Angewandte Chemie International Edition最新文献_第8页

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

Mitigating Diffusion-Induced Intragranular Cracking in Single-Crystal LiNi0.5Mn1.5O4 via Extended Solid-Solution Behavior

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202422726

Hyeonsol Shin, Agwu Ndukwe, Taemin Kim, Ji Hoon Lee, Guanchen Li, Hyeon Jeong Lee

{"title":"Mitigating Diffusion-Induced Intragranular Cracking in Single-Crystal LiNi0.5Mn1.5O4 via Extended Solid-Solution Behavior","authors":"Hyeonsol Shin, Agwu Ndukwe, Taemin Kim, Ji Hoon Lee, Guanchen Li, Hyeon Jeong Lee","doi":"10.1002/anie.202422726","DOIUrl":"https://doi.org/10.1002/anie.202422726","url":null,"abstract":"Single-crystal cathodes have been investigated for their inherent resistance to intergranular cracking due to the absence of grain boundaries. However, these materials exhibit significant intergranular cracking, and the underlying mechanisms remain unclear. In this study, we examined the impact of extended solid-solution reactions on mitigating crack formation in magnesium-doped single-crystal LiNi0.5Mn1.5O4 (Mg-SC-LNMO) cathodes. With Mg acting as a structural pillar, the overall volume change was reduced by nearly 50%, the two-phase reaction was effectively suppressed, and the Li-ion diffusion coefficient was doubled. Continuum modeling based on experimental observations demonstrates that Mg doping significantly reduces the internal stress induced by lithium diffusion, thereby preserving the mechanical integrity of single-crystal LNMO. This improvement leads to enhanced electrochemical performance and durability. Our study provides new insights into mechanically robust single-crystal cathodes and proposes a design strategy to improve the durability of next-generation Li-ion batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"134 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124816","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

Enhanced Interfacial Electric Field of an S−Scheme Heterojunction by an Ultrasonication-Triggered Piezoelectric Effect for Sonocatalytic Therapy of Bacterial Infections

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202500441

Junwu Wei, Guiyuan Zhang, Shuang Xie, Zhanlin Zhang, Tianyu Gao, Mengxue Zhang, Xiaohong Li

{"title":"Enhanced Interfacial Electric Field of an S−Scheme Heterojunction by an Ultrasonication-Triggered Piezoelectric Effect for Sonocatalytic Therapy of Bacterial Infections","authors":"Junwu Wei, Guiyuan Zhang, Shuang Xie, Zhanlin Zhang, Tianyu Gao, Mengxue Zhang, Xiaohong Li","doi":"10.1002/anie.202500441","DOIUrl":"https://doi.org/10.1002/anie.202500441","url":null,"abstract":"Sonodynamic therapy indicates advantages in combating antibiotics-resistant bacteria and deep tissue infections, but challenges remain in the less efficient charge transfer and reactive oxygen species (ROS) generation of sonosensitizers. Herein, an effective bactericidal strategy is developed through enhancing the interfacial electric field (IEF) of S-scheme heterojunctions by an ultrasonication-triggered piezoelectric effect. Hollow barium titanate (hBT) nanoparticles (NPs) were prepared through template etching, followed by in-situ assembly of tetrakis (4-carboxyphenyl)porphyrin (TCPP) with Zn2+ to obtain hBT@ZnTCPP. Both experimental and theoretical evidences support the notion that an IEF is generared from ZnTCPP to hBT. Compared to metalloporphyrins with Fe3+, Mn3+, Cu2+ and Ni2+, the stronger reduction of ZnTCPP induced by elevation of the orbital energy level of porphyrins after Zn2+ coordination leads to formation of S-scheme heterojunctions. The ultrasonication-activated polarization field enhances IEF and boosts energy band bending of hBT@ZnTCPP to promote electron-hole separations and ROS generations. Planktonic methicillin-resistant Staphylococcus aureus and their derived biofilms are completely destroyed within 5 min under ultrasonication through up-regulating genes of glucose catabolism and ion transportation and down-regulating genes of ribosomal synthesis and transmembrane transporter. Thus, this study demonstrates molecular-level modulation of energy levels for S-scheme heterojunction formation to achieve efficient sonocatalytic therapy of bacterial infections.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"66 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124810","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

Tailoring Sodium Carboxymethylcellulose Binders for High-Voltage LiCoO2 via Thermal Pulse Sintering

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202423796

Shiming Chen, Hengyao Zhu, Jiangxiao Li, Zu-Wei Yin, Taowen Chen, Xiangming Yao, Wenguang Zhao, Haoyu Xue, Xin Jiang, Yongsheng Li, Hengyu Ren, Jun Chen, Jun-Tao Li, Luyi Yang, Feng Pan

{"title":"Tailoring Sodium Carboxymethylcellulose Binders for High-Voltage LiCoO2 via Thermal Pulse Sintering","authors":"Shiming Chen, Hengyao Zhu, Jiangxiao Li, Zu-Wei Yin, Taowen Chen, Xiangming Yao, Wenguang Zhao, Haoyu Xue, Xin Jiang, Yongsheng Li, Hengyu Ren, Jun Chen, Jun-Tao Li, Luyi Yang, Feng Pan","doi":"10.1002/anie.202423796","DOIUrl":"https://doi.org/10.1002/anie.202423796","url":null,"abstract":"Polyvinylidene fluoride (PVDF), as the commercial cathode binder for lithium-ion batteries, presents several practical challenges, including insufficient conductivity, weak adhesion to active materials, and the use of toxic N-methylpyrrolidone for slurry preparation. However, while most water-soluble binders can address the aforementioned issues, they fail to meet the requirements of high-voltage cathodes. In this work, we innovatively employed a thermal pulse sintering strategy to modify carboxymethyl cellulose sodium (CMC), enabling their application in 4.6 V LiCoO2 (93% capacity retention after 200 cycles). This strategy facilitates the decomposition of electrochemically active carboxyl groups, leading to ring opening reactions that generate numerous ether linkages (-C-O-C-) without introducing undesirable side effects on LiCoO2. The resulting components form additional charge carrier (i.e., Li+ and e-) pathways on the cathode surface. Additionally, the heating process also promotes uniform coating of the binder on the surface of LiCoO2, creating a protective layer that inhibits interfacial side reactions. Through proposing a scalable and economic manufacturing technology of multifunctional binder, this work enlightens the avenues for practical high-energy-density batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124814","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

Improving the Methane Oxidation by Self-Adaptive Optimization of Liquid-Metal Catalysts

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202421554

Yuen Wu, Haoran Zhang, Yinhe Wang, Xiaokang Liu, Fan Wu, Xiaoqian Wang, Chunrong Ma, Xiao Han, Yihua Ran, Yan Zhang, Zhiwen Zhang, Qiang Xu, Zhandong Wang, Guozhen Zhang, Jing Wang, Jun Cai, Zhi Liu, Yu Zhang, Tao Yao, Jun Jiang

{"title":"Improving the Methane Oxidation by Self-Adaptive Optimization of Liquid-Metal Catalysts","authors":"Yuen Wu, Haoran Zhang, Yinhe Wang, Xiaokang Liu, Fan Wu, Xiaoqian Wang, Chunrong Ma, Xiao Han, Yihua Ran, Yan Zhang, Zhiwen Zhang, Qiang Xu, Zhandong Wang, Guozhen Zhang, Jing Wang, Jun Cai, Zhi Liu, Yu Zhang, Tao Yao, Jun Jiang","doi":"10.1002/anie.202421554","DOIUrl":"https://doi.org/10.1002/anie.202421554","url":null,"abstract":"Methane, a major greenhouse gas and abundant carbon resource, presents significant challenges in catalysis due to its high symmetry and thermodynamic stability, which tend to cause over-oxidation to CO2. Traditional catalysts require high temperatures and pressures to facilitate CH4 conversion, constrained by their rigid structures which lack the flexibility needed for optimizing complex reaction steps. This study introduces a novel Cu single atoms-embedded liquid metal catalyst (Cu-LMC) based on gallium alloys, characterized by dynamic, self-adaptive structures that provide enhanced catalytic performance and selectivity. Our findings reveal that Cu-LMC achieves a high methane conversion to methanol yield (5.9 mol·gCu-1·h-1) with a selectivity of 82%. The results show that mild surface oxidation significantly boosts the catalytic performance of Cu-LMC by increasing active copper sites through the formation of a Cu-O-Ga configuration while preserving the catalyst's structural flexibility. In-situ XPS and XAFS analyses, along with AIMD simulations, demonstrate that the Cu-LMC enables self-adaptive structural adjustments that lower methanol desorption energy and increase the energy barrier for by-product formation, optimizing the overall methane conversion process. The results underscore the importance of designing catalysts with dynamic and adaptable structures to overcome traditional limitations and improve efficiency in catalytic reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"82 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084039","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

Cyclometalated Iridium(III) Schiff Base Complexes for Chemiluminogenic Bioprobes

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-04 DOI: 10.1002/anie.202419856

Jing-Hui Zhu, Xin He, Yingnan Wu, Haiqiao Huang, Dekai Yang, Jianyuan Li, Minrui Gu, Lei Wang, Mingle Li, Xiaoqiang Chen, Xiaojun Peng

{"title":"Cyclometalated Iridium(III) Schiff Base Complexes for Chemiluminogenic Bioprobes","authors":"Jing-Hui Zhu, Xin He, Yingnan Wu, Haiqiao Huang, Dekai Yang, Jianyuan Li, Minrui Gu, Lei Wang, Mingle Li, Xiaoqiang Chen, Xiaojun Peng","doi":"10.1002/anie.202419856","DOIUrl":"https://doi.org/10.1002/anie.202419856","url":null,"abstract":"Chemiluminogenic bioimaging has emerged as a promising paradigm due to its independence from light excitation, thereby circumventing challenges related to light penetration depth and background autofluorescence. However, the availability of effective chemiluminophores remains limited, which substantially impedes their bio-applications. Herein, we discovered for the first time that cyclometalated iridium(III) Schiff base complexes can unexpectedly generate chemiluminescence. Notably, the chemiluminescence reaction was rapid, with a half-life of only 0.86 s, significantly faster than previously reported examples. Unlike conventional chemiluminescent scaffolds, the distinguishing feature of the chemiluminogenic iridium(III) complex is its unique intramolecular imine-to-amide conversion upon reaction with reactive oxygen species (ROS). Intriguingly, the chemiluminogenicity of these complexes is not influenced by the cyclometalating ligands but is closely associated with the Schiff base ligand, allowing for tuning of the emission colors via altering the cyclometalating ligands. Additionally, we formulated one of the Schiff base complexes (1) as water-soluble chemiluminogenic nanoparticles (CLNPs) and successfully employed them as activatable chemiluminescence bioprobes for precise and rapid imaging of hypochlorite-related biological events both in vitro and in vivo. We believe that this significant finding of the development of chemiluminogenic Schiff base complexes will greatly facilitate the designing of innovative chemiluminophores for theranostic applications.","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":"143084036","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

Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh-rate Zn Metal Anode

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202500295

Pan Xue, Can Guo, Wenbin Gong, Yuting Chen, Xiang Chen, Xiaoge Li, Jingyi Yang, Qichong Zhang, Kenneth Davey, Kaiping Zhu, Jianfeng Mao, Zaiping Guo

{"title":"Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh-rate Zn Metal Anode","authors":"Pan Xue, Can Guo, Wenbin Gong, Yuting Chen, Xiang Chen, Xiaoge Li, Jingyi Yang, Qichong Zhang, Kenneth Davey, Kaiping Zhu, Jianfeng Mao, Zaiping Guo","doi":"10.1002/anie.202500295","DOIUrl":"https://doi.org/10.1002/anie.202500295","url":null,"abstract":"Polymer interphase on Zn anodes obviates dendrite growth and side reactions, however has drawbacks of slow kinetics. Here, a multifunctional polymer interphase with fast kinectics is reported, using poly(phenazine-alt-pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π-conjugated structure and enriched polar pyridine (conjugated cyclic -C=N-) and carbonyl (C=O) groups, preferentially absorbs on the Zn anode to form a stable solid-electrolyte interpahse (SEI) layer in-situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π-conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de-solvation and diffusion of Zn2+. As a result, the Zn metal anode with PPPA/ZnSO4 electrolyte exhibits high Coulombic efficiency of 98.3% at current density of 20 mA cm−2, and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm−2 and plating/stripping capacity of 5 mAh cm−2. The Zn||MnO2 full battery exhibited a discharge capacity of 74.4 mAh g−1 after 5000 cycles at the current density of 2000 mA g−1, demonstrating practical feasibility.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084062","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

Amplified Production of a DNA Decoy Catalyzed by Intracellular MicroRNA

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202424421

Soshu Yasuda, Kunihiko Morihiro, Shuichiro Koga, Akimitsu Okamoto

{"title":"Amplified Production of a DNA Decoy Catalyzed by Intracellular MicroRNA","authors":"Soshu Yasuda, Kunihiko Morihiro, Shuichiro Koga, Akimitsu Okamoto","doi":"10.1002/anie.202424421","DOIUrl":"https://doi.org/10.1002/anie.202424421","url":null,"abstract":"DNA decoys are expected to be among the nucleic acid drugs used to downregulate the transcription process. However, spatially controlling the on/off efficacy of DNA decoys to avoid side effects on normal cells is challenging. To reduce undesired decoy function in normal cells, we adopted catalytic hairpin assembly (CHA) to produce a DNA duplex from a hairpin DNA pair in response to a specific microRNA (miRNA). We designed the DNA hairpin pairs to form a DNA decoy that binds to NF-kB, whose overexpression is related to many diseases, including cancer. The transformation of the DNA hairpin pair to the NF-kB DNA decoy was catalyzed by miR-21. Intracellular CHA progression and the inhibitory effect against NF-kB were observed only in miR-21 overexpressing cancer cells. The intracellular miR-21-catalyzed production of the NF-kB DNA decoy has the potential to reduce side effects on normal cells, thereby strengthening the therapeutic profile of the CHA-decoy system. This study is the first to use the CHA product itself as a selective therapeutic substance. The ability to customize the combination of catalytic miRNA and target transcription factors would allow our technology to serve as a “personalized drug discovery system” for a variety of challenging diseases, including cancer.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084042","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