Angewandte Chemie International Edition最新文献_第6页

The Last Piece of the Puzzle: Access to 7-Connected Zirconium Metal-Organic Frameworks for Hexane Separation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202424859

Xianhui Tang, Lei Jia, Xiaoliang Wang, Shengyi Su, Yongwei Chen, Xiang-Jing Kong, Zi-Ming Ye, Haomiao Xie, Wei Gong, Enping Du, Yan Liu, Kent O. Kirlikovali, Omar Farha, Yong Cui

{"title":"The Last Piece of the Puzzle: Access to 7-Connected Zirconium Metal-Organic Frameworks for Hexane Separation","authors":"Xianhui Tang, Lei Jia, Xiaoliang Wang, Shengyi Su, Yongwei Chen, Xiang-Jing Kong, Zi-Ming Ye, Haomiao Xie, Wei Gong, Enping Du, Yan Liu, Kent O. Kirlikovali, Omar Farha, Yong Cui","doi":"10.1002/anie.202424859","DOIUrl":"https://doi.org/10.1002/anie.202424859","url":null,"abstract":"Zirconium metal-organic frameworks (Zr-MOFs) exhibit a wide range of Zr6 cluster connectivities, from 3-connected to 12-connected, enabling diverse structural designs. However, odd-numbered connectivities, especially the 7-connected Zr-MOFs, are exceptionally rare due to geometric symmetry challenges. To address this, we developed a geometric pre-assembly strategy to achieve targeted cluster connectivity. Using this approach, we synthesized NU-5001 {[Zr6O4(OH)4(H4-L)2]}, a Zr-MOF featuring 7-connected Zr6 clusters, derived from the precursor 6-connected Zr-MOF, NU-5000 {[Zr6O4(OH)4(H3-L)2]}. NU-5000, constructed with a tritopic chiral linker H3-L {(R)-4,4',4''-[6'-chloro-2,2'-diethoxy-(1,1'-binaphthalene)-4,4',6-triyl]tribenzoic acid}, forms a (3,6)-connected ant topology. Introducing a tetratopic chiral linker, 1,1'-bi-2-naphthol tetracarboxylic acid H4-L {(R)-4,4',4'',4'''-[2,2'-diethoxy-(1,1'-binaphthalene)-4,4',6,6'-tetrayl]tetrabenzoic acid}, enabled an additional connection, resulting in NU-5001 with a (3,4,7)-connected topology. The H4-L linker acts as either fully 4-connected or 3-connected with one arm uncoordinated. Additionally, NU-5001M {[Zr6O4(OH)4(H4-L) (H3-L)]}, an isostructural variant, was synthesized using a mix of H3-L and H4-L linkers. NU-5001’s unique pore structure and slight flexibility enable distinct adsorption behaviors for hexane isomers, highlighting its potential for kinetic separations. This work completes the Zr6 cluster connectivity landscape and demonstrates the feasibility of tuning Zr-MOF connectivities through rational linker design, paving the way for rare, low-symmetry frameworks with tailored properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Fluoro-Fucosylation Enables the Interrogation of the Lea – LecB Interaction by BioNMR Spectroscopy

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202423782

Kathrin Siebold, Elena Chikunova, Nils Lorz, Christina Jordan, Alvar Gossert, Ryan Gilmour

{"title":"Fluoro-Fucosylation Enables the Interrogation of the Lea – LecB Interaction by BioNMR Spectroscopy","authors":"Kathrin Siebold, Elena Chikunova, Nils Lorz, Christina Jordan, Alvar Gossert, Ryan Gilmour","doi":"10.1002/anie.202423782","DOIUrl":"https://doi.org/10.1002/anie.202423782","url":null,"abstract":"Fucosylation patterns in cell-surface glycans are essential mediators of recognition and signalling. Aberrations in these signatures serve as vital diagnostic markers of disease progression, and so understanding fucose-protein interactions at the molecular level is crucial. Molecular editing of l-fucose (Fuc) at C2 with fluorine provides a platform to reconcile the ubiquity of fucosylation with the paucity of strategies to interrogate site-specific interactions. Through judicious introduction of a pseudo-equatorial fluorine [C(sp3)-F] adjacent to the anomeric position, β-selective fucosylation can be achieved with a range of diverse acceptors (>50:1): the selectivity of this process can be inverted through changes in the donor scaffold. Reaction development was driven by the desire to construct a fluorinated analogue of Lewis antigen a (F-Lea), in which fluorine replaces a key OH group at C2. Lea is a ligand for Lectin B (LecB) in the pathogen Pseudomonas aeruginosa and thus delineating the importance of key interactions in this complex has ramifications for drug discovery. Independent syntheses of Lea and F-Lea, and systematic bioNMR analyses with both glycans has unequivocally established the essential role of O2 of fucose in the Lea-LecB complex.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

In-tandem Electrochemical Reduction of Nitrate to Ammonia on Ultrathin-Sheet-Assembled Iron–Nickel Alloy Nanoflowers

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202500167

Kartick Chandra Majhi, Hongjiang Chen, Asma Batool, Qi Zhu, Yangxin Jin, Shengqin Liu, Patrick H.-L. Sit, Jason Chun-Ho Lam

{"title":"In-tandem Electrochemical Reduction of Nitrate to Ammonia on Ultrathin-Sheet-Assembled Iron–Nickel Alloy Nanoflowers","authors":"Kartick Chandra Majhi, Hongjiang Chen, Asma Batool, Qi Zhu, Yangxin Jin, Shengqin Liu, Patrick H.-L. Sit, Jason Chun-Ho Lam","doi":"10.1002/anie.202500167","DOIUrl":"https://doi.org/10.1002/anie.202500167","url":null,"abstract":"The development of alternative routes for ammonia (NH3) synthesis with high Faradaic efficiency (FE) is crucial for energy conservation and to achieve zero carbon emissions. Electrocatalytic nitrate (NO3−) reduction to NH3 (e-NO3RRA) is a promising alternative to the energy-intensive, fossil-fuel-driven Haber–Bosch process. The implementation of this innovative NH3 synthesis technique requires an efficient electrocatalyst and in-depth mechanistic understanding of e-NO3RRA. In this study, we developed an ultrathin sheet (µm) iron–nickel nanoflower alloy through electrodeposition and used it for e-NO3RRA under alkaline conditions. The prepared Fe–Ni alloy exhibited an FE of 97.28 ± 1.36% at −238 mVRHE with an NH3 yield rate of 3999.1 ± 242.59 mg h−1 cm−2. Experimental electrolysis, in-situ Raman spectroscopy, and density functional theory calculations showed that the adsorption and reduction of NO3− to NO2− occurred on the Fe surface, whereas subsequent hydrogenation of NO2− to NH3 occurred preferentially on the Ni surface. The catalysts exhibited comparable FE for at least 10 cycles, with a long-term stability of 216 h. Electron paramagnetic resonance results confirmed that adsorbed hydrogen was consumed during e-NO3RRA. This work introduces a sustainable, robust, and efficient Fe–Ni alloy electrocatalyst, offering an environmentally friendly approach for synthesizing NH3 from NO3−-contaminated water.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"39 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spatial Confinement of Dual Activatable DNAzyme Sensor in Cavity of DNA Nanocage for Logical Molecular Imaging

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202424684

Tingting Tu, Shuangyan Huan, Xueyan Feng, Guoliang Ke, Lele Li, Xiao-Bing Zhang

{"title":"Spatial Confinement of Dual Activatable DNAzyme Sensor in Cavity of DNA Nanocage for Logical Molecular Imaging","authors":"Tingting Tu, Shuangyan Huan, Xueyan Feng, Guoliang Ke, Lele Li, Xiao-Bing Zhang","doi":"10.1002/anie.202424684","DOIUrl":"https://doi.org/10.1002/anie.202424684","url":null,"abstract":"Despite intense interest in design of DNAzyme sensors for molecular detection and imaging in living cells, their intracellular applications are still hampered by limited spatial control and poor bio-stability. Here we present controlled spatial confinement of a rationally designed, miRNA-activatable DNAzyme sensor probe (mDz) within the cavity of DNA nanocage, enabling efficient intracellular delivery with improved bio-stability for AND-gate molecular imaging. The mDz that possesses inactive DNAzyme activity is designed by the introduction of a blocking DNA strand, while miR-21 mediated strand displacement reaction allows for the formation of an intact DNAzyme structure for metal-ion-mediated catalytic reaction. Furthermore, the DNA nanocage serves as a nanocarrier for intracellular delivery of mDz, in which the cavity is accessible to the dual targets for logical molecular imaging, while the confinement effect can provide steric protection of mDz by obstructing nuclease from entering the cavity of the DNA nanocage, resulting in enhanced bio-stability and improved molecular imaging precision. This strategy paves a way for the engineering of activatable DNA nanosensors with both self-delivery and self-protection capabilities to detect diverse intracellular targets.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

H-Bonds in Carbon Quantum Dot-anchored C3N5 to Boost Proton-Coupled Electron Transfer for Piezoelectric-Driven Hydrogen Peroxide Synthesis under Ambient Conditions

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202502390

Zhi Li, Kangbo Tong, Haojie Dong, Yatai Li, Kai Wang, Tengda Ding, Yang Yun, Yingtang Zhou, Mingshan Zhu

{"title":"H-Bonds in Carbon Quantum Dot-anchored C3N5 to Boost Proton-Coupled Electron Transfer for Piezoelectric-Driven Hydrogen Peroxide Synthesis under Ambient Conditions","authors":"Zhi Li, Kangbo Tong, Haojie Dong, Yatai Li, Kai Wang, Tengda Ding, Yang Yun, Yingtang Zhou, Mingshan Zhu","doi":"10.1002/anie.202502390","DOIUrl":"https://doi.org/10.1002/anie.202502390","url":null,"abstract":"Tuning proton-coupled electron transfer (PCET) is a promising strategy to boost the oxygen reduction reaction (ORR) for H2O2 synthesis, but the slow transmission rate of protons and electrons to active sites remains a significant bottleneck. To address this, we developed an H-bond-driven PCET process based on carbon quantum dotanchored C3N5 (CQDs-C3N5) for piezo-catalytic H2O2 synthesis. CQD-C3N5 exhibited a remarkable piezo-catalytic synthesis rate of 5025 μmol g⁻¹ h⁻¹ under ambient conditions. This efficiency is attributed to H-bonds between CQDs and C3N5, which accelerate PCET in the ORR. The piezoelectric-generated charges, from the dipole field of the C3N5 plane and protons in water, were rapidly transferred to the C rings of CQDs via H-bonds. This process facilitated the adsorption of oxygen onto C2 sites adjacent to carboxyl groups of CQDs, which in turn led to the formation of H2O2 through a rapidly protonated, indirect 2e− pathway. Additionally, a piezo-self-Fenton reaction system was constructed for oxytetracycline-rich wastewater purification, with effectively effects on chemical oxygen demand, antibiotic-resistant bacteria and antibiotic-resistant genes degradation. This study highlights the critical role of H-bond networks for tuning PCET in the ORR and provides a comprehensive understanding for the precise control of catalytic reaction kinetics through molecular structural engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"33 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Highly Precise Prediction of Micro- and Supra-pKa Based on 3D Descriptors Integrating Non-Covalent Interactions

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202424069

Siyuan Liu, Chi Yang, Long Zhang, Sanzhong Luo

{"title":"Highly Precise Prediction of Micro- and Supra-pKa Based on 3D Descriptors Integrating Non-Covalent Interactions","authors":"Siyuan Liu, Chi Yang, Long Zhang, Sanzhong Luo","doi":"10.1002/anie.202424069","DOIUrl":"https://doi.org/10.1002/anie.202424069","url":null,"abstract":"Accurate pKa prediction is crucial for understanding proton dissociation in complex molecular systems. However, existing models often face challenges in addressing subtle stereoelectronic effects and conformational flexibility. This study presents H-SPOC, a localized 3D descriptor that captures covalent and non-covalent interactions and incorporates solvent effects to predict site-specific pKa values accurately. H-SPOC was validated on multiple benchmark datasets, including SAMPL6, SAMPL7, and SAMPL8, where it outperformed state-of-the-art methods. H-SPOC also proved versatile across various applications, including aspirin's non-equilibrium conformations, glycine's microstate distributions, and the stereoelectronic anomalies of Janus Sponge and Meldrum's Acid. It addressed challenging supra-pKa predictions in crystalline environments and accurately correlated pKa with reaction rates, selectivity, tautomerism, and pharmacokinetic properties. With its chemically intuitive design and computational efficiency, H-SPOC provides an efficient framework for rapid and precise micro- and supra-pKa predictions, offering significant potential in drug discovery, catalysis, and materials science.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Robust Fully Screen-printed Perovskite Solar Cells Based on Synergistic Ostwald Ripening

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202425162

Changshun Chen, Chunyu Guo, Qing Yao, Jinpei Wang, Yutian Xu, Dengke Wang, Xiao Huang, Xueqin Ran, Yingdong Xia, Lingfeng Chao, Yonghua Chen

{"title":"Robust Fully Screen-printed Perovskite Solar Cells Based on Synergistic Ostwald Ripening","authors":"Changshun Chen, Chunyu Guo, Qing Yao, Jinpei Wang, Yutian Xu, Dengke Wang, Xiao Huang, Xueqin Ran, Yingdong Xia, Lingfeng Chao, Yonghua Chen","doi":"10.1002/anie.202425162","DOIUrl":"https://doi.org/10.1002/anie.202425162","url":null,"abstract":"Fully screen-printed process for low-cost manufacturing significantly enhances the commercial competitiveness of perovskite solar cells (PSCs). However, the controllable crystallization in screen-printed perovskite thin films using high - viscosity ionic liquids has been suggested to be difficult, which hampers further development of fully screen-printed perovskite devices in terms of application expansion and performance improvement. Here, we report a synergistic ripening strategy to fully control crystallization by employing methylamine propionate (MAPa) ionic liquid and water (H2O, moisture in the air). We found that a reversible and sustainable ripening process was activated by integrating MAPa/H2O in both externally and internally into perovskite crystals. MAPa effectively prevents the loss of organic salts and maintains the dispersion of Pb-I framework, preventing the perovskite component loss and decomposition. H2O and organic salts trends to form hydration complexes, which lowers the energy barrier and enhances the reactivity of the humidity-induced Ostwald ripening reaction. These improvements allow the perovskite films achieve controlled secondary growth, reducing defects and optimizing energy level alignment. The resulting fully screen-printed PSCs exhibits a record power conversion efficiency of 19.47% and an operational stability over 1,000 h with maintaining 91.6% of the highest efficiency under continuous light stress at maximum power point.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202422789

Yanfang Wang, Cheng Li, Yingzhi Li, Raquel de Benito, Jacob Williams, Joshua M. Stratford, Zhiqiang Li, Chun Zeng, Ning Qin, Hongzhi Wang, Yulin Cao, Dominic Gardner, Wilgner Lima da Silva, Sahil Tippireddy, Qingmeng Gan, Fangchang Zhang, Wen Luo, Joshua W. Makepeace, Ke-Jin Zhou, Kaili Zhang, Fucai Zhang, Phoebe K. Allan, Zhouguang Lu

{"title":"A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries","authors":"Yanfang Wang, Cheng Li, Yingzhi Li, Raquel de Benito, Jacob Williams, Joshua M. Stratford, Zhiqiang Li, Chun Zeng, Ning Qin, Hongzhi Wang, Yulin Cao, Dominic Gardner, Wilgner Lima da Silva, Sahil Tippireddy, Qingmeng Gan, Fangchang Zhang, Wen Luo, Joshua W. Makepeace, Ke-Jin Zhou, Kaili Zhang, Fucai Zhang, Phoebe K. Allan, Zhouguang Lu","doi":"10.1002/anie.202422789","DOIUrl":"https://doi.org/10.1002/anie.202422789","url":null,"abstract":"Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy-density lithium-ion batteries. However, achieving long-term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt-free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4% of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable rhombohedral symmetry (R-3m) with unique local structures. The face-sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration-induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de-/lithiation (< 2.3% along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"123 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Divergent Total Syntheses of Six Crinipellin-Type Diterpenoids through Tandem 4π-Electrocyclization/ Dicycloexpansion

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202501008

Tian Ke, Si-Hua Hou, Yun-Peng Wang, Kun Fang, Jing-Han Hu, Ka Lu, Yongqiang Tu

{"title":"Divergent Total Syntheses of Six Crinipellin-Type Diterpenoids through Tandem 4π-Electrocyclization/ Dicycloexpansion","authors":"Tian Ke, Si-Hua Hou, Yun-Peng Wang, Kun Fang, Jing-Han Hu, Ka Lu, Yongqiang Tu","doi":"10.1002/anie.202501008","DOIUrl":"https://doi.org/10.1002/anie.202501008","url":null,"abstract":"Crinipellins are a significant class of naturally occurring highly congested tetraquinane diterpenoids, with many members exhibiting bio-important antibacterial and anticancer activities. However, their complex structures, particularly their dense 5/5/5/5 tetracyclic frameworks, have made efficient synthesis challenging, leading chemists to attempt to create highly efficient and divergent routes. This study presents a concise, divergent synthesis of six crinipellins, completed in just 9–11 steps using commercially available materials. Particular highlights include: (1) a vital one-step 4π-electrocyclization/dicycloexpansion cascade that rapidly constructs the angular/fused tetraquinane scaffold with two contiguous quaternary carbons, and (2) strategic functionalizations through iso-propylation, methylation, and Wacker oxidation/ dehydrogenation, enabling the divergent syntheses of the six crinipellin members without using protecting groups. This approach provides a versatile platform for accessing additional crinipellin derivatives, which we believe will benefit the medicinal and biological research.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"37 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

NIR-II Emissive Oligonucleotides Grafted π-Conjugated Polymers for Low-Temperature Photothermal and Gene Combined Therapy

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202425654

Guiling Fan, Shengxin Hou, Ying Gu, Hengfeng Jiang, Wenkang Zhang, Weitao Wu, Mengying Wang, Leilei Tian

{"title":"NIR-II Emissive Oligonucleotides Grafted π-Conjugated Polymers for Low-Temperature Photothermal and Gene Combined Therapy","authors":"Guiling Fan, Shengxin Hou, Ying Gu, Hengfeng Jiang, Wenkang Zhang, Weitao Wu, Mengying Wang, Leilei Tian","doi":"10.1002/anie.202425654","DOIUrl":"https://doi.org/10.1002/anie.202425654","url":null,"abstract":"In order to address the strong hydrophobicity and function limitation of NIR-II emissive phototheranostic π-conjugated polymers (CPs), appropriate modifications are necessary to impart water dispersibility and functionality to CPs. This study uses DNA as the hydrophilic and functional unit to modify CPs, synthesizing CP-g-DNA amphiphilic copolymers and producing water-dispersible oligonucleotide-modified π-conjugated polymer nanoparticles (OCPNs) by self-assembly. In addition to DNA's gene regulation abilities that can combine with the low-temperature photothermal therapy of CPs for enhanced tumor therapy, OCPNs display unique characteristics as novel nanomaterials. On one side, DNA changes the π-π interactions and results in a two-fold enhancement in NIR-II fluorescence emission, which greatly benefits tumor imaging. On the other side, DNA varies the surface properties of OCPNs and the nano-bio interactions. OCPNs exhibit multiple cellular internalization pathways, including caveolae/lipid raft-mediated uptake for cytoplasm delivery, which may enhance gene transfection combined with the photothermal-promoted lysosome escape. Moreover, OCPNs can quickly accumulate in tumors due to their higher tissue penetration capability. Taken together, a strategy of using DNA to enable and advance the phototheranostic applications of CPs has been demonstrated, and the distinct properties of OCPNs will open up new biological application opportunities in the future.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0