Chemical Science最新文献_第9页

Revisiting the ion dynamics in LixCoO2 and NaxCoO2 再论LixCoO2和NaxCoO2的离子动力学

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc03394b

Ryoichi Tatara, Daisuke Igarashi, Masanobu Nakayama, Tomooki Hosaka, Kazuki Ohishi, Izumi Umegaki, Jumpei G. Nakamura, Akihiro Koda, Hiroto Ohta, Rasmus Palm, Martin Månsson, Eun Jeong Kim, Kei Kubota, Jun Sugiyama, Shinichi Komaba

{"title":"Revisiting the ion dynamics in LixCoO2 and NaxCoO2","authors":"Ryoichi Tatara, Daisuke Igarashi, Masanobu Nakayama, Tomooki Hosaka, Kazuki Ohishi, Izumi Umegaki, Jumpei G. Nakamura, Akihiro Koda, Hiroto Ohta, Rasmus Palm, Martin Månsson, Eun Jeong Kim, Kei Kubota, Jun Sugiyama, Shinichi Komaba","doi":"10.1039/d5sc03394b","DOIUrl":"https://doi.org/10.1039/d5sc03394b","url":null,"abstract":"Layered oxides (AMO2, where A = Li or Na and M = transition metal) are essential positive electrode materials for lithium- and sodium-ion batteries. A fundamental question in ion transport is whether Li+ or Na+ diffuses faster in these materials; however, distinguishing intrinsic diffusion properties from the effects of particle size and electrode composition is challenging. Using operando muon spin spectroscopy and molecular dynamics simulations, we determined the Li+ and Na+ self-diffusion coefficients in O3-LixCoO2, O3-NaxCoO2, and P2-NaxCoO2. Our findings revealed that Na+ diffusion is higher in the P2-type structure than in the O3-type structure primarily due to weaker electrostatic interactions. In the O3-type structure, Li+ diffuses faster than Na+, whose larger ionic size hinders mobility. These insights clarify the ion transport mechanisms and advance the design of next-generation battery materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189297","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

Constructing a Visible-Light-Excited Z-scheme Heterojunction by Engineering the Directional N-C/Cu Insertion layer: Overcoming the Work Function Mismatches 通过工程设计定向N-C/Cu插入层构建可见光激发z型异质结：克服功函数不匹配

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc05362e

Hao Gao, Xiaoxiao He, Jinbu Li, Qiang Zhu, Chengyu Qin, Liming Sun, Shuting Zhi, Lei Yang, Wenwen Zhan, Jianwei Zhao, Xi-Guang Han

{"title":"Constructing a Visible-Light-Excited Z-scheme Heterojunction by Engineering the Directional N-C/Cu Insertion layer: Overcoming the Work Function Mismatches","authors":"Hao Gao, Xiaoxiao He, Jinbu Li, Qiang Zhu, Chengyu Qin, Liming Sun, Shuting Zhi, Lei Yang, Wenwen Zhan, Jianwei Zhao, Xi-Guang Han","doi":"10.1039/d5sc05362e","DOIUrl":"https://doi.org/10.1039/d5sc05362e","url":null,"abstract":"The construction of S-scheme heterojunctions is constrained by stringent work function (Φ) matching between oxidation and reduction photocatalysts, which limits material selection. Here, we present an innovative interfacial engineering strategy to overcome Φ-mismatched barriers by introducing a nitrogen-doped carbon (N-C) mediator and Cu nanoparticles at the WO3/Cu2O interface. Through a \"post-deposition and pyrolysis\" approach, we fabricated a tightly integrated Z-scheme WO3/N-C/Cu/Cu2O heterojunction, where the N-C layer and metallic Cu synergistically redirect photogenerated carrier recombination, preserving the high redox potentials of WO3 (VB: +2.62 V) and Cu2O (CB: -1.41 V). Femtosecond transient absorption spectroscopy and electron paramagnetic resonance data revealed that interfacial electrons from WO3 transferred to N-C and recombined with holes originated from Cu2O on Cu via the directional N-C/Cu insertion layer. The optimized heterojunction exhibits exceptional photocatalytic performance under blue light (450 nm), achieving a 99% yield in homo-coupling of terminal alkyne to1,3-conjugated diynes and a hydrogen evolution rate 300-fold higher than that of conventional WO3/Cu2O. This work provides a universal paradigm for designing Z-scheme systems with mismatched components, unlocking new possibilities for solar energy conversion and organic synthesis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"372 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189299","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

A simple epoxide modification strategy to construct amino-functional poly(2-oxazoline) mRNA delivery vectors 一个简单的环氧化物修饰策略构建氨基功能聚（2-恶唑啉）mRNA传递载体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc04801j

Kuncheng Lv, Yibo Qi, Hanqin Zhao, Yuyan zhang, Ziyue An, Sheng Ma, Wantong Song

{"title":"A simple epoxide modification strategy to construct amino-functional poly(2-oxazoline) mRNA delivery vectors","authors":"Kuncheng Lv, Yibo Qi, Hanqin Zhao, Yuyan zhang, Ziyue An, Sheng Ma, Wantong Song","doi":"10.1039/d5sc04801j","DOIUrl":"https://doi.org/10.1039/d5sc04801j","url":null,"abstract":"Messenger RNA (mRNA) delivery vectors are pivotal in the realm of vaccines and gene therapy. While polymer-based delivery vectors have garnered growing interest owing to their tunable structures and favorable biocompatibility, achieving high delivery efficiency remains a critical challenge. Poly(2-oxazoline) (POx) emerges as a promising candidate in biomedicine, yet its exploration in mRNA delivery is nascent. Herein, we engineered poly[2-(5-aminopentyl)-2-oxazoline]-based (PAmOx) polymers as efficient mRNA delivery vectors through a straightforward one-step ring-opening reaction between the amino group on the PAmOx and the epoxide molecules. We conducted a systematic examination of how the degree of polymerization and the nature of grafted epoxide molecules influence mRNA delivery efficiency. In vitro experiments demonstrated that DP50-PE6, synthesized via a ring-opening reaction between 1,2-epoxydecane (E6) and PAmOx50, enhanced mRNA transfection efficiency by a staggering 3.3 × 105-fold compared with the parent PAmOx50. Consistent with the in vitro findings, in vivo intramuscular administration of the DP50-PE6/mRNA complex exhibited robust expression at the site of injection (1.8 × 106 p/sec/cm2/sr) and remained detectable for two days. Notably, following intravenous administration, the DP50-PE6/mRNA complex exhibited selective protein expression in the spleen which accounted for approximately 85.1% of the total expression observed across major organs. Further research revealed that the DP50-PE6/mOVA complex, when combined with anti-PD1, effectively inhibited tumor growth in the B16-OVA melanoma model, achieving a tumor suppression rate over 90%. These findings underscore the immense potential of POx-based vectors in mRNA delivery, setting the stage for the evolution of POx-inspired nucleic acid delivery vectors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189360","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

Ultrasound-Triggered Prodrug Activation via Sonochemically Induced Cleavage of a 3,5-Dihydroxybenzyl Carbamate Scaffold 超声诱导的3,5-二羟基苄基氨基甲酸酯支架劈裂的前药激活

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc05710h

Xuancheng Fu, Bowen Xu, Hirusha Liyanage, Cijun Zhang, Warren F Kincaid, Amber L Ford, Luke G. Westbrook, Seth D Brown, Tatum DeMarco, James Hougland, John Mark Franck, Xiaoran Hu

{"title":"Ultrasound-Triggered Prodrug Activation via Sonochemically Induced Cleavage of a 3,5-Dihydroxybenzyl Carbamate Scaffold","authors":"Xuancheng Fu, Bowen Xu, Hirusha Liyanage, Cijun Zhang, Warren F Kincaid, Amber L Ford, Luke G. Westbrook, Seth D Brown, Tatum DeMarco, James Hougland, John Mark Franck, Xiaoran Hu","doi":"10.1039/d5sc05710h","DOIUrl":"https://doi.org/10.1039/d5sc05710h","url":null,"abstract":"Spatiotemporal control of drug release in deep tissues is crucial for targeted treatment precision and minimized systemic side effects. Ultrasound is a non-invasive and clinically safe stimulus capable of deep-tissue penetration without requiring optical transparency. Here, we introduce an innovative strategy for controlling cargo release via ultrasound-triggered sonochemical cleavage of a 3,5-dihydroxybenzyl carbamate (DHBC) prodrug platform. We demonstrate that low-intensity therapeutic ultrasound (LITUS) effectively generates hydroxyl radicals in aqueous solutions, which hydroxylate DHBC to initiate spontaneous cleavage and cargo release. Using a protype chemotherapy prodrug (ProDOX) as a proof-of-concept, we show that LITUS irradiation triggers doxorubicin release to kill cancer cells in vitro. Remarkably, this sonochemical activation was successfully achieved through 2 cm of chicken breast, highlighting the deep-penetrating capability of our approach. Extending this strategy, we developed ProR848, a sono-activable prodrug of the Toll-like receptors (TLR) agonists R848, enabling remotely triggered, on-demand immune cell activation. Collectively, our results establish a novel and versatile sonochemical cleavage platform for ultrasound-targeted prodrug activation, offering significant potential for applications including controlled therapeutic release and responsive biomaterials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"101 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195352","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

Chemoselective Cyclodesulfurization vs Dehydration Enabled by Aqueous Microdroplet Chemistry 水微滴化学实现的化学选择性环脱硫与脱水

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc05557a

Manish Jana, Mousumi Saha, R. Graham Cooks

{"title":"Chemoselective Cyclodesulfurization vs Dehydration Enabled by Aqueous Microdroplet Chemistry","authors":"Manish Jana, Mousumi Saha, R. Graham Cooks","doi":"10.1039/d5sc05557a","DOIUrl":"https://doi.org/10.1039/d5sc05557a","url":null,"abstract":"Dehydration reactions are typically favored in microdroplets due to the relatively dry environment at the air–water interface. However, we demonstrate that cyclodesulfurization may outcompete dehydration under these conditions. We report on a catalyst-free method for inducing a two-step cyclodesulfurization in microdroplets under ambient conditions by reacting benzohydrazide with phenyl isothiocyanate. The reaction involves the formation of benzohydrazine-1-carbothioamide, a compound that contains two nucleophilic centers. During competing nucleophilic attacks by hydroxyl and thiol groups, reactive oxygen species at the droplet interface oxidize the thiol, forming the sulfoxylic and then the sulfurous acid. These transient reactive intermediates are detected using online mass spectrometry. The interfacial oxidation reduces thiol nucleophilicity, favoring hydroxyl-mediated nucleophilic attack to form 1,3,4-oxadiazole, a structural motif prevalent in pharmaceuticals. The reaction kinetics are influenced by reagent concentration and the droplet travel distance. The absence of dehydration (commonly found in microdroplet reactions) is a key finding of this work. Our findings also highlight the unique potential of charged microdroplets to promote chemoselective transformations, driven by the distinctive properties of the air–water interface.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"104 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189295","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

Antimicrobial and Breathable Membranes with Printed Carbon Nanotube-Silver Composite Conductive Layers for Electronic Sensing 抗菌和透气膜印刷碳纳米管-银复合导电层的电子传感

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc05696a

Huacui Xiang, Daniel Verrico, Taher Hafiz, Enjian He, Gary Wneck, Kun Hu, Guojun Liu, Yen Wei, Jiujiang Ji

{"title":"Antimicrobial and Breathable Membranes with Printed Carbon Nanotube-Silver Composite Conductive Layers for Electronic Sensing","authors":"Huacui Xiang, Daniel Verrico, Taher Hafiz, Enjian He, Gary Wneck, Kun Hu, Guojun Liu, Yen Wei, Jiujiang Ji","doi":"10.1039/d5sc05696a","DOIUrl":"https://doi.org/10.1039/d5sc05696a","url":null,"abstract":"With the accelerating advancement of wearable electronics, electronic skin (e-skin) has emerged as a promising technology for applications in health monitoring, prosthetics, and human-machine interfaces. Nonetheless, achieving simultaneous breathability, antibacterial properties, and high sensing fidelity presents a formidable challenge. In this study, we report a multifunctional electronic skin (e-skin) constructed from a modified Tecoflex (thermoplastic polyether-based polyurethane) electrospun nanofiber membrane (T-eNFM), integrating breathability, antibacterial activity, and high-fidelity sensing capabilities. The T-eNFM substrate promotes wearer comfort via its innate breathability while simultaneously inhibiting bacterial colonization through robust antimicrobial functionality. A composite of multi-walled carbon nanotubes (MWCNTs) and silver paste (Ag powder) was printed onto T-eNFM-3 to form a conductive, mechanically compliant sensing layer. The fabricated strain sensor exhibited a gauge factor of 5.81, while the multilayer pressure sensor displayed a sensitivity of 2.83 kPa⁻¹, rendering it ideally suited for monitoring cardiovascular physiological signals. This work outlines a blueprint for next-generation electronic skin devices by addressing the critical challenges of comfort, safety and multifunctionality.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189298","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

Silver(I)-Mediated Oxazoline Formation: A Mild Route to 2,4-Oxazoles in Peptides 银(I)介导的恶唑啉形成：肽中2,4-恶唑的温和途径

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc06351e

Adam S Pickett, Jacob Campbell, Katherine M Cox, Zainab A Bello, Erin R. Johnson, Carlie L Charron

引用次数: 0

Chiral heterogeneous photocatalysts for enantioselective synthesis: standing on the shoulders of organocatalysis 手性非均相光催化剂对映选择性合成：站在有机催化的肩膀上

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc07001e

Camilla Callegari, Marco Moroni, Davide Ravelli, Lorenzo Malavasi

引用次数: 0

Directing the Oxidative Folding of Disulfide-Rich Peptides for Enhanced Engineering and Applications 指导富含二硫化物肽的氧化折叠以增强工程和应用