J. Conor Townsley, Connor Smith, David M Lindsay, Gemma M. Liwicki, Nicholas Measom, Laura C Paterson, W. J. Kerr
Herein we report report the first use of accessible boron-containing compounds as highly effective directing groups for C–H activation and hydrogen isotope exchange. Selective ortho-activation and functionalisation at aromatic C-sp2 centres has been achieved across an array of aryl boronic ester species using an iridium-based, NHC/phosphine catalyst system at low loadings. The process is robust, with a wide scope of over 30 substrates, and delivers excellent levels of deuterium incorporation in a selective manner. Further utilisation of the resulting boron-containing isotopologues in cross-coupling chemistry has allowed the late-stage preparation of previously less accessible site-selectively labelled structures. This strategy has been exemplified via the preparation of an isotopically-labelled, biologically-active drug molecule.
{"title":"Widely-used Boronic Esters as Synthetically-versatile Directing Groups for C–H Activation and Hydrogen Isotope Exchange","authors":"J. Conor Townsley, Connor Smith, David M Lindsay, Gemma M. Liwicki, Nicholas Measom, Laura C Paterson, W. J. Kerr","doi":"10.1039/d5sc09113f","DOIUrl":"https://doi.org/10.1039/d5sc09113f","url":null,"abstract":"Herein we report report the first use of accessible boron-containing compounds as highly effective directing groups for C–H activation and hydrogen isotope exchange. Selective <em>ortho</em>-activation and functionalisation at aromatic C-sp<small><sup>2</sup></small> centres has been achieved across an array of aryl boronic ester species using an iridium-based, NHC/phosphine catalyst system at low loadings. The process is robust, with a wide scope of over 30 substrates, and delivers excellent levels of deuterium incorporation in a selective manner. Further utilisation of the resulting boron-containing isotopologues in cross-coupling chemistry has allowed the late-stage preparation of previously less accessible site-selectively labelled structures. This strategy has been exemplified via the preparation of an isotopically-labelled, biologically-active drug molecule.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962207","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}
With the ever-increasing demand for high-energy-density lithium-ion batteries (LIBs) in multiscale energy storage, safety concerns have emerged as critical obstacles hindering their widespread application. The excess heat generated during electrochemical process, if not properly managed, can accumulate and accelerate the aging of key cell components, potentially leading to catastrophic thermal runaway events such as fires and explosions. Thus far, considerable attention has been devoted to alleviating intense thermal runaway through fire-safe materials and energy-intensive thermal management technologies. However, the stabilization of the electrochemical environment through intrinsic thermal dissipation and temperature regulation governed by key material design has received comparatively little consideration. This paper aims to summarize the mechanism of thermal runway and highlight material advances for safer LIBs, with particular emphasis on the thermal-electrochemical synergy in mitigating localized overheating, stabilizing the electrochemical environment, and improving electrochemical performance. Subsequently, recent research progress in thermal management materials and strategies for dynamic temperature regulation is reviewed. Finally, current challenges are discussed, and future directions are proposed for material innovations that can be applied to high-energy-density and high-safety LIBs.
{"title":"Materials Design for Thermal-Improved Safe Lithium-Ion Batteries","authors":"Songpei Nan, Guoxin Gao, Wei Yu, Shujiang Ding, Dawei Ding","doi":"10.1039/d5sc08060f","DOIUrl":"https://doi.org/10.1039/d5sc08060f","url":null,"abstract":"With the ever-increasing demand for high-energy-density lithium-ion batteries (LIBs) in multiscale energy storage, safety concerns have emerged as critical obstacles hindering their widespread application. The excess heat generated during electrochemical process, if not properly managed, can accumulate and accelerate the aging of key cell components, potentially leading to catastrophic thermal runaway events such as fires and explosions. Thus far, considerable attention has been devoted to alleviating intense thermal runaway through fire-safe materials and energy-intensive thermal management technologies. However, the stabilization of the electrochemical environment through intrinsic thermal dissipation and temperature regulation governed by key material design has received comparatively little consideration. This paper aims to summarize the mechanism of thermal runway and highlight material advances for safer LIBs, with particular emphasis on the thermal-electrochemical synergy in mitigating localized overheating, stabilizing the electrochemical environment, and improving electrochemical performance. Subsequently, recent research progress in thermal management materials and strategies for dynamic temperature regulation is reviewed. Finally, current challenges are discussed, and future directions are proposed for material innovations that can be applied to high-energy-density and high-safety LIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962328","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}
Engineering molecular machines requires a precise knowledge of the mechanisms involved in programmed motions. Among artificial molecular machines, rotaxanes have emerged as a noteworthy model due to their ability to perform diverse and controlled motions, such as threading, shuttling, and pirouetting. In this work, we present a reliable theoretical framework to describe the threading motion during the assembly of rotaxane-like complexes. Our approach combines the climbing image Nudged Elastic Band method with the ANI-1ccx neural network potential, trained with gold-standard data. Energetic and structural variations along a normalized displacement coordinate allowed an accurate atomistic description of the threading process of different dumbbell-shaped molecules (axles) through the cavity of two different macrocyclic hosts (tori). Using the methodology herein proposed, two key steps are identified: stabilization through hydrogen bonds, which we call the claw mechanism, and the expansion of the macrocycle. An energy decomposition analysis, performed by single-point calculations on selected structures, allows analyzing the role of steric and electrostatic effects in the structural stabilization of the supramolecular assemblies. We find that, although ANI-1ccx was not explicitly trained for charged systems, this neural network potential effectively discriminates between different charged states. Furthermore, calculated potential energy barriers are in good agreement with experimental free energy barriers reported. The featured methodology has the potential to become a fundamental artificial intelligence-based tool for the study of diverse motions observed in supramolecular systems.
{"title":"The interlocking process in molecular machines explained by a combined approach: the nudged elastic band method and a machine learning potential","authors":"Lucio Peña-Zarate, Alberto Vela, Jorge Tiburcio","doi":"10.1039/d5sc08303f","DOIUrl":"https://doi.org/10.1039/d5sc08303f","url":null,"abstract":"Engineering molecular machines requires a precise knowledge of the mechanisms involved in programmed motions. Among artificial molecular machines, rotaxanes have emerged as a noteworthy model due to their ability to perform diverse and controlled motions, such as threading, shuttling, and pirouetting. In this work, we present a reliable theoretical framework to describe the threading motion during the assembly of rotaxane-like complexes. Our approach combines the climbing image Nudged Elastic Band method with the ANI-1ccx neural network potential, trained with gold-standard data. Energetic and structural variations along a normalized displacement coordinate allowed an accurate atomistic description of the threading process of different dumbbell-shaped molecules (axles) through the cavity of two different macrocyclic hosts (tori). Using the methodology herein proposed, two key steps are identified: stabilization through hydrogen bonds, which we call the claw mechanism, and the expansion of the macrocycle. An energy decomposition analysis, performed by single-point calculations on selected structures, allows analyzing the role of steric and electrostatic effects in the structural stabilization of the supramolecular assemblies. We find that, although ANI-1ccx was not explicitly trained for charged systems, this neural network potential effectively discriminates between different charged states. Furthermore, calculated potential energy barriers are in good agreement with experimental free energy barriers reported. The featured methodology has the potential to become a fundamental artificial intelligence-based tool for the study of diverse motions observed in supramolecular systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955817","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}
Riccardo Gnavi, FEDERICA DE NARDI, Carolina Meazzo, Simone Ghinato, Ettore Grimaldi, Andrea Maranzana, Cristina Prandi, Marco Blangetti
We disclose herein a mild and efficient organolithium-mediated protocol which enables the chemodivergent transformation of ortho-cresol derived O-aryl carbamates into diverse molecular structures by simply changing the nature of the reaction medium, working under air and at room temperature. The use of the biobased 2-MeTHF as solvent allows for the chemoselective preparation of α-hydroxy arylacetamides in a single synthetic operation with a remarkable functional group tolerance. Our strategy, which exploits the presence of molecular oxygen arising from the use of bench-type aerobic conditions, relies on a one-pot anionic homo-Fries rearrangement/amide enolate autoxidation sequence with two consecutive C-C/C-O bond formation events occurring at the same carbon atom. Furthermore, we also describe the successful use of a protic and bioinspired Deep Eutectic Solvents (DES) as an effective tool to tune the chemoselectivity of the proposed transformation. The fast internal protonolysis of the anion solution operated by the protic reaction medium results in an an interrupted metalation/rearrangement sequence, enabling the chemoselective preparation of arylacetamides under bench-type aerobic conditions owing to an efficient suppression of the oxidation step.
{"title":"Solvent-Controlled, Chemodivergent Oxidative Anionic Fries Rearrangement of O-Aryl Carbamates Under Aerobic Conditions","authors":"Riccardo Gnavi, FEDERICA DE NARDI, Carolina Meazzo, Simone Ghinato, Ettore Grimaldi, Andrea Maranzana, Cristina Prandi, Marco Blangetti","doi":"10.1039/d5sc09227b","DOIUrl":"https://doi.org/10.1039/d5sc09227b","url":null,"abstract":"We disclose herein a mild and efficient organolithium-mediated protocol which enables the chemodivergent transformation of <em>ortho</em>-cresol derived <em>O</em>-aryl carbamates into diverse molecular structures by simply changing the nature of the reaction medium, working under air and at room temperature. The use of the biobased 2-MeTHF as solvent allows for the chemoselective preparation of α-hydroxy arylacetamides in a single synthetic operation with a remarkable functional group tolerance. Our strategy, which exploits the presence of molecular oxygen arising from the use of bench-type aerobic conditions, relies on a one-pot anionic <em>homo</em>-Fries rearrangement/amide enolate autoxidation sequence with two consecutive C-C/C-O bond formation events occurring at the same carbon atom. Furthermore, we also describe the successful use of a protic and bioinspired Deep Eutectic Solvents (DES) as an effective tool to tune the chemoselectivity of the proposed transformation. The fast internal protonolysis of the anion solution operated by the protic reaction medium results in an an interrupted metalation/rearrangement sequence, enabling the chemoselective preparation of arylacetamides under bench-type aerobic conditions owing to an efficient suppression of the oxidation step.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955929","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}
Due to the inherent defects of photodynamic therapy (PDT), its application in the treatment of deep-tissue metastatic tumors remains challenging. To extend the applicability of PDT, a novel chemiexcited photosensitizer, Cy7-EOM, was developed by covalently coupling the photosensitizer Cy7 with a peroxycatechol derivative and encapsulatied within folate-modified and disulfide-containing nano-micelles. Upon targeted delivery and selective release, positive charged Cy7-EOM would target the mitochondria and efficiently generate singlet oxygen (1O2) through intramolecular chemical energy transfer (ICET), directly inducing mitochondrial damage and cell apoptosis, realizing an efficient PDT for deep-tissue metastatic tumors. Remarkably, the covalent tethering of the photosensitizer to the peroxyoxalate ensures their spatial proximity within 1 nm. This configuration profoundly boosts the ICET efficiency, achieving potent PDT even at low endogenous levels of H₂O₂. Moreover, the tumor-specific decomposition of the nano-micelles eliminating aggregation caused quenching effect and removing the diffusion barrier of 1O2, while in normal tissues the integrality of nano-micelles shields the lethal effects of 1O2. This method provides a new strategy for transforming adjuvant photosensitizers into direct therapeutic drugs, with significant potential for clinical application in the treatment of metastatic tumors.
{"title":"A highly effective self-supplying photosensitizer drug for deep-tissue metastatic tumors treatment","authors":"Hao Zhang, Hanxiang Li, Mingchao Xia, Yuhang Wang, Jingyu Zhou, Yue Tang, Hongyu Wang, Zhengze Yu, Bo Tang","doi":"10.1039/d5sc09043a","DOIUrl":"https://doi.org/10.1039/d5sc09043a","url":null,"abstract":"Due to the inherent defects of photodynamic therapy (PDT), its application in the treatment of deep-tissue metastatic tumors remains challenging. To extend the applicability of PDT, a novel chemiexcited photosensitizer, Cy7-EOM, was developed by covalently coupling the photosensitizer Cy7 with a peroxycatechol derivative and encapsulatied within folate-modified and disulfide-containing nano-micelles. Upon targeted delivery and selective release, positive charged Cy7-EOM would target the mitochondria and efficiently generate singlet oxygen (1O2) through intramolecular chemical energy transfer (ICET), directly inducing mitochondrial damage and cell apoptosis, realizing an efficient PDT for deep-tissue metastatic tumors. Remarkably, the covalent tethering of the photosensitizer to the peroxyoxalate ensures their spatial proximity within 1 nm. This configuration profoundly boosts the ICET efficiency, achieving potent PDT even at low endogenous levels of H₂O₂. Moreover, the tumor-specific decomposition of the nano-micelles eliminating aggregation caused quenching effect and removing the diffusion barrier of 1O2, while in normal tissues the integrality of nano-micelles shields the lethal effects of 1O2. This method provides a new strategy for transforming adjuvant photosensitizers into direct therapeutic drugs, with significant potential for clinical application in the treatment of metastatic tumors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955821","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}
Cycloparaphenylenes (CPPs) have long been focus of interest for their promising applications in materials science. Herein, we report the synthesis of electron-rich pyrene-fused nanohoops, [2]OMe-Pyr-[8]CPP and [4]OMe-Pyr-[8]CPP. Single-crystal analysis revealed an oval-shaped cavity with a herringbone molecular packing arrangement, thereby facilitating the formation of extended tubular structures in both derivatives. Photophysical studies revealed that the two pyrene-fused nanohoops exhibit nearly identical UV–vis absorption and fluorescence emission profiles. We further investigated the potential application of these nanohoops as dopants in organic solar cells (OSCs). When incorporated into D18:L8-BO-based OSCs, [2]OMe-Pyr-[8]CPP enhanced the power conversion efficiency (PCE) from 19.24% to 19.73%. Notably, [4]OMe-Pyr-[8]CPP delivered even better performance, achieving an impressive PCE of 19.96%.These observations indicate the more electron-rich nanohoop demonstrated superior performance in the present case. These results highlight functionalized CPPs as promising materials for high-performance OSCs, providing an effective strategy for photovoltaic efficiency enhancement.
{"title":"Pyrene-Embedded Nanohoops: Synthesis and Dopant Engineering for Organic Solar Cells with Enhanced Efficiency of 19.96%","authors":"Jing He, Wenlong Liu, Siwei Wu, Qi Xie, Zhe Lian, Xiaonan Li, Shengzhu Guo, Ying Wang, Xinjun Xu, Hua Jiang","doi":"10.1039/d5sc06584d","DOIUrl":"https://doi.org/10.1039/d5sc06584d","url":null,"abstract":"Cycloparaphenylenes (CPPs) have long been focus of interest for their promising applications in materials science. Herein, we report the synthesis of electron-rich pyrene-fused nanohoops, <strong>[2]OMe-Pyr-[8]CPP</strong> and <strong>[4]OMe-Pyr-[8]CPP</strong>. Single-crystal analysis revealed an oval-shaped cavity with a herringbone molecular packing arrangement, thereby facilitating the formation of extended tubular structures in both derivatives. Photophysical studies revealed that the two pyrene-fused nanohoops exhibit nearly identical UV–vis absorption and fluorescence emission profiles. We further investigated the potential application of these nanohoops as dopants in organic solar cells (OSCs). When incorporated into D18:L8-BO-based OSCs, <strong>[2]OMe-Pyr-[8]CPP</strong> enhanced the power conversion efficiency (PCE) from 19.24% to 19.73%. Notably, <strong>[4]OMe-Pyr-[8]CPP</strong> delivered even better performance, achieving an impressive PCE of 19.96%.These observations indicate the more electron-rich nanohoop demonstrated superior performance in the present case. These results highlight functionalized CPPs as promising materials for high-performance OSCs, providing an effective strategy for photovoltaic efficiency enhancement.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955822","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}
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}
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