Shilin Cui,Zhipeng Lu,Jaqueline C Lopez,Moritz Kränzlein,Christopher J Kim,Song Lin,Anne M LaPointe,Geoffrey W Coates
{"title":"Main-Chain Ketone Installation in Polyethylene Chains: A Metal-Free Strategy toward Photodegradable Plastics.","authors":"Shilin Cui,Zhipeng Lu,Jaqueline C Lopez,Moritz Kränzlein,Christopher J Kim,Song Lin,Anne M LaPointe,Geoffrey W Coates","doi":"10.1021/jacs.5c09943","DOIUrl":"https://doi.org/10.1021/jacs.5c09943","url":null,"abstract":"Polyethylene with in-chain isolated ketones is an attractive target for achieving photodegradability while maintaining polyolefin material properties. This work reports a method to functionalize post-consumer polyethylene through radical C-H activation to install TEMPO functionalities and subsequent oxidation to obtain in-chain isolated ketones without compromising the polymer molecular weights. This process does not require metals, catalysts, or expensive reagents and allows tunable ketone incorporation up to 3 mol %. The thermal and mechanical properties were investigated to demonstrate that the ketone-containing polyethylene could potentially work as a photodegradable alternative of existing polyethylene. Photodegradation of the ketone-containing polyethylene reveals a clear decrease in molecular weights and suggests random installation of functionalities. This approach enables the conversion of post-consumer polyethylene into ketone functionalized materials through simple chemical transformations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"99 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203733","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}
Lars van Turnhout, Alasdair Tew, Simon A. Dowland, Ebin Sebastian, Zhao Jiang, Rakesh Arul, Zhongzheng Yu, Akshay Rao
{"title":"Molecular Orientation Controls Triplet Exciton Dynamics in Organic Molecules Coupled to Lanthanide-Doped Nanoparticles","authors":"Lars van Turnhout, Alasdair Tew, Simon A. Dowland, Ebin Sebastian, Zhao Jiang, Rakesh Arul, Zhongzheng Yu, Akshay Rao","doi":"10.1021/jacs.5c13962","DOIUrl":"https://doi.org/10.1021/jacs.5c13962","url":null,"abstract":"Hybrid organic–inorganic materials, which combine the unique properties of organic semiconductors (OSCs) and inorganic nanoparticles, show great promise for optoelectronic applications. Understanding structure–function relationships in these nanohybrids is crucial for understanding the mechanisms governing their excited state dynamics, particularly those controlling triplet excitons, which are key to their performance. While previous studies focused primarily on triplet energy transfer (TET) across the interface, we study the full triplet exciton dynamics in OSCs coupled with various lanthanide-doped nanoparticles (LnNPs), with an emphasis on the impact of molecular orientation. We examine three anthracene carboxylic acid (ACA) isomers, differing in the position of the carboxylic acid group (1-, 2-, and 9-position) on the anthracene core. These isomers all exhibit similar triplet dynamics and low triplet yields (∼10%) when uncoordinated, but adopt distinct binding geometries on the LnNP surface, making them ideal for studying how coordination geometry influences triplet exciton dynamics. Using time-resolved optical spectroscopy, we observe significant variations in triplet generation rates, yields, lifetimes, and TET rates between the ACA isomers upon coordination onto the LnNPs. Triplet generation rates and yields are consistently highest in 1-ACA (up to 86%) and lowest in 2-ACA. TET rates are fastest for 9-ACA (up to 1.1 × 10<sup>8</sup> s<sup>–1</sup>) and slowest for 2-ACA. Notably, in the absence of TET, triplet exciton lifetimes exceed 0.1 ms for all LnNP@ACA nanohybrids. These results quantitatively describe how positional isomerism governs the triplet exciton dynamics in LnNP@OSC nanohybrids and highlight the pivotal role of molecular orientation in mediating interfacial photophysics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209905","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}
{"title":"Vitrification and Cold Crystallization of a One-Dimensional Perovskite-like Compound Enabled by Reorganizable Coordination Bonds and a Configurationally Restricted Cation.","authors":"Zi-Yi Du, Miao Xie, Wei-Yu Hu, Qing Wang, Wenbing Yuan, Chun Wu, Haiming Liu, Takayoshi Nakamura, Chun-Ting He, Rui-Kang Huang, Xiao-Ming Chen","doi":"10.1021/jacs.5c12026","DOIUrl":"https://doi.org/10.1021/jacs.5c12026","url":null,"abstract":"<p><p>Understanding glass formation and transformation remains a fundamental challenge in materials science. Here, we report the first example of vitrification and multifactor-triggered cold crystallization in a one-dimensional (1D) perovskite-like coordination polymer, (4-methylmorpholinium)[Cd(SCN)<sub>3</sub>]. By introducing cleavable and reorganizable Cd-S/N coordination bonds, we enable glass formation via melt-quenching, a process previously unachievable in 1D perovskite-like compounds. Comprehensive structural and spectroscopic analyses as well as molecular dynamics simulations, especially in-depth solid-state NMR analysis, reveal that reversible coordination bond reorganization and the restricted configurational freedom of the methylmorpholinium cation drive the glass-crystal transition. Combined dynamic and isothermal DSC studies demonstrate that cold crystallization proceeds via instantaneous nucleation and 1D crystal growth, driven by the confined rearrangement of the 4-methylmorpholinium cation. These findings establish a new vitrification mechanism based on dynamic coordination bonds, providing molecular-level insight into phase transitions in low-dimensional hybrid organic-inorganic perovskites or perovskite-like compounds and offering new strategies for glass-forming hybrid materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205031","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}
Marc Mora, Georgia Cohen, William Cranton, Olaia Anton, Amy E M Beedle, Guillaume Stirnemann, Sergi Garcia-Manyes
{"title":"Force-Triggered Thermodynamically Uphill Disulfide Reduction through Sulfur Oxidation State Control.","authors":"Marc Mora, Georgia Cohen, William Cranton, Olaia Anton, Amy E M Beedle, Guillaume Stirnemann, Sergi Garcia-Manyes","doi":"10.1021/jacs.5c13084","DOIUrl":"https://doi.org/10.1021/jacs.5c13084","url":null,"abstract":"<p><p>In addition to thermal energy, current, and light, mechanical forces activate chemical reactions, often steering reaction pathways that result in products different from those obtained under thermodynamic control. Single-molecule mechanochemistry experiments have probed how the forced activation of a single covalent bond results in accelerated scission of both homolytic and heterolytic bonds, and the ring-opening of strained mechanophores in long polymers. Due to its mechanistic simplicity, the concerted S<sub>N</sub>2 thiol-disulfide nucleophilic substitution has been successfully used as a model system to interrogate how the nucleophilicity of an attacking organic, low-oxidation state thiol determines the force dependency of the thiol/disulfide exchange rate. Inorganic sulfur-oxyanions are comparatively much less reactive. Whether mechanical forces can activate the rupture of a protein disulfide by sulfur-oxyanions featuring higher oxidation states remains unknown. Here we employ single-molecule force-clamp spectroscopy, complemented by density functional theory (DFT) calculations and colorimetric assay measurements, to show that the thermodynamically nonfavored reduction of a disulfide bond by inorganic oxyanions can be activated by mechanical force. Occurring within the core of a protein with a physiological mechanical role, the force-unlocked reactivity has a direct impact on protein elasticity.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205101","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}
Lulin Wang, Yike Huang, Yu Xin, Tianjiao Wang, Sen Luan, Minghua Dong, Bin Zhang, Xiaojun Shen, Qinglei Meng, Buxing Han, Huizhen Liu
{"title":"Zn Microenvironment Engineering for Aryl-C(sp<sup>2</sup>) Cleavage to Phenols and Tertiary Amines.","authors":"Lulin Wang, Yike Huang, Yu Xin, Tianjiao Wang, Sen Luan, Minghua Dong, Bin Zhang, Xiaojun Shen, Qinglei Meng, Buxing Han, Huizhen Liu","doi":"10.1021/jacs.5c10429","DOIUrl":"https://doi.org/10.1021/jacs.5c10429","url":null,"abstract":"<p><p>Cleaving inert aryl-C(sp<sup>2</sup>) bonds present a fundamental catalytic challenge due to their intrinsic robustness, yet it is essential for valorizing lignin into value-added chemicals. Current strategies predominantly convert aromatic rings to phenols at the expense of side-chain carbon utilization, compromising the atom economy. We report zinc coordination microenvironment engineering to achieve efficient aryl-C(sp<sup>2</sup>) cleavage in phenolic substrates with transformable side chains (e.g., ketones and alkenes), concurrently yielding phenols and tertiary amines. A nitrogen-coordinated zinc catalyst (ZnNC-900) delivered 90.0% phenol and 82.7% N,N-dimethylethylamine from 4-methoxyacetophenone. Significantly, this catalytic system demonstrates broad activity toward multiple native lignin sources, with bamboo lignin processing on a 5.0 g scale affording 1.04 g of alkyl-free phenolics (20.8 wt %) and 0.67 g of N,N-dimethylethylamine (13.4 wt %). Mechanistic studies via spectroscopy and DFT calculations demonstrate that the zinc microenvironment dictates the reaction pathway. Specifically, the ZnNC-900 catalyst, featuring zinc coordinated by three pyrrolic-N atoms and one pyridinic-N atom, reduces the energy barrier by 0.71 eV relative to ZnNC-600 (which exclusively has pyridinic-N coordination). This work provides a catalytic strategy to overcome the limitations of low atom economy, harsh conditions, and narrow substrate scope in lignin valorization.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205155","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}
{"title":"Deactivation of Interfacial Recombination Center for Thermally Stable Perovskite Solar Cells.","authors":"Xin Liang,Sanwan Liu,Tiankai Zhang,Matthias J Grotevent,Guiming Fu,Jae-Min Jang,Chae-Yeon Lee,Seong-Ho Cho,Yong Ming,Chandan Chandru Gudal,Sang Yoon Kim,Chan-Hwa Chung,Tae-Il Kim,Jun-Yeob Lee,Feng Gao,Moungi G Bawendi,Nam-Gyu Park","doi":"10.1021/jacs.5c11581","DOIUrl":"https://doi.org/10.1021/jacs.5c11581","url":null,"abstract":"We report here on deactivation of the recombination center at the perovskite/Spiro-MeOTAD interface for thermally stable perovskite solar cells (PSCs). Investigation into the chemical reactivity of oxidized Spiro-MeOTAD (Spiro-MeOTAD•+) reveals that the Spiro-MeOTAD•+-induced interfacial recombination center is a key factor contributing to lowering open-circuit voltage (VOC) and thereby power conversion efficiency (PCE) of PSCs under thermal stress. To deactivate the recombination center via suppressing chemical reactivity, a functional molecule of 3-aminopropyltriethoxysilane (APTES) is inserted between the perovskite film and the Spiro-MeOTAD-based hole transporting layer (HTL). The alkoxy head in APTES is found to coordinate with the perovskite, and the amino tail reacts with the triphenylamine moiety of Spiro-MeOTAD•+, which effectively captures the excess oxidized Spiro-MeOTAD. As a result, the nonradiative recombination of perovskite is deactivated and the oxidation level of HTL is modulated, leading to a significant increase in VOC from 1.032 to 1.19 V after introducing APTES, along with a certified PCE of 25.6%. Thermal stability tests at 85 °C for 1000 h following the ISOS-D2I protocol show that 82% of the initial PCE is retained by the deactivation approach.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"31 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194742","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}
Asmaa M A S Farrag, Koshiro Ota, Hideaki Yoshimura, Misao Takemoto, Takuma Mitarai, Takuya Kamikawa, Masahiro Abo, Vaibhav Pal Singh, Changyi Cui, Lu Zhou, Fumiyoshi Ishidate, Takahiro Fujiwara, Shin-Ichi Sato, Yuichiro Hori, Takeaki Ozawa, Kazuya Kikuchi, Motonari Uesugi
{"title":"Live-Cell Monitoring and Omics Analysis of Liquid-Solid Transitions of Biomolecular Condensates.","authors":"Asmaa M A S Farrag, Koshiro Ota, Hideaki Yoshimura, Misao Takemoto, Takuma Mitarai, Takuya Kamikawa, Masahiro Abo, Vaibhav Pal Singh, Changyi Cui, Lu Zhou, Fumiyoshi Ishidate, Takahiro Fujiwara, Shin-Ichi Sato, Yuichiro Hori, Takeaki Ozawa, Kazuya Kikuchi, Motonari Uesugi","doi":"10.1021/jacs.5c07340","DOIUrl":"https://doi.org/10.1021/jacs.5c07340","url":null,"abstract":"<p><p>Biomolecular condensates, or so-called membraneless organelles, transition from liquid into more solid-like states over time, contributing to the development of pathological conditions. The present study proposes a simple method using photoactive yellow protein (PYP) and its specific fluorescent covalent ligands to distinguish between the liquid and solid states of protein condensates in live cells. The method, compatible with fluorescence-activated cell sorting (FACS), correlates the stiffness of specific protein condensates with their accessibility to PYP ligands, enabling quantitative multicolor monitoring of condensate solidification. We applied this technique to 12 phase-separating proteins and their mutants, finding that TDP-43, particularly its A315T mutant linked to familial amyotrophic lateral sclerosis, most readily forms solid aggregates. Furthermore, this FACS-compatible strategy enabled the isolation of distinct cell populations based on condensate states, allowing for subsequent proteomic and transcriptomic analyses. Our findings demonstrate that condensate solidification is accompanied by the upregulated expression of extracellular matrix proteins, suggesting a previously unrecognized link between solid aggregate formation and extracellular matrix hardening.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205058","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}
{"title":"Photoredox Fe-Catalyzed Aminoalkylation toward Sterically Hindered Chiral β-Amino Acids.","authors":"Tianze Zhang,Pengwei Gu,Hanmin Huang","doi":"10.1021/jacs.5c12328","DOIUrl":"https://doi.org/10.1021/jacs.5c12328","url":null,"abstract":"β-Amino acids represent a vital class of structural motifs in natural products and pharmaceuticals, motivating sustained research efforts in organic synthesis and peptidomimetics. Despite the development of numerous methods for the preparation of β-amino acids, sterically hindered variants continue to pose challenges for their synthesis. In this context, an alternative approach via carboxyalkylation of prevalent tertiary amine scaffolds offers a promising yet underexplored strategy for the streamlined synthesis of β-amino acid derivatives. Herein, we report the development of an iron-porphyrin/photoredox dual catalytic system for the C(sp3)-C(sp3) cross-coupling of tertiary amines and α-halo acyl compounds, enabling the efficient assembly of sterically hindered β-amino acid frameworks. Mechanistic studies disclosed that the iron catalyst participates in the single-electron oxidation with α-carbonyl radical to generate a ferric enolate intermediate, thereby facilitating Mannich-type addition to afford the desired β-amino acid derivatives. Furthermore, the utilization of chiral auxiliaries enabled efficient stereocontrol over the aminoalkylation process, providing a platform for synthesizing a broad array of chiral β-amino acid derivatives.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"71 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194743","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}
{"title":"Biosynthesis of the 5-Isoxazolidinone-Containing Hexacyclic Structure of Parnafungin.","authors":"Zuodong Sun, Karl M Yost, Gerald F Bills, Yi Tang","doi":"10.1021/jacs.5c14217","DOIUrl":"https://doi.org/10.1021/jacs.5c14217","url":null,"abstract":"<p><p>Parnafungins A-D (<b>1</b>-<b>4</b>) are fungal natural products that inhibit eukaryotic poly(A)-polymerase and were first discovered by Merck & Co., Inc., through a <i>Candida albicans</i> Fitness Test (CaFT) screening program. The biological activity of parnafungins is a result of the unique fused hexacyclic structure highlighted by a 5-isoxazolidinone (5ILD) <i>N</i>-heterocycle. In this work, we characterize the complete biosynthetic pathway of parnafungins through heterologous reconstitution and enzymatic assays. Nearly half of the 26-gene biosynthetic gene cluster of parnafungin is responsible for the production of a known polyketide natural product, blennolide C. Starting from the blennolide C fragment, a three-enzyme cascade involving CoA-ligase ParJ, P450 ParO, and DUF829 ParD catalyzes the formal biaryl cross-coupling between blennolide C and anthranilate. Subsequent oxidative cyclization generates a phenanthridine product that is then reduced by atypical short-chain reductase ParT. <i>N</i>-Hydroxylation by flavin-dependent monooxygenase ParB and subsequent lactonization catalyzed by a homologue of dienenolactone hydrolase ParF form the 5ILD ring and complete the biosynthesis of <b>1</b> and <b>2</b>. Methylation of <b>1</b> forms parnafungin C (<b>3</b>), and lastly epoxidation forms parnafungin D (<b>4</b>). Together, our work revealed the chemical logic and enzymology in extending the biosynthetic pathway of a well-characterized natural product, blennolide C, to introduce considerable additional structural diversity that affords parnafungins with unique biological activity.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205082","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}
Alice E Green, Keyu Chen, Surjendu Bhattacharyya, Felix Allum, Sergey Usenko, Michael N R Ashfold, Thomas M Baumann, Kurtis D Borne, Mark Brouard, Michael Burt, Basile F E Curchod, Benjamin Erk, Ruaridh J G Forbes, Lea M Ibele, Rebecca A Ingle, Huynh Van Sa Lam, Xiang Li, Kang Lin, Tommaso Mazza, Joseph W McManus, Michael Meyer, Terence Mullins, Joao Pedro Figueira Nunes, Daniel E Rivas, Aljoscha Roerig, Arnaud Rouzée, Philipp Schmidt, John Searles, Björn Senfftleben, Henrik Stapelfeldt, Rico Mayro P Tanyag, Florian Trinter, Anbu Selvam Venkatachalam, Enliang Wang, Emily M Warne, Peter M Weber, Thomas J A Wolf, Till Jahnke, Artem Rudenko, Rebecca Boll, Daniel Rolles
{"title":"Visualizing the Three-Dimensional Arrangement of Hydrogen Atoms in Organic Molecules by Coulomb Explosion Imaging.","authors":"Alice E Green, Keyu Chen, Surjendu Bhattacharyya, Felix Allum, Sergey Usenko, Michael N R Ashfold, Thomas M Baumann, Kurtis D Borne, Mark Brouard, Michael Burt, Basile F E Curchod, Benjamin Erk, Ruaridh J G Forbes, Lea M Ibele, Rebecca A Ingle, Huynh Van Sa Lam, Xiang Li, Kang Lin, Tommaso Mazza, Joseph W McManus, Michael Meyer, Terence Mullins, Joao Pedro Figueira Nunes, Daniel E Rivas, Aljoscha Roerig, Arnaud Rouzée, Philipp Schmidt, John Searles, Björn Senfftleben, Henrik Stapelfeldt, Rico Mayro P Tanyag, Florian Trinter, Anbu Selvam Venkatachalam, Enliang Wang, Emily M Warne, Peter M Weber, Thomas J A Wolf, Till Jahnke, Artem Rudenko, Rebecca Boll, Daniel Rolles","doi":"10.1021/jacs.5c08730","DOIUrl":"https://doi.org/10.1021/jacs.5c08730","url":null,"abstract":"<p><p>Structure-sensitive methods based on femtosecond light or electron pulses are now making it possible to measure how molecular structures change during light-induced processes. Despite significant progress, high-fidelity imaging of nuclear positions remains a challenge even for relatively small molecular systems and, notably, regarding the positions of hydrogen atoms. As demonstrated in recent work, X-ray-induced Coulomb explosion imaging (CEI) may overcome this obstacle, as its sensitivity does not depend on the mass of the imaged atoms. The photoinduced ring opening of the heterocyclic molecule 2(5<i>H</i>)-thiophenone has attracted recent interest. Here, we show that CEI offers a powerful route to imaging the peripheral H atoms in this molecule and thus, more generally, to tracking detailed nuclear motions (e.g., isomerizations) in organic molecules on ultrafast time scales. Specifically, we record momentum-space Coulomb explosion images that report on the three-dimensional positioning of all nuclei within the molecule, for instance, distinguishing H atoms in C-H bonds that lie within or are directed out of the plane defined by the heavy atoms. The prospect of imaging peripheral H atoms to probe photochemical dynamics is explored by coupling ab initio molecular dynamics with classical Coulomb explosion simulations, thereby differentiating potential photoproduct isomers, including those whose structures primarily differ in the position of the hydrogens.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145205028","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}