Chemical Science最新文献_第4页

2D Spatial Structure Favored Tandem Catalysis Boosted Methane Direct Transformation to Methanol over Cu-FER 二维空间结构有利的串联催化促进了Cu-FER催化下甲烷直接转化为甲醇

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc02092a

Ning Liu, Tingting Zhang, Chengna Dai, Ruinian Xu, Gangqiang Yu, Ning Wang, Biaohua Chen

{"title":"2D Spatial Structure Favored Tandem Catalysis Boosted Methane Direct Transformation to Methanol over Cu-FER","authors":"Ning Liu, Tingting Zhang, Chengna Dai, Ruinian Xu, Gangqiang Yu, Ning Wang, Biaohua Chen","doi":"10.1039/d5sc02092a","DOIUrl":"https://doi.org/10.1039/d5sc02092a","url":null,"abstract":"Direct transformation of methane into methanol (DMTM) remains a significant challenge of C1 chemistry. Herein, we investigate the continuous N2O-DMTM over Cu-FER zeolite. A two-dimensional (2D) spatial structure favored tandem catalysis is for the first time unraveled, that leads to boosted (CH3OH+DME) productivity, corresponding to 2736 μmol gcat-1 h-1 or 58,368 mmol molCu-1 h-1 of CH3OH, and improved reaction stability (passing through 100 h’s long-term test). A unique dual Cu single atom site located at parallel 6 membered ring (MR) of 8 MR channel can be generated, which serves as the primary CH3OH production active site exhibiting super higher activity than those of traditional monomeric [Cu]+ and Cu dimer sites. The generated CH3OH can subsequently diffuse from 8 MR channel into 10 MR main channel and directly react with the radicals of CH3- and OH- to produce DME, which not only favor DME production but also efficiently prevent carbon deposition. Present work highlights a tandem catalysis over Cu-FER, which would substantially favor other efficient catalyst design for N2O-DMTM.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252497","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}

引用次数: 0

Correction: On-surface synthesis of organometallic nanorings linked by unconventional intermediates of the Ullmann reaction 修正：由Ullmann反应的非常规中间体连接的有机金属纳米环的表面合成

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc90129d

Xiaoyang Zhao, Liqian Liu, Zhipeng Zhang, Tianchen Qin, Jun Hu, Lei Ying, Junfa Zhu, Tao Wang, Xinrui Miao

引用次数: 0

Orbital-Based Bonding Analysis in Solids 固体中基于轨道的成键分析

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc02936h

Peter Christian Müller, Linda S Reitz, David Hemker, Richard Dronskowski

{"title":"Orbital-Based Bonding Analysis in Solids","authors":"Peter Christian Müller, Linda S Reitz, David Hemker, Richard Dronskowski","doi":"10.1039/d5sc02936h","DOIUrl":"https://doi.org/10.1039/d5sc02936h","url":null,"abstract":"As of today, there is certainly no doubt about the quantum character of the atomistic world, most straightforwardly calculated by using wave mechanics and Schrödinger’s fundamental equation from 1926. Even though one century has passed, the paramount importance of the wave function, which determines everything down to the last detail, remains unchanged, and the wave function is most conveniently approximated by a combination of orbitals, one-electron wave functions for atoms, molecules, and also solids. And it is precisely this “orbital basis” that serves as a gateway to understanding the very interactions that cause atoms to condense into solids, just like for molecules. The analysis of quantum-chemical interactions and the nature of the chemical bonding between atoms in solids by use of orbitals will be our topic in this perspective, starting with the glorious past, going over to the current practice and, of course, the magnificent prospects for the future. As electronic structures for periodic solids are most often calculated using plane waves (instead of orbitals), for simple reasons of translational symmetry and Bloch’s fundamental theorem, a unitary transformation to atomic or molecular orbitals is needed for final inspection, technically solved by the LOBSTER quantum-chemistry package. LOBSTER allows for the calculation of wave function-based atomic charges, various population analyses and periodic bonding indicators, first-principles bond orders, two- and multi-centre bonding analysis, fragment-molecular analysis, and a lot more. All those techniques are illustrated from three solid-state systems deriving from carbonate chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"36 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238195","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}

引用次数: 0

Bulk and Interface Engineering of Prussian Blue Analogues Cathodes for High-Performance Sodium-Ion Batteries 高性能钠离子电池普鲁士蓝类似物阴极的体积和界面工程

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc02819a

Boao Zhou, Yun Gao, Xihao Lin, Bin Yang, Ning Kang, Yun Qiao, Hang Zhang, Li Li, Shulei Chou

{"title":"Bulk and Interface Engineering of Prussian Blue Analogues Cathodes for High-Performance Sodium-Ion Batteries","authors":"Boao Zhou, Yun Gao, Xihao Lin, Bin Yang, Ning Kang, Yun Qiao, Hang Zhang, Li Li, Shulei Chou","doi":"10.1039/d5sc02819a","DOIUrl":"https://doi.org/10.1039/d5sc02819a","url":null,"abstract":"Prussian blue analogues (PBAs) possess a unique three-dimensional crystal structure, which provides ample space for the movement of sodium ions (Na+), making them an ideal choice for cathode materials in sodium-ion batteries (SIBs). However, the bulk phase of PBAs typically contains amounts of crystal water and vacancies, which compromise the integrity of the lattice and impede the migration of Na+. Additionally, interface-related issues, such as side reactions and the dissolution of transition metal ions, severely limit the reversible capacity and cycle stability of PBAs-based cathode materials. Therefore, addressing these challenges from bulk and interface of PBAs is critical for the development of high-performance cathode materials for SIBs. This review aims to provide insights into potential strategies for overcoming these limitations and enhancing the electrochemical performance of PBAs. Firstly, the structure, morphology, and reaction mechanisms of PBAs are summarized systematically. The key challenges hindering the commercialization of PBAs are then categorized in this review. Several effective strategies for addressing these challenges are provided, including bulk phase engineering (thermal treatment, element doping, and etching), interface engineering (coating, ion exchange, and electrolyte additives), and the co-regulation of bulk and interface. Finally, the future commercialization prospects of PBAs are discussed, highlighting the necessary steps for transitioning from laboratory-scale research to industrial-scale production.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238199","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}

引用次数: 0

Engineering antisense oligonucleotides for targeted mRNA degradation through lysosomal trafficking 工程反义寡核苷酸通过溶酶体运输靶向mRNA降解

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc03751d

Disha Kashyap, Thomas Milne, Michael John Booth

{"title":"Engineering antisense oligonucleotides for targeted mRNA degradation through lysosomal trafficking","authors":"Disha Kashyap, Thomas Milne, Michael John Booth","doi":"10.1039/d5sc03751d","DOIUrl":"https://doi.org/10.1039/d5sc03751d","url":null,"abstract":"Antisense oligonucleotides (ASOs) can modulate gene expression at the mRNA level, providing the ability to tackle conventionally undruggable targets and usher in an era of personalized medicine. A key mode of action for ASOs relies upon RNase H-engagement in the nucleus, however, most mature mRNA is present in the cytoplasm. This disconnect limits the efficacy and biomedical applications of ASOs. In this paper, we have established a new mechanism of action for achieving potent and targeted mRNA knockdown by leveraging a lysosomal degradation pathway. To achieve this, we employ autophagosome-tethering compound (ATTEC) technology that utilises bifunctional small molecules for lysosomal trafficking. In this manner, to induce degradation of target mRNA located in the cytoplasm, we conjugated an ATTEC warhead, ispinesib, to RNase H-inactive ASOs. These fully 2′-O-Methylated RNase H-inactive ASOs have higher chemical stability and tighter mRNA binding than conventional ‘gapmer’ sequences, but cannot be recognised by RNase H. Using our lysosomal trafficking antisense oligonucleotide (LyTON) technology, we show significant lysosome-dependent knockdown of multiple molecular targets in various cell lines, via transfection and gymnotic uptake. The LyTON modification is also able to boost the knockdown efficacy of RNase H-active 'gapmer' ASOs. Engineered to degrade mRNA independent of RNase H recognition, LyTONs will enable gene silencing using oligonucleotide chemistries with higher chemical stability, tighter mRNA binding affinity, and improved cell delivery profiles. This will enable us to target a wider range of disease-relevant mRNA, potentially leading to the development of new therapies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252198","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}

引用次数: 0

Stretchable Electrode Enabled Electrochemical Mass Spectrometry for In Situ and Complementary Analysis of Cellular Mechanotransduction 可拉伸电极电化学质谱法用于细胞机械传导的原位和互补分析

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc02191j

Haotian Wang, Jing Yan, Jiamei Lin, Caiying Zhang, Xinglei Zhang, Rui Su, Yan-Ling Liu, Jiaquan Xu

{"title":"Stretchable Electrode Enabled Electrochemical Mass Spectrometry for In Situ and Complementary Analysis of Cellular Mechanotransduction","authors":"Haotian Wang, Jing Yan, Jiamei Lin, Caiying Zhang, Xinglei Zhang, Rui Su, Yan-Ling Liu, Jiaquan Xu","doi":"10.1039/d5sc02191j","DOIUrl":"https://doi.org/10.1039/d5sc02191j","url":null,"abstract":"Mechanotransduction exerts a profound influence on diverse cellular processes via the activated signalling pathways. Although the currently established methods could reveal force-induced ultimate changes in specific biochemical cues, they fail to provide the real-time and comprehensive information about the complicated signaling events. Herein, we report a stretchable electrode enabled electrochemical mass spectrometry for in situ and complementary analysis of cellular mechanotransduction. The stretchable electrode functions as not only an electrochemical sensor for tracking the electroactive molecules released from stretched-cells cultured thereon, but also an ionization source to ionize the intracellular metabolites for mass spectrometry analysis. As a concept application, the endothelial mechanotransduction mediated NO pathway was found to be different in transient stimulation and prolonged stimulation for the first time. This work provides a revealing strategy for in situ and comprehensive analysis of the biomolecules involved in cellular mechanotransduction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238197","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}

引用次数: 0

The Mechanism of Spin-Phonon Relaxation in Endohedral Metallofullerene Single Molecule Magnets 内嵌金属富勒烯单分子磁体的自旋声子弛豫机制

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d4sc07786e

Tanu Sharma, Rupesh Kumar Tiwari, Sourav Dey, Antonio Mariano, Alessandro Lunghi, Gopalan Rajaraman

{"title":"The Mechanism of Spin-Phonon Relaxation in Endohedral Metallofullerene Single Molecule Magnets","authors":"Tanu Sharma, Rupesh Kumar Tiwari, Sourav Dey, Antonio Mariano, Alessandro Lunghi, Gopalan Rajaraman","doi":"10.1039/d4sc07786e","DOIUrl":"https://doi.org/10.1039/d4sc07786e","url":null,"abstract":"This study presents the first-ever investigation of spin-phonon coupling mechanisms in fullerene-based single-molecule magnets (SMMs) using ab initio CASSCF combined with DFT calculations. While lanthanide-based SMMs, particularly those with DyIII ions, are known for their impressive blocking temperatures and relaxation barriers, endohedral metallofullerene (EMFs) offer a unique platform for housing low-coordinated lanthanides within rigid carbon cages. We have explored the spin dynamics of in DyScS@C82 exhibiting among the highest blocking temperature (TB) reported. Through our computational analysis, we reveal that while the fullerene cage enhances crystal field splitting and provides structural stability without significantly contributing to spin-relaxation-driving low-energy phonons, the internal ionic motion emerges as the primary factor controlling spin relaxation and limiting blocking temperature. This computational investigation into the spin dynamics of EMF-based SMMs provides key insights into their magnetic behaviour for the first time and suggests potential strategies for improving their performance towards futuristic SMMs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238198","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}

引用次数: 0

Correction: Ultrahigh photocatalytic hydrogen evolution of linear conjugated terpolymers enabled by an ultra-low ratio of the benzothiadiazole monomer 校正：超低比例的苯并噻唑单体使线性共轭三元聚合物的超高光催化析氢成为可能

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc90121a

Zheng-Hui Xie, Gang Ye, Hao Gong, Pachaiyappan Murugan, Can Lang, Yi-Fan Dai, Kai Yang, Shi-Yong Liu

引用次数: 0

“Dual lock-and-key” Triggered and Endoplasmic Reticulum Targeting Nanophotosensitizers for Activatable Type-I Photodynamic and Photothermal Therapies “双锁-钥匙”触发和内质网靶向纳米光敏剂用于可激活的i型光动力和光热治疗

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc01987g

Rumeng Zhan, Weijie Zhou, Hongyu Ma, Menghui Zou, Mingming Zhang, Weian Zhang, Jia Tian

{"title":"“Dual lock-and-key” Triggered and Endoplasmic Reticulum Targeting Nanophotosensitizers for Activatable Type-I Photodynamic and Photothermal Therapies","authors":"Rumeng Zhan, Weijie Zhou, Hongyu Ma, Menghui Zou, Mingming Zhang, Weian Zhang, Jia Tian","doi":"10.1039/d5sc01987g","DOIUrl":"https://doi.org/10.1039/d5sc01987g","url":null,"abstract":"Photodynamic therapy (PDT) has emerged as a critical modality in cancer treatment with the merits of non-invasiveness, spatiotemporal control, and minimal drug resistance. However, the clinical application of PDT is often hindered by the inherent limitations of side effects caused by “always on” state of reactive oxygen species (ROS) and low ROS generation efficiency in hypoxic tumors. To overcome these limitations, we developed a tumor microenvironment (TME) “dual lock-and-key” triggered and Endoplasmic Reticulum (ER) Targeting nanophotosensitizerr for fluorescence imaging-guided activatable Type-I PDT and photothermal therapy (PTT). This “smart” nanophotosensitizer maintains an \"off\" state during systemic circulation, and specifically activated only in acidic and GSH-overexpressed TME (\"on\" state), where the fluorescence, ROS generation, and photothermal photothermal conversion capabilities were recovered, leading to precise and enhanced phototherapies in tumor sites with minimizing side effects. Sulfur-substituted and ER-targeting hemicyanine leads to a large red-shift absorption, concurrent Type-I ROS production and photothermal conversion on ER, thereby enhanced protein deactivation and ER stress. Comprehensive in vitro and in vivo investigations demonstrated that the TME dual triggered activatable nanophotosesitizer, upon NIR laser irradiation, effectively kill tumor cells, and significantly suppressing tumor growth by fluorescence imaging-guided Type-I PDT and PTT. This work provides a pathway for developing tumor microenvironment-triggered precise phototherapeutics with improved biosafety and clinical translation potential.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238175","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}

引用次数: 0

Diastereoselective Scholl reaction: Point-to-helical chirality transfer in molecular nanographenes 非对映选择性Scholl反应：分子纳米石墨烯中的点-螺旋手性转移

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-09 DOI: 10.1039/d5sc02563j

Sergio Marcos López, Manuel Buendía, Israel Fernández, Salvatore Filippone, Nazario Martín

引用次数: 0