The development of violet-blue organic light-emitting diodes (OLEDs) with narrowband emission, high color purity and efficiency remains a formidable challenge, particularly under the stringent requirements of the wide-color-gamut display standards. Here, we propose a molecular design strategy that integrates oxygen-bridged triarylboron π-extension with precise heteroatom modulation to construct tetraboron-based MR-TADF emitters 4M-BOB4 and 4F-BOB4. The emitters adopt a ladder-type fused framework with a highly ordered arrangement of boron, nitrogen, and oxygen atoms, while fluorine substitution shifts the emission region from deep-blue to violet-blue. The incorporation of oxygen atoms not only regulates electronic delocalization and frontier orbital distribution, but also contributes to sharpening the emission bandwidth through localized conjugation modulation. As a result, 4F-BOB4 exhibits ultra-narrow emission in solution (with a full-width at half maximum of 14 nm), and corresponding OLED devices exhibit a maximum external quantum efficiency (EQEmax) of 20.9%. Notably, the device based on 4F-BOB4 exhibits a CIEy value ≤0.030, underscoring its status as one of the most color-pure violet-blue emitters reported to date. This work highlights the potential of rational π-framework engineering and localized electronic modulation as a generalizable approach to next-generation high-performance narrowband OLEDs.
{"title":"Ladder-type π-conjugated frameworks with multi-heteroatom modulation for narrowband violet-blue multiple-resonance emitters with a low CIEy of 0.03","authors":"Jian-Rong Wu, Yue-Jian Yang, Hai-Tian Yuan, Shi-Jie Ge, Yang-Kun Qu, Hai-Xiao Jiang, Yin Liu, Dong-Ying Zhou, Liang-Sheng Liao, Zuo-Quan Jiang","doi":"10.1039/d5sc09014h","DOIUrl":"https://doi.org/10.1039/d5sc09014h","url":null,"abstract":"The development of violet-blue organic light-emitting diodes (OLEDs) with narrowband emission, high color purity and efficiency remains a formidable challenge, particularly under the stringent requirements of the wide-color-gamut display standards. Here, we propose a molecular design strategy that integrates oxygen-bridged triarylboron π-extension with precise heteroatom modulation to construct tetraboron-based MR-TADF emitters 4M-BOB4 and 4F-BOB4. The emitters adopt a ladder-type fused framework with a highly ordered arrangement of boron, nitrogen, and oxygen atoms, while fluorine substitution shifts the emission region from deep-blue to violet-blue. The incorporation of oxygen atoms not only regulates electronic delocalization and frontier orbital distribution, but also contributes to sharpening the emission bandwidth through localized conjugation modulation. As a result, 4F-BOB4 exhibits ultra-narrow emission in solution (with a full-width at half maximum of 14 nm), and corresponding OLED devices exhibit a maximum external quantum efficiency (EQE<small><sub>max</sub></small>) of 20.9%. Notably, the device based on 4F-BOB4 exhibits a CIE<small><sub><em>y</em></sub></small> value ≤0.030, underscoring its status as one of the most color-pure violet-blue emitters reported to date. This work highlights the potential of rational π-framework engineering and localized electronic modulation as a generalizable approach to next-generation high-performance narrowband OLEDs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044883","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}
Mechanically robust polyacrylic acid (PAA) binders are extensively investigated for improving the structural stability and extending the cycle life of Si anodes. However, PAA cannot simultaneously suppress interfacial side reactions, preserve structural integrity, and ensure efficient ion transport. This paper presents a mechanically elastic polymeric binder, PCZn, that integrates locally positive charges to introduce a LiF-rich interface and high ionic conductivity within a triangular architecture established through the triadic interaction of a long-chain PAA adhesive, cross-linking agent chitosan oligosaccharide, and cation donor zinc gluconate. PCZn imparts a highly reversible anti-strain capability, a conformal LiF-rich solid-electrolyte-interface layer, and high ionic conductivity to Si anodes, resulting in remarkable electrochemical performance with a high capacity of 1210 mAh•g -1 after 450 cycles at 3 A•g -1 and enhanced fast-charging capability of 1468 mAh•g -1 at 8 A•g -1 . Thus, concurrently addressing mechanical failure, interfacial instability, and sluggish kinetics of Si anodes through advanced binder design will help develop high-energy-density next-generation batteries with long cycle lives.
{"title":"A fluorine-absorbing and mechanically elastic binder with triangular architecture enables both bulk-and interface-stable Si anodes","authors":"Zhipeng Wang, Qitao Shi, Weiqi Song, Luwen Li, Jiaqi Wang, Cheng Zhang, Alicja Bachmatiuk, Chen Lu, Peichao Zou, Jin-Ho Choi, Yanbin Shen, Ruizhi Yang, Mark Rümmeli","doi":"10.1039/d5sc09750a","DOIUrl":"https://doi.org/10.1039/d5sc09750a","url":null,"abstract":"Mechanically robust polyacrylic acid (PAA) binders are extensively investigated for improving the structural stability and extending the cycle life of Si anodes. However, PAA cannot simultaneously suppress interfacial side reactions, preserve structural integrity, and ensure efficient ion transport. This paper presents a mechanically elastic polymeric binder, PCZn, that integrates locally positive charges to introduce a LiF-rich interface and high ionic conductivity within a triangular architecture established through the triadic interaction of a long-chain PAA adhesive, cross-linking agent chitosan oligosaccharide, and cation donor zinc gluconate. PCZn imparts a highly reversible anti-strain capability, a conformal LiF-rich solid-electrolyte-interface layer, and high ionic conductivity to Si anodes, resulting in remarkable electrochemical performance with a high capacity of 1210 mAh•g -1 after 450 cycles at 3 A•g -1 and enhanced fast-charging capability of 1468 mAh•g -1 at 8 A•g -1 . Thus, concurrently addressing mechanical failure, interfacial instability, and sluggish kinetics of Si anodes through advanced binder design will help develop high-energy-density next-generation batteries with long cycle lives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070683","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}
Li-alloying-type anodes (Si, Sn, Ge, etc.) are a potent enabler for high-energy lithium-ion batteries (LIBs), offering outstanding Li-storage capacity. However, their practical use is hampered by severe volume fluctuations during cycling, which lead to particle pulverization, unstable interphase, and thus the shortened lifespan. Engineered porous structures have emerged as a key to solving these challenges. This review focuses on the porous alloying-type particles (ATPs) for LIB anodes. Firstly, the structural evolution of ATPs with or without pores during lithiation is analyzed using a graphite anode as a reference, highlighting the critical role of intraparticle rather than interparticle pores. Synthetic methodologies for fabricating porous ATPs are summarized and categorized into bottom-up, top-down, and transcription approaches, with special emphasis on their scalability for practical application. Recent progress in elucidating the in-cell evolution of pores and the key function of intraparticle pores are discussed in detail, emphasizing the contrasting effects of open versus closed pores. We also review representative diagnostic techniques for quantitative pore characterization, and the advanced binders or electrolytes that stabilize porous ATPs in the context of practical pouch or cylindrical cells. Lastly, we discuss cell-level considerations and operating procedures, outlining future research directions toward post-intercalation anodes for both liquid- and solid-state LIBs.
{"title":"Porous Alloying-Type Particles for Practical Lithium-ion Battery Anodes","authors":"Yiteng Luo, Sai Ho Pun, He Yan, Wei Liu","doi":"10.1039/d5sc08594b","DOIUrl":"https://doi.org/10.1039/d5sc08594b","url":null,"abstract":"Li-alloying-type anodes (Si, Sn, Ge, etc.) are a potent enabler for high-energy lithium-ion batteries (LIBs), offering outstanding Li-storage capacity. However, their practical use is hampered by severe volume fluctuations during cycling, which lead to particle pulverization, unstable interphase, and thus the shortened lifespan. Engineered porous structures have emerged as a key to solving these challenges. This review focuses on the porous alloying-type particles (ATPs) for LIB anodes. Firstly, the structural evolution of ATPs with or without pores during lithiation is analyzed using a graphite anode as a reference, highlighting the critical role of intraparticle rather than interparticle pores. Synthetic methodologies for fabricating porous ATPs are summarized and categorized into bottom-up, top-down, and transcription approaches, with special emphasis on their scalability for practical application. Recent progress in elucidating the in-cell evolution of pores and the key function of intraparticle pores are discussed in detail, emphasizing the contrasting effects of open versus closed pores. We also review representative diagnostic techniques for quantitative pore characterization, and the advanced binders or electrolytes that stabilize porous ATPs in the context of practical pouch or cylindrical cells. Lastly, we discuss cell-level considerations and operating procedures, outlining future research directions toward post-intercalation anodes for both liquid- and solid-state LIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044882","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}
Xiaoshuang Xiang, Mathias Hermann, Lei Ye, Philipp Seitz, Lilian Estaque, Gregory Pieters, Thomas Drewello, Birgit Esser
Conjugated nanohoops, such as [n]cycloparaphenylenes ([n]CPPs) and derivatives, exhibit unique structural and optoelectronic properties, making them promising candidates for applications in optoelectronic materials, and as hosts for supramolecular chemistry. Using π-systems unsymmetric to rotation or incorporating chiral units can furnish chiral nanohoops. We herein present the synthesis and characterization of diketo[8]- and diketo[9]CPP, along with their corresponding dibenzo[a,e]pentalene (DBP) derivatives, DBP[8]- and DBP[9]CPP. Due to the central chirality of the diketone-units, these nanohoops are chiral without the possibility of racemization through rotation, and show distinct chiroptical properties. The diketo[n]CPPs possess high fluorescence quantum yields of 87% (n = 8) and 92% (n = 9). The shape-adaptive property of diketo[n]CPPs, facilitated by the tunable angle of the diketo unit, enables efficient host-guest interactions with fullerenes. Fluorescence titration revealed similar binding constant for both fullerenes C60 and C70 (5 × 104 – 7 × 104 M−1 in toluene), corroborated by DFT calculations that illustrate adaptive changes in nanohoop geometry upon fullerene complexation. ESI-MS is employed to generate ionized [1:1] host-guest complexes of diketo[9]CPP and DBP[9]CPP with C60 and C70 as guests. The relative stabilities of these complexes is evaluated in energy-resolved collision experiments.
{"title":"Diketo[n]CPPs as Chiral and Shape-adaptive Fullerene Hosts and Precursors to DBP[n]CPPs","authors":"Xiaoshuang Xiang, Mathias Hermann, Lei Ye, Philipp Seitz, Lilian Estaque, Gregory Pieters, Thomas Drewello, Birgit Esser","doi":"10.1039/d5sc05305f","DOIUrl":"https://doi.org/10.1039/d5sc05305f","url":null,"abstract":"Conjugated nanohoops, such as [n]cycloparaphenylenes ([n]CPPs) and derivatives, exhibit unique structural and optoelectronic properties, making them promising candidates for applications in optoelectronic materials, and as hosts for supramolecular chemistry. Using π-systems unsymmetric to rotation or incorporating chiral units can furnish chiral nanohoops. We herein present the synthesis and characterization of diketo[8]- and diketo[9]CPP, along with their corresponding dibenzo[a,e]pentalene (DBP) derivatives, DBP[8]- and DBP[9]CPP. Due to the central chirality of the diketone-units, these nanohoops are chiral without the possibility of racemization through rotation, and show distinct chiroptical properties. The diketo[n]CPPs possess high fluorescence quantum yields of 87% (n = 8) and 92% (n = 9). The shape-adaptive property of diketo[n]CPPs, facilitated by the tunable angle of the diketo unit, enables efficient host-guest interactions with fullerenes. Fluorescence titration revealed similar binding constant for both fullerenes C60 and C70 (5 × 104 – 7 × 104 M−1 in toluene), corroborated by DFT calculations that illustrate adaptive changes in nanohoop geometry upon fullerene complexation. ESI-MS is employed to generate ionized [1:1] host-guest complexes of diketo[9]CPP and DBP[9]CPP with C60 and C70 as guests. The relative stabilities of these complexes is evaluated in energy-resolved collision experiments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"288 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044887","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}
Gangliosides are vital cell membrane components whose metabolic dysregulation is implicated in various cancers. However, a systems-level understanding of their metabolism has been hindered by their structural complexity and low cellular abundance. Herein, we have developed a deep profiling workflow for gangliosides that integrates selective enrichment, liquid chromatography-ion mobility spectrometry, and isomer-resolved tandem mass spectrometry. This workflow enhances detection sensitivity 100-fold, enabling the identification of 391 ganglioside structures in human breast adenocarcinoma cell line (MCF-7) at multiple structural levels. We further reveal a coordinated remodeling of gangliosides in MCF-7 cancer cells, including shifts toward a-series glycans, increased incorporation of long-chain sphingosine bases, and altered C=C location isomers. By integrating these lipidomic findings with targeted gene expression analysis and quantitative proteomics, we reconstruct a ganglioside biosynthetic network that delineates dysregulation across five key structural modules. This lipid-centric approach offers new insights into metabolic reprogramming of gangliosides and holds potential for studying lipid metabolism in diverse diseases.
{"title":"Deep Profiling Reveals Coordinated Remodeling of Ganglioside Metabolism in MCF-7 Breast Cancer Cell Line","authors":"Yichun Wang, Gaoge Sun, Hang Yin, Yu Xia","doi":"10.1039/d5sc09445c","DOIUrl":"https://doi.org/10.1039/d5sc09445c","url":null,"abstract":"Gangliosides are vital cell membrane components whose metabolic dysregulation is implicated in various cancers. However, a systems-level understanding of their metabolism has been hindered by their structural complexity and low cellular abundance. Herein, we have developed a deep profiling workflow for gangliosides that integrates selective enrichment, liquid chromatography-ion mobility spectrometry, and isomer-resolved tandem mass spectrometry. This workflow enhances detection sensitivity 100-fold, enabling the identification of 391 ganglioside structures in human breast adenocarcinoma cell line (MCF-7) at multiple structural levels. We further reveal a coordinated remodeling of gangliosides in MCF-7 cancer cells, including shifts toward a-series glycans, increased incorporation of long-chain sphingosine bases, and altered C=C location isomers. By integrating these lipidomic findings with targeted gene expression analysis and quantitative proteomics, we reconstruct a ganglioside biosynthetic network that delineates dysregulation across five key structural modules. This lipid-centric approach offers new insights into metabolic reprogramming of gangliosides and holds potential for studying lipid metabolism in diverse diseases.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"117 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044888","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}
Modified mRNA technology has transformed vaccine development by enabling rapid and precise antigen production. The incorporation of adjuvants may further enhance innate immune activation, thereby improving the efficacy of mRNA vaccines. However, inappropriate vaccine kinetics leading to excessive activation of the innate immune system can inhibit the mTORC1 pathway and impair antigen mRNA translation, ultimately limiting vaccine potency. Herein, we present the development of a time-ordered-expression mRNA (TOE mRNA) based on ADAR-mediated A-to-I base editing. Upon cellular entry, TOE mRNA initiates immediate antigen translation, while the adjuvant encoded within the same mRNA is translated approximately 12 hours post-antigen expression. This delayed adjuvant expression ensures sustained activation of the mTORC1 pathway and robust antigen expression, effectively overcoming the limitations imposed by suboptimal vaccine kinetics. We demonstrate that vaccines utilizing TOE mRNA encoding a tumor neoantigen (for normal translation) and an IL-12 adjuvant (with delayed translation) elicit significantly enhanced antitumor immune responses. TOE mRNA technology represents a promising platform for advancing next-generation mRNA vaccines with improved efficacy.
{"title":"Time-ordered-expression mRNA (TOE mRNA) for melanoma RNA vaccines","authors":"Xiangdong Zhang, Xucong Teng, Yicong Dai, Ningqiang Gong, Qiushuang Zhang, Difei Hu, Yuncong Wu, Hongwei Hou, Jinghong Li","doi":"10.1039/d5sc07482g","DOIUrl":"https://doi.org/10.1039/d5sc07482g","url":null,"abstract":"Modified mRNA technology has transformed vaccine development by enabling rapid and precise antigen production. The incorporation of adjuvants may further enhance innate immune activation, thereby improving the efficacy of mRNA vaccines. However, inappropriate vaccine kinetics leading to excessive activation of the innate immune system can inhibit the mTORC1 pathway and impair antigen mRNA translation, ultimately limiting vaccine potency. Herein, we present the development of a time-ordered-expression mRNA (TOE mRNA) based on ADAR-mediated A-to-I base editing. Upon cellular entry, TOE mRNA initiates immediate antigen translation, while the adjuvant encoded within the same mRNA is translated approximately 12 hours post-antigen expression. This delayed adjuvant expression ensures sustained activation of the mTORC1 pathway and robust antigen expression, effectively overcoming the limitations imposed by suboptimal vaccine kinetics. We demonstrate that vaccines utilizing TOE mRNA encoding a tumor neoantigen (for normal translation) and an IL-12 adjuvant (with delayed translation) elicit significantly enhanced antitumor immune responses. TOE mRNA technology represents a promising platform for advancing next-generation mRNA vaccines with improved efficacy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044885","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}
The synthesis of two [1H]/[2H] discriminated bianthryl atropisotopomers (i.e., isotopically chiral atropisomers, vide infra) with ≥ 97% enantiomeric excess (ee) from the atropisomers of commercial (aS)-and (aR)-1,1′-bi-2-naphthol (BINOL, > 99% ee) is described. The approach is based on enantiospecific [4 + 2] cycloaddition reactions of aryne atropisomer intermediates with [2H4]-furan. Overall, the six-step (from enantiopure BINOL) reaction sequence to the bianthryl atropisotopomers described herein is occurring without significant erosion of the molecular stereogenic information. This is substantiated experimentally by three direct spectroscopic methods that do not necessitate chemical derivatization: i) mirror specific optical rotations as a proof of optical activity and also a proof of their equivalent ee, ii) mirror vibrational circular dichroism (VCD) spectra as a proof of their equivalent ee and for the confirmation of their absolute configurations (AC), and, iii) for the first time, anisotropic 2H/13C NMR in lyotropic chiral liquid crystals for the determination of their ee for one of them. In a broader and foreseeable perspective, the enantiospecific synthetic approach considered in this work to access bianthryl atropisotopomers from BINOL is simple and scalable, which should enable the production of a diverse range of atropisotopomers in a near future, possibly embedding never examined isotopes (e.g., [3H]). The availability of this class of isotopically chiral compounds in high isotopic and enantiomeric purity is a real asset for the development of precision chiral spectroscopies.
{"title":"[1H]/[2H] discriminated bianthryl atropisotopomers: enantiospecific syntheses from BINOL and direct multi-spectroscopic analyses of their isotopic chirality","authors":"Florian Rigoulet, Guillaume Dauvergne, Jean-Valère Naubron, Philippe Lesot, Christie Aroulanda, Yoann Coquerel","doi":"10.1039/d5sc09200k","DOIUrl":"https://doi.org/10.1039/d5sc09200k","url":null,"abstract":"The synthesis of two [<small><sup>1</sup></small>H]/[<small><sup>2</sup></small>H] discriminated bianthryl atropisotopomers (i.e., isotopically chiral atropisomers, vide infra) with ≥ 97% enantiomeric excess (ee) from the atropisomers of commercial (aS)-and (aR)-1,1′-bi-2-naphthol (BINOL, > 99% ee) is described. The approach is based on enantiospecific [4 + 2] cycloaddition reactions of aryne atropisomer intermediates with [<small><sup>2</sup></small>H<small><sub>4</sub></small>]-furan. Overall, the six-step (from enantiopure BINOL) reaction sequence to the bianthryl atropisotopomers described herein is occurring without significant erosion of the molecular stereogenic information. This is substantiated experimentally by three direct spectroscopic methods that do not necessitate chemical derivatization: i) mirror specific optical rotations as a proof of optical activity and also a proof of their equivalent ee, ii) mirror vibrational circular dichroism (VCD) spectra as a proof of their equivalent ee and for the confirmation of their absolute configurations (AC), and, iii) for the first time, anisotropic <small><sup>2</sup></small>H/<small><sup>13</sup></small>C NMR in lyotropic chiral liquid crystals for the determination of their ee for one of them. In a broader and foreseeable perspective, the enantiospecific synthetic approach considered in this work to access bianthryl atropisotopomers from BINOL is simple and scalable, which should enable the production of a diverse range of atropisotopomers in a near future, possibly embedding never examined isotopes (e.g., [<small><sup>3</sup></small>H]). The availability of this class of isotopically chiral compounds in high isotopic and enantiomeric purity is a real asset for the development of precision chiral spectroscopies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"296 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057140","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}
Tengteng Lyu, Jonathan B. Lefton, Martin Etter, Shrikant Bhat, Wenhao Liu, Bing Lv, Luke J. Kwan, Hao Yan, Tomče Runčevski
The orderly arrangement of molecules in crystals provides a unique platform for the control of reactivity, where spatial vicinity and orientation of the molecules determines the course of the reaction. Common wisdom assumes that densest crystal packings of the reactant molecules are most favorable for pressure-induced topochemical reactions. Based on thermodynamic and spatial arguments, here we show that the densest crystal packing may not be the most optimal platform for chemical synthesis. Instead, introducing void space within the crystal lattice significantly improves, and even enables, chemical reaction. In case of sorbic acid confined between brucite-type layers, this reactivity is used to modify the optical, spectroscopic and magnetic properties of the 2D layers, and to synthesize a retrievable polymeric product.
{"title":"Making Room for Reactivity in Topochemical Transformations under Pressure","authors":"Tengteng Lyu, Jonathan B. Lefton, Martin Etter, Shrikant Bhat, Wenhao Liu, Bing Lv, Luke J. Kwan, Hao Yan, Tomče Runčevski","doi":"10.1039/d5sc05793k","DOIUrl":"https://doi.org/10.1039/d5sc05793k","url":null,"abstract":"The orderly arrangement of molecules in crystals provides a unique platform for the control of reactivity, where spatial vicinity and orientation of the molecules determines the course of the reaction. Common wisdom assumes that densest crystal packings of the reactant molecules are most favorable for pressure-induced topochemical reactions. Based on thermodynamic and spatial arguments, here we show that the densest crystal packing may not be the most optimal platform for chemical synthesis. Instead, introducing void space within the crystal lattice significantly improves, and even enables, chemical reaction. In case of sorbic acid confined between brucite-type layers, this reactivity is used to modify the optical, spectroscopic and magnetic properties of the 2D layers, and to synthesize a retrievable polymeric product.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044884","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}
We demonstrate electrostatic decatalysis, where long-range Coulomb interactions selectively screen parasitic chemistry, leading to distinct catalytic selectivity outcomes. By reconfiguring interfacial electrostatic landscapes, this approach achieves site and flux selective screening of competing reactions while promoting ammonia electrosynthesis. Molecular dynamics simulations reveal a near sevenfold enhancement in substrate enrichment factors, arising from optimized electrostatic screening and strategic charge distribution. Experimentally, we observe more than a twofold increase in ammonia Faradaic efficiency at practically relevant current densities, suggesting electrostatic contributes to reaction selectivity with energy savings exceeding 50% relative to conventional benchmarks. Importantly, the Coulombic screening strategy exhibits pH-insensitive universality, enabling broad applicability for electrochemical process modulations.
{"title":"Electrostatic Decatalysis through Coulombic Screening","authors":"Bhojkumar Nayak, Abdul Raafik Arattu Thodika, Hemanga Pradhan, Rahul Mahadeo Mendhe, Musthafa Ottakam Thotiyl","doi":"10.1039/d5sc08236f","DOIUrl":"https://doi.org/10.1039/d5sc08236f","url":null,"abstract":"We demonstrate electrostatic decatalysis, where long-range Coulomb interactions selectively screen parasitic chemistry, leading to distinct catalytic selectivity outcomes. By reconfiguring interfacial electrostatic landscapes, this approach achieves site and flux selective screening of competing reactions while promoting ammonia electrosynthesis. Molecular dynamics simulations reveal a near sevenfold enhancement in substrate enrichment factors, arising from optimized electrostatic screening and strategic charge distribution. Experimentally, we observe more than a twofold increase in ammonia Faradaic efficiency at practically relevant current densities, suggesting electrostatic contributes to reaction selectivity with energy savings exceeding 50% relative to conventional benchmarks. Importantly, the Coulombic screening strategy exhibits pH-insensitive universality, enabling broad applicability for electrochemical process modulations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"50 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034116","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}
Alivia Mukherjee, Summer Y. Wu, David J. Cooper, Rachel Hendrickson, Roseanne J. Sension, Nicolai Lehnert, James E. Penner-Hahn
A wide range of proteins and enzymes depend on alkylcobalamins (alkylCbl or vitamin B12) for their activities, owing to the unique, biologically relevant Co–C bond. CarH, a regulatory protein in the bacterial carotenoid biosynthetic pathway, utilizes the photosensitivity of the Co–C bond in adenosylcobalamin (AdoCbl) for gene regulation. B12-dependent reductive dehalogenases rely on chemical Co–C bond cleavage to form a Co(III)–halide bond during catalysis. Ultrafast spectroscopy demonstrates that photolytic Co–C bond cleavage in cobalamins begins with the generation of a Co(II) species and an alkyl radical. Interestingly, both CarH and reductive dehalogenases are thought to generate a highly reactive Co(I) species as part of their reactivity. We have used time-resolved measurements of alkylCbls under single turnover conditions to better characterize this reactivity. We demonstrate that Co(I) can be generated in nearly quantitative yield during anaerobic photolysis of alkylCbls in aqueous solution. Remarkably, the addition of alkyl halide to this Co(I) species does not produce quantitative yield of Co(III)-alkylCbl species as would be expected given the “supernucleophilic” nature of the Co(I) center. Instead, we find a branching pathway which has significant implications in Cbl-dependent enzymes and vitamin B12 based organometallic photochemistry. Finally, we demonstrate that both the final oxidation state of the cobalamin product and the fate of the organic radical formed are solvent-dependent, an observation that has implications for CarH photochemistry.
{"title":"Shining light on the mechanism of photochemical alkene formation in vitamin B12","authors":"Alivia Mukherjee, Summer Y. Wu, David J. Cooper, Rachel Hendrickson, Roseanne J. Sension, Nicolai Lehnert, James E. Penner-Hahn","doi":"10.1039/d5sc07054f","DOIUrl":"https://doi.org/10.1039/d5sc07054f","url":null,"abstract":"A wide range of proteins and enzymes depend on alkylcobalamins (alkylCbl or vitamin B<small><sub>12</sub></small>) for their activities, owing to the unique, biologically relevant Co–C bond. CarH, a regulatory protein in the bacterial carotenoid biosynthetic pathway, utilizes the photosensitivity of the Co–C bond in adenosylcobalamin (AdoCbl) for gene regulation. B<small><sub>12</sub></small>-dependent reductive dehalogenases rely on chemical Co–C bond cleavage to form a Co(<small>III</small>)–halide bond during catalysis. Ultrafast spectroscopy demonstrates that photolytic Co–C bond cleavage in cobalamins begins with the generation of a Co(<small>II</small>) species and an alkyl radical. Interestingly, both CarH and reductive dehalogenases are thought to generate a highly reactive Co(<small>I</small>) species as part of their reactivity. We have used time-resolved measurements of alkylCbls under single turnover conditions to better characterize this reactivity. We demonstrate that Co(<small>I</small>) can be generated in nearly quantitative yield during anaerobic photolysis of alkylCbls in aqueous solution. Remarkably, the addition of alkyl halide to this Co(<small>I</small>) species does not produce quantitative yield of Co(<small>III</small>)-alkylCbl species as would be expected given the “supernucleophilic” nature of the Co(<small>I</small>) center. Instead, we find a branching pathway which has significant implications in Cbl-dependent enzymes and vitamin B<small><sub>12</sub></small> based organometallic photochemistry. Finally, we demonstrate that both the final oxidation state of the cobalamin product and the fate of the organic radical formed are solvent-dependent, an observation that has implications for CarH photochemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034118","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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