Oleksii Zdorevskyi, Johannes Laukkanen, Vivek Sharma
Redox chemistry of quinones is an essential component of life on earth. In the mitochondrial electron transport chain, ubiquinone molecule is reduced to ubiquinol by respiratory complex I to drive the synthesis of ATP. By performing both classical and hybrid QM/MM simulations on high-resolution cryo-EM structures, including quantitative free energy calculations, we show that semiquinone species in complex I is anionic in nature and can be trapped in the active site chamber for its subsequent reduction. Two-electron reduction of ubiquinone yields a metastable ubiquinol anion, which is electrostatically pushed by 15-20 Å towards the exit of the ubiquinone binding chamber to drive the proton pump of complex I. As part of the two-electron reduction of ubiquinone, protonic rearrangements take place in the active site in which a highly conserved histidine converts from its one tautomeric state to another. The combined findings challenge the currently held views on quinone redox chemistry of respiratory complex I and provide a detailed and testable mechanistic picture of proton-coupled electron transfer reaction at its active site in wild-type and mutant conditions.
{"title":"Catalytic relevance of quinol anion in biological energy conversion by respiratory complex I","authors":"Oleksii Zdorevskyi, Johannes Laukkanen, Vivek Sharma","doi":"10.1039/d5sc07500a","DOIUrl":"https://doi.org/10.1039/d5sc07500a","url":null,"abstract":"Redox chemistry of quinones is an essential component of life on earth. In the mitochondrial electron transport chain, ubiquinone molecule is reduced to ubiquinol by respiratory complex I to drive the synthesis of ATP. By performing both classical and hybrid QM/MM simulations on high-resolution cryo-EM structures, including quantitative free energy calculations, we show that semiquinone species in complex I is anionic in nature and can be trapped in the active site chamber for its subsequent reduction. Two-electron reduction of ubiquinone yields a metastable ubiquinol anion, which is electrostatically pushed by 15-20 Å towards the exit of the ubiquinone binding chamber to drive the proton pump of complex I. As part of the two-electron reduction of ubiquinone, protonic rearrangements take place in the active site in which a highly conserved histidine converts from its one tautomeric state to another. The combined findings challenge the currently held views on quinone redox chemistry of respiratory complex I and provide a detailed and testable mechanistic picture of proton-coupled electron transfer reaction at its active site in wild-type and mutant conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089716","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}
Anne M. Fabricant, Román Picazo-Frutos, Florin Teleanu, Gregory Jon Rees, Raphael Kircher, Mengjiang Lin, William Evans, Paul-Martin Luc, Robert House, Peter G. Bruce, Peter Krüger, John Blanchard, James Eills, Kirill Fedorovich Sheberstov, Rainer Körber, Dmitry Budker, Danila A. Barskiy, Alexej Jerschow
Rechargeable batteries represent a key transformative technology for electric vehicles, portable electronics, and renewable energy. Yet, there are few nondestructive diagnostic techniques compatible with realistic commercial cell enclosures. Many battery failures result from the loss or chemical degradation of electrolyte. In this work, we present measurements through battery enclosures that allow quantification of electrolyte amount and composition. The study employs instrumentation and techniques developed in the context of zero-to-ultralow-field nuclear magnetic resonance (ZULF NMR), with quantum magnetometers as the detection elements (atomic optically pumped magnetometers, OPMs, and superconducting quantum interference devices, SQUIDs, used in this work). In contrast to conventional NMR methodology, which suffers from skin-depth limitations, the reduced resonance frequencies in ZULF NMR make battery housing and electrodes transparent to the electromagnetic fields involved. As demonstrated here through simulation and experiment, both the solvent and lithium-salt components of the electrolyte (lithium hexafluorophosphate, LiPF6) signature can be quantified using our techniques. Further, we show that ZULF-NMR apparatus is compatible with measurement of pouch-cell batteries.
{"title":"Enabling nondestructive observation of electrolyte composition in batteries with ultralow-field nuclear magnetic resonance","authors":"Anne M. Fabricant, Román Picazo-Frutos, Florin Teleanu, Gregory Jon Rees, Raphael Kircher, Mengjiang Lin, William Evans, Paul-Martin Luc, Robert House, Peter G. Bruce, Peter Krüger, John Blanchard, James Eills, Kirill Fedorovich Sheberstov, Rainer Körber, Dmitry Budker, Danila A. Barskiy, Alexej Jerschow","doi":"10.1039/d5sc04419g","DOIUrl":"https://doi.org/10.1039/d5sc04419g","url":null,"abstract":"Rechargeable batteries represent a key transformative technology for electric vehicles, portable electronics, and renewable energy. Yet, there are few nondestructive diagnostic techniques compatible with realistic commercial cell enclosures. Many battery failures result from the loss or chemical degradation of electrolyte. In this work, we present measurements through battery enclosures that allow quantification of electrolyte amount and composition. The study employs instrumentation and techniques developed in the context of zero-to-ultralow-field nuclear magnetic resonance (ZULF NMR), with quantum magnetometers as the detection elements (atomic optically pumped magnetometers, OPMs, and superconducting quantum interference devices, SQUIDs, used in this work). In contrast to conventional NMR methodology, which suffers from skin-depth limitations, the reduced resonance frequencies in ZULF NMR make battery housing and electrodes transparent to the electromagnetic fields involved. As demonstrated here through simulation and experiment, both the solvent and lithium-salt components of the electrolyte (lithium hexafluorophosphate, LiPF6) signature can be quantified using our techniques. Further, we show that ZULF-NMR apparatus is compatible with measurement of pouch-cell batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089717","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}
Shira Haber, Nicodemo R. Ciccia, Zhengxing Peng, Feipeng Yang, Julia Im, Mutian Hua, Sophia N. Fricke, Raynald Giovine, Brett A. Helms, Cheng Wang, John F. Hartwig, Jeffrey A. Reimer
Amidation of polyethylenes creates a range of amide-containing materials with enhanced properties, but the effect of these functional groups on the microstructure of these new materials is not known. Here we employ solid-state nuclear magnetic resonance (NMR) techniques to analyze the microstructure of amide-modified polyethylenes. While a decrease in crystallinity was observed with increasing amounts of functionalization, we found by measuring the chain mobility of the crystalline, amorphous, and interphasial regions of the polyethylenes with NMR relaxation techniques that the grafted amidyl groups partition into the rigid amorphous fraction (RAF) between the crystalline and amorphous regions. The chemical specificity of these NMR experiments creates precise assessments of the location of functional groups within the materials. Together, these insights into the microstructure and morphology of amide-containing polyethylenes lay a foundation for a deeper understanding of the structure and properties of functional polyolefins.
{"title":"Microstructure of amide-functionalized polyethylenes determined by NMR relaxometry","authors":"Shira Haber, Nicodemo R. Ciccia, Zhengxing Peng, Feipeng Yang, Julia Im, Mutian Hua, Sophia N. Fricke, Raynald Giovine, Brett A. Helms, Cheng Wang, John F. Hartwig, Jeffrey A. Reimer","doi":"10.1039/d5sc08878j","DOIUrl":"https://doi.org/10.1039/d5sc08878j","url":null,"abstract":"Amidation of polyethylenes creates a range of amide-containing materials with enhanced properties, but the effect of these functional groups on the microstructure of these new materials is not known. Here we employ solid-state nuclear magnetic resonance (NMR) techniques to analyze the microstructure of amide-modified polyethylenes. While a decrease in crystallinity was observed with increasing amounts of functionalization, we found by measuring the chain mobility of the crystalline, amorphous, and interphasial regions of the polyethylenes with NMR relaxation techniques that the grafted amidyl groups partition into the rigid amorphous fraction (RAF) between the crystalline and amorphous regions. The chemical specificity of these NMR experiments creates precise assessments of the location of functional groups within the materials. Together, these insights into the microstructure and morphology of amide-containing polyethylenes lay a foundation for a deeper understanding of the structure and properties of functional polyolefins.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070662","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}
Denise Poire, Cornelius Constantin Maria Bernitzky, Mathesh Vaithiyanathan, Berta M. Martins, Christian Lorent, Tamanna Manjur Ahamad, Vladimir Pelmenschikov, Igor V. Sazanovich, Gregory M Greetham, Ingo Zebger, Holger Dobbek, Maria Andrea Mroginski, Marius Horch
Acetyl-CoA synthase (ACS) catalyzes the condensation of acetyl-CoA from carbon monoxide (CO), a methyl group, and coenzyme A, enabling the fixation of CO into biomolecules. Recent low-temperature ENDOR studies proposed that the enzyme can bind two CO ligands in its reduced Ared-CO state, reshaping the view of CO coordination and inhibition of ACS. However, whether this two-CO model reflects a physiologically relevant state has remained an open question. To address this issue, we examined ACS under near-native, ambient conditions using ultrafast and two-dimensional infrared spectroscopy, complemented by anharmonic frequency calculations. These methods provide a wealth of structural and dynamical information beyond insights from conventional IR absorption spectroscopy, allowing a direct view of CO coordination in the Ared-CO state. Our results demonstrate that ACS binds a single CO ligand under ambient conditions. This finding clarifies the stoichiometry of CO coordination in ACS and underscores the broader potential of advanced IR spectroscopy, combined with computation, to unravel ligand binding in complex bioorganometallic systems.
{"title":"From Two to One: Resolving CO Binding in Acetyl-CoA Synthase","authors":"Denise Poire, Cornelius Constantin Maria Bernitzky, Mathesh Vaithiyanathan, Berta M. Martins, Christian Lorent, Tamanna Manjur Ahamad, Vladimir Pelmenschikov, Igor V. Sazanovich, Gregory M Greetham, Ingo Zebger, Holger Dobbek, Maria Andrea Mroginski, Marius Horch","doi":"10.1039/d5sc08875e","DOIUrl":"https://doi.org/10.1039/d5sc08875e","url":null,"abstract":"Acetyl-CoA synthase (ACS) catalyzes the condensation of acetyl-CoA from carbon monoxide (CO), a methyl group, and coenzyme A, enabling the fixation of CO into biomolecules. Recent low-temperature ENDOR studies proposed that the enzyme can bind two CO ligands in its reduced A<small><sub>red</sub></small>-CO state, reshaping the view of CO coordination and inhibition of ACS. However, whether this two-CO model reflects a physiologically relevant state has remained an open question. To address this issue, we examined ACS under near-native, ambient conditions using ultrafast and two-dimensional infrared spectroscopy, complemented by anharmonic frequency calculations. These methods provide a wealth of structural and dynamical information beyond insights from conventional IR absorption spectroscopy, allowing a direct view of CO coordination in the A<small><sub>red</sub></small>-CO state. Our results demonstrate that ACS binds a single CO ligand under ambient conditions. This finding clarifies the stoichiometry of CO coordination in ACS and underscores the broader potential of advanced IR spectroscopy, combined with computation, to unravel ligand binding in complex bioorganometallic systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089718","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}
Alkaline hydrogen peroxide (H2O2) is highly desirable for critical applications due to its superior stability and reactivity, but is incompatible with conventional near-neutral production methods. While covalent organic frameworks (COFs) show promise for photocatalytic H2O2 generation, their alkaline performance is severely limited by poor charge dynamics and inadequate hydrophilicity, hindering the essential 2e− oxygen reduction reaction (ORR: O2 + 2e− + H2O → HO₂− + OH−) and 4e− water oxidation reaction (WOR: 4OH− → O2 + 2H2O + 4e−). This work pioneers a dual-engineering strategy (molecular orbital and interfacial hydrogen-bonding network engineering) within β-ketoenamine-linked COFs to overcome these challenges simultaneously. By contrasting phenazine-based (TP-PZ-COF) and anthracene-based (TP-AN-COF) COFs, we demonstrate that strategic integration of sp2-N heteroatoms modulates molecular orbitals and enhances n→π* transitions, optimizing charge separation and transport for efficient 2e− ORR and 4e− WOR. Concurrently, the planar phenazine units form robust hydrogen-bonding networks that dramatically boost hydroxide ion (OH−) affinity and interfacial enrichment, thereby accelerating 4e− WOR kinetics. This integrated approach enabled TP-PZ-COF to achieve an exceptional alkaline H2O2 production rate of 4961 μmol g−1 h−1 under 0.01 M NaOH, representing an 8.1-fold increase over TP-AN-COF (606 μmolg−1 h−1). The generated H₂O₂ efficiently degraded industrial dye pollutants. Direct experimental and theoretical validations confirm the cooperative mechanism between charge dynamics optimization and OH− affinity enhancement, providing a new blueprint for designing on-demand alkaline H2O2 photocatalysts.
{"title":"Alkaline-adaptive covalent organic framework photocatalysts: synergistic molecular orbital and hydrogen-bond network engineering for H2O2 production","authors":"Zhiwu Yu, Jiayi Zhang, Xiaolong Zhang, Xuwen Sun, Guihong Wu, Zhiyun Zhang, Fengtao Yu, Jianli Hua","doi":"10.1039/d5sc08298f","DOIUrl":"https://doi.org/10.1039/d5sc08298f","url":null,"abstract":"Alkaline hydrogen peroxide (H2O2) is highly desirable for critical applications due to its superior stability and reactivity, but is incompatible with conventional near-neutral production methods. While covalent organic frameworks (COFs) show promise for photocatalytic H2O2 generation, their alkaline performance is severely limited by poor charge dynamics and inadequate hydrophilicity, hindering the essential 2e− oxygen reduction reaction (ORR: O2 + 2e− + H2O → HO₂− + OH−) and 4e− water oxidation reaction (WOR: 4OH− → O2 + 2H2O + 4e−). This work pioneers a dual-engineering strategy (molecular orbital and interfacial hydrogen-bonding network engineering) within β-ketoenamine-linked COFs to overcome these challenges simultaneously. By contrasting phenazine-based (TP-PZ-COF) and anthracene-based (TP-AN-COF) COFs, we demonstrate that strategic integration of sp2-N heteroatoms modulates molecular orbitals and enhances n→π* transitions, optimizing charge separation and transport for efficient 2e− ORR and 4e− WOR. Concurrently, the planar phenazine units form robust hydrogen-bonding networks that dramatically boost hydroxide ion (OH−) affinity and interfacial enrichment, thereby accelerating 4e− WOR kinetics. This integrated approach enabled TP-PZ-COF to achieve an exceptional alkaline H2O2 production rate of 4961 μmol g−1 h−1 under 0.01 M NaOH, representing an 8.1-fold increase over TP-AN-COF (606 μmolg−1 h−1). The generated H₂O₂ efficiently degraded industrial dye pollutants. Direct experimental and theoretical validations confirm the cooperative mechanism between charge dynamics optimization and OH− affinity enhancement, providing a new blueprint for designing on-demand alkaline H2O2 photocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"103 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070664","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}
Kai Wang, Xiaoying Mao, Wuyan Xie, Xiaoyan Liu, Qin Zhou, Dan Wu, Qing Zhu, Bin Liu
The clinical application of conventional photodynamic therapy (PDT) is often limited by the nonspecific phototoxicity of "always-on" photosensitizers. Activatable photosensitizers (aPS) have emerged as a promising solution to this challenge. These smart agents are designed to remain inactive under normal physiological conditions and become activated only by disease-specific stimuli, thereby significantly improving treatment specificity and safety. This review summarizes the key design strategies for developing effective aPS. We focus on the general principles of utilizing various quenching mechanisms, such as energy or electron transfer processes and aggregation behavior control, to suppress photosensitizer activity until a specific trigger is encountered. Representative examples are discussed to illustrate how these designs respond to biomarkers like enzymes, glutathione, or acidic pH to activate therapeutic functions. By minimizing off-target effects and enhancing spatial control, these mechanism-guided approaches pave the way for more precise and clinically viable PDT protocols, aligning with the core objectives of precision medicine.
{"title":"Mechanism-Guided Design of Specific-Activated Photosensitizers for Precision Photodynamic Therapy","authors":"Kai Wang, Xiaoying Mao, Wuyan Xie, Xiaoyan Liu, Qin Zhou, Dan Wu, Qing Zhu, Bin Liu","doi":"10.1039/d5sc09499b","DOIUrl":"https://doi.org/10.1039/d5sc09499b","url":null,"abstract":"The clinical application of conventional photodynamic therapy (PDT) is often limited by the nonspecific phototoxicity of \"always-on\" photosensitizers. Activatable photosensitizers (aPS) have emerged as a promising solution to this challenge. These smart agents are designed to remain inactive under normal physiological conditions and become activated only by disease-specific stimuli, thereby significantly improving treatment specificity and safety. This review summarizes the key design strategies for developing effective aPS. We focus on the general principles of utilizing various quenching mechanisms, such as energy or electron transfer processes and aggregation behavior control, to suppress photosensitizer activity until a specific trigger is encountered. Representative examples are discussed to illustrate how these designs respond to biomarkers like enzymes, glutathione, or acidic pH to activate therapeutic functions. By minimizing off-target effects and enhancing spatial control, these mechanism-guided approaches pave the way for more precise and clinically viable PDT protocols, aligning with the core objectives of precision medicine.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089719","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}
Annulative π-extension (APEX) reaction is a useful aromatic ring-fusion method for synthesis of large polycyclic aromatic hydrocarbons (PAHs) from unfunctionalized small PAHs. While APEX reactions in K-, M-, bay-regions of PAHs have been developed, L-region selective APEX is yet to be achieved. Herein, we report a stepwise L-region selective APEX of unfunctionalized PAHs by dearomative activation with N-methyltriazoline dione, followed by Pd-catalyzed annulation with aryl Grignard reagents. Various difficult-to-synthesize core-expanded PAHs can be synthesized by L-APEX from unfunctionalized naphthalene, phenanthrene, chrysene, and [4]helicene.
{"title":"L-Region-selective annulative π-extension through dearomative activation of polycyclic aromatic hydrocarbons","authors":"Kanami Nakata, Wataru Matsuoka, Hideto Ito, Kenichiro Itami","doi":"10.1039/d5sc09309k","DOIUrl":"https://doi.org/10.1039/d5sc09309k","url":null,"abstract":"Annulative π-extension (APEX) reaction is a useful aromatic ring-fusion method for synthesis of large polycyclic aromatic hydrocarbons (PAHs) from unfunctionalized small PAHs. While APEX reactions in <em>K</em>-, <em>M</em>-, <em>bay</em>-regions of PAHs have been developed, <em>L</em>-region selective APEX is yet to be achieved. Herein, we report a stepwise L-region selective APEX of unfunctionalized PAHs by dearomative activation with <em>N</em>-methyltriazoline dione, followed by Pd-catalyzed annulation with aryl Grignard reagents. Various difficult-to-synthesize core-expanded PAHs can be synthesized by <em>L</em>-APEX from unfunctionalized naphthalene, phenanthrene, chrysene, and [4]helicene.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070663","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}
Ryoga Nambu, jun kikuchi, Arimasa Matsumoto, Naohiko Yoshikai
Atropisomerism around a carbon–iodine(III) bond represents a rare form of chirality centered on a long, polarizable hypervalent linkage. Embedding this C–I(III) bond into an inherently asymmetric, diadamantylated triazole scaffold creates a vivid platform that reveals how such a bond responds to steric and electronic perturbations. Neutral triazole- and cationic triazolium-benziodoxoles display similarly high atropostability (racemization half-lives of several years at 25 °C), arising from opposing effects introduced by N-methylation: electronic weakening of the C–I bond versus steric buttressing that restricts rotation. Under acidic conditions, however, their behaviors diverge; the triazole derivative undergoes accelerated rotation, whereas the triazolium analogue retains substantial configurational stability. The CF3 groups of the benziodoxole ring serve as sensitive 19F NMR reporters for two complementary modes of chiral recognition. The neutral triazole engages BINOL through directional hydrogen bonding, whereas the triazolium derivative binds phosphate anions via halogen bonding and electrostatic interaction. Together, these results establish the hypervalent C–I(III) bond as a stereoelectronically tunable rotational element—an axle that enables molecular rotors combining well-defined rotational dynamics with switchable recognition behavior.
{"title":"Carbon–iodine atropisomerism on triazole and triazolium frameworks: A breathing axle with divergent adaptivity","authors":"Ryoga Nambu, jun kikuchi, Arimasa Matsumoto, Naohiko Yoshikai","doi":"10.1039/d5sc09936f","DOIUrl":"https://doi.org/10.1039/d5sc09936f","url":null,"abstract":"Atropisomerism around a carbon–iodine(III) bond represents a rare form of chirality centered on a long, polarizable hypervalent linkage. Embedding this C–I(III) bond into an inherently asymmetric, diadamantylated triazole scaffold creates a vivid platform that reveals how such a bond responds to steric and electronic perturbations. Neutral triazole- and cationic triazolium-benziodoxoles display similarly high atropostability (racemization half-lives of several years at 25 °C), arising from opposing effects introduced by N-methylation: electronic weakening of the C–I bond versus steric buttressing that restricts rotation. Under acidic conditions, however, their behaviors diverge; the triazole derivative undergoes accelerated rotation, whereas the triazolium analogue retains substantial configurational stability. The CF3 groups of the benziodoxole ring serve as sensitive 19F NMR reporters for two complementary modes of chiral recognition. The neutral triazole engages BINOL through directional hydrogen bonding, whereas the triazolium derivative binds phosphate anions via halogen bonding and electrostatic interaction. Together, these results establish the hypervalent C–I(III) bond as a stereoelectronically tunable rotational element—an axle that enables molecular rotors combining well-defined rotational dynamics with switchable recognition behavior.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070679","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}
Vibrational spectroscopy is a technique of wide use in fields like analytical chemistry, biomedical applications, and pharmacology. The technique is cost-effective and very popular. However, a reliable assignment of vibrational spectra may be hard to achieve for large molecular systems or when nuclear quantum effects (NQEs) are sizeable. These aspects hamper the effectiveness of vibrational spectroscopy as an analytical and characterization tool. Computational approaches may help overcome the shortcomings of a purely experimental investigation. For instance, classical molecular dynamics is computationally cheap and easy to perform also by a non-expert user, but it cannot account for NQEs. The latter can be included in an affordable way if approximate quantum mechanical methods based on classical trajectories are employed. Here we review the main theoretical approaches based on classical trajectories and able to deal with NQEs in vibrational spectroscopy. We start by reporting on the possibility to employ methods derived from the path integral representation of quantum mechanics, i.e. semiclassical (SC) dynamics, centroid molecular dynamics (CMD), ring polymer molecular dynamics (RPMD), and their variants. Then, other techniques like the quantum thermal bath (QTB) and the quasi-classical trajectory (QCT) method are highlighted. All but SC methods are based on a fully classical real-time propagation. This review aims at increasing the awareness of useful and ready-to-use classical-trajectory-based computational techniques among the broader community of experimental researchers, developers, and applied scientists, who employ vibrational spectroscopy in their everyday’s activity.
{"title":"Quantum vibrational spectroscopy with classical trajectories","authors":"Riccardo Conte, Chiara Aieta, Michele Ceotto","doi":"10.1039/d5sc09965j","DOIUrl":"https://doi.org/10.1039/d5sc09965j","url":null,"abstract":"Vibrational spectroscopy is a technique of wide use in fields like analytical chemistry, biomedical applications, and pharmacology. The technique is cost-effective and very popular. However, a reliable assignment of vibrational spectra may be hard to achieve for large molecular systems or when nuclear quantum effects (NQEs) are sizeable. These aspects hamper the effectiveness of vibrational spectroscopy as an analytical and characterization tool. Computational approaches may help overcome the shortcomings of a purely experimental investigation. For instance, classical molecular dynamics is computationally cheap and easy to perform also by a non-expert user, but it cannot account for NQEs. The latter can be included in an affordable way if approximate quantum mechanical methods based on classical trajectories are employed. Here we review the main theoretical approaches based on classical trajectories and able to deal with NQEs in vibrational spectroscopy. We start by reporting on the possibility to employ methods derived from the path integral representation of quantum mechanics, i.e. semiclassical (SC) dynamics, centroid molecular dynamics (CMD), ring polymer molecular dynamics (RPMD), and their variants. Then, other techniques like the quantum thermal bath (QTB) and the quasi-classical trajectory (QCT) method are highlighted. All but SC methods are based on a fully classical real-time propagation. This review aims at increasing the awareness of useful and ready-to-use classical-trajectory-based computational techniques among the broader community of experimental researchers, developers, and applied scientists, who employ vibrational spectroscopy in their everyday’s activity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056971","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}
Solid-state sodium batteries (SSSBs) have attracted increasing attention as a promising alternative for large-scale energy storage owing to their intrinsic safety, material abundance, and potential cost advantages. Significant progress has been made in developing diverse solid-state electrolytes, including polymers, inorganic ceramics, and hybrid systems, many of which exhibit impressive bulk ionic conductivity. However, the translation of these materials-level properties into durable, high-performance solid-state sodium batteries remains limited, indicating that bulk ion transport alone does not govern practical cell behavior. In this Review, we adopt an interface-centered and issue-driven perspective to analyze the key challenges in SSSBs. Rather than providing a materials-category-based summary, we focus on dominant interfacial failure mechanisms and their sodium origins. Chemical and electrochemical instability, electrical blocking associated with space-charge effects and grain boundaries, mechanical degradation arising from elastic and thermal mismatch, and defect-assisted sodium dendrite penetration are discussed within a unified mechanistic framework. These interfacial processes are shown to be intrinsically coupled, collectively controlling effective ion transport, critical current density, and long-term cell stability. Building on this understanding, we critically assess why high bulk ionic conductivity has not translated into robust full-cell performance and emphasize the limitations of conductivity as a single performance metric. We further discuss general design principles for interface engineering across different electrolyte families and revisit lessons from technologically mature sodium battery systems to clarify realistic pathways toward practical implementation. By linking interfacial chemistry, defect physics, and mechanical properties, this Review aims to provide a coherent framework and forward-looking guidance for the rational design of next-generation SSSBs.
{"title":"Interfacial Failure Mechanisms and Design Principles in Solid-State Sodium Batteries","authors":"Mingyue Wang, Qing Zhong, Yue Wang, Xu Liu, Dongyang Zhang, Shujiang Ding","doi":"10.1039/d5sc09313a","DOIUrl":"https://doi.org/10.1039/d5sc09313a","url":null,"abstract":"Solid-state sodium batteries (SSSBs) have attracted increasing attention as a promising alternative for large-scale energy storage owing to their intrinsic safety, material abundance, and potential cost advantages. Significant progress has been made in developing diverse solid-state electrolytes, including polymers, inorganic ceramics, and hybrid systems, many of which exhibit impressive bulk ionic conductivity. However, the translation of these materials-level properties into durable, high-performance solid-state sodium batteries remains limited, indicating that bulk ion transport alone does not govern practical cell behavior. In this Review, we adopt an interface-centered and issue-driven perspective to analyze the key challenges in SSSBs. Rather than providing a materials-category-based summary, we focus on dominant interfacial failure mechanisms and their sodium origins. Chemical and electrochemical instability, electrical blocking associated with space-charge effects and grain boundaries, mechanical degradation arising from elastic and thermal mismatch, and defect-assisted sodium dendrite penetration are discussed within a unified mechanistic framework. These interfacial processes are shown to be intrinsically coupled, collectively controlling effective ion transport, critical current density, and long-term cell stability. Building on this understanding, we critically assess why high bulk ionic conductivity has not translated into robust full-cell performance and emphasize the limitations of conductivity as a single performance metric. We further discuss general design principles for interface engineering across different electrolyte families and revisit lessons from technologically mature sodium battery systems to clarify realistic pathways toward practical implementation. By linking interfacial chemistry, defect physics, and mechanical properties, this Review aims to provide a coherent framework and forward-looking guidance for the rational design of next-generation SSSBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"86 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056973","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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