Pub Date : 2026-02-11DOI: 10.1021/acssensors.5c03824
Kun Luo,Zhijian Peng,Xiuli Fu
Two-dimensional conductive metal−organic frameworks (2D c-MOFs) combine tunable pore structures with electronic conductivity, which demonstrate significant potential in the field of room-temperature gas sensors. This review summarizes the current understanding of the fundamental sensing mechanisms of 2D c-MOFs, including adsorption-driven charge transfer, metal-center redox activity, ligand-mediated interactions, and structure-induced modulation of electronic transport. Thereafter, a systematic, design-oriented classification of strategies for 2D c-MOFs based sensors is presented to enhance their performance, including the tuning of metal nodes and mixed ligands, control of micro and nanomorphology, noble-metal nanoparticle decoration, formation of heterostructures and composites, and usage of field-effect transistors. Additionally, the following issues are addressed to translate 2D c-MOFs from promising materials into deployed sensors: long-term stability, humidity management, and fabrication of scalable devices. Future research focuses are proposed so as to unlock the full potential of 2D c-MOFs for practical sensing applications.
{"title":"Two-Dimensional Conductive Metal−Organic Frameworks for Gas Sensors: Mechanisms and Design Strategies","authors":"Kun Luo,Zhijian Peng,Xiuli Fu","doi":"10.1021/acssensors.5c03824","DOIUrl":"https://doi.org/10.1021/acssensors.5c03824","url":null,"abstract":"Two-dimensional conductive metal−organic frameworks (2D c-MOFs) combine tunable pore structures with electronic conductivity, which demonstrate significant potential in the field of room-temperature gas sensors. This review summarizes the current understanding of the fundamental sensing mechanisms of 2D c-MOFs, including adsorption-driven charge transfer, metal-center redox activity, ligand-mediated interactions, and structure-induced modulation of electronic transport. Thereafter, a systematic, design-oriented classification of strategies for 2D c-MOFs based sensors is presented to enhance their performance, including the tuning of metal nodes and mixed ligands, control of micro and nanomorphology, noble-metal nanoparticle decoration, formation of heterostructures and composites, and usage of field-effect transistors. Additionally, the following issues are addressed to translate 2D c-MOFs from promising materials into deployed sensors: long-term stability, humidity management, and fabrication of scalable devices. Future research focuses are proposed so as to unlock the full potential of 2D c-MOFs for practical sensing applications.","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":"46 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152354","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}
Electrocatalytic systems for low-concentration CO2 reduction still face significant challenges in the mass transport and electronic modulation of catalyst active sites. This study developed a gas-molecular shear strategy for constructing nickel single atoms (Ni SAs) and nanocluster (NC)-doped carbon nanofiber catalysts (Ni/TCNFS-10CA; CA = cyanuric acid) featuring carbon vacancy defect engineering and hierarchical porous channels, which created a microenvironment that enhances CO2 adsorption and enrichment. Density functional theory (DFT) and experimental analysis revealed the effects of carbon vacancy defect-engineered Ni NCs on Ni SAs: (1) The introduction of carbon defects can regulate the local electronic structure and pore size, thereby achieving efficient enrichment and adsorption of CO2. (2) Carbon vacancy defects can optimize the key *COOH adsorption and reduce the desorption energy of *CO. The resulting catalyst achieved a near-unity Faradaic efficiency (FE) for CO (FECO ≈100%) over a broad potential window. Notably, it maintained a high FECO of 88.2% under a 20% CO2 atmosphere. The catalyst exhibited durability exceeding 306 h (1102 cycles) in a Zn-CO2 battery and over 80 h (288 cycles) in a Zn-CO2 (20% CO2) battery. This work proposes a high-activity carbon vacancy defect engineering strategy, delivering an innovative approach for efficient ECO2RR and the direct conversion of industrial flue gases.
用于低浓度CO2还原的电催化系统在催化剂活性位点的质量传输和电子调制方面仍然面临重大挑战。本研究开发了一种气体-分子剪切策略来构建镍单原子（Ni SAs）和纳米簇（NC）掺杂的碳纳米纤维催化剂（Ni/TCNFS-10CA; CA =氰脲酸），该策略具有碳空位缺陷工程和分层多孔通道，创造了一个增强CO2吸附和富集的微环境。密度泛函理论（DFT）和实验分析揭示了碳空位缺陷工程Ni NCs对Ni SAs的影响：(1)碳空位缺陷的引入可以调节局部电子结构和孔径，从而实现对CO2的高效富集和吸附。(2)碳空位缺陷可以优化*COOH的关键吸附，降低*CO的解吸能。所得到的催化剂在较宽的电位窗口内获得了CO的接近统一的法拉第效率（FE） （FECO≈100%）。值得注意的是，在20%的二氧化碳气氛下，它保持了88.2%的高FECO。该催化剂在Zn-CO2电池中表现出超过306小时（1102次循环）的耐久性，在Zn-CO2 （20% CO2）电池中表现出超过80小时（288次循环）的耐久性。这项工作提出了一种高活性碳空位缺陷工程策略，为高效的ECO2RR和工业烟气的直接转化提供了一种创新方法。
{"title":"Gas-Molecular-Shearing Carbon Vacancy Defect Networks on Ni-Doped Carbon Fibers for High-Efficiency Low-Concentration CO2 Enrichment and Electrocatalytic Reduction","authors":"Jinsheng Lai,Youpeng Xiong,Aerman Habadati,Meng Li,Mei Zhang,Tianwen Fang,Ke Yi,Yuzhu Ding,Xinghuan Liu,Xin Jia","doi":"10.1021/acscatal.5c08111","DOIUrl":"https://doi.org/10.1021/acscatal.5c08111","url":null,"abstract":"Electrocatalytic systems for low-concentration CO2 reduction still face significant challenges in the mass transport and electronic modulation of catalyst active sites. This study developed a gas-molecular shear strategy for constructing nickel single atoms (Ni SAs) and nanocluster (NC)-doped carbon nanofiber catalysts (Ni/TCNFS-10CA; CA = cyanuric acid) featuring carbon vacancy defect engineering and hierarchical porous channels, which created a microenvironment that enhances CO2 adsorption and enrichment. Density functional theory (DFT) and experimental analysis revealed the effects of carbon vacancy defect-engineered Ni NCs on Ni SAs: (1) The introduction of carbon defects can regulate the local electronic structure and pore size, thereby achieving efficient enrichment and adsorption of CO2. (2) Carbon vacancy defects can optimize the key *COOH adsorption and reduce the desorption energy of *CO. The resulting catalyst achieved a near-unity Faradaic efficiency (FE) for CO (FECO ≈100%) over a broad potential window. Notably, it maintained a high FECO of 88.2% under a 20% CO2 atmosphere. The catalyst exhibited durability exceeding 306 h (1102 cycles) in a Zn-CO2 battery and over 80 h (288 cycles) in a Zn-CO2 (20% CO2) battery. This work proposes a high-activity carbon vacancy defect engineering strategy, delivering an innovative approach for efficient ECO2RR and the direct conversion of industrial flue gases.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"211 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152440","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}
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}
Polysiloxanes are widely used in various household, industrial, and biomedical products; however, the effects of their composition and sequence on the melt viscosity have not been investigated in detail. A series of discrete linear oligosiloxanes with precisely controlled compositions and sequences was prepared in this study, and the relationship between their molecular structures and melt viscosities was examined. The oligomers possessed linear structures composed of dimethylsiloxy (D) and diphenylsiloxy (P) units with trimethylsiloxy (M) ends. P-repeat oligomers contained consecutive P blocks including exact numbers of P units. The prepared oligomers were employed to explore the specific effects of block structures. The 26-meric sequence isomers exhibited identical M/D/P compositions and four sequence-repeating blocks: (PD)12, (PPDD)6, (PPPDDD)4, and (PPPPDDDD)3. This facile synthetic methodology enabled the preparation of well-defined oligomers on the gram scale and estimation of their melt viscosities through actual measurements. The oligodimethylsiloxanes were also compared using previously reported viscosity values. Each oligosiloxane was uniform in terms of the M/D/P composition, sequence, and molecular weight. These oligosiloxanes were distinguished by their viscosity–molecular weight relationships; a steep enhancement in viscosity with an increasing number of consecutively repeated P units and a distinct influence of block sequence patterns on the viscosity of the 26-mers were observed. To gain molecular insights, the oligosiloxane viscosities were analyzed using the Rouse model and its modifications, and the effects of structural factors on the melt viscosity of the oligosiloxanes were discussed. The findings of this work demonstrate that appropriate Rouse model variants can effectively explain how the composition and sequence influence the melt viscosity of oligosiloxanes.
{"title":"Structure–melt viscosity relationship of discrete sequence-specific linear oligo(dimethylsiloxane-co-diphenylsiloxane)s","authors":"Hiroyuki Minamikawa, Takahiro Kawatsu, Kazuhiro Matsumoto","doi":"10.1039/d5py00958h","DOIUrl":"https://doi.org/10.1039/d5py00958h","url":null,"abstract":"Polysiloxanes are widely used in various household, industrial, and biomedical products; however, the effects of their composition and sequence on the melt viscosity have not been investigated in detail. A series of discrete linear oligosiloxanes with precisely controlled compositions and sequences was prepared in this study, and the relationship between their molecular structures and melt viscosities was examined. The oligomers possessed linear structures composed of dimethylsiloxy (<strong>D</strong>) and diphenylsiloxy (<strong>P</strong>) units with trimethylsiloxy (<strong>M</strong>) ends. <strong>P</strong>-repeat oligomers contained consecutive <strong>P</strong> blocks including exact numbers of <strong>P</strong> units. The prepared oligomers were employed to explore the specific effects of block structures. The 26-meric sequence isomers exhibited identical <strong>M</strong>/<strong>D</strong>/<strong>P</strong> compositions and four sequence-repeating blocks: (<strong>PD</strong>)<small><sub>12</sub></small>, (<strong>PPDD</strong>)<small><sub>6</sub></small>, (<strong>PPPDDD</strong>)<small><sub>4</sub></small>, and (<strong>PPPPDDDD</strong>)<small><sub>3</sub></small>. This facile synthetic methodology enabled the preparation of well-defined oligomers on the gram scale and estimation of their melt viscosities through actual measurements. The oligodimethylsiloxanes were also compared using previously reported viscosity values. Each oligosiloxane was uniform in terms of the <strong>M</strong>/<strong>D</strong>/<strong>P</strong> composition, sequence, and molecular weight. These oligosiloxanes were distinguished by their viscosity–molecular weight relationships; a steep enhancement in viscosity with an increasing number of consecutively repeated <strong>P</strong> units and a distinct influence of block sequence patterns on the viscosity of the 26-mers were observed. To gain molecular insights, the oligosiloxane viscosities were analyzed using the Rouse model and its modifications, and the effects of structural factors on the melt viscosity of the oligosiloxanes were discussed. The findings of this work demonstrate that appropriate Rouse model variants can effectively explain how the composition and sequence influence the melt viscosity of oligosiloxanes.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The clinical translation of cancer nanomedicine is significantly impeded by biological barriers, including rapid immune clearance, the heterogeneous tumor microenvironment (TME), and the limited efficacy of passive targeting. While single-source cell membrane coatings offer partial solutions, they are often constrained by functional incompleteness. The emergence of hybrid membrane-camouflaged nanomedicines (HMCNs), fabricated by fusing membranes from distinct cell types, represents a paradigm shift. This biomimetic strategy ingeniously engineers bio-interfaces that synergistically integrate multifunctional properties, such as prolonged circulation, active targeting, and TME modulation, thereby overcoming the limitations of single-membrane systems. This review systematically deconstructs the rational design principles governing HMCNs, emphasizing source cell selection based on functional complementarity to avoid signal conflict. We further delve into mechanism-driven engineering, exploring advanced fusion methodologies and characterization techniques essential for ensuring structural and functional fidelity. The functional diversification of HMCNs is highlighted through their application in multimodal synergistic therapies (e.g., photothermal-immunotherapy, chemo-gene therapy) and intelligent theranostic platforms. Finally, we critically discuss prevailing challenges in batch consistency and scalable production, and envision future directions, including smart stimulus-responsive systems, AI-aided design, and patient-specific nanoplatforms. By bridging biology, chemistry, and materials science, HMCNs establish a versatile and potent paradigm for next-generation cancer therapeutics.
{"title":"Hybrid membrane-camouflaged nanomedicines for precision oncology: rational design, mechanism innovation, and diversified applications","authors":"Shuyao Cai, Zhenghui Chen, Yaoyao Lv, Dongdong Xu, Yang Li, Shouchun Yin","doi":"10.1016/j.ccr.2026.217681","DOIUrl":"https://doi.org/10.1016/j.ccr.2026.217681","url":null,"abstract":"The clinical translation of cancer nanomedicine is significantly impeded by biological barriers, including rapid immune clearance, the heterogeneous tumor microenvironment (TME), and the limited efficacy of passive targeting. While single-source cell membrane coatings offer partial solutions, they are often constrained by functional incompleteness. The emergence of hybrid membrane-camouflaged nanomedicines (HMCNs), fabricated by fusing membranes from distinct cell types, represents a paradigm shift. This biomimetic strategy ingeniously engineers bio-interfaces that synergistically integrate multifunctional properties, such as prolonged circulation, active targeting, and TME modulation, thereby overcoming the limitations of single-membrane systems. This review systematically deconstructs the rational design principles governing HMCNs, emphasizing source cell selection based on functional complementarity to avoid signal conflict. We further delve into mechanism-driven engineering, exploring advanced fusion methodologies and characterization techniques essential for ensuring structural and functional fidelity. The functional diversification of HMCNs is highlighted through their application in multimodal synergistic therapies (e.g., photothermal-immunotherapy, chemo-gene therapy) and intelligent theranostic platforms. Finally, we critically discuss prevailing challenges in batch consistency and scalable production, and envision future directions, including smart stimulus-responsive systems, AI-aided design, and patient-specific nanoplatforms. By bridging biology, chemistry, and materials science, HMCNs establish a versatile and potent paradigm for next-generation cancer therapeutics.","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"299 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153416","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: 10.1016/j.aca.2026.345229
Xiaoyuan Ma, Xi Ma, Muxi Zhang, Jinchi Han, Zhouping Wang
Background
As one of the most common mycotoxins, Zearalenone (ZEN) not only contaminates cereal crops but also exists in processed grain products for its chemical stability. After entering human body through the food chain, ZEN exhibits remarkable bioaccumulation properties, which poses varying degrees of harmful effects to human health. The traditional chromatography instrumental methods require expensive equipment and complex experimental procedures. The aim of this manuscript is to develop a facile and accurate method for ZEN detection in food samples.
Results
Here, a SERS platform was developed for ZEN detection using COF and noble metal nanomaterial with nitroreductase (NTR)-like activity. First, magnetic COF loaded with gold nanoparticles (MCOF-Au) were synthesized as SERS enhancement substrates with partial NTR activity. Simultaneously, palladium-loaded dumbbell-shaped gold nanorods (AuNR/Pd) were prepared and served as the primary NTR in the 4-NTP/NaBH4 system, significantly enhancing both catalytic activity and SERS signal. After nucleic acid functionalization, the two components assembled. The addition of ZEN regulated the assemble of AuNR/Pd on MCOF-Au. Following magnetic separation, the catalytic and SERS activities changed in the precipitate. Using the Raman peak of the output product 4-ATP at 390 cm-1 as the quantitative marker, the method showed a linear range in 0.001 μg/kg-1000 μg/kg. The LOD was calculated as 1.88×10-4 μg/kg, and spiked recoveries in wheat flour and corn ranged from 88.91% to 115.78%, demonstrating high sensitivity and reliability for real-sample detection.
Significance
This aptasensor integrates the high sensitivity of Raman signals with the selectivity of aptamers, providing a robust and efficient tool for accurate ZEN detection in food. COF based nanocomposites are proved to have remarkable NTR activity and the catalytic product 4-ATP exhibits prominent Raman signal, making it suitable for quantitative detection. This design offers a versatile platform for food safety monitoring and public health protection.
{"title":"Nanozyme fabrication based on magnetic COFs and gold nanorods and its SERS detection of zearalenone","authors":"Xiaoyuan Ma, Xi Ma, Muxi Zhang, Jinchi Han, Zhouping Wang","doi":"10.1016/j.aca.2026.345229","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345229","url":null,"abstract":"<h3>Background</h3>As one of the most common mycotoxins, Zearalenone (ZEN) not only contaminates cereal crops but also exists in processed grain products for its chemical stability. After entering human body through the food chain, ZEN exhibits remarkable bioaccumulation properties, which poses varying degrees of harmful effects to human health. The traditional chromatography instrumental methods require expensive equipment and complex experimental procedures. The aim of this manuscript is to develop a facile and accurate method for ZEN detection in food samples.<h3>Results</h3>Here, a SERS platform was developed for ZEN detection using COF and noble metal nanomaterial with nitroreductase (NTR)-like activity. First, magnetic COF loaded with gold nanoparticles (MCOF-Au) were synthesized as SERS enhancement substrates with partial NTR activity. Simultaneously, palladium-loaded dumbbell-shaped gold nanorods (AuNR/Pd) were prepared and served as the primary NTR in the 4-NTP/NaBH<sub>4</sub> system, significantly enhancing both catalytic activity and SERS signal. After nucleic acid functionalization, the two components assembled. The addition of ZEN regulated the assemble of AuNR/Pd on MCOF-Au. Following magnetic separation, the catalytic and SERS activities changed in the precipitate. Using the Raman peak of the output product 4-ATP at 390 cm<sup>-1</sup> as the quantitative marker, the method showed a linear range in 0.001 μg/kg-1000 μg/kg. The LOD was calculated as 1.88×10<sup>-4</sup> μg/kg, and spiked recoveries in wheat flour and corn ranged from 88.91% to 115.78%, demonstrating high sensitivity and reliability for real-sample detection.<h3>Significance</h3>This aptasensor integrates the high sensitivity of Raman signals with the selectivity of aptamers, providing a robust and efficient tool for accurate ZEN detection in food. COF based nanocomposites are proved to have remarkable NTR activity and the catalytic product 4-ATP exhibits prominent Raman signal, making it suitable for quantitative detection. This design offers a versatile platform for food safety monitoring and public health protection.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"32 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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