Symmetry-breaking charge separation (SB-CS) is a fundamental process in natural photosynthetic systems, serving as the primary trigger for electron transfer and ultimately leading to the formation of a charge separated state. This mechanism has also been leveraged in optoelectronic devices to minimize energy loss and improve solar energy conversion efficiency. However, in organic solar cells (OSCs) studies, SB-CS has predominantly been observed in polar environments, and the roles of molecular aggregation in modulating this process remain unclear. Herein, we investigated the influence of aggregation and solvent polarity on the SB-CS of the perylene diimide trimer (PDI-III) in different solvents. Steady-state absorption and fluorescence spectroscopy reveal that PDI-III exhibits a biphasic aggregation behavior depending on solvent polarity, with stronger aggregation occurring in both nonpolar and highly polar solvents than in solvents of intermediate polarity. Femtosecond transient absorption spectroscopy and time-resolved infrared spectroscopy indicate that SB-CS also emerges in toluene, with an extent that lies between those observed in chloroform and acetone. Further analysis suggests that in toluene, intermolecular aggregation strengthens π-π interactions and electronic coupling, thereby enabling SB-CS even in the absence of substantial solvent polarity. In acetone, intramolecular aggregation, together with strong solvent polarity, leads to more efficient SB-CS than in chloroform. Collectively, these results establish a clear mechanistic framework for how aggregation and solvent polarity govern SB-CS in PDI-III, offering guiding principles for minimizing energy loss while maintaining high photocurrent in next-generation OSCs.
{"title":"Symmetry-Breaking Charge Separation in Perylene Diimide Trimers: Effects of Aggregation and Solvent Polarity","authors":"Lie Tian, Guangliu Ran, Shixuan Zheng, Wenkai Zhang","doi":"10.1039/d5sc09357k","DOIUrl":"https://doi.org/10.1039/d5sc09357k","url":null,"abstract":"Symmetry-breaking charge separation (SB-CS) is a fundamental process in natural photosynthetic systems, serving as the primary trigger for electron transfer and ultimately leading to the formation of a charge separated state. This mechanism has also been leveraged in optoelectronic devices to minimize energy loss and improve solar energy conversion efficiency. However, in organic solar cells (OSCs) studies, SB-CS has predominantly been observed in polar environments, and the roles of molecular aggregation in modulating this process remain unclear. Herein, we investigated the influence of aggregation and solvent polarity on the SB-CS of the perylene diimide trimer (PDI-III) in different solvents. Steady-state absorption and fluorescence spectroscopy reveal that PDI-III exhibits a biphasic aggregation behavior depending on solvent polarity, with stronger aggregation occurring in both nonpolar and highly polar solvents than in solvents of intermediate polarity. Femtosecond transient absorption spectroscopy and time-resolved infrared spectroscopy indicate that SB-CS also emerges in toluene, with an extent that lies between those observed in chloroform and acetone. Further analysis suggests that in toluene, intermolecular aggregation strengthens π-π interactions and electronic coupling, thereby enabling SB-CS even in the absence of substantial solvent polarity. In acetone, intramolecular aggregation, together with strong solvent polarity, leads to more efficient SB-CS than in chloroform. Collectively, these results establish a clear mechanistic framework for how aggregation and solvent polarity govern SB-CS in PDI-III, offering guiding principles for minimizing energy loss while maintaining high photocurrent in next-generation OSCs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462061","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}
Alkyl-substituted dihydropyrimidines (DHPyms), synthesised via the Biginelli reaction, are introduced as tunable alternatives to 4-alkyl Hantzsch Dihydropyridines (DHPs) in radical chemistry. Leveraging the modularity of the Biginelli reaction, we systematically explored the redox properties, UV/vis absorption, and synthetic potential of DHPyms in radical-mediated transformations, identifying dimethylamino-substituted DHPym as a highly reactive, bench-stable, and easily synthesised alkyl radical precursor.
{"title":"Biginelli Dihydropyrimidines: A Tunable Class of Alkyl Radical Precursors","authors":"Shahilan Ratnam, Shreya Unone, Nabeel Alia, Enyu Denny Hafeneger, Daniel Janssen-Müller","doi":"10.1039/d6sc00376a","DOIUrl":"https://doi.org/10.1039/d6sc00376a","url":null,"abstract":"Alkyl-substituted dihydropyrimidines (DHPyms), synthesised via the Biginelli reaction, are introduced as tunable alternatives to 4-alkyl Hantzsch Dihydropyridines (DHPs) in radical chemistry. Leveraging the modularity of the Biginelli reaction, we systematically explored the redox properties, UV/vis absorption, and synthetic potential of DHPyms in radical-mediated transformations, identifying dimethylamino-substituted DHPym as a highly reactive, bench-stable, and easily synthesised alkyl radical precursor.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147454537","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 exposed facets of supported metal catalysts play a crucial role in catalytic hydrogenation performance. However, the internal relationship between the support crystal facet and catalytic performance needs to be further explored. Herein, a series of well-defined Pt/Co3O4-x catalysts are fabricated with similar Pt nanoparticle sizes, identical metal loadings, and tailored Co3O4 crystal facets (x = o, t, c; where “o”, “t”, and “c” denote Co3O4 exposing predominantly (111), mixed (111)/(100), and (100) facets, respectively). The electronic structure of Pt nanoparticles and the hydrogen spillover capability of Pt/Co3O4 are modulated by exposing different crystal facets of Co3O4. For the 4-nitrophenol (4-NP) hydrogenation reaction with H2 as the hydrogen source, the Pt/Co3O4-o catalyst with more Pt0 species and stronger hydrogen spillover capability exhibits the best hydrogenation activity with a turnover frequency (TOF) of 164.2 h−1. Mechanistic studies indicate that, compared with Pt/Co3O4-c, the Pt/Co3O4-o exhibits weaker adsorption and activation of the nitro group, while its ability to activate H2 is stronger. The enhanced catalytic activity of Pt/Co3O4-o is attributed to promoted hydrogen activation and spillover. This work highlights support crystal facet engineering for regulating the electronic structure and hydrogen spillover effect, which provides in-depth insight into catalyst design and hydrogenation mechanism.
{"title":"Promoted hydrogen activation and spillover over Pt/Co3O4 by facet engineering of Co3O4 for enhanced catalytic hydrogenation","authors":"Hui Yun, Jiao Feng, Wanying Peng, Mi Xiong","doi":"10.1039/d5sc09402j","DOIUrl":"https://doi.org/10.1039/d5sc09402j","url":null,"abstract":"The exposed facets of supported metal catalysts play a crucial role in catalytic hydrogenation performance. However, the internal relationship between the support crystal facet and catalytic performance needs to be further explored. Herein, a series of well-defined Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>-x catalysts are fabricated with similar Pt nanoparticle sizes, identical metal loadings, and tailored Co<small><sub>3</sub></small>O<small><sub>4</sub></small> crystal facets (x = o, t, c; where “o”, “t”, and “c” denote Co<small><sub>3</sub></small>O<small><sub>4</sub></small> exposing predominantly (111), mixed (111)/(100), and (100) facets, respectively). The electronic structure of Pt nanoparticles and the hydrogen spillover capability of Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small> are modulated by exposing different crystal facets of Co<small><sub>3</sub></small>O<small><sub>4</sub></small>. For the 4-nitrophenol (4-NP) hydrogenation reaction with H<small><sub>2</sub></small> as the hydrogen source, the Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>-o catalyst with more Pt<small><sup>0</sup></small> species and stronger hydrogen spillover capability exhibits the best hydrogenation activity with a turnover frequency (TOF) of 164.2 h<small><sup>−1</sup></small>. Mechanistic studies indicate that, compared with Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>-c, the Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>-o exhibits weaker adsorption and activation of the nitro group, while its ability to activate H<small><sub>2</sub></small> is stronger. The enhanced catalytic activity of Pt/Co<small><sub>3</sub></small>O<small><sub>4</sub></small>-o is attributed to promoted hydrogen activation and spillover. This work highlights support crystal facet engineering for regulating the electronic structure and hydrogen spillover effect, which provides in-depth insight into catalyst design and hydrogenation mechanism.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440455","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}
Sara Yoshikawa, Tokuhisa Kawawaki, Sakiat SH Hossain, Yuichi Negishi
Atomically precise metal nanoclusters (NCs) stabilized by organic ligands are promising functional materials in various fields owing to their unique geometric and electronic structures. However, many such NCs exhibit insufficient stability, e.g., processes such as alloying can induce structural destabilization. Gold (Au) NCs can be protected by introducing multi-site thiolates (SR), which form exceptionally strong Au–S bonds, thus enhancing the stability of the NCs and expanding their practical applicability. However, multi-site SR protection using bidentate ligands often leads to undesirable polymerization due to inter-NC cross-linking. The present study addresses this issue by elucidating the mechanism governing the formation of Au NCs co-protected by both bidentate (SR'S) and monodentate (SR) ligands. The key impacts of ligand flexibility and site-specific exchange kinetics are identified, thereby providing crucial insights to support the strategic design and synthesis of stable, multi-site SR-protected Au NCs with rigid, well-defined architectures.
{"title":"Mechanism Governing the Formation of Atomically Precise Dithiolate-Protected Gold Nanoclusters","authors":"Sara Yoshikawa, Tokuhisa Kawawaki, Sakiat SH Hossain, Yuichi Negishi","doi":"10.1039/d6sc00460a","DOIUrl":"https://doi.org/10.1039/d6sc00460a","url":null,"abstract":"Atomically precise metal nanoclusters (NCs) stabilized by organic ligands are promising functional materials in various fields owing to their unique geometric and electronic structures. However, many such NCs exhibit insufficient stability, e.g., processes such as alloying can induce structural destabilization. Gold (Au) NCs can be protected by introducing multi-site thiolates (SR), which form exceptionally strong Au–S bonds, thus enhancing the stability of the NCs and expanding their practical applicability. However, multi-site SR protection using bidentate ligands often leads to undesirable polymerization due to inter-NC cross-linking. The present study addresses this issue by elucidating the mechanism governing the formation of Au NCs co-protected by both bidentate (SR'S) and monodentate (SR) ligands. The key impacts of ligand flexibility and site-specific exchange kinetics are identified, thereby providing crucial insights to support the strategic design and synthesis of stable, multi-site SR-protected Au NCs with rigid, well-defined architectures.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440325","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}
Himanshu Gupta, Ethan P Shapera, Xiaojuan Yu, Xiaoyu Wang, Patrick Smith, Pragati Pandey, Michael Gau, Stefan Minasian, Eva Zurek, Jochen Autschbach, James M. Kikkawa, Eric J. Schelter
Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF]4[Ce2Cl10] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce2Cl10]4-. Intermolecular interactions between the stacked organic units of the crystal result in CT bands in the visible-NIR region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ~40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce2Cl10]4- anions to the π-stacked [DBTTF]22+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.
{"title":"Leveraging the Redox Activities of Cerium and Dibenzotetrathiafulvalene to Discover a Photo-Responsive Magnetic Material","authors":"Himanshu Gupta, Ethan P Shapera, Xiaojuan Yu, Xiaoyu Wang, Patrick Smith, Pragati Pandey, Michael Gau, Stefan Minasian, Eva Zurek, Jochen Autschbach, James M. Kikkawa, Eric J. Schelter","doi":"10.1039/d5sc08870d","DOIUrl":"https://doi.org/10.1039/d5sc08870d","url":null,"abstract":"Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF]4[Ce2Cl10] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce2Cl10]4-. Intermolecular interactions between the stacked organic units of the crystal result in CT bands in the visible-NIR region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ~40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce2Cl10]4- anions to the π-stacked [DBTTF]22+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"08 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147448340","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}
Ivan Antsiburov, Raphael Bühler, Johannes Stephan, Maxim Erdyakov, Christian Gemel, Samia Kahlal, Olivier Cador, Thierry Guizouarn, Jean-Yves Saillard, Karsten Meyer, Roland A. Fischer
The stabilization of zero oxidation state group (IV) metal centers in readily accessible compounds on a preparative scale remains a significant challenge. Substituting hydrocarbon ligands in the precursor complexes [Ti(η6-toluene)2] and [Zr(η6-cycloheptatriene)2] with monovalent GaTMP (TMP = 2,2,6,6-tetramethylpiperidinyl) yields the first homoleptic seven-coordinate Ti0 and Zr0 complexes, [Ti(GaTMP)7] (1) and [Zr(GaTMP)7] (2), which are exclusively coordinated by metalloligands. The bonding situation of 1 and 2 was rationalized through DFT calculations, revealing the critical importance of tangential Ga····Ga covalent interactions for stabilizing the compounds. Oxidation of 2 leads to the formation of [Zr(GaTMP)8]2+ (5), showcasing a similar bonding situation. These Ga····Ga interactions arise from significant π-backbonding from the Ti0 and Zr0 centers into the constructive combinations of the diffuse 4p orbitals of the Ga(I) centers. This unique cooperative feature of the all-Ga metalloligand sphere marks a clear distinction from the bonding properties of formally isolobal carbonyls, phosphines, or N-heterocyclic carbenes.
{"title":"Homoleptic seven-coordinate Ti(0) and Zr(0) through a new stabilization mode","authors":"Ivan Antsiburov, Raphael Bühler, Johannes Stephan, Maxim Erdyakov, Christian Gemel, Samia Kahlal, Olivier Cador, Thierry Guizouarn, Jean-Yves Saillard, Karsten Meyer, Roland A. Fischer","doi":"10.1039/d6sc00226a","DOIUrl":"https://doi.org/10.1039/d6sc00226a","url":null,"abstract":"The stabilization of zero oxidation state group (IV) metal centers in readily accessible compounds on a preparative scale remains a significant challenge. Substituting hydrocarbon ligands in the precursor complexes [Ti(η<small><sup>6</sup></small>-toluene)<small><sub>2</sub></small>] and [Zr(η<small><sup>6</sup></small>-cycloheptatriene)<small><sub>2</sub></small>] with monovalent GaTMP (TMP = 2,2,6,6-tetramethylpiperidinyl) yields the first homoleptic seven-coordinate Ti<small><sup>0</sup></small> and Zr<small><sup>0</sup></small> complexes, [Ti(GaTMP)<small><sub>7</sub></small>] (<strong>1</strong>) and [Zr(GaTMP)<small><sub>7</sub></small>] (<strong>2</strong>), which are exclusively coordinated by metalloligands. The bonding situation of <strong>1</strong> and <strong>2</strong> was rationalized through DFT calculations, revealing the critical importance of tangential Ga····Ga covalent interactions for stabilizing the compounds. Oxidation of <strong>2</strong> leads to the formation of [Zr(GaTMP)<small><sub>8</sub></small>]<small><sup>2+</sup></small> (<strong>5</strong>), showcasing a similar bonding situation. These Ga····Ga interactions arise from significant π-backbonding from the Ti<small><sup>0</sup></small> and Zr<small><sup>0</sup></small> centers into the constructive combinations of the diffuse 4p orbitals of the Ga(I) centers. This unique cooperative feature of the all-Ga metalloligand sphere marks a clear distinction from the bonding properties of formally isolobal carbonyls, phosphines, or N-heterocyclic carbenes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"84 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147440326","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}
Lachlan Barton Cox, Pall Thordarson, Felix Rizzuto
Folded RNA structures are increasingly being recognised as key regulators in biological processes, yet the RNA i-motif remains poorly characterised due to its low stability and lack of selective molecular probes. Here, we describe the first ligand – a short peptide – that binds the elusive RNA i-motif. Our minimalist peptide RGGFGGRGG is derived from the intrinsically disordered region of the protein Nucleolin and binds to folded RNA over DNA with >5-fold selectivity. The binding of two peptide molecules folds the RNA i-motif at a higher pH than under native conditions. This folded, peptide-bound structure can still bind other guests, such as the intercalator thiazole orange, displaying heteroallosteric properties. Our peptide binding is driven by more than simple electrostatic attraction, exploiting the subtle differences in steric complementarity and hydration of the compact RNA structures relative to DNA congeners and unfolded strands. Our findings underline the potential of minimalistic peptide scaffolds as selective binders for non-canonical RNA structures, allowing for the probing and modulation of RNA topologies.
{"title":"Peptide-Directed Folding of the Elusive RNA i-Motif","authors":"Lachlan Barton Cox, Pall Thordarson, Felix Rizzuto","doi":"10.1039/d6sc01203e","DOIUrl":"https://doi.org/10.1039/d6sc01203e","url":null,"abstract":"Folded RNA structures are increasingly being recognised as key regulators in biological processes, yet the RNA i-motif remains poorly characterised due to its low stability and lack of selective molecular probes. Here, we describe the first ligand – a short peptide – that binds the elusive RNA i-motif. Our minimalist peptide RGGFGGRGG is derived from the intrinsically disordered region of the protein Nucleolin and binds to folded RNA over DNA with >5-fold selectivity. The binding of two peptide molecules folds the RNA i-motif at a higher pH than under native conditions. This folded, peptide-bound structure can still bind other guests, such as the intercalator thiazole orange, displaying heteroallosteric properties. Our peptide binding is driven by more than simple electrostatic attraction, exploiting the subtle differences in steric complementarity and hydration of the compact RNA structures relative to DNA congeners and unfolded strands. Our findings underline the potential of minimalistic peptide scaffolds as selective binders for non-canonical RNA structures, allowing for the probing and modulation of RNA topologies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"36 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147454538","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}
Samantha Firth, William Earl, Denis Thaqi, YoungJin Hong, Charlotte O'Hern, Gemma Luscombe, Dalton Ngu, Zhenyao Luo, Chacko Jobichen, Bostjan Kobe, Alastair G McEwan, Karrera Djoko
Many bacteria use copper (Cu) to drive key redox reactions and energy metabolism, and they often rely on metallochaperones to deliver Cu to Cu-dependent enzymes. However, why trafficking by metallochaperones is needed, and why Cu cannot transfer directly from cellular sources to the target enzymes, is not well understood. Here, we show that the PCuAC-family metallochaperone AccA from the periplasm of Neisseria gonorrhoeae delivers Cu to the Cu-dependent nitrite reductase AniA, enabling growth and nitrite respiration in O2-limiting conditions. Although purified AccA binds both Cu(I) and Cu(II) ions, only the Cu(I)-binding site is essential for activating AniA in N. gonorrhoeae cells. Unexpectedly, the Cu(I)-binding affinity of AniA is >50 times weaker than that of AccA, suggesting that Cu delivery occurs against a favourable affinity gradient. We propose that AccA is needed because AniA cannot compete with the periplasmic milieu for binding Cu, providing a new principle to understand how bacteria control Cu trafficking.
{"title":"AccA from Neisseria gonorrhoeae provides a new framework for understanding periplasmic copper metallochaperones.","authors":"Samantha Firth, William Earl, Denis Thaqi, YoungJin Hong, Charlotte O'Hern, Gemma Luscombe, Dalton Ngu, Zhenyao Luo, Chacko Jobichen, Bostjan Kobe, Alastair G McEwan, Karrera Djoko","doi":"10.1039/d5sc08738d","DOIUrl":"https://doi.org/10.1039/d5sc08738d","url":null,"abstract":"Many bacteria use copper (Cu) to drive key redox reactions and energy metabolism, and they often rely on metallochaperones to deliver Cu to Cu-dependent enzymes. However, why trafficking by metallochaperones is needed, and why Cu cannot transfer directly from cellular sources to the target enzymes, is not well understood. Here, we show that the PCu<small><sub>A</sub></small>C-family metallochaperone AccA from the periplasm of <em>Neisseria gonorrhoeae </em>delivers Cu to the Cu-dependent nitrite reductase AniA, enabling growth and nitrite respiration in O<small><sub>2</sub></small>-limiting conditions. Although purified AccA binds both Cu(I) and Cu(II) ions, only the Cu(I)-binding site is essential for activating AniA in <em>N. gonorrhoeae </em>cells. Unexpectedly, the Cu(I)-binding affinity of AniA is >50 times weaker than that of AccA, suggesting that Cu delivery occurs against a favourable affinity gradient. We propose that AccA is needed because AniA cannot compete with the periplasmic milieu for binding Cu, providing a new principle to understand how bacteria control Cu trafficking.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"51 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461935","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}
Hydrogen production from sustainable seawater splitting technology is restricted by the side reactions of chlorine evolution and chlorine oxidation on anode. Different from the common catalyst design strategy, i.e., selecting materials repelling chloride ions, herein, we find that the strong adsorption of chloride ions on noble metal can be an advantage. We design a heterostructure catalyst consisting of atomically dispersed Ru doped IrOx nanocluster/a-Co(OH)2 nanosheet. This as-synthesized catalyst only requires an overpotential of 206 mV to drive 100 mA cm-2, and it can withstand continuous catalysis as long as 310 h under 500 mA cm-2. In situ spectroscopy and theoretical calculations show that Cl⁻ ion adsorption on IrOx clusters at low overpotentials promotes the phase transition of α-Co(OH)2 to CoOOH, lowering the OER barrier at the Ru site and resulting in a significantly reduced theoretical overpotential of 200 mV for Ru-IrOx-Cl/CoOOH. Our work demonstrates a catalyst with Cl- adsorption-promoted OER activity, in contrast to the traditional Cl- repelling catalyst design strategy for seawater splitting.
可持续海水裂解制氢技术受阳极氯析出和氯氧化副反应的制约。不同于通常的催化剂设计策略，即选择排斥氯离子的材料，在这里，我们发现氯离子对贵金属的强吸附可以是一个优势。我们设计了一种由原子分散的Ru掺杂IrOx纳米簇/a- co (OH)2纳米片组成的异质结构催化剂。这种合成的催化剂只需要206 mV的过电位就可以驱动100 mA cm-2，并且在500 mA cm-2下可以承受长达310 h的连续催化。原位光谱和理论计算表明，低过电位下Cl - ion在IrOx簇上的吸附促进了α-Co(OH)2向CoOOH的相变，降低了Ru位点的OER势垒，使Ru-IrOx-Cl/CoOOH的理论过电位显著降低200 mV。我们的工作展示了一种具有Cl-吸附促进OER活性的催化剂，与传统的海水分裂Cl-排斥催化剂设计策略形成对比。
{"title":"Chloride-Induced Easier Phase Transformation and Catalytic Synergy for Enhanced Seawater Splitting","authors":"Haibin Ma, Yuxiang Jin, Xiaoyan Zhou, Yujie Cui, Yang Zhao, Chia-Yu Chang, Min-Hsin Yeh, Wei-Hsiang Huang, Erhong Song, Jiwei Ma, Hongfei Cheng","doi":"10.1039/d5sc09403h","DOIUrl":"https://doi.org/10.1039/d5sc09403h","url":null,"abstract":"Hydrogen production from sustainable seawater splitting technology is restricted by the side reactions of chlorine evolution and chlorine oxidation on anode. Different from the common catalyst design strategy, i.e., selecting materials repelling chloride ions, herein, we find that the strong adsorption of chloride ions on noble metal can be an advantage. We design a heterostructure catalyst consisting of atomically dispersed Ru doped IrO<small><sub>x</sub></small> nanocluster/a-Co(OH)<small><sub>2</sub></small> nanosheet. This as-synthesized catalyst only requires an overpotential of 206 mV to drive 100 mA cm<small><sup>-2</sup></small>, and it can withstand continuous catalysis as long as 310 h under 500 mA cm<small><sup>-2</sup></small>. In situ spectroscopy and theoretical calculations show that Cl⁻ ion adsorption on IrO<small><sub>x</sub></small> clusters at low overpotentials promotes the phase transition of α-Co(OH)<small><sub>2</sub></small> to CoOOH, lowering the OER barrier at the Ru site and resulting in a significantly reduced theoretical overpotential of 200 mV for Ru-IrO<small><sub>x</sub></small>-Cl/CoOOH. Our work demonstrates a catalyst with Cl<small><sup>-</sup></small> adsorption-promoted OER activity, in contrast to the traditional Cl<small><sup>-</sup></small> repelling catalyst design strategy for seawater splitting.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"55 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393700","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}
Mingyue Wang, Yue Wang, Na Li, Qing Zhong, Min Zhu, Dongyang Zhang, Shujiang Ding
The high-value recycling of spent lithium-ion battery separators and the rational design of hard carbon anodes are critical for sustainable sodium-ion batteries. Herein, a sulfonation-induced crosslinking strategy is proposed to regulate the carbonization behavior of recycled polypropylene (PP) separators, enabling their direct conversion into structure-tailored hard carbon via a one-step carbonization process. Sulfonation not only introduces sulfonic functionalities but, more importantly, induces intermolecular crosslinking, which suppresses severe chain scission and volatilization during thermal treatment and transforms the decomposition pathway into a solid-state carbonization process. As a result, the structure-tailored HC is constructed by chemically regulating the carbonization behavior of recycled PP separators, enabling efficient sodium storage with clarified structure–sodium storage correlations. When applied as anodes for SIBs, the PP-derived HC exhibits high reversible capacity of 293.0 mAh g-1 at 0.2 C and superior rate capability of 77.1 mAh g-1 at 10 C. For long-term cyclic performance, the capacity maintained at 222.7 mAh g-1 after 1000 cycles at 1 C with a capacity retention of 89.1%. When coupled with Na3V2(PO4)3 cathode, the full cell can deliver a capacity of 83.0 mAh g-1 after 200 cycles with 80.1% retention. This work demonstrates that chemical regulation of the carbonization pathway provides an effective route for both high-value separator recycling and structure-oriented hard carbon design for sodium-ion batteries.
废锂离子电池隔膜的高价值回收和硬碳阳极的合理设计是钠离子电池可持续发展的关键。本文提出了一种磺化诱导交联策略来调节再生聚丙烯（PP）分离器的炭化行为，使其通过一步炭化过程直接转化为结构定制的硬碳。磺化不仅引入了磺化官能团，更重要的是诱导了分子间交联，抑制了热处理过程中严重的断链和挥发，将分解途径转变为固态碳化过程。因此，结构定制的HC是通过化学调节再生PP分离器的碳化行为来构建的，通过明确的结构-钠存储关系，实现了高效的钠存储。当应用于sib阳极时，pp衍生的HC在0.2 C时具有293.0 mAh g-1的高可逆容量，在10 C时具有77.1 mAh g-1的优越倍率容量。对于长期循环性能，在1 C下循环1000次后容量保持在222.7 mAh g-1，容量保持率为89.1%。当与Na3V2(PO4)3阴极耦合时，完整电池在200次循环后可以提供83.0 mAh g-1的容量，保留率为80.1%。这项工作表明，化学调控碳化途径为高价值分离器回收和钠离子电池结构导向硬碳设计提供了有效途径。
{"title":"Chemical Regulation of Carbonization Enables Structure-Tailored Hard Carbon Anodes from Recycled Polypropylene Separators","authors":"Mingyue Wang, Yue Wang, Na Li, Qing Zhong, Min Zhu, Dongyang Zhang, Shujiang Ding","doi":"10.1039/d6sc00807k","DOIUrl":"https://doi.org/10.1039/d6sc00807k","url":null,"abstract":"The high-value recycling of spent lithium-ion battery separators and the rational design of hard carbon anodes are critical for sustainable sodium-ion batteries. Herein, a sulfonation-induced crosslinking strategy is proposed to regulate the carbonization behavior of recycled polypropylene (PP) separators, enabling their direct conversion into structure-tailored hard carbon via a one-step carbonization process. Sulfonation not only introduces sulfonic functionalities but, more importantly, induces intermolecular crosslinking, which suppresses severe chain scission and volatilization during thermal treatment and transforms the decomposition pathway into a solid-state carbonization process. As a result, the structure-tailored HC is constructed by chemically regulating the carbonization behavior of recycled PP separators, enabling efficient sodium storage with clarified structure–sodium storage correlations. When applied as anodes for SIBs, the PP-derived HC exhibits high reversible capacity of 293.0 mAh g-1 at 0.2 C and superior rate capability of 77.1 mAh g-1 at 10 C. For long-term cyclic performance, the capacity maintained at 222.7 mAh g-1 after 1000 cycles at 1 C with a capacity retention of 89.1%. When coupled with Na3V2(PO4)3 cathode, the full cell can deliver a capacity of 83.0 mAh g-1 after 200 cycles with 80.1% retention. This work demonstrates that chemical regulation of the carbonization pathway provides an effective route for both high-value separator recycling and structure-oriented hard carbon design for sodium-ion batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"78 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147384003","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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