Pub Date : 2026-01-26DOI: 10.1016/j.chempr.2026.102935
Yee Lin Phang, Feng-Lian Zhang, Yi-Feng Wang
{"title":"Electrochemistry enables room-temperature Matteson-type homologation with trifluoromethyl arenes as carbenoid precursors","authors":"Yee Lin Phang, Feng-Lian Zhang, Yi-Feng Wang","doi":"10.1016/j.chempr.2026.102935","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102935","url":null,"abstract":"","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1016/j.chempr.2026.102944
Yuxin Guo, Daokuan An, Lu-Lu Qu, Xiaochen Dong
{"title":"Boosting immunocyte activation for cell therapy with a phase-separation culture system","authors":"Yuxin Guo, Daokuan An, Lu-Lu Qu, Xiaochen Dong","doi":"10.1016/j.chempr.2026.102944","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102944","url":null,"abstract":"","PeriodicalId":268,"journal":{"name":"Chem","volume":"14 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.chempr.2025.102834
Ferran Esteve, Martina Mazzaferro, Jean-Marie Lehn
{"title":"Write and erase: Macrocyclic effectors regulate imine expression in water","authors":"Ferran Esteve, Martina Mazzaferro, Jean-Marie Lehn","doi":"10.1016/j.chempr.2025.102834","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102834","url":null,"abstract":"","PeriodicalId":268,"journal":{"name":"Chem","volume":"7 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102691
Xun Li , Yohan Gisbert , Maxime Ledent , Damien Sluysmans , Gwénaël Rapenne , Claire Kammerer , Anne-Sophie Duwez
A variety of rotary molecular machine prototypes powered by light, chemical energy, or electrons have been synthesized and their operation in solution, gels, or on surfaces has been demonstrated. However, little data regarding their performances have been disclosed. Here, we report on the synthesis of molecules incorporating a five-arm rotor and the direct measurement of the work required to block the rotation around the central atom. We used single-molecule force spectroscopy (SMFS) to detect the free rotary oscillations and measure the work performed by the molecules against the mechanical load. We show that the chemical nature of the arms influences the energy barrier, causing differences in the work that the molecules can generate. Our results illustrate that SMFS, which is now widely used to probe linear displacements at a few tens of nanometer scale in macromolecules, can detect rotary motions around a single atom in a tiny synthetic molecule.
{"title":"Probing the free rotary oscillations around a single ruthenium atom in an organometallic complex","authors":"Xun Li , Yohan Gisbert , Maxime Ledent , Damien Sluysmans , Gwénaël Rapenne , Claire Kammerer , Anne-Sophie Duwez","doi":"10.1016/j.chempr.2025.102691","DOIUrl":"10.1016/j.chempr.2025.102691","url":null,"abstract":"<div><div>A variety of rotary molecular machine prototypes powered by light, chemical energy, or electrons have been synthesized and their operation in solution, gels, or on surfaces has been demonstrated. However, little data regarding their performances have been disclosed. Here, we report on the synthesis of molecules incorporating a five-arm rotor and the direct measurement of the work required to block the rotation around the central atom. We used single-molecule force spectroscopy (SMFS) to detect the free rotary oscillations and measure the work performed by the molecules against the mechanical load. We show that the chemical nature of the arms influences the energy barrier, causing differences in the work that the molecules can generate. Our results illustrate that SMFS, which is now widely used to probe linear displacements at a few tens of nanometer scale in macromolecules, can detect rotary motions around a single atom in a tiny synthetic molecule.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102691"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144778643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102702
Wei Yang , Yu Lan , Yihang Bai , Zhenyan Zhao , Yawen Song , Ruiying Chang , Xuwei Shang , Shuang Li , Shiqi Jia , Shihan Liu , Shi-Jun Li , Linbin Niu
Due to the unique mildness and good penetration ability of low-energy light (λ > 595 nm), assembling a low-energy photoredox catalytic platform in situ to circumvent the pre-preparation of the low-energy photocatalyst is intriguing and significant. Herein, we describe a manganese low-energy photoredox catalytic platform generated by the modular in situ assembly of manganese(II) salt, bidentate N ligand, nucleophilic azide reagent, and alcohol, which can enable the generation of valuable azido radicals under 850 nm light irradiation and is further used to furnish the oxidative remodeling nitrogenation of alkenes via carbon-carbon double-bond cleavage to afford value-added ketonitriles, ketones, or nitriles with excellent functional group compatibility. The utility of this procedure is underscored by late-stage functionalization of drug/natural molecule derivatives and the streamlined synthesis of anabasine, showcasing its unique potential for applications in synthetic organic chemistry and biomedicine.
{"title":"Manganese low-energy photocatalysis for remodeling nitrogenation of alkenes","authors":"Wei Yang , Yu Lan , Yihang Bai , Zhenyan Zhao , Yawen Song , Ruiying Chang , Xuwei Shang , Shuang Li , Shiqi Jia , Shihan Liu , Shi-Jun Li , Linbin Niu","doi":"10.1016/j.chempr.2025.102702","DOIUrl":"10.1016/j.chempr.2025.102702","url":null,"abstract":"<div><div>Due to the unique mildness and good penetration ability of low-energy light (λ > 595 nm), assembling a low-energy photoredox catalytic platform <em>in situ</em> to circumvent the pre-preparation of the low-energy photocatalyst is intriguing and significant. Herein, we describe a manganese low-energy photoredox catalytic platform generated by the modular <em>in situ</em> assembly of manganese(II) salt, bidentate <em>N</em> ligand, nucleophilic azide reagent, and alcohol, which can enable the generation of valuable azido radicals under 850 nm light irradiation and is further used to furnish the oxidative remodeling nitrogenation of alkenes via carbon-carbon double-bond cleavage to afford value-added ketonitriles, ketones, or nitriles with excellent functional group compatibility. The utility of this procedure is underscored by late-stage functionalization of drug/natural molecule derivatives and the streamlined synthesis of anabasine, showcasing its unique potential for applications in synthetic organic chemistry and biomedicine.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102702"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145969280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102690
Ludovic Bellon
In this issue of Chem, Li et al. describe the use of atomic force spectroscopy for detecting, stalling, and characterizing single-molecule rotors. Their work extends force spectroscopy beyond linear deformations, offering a powerful, accessible alternative to tunneling microscopy for probing molecular rotation and associated energy landscapes.
{"title":"Force spectroscopy on molecular rotors","authors":"Ludovic Bellon","doi":"10.1016/j.chempr.2025.102690","DOIUrl":"10.1016/j.chempr.2025.102690","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Li et al. describe the use of atomic force spectroscopy for detecting, stalling, and characterizing single-molecule rotors. Their work extends force spectroscopy beyond linear deformations, offering a powerful, accessible alternative to tunneling microscopy for probing molecular rotation and associated energy landscapes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102690"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145969251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102698
Jin-Liang Lin , Ran Liu , Francis Adoah , Zhou Cao , Shengzhe Qiu , Ningyue Chen , Feng Sun , Zhikang Wu , Chuan-Kui Wang , Bingqian Xu , Enrique del Barco , Yuan Li
The ability to test the limits of diodes scaled down to the molecular (quantum) scale could advance the development of nanoelectronic devices. So far, strategies for molecular rectification have mostly relied on the intrinsic asymmetry of molecules or on changes in the external environment. These approaches require complex synthetic designs or specific device structures, and their performance is far beyond theoretical prediction. Here, we report an alternative strategy that leads to giant rectification by inducing a topological change in the molecular conformation through unidirectional electric-field-driven electron delocalization, an approach also applicable to molecules without asymmetric structures. This method reverses the polarity of the applied bias, which induces the rectifying group to oxidize and transition from a buckled and cross-conjugated group into a planar aromatic group. As a result, the transformed molecule forms a fully conjugated structure resulting in a substantial increase in the current density.
{"title":"Large current rectification inside symmetric molecular junctions caused by redox-coupled conformational changes","authors":"Jin-Liang Lin , Ran Liu , Francis Adoah , Zhou Cao , Shengzhe Qiu , Ningyue Chen , Feng Sun , Zhikang Wu , Chuan-Kui Wang , Bingqian Xu , Enrique del Barco , Yuan Li","doi":"10.1016/j.chempr.2025.102698","DOIUrl":"10.1016/j.chempr.2025.102698","url":null,"abstract":"<div><div>The ability to test the limits of diodes scaled down to the molecular (quantum) scale could advance the development of nanoelectronic devices. So far, strategies for molecular rectification have mostly relied on the intrinsic asymmetry of molecules or on changes in the external environment. These approaches require complex synthetic designs or specific device structures, and their performance is far beyond theoretical prediction. Here, we report an alternative strategy that leads to giant rectification by inducing a topological change in the molecular conformation through unidirectional electric-field-driven electron delocalization, an approach also applicable to molecules without asymmetric structures. This method reverses the polarity of the applied bias, which induces the rectifying group to oxidize and transition from a buckled and cross-conjugated group into a planar aromatic group. As a result, the transformed molecule forms a fully conjugated structure resulting in a substantial increase in the current density.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102698"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145969279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102740
Finn Gude , Annkathrin Bohne , Maria Dell , Jonathan Franke , Kyle L. Dunbar , Michael Groll , Christian Hertweck
Closthioamide (CTA) is a potent antibiotic with a unique polythioamide scaffold produced by Ruminiclostridium cellulolyticum. Unlike classical non-ribosomal peptide synthetases (NRPSs), which use modular adenylation and condensation domains, CTA biosynthesis proceeds through non-canonical standalone enzymes. Central to this process is the papain-like ligase CtaG, which catalyzes amide bond formation between two distinct peptidyl carrier proteins (PCPs): CtaH, presenting para-hydroxybenzoic acid (PHBA), and CtaE, carrying a tri-β-alanine ((βAla)3) chain. Using biochemical assays, chemical probes, crystallography, and mutational analysis, we show that CtaG operates via a ping-pong mechanism involving an enzyme-bound intermediate. A single substrate tunnel mediates directional transfer, enabling distal chain elongation that mirrors solid-phase peptide synthesis. Structure-based genome mining revealed homologous enzymes in the biosynthetic pathways of petrobactin, butirosin, and methylolanthanin. Together, our findings uncover a previously overlooked class of thiotemplated ligases and provide a mechanistic blueprint for engineering ribosome-independent peptide assembly lines.
{"title":"Distal peptide elongation by a protease-like ligase and two distinct carrier proteins","authors":"Finn Gude , Annkathrin Bohne , Maria Dell , Jonathan Franke , Kyle L. Dunbar , Michael Groll , Christian Hertweck","doi":"10.1016/j.chempr.2025.102740","DOIUrl":"10.1016/j.chempr.2025.102740","url":null,"abstract":"<div><div>Closthioamide (CTA) is a potent antibiotic with a unique polythioamide scaffold produced by <em>Ruminiclostridium cellulolyticum</em>. Unlike classical non-ribosomal peptide synthetases (NRPSs), which use modular adenylation and condensation domains, CTA biosynthesis proceeds through non-canonical standalone enzymes. Central to this process is the papain-like ligase CtaG, which catalyzes amide bond formation between two distinct peptidyl carrier proteins (PCPs): CtaH, presenting para-hydroxybenzoic acid (PHBA), and CtaE, carrying a tri-β-alanine ((βAla)<sub>3</sub>) chain. Using biochemical assays, chemical probes, crystallography, and mutational analysis, we show that CtaG operates via a ping-pong mechanism involving an enzyme-bound intermediate. A single substrate tunnel mediates directional transfer, enabling distal chain elongation that mirrors solid-phase peptide synthesis. Structure-based genome mining revealed homologous enzymes in the biosynthetic pathways of petrobactin, butirosin, and methylolanthanin. Together, our findings uncover a previously overlooked class of thiotemplated ligases and provide a mechanistic blueprint for engineering ribosome-independent peptide assembly lines.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102740"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1016/j.chempr.2025.102737
Alexander A. Vinogradov , Hiroaki Suga
Recent advances in enzymology are enabled by the methods for high-throughput kinetic measurements. Common instrumentation-based techniques can examine thousands of enzymatic reactions in parallel, but scaling the throughput further can be challenging. Here, we establish DOMEK (mRNA-display-based one-shot measurement of enzymatic kinetics), an integrated experimental and computational pipeline for ultra-high-throughput kinetic measurements using mRNA display-derived next-generation sequencing data. The method can accurately determine kcat/KM specificity constants of post-translational modification enzyme substrates. We benchmark the platform by measuring kcat/KM values for ∼2.86 × 105 peptide substrates of a dehydroalanine reductase and leverage the resulting data to build interpretable models of the substrate fitness landscape. The resulting model accurately decomposes reaction activation energies of a peptide substrate into energetic contributions of individual amino acids to reveal microscopic and macroscopic aspects of the enzyme catalysis. Our results establish a generalizable, enzyme-agnostic framework for scaling kinetic measurements to millions of reactions.
{"title":"Measuring kcat/KM values for over 200,000 enzymatic substrates with mRNA display","authors":"Alexander A. Vinogradov , Hiroaki Suga","doi":"10.1016/j.chempr.2025.102737","DOIUrl":"10.1016/j.chempr.2025.102737","url":null,"abstract":"<div><div>Recent advances in enzymology are enabled by the methods for high-throughput kinetic measurements. Common instrumentation-based techniques can examine thousands of enzymatic reactions in parallel, but scaling the throughput further can be challenging. Here, we establish DOMEK (mRNA-display-based one-shot measurement of enzymatic kinetics), an integrated experimental and computational pipeline for ultra-high-throughput kinetic measurements using mRNA display-derived next-generation sequencing data. The method can accurately determine k<sub>cat</sub>/K<sub>M</sub> specificity constants of post-translational modification enzyme substrates. We benchmark the platform by measuring k<sub>cat</sub>/K<sub>M</sub> values for ∼2.86 × 10<sup>5</sup> peptide substrates of a dehydroalanine reductase and leverage the resulting data to build interpretable models of the substrate fitness landscape. The resulting model accurately decomposes reaction activation energies of a peptide substrate into energetic contributions of individual amino acids to reveal microscopic and macroscopic aspects of the enzyme catalysis. Our results establish a generalizable, enzyme-agnostic framework for scaling kinetic measurements to millions of reactions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":"Article 102737"},"PeriodicalIF":19.6,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144930565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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