Chemical Science最新文献

Dearomative Cyclopropanation and Aziridination Reactions of Unactivated Quinolines Using Sulfones as Carbene Equivalents

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-10 DOI: 10.1039/d6sc05621k

Charles R. Teeples,Ellia H. Osofsky,Liam P. Murphy,Sidney M Wilkerson-Hill

{"title":"Dearomative Cyclopropanation and Aziridination Reactions of Unactivated Quinolines Using Sulfones as Carbene Equivalents","authors":"Charles R. Teeples,Ellia H. Osofsky,Liam P. Murphy,Sidney M Wilkerson-Hill","doi":"10.1039/d6sc05621k","DOIUrl":"https://doi.org/10.1039/d6sc05621k","url":null,"abstract":"The Büchner ring expansion is a powerful transformation that converts 2-dimensional aromatic feedstocks to cycloheptatrienes via 3-dimensional cyclopropane products. When using metallocarbenes, this reaction is mainly limited to electron-rich aromatics such as benzenes, naphthalenes, indoles, and pyrroles. Herein, we report a tandem cyclopropanation-aziridination sequence of quinolines and isoquinolines using magnesiated sulfone reagents to afford benzannulated cyclopropylaziridines (18 examples 36–94%, 1H NMR), which in some cases are isolable. The resulting aziridines readily undergo solvolysis reactions or nucleophilic additions to afford ring-opened products (16 examples, 34–75% yield over 2 steps). Quinolines with substituents on the 2- and 3-positions undergo cyclopropanation without tandem aziridination, leaving imine functionality intact (4 examples, 47–60% yield). The rate of deprotonation of different (tert-butyl)(alkyl)sulfones and (aryl)(alkyl)sulfones were measured using deuterium labeling which revealed important structural effects that correlate to the efficiency of the tandem cyclopropanation-aziridination reaction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374950","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

Homoconjugation-Induced Fluorescence Enhancement in C3v-Symmetric Pyrene- and Phenanthrene-Embedded Triptycenes

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-10 DOI: 10.1039/d6sc07032a

Puyi Huang,Yu Watanabe,Mashahiro Yamashina,Shinji Toyota

{"title":"Homoconjugation-Induced Fluorescence Enhancement in C3v-Symmetric Pyrene- and Phenanthrene-Embedded Triptycenes","authors":"Puyi Huang,Yu Watanabe,Mashahiro Yamashina,Shinji Toyota","doi":"10.1039/d6sc07032a","DOIUrl":"https://doi.org/10.1039/d6sc07032a","url":null,"abstract":"π-Extension of triptycene provides an effective strategy for constructing three-dimensional π-conjugated molecules featuring through-space homoconjugation. However, because π-extended triptycenes composed solely of polycyclic aromatic hydrocarbon (PAH) units have rarely been explored, the intrinsic effects of homoconjugation on embedded PAH units remain poorly understood. Herein, we report the synthesis of C3v-symmetric pyrene-and phenanthrene-embedded triptycenes as model systems for investigating the intrinsic effects of homoconjugation. The π-extended triptycenes were synthesized by Negishi cross-coupling followed by Pt-catalyzed cyclization and fully characterized by spectroscopic and single-crystal X-ray diffraction analyses. DFT calculations revealed that the homoconjugation promotes delocalization of the frontier molecular orbitals over the molecular framework and narrows the HOMO-LUMO gap, leading to bathochromic shifts in the absorption and emission bands. More importantly, TD-DFT calculations revealed that homoconjugation substantially increased the allowed character of the S0←S1 transition in the parent PAHs, resulting in significantly increased oscillator strengths, radiative decay rates, and fluorescence quantum yields. These findings establish homoconjugation as an effective molecular design principle for tuning the electronic structure and optical properties of three-dimensional PAHbased π-conjugated molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374981","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

Enzyme-Deoxygenated Photoiniferter Polymerization for the High-Throughput Discovery of Ultrahigh Molecular Weight Polymer Adhesives 酶-脱氧光干扰素聚合高通量发现超高分子量聚合物胶粘剂

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc05848e

Sumeet Das,Lily Diodati,Krushna Mishra,Muskan FNU,Amado Orden,Prajakatta Mulay,Michael E. Harris,Brent S. Sumerlin,Amal Narayanan

{"title":"Enzyme-Deoxygenated Photoiniferter Polymerization for the High-Throughput Discovery of Ultrahigh Molecular Weight Polymer Adhesives","authors":"Sumeet Das,Lily Diodati,Krushna Mishra,Muskan FNU,Amado Orden,Prajakatta Mulay,Michael E. Harris,Brent S. Sumerlin,Amal Narayanan","doi":"10.1039/d6sc05848e","DOIUrl":"https://doi.org/10.1039/d6sc05848e","url":null,"abstract":"Despite the long-standing recognition that ultrahigh molecular weight (UHMW) polymers give rise to chain-length-derived emergent material properties, the synthesis of functional UHMW polymers remains synthetically challenging due to oxygen-mediated radical quenching and chain growth limitations in conventional polymerization methodologies. In this study, we introduce an enzyme-deoxygenated photoiniferter polymerization (Enz-PI) that eliminates oxygen sensitivity from photoiniferter polymerization by incorporating a glucose oxidase-mediated in situ oxygen-scavenging pathway. Enz-PI allows controlled synthesis of UHMW polymers with low dispersity without using specialized deoxygenation techniques, while maintaining enzyme stability for subsequent chain extension reactions. The mild, oxygen-tolerant conditions also facilitate high-throughput polymerization in low-volume formats, enabling the creation of a chemically diverse UHMW binary copolymer library. The adhesion performance characterization of these UHMW copolymers reveals composition-dependent and synergistic adhesion behaviors, highlighting the interplay between interfacial interactions and bulk energy dissipation in UHMW polymer adhesion. This work offers a framework for oxygen-tolerant access to UHMW polymers and rapid discovery of functional polymer adhesives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368247","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

Engineered genome structural diversification for structure-function mapping 用于结构功能定位的工程基因组结构多样化

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc06941j

Ye Wang,Zong-Heng Fu,Qing Li,Fuchou Tang,Sijie Zhou,Ying-Jin Yuan

{"title":"Engineered genome structural diversification for structure-function mapping","authors":"Ye Wang,Zong-Heng Fu,Qing Li,Fuchou Tang,Sijie Zhou,Ying-Jin Yuan","doi":"10.1039/d6sc06941j","DOIUrl":"https://doi.org/10.1039/d6sc06941j","url":null,"abstract":"Structural variants (SVs) are major drivers of genome evolution and disease. However, their functional consequences are often inferred from naturally occurring rearrangements, while direct experimental testing of complex SVs remains challenging. Here, we define engineered genome structural diversification as a framework for controlled, library-level structural search. By installing or exploiting programmable rearrangement systems, these approaches generate libraries of alternative genome architectures within defined boundaries and time windows. The resulting structural states can be identified and paired with molecular, cellular or chemical phenotypes. We focus on two system classes: genome-scale structural diversification and local functional architecture diversification. Genome-scale rearrangement probes whole-genome plasticity, whereas local rearrangement links functional architectures to expression states and phenotypic outputs. We further discuss related systems that use local DNA rearrangements to label cells or record cellular histories. We also emphasize that differences in cell survival across genome architectures can complicate the interpretation of observed structure-phenotype associations. Finally, the distinctive structure-phenotype datasets generated by this framework could be used to train artificial intelligence models that guide genome design towards desired cellular functions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368240","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

Tuning Structure and Catalysis of Rhodium Complexes with Pincer-type Period 4 Metalloligands 钳型金属配体铑配合物的调谐结构及催化作用

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc06275j

Zhenyao Li,Jun Takaya

引用次数: 0

π-Bridge Engineering of NIR-II Fluorophore Nanoparticles for High-Contrast Bioimaging and Image-Guided Surgery 用于高对比度生物成像和图像引导手术的NIR-II荧光团纳米粒子的π桥工程

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc05521d

weigeng huang,Danmin Lin,Jun Zhu,Jiayi Chen,Shilin Chen,Hongxuan Liang,Dingyuan Yan,Dong Wang,Ben Zhong Tang

{"title":"π-Bridge Engineering of NIR-II Fluorophore Nanoparticles for High-Contrast Bioimaging and Image-Guided Surgery","authors":"weigeng huang,Danmin Lin,Jun Zhu,Jiayi Chen,Shilin Chen,Hongxuan Liang,Dingyuan Yan,Dong Wang,Ben Zhong Tang","doi":"10.1039/d6sc05521d","DOIUrl":"https://doi.org/10.1039/d6sc05521d","url":null,"abstract":"Early and accurate diagnosis is essential to timely clinical intervention. Compared with conventional imaging modalities such as magnetic resonance imaging and computed tomography, which remain subject to high cost, inadequate resolution, or ionizing radiation, near-infrared (NIR) fluorescence imaging provides high sensitivity, excellent spatial resolution, and minimal invasiveness. Nevertheless, the development of highly bright NIR fluorophores remains challenging because simultaneous optimization of the molar absorption coefficient (ε) and quantum yield (QY) is difficult to achieve. Here, TPE-HEXOT-DPTQ is rationally designed through π-bridge engineering to balance molecular planarity and distortion. The concurrent optimization of ε and QY endowed TPE-HEXOT-DPTQ nanoparticles with the highest fluorescence brightness, together with exceptional colloidal stability, photostability, and biocompatibility. In vivo NIR-II fluorescence imaging demonstrated remarkable tissue penetration, high spatial resolution, and superior signal-to-background ratios, enabling clear visualization of intricate vascular architectures, including cerebral and auricular vasculature. In subcutaneous breast cancer and orthotopic colorectal tumor models, TPE-HEXOT-DPTQ nanoparticles not only achieved high-contrast tumor imaging but also enable precise surgical resection of malignant tissues. This work establishes a rational molecular design strategy for high-performance NIR-II fluorophores and highlights their considerable promise for bioimaging and imaging-guided surgery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368245","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: Surfactant-chaperoned donor–acceptor–donor NIR-II dye strategy efficiently circumvents intermolecular aggregation to afford enhanced bioimaging contrast 更正：表面活性剂伴随的供体-受体-供体NIR-II染料策略有效地规避了分子间聚集，从而增强了生物成像对比度

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc90215d

Tianyang Han,Yajun Wang,Jiajun Xu,Ningning Zhu,Lang Bai,Xiangping Liu,Bin Sun,Chenlong Yu,Qinglun Meng,Jiaqi Wang,Qi Su,Qing Cai,Kenneth S. Hettie,Yuewei Zhang,Shoujun Zhu,Bai Yang

引用次数: 0

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc07104j

Alexandra Bryant,Linlin Wang,Caleb Byrd,Yi Xiao

{"title":"","authors":"Alexandra Bryant,Linlin Wang,Caleb Byrd,Yi Xiao","doi":"10.1039/d6sc07104j","DOIUrl":"https://doi.org/10.1039/d6sc07104j","url":null,"abstract":"The anti-epileptic drug lamotrigine has a range of concentrations within which it is effective and unlikely to cause toxicity. However, inter- and intra-individual variation in pharmacokinetics makes it difficult to appropriately dose this drug, necessitating frequent and careful monitoring. Gold-standard quantitative methods such as immunoassays typically require sample preparation, analysis by trained personnel in centralized laboratories and have long turnaround times, rendering them inadequate for timely, convenient, and frequent dose adjustments. To address this issue, we develop an electrochemical aptamer-based (EAB) sensor capable of detecting physiologically relevant concentrations of lamotrigine in unprocessed whole blood. We first discover a new DNA aptamer that binds specifically lamotrigine with a dissociation constant (KD) of ~0.8 µM. We then adapted this aptamer in an EAB sensor, demonstrating rapid detection of clinically relevant levels of lamotrigine in whole blood. Importantly, our sensor shows excellent specificity against the major metabolite of lamotrigine, other anti-epileptics, and commonly used pharmaceuticals. With the capability to directly and rapidly quantify lamotrigine in unprocessed blood samples, this EAB sensor represents the simplest, fastest, and most convenient approach to lamotrigine detection to date. With further validation and optimization, the sensor described here could facilitate therapeutic monitoring of lamotrigine at the point-of-care.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"133 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374948","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

Electron-Donor-Catalyzed E→Z Isomerization of Styrenic Amides 电子供体催化苯乙烯酰胺的E→Z异构化

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc07008f

Xiaoxia Zhang,Jianjing Yang,Yue Wang,Lirong Xu,Yongxin Li,Mingming Yu,Wei Wei,Xi Li,Yuan-Ye Jiang,Jiangwei Wen

{"title":"Electron-Donor-Catalyzed E→Z Isomerization of Styrenic Amides","authors":"Xiaoxia Zhang,Jianjing Yang,Yue Wang,Lirong Xu,Yongxin Li,Mingming Yu,Wei Wei,Xi Li,Yuan-Ye Jiang,Jiangwei Wen","doi":"10.1039/d6sc07008f","DOIUrl":"https://doi.org/10.1039/d6sc07008f","url":null,"abstract":"The geometric configuration of C=C bonds exerts a dominant influence on the biological activity and physical properties of alkene-bearing molecules.1-5 Contra-thermodynamic E→Z photoisomerization provides an atom-economical route to valuable Z-alkenes, yet for decades, nearly all established photocatalytic systems for this transformation have relied on triplet energy transfer (EnT) mechanisms. By contrast, isomerization pathways proceeding through electron-donor-catalyzed (EDC) manifolds driven by sequential secondary photoexcitation remain underexplored. Herein, we report a mechanistically distinct electron-donor-catalyzed E→Z isomerization of styrenic amides that proceeds via a competitive SET-induced secondary-excitation pathway. Using indole as the reversible electron-donor catalyst, the reaction operates efficiently at room temperature under ambient air upon irradiation with low-energy 390 nm LEDs. Spectroscopic studies and density functional theory (DFT) calculations validate a catalytic cycle involving sequential photoexcitation, SET, radical-anion-mediated C=C bond rotation, and electron rebound. This system delivers excellent yields and exceptional Z/E stereoselectivity across a broad array of styrenic amides, retains robust reactivity and stereocontrol in gram-scale synthesis, and enables stereochemical editing of styrenic amide-containing pharmaceutical motifs alongside a concise two-step synthesis of an H3R antagonist.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368241","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

Snapshots of the Multifunctional Role of Lewis Acids Captured in Dynamic Ni-Mg Heterometallic Complexes 动态Ni-Mg异质金属配合物中捕获的路易斯酸的多功能作用的快照

IF 8.4 1区化学

Chemical Science Pub Date : 2026-11-09 DOI: 10.1039/d6sc07210k

Fernando Gonzalez,Manar M. Shoshani

{"title":"Snapshots of the Multifunctional Role of Lewis Acids Captured in Dynamic Ni-Mg Heterometallic Complexes","authors":"Fernando Gonzalez,Manar M. Shoshani","doi":"10.1039/d6sc07210k","DOIUrl":"https://doi.org/10.1039/d6sc07210k","url":null,"abstract":"The combination of transition metals and Lewis-acidic metals have documented success in accessing new reactivity. Well-defined scaffolds that emulate key properties of Lewis acidic metals in catalysis, such as their coordinative function and ion mobility are lacking. In this report, we disclose heterometallic Ni-Mg complexes on the site-differentiated tetraaryl bisphosphine ligand framework. Through the Ni-bisphosphine complex (1) Mg(II) ions were introduced forming neutral, well-defined bisphosphine Ni-Mg 1,5 cyclooctadiene and 3-hexyne coordination complexes 2 and 3, respectively. Complexes 2 and 3 feature a Ni-Mg bonding interaction supported by crystallographic and computational studies that is best described as sigma-accepting. The influence of the Mg center in the reduction potential is observed through a ~ 1 V anodic shift in 2 compared to 1 in THF. The novel ligand environment enables the coordinatively labile Mg site to adopt a cis-disposition at Ni and the unsaturation of Mg is evident through binding (formation of 2-L) and activation of Lewis bases, as showcased in the reduction of pyridine, forming 4, a metalla-aziridine. Remarkably, formation of 4 also reveals a previously undisclosed capability of Lewis acidic metals in heterometallic complexes; the mobility of a metal ion. The mobility of the Mg-cation is observed through a dynamic site migration to a neighboring amide site and both the Mg-site exchange and the reduction of pyridine are reversible processes. Finally, addition of an electrophile to 4 produced a CC-coupled N-heterocyclic product, an overall result of reductive coupling of pyridine. These findings unveil the multifunctional role of Mg ions in heterometallic complexes and result in cooperative activation and functionalization by well-defined assemblies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368246","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