abstract":"<p><p>Supramolecular assemblies of a concaved aromatic host as electron donor (D) and a cationic heterocyclic guest as electron acceptor (A) are reported. These molecular units were noncovalently bound to afford charge-transfer (CT) complexes in solution and a CT co-crystal, displaying drastic color change from colorless to orange. The binding motif of the assemblies in the solution state was analyzed by NMR spectroscopic analysis and visualized by X-ray crystallographic analysis. Theoretical calculations for the assemblies revealed electronic communication between the D and A fragments, proving their CT characteristics. The CT complexes were stabilized by not only CT and cation-π interactions but also coulomb interaction between cationic acceptor unit and its anion supported by a hydrogen bond with a hydroxy group in the aromatic host, resulted in enhancement of orbital overlapping of the D-A fragments. Owing to the strong D-A interaction in the assemblies, the CT complexes undergo ultrafast charge recombination on a femtosecond timescale after photoexcitation of the CT transition, as confirmed by transient absorption spectroscopy. These results demonstrate that understanding of assembly motif and its noncovalent interactions can lead to create optical materials manupulating electron transition dynamics.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501042"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953999","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}
Alice Gable, Emmi Pohjolainen, Gerrit Groenhof, Fabien B L Cougnon
{"title":"Chirality Effects in Peptide-Based Dynamic Combinatorial Chemistry.","authors":"Alice Gable, Emmi Pohjolainen, Gerrit Groenhof, Fabien B L Cougnon","doi":"10.1002/chem.202501298","DOIUrl":"10.1002/chem.202501298","url":null,"abstract":"<p><p>Naturally occurring peptides are almost exclusively composed of L-amino acids, and the incorporation of D-amino acids can profoundly alter their ability to fold and self-assemble. Here we explore the effects of chirality on the formation of disulfide dynamic combinatorial libraries (DCLs) generated by short cysteine-rich peptides. Our findings consistently show that heterochiral tripeptides form more diverse DCLs than their homochiral counterparts. The most complex library appears to encompass all possible cyclic species up to 19mers. Given that each of these species exists as a mixture of parallel and antiparallel isomers, we estimate this library to contain a total of 2,045 distinct compounds-a remarkable result considering that the library generated by the analogous homochiral peptide predominantly contains two dimers. In certain situations, peptide chirality also affects the relative stability of parallel and antiparallel isomers. Taken together, these results show that small changes in peptide chirality can be dramatically amplified through the formation of cyclic species.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501298"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951812","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}
Christoph Riesinger, Lisa Zimmermann, Robert Szlosek, Gábor Balázs, Jan Wieneke, Lisa-Marie Orel, Luis Dütsch, Manfred Scheer
{"title":"Functionalization, Fragmentation, and Expansion of cyclo-P<sub>4</sub>R<sub>2</sub> Ligands.","authors":"Christoph Riesinger, Lisa Zimmermann, Robert Szlosek, Gábor Balázs, Jan Wieneke, Lisa-Marie Orel, Luis Dütsch, Manfred Scheer","doi":"10.1002/chem.202501305","DOIUrl":"10.1002/chem.202501305","url":null,"abstract":"<p><p>In this study, three isolobal complexes of the form [{L<sub>n</sub>M}(η<sup>3</sup>-P<sub>4</sub>R<sub>2</sub>)]<sup>+</sup> ({L<sub>n</sub>M} = {CpMo(CO)<sub>2</sub>} (A), {Cp'''Ni} (B), {Cp'''Co}<sup>-</sup> (C), R = Ph, iPr; Cp''' = 1,2,4-<sup>t</sup>Bu<sub>3</sub>C<sub>5</sub>H<sub>2</sub>) are reacted with nucleophilic carbenes (L). While C does not show any reactivity, the cationic complexes A and B undergo addition reactions. The respective products [CpMo(CO)<sub>2</sub>(η<sup>3</sup>-P<sub>4</sub>R<sub>2</sub>L)]<sup>+</sup> (1a - d) and [Cp'''Ni(η<sup>1:1</sup>-P<sub>4</sub>R<sub>2</sub>L)]<sup>+</sup> (3a - d) show different geometries for the L-P<sub>3</sub>PR<sub>2</sub> ligands. Their reactivity towards EtO<sup>-</sup> results in either a simple addition (for 1) or a complex addition, ring-opening, rearrangement sequence (for 3). Moreover, [Cp'''Ni(η<sup>2</sup>-IDippPP(OEt)PP<sup>i</sup>Pr<sub>2</sub>)] (4) could be methylated by the reaction with MeOTf, which affords an iso-tetraphosphine ligand, marking the first example of complete functionalization of a polyphosphorus ligand to a complexed phosphine. Mechanistic studies shed light upon the fundamental principles, which differentiate the influence of the isolobal {CpMo(CO)<sub>2</sub>}, {Cp'''Ni}, and {Cp'''Co}<sup>-</sup> transition metal units. Lastly, 3a-d were chosen as model substrates for further nucleophilic functionalization. In this regard, 3 reacts with [CN]<sup>-</sup> in a [3+1] fragmentation reaction affording the dimerized species [{Cp'''Ni}<sub>2</sub>(μ,η<sup>1:1:1:1</sup>-cyclo-P<sub>4</sub>(PR<sub>2</sub>)<sub>2</sub>)] (6a: R = Ph, 6b: R = <sup>i</sup>Pr) together with IDippP-CN. In contrast, the reaction with [ECO]<sup>-</sup> (E = P, As) led to an extension of the pnictogen framework yielding [Cp'''Ni(η<sup>1:1</sup>-EP<sub>4</sub>Ph<sub>2</sub>IDipp)] (8a: E = P, 8b: E = As).</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501305"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143956527","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":"Dual-Organelle-Targeted Fluorescent Probe for Lipid Droplets and Endoplasmic Reticulum Using Bay-Region Substituted Perylene Diimides.","authors":"Jinping Liu, Xiaoyu Bu, Zikang Yang, Linshuai Yang, Qi Ai, Baoxiang Gao","doi":"10.1002/chem.202500772","DOIUrl":"10.1002/chem.202500772","url":null,"abstract":"<p><p>In the complex cellular microenvironment, lipid droplets (LDs) and the endoplasmic reticulum (ER) are essential for maintaining cellular homeostasis. Their interactions are crucial for regulating processes such as lipid metabolism. Nevertheless, simultaneously monitoring these two organelles remains a challenging task. In this study, a dual-organelle-targeted perylene diimides (PDIs) based probe, LD-ER-PDI, by incorporating a 2-azetidinone substituent in the bay-region and two distinct targeting groups for LDs and ER at opposite ends of the imide positions was developed, enabling discrimination between LDs and ER. Moreover, it can effectively visualize the dynamic behaviors of LDs and ER under starvation and oleic acid-treated conditions, and also allows real-time monitoring of LDs formation from the ER. This work not only provides a valuable tool for studying the dynamic interactions between LDs and ER but also highlights a strategy for designing dual-organelle-targeted fluorescent probes.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500772"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953675","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}
Lukas Enders, Riccardo Mobili, Louis Fensterbank, Juho Helaja, Virginie Mouriès-Mansuy
{"title":"Bifunctional Chiral ImPy-Carbene Ligands. H-Bonding Controlled Reactivity and Enantioselectivity in Au(I)-Catalysis.","authors":"Lukas Enders, Riccardo Mobili, Louis Fensterbank, Juho Helaja, Virginie Mouriès-Mansuy","doi":"10.1002/chem.202501259","DOIUrl":"10.1002/chem.202501259","url":null,"abstract":"<p><p>Bifunctional chiral N-heterocyclic carbene ligands have been devised for enantioselective gold(I) catalysis. Based on a single C-stereogenic center derived from chiral pool α-aminoacids and connecting an imidazopyridine core to an arylurea motif, enantioselective gold(I)-catalyzed cycloisomerization reactions could be achieved. High enantioselectivities were notably observed for substrates presenting a pendant propargyl alcohol on 2-naphthol and 1,6-enyne scaffolds. In the latter case, the catalyst shows a high degree of selectivity for the unprecedented 6-endo-dig biscyclization of these substrates to give cyclopropyl-fused 6-ring heterocycles with a free OH functionality instead of the previously reported furan-fused products. This unusual selectivity was investigated by DFT studies, which suggested the dual role of the carbonyl group of the urea moiety: first as an H-bond acceptor in the catalytic cycle to direct the enantioselectivity and second as a cooperative group in the hydrogen shift leading to deauration.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501259"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952203","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":"Matrix Isolation and Solvation of the Benzonitrile Radical Anion.","authors":"Shubhra Sarkar, Ankit Somani, Wolfram Sander","doi":"10.1002/chem.202501150","DOIUrl":"https://doi.org/10.1002/chem.202501150","url":null,"abstract":"<p><p>Solvated electrons, one of the strongest reducing agents, exhibit short lifetimes in the range of pico- to milliseconds when generated photochemically or by radiolysis in solution. In contrast, solvated electrons produced using sodium metal in liquid ammonia are stable for days and have long been used in synthetic chemistry. Using sodium atoms as an electron source, we were able to trap solvated electrons in low-density amorphous (LDA) water ice matrices with lifetimes of several days and use these electrons as reducing reagent. In LDA matrices doped with benzonitrile 1 these electrons react with 1 to form the benzonitrile radical anion 2. In argon matrices, in the absence of water, only small amounts of 2 were observed after deposition, and most of the sodium and 1 remained unreacted. The yield of radical anion 2 is significantly higher in amorphous water ice than in solid argon. The photoexcitation of radical anion 2 in both argon and LDA water ice matrices resulted in a reversal of the electron transfer under back formation of benzonitrile 1. Annealing of argon matrices doped with small amounts of water containing 2 resulted in the formation of 1:1 and 2:1 hydrogen-bonded complexes between water and radical anion 2.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501150"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143954003","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":"Recent Advances in Detergent Chemistry and Handling Support Membrane Protein Analysis Including Lipid Interactions.","authors":"Katharina Alker, Jan-Simon Behnke, Leonhard Hagen Urner","doi":"10.1002/chem.202501549","DOIUrl":"https://doi.org/10.1002/chem.202501549","url":null,"abstract":"<p><p>Non-ionic detergents are key reagents for the characterization of membrane protein drug targets. Suitable detergents are commonly identified by trial and error, which leads to failed preparations and raising costs. Recent findings suggest that not only the chemistry of detergents but also the strategy with which detergents and proteins are brought together impact the successes of investigations. To facilitate the future development of non-ionic detergents in membrane protein research, herein, we review chemical design concepts and detergent exchange strategies for a successful integration of detergents into the analysis of challenging membrane protein complexes. Our overview reveals exciting opportunities to tackle existing challenges, including the stabilization of G-protein coupled receptors, the development of fluorinated detergents for studying protein-lipid binding, top-down design of detergents, and hybrid detergents for the identification of non-canonical lipid associations to proteins with relevance to antibiotic research. Our review will facilitate the development of chemical tools for the biophysical characterization of membrane proteins and support the discovery of biological findings in the future.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501549"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143956441","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}
Virginia Guiotto, Maria Sole Notari, Diletta Morelli Venturi, Alberto Ricchebuono, Melissa Castagnoli, Christoph Meier, Francesca Nardelli, Lucia Calucci, Matteo Signorile, Marco Taddei, Valentina Crocella', Ferdinando Costantino
{"title":"A Flexible, Perfluorinated Analogue of Aluminum Fumarate Metal-Organic Framework.","authors":"Virginia Guiotto, Maria Sole Notari, Diletta Morelli Venturi, Alberto Ricchebuono, Melissa Castagnoli, Christoph Meier, Francesca Nardelli, Lucia Calucci, Matteo Signorile, Marco Taddei, Valentina Crocella', Ferdinando Costantino","doi":"10.1002/chem.202500130","DOIUrl":"https://doi.org/10.1002/chem.202500130","url":null,"abstract":"<p><p>Herein we report the synthesis of Al-TFS, a novel aluminum metal-organic framework (MOF) based on tetrafluorosuccinic acid (H2TFS), of formula Al(OH)(TFS)·1.5H2O, introducing a new member to the family of perfluorinated MOFs. The structure of the MOF, solved ab-initio from laboratory powder X-ray diffraction data, displays structural analogies with that of the commercially available Al-fumarate (Basolite A520). The structure is composed of 1D infinite OH-bridged Al octahedra chains connected by the dicarboxylic linkers, designing rhombic channels decorated by fluorine atoms. Upon water removal, the MOF undergoes a phase transition leading to a moderate expansion of the unit cell. Volumetric analysis revealed the presence of ultra-micropores with a size lower than 4 Å. Gas sorption measurements demonstrated for Al-TFS a slightly higher CO2 selectivity compared to N2 and CH4 than the Al-fumarate analogue, with peculiar shapes of the isotherms suggesting a dynamic response of the framework to CO2 adsorption. Using different complementary techniques (in situ infrared spectroscopy, powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, gas/vapor sorption), and density functional theory simulations, the flexibility of the new MOF was disclosed, highlighting the significant impact of fluorination in tailoring materials with structural flexibility and peculiar adsorption properties.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500130"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951200","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}
Lorenzo Branzi, Joseph Martyn, Lucy Fitzsimmons, Yurii K Gun'ko
{"title":"Chirality in Transition Metal Dichalcogenide Nanostructures.","authors":"Lorenzo Branzi, Joseph Martyn, Lucy Fitzsimmons, Yurii K Gun'ko","doi":"10.1002/chem.202404765","DOIUrl":"10.1002/chem.202404765","url":null,"abstract":"<p><p>The fascinating properties introduced by the breaking of mirror symmetry have recently motivated a rising interest in chirality in nanomaterials. In particular, transition metal (TM) dichalcogenides (TMDs) are a wide group of technologically relevant 2D layered materials where recent efforts in the introduction of chirality have shown promising results, attracting great attention for future studies and potential applications. This review article is focused on the development of chirality in TM dichalcogenide nanostructures, dealing with the synthetic strategies that have been adopted to produce chiral TMDs both via solution-phase and vapor-phase syntheses along with the characterization of their chiroptical properties. A broad range of examples, including a variety of nanostructures such as 0D quantum dots (QDs), 1D nanotubes, 2D flakes, and more complex 3D nanostructures as well as different origins of chirality are considered. Critical analysis of potential pitfalls in the assessment of the materials' chirality are discussed. A broad range of exciting properties and applications associated with the materials' chirality, including: nanomedicine, enantioselective catalysis, spin-dependent electrocatalysis, spintronics, and nonlinear optics, are also presented in the review.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404765"},"PeriodicalIF":3.9,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951286","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}