Molecular chirality is significantly important for drug synthesis, material design, and other life activities. Thus, developing an efficient, convenient, and rapid technique for chiral recognition is of great industrial and physiological significance. Here, we demonstrate an electrochemical method for the sensitive real-time recognition of chiral molecules by using high-density chiral nanochannels. The chiral porphyrins direct the self-assembly of porphyrin-cored star homopolymers (p-HP) into ordered helical porphyrin arrays, providing chiral-selective nanochannels with enantioselective recognition capabilities. This well-defined assembly enables dual functionality of osmotic energy conversion and chiral molecule recognition, which is combined with a self-powered nanosensor for chiral molecule recognition. This work bridges the gap between molecular chirality and macroscopic membrane engineering, offering a sustainable platform for convenient chiral molecule recognition.
{"title":"Self-Assembled Chiral Nanochannel Arrays with Amplified Signal for Self-Powered Enantiomer Discrimination","authors":"Hua Yang,Yichen Hou,Chao Li,Lei Jiang","doi":"10.1021/jacs.5c18501","DOIUrl":"https://doi.org/10.1021/jacs.5c18501","url":null,"abstract":"Molecular chirality is significantly important for drug synthesis, material design, and other life activities. Thus, developing an efficient, convenient, and rapid technique for chiral recognition is of great industrial and physiological significance. Here, we demonstrate an electrochemical method for the sensitive real-time recognition of chiral molecules by using high-density chiral nanochannels. The chiral porphyrins direct the self-assembly of porphyrin-cored star homopolymers (p-HP) into ordered helical porphyrin arrays, providing chiral-selective nanochannels with enantioselective recognition capabilities. This well-defined assembly enables dual functionality of osmotic energy conversion and chiral molecule recognition, which is combined with a self-powered nanosensor for chiral molecule recognition. This work bridges the gap between molecular chirality and macroscopic membrane engineering, offering a sustainable platform for convenient chiral molecule recognition.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152568","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}
The synthesis of covalent organic frameworks (COFs) is still largely driven by chemists’ literature-informed intuition and iterative trial-and-error, which can be difficult to scale and reproduce. Here we present a chemist-guided human–AI workflow that digitizes this reasoning loop─search, hypothesis formation, and iteration─by coupling a structured literature knowledge base with retrieval-augmented large language models and experiment-aware updates. We first construct a COF synthesis knowledge base containing 2709 protocols extracted from over 800 publications. Given an unseen linker combination, the workflow retrieves a Top-K neighborhood and assembles evidence through stratified sampling and context permutation, generating a range-type synthesis prior over solvent system, catalyst, temperature, time, and stoichiometry. A diagnosis module then interprets macroscopic observations together with powder X-ray diffraction (PXRD) files using a failure taxonomy and proposes targeted updates and next-round experiments. In leave-one-out benchmarks on 60 held-out COFs, the best context-assembly and self-consensus settings improve solvent–catalyst hit rates from baseline levels to up to 0.83, supporting robust transfer beyond individual case studies. We demonstrate the workflow by synthesizing two fluorinated COFs, TAPPy-4F and TAPPy-8F, both exhibiting crystallinity and permanent porosity. By simulating the chemist’s reasoning loop, this human-AI system integrates expert knowledge with model-driven exploration, offering a generalizable and scalable paradigm for the rational design of complex reticular materials.
{"title":"Chemist-Guided Human–AI Workflow for Covalent Organic Framework Synthesis","authors":"Lihan Chen,Zhen Lu,Lin Chen,Linxi Hou,Dong Zhang","doi":"10.1021/jacs.5c20068","DOIUrl":"https://doi.org/10.1021/jacs.5c20068","url":null,"abstract":"The synthesis of covalent organic frameworks (COFs) is still largely driven by chemists’ literature-informed intuition and iterative trial-and-error, which can be difficult to scale and reproduce. Here we present a chemist-guided human–AI workflow that digitizes this reasoning loop─search, hypothesis formation, and iteration─by coupling a structured literature knowledge base with retrieval-augmented large language models and experiment-aware updates. We first construct a COF synthesis knowledge base containing 2709 protocols extracted from over 800 publications. Given an unseen linker combination, the workflow retrieves a Top-K neighborhood and assembles evidence through stratified sampling and context permutation, generating a range-type synthesis prior over solvent system, catalyst, temperature, time, and stoichiometry. A diagnosis module then interprets macroscopic observations together with powder X-ray diffraction (PXRD) files using a failure taxonomy and proposes targeted updates and next-round experiments. In leave-one-out benchmarks on 60 held-out COFs, the best context-assembly and self-consensus settings improve solvent–catalyst hit rates from baseline levels to up to 0.83, supporting robust transfer beyond individual case studies. We demonstrate the workflow by synthesizing two fluorinated COFs, TAPPy-4F and TAPPy-8F, both exhibiting crystallinity and permanent porosity. By simulating the chemist’s reasoning loop, this human-AI system integrates expert knowledge with model-driven exploration, offering a generalizable and scalable paradigm for the rational design of complex reticular materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"177 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152579","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}
The heterogenization of molecular catalysts to be compatible with industrialization demands still faces great challenges. In this work, we demonstrate for the first time that the activity of a molecular catalyst is unrestricted when installed in nanostructured coordination polymers (CPs). CPs that can be used to obtain ultrafine nanowires by ultrasound exfoliation are extremely limited. We illustrate that chain-like CPs can be designed using electrostatic ligand-capped low-coordination-number metal ions and electropositive ligands as building blocks. This guides the preparation of the three-dimensional (3D) chain-like CPs from chloride ion-capped Cu-based chromophores and 1,1’-(1,4-phenylenebis(methylene))bis(3-carboxy quinolin-1-ium) chloride; subsequently, ultrafine sub-1 nm nanowires were obtained via ultrasound exfoliation. The formed ultrafine sub-1 nm CP nanowires demonstrate high activity enhancement for functionalization of C(sp3)−H bonds with conversion being significantly increased for alkylation, thiolation, and oxidation of C(sp3)−H bonds after exposure to external surfaces of the flexible nanowires. Therefore, the observed activity increases in the order CuCl2 < bulk CP crystals < CP nanowires in functionalization of C(sp3)−H bonds. This work not only provides a strategy for constructing chain-like CPs and their ultrafine nanowires but also paves the way for expanding the diversity of the ultrafine 1D CP nanowires.
{"title":"Ultrafine Sub-1 nm One-Dimensional Coordination Polymer Nanowires for Boosting Photocatalytic Functionalization of Inert C(sp3)–H Bonds","authors":"Songtao Liu,Guanfeng Ji,Yefei Wang,Liang Zhao,Cheng He,Chunhong Liu,Chunying Duan","doi":"10.1021/jacs.5c21627","DOIUrl":"https://doi.org/10.1021/jacs.5c21627","url":null,"abstract":"The heterogenization of molecular catalysts to be compatible with industrialization demands still faces great challenges. In this work, we demonstrate for the first time that the activity of a molecular catalyst is unrestricted when installed in nanostructured coordination polymers (CPs). CPs that can be used to obtain ultrafine nanowires by ultrasound exfoliation are extremely limited. We illustrate that chain-like CPs can be designed using electrostatic ligand-capped low-coordination-number metal ions and electropositive ligands as building blocks. This guides the preparation of the three-dimensional (3D) chain-like CPs from chloride ion-capped Cu-based chromophores and 1,1’-(1,4-phenylenebis(methylene))bis(3-carboxy quinolin-1-ium) chloride; subsequently, ultrafine sub-1 nm nanowires were obtained via ultrasound exfoliation. The formed ultrafine sub-1 nm CP nanowires demonstrate high activity enhancement for functionalization of C(sp3)−H bonds with conversion being significantly increased for alkylation, thiolation, and oxidation of C(sp3)−H bonds after exposure to external surfaces of the flexible nanowires. Therefore, the observed activity increases in the order CuCl2 < bulk CP crystals < CP nanowires in functionalization of C(sp3)−H bonds. This work not only provides a strategy for constructing chain-like CPs and their ultrafine nanowires but also paves the way for expanding the diversity of the ultrafine 1D CP nanowires.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152585","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}
Pub Date : 2026-02-11DOI: 10.1021/acs.orglett.6c00128
Lei Zhao,Chungui Xue,Caijin Lei,Jie Tang,Wei Hu,Mengya Wan,Chuan Xiao,Guangbin Cheng,Hongwei Yang
This study reports the synthesis of three novel heterocycle triazolopyrimidine compounds with vicinal amino-nitro groups by introducing dinitropyrazole, nitrooxadiazole, and trinitromethyl groups into the fused-ring framework, respectively. Target compounds 3, 6, and 9 were obtained by subjecting substrates 1, 4, and 7, respectively, to a nucleophilic substitution cyclization reaction with 3,3-diethoxypropionitrile, followed by a nitration step. Among them, 2-(4,5-dinitro-1H-pyrazol-3-yl)-6-nitro-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (3) and 6-nitro-2-(4-nitro-1,2,5-oxadiazol-3-yl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (6) exhibited moderate detonation performance (Dv = 7769 m·s–1and P = 25.1 GPa ; Dv = 8258 m·s–1 and P = 29.4 GPa), low sensitivity (IS = 30 and 24 J; FS = 288 and 240 N) and high thermal stability (Td = 277 and 263 °C). Even more outstanding is 6-nitro-2-(trinitromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (9), which exhibits detonation performance (Dv = 8716 m·s–1) close to that of the classic explosive cyclotrimethylenetrinitramine (RDX: Dv = 8795 m·s–1, IS = 7.5 J, FS = 120 N), but exhibiting lower sensitivity (IS = 16 J, FS = 168 N), making it highly promising as a novel high-energy, low-sensitivity energetic material. This work expands their potential applications as high-energy, low-sensitivity explosives.
{"title":"Construction of Heterocyclic-Triazolopyrimidine Framework for Energetic Compounds: High-Energy, Low-Sensitivity Explosives","authors":"Lei Zhao,Chungui Xue,Caijin Lei,Jie Tang,Wei Hu,Mengya Wan,Chuan Xiao,Guangbin Cheng,Hongwei Yang","doi":"10.1021/acs.orglett.6c00128","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00128","url":null,"abstract":"This study reports the synthesis of three novel heterocycle triazolopyrimidine compounds with vicinal amino-nitro groups by introducing dinitropyrazole, nitrooxadiazole, and trinitromethyl groups into the fused-ring framework, respectively. Target compounds 3, 6, and 9 were obtained by subjecting substrates 1, 4, and 7, respectively, to a nucleophilic substitution cyclization reaction with 3,3-diethoxypropionitrile, followed by a nitration step. Among them, 2-(4,5-dinitro-1H-pyrazol-3-yl)-6-nitro-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (3) and 6-nitro-2-(4-nitro-1,2,5-oxadiazol-3-yl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (6) exhibited moderate detonation performance (Dv = 7769 m·s–1and P = 25.1 GPa ; Dv = 8258 m·s–1 and P = 29.4 GPa), low sensitivity (IS = 30 and 24 J; FS = 288 and 240 N) and high thermal stability (Td = 277 and 263 °C). Even more outstanding is 6-nitro-2-(trinitromethyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine (9), which exhibits detonation performance (Dv = 8716 m·s–1) close to that of the classic explosive cyclotrimethylenetrinitramine (RDX: Dv = 8795 m·s–1, IS = 7.5 J, FS = 120 N), but exhibiting lower sensitivity (IS = 16 J, FS = 168 N), making it highly promising as a novel high-energy, low-sensitivity energetic material. This work expands their potential applications as high-energy, low-sensitivity explosives.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"89 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152593","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}
Monoclonal antibodies are the cornerstone biopharmaceuticals whose safety and efficacy critically depend on their higher-order structure (HOS). Nuclear magnetic resonance (NMR) spectroscopy has emerged as a promising tool for HOS evaluation, yet its application has largely relied on fingerprinting approaches without residue-level interpretation. Here, we report site-specific assignments of methyl resonances in the Fc region of human IgG1, established through amino acid-selective labeling and correlation with backbone resonances using scalar coupling and NOE connectivities, further supported by mutagenesis. These assignments allowed us to identify glycoform-dependent spectral variations, including distinct signatures of core fucosylation and terminal galactosylation, as well as an Fc-specific amino acid substitution. Importantly, these spectral probes were detectable even in antibodies at natural isotopic abundance, enabling practical applications to therapeutic products without isotopic labeling. Furthermore, dynamic filtering highlighted methyl resonances from hinge and receptor-binding residues with elevated mobility, providing localized insights into functional sites. Collectively, our results establish unlabeled methyl NMR as a robust platform for sensitive and practical HOS assessment of therapeutic antibodies. This approach is broadly applicable to monitor glycosylation heterogeneity, chemical modifications, and batch-to-batch consistency, thereby offering a valuable framework for development and quality control of both innovative biopharmaceuticals and biosimilars.
{"title":"Unlabeled NMR Approach with Site-Specific Methyl Assignments for Structural Evaluation of the IgG1 Fc Region","authors":"Saeko Yanaka,Yuuki Koseki,Yohei Miyanoiri,Toshio Yamazaki,Tsutomu Terauchi,Daichi Kaneko,Yukiko Isono,Kohei Tomita,Sachiko Kondo,Masayoshi Onitsuka,Maho Yagi-Utsumi,Hirokazu Yagi,Akiko Ishii-Watabe,Koichi Kato","doi":"10.1021/jacs.5c18997","DOIUrl":"https://doi.org/10.1021/jacs.5c18997","url":null,"abstract":"Monoclonal antibodies are the cornerstone biopharmaceuticals whose safety and efficacy critically depend on their higher-order structure (HOS). Nuclear magnetic resonance (NMR) spectroscopy has emerged as a promising tool for HOS evaluation, yet its application has largely relied on fingerprinting approaches without residue-level interpretation. Here, we report site-specific assignments of methyl resonances in the Fc region of human IgG1, established through amino acid-selective labeling and correlation with backbone resonances using scalar coupling and NOE connectivities, further supported by mutagenesis. These assignments allowed us to identify glycoform-dependent spectral variations, including distinct signatures of core fucosylation and terminal galactosylation, as well as an Fc-specific amino acid substitution. Importantly, these spectral probes were detectable even in antibodies at natural isotopic abundance, enabling practical applications to therapeutic products without isotopic labeling. Furthermore, dynamic filtering highlighted methyl resonances from hinge and receptor-binding residues with elevated mobility, providing localized insights into functional sites. Collectively, our results establish unlabeled methyl NMR as a robust platform for sensitive and practical HOS assessment of therapeutic antibodies. This approach is broadly applicable to monitor glycosylation heterogeneity, chemical modifications, and batch-to-batch consistency, thereby offering a valuable framework for development and quality control of both innovative biopharmaceuticals and biosimilars.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"242 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152605","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}
Pub Date : 2026-02-11DOI: 10.1021/acssuschemeng.5c11739
Patrick A. Bailie,Pamela J. Walsh,Andrew C. Marr,Patricia C. Marr
A class of NaturIL gels was prepared from alginate and ionic liquids containing ions that can be derived from nature. Aqueous Cholinium Amino Acid Ionic Liquids (ChAAILs) solutions with sodium alginate derived from Laminaria digitata were cross-linked by calcium ions and the variation of rheological properties investigated relative to the parent hydrogel. Viscoelastic gels were formed for the four amino acid anions [Pro], [Gly], [Lys] and [Val] and their rheological properties were compared to those of an analogous hydrogel. All four were found to be stiffer and more viscoelastic than the hydrogel and have properties that varied as the amino acid anion was changed.
{"title":"NaturIL Gels: Gels Formed from the Synergy of Alginates and Bioderived Ions. Tunable Gels from Seaweed","authors":"Patrick A. Bailie,Pamela J. Walsh,Andrew C. Marr,Patricia C. Marr","doi":"10.1021/acssuschemeng.5c11739","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11739","url":null,"abstract":"A class of NaturIL gels was prepared from alginate and ionic liquids containing ions that can be derived from nature. Aqueous Cholinium Amino Acid Ionic Liquids (ChAAILs) solutions with sodium alginate derived from Laminaria digitata were cross-linked by calcium ions and the variation of rheological properties investigated relative to the parent hydrogel. Viscoelastic gels were formed for the four amino acid anions [Pro], [Gly], [Lys] and [Val] and their rheological properties were compared to those of an analogous hydrogel. All four were found to be stiffer and more viscoelastic than the hydrogel and have properties that varied as the amino acid anion was changed.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"59 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152382","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}
Monoclonal antibodies are widely used biotherapeutics, whose efficacy and pharmacokinetics critically depend on their structural integrity. Among chemical degradation pathways, methionine oxidation is a particularly important post-translational modification that compromises antibody stability, Fc receptor binding, and thereby FcRn-mediated recycling and FcγR-mediated effector functions. However, the structural consequences of oxidation remain poorly understood, largely due to the subtle and localized nature of the modification. Here, we present an integrated analytical framework combining methyl-based NMR spectroscopy, selective enzymatic reduction, and peptide mapping to resolve methionine oxidation in the Fc region of human IgG1 antibodies at residue- and stereochemical-level resolution. By selectively labeling methionine methyl groups, we monitored oxidation-induced spectral changes in conserved Fc residues Met252 and Met428. Site-directed mutagenesis revealed a mutual influence between these residues, consistent with their spatial proximity at the CH2–CH3 domain interface. Stereospecific reduction with methionine sulfoxide reductase A enabled the assignment of R- and S-isomers, while peptide mapping by liquid chromatography–mass spectrometry corroborated the NMR findings. This combined approach demonstrated that Met252, which is solvent-exposed, is more susceptible to oxidation than buried Met428 and that both residues display stereochemical heterogeneity that modulates local structure. By bridging chemical modifications and higher-order structural perturbations, this integrated framework provides mechanistic insights into how methionine oxidation impairs antibody function. More broadly, it establishes a basis for quality assurance and rational design of therapeutic antibodies with improved stability.
{"title":"Stereochemical and Structural Characterization of Methionine Oxidation in the IgG1 Fc Region by Integrated NMR and LC-MS Analysis","authors":"Maho Yagi-Utsumi,Saeko Yanaka,Noritaka Hashii,Kohei Tomita,Takashi Misawa,Yosuke Demizu,Akiko Ishii-Watabe,Koichi Kato","doi":"10.1021/acs.analchem.5c06092","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c06092","url":null,"abstract":"Monoclonal antibodies are widely used biotherapeutics, whose efficacy and pharmacokinetics critically depend on their structural integrity. Among chemical degradation pathways, methionine oxidation is a particularly important post-translational modification that compromises antibody stability, Fc receptor binding, and thereby FcRn-mediated recycling and FcγR-mediated effector functions. However, the structural consequences of oxidation remain poorly understood, largely due to the subtle and localized nature of the modification. Here, we present an integrated analytical framework combining methyl-based NMR spectroscopy, selective enzymatic reduction, and peptide mapping to resolve methionine oxidation in the Fc region of human IgG1 antibodies at residue- and stereochemical-level resolution. By selectively labeling methionine methyl groups, we monitored oxidation-induced spectral changes in conserved Fc residues Met252 and Met428. Site-directed mutagenesis revealed a mutual influence between these residues, consistent with their spatial proximity at the CH2–CH3 domain interface. Stereospecific reduction with methionine sulfoxide reductase A enabled the assignment of R- and S-isomers, while peptide mapping by liquid chromatography–mass spectrometry corroborated the NMR findings. This combined approach demonstrated that Met252, which is solvent-exposed, is more susceptible to oxidation than buried Met428 and that both residues display stereochemical heterogeneity that modulates local structure. By bridging chemical modifications and higher-order structural perturbations, this integrated framework provides mechanistic insights into how methionine oxidation impairs antibody function. More broadly, it establishes a basis for quality assurance and rational design of therapeutic antibodies with improved stability.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"29 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152386","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}
Alkenylboronates represent a cornerstone functional group in modern organic synthesis owing to their versatile reactivity in Suzuki–Miyaura cross-coupling reactions and other key transformations. However, catalytic asymmetric methods for producing stereodefined tetrasubstituted axially chiral alkenylboronates remain underdeveloped. Here, we report a copper-catalyzed atroposelective protoboration of allenes, providing a facile strategy to access tetrasubstituted axially chiral Z-alkenylboronates with excellent regio- and atroposelectivities. The enantiomerically enriched axially chiral alkenylboronates could be further transformed into diverse stereodefined tetrasubstituted axially chiral olefins via the cross-coupling reaction of the C–B bond. This methodology also provides a new avenue to construct C–C or C–N axially chiral alkene–phosphine frameworks.
{"title":"Cu-Catalyzed Atroposelective Protoboration of Allenes to Access Stereodefined Tetrasubstituted Axially Chiral Alkenylboronates","authors":"Baoli Li,Zhan Huang,Shichao Hong,Liangzhi Pang,Yan Wu,Xuechen Li,Hao Li,Hua-Jie Jiang,Jie Yu,Xue Zhang,Qiankun Li","doi":"10.1021/acs.orglett.6c00026","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00026","url":null,"abstract":"Alkenylboronates represent a cornerstone functional group in modern organic synthesis owing to their versatile reactivity in Suzuki–Miyaura cross-coupling reactions and other key transformations. However, catalytic asymmetric methods for producing stereodefined tetrasubstituted axially chiral alkenylboronates remain underdeveloped. Here, we report a copper-catalyzed atroposelective protoboration of allenes, providing a facile strategy to access tetrasubstituted axially chiral Z-alkenylboronates with excellent regio- and atroposelectivities. The enantiomerically enriched axially chiral alkenylboronates could be further transformed into diverse stereodefined tetrasubstituted axially chiral olefins via the cross-coupling reaction of the C–B bond. This methodology also provides a new avenue to construct C–C or C–N axially chiral alkene–phosphine frameworks.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"7 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152557","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}
Traditional triethylamine (TEA) gas sensors suffer from the drawback of high detection limits due to the low charge-transfer ability of materials. Herein, the Pr3+-doped WO3 one-dimensional (1D) yoga-pillar-shaped nanorods have been successfully synthesized via electrostatic spinning and oxidative calcination. The gas sensor based on WO3:1%Pr3+ 1D yoga-pillar-shaped nanorods exhibits excellent performance in terms of rapid response (3-fold), higher response (3.75-fold), and lower detection limits compared with the WO3 gas sensor. Furthermore, the sensor features excellent repeatability and long-term stability, indicating the potential commercial value. The findings reveal that doping Pr3+ is one of the effective strategies to improve the gas-sensing performance of WO3. Based on the above analysis, as well as literature reports, the gas-sensing mechanism is explored systematically. The enhancement can be attributed to the formation of impurity energy levels, which can effectively optimize the band structure and facilitate electron transfer. The recombination between electrons in the conduction band and holes in the valence band is partly suppressed, providing more opportunities for electron exchange between WO3 and oxygen molecules. The content of chemically adsorbed oxygen on the WO3 surface has significantly increased, which is one of the fundamental reasons for the improvement in gas sensitivity. In addition, the practical value of the WO3:1%Pr3+ 1D yoga-pillar-shaped nanorod gas sensor is demonstrated by testing the freshness of fish stored under various conditions. This work presents a high-performance ppb-level TEA detection method and broadens the application scope of WO3 gas sensors.
{"title":"Pr3+-Doped WO3 1D Yoga-Pillar-Shaped Nanorod Gas Sensor: A High-Performance Ppb-Level Triethylamine Gas Sensor for Fish Freshness Monitoring","authors":"Jiale Wang,Xiang Zhao,Xiang Li,Rundong Xue,Dan Li,Feng Li,Ying Yang,Tianqi Wang,Duanduan Yin,Xiangting Dong","doi":"10.1021/acssensors.5c03942","DOIUrl":"https://doi.org/10.1021/acssensors.5c03942","url":null,"abstract":"Traditional triethylamine (TEA) gas sensors suffer from the drawback of high detection limits due to the low charge-transfer ability of materials. Herein, the Pr3+-doped WO3 one-dimensional (1D) yoga-pillar-shaped nanorods have been successfully synthesized via electrostatic spinning and oxidative calcination. The gas sensor based on WO3:1%Pr3+ 1D yoga-pillar-shaped nanorods exhibits excellent performance in terms of rapid response (3-fold), higher response (3.75-fold), and lower detection limits compared with the WO3 gas sensor. Furthermore, the sensor features excellent repeatability and long-term stability, indicating the potential commercial value. The findings reveal that doping Pr3+ is one of the effective strategies to improve the gas-sensing performance of WO3. Based on the above analysis, as well as literature reports, the gas-sensing mechanism is explored systematically. The enhancement can be attributed to the formation of impurity energy levels, which can effectively optimize the band structure and facilitate electron transfer. The recombination between electrons in the conduction band and holes in the valence band is partly suppressed, providing more opportunities for electron exchange between WO3 and oxygen molecules. The content of chemically adsorbed oxygen on the WO3 surface has significantly increased, which is one of the fundamental reasons for the improvement in gas sensitivity. In addition, the practical value of the WO3:1%Pr3+ 1D yoga-pillar-shaped nanorod gas sensor is demonstrated by testing the freshness of fish stored under various conditions. This work presents a high-performance ppb-level TEA detection method and broadens the application scope of WO3 gas sensors.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":"156 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152355","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}
Our previous study demonstrated that apurinic/apyrimidinic endonuclease 1 (APE1) and miR-514a are significantly overexpressed in the cytoplasm of drug-resistant neuroblastoma (NB) cells. Furthermore, we have developed a novel strategy for monitoring drug resistance in NB by targeting cytoplasmic APE1 and miR-514a. The overexpression of key enzymes in the mitochondrial base excision repair pathway, along with dysregulated miRNAs, is closely associated with chemotherapy resistance in tumors. Therefore, this study leverages cytochrome c (cyt c), located in the inner mitochondrial membrane as a targeting agent and the mitochondria-specific expression of 16S rRNA as a response switch to develop a spatially resolved, sequential activation system for an allosteric DNA nanomachine (AP-miR-tFNA), enabling in vivo detection of APE1 and miR-514a within mitochondria and facilitating molecular imaging of NB. AP-miR-tFNA sequentially responds to cyt c, 16S rRNA, miR-514a, and APE1, thereby undergoing a conformational change that efficiently achieves progressive dissociation of the fluorophore from the quencher through a sequential mechanism, ultimately generating a detectable fluorescence signal. Experimental results demonstrate that AP-miR-tFNA enables in vivo monitoring of drug resistance in NB, providing an innovative and dependable approach for monitoring therapeutic resistance in NB. In particular, AP-miR-tFNA enables in situ detection of APE1 and miR-514a within NB plasma exosomes, thereby allowing non-invasive differentiation between high-risk and low-to-intermediate-risk NB, as well as between drug-resistant NB and non-drug-resistant NB.
{"title":"Spatially Resolved Sequential Activation of Allosteric DNA for In Vivo Dual-Target Detection within Mitochondria: A Strategy to Visualize of Drug-Resistant Neuroblastoma","authors":"Jingzhe Zang,Yingyu Zhang,Kangbo Liu,Yuyin Xu,Liang Zhao,Wentao Wang,Mengxin Zhang,Xueyi Qin,Qionglin Wang,Xianwei Zhang,Wancun Zhang","doi":"10.1021/acssensors.5c04083","DOIUrl":"https://doi.org/10.1021/acssensors.5c04083","url":null,"abstract":"Our previous study demonstrated that apurinic/apyrimidinic endonuclease 1 (APE1) and miR-514a are significantly overexpressed in the cytoplasm of drug-resistant neuroblastoma (NB) cells. Furthermore, we have developed a novel strategy for monitoring drug resistance in NB by targeting cytoplasmic APE1 and miR-514a. The overexpression of key enzymes in the mitochondrial base excision repair pathway, along with dysregulated miRNAs, is closely associated with chemotherapy resistance in tumors. Therefore, this study leverages cytochrome c (cyt c), located in the inner mitochondrial membrane as a targeting agent and the mitochondria-specific expression of 16S rRNA as a response switch to develop a spatially resolved, sequential activation system for an allosteric DNA nanomachine (AP-miR-tFNA), enabling in vivo detection of APE1 and miR-514a within mitochondria and facilitating molecular imaging of NB. AP-miR-tFNA sequentially responds to cyt c, 16S rRNA, miR-514a, and APE1, thereby undergoing a conformational change that efficiently achieves progressive dissociation of the fluorophore from the quencher through a sequential mechanism, ultimately generating a detectable fluorescence signal. Experimental results demonstrate that AP-miR-tFNA enables in vivo monitoring of drug resistance in NB, providing an innovative and dependable approach for monitoring therapeutic resistance in NB. In particular, AP-miR-tFNA enables in situ detection of APE1 and miR-514a within NB plasma exosomes, thereby allowing non-invasive differentiation between high-risk and low-to-intermediate-risk NB, as well as between drug-resistant NB and non-drug-resistant NB.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":"92 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152360","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}
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