Journal of the American Chemical Society最新文献

{"title":"Synthesis and Reactivity of an Iron–Tin Complex with Adjacent Stannylidyne and Ferriostannylene Units","authors":"Yang Liu, Franz F. Westermair, Isabelle Becker, Sebastian Hauer, Michael Bodensteiner, Christoph Hennig, Gábor Balázs, Franc Meyer, Ruth M. Gschwind, Robert Wolf","doi":"10.1021/jacs.4c18423","DOIUrl":"https://doi.org/10.1021/jacs.4c18423","url":null,"abstract":"Heavier transition metal carbyne analogs hold significant potential for cooperative activation of small molecules. However, complexes containing more than one heavier tetrylidyne ligand RE (E = Si, Ge, Sn, Pb) are rare due to the high oligomerization tendency of RE ligands. In this study, we describe the complex [Fe(SnAr’)₂] (<b>1</b>; Ar’ = 2,6-Dipp₂-C₆H₃, Dipp = 2,6-<i>ⁱ</i>Pr₂–C₆H₃), which features adjacent Fe–Sn single and double bonds. Complex <b>1</b> exhibits versatile reactivity with transition metal and main group compounds. Treatment of complex <b>1</b> with Ni(COD)₂ (COD = 1,5-cyclooctadiene) yields the tetranuclear complex [Fe(μ-SnAr’)₂Ni] (<b>2</b>), characterized by an unusual “push–pull” interaction between nickel(0) and the two coordinating Sn atoms, as revealed by quantum chemical studies. The reaction of complex <b>1</b> with AlBr₃ results in Al–Br bond cleavage and Ar’ migration to aluminum. CH₃I adds oxidatively to the Sn atom that is singly bonded to Fe, while PMe₃ coordinates to Fe, inducing reversible cleavage of the Fe═Sn double bond. In addition, complex <b>1</b> activates inorganic molecules. CO₂ undergoes disproportionation to produce a carbonate-bridged Ar’Sn(μ–OCO₂)SnAr’ ligand, whereas CS₂ is reductively coupled to form an ethylene tetrathiolate ligand ([C₂S₄]^4–). The reaction with white phosphorus (P₄) generates an unusual Ar’P₄Sn₂Ar’ ligand. This multifaceted reactivity illustrates the behavior of the Fe and Sn sites in complex <b>1</b>, suggesting that complexes of this type are promising reagents for small molecule activation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"21 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385037","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}

{"title":"Single-Molecule-Sensitive Three-Dimensional Atomic Heterostructures with Extreme Light-Matter Coupling","authors":"Yi-Jui Yeh, Shao-Yu Chen, Wesley Wei-Wen Hsiao, Yoshifumi Oshima, Mari Takahashi, Shinya Maenosono, Kuo-Lun Tung, Wei-Hung Chiang","doi":"10.1021/jacs.4c15029","DOIUrl":"https://doi.org/10.1021/jacs.4c15029","url":null,"abstract":"Three-dimensional heterostructures (3DHS) with controlled compositions and tuned properties are highly desired for fundamental studies and applications in optoelectronics, nanocatalysis, clean energy, and biomedicine. However, conventional nanostructure engineering is hindered by challenges such as poor structural control, time- and energy-intensive processes, the use of hazardous and expensive chemicals, and harsh conditions. Here, we report plasma-assisted epitaxy (PAE) engineering of a metal–organic 3DHS with extreme light-matter interaction for rapid single-molecule-level sensing. Plasmonic-active 3DHS composed of structure-tuned gold–silver core–shell nanoparticles (AuAgCSNPs) was precisely engineered using stable and scalable microplasma-enabled nanofabrication under ambient conditions. The engineered AuAgCSNP-based 3DHS possessed exceptional Raman enhancement under suitable laser excitation, leading to single-molecule detection of SARS-CoV-2 spike proteins in simulated human saliva via surface-enhanced Raman scattering (SERS). The developed plasma fabrication method allows the production of centimeter-scale SERS-active metal–organic 3DHS on disposable, flexible, lightweight, and cost-effective substrates, thereby opening a new avenue for next-generation biosensing, nanoelectronics, nanocatalysis, and biomedical applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"59 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393864","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}

{"title":"Charge Density Wave and Superconductivity in BaSbTe2S Heterolayer Crystal with 2D Te Square Nets","authors":"Zhong-Zhen Luo, Hengdi Zhao, Weizhao Cai, Shima Shahabfar, Juncen Li, Songting Cai, Jameson Berg, Tushar Bhowmick, Jin-Ke Bao, Shiqiang Hao, Yihui He, Weiping Guo, Duck Young Chung, Yan Yu, Suchismita Sarker, Matthew Grayson, Christopher Wolverton, Vinayak P. Dravid, Wendan Cheng, Zhigang Zou, Stephan Rosenkranz, Christos D. Malliakas, Shanti Deemyad, Mercouri G. Kanatzidis","doi":"10.1021/jacs.4c16505","DOIUrl":"https://doi.org/10.1021/jacs.4c16505","url":null,"abstract":"Low-dimensional materials with charge density waves (CDW) are attractive for their potential to exhibit superconductivity and nontrivial topological electronic features. Here we report the two-dimensional (2D) chalcogenide, BaSbTe₂S which acts as a new platform hosting these phenomena. The crystal structure of BaSbTe₂S is composed of alternating atomically thin Te square-net layers and double rock-salt type [(SbTeS)₂]^2– slabs separated with Ba²⁺ atoms. Due to the electronic instability of the Te square net, an incommensurately modulated structure is triggered and confirmed by both single-crystal X-ray diffraction, electron diffraction, and the presence of an energy bandgap in this compound. Our first-principles electronic structure analysis and investigation of structural dynamical instability suggest that the Te network plays a dominant role in its origin. The incommensurate structure is refined with a modulation vector of <i><b>q</b></i> = 0.351(1)<i>b</i>* using an orthorhombic cell of <i>a</i> = 4.4696(5) Å, <i>b</i> = 4.4680(5) Å, and <i>c</i> = 15.999(2) Å under superspace group <i>Pmm</i>2(0β0)000 at 293 K. The modulation vector <i><b>q</b></i> varies as a function of both occupancy of Te in the square net and temperature, indicating the CDW order can be modulated by local distortions. The CDW can be suppressed by pressure, leading to the emergence of superconductivity with a <i>T</i>_c up to 7.5 K at 13.6 GPa, suggesting a competition between the CDW order and superconductivity. Furthermore, electrical transport under the magnetic field reveals the existence of compensated high mobility electron- and hole-bands near the Fermi surface (μ ∼600–3500 cm²V^–1s^–1), suggesting Dirac-like band dispersion.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"65 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385034","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}

{"title":"Host–Guest Chemistry-Mediated Biomimetic Chemoenzymatic Synthesis of Complex Glycosphingolipids","authors":"Yuan Ma, Yating Liu, Chang Cao, Jiarong Peng, Yinyu Jiang, Tiehai Li","doi":"10.1021/jacs.4c17725","DOIUrl":"https://doi.org/10.1021/jacs.4c17725","url":null,"abstract":"Glycosphingolipids (GSLs) are amphipathic complex biomolecules constituted of hydrophilic glycans covalently linked to hydrophobic lipids via glycosidic bonds. GSLs are widely distributed in cells and tissues, where they play crucial roles in various biological functions and disease processes. However, the heterogeneity and complexity of GSLs make it difficult to explore their precise biofunctions due to obstacles in obtaining well-defined structures. Herein, we report a host–guest-chemistry-mediated biomimetic chemoenzymatic approach for the efficient synthesis of diverse complex GSLs. A key feature of this approach is that the use of methyl-β-cyclodextrin enables amphipathic glycolipids forming water-soluble inclusion complexes to improve their solubility in aqueous media, thereby facilitating enzyme-catalyzed reactions. The power and applicability of our approach are demonstrated by the streamlined synthesis of biologically important globo-, ganglio-, neolacto-, and lacto-series GSLs library containing 20 neutral and acidic glycolipids with different fucosylation and sialylation patterns. The developed method will open new avenues to easily access a wide range of complex GSLs for biomedical applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"86 2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393871","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}

{"title":"Reduction-Interrupted Tandem Reaction for General Synthesis of Functional Amino Acids by a Heterogeneous Cobalt Catalyst","authors":"Haotian Hua, Chenggang Ci, Pierre H. Dixneuf, Min Zhang","doi":"10.1021/jacs.4c15284","DOIUrl":"https://doi.org/10.1021/jacs.4c15284","url":null,"abstract":"Despite their significant importance in numerous fields, the challenges in direct and diverse synthesis of γ-amino-α-hydroxybutyric acids (AHBAs) pose substantial obstacles to explore their functions. Here, by preparation of a <i>N</i>-doped carbon-supported bifunctional cobalt catalyst (Co-DAPhen/C), it was applied to develop a reductive tandem reaction for general synthesis of AHBA derivatives from cheap and abundant nitroarenes, formaldehyde, and acrylates. This catalytic three-component reaction features broad substrate and functionality tolerance, an easily accessible and reusable catalyst, and high step and atom economy. The active Co sites of the catalyst are involved in the mild reduction processes with formic acid, whereas the N-doped carbon support enriches the HCHO and acrylates by physical adsorption, thus favoring the capture of hydroxylamine and nitrone intermediates via condensation and 1,3-dipolar cycloaddition, respectively. Such a metal–support synergy interrupts the conventional reduction of nitroarenes into anilines and results in a novel tandem reaction route. In this work, the concept merging mild reduction and effective intermediate transformations is anticipated to develop more useful tandem reactions by rational catalyst design.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"41 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393865","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}

{"title":"Molecular Self-Gating Inside a Zeolite Catalyst","authors":"Zhiqiang Liu, Caiyi Lou, Jiamin Yuan, Xiaomin Tang, Yuzhou Fan, Ji Qi, Rui Zhang, Peng Peng, Guoliang Liu, Shutao Xu, Anmin Zheng","doi":"10.1021/jacs.4c17510","DOIUrl":"https://doi.org/10.1021/jacs.4c17510","url":null,"abstract":"Diffusion is a ubiquitous process that is strongly correlated with concentration. Based on developed three-dimensional free energy and a continuous-time random-walk coarse-graining method, we found the optimal diffusion pathway under confinement, determined all diffusional energy barriers, and identified the major units of zeolite where molecular diffusion is limited. Interestingly, a novel diffusion mechanism was determined in the nanopore of a zeolite catalyst by molecular dynamics simulation, pulsed field gradient, and 2D exchange spectroscopy (EXSY) NMR experiments. We describe a “molecular self-gating effect” that effectively predominates the diffusion process in cage-type (e.g., RHO and MER) zeolites through a “traffic jam” and a “smooth traffic” process. Initially, transport is hindered by molecules forming a gate (traffic jam); then, as the number of molecules reaches a certain threshold, diffusion increases rapidly due to the synergistic collisions of aggregated molecules upon the gate (smooth traffic). This unique diffusion behavior is observed here for the first time and illustrates a microscopic mechanism dictated by the molecular self-gating effect in a confined space. The exploitable diffusion disclosed herein should shed new light on the fundamental understanding of transport, as well as enrich diffusion behavior under confinement.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385035","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}

{"title":"Peptide Backbone Editing via Post-Translational O to C Acyl Shift","authors":"Carly K. Schissel, Helena Roberts-Mataric, Isaac J. Garcia, Hana Kang, Riaz Mowzoon-Mogharrabi, Matthew B. Francis, Alanna Schepartz","doi":"10.1021/jacs.4c14103","DOIUrl":"https://doi.org/10.1021/jacs.4c14103","url":null,"abstract":"Despite tremendous efforts to engineer translational machinery, replacing the encoded peptide backbone with new-to-nature structures remains a significant challenge. C, H, O, and N are the elements of life, yet ribosomes are capable of forming only C–N bonds as amides, C–O bonds as esters, and C–S bonds as thioesters. There is no current strategy to site-selectively form C–C bonds as ketones embedded in the backbones of ribosomal products. As an alternative to direct ribosomal C–C bond formation, here we report that peptides containing a dehydrolactic acid motif rapidly isomerize to generate backbone-embedded α,γ-diketoamides via a spontaneous formal O to C acyl shift rearrangement. The dehydrolactic acid motif can be introduced into peptides ribosomally or via solid-phase synthesis using α-hydroxyphenylselenocysteine followed by oxidation. Subsequent incubation at physiological pH produces an α,γ-diketoamide that can be diversified using a variety of nucleophiles, including hydrazines and hydroxylamines, to form pyrazoles and oximes, respectively. All of these groups remain embedded directly within the polypeptide backbone. This general strategy for peptide backbone editing, predicated on an intricate cascade of acyl rearrangements, provides the first nonenzymatic example of a C–C bond forming reaction to take place within a peptide backbone. The products so-produced are easily diversified into protein-like materials with backbone-embedded heterocycles. Application of this peptide editing strategy should accelerate the discovery of genetically encoded molecules whose properties more closely resemble those of bioactive natural products.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"52 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393863","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}

{"title":"Functionalized Docetaxel Probes for Refined Visualization of Mitotic Spindles by Expansion Microscopy","authors":"Gang Wen, Xiong Chen, Patrick Eiring, Volker Leen, Johan Hofkens, Markus Sauer","doi":"10.1021/jacs.4c15608","DOIUrl":"https://doi.org/10.1021/jacs.4c15608","url":null,"abstract":"Visualizing the ultrastructure of mitotic spindles, the macromolecular machines that segregate chromosomes during mitosis, by fluorescence imaging remains challenging. Here we introduce an azido- and amino-functionalized docetaxel probe, which upon labeling of microtubules can be fixed, click-labeled and linked into hydrogels. The new probe is particularly useful for super-resolution imaging of dense microtubule structures in mitotic spindles. Multicolor expansion microscopy of mitotic cells allowed us to visualize the different phases of mitosis with unprecedented spatial resolution.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"208 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393867","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}

{"title":"Bioorthogonal Reaction of β-Chloroacroleins with meta-Aminothiophenol to Develop Near-Infrared Fluorogenic Probes for Simultaneous Two-color Imaging","authors":"Liping Wang, Yujie Huang, Jing Wang, Yulan Jiang, Bang-Ping Jiang, Hua Chen, Hong Liang, Xing-Can Shen","doi":"10.1021/jacs.4c16074","DOIUrl":"https://doi.org/10.1021/jacs.4c16074","url":null,"abstract":"Highly fluorogenic probe based bioorthogonal chemistry has become a promising tool in biomedical applications. However, the majority of fluorogenic probes are designed by introducing a bioorthogonal partner as a fluorescence quencher into classical fluorophores, and these probes exhibit a deteriorating fluorogenicity as the emission wavelength shifts toward the near-infrared (NIR) region, greatly limiting their applications in vivo. Herein, we report a novel fluorogenic bioorthogonal reaction involving <i>β-</i>chloroacroleins (<i><b>β-</b></i><b>CAs</b>) and <i>meta-</i>aminothiophenol (<i><b>m-</b></i><b>AT</b>_<b>1</b>), whose fluorescence increases more than 500-fold upon in situ generating fluorophores. <i><b>β-</b></i><b>CAs</b> are stable under physiological conditions and react rapidly (<i><b>β-</b></i><b>CA</b>_<b>9</b>, <i>k</i>₂ <i>=</i> 2.2 × 10² M^–1 s^–1, in H₂O) and chemoselectively with <i><b>m-</b></i><b>AT</b>_<b>1</b> in the presence of biological nucleophiles, and delightfully, the reaction proceeds swiftly even under solvent-free conditions. Furthermore, manipulating the conjugate length of <i><b>β-</b></i><b>CAs</b> enables the emission wavelength of the probes to be fine-tuned from 627 to 778 nm. These probes allow the simultaneous labeling of multiple cellular organelles without washing steps, and two-color tumor visualization is achieved in living mice. We believe this study not only provides new insights for the development of NIR fluorogenic probes with superior turn-on behaviors but also presents a promising fluorogenic bioorthogonal reaction <b>CA-AT</b> with widespread potential applications in biomedical research.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"63 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385033","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}

{"title":"In Crystallo Wolff Rearrangement of a Metalated Diazoester: Structural Confirmation of the Singlet Carbene Wolff-Intermediate","authors":"Ze-Jie Lv, Arnd Fitterer, Regine Herbst-Irmer, Serhiy Demeshko, Hendrik Verplancke, Max C. Holthausen, Sven Schneider","doi":"10.1021/jacs.4c18289","DOIUrl":"https://doi.org/10.1021/jacs.4c18289","url":null,"abstract":"The Wolff rearrangement (WR) is widely used for the synthesis of ketenes from diazoketones and -esters. Stepwise WR reactions are proposed to proceed through transient carbonylcarbene (R–C–C(O)–R′) intermediates, which so far have evaded structural characterization. Here, a Wolff metallocarbene (Pt^II–C–C(O)–OEt) is reported as a fleeting intermediate in the photoinitiated fragmentation of a diazoester ligand. Frozen solution and crystal matrix isolation experiments enabled the spectroscopic, magnetic, crystallographic, and computational characterization of this highly reactive species. All methods confirmed a singlet ground state for the WR metallocarbene, which is stabilized by π interactions with the carboxyl substituent, thus complementing computational and transient spectroscopy studies for classic organic WR reactions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"52 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385036","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}