Chemical Science最新文献_第8页

Radical chemistry in atmospheric ice analogs forms persistent trifluoroacetic acid. 大气冰类似物中的自由基化学形成持久性三氟乙酸。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-06 DOI: 10.1039/d6sc05084k

Mason McAnally, Koushik Mondal, Yuheng Luo, Nils W Melbourne, Pooja Chahal, Xilin Bai, Jinghui Lu, Baoyu Song, Xinxuan Wang, Andrew M Turner, Alexandre Bergantini, Souvick Biswas, Rui Sun, Tao Yang, Ralf I Kaiser

{"title":"Radical chemistry in atmospheric ice analogs forms persistent trifluoroacetic acid.","authors":"Mason McAnally, Koushik Mondal, Yuheng Luo, Nils W Melbourne, Pooja Chahal, Xilin Bai, Jinghui Lu, Baoyu Song, Xinxuan Wang, Andrew M Turner, Alexandre Bergantini, Souvick Biswas, Rui Sun, Tao Yang, Ralf I Kaiser","doi":"10.1039/d6sc05084k","DOIUrl":"10.1039/d6sc05084k","url":null,"abstract":"Trifluoroacetic acid (TFA, CF3COOH), the most prevalent per- and polyfluoroalkyl substance (PFAS), is accumulating globally in precipitation, soils, and drinking water, yet its formation remains unresolved. Atmospheric models emphasize gas-phase oxidation of hydrofluorocarbons and hydrofluoroolefins, but measured abundances often exceed predictions, implying missing chemistry. Here, we identify a condensed-phase radical pathway to TFA in cryogenic trifluoromethane/carbon dioxide ice analogs. Energetic processing generates trifluoromethyl (CF3) and hydroxycarbonyl (HOCO) radicals that undergo barrierless recombination to form TFA. Fourier transform infrared spectroscopy tracks reactive intermediates and carboxylic acid functional groups, while synchrotron vacuum-ultraviolet photoionization reflectron time-of-flight mass spectrometry provides isomer-selective detection of TFA and diagnostic dimer fragments. These results support CF3-HOCO recombination as a potential condensed-phase route linking fluorocarbon degradation to persistent PFAS formation, highlighting the potential role of ice crystals and cloud particles as chemical reactors in atmospheric fluorine chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13641192/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Control of axial stereochemistry for the enantioselective construction of a QUINAP library. 对映选择构建QUINAP文库的轴向立体化学控制。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-06 DOI: 10.1039/d6sc06573b

Jie Zhang, Dingkai Lou, Mengli Wang, Can Zhu

{"title":"Control of axial stereochemistry for the enantioselective construction of a QUINAP library.","authors":"Jie Zhang, Dingkai Lou, Mengli Wang, Can Zhu","doi":"10.1039/d6sc06573b","DOIUrl":"https://doi.org/10.1039/d6sc06573b","url":null,"abstract":"QUINAP, a classic axially chiral P,N-ligand based on the skeleton of an atropisomeric heterobiaryl, has been widely applied in various types of enantioselective transformations. To date, the efficient construction of a QUINAP library with high enantioselectivity is still underdeveloped. Herein, we report a two-step synthesis of QUINAP derivatives from racemic QUINOLs with high enantioselectivity by controlling the dynamic axial stereochemistry in heterobiaryl skeletons. Under heating, solvent-dependent crystallization-induced deracemization (CID) of QUINOLs was realized with chiral ammonium salt. Subsequently, palladium-catalyzed stereospecific phosphination of enantioenriched QUINOLs delivered QUINAP products with high enantiopurity. The bidentate phosphine ligand dppp (1,3-bis(diphenylphosphino)propane) plays a key role in favoring the phosphination pathway over axial rotation. Density functional theory (DFT) calculations have provided clear insights into the palladium-catalyzed stereospecific phosphination pathway. Finally, construction of a QUINAP library was accomplished with excellent enantiopurity, and it was successfully applied in the A3-coupling and alkene hydroboration reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13662651/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Programming photoactuation by modulating the degree of charge-separation in DASA-based liquid crystal elastomers. 通过调制dasa基液晶弹性体的电荷分离度来编程光致动。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-06 DOI: 10.1039/d6sc05729b

Arnab Nandi, Jesus Guillen Campos, Waseem Shindy, Javier Read de Alaniz

{"title":"Programming photoactuation by modulating the degree of charge-separation in DASA-based liquid crystal elastomers.","authors":"Arnab Nandi, Jesus Guillen Campos, Waseem Shindy, Javier Read de Alaniz","doi":"10.1039/d6sc05729b","DOIUrl":"10.1039/d6sc05729b","url":null,"abstract":"Photoresponsive soft actuators enable light-driven shape changes with spatial and temporal control, typically achieved by integrating molecular photoswitches into liquid crystal elastomers (LCEs). Commonly, the structure-property relationship of photoswitches is well explored in dilute solution phase. However, connecting solution-phase molecular electronic structure to function in crosslinked LCEs remains challenging. Here, we use donor-acceptor Stenhouse adducts (DASAs) as a tunable photoswitch family to engineer an electronically diverse DASA-LCE platform with varied charge separation. A series of five DASAs spanning neutral to strongly zwitterionic character were incorporated into siloxane-based LCEs via late-stage functionalization. The solution-phase solvatochromic slope serves as a spectroscopic descriptor for ground-state push-pull character and reveals a strong linear correlation with solid-state reversible photofading rate coefficients, establishing a unique molecular-level predictor for DASA-based LCE switching. Increasing charge separation produces a continuum of LCE responses: neutral DASAs undergo efficient photoisomerization that drives reversible uniaxial contraction. In contrast, zwitterionic DASAs drive photothermal bending, enabling bilayer actuators with biomimetic crawling (0.2 cm s-1) and jumping. These results establish a design rule linking DASA electronic structure to macroscopic actuation and provide a practical screening metric for white-light-responsive LCE actuators.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13666557/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149191599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Harnessing phosphine oxide interactions with HF and HBF₄ to enable the hydrofluorination of alkynes. 利用氧化膦与HF和HBF4的相互作用，实现炔烃的氢氟化。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-06 DOI: 10.1039/d6sc05829a

Ouchan He, Froze Jameel, Martin Kaupp, Thomas Braun

引用次数: 0

PNA-ligand conjugates enable site-selective and directional targeting of adjacent G-quadruplexes. pna -配体偶联物可以选择性和定向靶向相邻的g -四联体。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-05 DOI: 10.1039/d6sc04697e

Raffaele Graziano, Enrico Cadoni, Simona Marzano, Valentina Arciuolo, Naura Fakhira Antariksa, Marco Di Antonio, Jussara Amato, Annemieke Madder, Bruno Pagano

{"title":"PNA-ligand conjugates enable site-selective and directional targeting of adjacent G-quadruplexes.","authors":"Raffaele Graziano, Enrico Cadoni, Simona Marzano, Valentina Arciuolo, Naura Fakhira Antariksa, Marco Di Antonio, Jussara Amato, Annemieke Madder, Bruno Pagano","doi":"10.1039/d6sc04697e","DOIUrl":"10.1039/d6sc04697e","url":null,"abstract":"G-quadruplexes (G4s) are non-canonical DNA structures enriched in gene promoters and involved in transcriptional regulation, making them attractive drug targets, albeit difficult to target individually with high specificity due to their structural similarity. In the human c-KIT promoter, three adjacent G4 motifs (c-KIT1, c-KIT*, and c-KIT2) modulate oncogene expression, yet their individual contributions remain poorly understood, posing a significant challenge for selective targeting and underscoring the need for tools capable of discriminating between closely spaced G4s. Here, we report a dual-recognition strategy that combines the sequence specificity of peptide nucleic acids (PNAs) with the stabilizing properties of a G4 ligand to achieve site-selective and programmable targeting of neighboring G4s. Sequence-specific base pairing enables the PNA probe to recognize the flanking region between the c-KIT1 and c-KIT* motifs, positioning the ligand in proximity to a defined G4 structure and enabling directional and selective stabilization. Ligand conjugation at the N- or C-terminus of the PNA directs selective targeting of individual G4 units, while dual conjugation enables their simultaneous stabilization. This approach provides positional control not accessible with conventional small-molecule ligands and establishes a modular platform for targeting G4s within regions containing closely spaced motifs. A dual luciferase assay revealed that targeted G4 stabilization within the c-KIT promoter leads to distinct transcriptional outcomes in cells, indicating distinct regulatory roles of the c-KIT1 and c-KIT* motifs. This PNA-ligand platform enables site-specific recognition and discrimination between adjacent G4s and provides a general framework for selective chemical intervention in G4-regulated oncogenes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13648328/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Correction: Robust biomimetic MOF featuring a negative pocket for precise recognition of uranyl, enabling ultrahigh U/V selectivity and rapid uranium extraction from seawater. 修正：强大的仿生MOF具有精确识别铀的负口袋，实现超高的U/V选择性和从海水中快速提取铀。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-05 eCollection Date: 2026-10-15 DOI: 10.1039/d6sc90189a

Anni Ye, Yuxuan Liu, Lele Gong, Xianqing Xie, Feng Luo

引用次数: 0

Unlocking catalytic asymmetric transformations of sulfilimidoyl fluorides toward chiral sulfinimidate esters. 解锁催化不对称转化为手性亚胺酰氟酯。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-05 DOI: 10.1039/d6sc06421c

He-Ping Li, Ze Zhao, Meng Li, Xuan Jin, Xiang-Hong He, Jin Zhang, Wei Huang, Cheng Peng, Gu Zhan, Bo Han

{"title":"Unlocking catalytic asymmetric transformations of sulfilimidoyl fluorides toward chiral sulfinimidate esters.","authors":"He-Ping Li, Ze Zhao, Meng Li, Xuan Jin, Xiang-Hong He, Jin Zhang, Wei Huang, Cheng Peng, Gu Zhan, Bo Han","doi":"10.1039/d6sc06421c","DOIUrl":"https://doi.org/10.1039/d6sc06421c","url":null,"abstract":"The rational design of bioactive molecules increasingly utilizes sulfur-containing groups such as sulfoximines and sulfilimines. While sulfonimidoyl fluorides have emerged as versatile chiral S(vi) electrophiles enabling efficient asymmetric synthesis of sulfoximines, their S(iv) counterparts, sulfilimidoyl fluorides, have remained inaccessible in asymmetric catalysis due to their intrinsic instability and configurational lability. Central to this strategy is a bifunctional tertiary amine-hydrogen-bond donor catalyst that enables selective conversion of a transient sulfur(iv) intermediate. Mechanistic studies support a dynamic kinetic resolution process involving a sulfilimidoyl fluoride intermediate, providing a distinct strategy for accessing S-stereogenic sulfur(iv) compounds. The method exhibits a broad substrate scope, encompassing a wide range of sulfenamides and alcohols. Notably, an idebenone-derived sulfinimidate ester (3bg) exhibits prolonged intracellular persistence, while both S-3bg and racemic 3bg exhibit improved anti-inflammatory activity. This work provides a new strategy for asymmetric transformation of sulfilimidoyl fluoride intermediates and expands access to synthetically and biologically valuable sulfur stereocenters for drug discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13656016/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Function-preserving photooxidation of AS1411 aptamer by a G-quadruplex-guided photosensitizer. g -四聚物引导光敏剂对AS1411适体的保功能光氧化作用。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-05 DOI: 10.1039/d6sc06144c

Maria V Cottini, Karolina Saczuk, Jakub Trojnar, Lucía López-Pacios, Dario Puchán Sánchez, Arthur H G David, Ikenna Obi, Nasim Sabouri, Juan J Nogueira, Marta Dudek, Clément Cabanetos, Lara Martínez-Fernández, Jan Jamroskovic, Marco Deiana

{"title":"Function-preserving photooxidation of AS1411 aptamer by a G-quadruplex-guided photosensitizer.","authors":"Maria V Cottini, Karolina Saczuk, Jakub Trojnar, Lucía López-Pacios, Dario Puchán Sánchez, Arthur H G David, Ikenna Obi, Nasim Sabouri, Juan J Nogueira, Marta Dudek, Clément Cabanetos, Lara Martínez-Fernández, Jan Jamroskovic, Marco Deiana","doi":"10.1039/d6sc06144c","DOIUrl":"https://doi.org/10.1039/d6sc06144c","url":null,"abstract":"AS1411 is a G-quadruplex (G4) aptamer that binds nucleolin (NCL) and is widely used to promote cancer-associated delivery of photoactive cargos. Yet the fate of AS1411 after photosensitizer loading and light activation remains unclear as reactive oxygen species (ROS) generation could disrupt its guanine-rich fold and abolish NCL recognition, or remain locally confined while preserving targeting function. Here, we address this question using DBI-POE, a heavy-atom-free dibenzothioxanthene imide photosensitizer combining G4 recognition, fluorescence activation, and ROS generation. In this system, AS1411 converts weakly emissive, radical-prone DBI-POE aggregates into a fluorescent G4-bound complex with singlet oxygen (1O2)-biased reactivity and attenuated radical-probe responses. 1H NMR spectroscopy, quantum-mechanical (QM) calculations, molecular dynamics (MD) simulations, and primer-extension mapping support preferential DBI-POE association with the 3'-terminal tetrad region and are consistent with a partially intercalated binding model. Upon irradiation, this complex undergoes site-localized guanine oxidation. This damage is suppressed under non-G4-forming conditions and in G4-disrupted controls. Remarkably, oxidation preserves the BG4-recognized G4 epitope and full-length NCL binding, defining a DBI-POE-specific, function-preserving mode of aptamer-guided photosensitization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13659297/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Towards next generation enzyme mimics through local electric field control in organic cage catalysts. 在有机笼型催化剂中通过局部电场控制实现新一代酶模拟。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-02 DOI: 10.1039/d6sc04940k

Marco Vitek, Igor Rončević, Keith G Andrews

{"title":"Towards next generation enzyme mimics through local electric field control in organic cage catalysts.","authors":"Marco Vitek, Igor Rončević, Keith G Andrews","doi":"10.1039/d6sc04940k","DOIUrl":"https://doi.org/10.1039/d6sc04940k","url":null,"abstract":"Electric fields (EFs) can, in principle, accelerate chemical reactions by preferentially stabilising charge distribution in transition states. In practice, strategies for aligning tuneable EFs across reaction sites in artificial molecular systems remain scarce. Here, using modelling, we establish the potential of dipolar supramolecular cavities as an approach to quantify and optimise solution-phase EF catalysis. By positioning pairs of charged substituents on a cage catalyst exterior, we align tuneable, oriented, local fields with reaction dipoles without introducing through-bond effects. We introduce a finite capacitor model to evaluate EFs in dipolar cavities and show cavities of 1 nm can generate EF strengths comparable to enzymes (∼0.2 V Å-1). We validate this model computationally by quantifying EF-dependent catalysis in synthetically accessible analogues of an existing acyl-transfer cage catalyst, obtaining a large 13 kcal mol-1 per V Å-1 dependency. Roughly half of the generated field interaction energy is translated into catalysis, yielding a projected rate acceleration of two orders of magnitude. Optimal EF catalysis required constraining and aligning both the reactant complex and transition state in the EF, suggesting that enzymes may employ strong binding to maximise EF catalysis by preserving electrostatically strained substrate configurations in local fields.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13631960/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Glycopolymer-based nanofibers with tunable polyelectrolyte content for modulating cellular interactions and drug delivery. 具有可调聚电解质含量的甘聚聚合物基纳米纤维，用于调节细胞相互作用和药物传递。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-02 DOI: 10.1039/d6sc06330f

Hannah Schnicke, Harvey K MacKenzie, J Diego Garcia-Hernandez, Steven T G Street, Zachary M Hudson, Ian Manners

{"title":"Glycopolymer-based nanofibers with tunable polyelectrolyte content for modulating cellular interactions and drug delivery.","authors":"Hannah Schnicke, Harvey K MacKenzie, J Diego Garcia-Hernandez, Steven T G Street, Zachary M Hudson, Ian Manners","doi":"10.1039/d6sc06330f","DOIUrl":"https://doi.org/10.1039/d6sc06330f","url":null,"abstract":"Polymer-based nanoparticles are emerging as a promising class of nanomedicines, yet are typically limited to spherical morphologies with limited control over particle size. As nanoparticle morphology, size, dispersity and surface chemistry dictate their biological performance, developing nanoparticles with precise control over these parameters is essential for the design of next-generation nanomedicines. Here, we report one-dimensional triblock nanofibers with a dual-functional corona, that combine the minimal cytotoxicity of a polyfructose glycopolymer and the improved cellular interaction of polyamine polyelectrolytes. Living crystallization-driven self-assembly enables precise length and dispersity control of poly(fluorene trimethylene carbonate)-b-polyfructose nanofibers from 46 nm to 1.15 µm, with excellent long-term colloidal stability in water. These nanoparticles were then loaded with the anticancer drug paclitaxel, and its delivery to MDA-MB-231 breast cancer cells was investigated. IC50 values as low as 0.038 µg mL-1 were measured, outperforming free paclitaxel. Flow cytometry and confocal laser scanning microscopy revealed cellular internalization of all crystalline triblock nanofibers by breast cancer cells. Nanofibers with solely amine-based coronas showed superior cellular uptake with low lysosomal accumulation but heightened cytotoxicity, whereas bifunctional nanofibers containing a central polyfructose segment undergo cellular uptake with moderate lysosomal accumulation and minimal cytotoxicity. These results highlight that the precise control over size, sequence and surface chemistry imparted by living CDSA permits systematic tuning of the biological performance of nanoparticles, establishing crystalline triblock nanofibers as a platform for the future design of drug delivery systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13632826/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0