Lian Chen, Fan Li, Kaiyang Liu, Feng Wang, Zhengshuai Bai, Yanyan Zhang, Yuxin Tang
Hard carbon is recognized as a promising anode material for sodium-ion batteries, but its practical application is constrained by low initial Coulombic efficiency (ICE), insufficient reversible capacity, and poor rate performance, which are rooted in inadequate pseudo-graphitic domains structure and uncontrolled sodium cluster formation. Herein, we propose a nanoconfinement strategy via graphene orientation-guided graphitization to achieve high-rate performance of cellulose-derived hard carbon. The oxygen-functional groups of graphene form stable cross-linking structure with cellulose to suppress disordered defects, while the sp2-hybridized carbon skeleton guides directional arrangement of carbon layers, synergistically constructing confined structure with abundant pseudo-graphitic domains and size-tunable closed pores. Benefiting from this optimized structure, the resultant electrode achieves a high specific capacity of 323.9 mAh g-1, an ICE of 89.9%, and excellent rate performance (226.8 mAh g-1 at 3.0 A g-1). More importantly, the sodium metal clusters are for the first time observed via nanoconfinement induction with the filling stage achieving their controllable densification by enhancing micropore confinement. This further validates and reinforces the new adsorption-intercalation-pore filling mechanism for sodium clusters densification. This work highlights nanoconfinement induction for high-rate hard carbon anodes, promoting the application of sodium-ion batteries in large-scale energy storage systems
硬碳是一种很有前途的钠离子电池负极材料，但其实际应用受到初始库仑效率（ICE）低、可逆容量不足和速率性能差的限制，其根源在于伪石墨畴结构不充分和钠簇形成不受控制。在此，我们提出了一种通过石墨烯取向引导石墨化的纳米限制策略，以实现纤维素衍生硬碳的高速率性能。石墨烯的氧官能团与纤维素形成稳定的交联结构，抑制无序缺陷，而sp2杂化碳骨架引导碳层的定向排列，协同构建具有丰富伪石墨畴和大小可调闭孔的封闭结构。得益于这种优化的结构，所得电极获得了323.9 mAh g-1的高比容量，89.9%的ICE，以及出色的倍率性能（3.0 a g-1时226.8 mAh g-1）。更重要的是，首次通过纳米约束诱导观察到金属钠簇，填充阶段通过增强微孔约束实现了其可控致密化。这进一步验证和强化了钠团簇致密化的吸附-插层-孔隙填充新机制。本工作强调了高速率硬碳阳极的纳米约束感应，促进了钠离子电池在大规模储能系统中的应用
{"title":"Nanoconfinement-induced high-rate performance of hard carbon for densified sodium clusters storage","authors":"Lian Chen, Fan Li, Kaiyang Liu, Feng Wang, Zhengshuai Bai, Yanyan Zhang, Yuxin Tang","doi":"10.1039/d5sc09998f","DOIUrl":"https://doi.org/10.1039/d5sc09998f","url":null,"abstract":"Hard carbon is recognized as a promising anode material for sodium-ion batteries, but its practical application is constrained by low initial Coulombic efficiency (ICE), insufficient reversible capacity, and poor rate performance, which are rooted in inadequate pseudo-graphitic domains structure and uncontrolled sodium cluster formation. Herein, we propose a nanoconfinement strategy via graphene orientation-guided graphitization to achieve high-rate performance of cellulose-derived hard carbon. The oxygen-functional groups of graphene form stable cross-linking structure with cellulose to suppress disordered defects, while the sp2-hybridized carbon skeleton guides directional arrangement of carbon layers, synergistically constructing confined structure with abundant pseudo-graphitic domains and size-tunable closed pores. Benefiting from this optimized structure, the resultant electrode achieves a high specific capacity of 323.9 mAh g-1, an ICE of 89.9%, and excellent rate performance (226.8 mAh g-1 at 3.0 A g-1). More importantly, the sodium metal clusters are for the first time observed via nanoconfinement induction with the filling stage achieving their controllable densification by enhancing micropore confinement. This further validates and reinforces the new adsorption-intercalation-pore filling mechanism for sodium clusters densification. This work highlights nanoconfinement induction for high-rate hard carbon anodes, promoting the application of sodium-ion batteries in large-scale energy storage systems","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"55 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962354","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}
shanchao wu, Zhihui Zhang, Zilong Zhao, Cheng Cui, Weihong Tan
Nucleic acid therapeutics are rapidly emerging as a transformative drug paradigm, offering precise and programmable regulation of gene expression across a broad spectrum of diseases. This review summarizes recent advances in key platforms—including antisense oligonucleotides, siRNA, miRNA, mRNA, and aptamers—emphasizing their unique mechanisms of action and therapeutic potential. We systematically outline critical contributions of chemical modification and delivery engineering, including backbone and sugar modifications, site-specific design, N-acetylgalactosamine (GalNAc) conjugation, and lipid nanoparticles, which collectively enhance stability, target specificity, and clinical applicability. Finally, we discuss persistent challenges such as immune activation, large-scale manufacturing, and long-term safety, and provide perspectives on future directions involving CRISPR-based gene editing, synthetic biology, nanotechnology, smart delivery systems, and combination therapies, aiming to offer strategic insights for the development and clinical translation of nucleic acid drugs.
{"title":"Navigating the Next Frontier in Biomedicine: Breakthroughs and Insights in Nucleic Acid Therapeutics","authors":"shanchao wu, Zhihui Zhang, Zilong Zhao, Cheng Cui, Weihong Tan","doi":"10.1039/d5sc06966a","DOIUrl":"https://doi.org/10.1039/d5sc06966a","url":null,"abstract":"Nucleic acid therapeutics are rapidly emerging as a transformative drug paradigm, offering precise and programmable regulation of gene expression across a broad spectrum of diseases. This review summarizes recent advances in key platforms—including antisense oligonucleotides, siRNA, miRNA, mRNA, and aptamers—emphasizing their unique mechanisms of action and therapeutic potential. We systematically outline critical contributions of chemical modification and delivery engineering, including backbone and sugar modifications, site-specific design, N-acetylgalactosamine (GalNAc) conjugation, and lipid nanoparticles, which collectively enhance stability, target specificity, and clinical applicability. Finally, we discuss persistent challenges such as immune activation, large-scale manufacturing, and long-term safety, and provide perspectives on future directions involving CRISPR-based gene editing, synthetic biology, nanotechnology, smart delivery systems, and combination therapies, aiming to offer strategic insights for the development and clinical translation of nucleic acid drugs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955805","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}
Fang Chen, Jun He, Attia Shaheen, Yi Hu, Shern-Long Lee
Significant research in materials chemistry has focused on the design and fabrication of organic materials and their self-assembled architectures for a wide range of applications, such as organic transistors, photovoltaic cells, and surface functionalization, to name just a few. For binary supramolecular systems, however, the increased complexity that involves hetero-molecular interactions often leads to challenges, for instance, undesired phase segregation. Using scanning tunnelling microscopy (STM), we show that thermal activation (from 25 °C to 60 °C) can drive a transition from phase separation to thermodynamically stable co-crystallization for a host–guest system comprising trimesic acid and a tetrathiafulvalene derivative. Our STM data revealed that the co-crystals varied from the chicken-wire type to a flower type as a function of annealing temperature (from 60 °C up to 80 °C). Their molecular interactions and adsorption energy and thus the corresponding stability constitute the energy landscape, which is derived from force-field simulations. This transformation could be governed by the modulation of molecule–substrate interactions, intermolecular bonding, and hetero-molecular attractions, offering a thermally tuneable route toward supramolecular co-assemblies.
{"title":"Thermal-mediated modulation of binary supramolecular self-assembly from phase separation to co-crystallization at the liquid–solid surface","authors":"Fang Chen, Jun He, Attia Shaheen, Yi Hu, Shern-Long Lee","doi":"10.1039/d5sc06698k","DOIUrl":"https://doi.org/10.1039/d5sc06698k","url":null,"abstract":"Significant research in materials chemistry has focused on the design and fabrication of organic materials and their self-assembled architectures for a wide range of applications, such as organic transistors, photovoltaic cells, and surface functionalization, to name just a few. For binary supramolecular systems, however, the increased complexity that involves hetero-molecular interactions often leads to challenges, for instance, undesired phase segregation. Using scanning tunnelling microscopy (STM), we show that thermal activation (from 25 °C to 60 °C) can drive a transition from phase separation to thermodynamically stable co-crystallization for a host–guest system comprising trimesic acid and a tetrathiafulvalene derivative. Our STM data revealed that the co-crystals varied from the chicken-wire type to a flower type as a function of annealing temperature (from 60 °C up to 80 °C). Their molecular interactions and adsorption energy and thus the corresponding stability constitute the energy landscape, which is derived from force-field simulations. This transformation could be governed by the modulation of molecule–substrate interactions, intermolecular bonding, and hetero-molecular attractions, offering a thermally tuneable route toward supramolecular co-assemblies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"385 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955818","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}
Xi Zhang, Shan Zhao, Chen Zhou, Guo Chen, Liru Cao, Jian Lin, Chen Tang, Zhi-Yan Liu, Piao He, Xiao-Yi Yi
A series of ruthenium(II)-cymene complexes [(η6-p-cymene)Ru(pp)Cl] (1 - 4) and corresponding NH3-ligated complexes [(η6-p-cymene)Ru(pp)(NH3)]PF6 ([1-NH3]PF6 - [4-NH3]PF6), where cymene = 4-isopropyltoluene, pp- = pyridylpyrrole ligand, have been designed and synthesized. The structural modifications of pp- ligands are accomplished through the attributions of an increasing number of electron-donating methyl group on pyrrole unit. The solid-state structural analysis show that these complexes have a typical piano-stool structure. The electrochemical studies of these complexes illustrate that introduction of methyl group at the pp- ligand can greatly decrease oxidation potential of RuIII/II from 0.49 V vs. Cp2Fe+/0 for [1-NH3]PF6 to 0.16 V vs. Cp2Fe+/0 for [4-NH3]PF6. The controlled potential coulometry experiments displays these complexes have selective catalysis for oxidation of NH3 to N2H4 with turnover number up to 453.2 at Eapp 0.8 V vs. Cp2Fe+/0 for [4-NH3]PF6 complex. The kinetical and calculated thermodynamical studies show that bimolecular coupling of RuII-aminyl pathway and ammonia nucleophilic attack of RuIV-imide (generated from disproportionation of RuIII-amide) pathway are involved in N-N formation.
{"title":"Selective NH3-to-N2H4 Conversion Electrocatalysed by Ruthenium(II)-Cymene Complexes","authors":"Xi Zhang, Shan Zhao, Chen Zhou, Guo Chen, Liru Cao, Jian Lin, Chen Tang, Zhi-Yan Liu, Piao He, Xiao-Yi Yi","doi":"10.1039/d5sc08826g","DOIUrl":"https://doi.org/10.1039/d5sc08826g","url":null,"abstract":"A series of ruthenium(II)-cymene complexes [(η<small><sup>6</sup></small>-p-cymene)Ru(pp)Cl] (<strong>1 </strong>- <strong>4</strong>) and corresponding NH<small><sub>3</sub></small>-ligated complexes [(η<small><sup>6</sup></small>-p-cymene)Ru(pp)(NH<small><sub>3</sub></small>)]PF<small><sub>6</sub></small> ([<strong>1-NH<small><sub>3</sub></small></strong>]PF<small><sub>6</sub></small> - [<strong>4-NH<small><sub>3</sub></small></strong>]PF<small><sub>6</sub></small>), where cymene = 4-isopropyltoluene, pp<small><sup>-</sup></small> = pyridylpyrrole ligand, have been designed and synthesized. The structural modifications of pp<small><sup>-</sup></small> ligands are accomplished through the attributions of an increasing number of electron-donating methyl group on pyrrole unit. The solid-state structural analysis show that these complexes have a typical piano-stool structure. The electrochemical studies of these complexes illustrate that introduction of methyl group at the pp<small><sup>-</sup></small> ligand can greatly decrease oxidation potential of Ru<small><sup>III/II</sup></small> from 0.49 V vs. Cp<small><sub>2</sub></small>Fe<small><sup>+/0</sup></small> for [<strong>1-NH<small><sub>3</sub></small></strong>]PF<small><sub>6</sub></small> to 0.16 V vs. Cp<small><sub>2</sub></small>Fe<small><sup>+/0</sup></small> for [<strong>4-NH<small><sub>3</sub></small></strong>]PF<small><sub>6</sub></small>. The controlled potential coulometry experiments displays these complexes have selective catalysis for oxidation of NH<small><sub>3</sub></small> to N<small><sub>2</sub></small>H<small><sub>4</sub></small> with turnover number up to 453.2 at E<small><sub>app</sub></small> 0.8 V vs. Cp<small><sub>2</sub></small>Fe<small><sup>+/0</sup></small> for [<strong>4-NH<small><sub>3</sub></small></strong>]PF<small><sub>6</sub></small> complex. The kinetical and calculated thermodynamical studies show that bimolecular coupling of Ru<small><sup>II</sup></small>-aminyl pathway and ammonia nucleophilic attack of Ru<small><sup>IV</sup></small>-imide (generated from disproportionation of Ru<small><sup>III</sup></small>-amide) pathway are involved in N-N formation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972456","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}
Breaking the trade-off between stability and switching functionality remains a pivotal challenge in substrate-supported molecular switches. Herein, we propose a design strategy using A3B-type intermetallic alloys as substrates to realize a hybrid-bonding precursor state that concurrently achieves robust interfacial stability and enhanced current-switching ratios. We demonstrate that this bistability can be directly predicted from the atomic covalent radius and d-band centers of surface metals. Remarkably, we uncover a distinctive V-shaped relationship between the d-band center of host metal and valence electron number of the guest metal, governed by the occupancy of d-d anti-bonding states. Furthermore, we elucidate the essential role of geometric and quantum primogenic effects in modulating d-d orbital interactions, resolving longstanding controversies regarding d-band modulation mechanisms for alloys. By incorporating intrinsic parameters, including valence electron number, atomic radius, and orbital radius of guest metals, we develop a generalizable descriptor for accurately predicting the d-band center of host metals (R2 > 0.90). This work not only accelerates the exploration of robust room-temperature molecular switches, but also establishes a rational design framework for high-performance intermetallic substrates with optimal adsorption properties, thereby significantly reducing reliance on costly density functional theory calculations.
{"title":"A Predictive Descriptor for d-Band Center in Intermetallic Alloys Accelerates the Design of Robust Molecular Switches","authors":"Sha Yang, Junjun Zhou, Yirong Zhang, Guolin Cao, Ji-Chang Ren, Wei Liu","doi":"10.1039/d5sc08297h","DOIUrl":"https://doi.org/10.1039/d5sc08297h","url":null,"abstract":"Breaking the trade-off between stability and switching functionality remains a pivotal challenge in substrate-supported molecular switches. Herein, we propose a design strategy using A<small><sub>3</sub></small>B-type intermetallic alloys as substrates to realize a hybrid-bonding precursor state that concurrently achieves robust interfacial stability and enhanced current-switching ratios. We demonstrate that this bistability can be directly predicted from the atomic covalent radius and d-band centers of surface metals. Remarkably, we uncover a distinctive V-shaped relationship between the d-band center of host metal and valence electron number of the guest metal, governed by the occupancy of d-d anti-bonding states. Furthermore, we elucidate the essential role of geometric and quantum primogenic effects in modulating d-d orbital interactions, resolving longstanding controversies regarding d-band modulation mechanisms for alloys. By incorporating intrinsic parameters, including valence electron number, atomic radius, and orbital radius of guest metals, we develop a generalizable descriptor for accurately predicting the d-band center of host metals (R<small><sup>2</sup></small> > 0.90). This work not only accelerates the exploration of robust room-temperature molecular switches, but also establishes a rational design framework for high-performance intermetallic substrates with optimal adsorption properties, thereby significantly reducing reliance on costly density functional theory calculations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955819","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 presence of trace amounts of impurities can have unprecedented effects on the luminescence features of organic room temperature phosphorescent (ORTP) materials, requiring conscientious investigation. In this study, we have compared the photoluminescence properties of biphenyl-4-carboxylic acid (BCA) and biphenyl-4,4′-dicarboxylic acid (BDCA), synthesized via two distinct synthetic routes-Friedel-Crafts (FC-BCA or FC-BDCA) and cross-coupling (cc-BCA or cc-BDCA) pathways and observed remarkable orange phosphorescence in FC-BCA or FC-BDCA which were absent in cc-BCA or cc-BDCA. Our investigations identified traces (<0.3 mol%) of diphenylbenzil based impurities, formed as byproducts during Friedel-Crafts acylation of biphenyl, responsible for the RTP activation in FC-BCA or FC-BDCA. Bicomponent solids prepared by deliberately doping traces of DPB into various organic matrices ensued tunable RTP color (green to red) with high quantum yield (26.4 %) and lifetime up to 1.6 ms. Comprehensive experimental investigations substantiated with theoretical studies revealed that photoexcited conformational dynamics of guest DPB are responsible for RTP color variation concertedly involving multiple energy transfer channels, e.g., singlet-to-singlet (SSET), triplet-to-triplet (TTET). It presents a novel trace doping strategy for developing RTP materials with tunable optical features by synergistically controlling the ground and excited state geometries of a single guest molecule, which is rarely reported in the literature. Furthermore, by employing a suitable host matrix, we successfully stabilized a linear conformer of guest DPB in the ground state, which is otherwise unstable, resulted in improved quantum yield. Simultaneously, we report an unusual RTP from commercial BDCA, which we suspect to be caused by the presence of diphenylbenzil-based impurities, reiteratively emphasizing the importance of exercising caution whenever a system exhibits unusual properties.
{"title":"'Impurity'-driven Tunable Organic Room Temperature Phosphorescence via Conformational Regulation in Multi Host/Guest Systems","authors":"Arnab Dutta, Utkarsh Singh, Swapan Pati, Uday Maitra","doi":"10.1039/d5sc08129g","DOIUrl":"https://doi.org/10.1039/d5sc08129g","url":null,"abstract":"The presence of trace amounts of impurities can have unprecedented effects on the luminescence features of organic room temperature phosphorescent (ORTP) materials, requiring conscientious investigation. In this study, we have compared the photoluminescence properties of biphenyl-4-carboxylic acid (BCA) and biphenyl-4,4′-dicarboxylic acid (BDCA), synthesized via two distinct synthetic routes-Friedel-Crafts (FC-BCA or FC-BDCA) and cross-coupling (cc-BCA or cc-BDCA) pathways and observed remarkable orange phosphorescence in FC-BCA or FC-BDCA which were absent in cc-BCA or cc-BDCA. Our investigations identified traces (<0.3 mol%) of diphenylbenzil based impurities, formed as byproducts during Friedel-Crafts acylation of biphenyl, responsible for the RTP activation in FC-BCA or FC-BDCA. Bicomponent solids prepared by deliberately doping traces of DPB into various organic matrices ensued tunable RTP color (green to red) with high quantum yield (26.4 %) and lifetime up to 1.6 ms. Comprehensive experimental investigations substantiated with theoretical studies revealed that photoexcited conformational dynamics of guest DPB are responsible for RTP color variation concertedly involving multiple energy transfer channels, e.g., singlet-to-singlet (SSET), triplet-to-triplet (TTET). It presents a novel trace doping strategy for developing RTP materials with tunable optical features by synergistically controlling the ground and excited state geometries of a single guest molecule, which is rarely reported in the literature. Furthermore, by employing a suitable host matrix, we successfully stabilized a linear conformer of guest DPB in the ground state, which is otherwise unstable, resulted in improved quantum yield. Simultaneously, we report an unusual RTP from commercial BDCA, which we suspect to be caused by the presence of diphenylbenzil-based impurities, reiteratively emphasizing the importance of exercising caution whenever a system exhibits unusual properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955820","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}
Hyun Wook Choi, Deniz Kahraman, Wei-Jia Chen, Lai-Sheng Wang
Understanding the boron-coinage-metal interactions is critical for understanding the nucleation and growth mechanisms of borophene on coinage-metal substrates. Binary metal-boron clusters provide ideal models for obtaining atomic-level information about the metal-boron interactions. Here we report an investigation of the structure and bonding of the AgB8− cluster as a model system to gain insight into the interaction of boron with silver, the most inert substrate to grow borophene. Photoelectron spectroscopy reveals that the spectra of AgB8− resemble those of bare B8−, suggesting extremely weak chemical interactions between Ag and boron. Quantum calculations show that AgB8− (Cs, 1A′) consists of a B8 borozene weakly interacting with a Ag atom on its edge. Chemical bonding analyses find that the Ag atom interacts with the B8 motif primarily through its 5s orbital with little perturbation to the structure and bonding of the B8 borozene. Compared to CuB8− and AuB8−, Ag is found to have the weakest interaction with the B8 motif, consistent with that fact that silver substrates are the most inert for borophene syntheses.
{"title":"Probing the Weak Interaction between Silver and Boron","authors":"Hyun Wook Choi, Deniz Kahraman, Wei-Jia Chen, Lai-Sheng Wang","doi":"10.1039/d5sc08598e","DOIUrl":"https://doi.org/10.1039/d5sc08598e","url":null,"abstract":"Understanding the boron-coinage-metal interactions is critical for understanding the nucleation and growth mechanisms of borophene on coinage-metal substrates. Binary metal-boron clusters provide ideal models for obtaining atomic-level information about the metal-boron interactions. Here we report an investigation of the structure and bonding of the AgB<small><sub>8</sub></small><small><sup>−</sup></small> cluster as a model system to gain insight into the interaction of boron with silver, the most inert substrate to grow borophene. Photoelectron spectroscopy reveals that the spectra of AgB<small><sub>8</sub></small><small><sup>−</sup></small> resemble those of bare B<small><sub>8</sub></small><small><sup>−</sup></small>, suggesting extremely weak chemical interactions between Ag and boron. Quantum calculations show that AgB<small><sub>8</sub></small><small><sup>−</sup></small> (<em>C<small><sub>s</sub></small></em>, <small><sup>1</sup></small>A′) consists of a B<small><sub>8</sub></small> borozene weakly interacting with a Ag atom on its edge. Chemical bonding analyses find that the Ag atom interacts with the B<small><sub>8</sub></small> motif primarily through its 5<em>s</em> orbital with little perturbation to the structure and bonding of the B<small><sub>8</sub></small> borozene. Compared to CuB<small><sub>8</sub></small><small><sup>−</sup></small> and AuB<small><sub>8</sub></small><small><sup>−</sup></small>, Ag is found to have the weakest interaction with the B<small><sub>8</sub></small> motif, consistent with that fact that silver substrates are the most inert for borophene syntheses.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993358","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}
Garnet-type solid-state electrolytes (SSEs) are promising candidates for next-generation solid-state batteries (SSBs) owing to their high ionic conductivity, robust mechanical strength, and broad electrochemical stability window. However, exposure to ambient air results in the formation of a Li2CO3 passivation layer on the surface, significantly reducing ionic conductivity and deteriorating interfacial wettability, thereby severely impairing the electrochemical performance of SSBs. This review systematically analyzes the formation mechanisms and influencing factors of Li2CO3 contamination on garnet-type SSE surfaces. It summarizes recent strategies for suppressing Li2CO3 formation, including sintering process optimization, elemental doping, and grain boundary/interface engineering. Among these approaches, interfacial treatments have attracted considerable attention owing to their cost-effectiveness and operational efficiency. This review focuses on categorizing diverse treatment strategies for improving electrode/electrolyte interfacial contact, including physical cleaning, chemical treatment and conversion, and the modification with interfacial interlayers—specifically detailing types such as inorganic, organic, and organic-inorganic composite interlayers. Finally, the future prospects of garnet-type SSEs in high-performance SSBs are discussed, pointing out the need for in-depth research into the formation and evolution mechanisms of Li2CO3 and the development of more efficient interface control strategies. This review systematically examines interfacial challenges in garnet-type SSEs, with the ultimate goal of facilitating the development of stable all-solid-state lithium metal batteries and accelerating their commercialization.
{"title":"Mitigation strategies for Li2CO3 contamination in garnet-type solid-state electrolytes: Formation mechanisms and interfacial engineering","authors":"Bin Hao, Qiushi Wang, Fangyuan Zhao, Jialong Wu, Weiheng Chen, Zhong-Jie Jiang, Zhongqing Jiang","doi":"10.1039/d5sc09699e","DOIUrl":"https://doi.org/10.1039/d5sc09699e","url":null,"abstract":"Garnet-type solid-state electrolytes (SSEs) are promising candidates for next-generation solid-state batteries (SSBs) owing to their high ionic conductivity, robust mechanical strength, and broad electrochemical stability window. However, exposure to ambient air results in the formation of a Li2CO3 passivation layer on the surface, significantly reducing ionic conductivity and deteriorating interfacial wettability, thereby severely impairing the electrochemical performance of SSBs. This review systematically analyzes the formation mechanisms and influencing factors of Li2CO3 contamination on garnet-type SSE surfaces. It summarizes recent strategies for suppressing Li2CO3 formation, including sintering process optimization, elemental doping, and grain boundary/interface engineering. Among these approaches, interfacial treatments have attracted considerable attention owing to their cost-effectiveness and operational efficiency. This review focuses on categorizing diverse treatment strategies for improving electrode/electrolyte interfacial contact, including physical cleaning, chemical treatment and conversion, and the modification with interfacial interlayers—specifically detailing types such as inorganic, organic, and organic-inorganic composite interlayers. Finally, the future prospects of garnet-type SSEs in high-performance SSBs are discussed, pointing out the need for in-depth research into the formation and evolution mechanisms of Li2CO3 and the development of more efficient interface control strategies. This review systematically examines interfacial challenges in garnet-type SSEs, with the ultimate goal of facilitating the development of stable all-solid-state lithium metal batteries and accelerating their commercialization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968941","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}
Mitochondrial DNA (mtDNA) mutations play critical roles in tumor progression and metabolic reprogramming. Controllable gene editing within tumor cell mitochondria remains a challenge due to the double-membrane barrier and the lack of tumor-selective activation. Herein, we report a dual-responsive CRISPR/Cas delivery platform (UCRP-TPP) that enables spatiotemporally regulated mtDNA editing for targeted tumor therapy. This nanoplatform integrates near infrared light-responsive upconversion nanoparticle (UCNP), an apurinic endonuclease 1 (APE-1)-responsive DNA complex, and a mitochondrial-targeting ligand (TPP), ensuring selective activation and mitochondrial release of Cas9/sgRNA complexes. Upon activation by endogenous APE-1 enzyme and exogenous NIR light, UCRP-TPP induces mtDNA editing by CRISPR/Cas, which leads to mtDNA copy number reduction, mitochondrial membrane depolarization, reactive oxygen species generation, and tumor cell apoptosis. In vivo studies further confirm the robust antitumor efficacy of UCRP-TPP-based nanoplatform. This work presents a versatile and controllable mitochondrial gene-editing strategy.
{"title":"Spatiotemporally Regulated Mitochondrial Genome Editing via Enzyme and NIR-Activated CRISPR/Cas9 nanoplatform","authors":"Fei Yang, Qianqin Ran, Jiahui Chen, Guochen Bao, Yuezhong Xian, Cuiling Zhang","doi":"10.1039/d5sc07976d","DOIUrl":"https://doi.org/10.1039/d5sc07976d","url":null,"abstract":"Mitochondrial DNA (mtDNA) mutations play critical roles in tumor progression and metabolic reprogramming. Controllable gene editing within tumor cell mitochondria remains a challenge due to the double-membrane barrier and the lack of tumor-selective activation. Herein, we report a dual-responsive CRISPR/Cas delivery platform (UCRP-TPP) that enables spatiotemporally regulated mtDNA editing for targeted tumor therapy. This nanoplatform integrates near infrared light-responsive upconversion nanoparticle (UCNP), an apurinic endonuclease 1 (APE-1)-responsive DNA complex, and a mitochondrial-targeting ligand (TPP), ensuring selective activation and mitochondrial release of Cas9/sgRNA complexes. Upon activation by endogenous APE-1 enzyme and exogenous NIR light, UCRP-TPP induces mtDNA editing by CRISPR/Cas, which leads to mtDNA copy number reduction, mitochondrial membrane depolarization, reactive oxygen species generation, and tumor cell apoptosis. In vivo studies further confirm the robust antitumor efficacy of UCRP-TPP-based nanoplatform. This work presents a versatile and controllable mitochondrial gene-editing strategy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"218 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962208","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}
Cheng-Zhuo Du, Minqiang Mai, Pei-Han Gao, Yi-Chao Zhao, Xiang-Yu Gao, Dongdong Zhang, Lian Duan, Chunming Cui, Xiao-Ye Wang
Multi-resonance (MR) materials based on 1,4-BN-heteroarenes have attracted extensive attention in recent years for narrowband electroluminescence. Extending the π-conjugation of MR skeletons is a widely adopted strategy to regulate their emission colors, but it inevitably induces structural distortion and undesirable vibronic couplings, thus broadening the emission bandwidth. Herein, we design and synthesize new MR emitters via π-extension of a classic MR backbone (CzBN) and disclose how the twisted structure plays a positive role in reducing emission bandwidth. Specifically, π-extension of CzBN to form a [5]helicene substructure (BN-5H) induces serious vibrations, while further extending the helicene moiety to build a [7]helicene substructure (BN-7H) suppresses undesirable vibrations by locking the conformation. As a consequence, BN-7H achieves a smaller full-width at half-maximum (FWHM) of 28 nm compared with BN-5H (33 nm) in organic lightemitting diodes with longer device lifetime. These results break the traditional cognition of the detrimental effect of highly twisted structure on narrowband emission and offer a new design concept for the future development of narrowband electroluminescence materials.
{"title":"Unraveling the Positive Effect of Twisted Helicene Structure on Narrowband Electroluminescence","authors":"Cheng-Zhuo Du, Minqiang Mai, Pei-Han Gao, Yi-Chao Zhao, Xiang-Yu Gao, Dongdong Zhang, Lian Duan, Chunming Cui, Xiao-Ye Wang","doi":"10.1039/d5sc08405a","DOIUrl":"https://doi.org/10.1039/d5sc08405a","url":null,"abstract":"Multi-resonance (MR) materials based on 1,4-BN-heteroarenes have attracted extensive attention in recent years for narrowband electroluminescence. Extending the π-conjugation of MR skeletons is a widely adopted strategy to regulate their emission colors, but it inevitably induces structural distortion and undesirable vibronic couplings, thus broadening the emission bandwidth. Herein, we design and synthesize new MR emitters via π-extension of a classic MR backbone (CzBN) and disclose how the twisted structure plays a positive role in reducing emission bandwidth. Specifically, π-extension of CzBN to form a [5]helicene substructure (BN-5H) induces serious vibrations, while further extending the helicene moiety to build a [7]helicene substructure (BN-7H) suppresses undesirable vibrations by locking the conformation. As a consequence, BN-7H achieves a smaller full-width at half-maximum (FWHM) of 28 nm compared with BN-5H (33 nm) in organic lightemitting diodes with longer device lifetime. These results break the traditional cognition of the detrimental effect of highly twisted structure on narrowband emission and offer a new design concept for the future development of narrowband electroluminescence materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962356","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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