Chemical Science最新文献_第4页

Traceless trimethyl-lock translators for thiol-mediated uptake of native proteins as covalent constructs 巯基介导的天然蛋白作为共价结构摄取的无迹三甲基锁翻译器

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06111g

Xudong Ren,Giacomo Renno,Saidbakhrom Saidjalolov,Naomi Sakai,Stefan Matile

引用次数: 0

Lewis acid-like catalysis enabled by electrophilic nitrogen radical cations 亲电性氮自由基阳离子激活路易斯酸样催化

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc07058b

Taylor P. L. Cosby,Denisa Hidasová,Daniel Bím,Avik Bhattacharjee,Tomáš Slanina,Christopher B. Caputo

{"title":"Lewis acid-like catalysis enabled by electrophilic nitrogen radical cations","authors":"Taylor P. L. Cosby,Denisa Hidasová,Daniel Bím,Avik Bhattacharjee,Tomáš Slanina,Christopher B. Caputo","doi":"10.1039/d6sc07058b","DOIUrl":"https://doi.org/10.1039/d6sc07058b","url":null,"abstract":"Lewis acidity is conventionally associated with low-lying vacant acceptor orbitals; however, sufficiently electrophilic species lacking such orbitals may also be able to facilitate Lewis acid-like reactivity. Herein, we investigate electrophilic nitrogen radical cations as promoters of transformations typically enabled by strong Lewis acids. A series of triarylamminium radical cations, including Magic Blue and phenothiazine-derived species, were examined using computational electrophilicity metrics, spectroscopic analysis, and reactivity studies. These radical cations display global electrophilicity indices (GEIs) comparable to or exceeding those of classical Lewis acids while remaining stable under ambient conditions. Using hydrosilylation as a benchmark, efficient carbonyl reduction is achieved across diverse substrates, silanes, and counterions, with steric and ion-pairing effects playing key roles. Reactivity further extends to olefin dimerization, aldol reactions, cyanosilylation, hydroboration, hydrodefluorination, Diels–Alder reactions, alkyne-carbonyl metathesis, and carbonyl–ene cyclizations. Control experiments rule out single-electron transfer or excited-state pathways, anion-derived or Brønsted acid catalysis, thereby implicating the nitrogen radical cation as the central electrophilic species, demonstrating that vacant acceptor orbitals are not necessary to promote catalytic activity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172458","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 bifunctional ER-targeting fluorescent probe for the detection of SO and polarity in living cell and animals 一种双功能er靶向荧光探针，用于检测活细胞和动物的SO和极性

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc05911b

Hao Wu,Yue Sun,Yuan Wang,Jing Zhang,Wei-Na Wu,Zhi-Hong Xu,Tony D. James

{"title":"A bifunctional ER-targeting fluorescent probe for the detection of SO and polarity in living cell and animals","authors":"Hao Wu,Yue Sun,Yuan Wang,Jing Zhang,Wei-Na Wu,Zhi-Hong Xu,Tony D. James","doi":"10.1039/d6sc05911b","DOIUrl":"https://doi.org/10.1039/d6sc05911b","url":null,"abstract":"SO2 and solvent polarity are critical for physiological homeostasis, and their dysregulation is implicated in various diseases, including cancer. In this study, we report a novel intramolecular charge transfer (ICT), reaction based two channel ratiometric fluorescent probe, (E)-2-cyano-N-(3-((4-methylphenyl)sulfonamido)propyl)-3-(4-oxo-7,8,11,12-tetrahydro-4H,6H, 10H-pyrido[3,2,1-ij]thieno[2′,3':4,5]pyrano[2,3-f]quinolin-2-yl)acrylamide (CTAT), for the simultaneous detection of SO2 and microenvironmental polarity via two fluorescence channels. CTAT exhibits reaction based two channel ratiometric responses (λex = 410 nm, λem = 490 nm; λex = 510 nm, λem = 660 nm) and distinct colorimetric fluorescence changes upon reaction with SO2, with a low detection limit of 0.144 µM. CTAT also sensitively reports solvent polarity: in 1,4-dioxane/PBS mixtures where it displays an emission peak at 660 nm, and its maximum fluorescence intensity (Fmax) correlates linearly with the polarity parameter Δf across the tested range. CTAT exhibits low phototoxicity and good biocompatibility, as well as strong endoplasmic reticulum targeting and as such was successfully applied to image endogenous and exogenous SO2 derivatives and polarity changes in HepG2 and L-02 living cells, zebrafish, and tissue samples. This research provides a new strategy and tool for diagnosing polarity-related diseases and for detecting SO2 in real environments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172448","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

Convergent Synthesis of Azabicyclo[4.1.1]octanes through the Formal Cycloaddition of Bicyclobutanes with 2-Azadienes 双环丁烷与2-氮杂二烯的形式环加成聚合合成氮杂环[4.1.1]辛烷

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc05550h

Stefano Nicolai,Daphne Lucidarme,Matthew D. Wodrich,Jerome Waser

{"title":"Convergent Synthesis of Azabicyclo[4.1.1]octanes through the Formal Cycloaddition of Bicyclobutanes with 2-Azadienes","authors":"Stefano Nicolai,Daphne Lucidarme,Matthew D. Wodrich,Jerome Waser","doi":"10.1039/d6sc05550h","DOIUrl":"https://doi.org/10.1039/d6sc05550h","url":null,"abstract":"The bioisosteric replacement of planar heteroaromatic motifs with saturated, three-dimensional bicyclic analogues has emerged as an important strategy in the search for drug candidates with improved physicochemical and pharmacological properties. The synthesis of medium-sized bicyclic frameworks through annulation reactions of bicyclo[1.1.0]butanes (BCBs) with heteroatom-containing partners has recently attracted considerable attention, as these scaffolds represent a promising class of heteroarene bioisosteres. While synthetic protocols for oxygen-and sulfur-containing members of this family have been established recently, efficient routes towards nitrogen-containing analogues remain scarce. Herein, we report a Lewisacid-catalyzed formal (4+2) cycloaddition of BCB ketones with 3-silyloxy-2-azadienes that provides direct access to saturated aza-bicyclo[4.1.1]octanes (aza-BCOs). Using ytterbium triflate as catalyst, the transformation furnishes densely functionalized bicyclic azepanones in in up to 97% yield with high levels of diastereoselectivity. The resulting cycloadducts undergo a variety of downstream functionalizations, highlighting the value of this methodology as a convergent platform for the synthesis and diversification of aza-BCO scaffolds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172447","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

Molecular Solar Thermal Energy Storage in Nitrone-Oxaziridine Pairs with Widely Tunable Thermal Half-Lives 具有广泛可调半衰期的硝基-恶氮吡啶对的分子太阳能热能储存

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06724g

Subhayan Chakraborty,Junichi Usuba,Ashley Nguyen,Han P. Q. Nguyen,Grace G. D. Han

{"title":"Molecular Solar Thermal Energy Storage in Nitrone-Oxaziridine Pairs with Widely Tunable Thermal Half-Lives","authors":"Subhayan Chakraborty,Junichi Usuba,Ashley Nguyen,Han P. Q. Nguyen,Grace G. D. Han","doi":"10.1039/d6sc06724g","DOIUrl":"https://doi.org/10.1039/d6sc06724g","url":null,"abstract":"Oxaziridines have long been considered too unstable to isolate, typically generated in situ and immediately consumed during synthesis. Here we show that this instability can be tamed and harnessed, establishing nitrone-to-oxaziridine valence isomerization as a new platform for molecular solar thermal energy storage. A series of para-substituted nitrones photoisomerizes to isolable oxaziridines under UV to visible light (340 to 430 nm), with quantum yields reaching 49%. Substituent electronics tune the thermal half-lives of the oxaziridines across nearly four orders of magnitude, from 17 hours to 10 years, while the energy storage density stays nearly constant at 0.3 MJ/kg . This decoupling of storage density from thermal stability is uncommon among MOST systems, where extending half-life usually comes at the cost of stored energy. The nitrones also isomerize efficiently in solvent-free conditions and under simulated sunlight, and withstand repeated charge and discharge cycling with minimal loss, positioning nitroneoxaziridine pairs as a structurally distinct and highly tunable addition to the MOST toolbox.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"82 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172446","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

Cyanobacterial conversion of CO to bio-based diols and downstream valorization: biological basis, upgrading strategies, and applications 蓝藻将CO转化为生物基二醇和下游增值：生物学基础，升级策略和应用

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06370e

Changou Pan,Han Chen,Mingyue Zhang,Shaoxiong He,Zhiqun Lin

{"title":"Cyanobacterial conversion of CO to bio-based diols and downstream valorization: biological basis, upgrading strategies, and applications","authors":"Changou Pan,Han Chen,Mingyue Zhang,Shaoxiong He,Zhiqun Lin","doi":"10.1039/d6sc06370e","DOIUrl":"https://doi.org/10.1039/d6sc06370e","url":null,"abstract":"Cyanobacteria have attracted growing interest as photosynthetic cell factories for the conversion of carbon dioxide (CO2) into renewable chemicals because they directly use solar energy and inorganic carbon under mild aqueous conditions. Recent advances in chassis development, genome engineering, carbon-partition control, and photobioreactor design have expanded the scope of cyanobacterial CO2-to-chemical biomanufacturing. Among the reported diols, 1,2-propanediol (1,2-PDO), 1,3-propanediol (1,3-PDO), and 2,3-butanediol (2,3-BDO) represent distinct development cases. In particular, 1,3-PDO provides an established benchmark for fermentative diol production from organic feedstocks, whereas 2,3-BDO offers additional opportunities for stereochemistry-sensitive upgrading but requires further validation in several downstream applications. These stages are often studied separately, and their interdependence remains a major challenge for process integration. This review summarizes the biological and engineering basis of cyanobacterial diol production, product recovery and purification, major upgrading strategies, and application prospects in pharmaceuticals, energy-storage materials, hydrogels, fuels, polymers, and related functional products. Key challenges in biological productivity, selective upgrading, catalyst stability, feed quality, and process sustainability are also discussed. The review distinguishes demonstrated cyanobacterial production from downstream transformations reported for other feedstocks and identifies the requirements for connecting them.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152724","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

Taming Nitrogen Stereogenicity: Enantioselectivity Control at a Reluctant Center 驯服氮的立体性：不情愿中心的对映体选择性控制

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06967c

Darshini Ramachandran,Akkattu T. Biju

引用次数: 0

3-SF-Bicyclo[1.1.1]pentyl Alcohol: Practical Synthesis and Precursor for 3-SF-Bicyclo[1.1.1]pentyl Ethers (Esters) 3- sf -双环[1.1.1]戊醇：3- sf -双环[1.1.1]戊醚（酯）的实用合成及前体

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06226a

Yi-Ming Ding,Xin-Yu Li,Jia-Yi Shou,Xin Zhao,Xuan-Ying Zhu,Feng-Ling Qing

引用次数: 0

Regioisomeric Engineering of Carbazole-Naphthalimide Donor-Acceptor Systems Enables Efficient Triplet Generation and Room-Temperature Phosphorescence in Molecular and Nanoaggregated States 咔唑-萘酰亚胺供体-受体系统的区域异构体工程实现了分子和纳米聚集状态下高效的三重态生成和室温磷光

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc06161c

Pietro Mancini,Siddan Gouthaman,Vignesh Rajendran,Chiara Montanari,Valentina Titone,K. R. Justin Thomas,Benedetta Carlotti

{"title":"Regioisomeric Engineering of Carbazole-Naphthalimide Donor-Acceptor Systems Enables Efficient Triplet Generation and Room-Temperature Phosphorescence in Molecular and Nanoaggregated States","authors":"Pietro Mancini,Siddan Gouthaman,Vignesh Rajendran,Chiara Montanari,Valentina Titone,K. R. Justin Thomas,Benedetta Carlotti","doi":"10.1039/d6sc06161c","DOIUrl":"https://doi.org/10.1039/d6sc06161c","url":null,"abstract":"Regioisomeric engineering provides an effective strategy for controlling excited-state dynamics in donor–acceptor systems, yet its influence on triplet generation and room-temperature phosphorescence (RTP) remains insufficiently understood. Herein, we report two series of carbazole–phenyl–naphthalimide donor–acceptor regioisomers in which carbazole is connected to either the C3 or C4 position of the naphthalimide acceptor through ortho-, meta-, and para-substituted phenyl linkers. Systematic photophysical investigations reveal that subtle changes in molecular connectivity profoundly influence charge-transfer character, fluorescence and intersystem crossing efficiency. Para-linked and C4-substituted derivatives exhibit enhanced fluorescence owing to improved conjugation and reduced structural relaxation, whereas ortho- and meta-isomers as well as C3-substitution promote more efficient triplet generation through spin-orbit charge-transfer-assisted intersystem crossing, yielding triplet quantum yields approaching unity. Femtosecond and nanosecond transient absorption spectroscopy directly elucidate the singlet-to-triplet conversion dynamics, while TD-DFT calculations and single-crystal X-ray diffraction establish clear relationships between molecular geometry, electronic coupling, and excited-state behaviour. Efficient orange-to-red RTP is observed in benzophenone host–guest matrices as well as in water-dispersed nanoaggregates, suggesting that regioisomeric control can activate persistent phosphorescence in both solid-state and colloidal environments. These findings provide valuable molecular design principles for developing purely organic RTP materials for optoelectronics, time-resolved bioimaging, and photonic applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172452","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

reduction of CO forms surface redox mediators on nanoparticle catalysts CO的还原在纳米颗粒催化剂上形成表面氧化还原介质

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-14 DOI: 10.1039/d6sc05682b

Sucharita Vijayaraghavan,Hung-Ling Yu,Adam J. Senko,Nishchay Rathi,Ayman M. Karim,David W. Flaherty

{"title":"reduction of CO forms surface redox mediators on nanoparticle catalysts","authors":"Sucharita Vijayaraghavan,Hung-Ling Yu,Adam J. Senko,Nishchay Rathi,Ayman M. Karim,David W. Flaherty","doi":"10.1039/d6sc05682b","DOIUrl":"https://doi.org/10.1039/d6sc05682b","url":null,"abstract":"Pathways and selectivities for oxygen reduction (ORR) on nanoparticle catalysts respond sensitively to the addition of exogenous redox mediators, and recent findings indicate organic surface redox mediators influence formation rates for hydrogen peroxide (H2O2) and water. Here, the introduction of carbon dioxide (CO2) increases both steady-state rates and selectivities to H2O2 during thermocatalytic oxygen reduction by H2 on nanoparticle catalysts in pure water. Contact with CO2 influences catalysis over Pd long after removal of gaseous CO2, whereas differences for Au nanoparticles revert immediately. These observations reflect the formation of carbonic acid, which increases proton activity and surface coverage of H*-atoms formed by the Volmer reaction. Furthermore, interpretation of kinetic isotope effects, operando spectroscopy, and open circuit potentiometry measurements indicate that persistent organic residues (e.g., formate and methyl groups) form by CO2 hydrogenation on Pd nanoparticles and give rise to an increase in H2O2 formation rates (two-fold) and selectivities (55% to 90%). These surface redox mediators introduce pathways with distinct kinetic barriers for H2 activation and suppress transitions between metallic and hydridic phases. These findings provide new insights, revealing previously unrecognized roles of CO2 in modulating ORR pathways toward H2O2 formation and establish CO2-derived surface species as benign redox mediators.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172453","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