Journal of the American Chemical Society最新文献

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Caught in the Middle: A Rigid DNA Label That Provides an Incisive Picture of DNA Conformational Flexibility in Protein-DNA Complexes. 夹在中间:一个刚性DNA标签,提供了蛋白质-DNA复合物中DNA构象灵活性的深刻图像。
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-23 DOI: 10.1021/jacs.5c01823
Joshua Casto,Shramana Palit,Anthony Little,Zikri Hasanbasri,Linda Jen-Jacobson,Sunil Saxena
{"title":"Caught in the Middle: A Rigid DNA Label That Provides an Incisive Picture of DNA Conformational Flexibility in Protein-DNA Complexes.","authors":"Joshua Casto,Shramana Palit,Anthony Little,Zikri Hasanbasri,Linda Jen-Jacobson,Sunil Saxena","doi":"10.1021/jacs.5c01823","DOIUrl":"https://doi.org/10.1021/jacs.5c01823","url":null,"abstract":"Measurement of the conformation of DNA in protein-DNA complexes is important to decipher the role of the DNA conformation and dynamics in protein recognition and function. In this work, we report a rigid nucleotide-independent spin label that places paramagnetic Cu(II) within the DNA helix. The labeling strategy exploits the chelation of Cu(II) to two 8-aminoquinoline moieties, one in each strand. Because the rigidity of the probe avoids potentially confounding motions of the label itself, EPR signals can resolve 2-3 Å changes in interspin distance; the breadth of the distance distribution reports dynamic fluctuations from the most probable conformation. Continuous wave and pulsed electron paramagnetic resonance spectroscopy (EPR) shows that Cu(II) coordinates properly to the labeling sites. Measurements of the interspin dipolar interaction on DNA oligonucleotides with two labels placed at various distances demonstrate that the label provides accurate and narrow distance distributions sensitive to DNA conformation and flexibility. Molecular dynamics simulations support these interpretations. We utilized this label to measure the conformations of DNA when the type II restriction endonuclease EcoRV binds to its specific recognition sequence. The results provide in-solution evidence that the EcoRV endonuclease induces axial DNA bending in the absence of metal ions, contrary to a long-standing belief. Furthermore, the distance distribution narrows upon protein binding and even further on subsequent metal binding, implying that bound protein constrains the bending dynamics of DNA. This method provides a novel and accurate approach to assess DNA conformation and dynamics in solution.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"135 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122380","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
Discovery of an Interlocked and Interwoven Molecular Topology in Nanocarbons via Dynamic C–C Bond Formation 通过动态碳-碳键形成发现纳米碳的互锁和交织分子拓扑结构
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-23 DOI: 10.1021/jacs.5c04268
Harrison M. Bergman, Angela T. Fan, Christopher G. Jones, August J. Rothenberger, Kunal K. Jha, Rex C. Handford, Hosea M. Nelson, Yi Liu, T. Don Tilley
{"title":"Discovery of an Interlocked and Interwoven Molecular Topology in Nanocarbons via Dynamic C–C Bond Formation","authors":"Harrison M. Bergman, Angela T. Fan, Christopher G. Jones, August J. Rothenberger, Kunal K. Jha, Rex C. Handford, Hosea M. Nelson, Yi Liu, T. Don Tilley","doi":"10.1021/jacs.5c04268","DOIUrl":"https://doi.org/10.1021/jacs.5c04268","url":null,"abstract":"Topologically complex carbon nanostructures are an exciting but largely unexplored class of materials due to their challenging synthesis. Previous methods are low yielding because they rely on irreversible C<sub>sp<sup>2</sup></sub>–C<sub>sp<sup>2</sup></sub> bond formation, which necessitates complex templating strategies to enforce entanglement. Here, reversible zirconocene coupling of alkynes is developed as a new method to access complex molecular topologies, where dynamic C–C bond formation facilitates entanglement under thermodynamic control, allowing the use of simple precursors without the need for preassembly. This strategy enables the scalable, high-yield synthesis of three topologically distinct nanocarbons, including the serendipitous discovery of a structure containing a new topological motif that was not previously identified or realized synthetically. This motif, consisting of an unusual combination of interlocking and interweaving, was recognized to be generalizable to a new topological class of molecules, introduced here as perplexanes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122891","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
An Adaptive Palladium Single-Atom Catalyst Enabling Reactivity Switching between Borylation and C-C Coupling. 一种自适应钯单原子催化剂,使反应性在硼化和C-C偶联之间切换。
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-23 DOI: 10.1021/jacs.4c17943
Vitthal B Saptal,Clara Saetta,Adriana Laufenböck,Martin Sterrer,Ik Seon Kwon,Andrea Lucotti,Matteo Tommasini,Ondřej Tomanec,Aristides Bakandritsos,Giovanni Di Liberto,Gianfranco Pacchioni,Gianvito Vilé
{"title":"An Adaptive Palladium Single-Atom Catalyst Enabling Reactivity Switching between Borylation and C-C Coupling.","authors":"Vitthal B Saptal,Clara Saetta,Adriana Laufenböck,Martin Sterrer,Ik Seon Kwon,Andrea Lucotti,Matteo Tommasini,Ondřej Tomanec,Aristides Bakandritsos,Giovanni Di Liberto,Gianfranco Pacchioni,Gianvito Vilé","doi":"10.1021/jacs.4c17943","DOIUrl":"https://doi.org/10.1021/jacs.4c17943","url":null,"abstract":"The development of single-atom catalysts (SACs) with site-specific and tunable catalytic functionalities remains a highly desirable yet challenging goal in catalysis. In this study, we report a SAC featuring anisotropic coordination cavities synthesized via a one-step polymerization of 2,6-diaminopyridine and cyanuric chloride. These cavities provide a robust framework for anchoring isolated Pd single atoms with exceptional stability. The unique broken symmetry of the catalyst's local structure enables precise control over reaction pathways, allowing reactivity to be switched between distinct catalytic outcomes. Specifically, under tailored reaction conditions, the catalyst can either halt at the borylation step or proceed seamlessly to Suzuki coupling in a self-cascade process. Mechanistic studies unveil the pivotal role of Pd single atoms in driving key steps, including oxidative addition, base exchange, and reductive elimination. Furthermore, green metrics demonstrate the process's sustainability, with minimized waste generation and reduced reliance on hazardous reagents in the self-cascade transformation. This work establishes an innovative benchmark in the field of single-atom catalysis: by enabling complex, multistep transformations via strategic activation of multiple functional groups, this catalyst exemplifies the potential of self-cascade processes to revolutionize synthetic chemistry via catalysis engineering.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"15 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122211","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
Engineering Supramolecular Hydrogen Bonding Interactions into Dynamic Covalent Polymers To Obtain Double Dynamic Biomaterials. 工程超分子氢键相互作用到动态共价聚合物中以获得双动态生物材料。
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-23 DOI: 10.1021/jacs.4c15102
Jasper G M Aarts,Maritza M Rovers,Martin G T A Rutten,Patricia Y W Dankers
{"title":"Engineering Supramolecular Hydrogen Bonding Interactions into Dynamic Covalent Polymers To Obtain Double Dynamic Biomaterials.","authors":"Jasper G M Aarts,Maritza M Rovers,Martin G T A Rutten,Patricia Y W Dankers","doi":"10.1021/jacs.4c15102","DOIUrl":"https://doi.org/10.1021/jacs.4c15102","url":null,"abstract":"Inspired by dynamic systems in nature, we can introduce dynamics into synthetic biomaterials through dynamic covalent bonds or supramolecular interactions. Combining both types of dynamic interactions may allow for advanced and innovative networks with multiple levels of dynamicity. Here we present two types of solid materials consisting of either dynamic covalent imine bonds or a combination of these dynamic covalent bonds with supramolecular hydrogen bonding ureido-pyrimidinone (UPy) units to obtain double dynamic materials. We showed the facile synthesis and formulation of both materials at room temperature. The thermal and physical properties of each material are highly tunable by altering the ratio and type of cross-linker. Interestingly, we showed that minimal amounts of UPy units result in a drastic increase in material mechanics. Furthermore, we show that both types of materials are suitable as biomaterials through functionalization with cell-adhesive peptides, through either a dynamic covalent imine bond or a supramolecular UPy moiety.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"4 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122252","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
The Critical Role of Chemistry in Advancing Quantum Information Science. 化学在推进量子信息科学中的关键作用。
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-23 DOI: 10.1021/jacs.5c04128
Linda Nhon,Theodore Goodson
{"title":"The Critical Role of Chemistry in Advancing Quantum Information Science.","authors":"Linda Nhon,Theodore Goodson","doi":"10.1021/jacs.5c04128","DOIUrl":"https://doi.org/10.1021/jacs.5c04128","url":null,"abstract":"Advancements in the field of Quantum Information Science (QIS) are expected to produce groundbreaking technologies in computing, sensing, and communications. These developments could have an impact on the economy and workforce of the United States. In order to achieve this vision and sustain U.S. leadership in QIS, however, a robust research enterprise needs to be established. Presently, QIS has reached an inflection point for new discoveries; searching for novel quantum molecular materials that are operational, practical, and efficient is now the new frontier. Since chemistry is the study of manipulating molecular properties across different lengths and time-scales, it has a tremendous opportunity to take a leading role in this untapped domain. Blending QIS and chemistry together will accelerate progress in designing new quantum molecular materials, developing novel measurement tools and techniques, and establishing new quantum computing standards. A recent National Academies of Sciences, Engineering, and Medicine (NASEM) report, Advancing Chemistry and Quantum Information Science, points to fundamental research areas at the interface of these two disciplines that should be pursued in the near-term. Here, a brief overview of these research directions as well as collaboration and infrastructure needs identified from the report are presented.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"137 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122209","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
Mechanometallaphotoredox Catalysis: Utilizing Increased Throughput Mechanochemistry to Develop Solvent-Minimized Aryl Amination and C(sp2)-C(sp3) Cross-Coupling Reactions with Increased Tolerance to Aerobic Conditions. 机械金属光氧化还原催化:利用提高通量的机械化学来开发溶剂最小化芳基胺化和C(sp2)-C(sp3)交叉偶联反应,增加对有氧条件的耐受性。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-22 DOI: 10.1021/jacs.5c05503
Francis Millward, Eli Zysman-Colman
{"title":"<i>Mechanometallaphotoredox</i> Catalysis: Utilizing Increased Throughput Mechanochemistry to Develop Solvent-Minimized Aryl Amination and C(sp2)-C(sp3) Cross-Coupling Reactions with Increased Tolerance to Aerobic Conditions.","authors":"Francis Millward, Eli Zysman-Colman","doi":"10.1021/jacs.5c05503","DOIUrl":"https://doi.org/10.1021/jacs.5c05503","url":null,"abstract":"<p><p>Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly use toxic organic solvents such as DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, the synergistic union of mechanochemistry and photocatalysis, is compatible with this class of dual catalysis reactions involving both photocatalyst and nickel(II) cocatalysts. Using ball milling, these mechanistically complex reactions can be conducted in the absence of a bulk solvent and under air, affording high-yielding aryl aminations and C(sp2)-C(sp3) cross-couplings with alkyl carboxylic acids, alkyl trifluoroborate salts, and alkyl bromides. These advances are facilitated by the introduction of a novel reaction vessel design for conducting four mechanophotocatalysis reactions simultaneously. This work highlights the promise of solvent-minimized photocatalysis reactions, demonstrating that in these examples bulk solvent is redundant, thus significantly reducing this waste stream. Through time-resolved photoluminescence studies, we observed that the excited states of five different photocatalysts were quenched by oxygen more significantly in solution than in the solid state, providing evidence for the origin of the increased tolerance to aerobic conditions that these mechanophotocatalysis reactions experience.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118325","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
Photocatalytic Phosphine-Mediated Deoxygenative [3 + 2] Cycloaddition of α,β-Unsaturated Carbonyls and Alkenes 光催化膦介导的α,β-不饱和羰基和烯烃的脱氧[3 + 2]环加成
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-22 DOI: 10.1021/jacs.5c03665
Jiayan Qiu, Xuemei Zhang, Hanliang Zheng, Gangguo Zhu
{"title":"Photocatalytic Phosphine-Mediated Deoxygenative [3 + 2] Cycloaddition of α,β-Unsaturated Carbonyls and Alkenes","authors":"Jiayan Qiu, Xuemei Zhang, Hanliang Zheng, Gangguo Zhu","doi":"10.1021/jacs.5c03665","DOIUrl":"https://doi.org/10.1021/jacs.5c03665","url":null,"abstract":"Tertiary phosphine is a powerful nucleophile that enables numerous synthetically important reactions. However, the exclusive reliance on a two-electron pathway has restricted the development of phosphine chemistry. We report here a visible light photocatalytic phosphine-mediated deoxygenative [3 + 2] cycloaddition of α,β-unsaturated carbonyls and activated alkenes, providing facile access to polysubstituted cyclopentenes from readily accessible starting materials in promising yields with good substrate scope. Mechanistic investigations corroborate the transient involvement of a phosphine radical cation and consequent α-addition (α to electron-withdrawing groups) to C–C double bonds due to the inherent electrophilicity of the radical cation, as opposed to the traditional nucleophilic β-addition of phosphine. The ensuing single electron transfer reduction, Michael addition, and 1,4-proton transfer cascade furnish a phosphorus ylide, which undergoes an intramolecular Wittig reaction to finish the construction of the cyclopentenes. This work demonstrates that tertiary phosphine can serve as a convenient reagent for carbonyl deoxygenation and act as a traceless directing group for controllable cross-coupling of two distinct alkenes, providing new avenues to expand the frontiers of phosphine chemistry and synthetic chemistry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"38 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114444","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
Adenosine-Triggered Dynamic and Transient Aptamer-Based Networks Integrated in Liposome Protocell Assemblies 脂质体原细胞组装中腺苷触发的动态和瞬态适配体网络
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-22 DOI: 10.1021/jacs.5c05090
Yu Ouyang, Yang Sung Sohn, Xinghua Chen, Rachel Nechushtai, Eli Pikarsky, Fan Xia, Fujian Huang, Itamar Willner
{"title":"Adenosine-Triggered Dynamic and Transient Aptamer-Based Networks Integrated in Liposome Protocell Assemblies","authors":"Yu Ouyang, Yang Sung Sohn, Xinghua Chen, Rachel Nechushtai, Eli Pikarsky, Fan Xia, Fujian Huang, Itamar Willner","doi":"10.1021/jacs.5c05090","DOIUrl":"https://doi.org/10.1021/jacs.5c05090","url":null,"abstract":"The development of transient dissipative nucleic-acid–based reaction circuits and constitutional dynamic networks attracts growing interest as a means of emulating native dynamic reaction circuits. Recent efforts applying enzymes, DNAzymes, or light as catalysts controlling the transient, dissipative functions of DNA networks and circuits were reported. Moreover, the integration of the dynamic networks in protocell assemblies and the identification of potential applications are challenging objectives. Here, we introduce the adenosine (AD) aptamer subunit complex coupled with adenosine deaminase (ADA) as a versatile recognition/catalytic framework for driving transient allosterically AD-stabilized DNAzyme circuits or dissipative AD-stabilized constitutional dynamic networks. In addition, the AD/ADA-driven transient frameworks are integrated into liposome assemblies as protocell models. Functionalized liposomes carrying allosterically ATP-stabilized DNAzymes cleaving EGR-1 mRNA are fused with MCF-7 breast cancer cells, demonstrating effective gene therapy and selective apoptosis of cancer cells.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"56 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122900","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 Situ Monitoring of Molten Chloride Salt Chemistry and Corrosion Using a Microelectrode 用微电极原位监测熔融氯盐化学和腐蚀
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-22 DOI: 10.1021/jacs.5c03651
Changkyu Kim, Adrien Couet
{"title":"In Situ Monitoring of Molten Chloride Salt Chemistry and Corrosion Using a Microelectrode","authors":"Changkyu Kim, Adrien Couet","doi":"10.1021/jacs.5c03651","DOIUrl":"https://doi.org/10.1021/jacs.5c03651","url":null,"abstract":"This study investigated, for the first time, the applicability of a borosilicate glass-coated tungsten microelectrode for in situ monitoring of localized surface electrochemical processes, such as corrosion. The diffusion of Eu<sup>3+</sup> ions was analyzed via cyclic voltammetry from 400 to 550 °C. The microelectrode consistently overestimated diffusion coefficients compared to the macroelectrode results due to additional intrinsic glass electrode current (IGEC) originating from the borosilicate glass coating, as confirmed by EIS. Further analysis revealed that the effective capacitance of the borosilicate glass increases with temperature, and corrected diffusion values were obtained after subtracting the IGEC. To assess the microelectrode’s performance for novel high-temperature scanning electron-chemical microscopy applications, approach curve tests were conducted near insulating alumina and corroding Ni–20Cr surfaces. The current response depended strongly on approach speed and temperature. Approaching the insulating alumina at lower temperatures and faster speeds induced artifacts likely from convection-driven interference and limited ionic mobility. Near the corroding Ni–20Cr surface, slower approach speeds enhanced deposition effects at more negative potentials. Additionally, time-dependent OCP profiling near Ni–20Cr captured the evolution of local redox potential gradients. These results emphasize the need to carefully optimize operational parameters and highlight the potential of microelectrodes for localized electrochemical measurements in molten salt environments.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"54 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114429","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
Electronic Structure Modulation in GeTe by Hg and Sb Codoping Leads to High Thermoelectric Performance. Hg和Sb共掺杂对GeTe的电子结构进行调制可获得高热电性能。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2025-05-22 DOI: 10.1021/jacs.5c05116
Paribesh Acharyya, Animesh Das, Raagya Arora, Manisha Samanta, Subarna Das, Tanmoy Ghosh, Umesh V Waghmare, Kanishka Biswas
{"title":"Electronic Structure Modulation in GeTe by Hg and Sb Codoping Leads to High Thermoelectric Performance.","authors":"Paribesh Acharyya, Animesh Das, Raagya Arora, Manisha Samanta, Subarna Das, Tanmoy Ghosh, Umesh V Waghmare, Kanishka Biswas","doi":"10.1021/jacs.5c05116","DOIUrl":"10.1021/jacs.5c05116","url":null,"abstract":"<p><p>Electronic band convergence and the introduction of doping-induced midgap states near the Fermi level offer a compelling mechanism for modulating the electronic structure to achieve high thermoelectric performance. Germanium telluride (GeTe), with its unique crystal and electronic structure, holds great promise for thermoelectric (TE) power generation. However, a high p-type carrier concentration coupled with high lattice thermal conductivity limits its TE performance. Herein, we report an impressive thermoelectric figure of merit (zT) of ∼2.4 (∼2.6 with Dulong-Petit <i>C</i><sub>p</sub>) at 727 K in Hg and Sb codoped GeTe, achieved through the synergistic effects of electronic structure optimization and lattice thermal conductivity reduction. Hg doping in GeTe boosts the Seebeck coefficient by facilitating the valence band convergence. Importantly, a hybridized midgap band emerges upon Hg doping, through the antibonding interaction of Hg 6s and p orbitals of Te and Ge. Further codoping of Sb makes the midgap state more localized and shifts the <i>E</i><sub>F</sub> up to pin the midgap electronic band, resulting in an enhanced electronic density of states near <i>E</i><sub>F</sub>, as validated by first-principles density functional theory (DFT) calculations of the electronic band structure and experimental Pisarenko analysis. This leads to a significant enhancement of the Seebeck coefficient in Hg and Sb codoped GeTe. Further, when Hg doping exceeds the solid solution limit, it forms HgTe nanoprecipitates in the GeTe matrix, suppressing the lattice thermal conductivity. We have constructed a double-leg TE device using the developed material as a p-type leg, which exhibits a promising output power density of 0.77 W/cm<sup>2</sup> for the Δ<i>T</i> = 440 K, underscoring the material's potential for high-performance TE applications.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118331","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
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