Journal of the American Chemical Society最新文献

{"title":"Bacteria-Mediated Intracellular Radical Polymerizations","authors":"Eleonora Ornati, Jules Perrard, Tobias A. Hoffmann, Raissa Bonon, Nico Bruns","doi":"10.1021/jacs.4c17257","DOIUrl":"https://doi.org/10.1021/jacs.4c17257","url":null,"abstract":"Intracellular radical polymerizations allow for the direct bioorthogonal synthesis of various synthetic polymers within living cells, thereby providing a pathway to polymer-modified cells or the fermentative production of polymers. Here, we show that <i>Escherichia coli</i> cells can initiate the polymerization of various acrylamide, acrylic, and methacrylic monomers through an atom transfer radical reaction triggered by the activity of naturally occurring biomolecules within the bacterial cells. Intracellular radical polymerizations were confirmed by nuclear magnetic resonance spectroscopy, gel permeation chromatography of polymers extracted from the cells, and fluorescence labeling of the polymer directly inside the cells. The effect of polymerization on cell behavior and the response of the cells to polymerization was investigated through fluorescence microscopy and flow cytometry techniques, as well as metabolic and membrane integrity assays. The polymer synthesis and resulting products are cell-compatible, as indicated by the high viability of the polymerized cells. <i>In cellulo</i> synthesis of synthetic polymers containing fluorescent dyes was also achieved. These results not only enhance our understanding of the untapped potential of bacterial cells as living catalysts for polymer production but also reveal intracellular polymerization based on atom transfer radical polymerization initiators as a bioorthogonal tool for cell engineering and synthetic biology.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"52 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539192","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":"Tailoring Activation Intermediates of CO2 Initiates C–N Coupling for Highly Selective Urea Electrosynthesis","authors":"Chao Zhao, Yu Jin, Jingkang Yuan, Qilin Hou, He Li, Xiaoqing Yan, Honghui Ou, Guidong Yang","doi":"10.1021/jacs.5c00583","DOIUrl":"https://doi.org/10.1021/jacs.5c00583","url":null,"abstract":"Electrocatalyzed reduction of CO₂ and NO₃^– to synthesize urea is a highly desirable, but challenging reaction. The bottleneck of this reaction is the C–N coupling of CO₂ and NO₃^– reduction intermediates. In particular, the uncertainty of CO₂ multielectron reduction intermediates severely affects the selectivity and activity of C–N coupling processes involving multiple electron and proton transfers. Here, we present a novel tandem catalyst with two compatible single-atom active sites of Au and Cu on red phosphorus (RP-AuCu) that efficiently converts CO₂ and NO₃^– to urea. Experimental and theoretical prediction results confirmed that the active center of Au on red phosphorus promotes electron transfer between CO₂ molecules and red phosphorus, thereby regulating CO₂ activation intermediates to produce electrophilic *COOH. In addition, the active center of Cu on red phosphorus can enhance the electrophilic attack of *COOH species on *NH₂, thus promoting the selective formation of C–N bonds. Consequently, RP-AuCu exhibited a urea yield of 22.9 mmol g_cat.^–1 h^–1 and a Faraday efficiency of 88.5% (−0.6 V_RHE), representing one of the highest levels of electrocatalytic urea synthesis. This work deepens the understanding of the C–N coupling mechanism and provides an interesting catalyst design approach for the efficient and sustainable production of C–N compounds.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539196","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":"Solution Synthesis of Single Crystalline Zinc Nanowires","authors":"Dasai Ban, Mingtao Chen, Fan Guo, Shengnan Xu, Jiaxing Huang","doi":"10.1021/jacs.4c18640","DOIUrl":"https://doi.org/10.1021/jacs.4c18640","url":null,"abstract":"Nanowires of relatively stable metals, including Au, Ag, Cu, Pt, and Pd have garnered much attention for their highly anisotropic shapes, unique properties, and demonstrated potential applications. However, nanowires of more reactive metals, such as Zn, are much less explored. Here, we report a solution-phase synthesis that generates single crystalline Zn nanowires in high yield that remain air stable for months due to a native oxide layer protecting the metal surface. The diameter of the nanowires is around 50–90 nm and the length extends well over 20 μm along ⟨0001⟩ and ⟨1<span>2</span>10⟩ directions. These high aspect ratio nanowires readily form percolated network when blended in resins, which could bring new opportunities for Zn-based anticorrosion coatings. In a proof-of-concept, by replacing Zn microparticles with nanowires, comparable anticorrosion performance can be achieved while reducing Zn loading by 75 wt % and overall coating weight by 60%. This discovery provides a material foundation to explore the synthesis and properties of relatively reactive metal nanostructures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"36 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546866","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":"Deep-Red and Ultrafast Photocatalytic Proximity Labeling Empowered In Situ Dissection of Tumor-Immune Interactions in Primary Tissues","authors":"Zhizheng Lou, Yan Zhang, Xuan Liang, Mengrui Cao, Yicong Ma, Peng R. Chen, Xinyuan Fan","doi":"10.1021/jacs.4c17879","DOIUrl":"https://doi.org/10.1021/jacs.4c17879","url":null,"abstract":"Immunotherapy efficacy in solid tumors varies greatly, influenced by the tumor microenvironment (TME) and the dynamic tumor-immune interactions within it. Decoding these interactions <i>in situ</i> with minimal interference with native tissue architecture and delicate immune responses is critical for understanding tumor progression and optimizing therapeutic strategies. Here, we introduce CAT-Tissue, a novel deep-red photocatalytic proximity labeling method that enables ultrafast, high-resolution profiling of tumor-immune interactions in primary tissues. By leveraging nanobody-Chlorin e6 as the photocatalyst and biotin-aniline as the probe, CAT-Tissue enabled the rapid and comprehensive detection of various tumor-immune interactions in both coculture systems and primary tumor sections. Coupled with bulk RNA-sequencing, CAT-Tissue revealed distinct gene expression patterns between tumor-neighboring and tumor-distal lymphocytes, highlighting the recognition and immune responses of tumor-neighboring CD8⁺ T cells, which exhibited activated, effector, and exhausted phenotypes. By leveraging a deep-red photocatalytic proximity cell labeling strategy with excellent tissue penetration and biocompatibility, CAT-Tissue offers a nongenetically encoded platform with high sensitivity and spatiotemporal controllability for rapid profiling tumor-immune interactions within complex tissue environments <i>in situ</i>, which may advance our understanding of tumor immunology and guide the development of more effective immunotherapies.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546927","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":"High-Energy Density Li-Ion Battery Cathode Using Only Industrial Elements","authors":"Eshaan S. Patheria, Pedro Guzman, Leah S. Soldner, Michelle D. Qian, Colin T. Morrell, Seong Shik Kim, Kyle Hunady, Elena R. Priesen Reis, Nicholas V. Dulock, James R. Neilson, Johanna Nelson Weker, Brent Fultz, Kimberly A. See","doi":"10.1021/jacs.4c18440","DOIUrl":"https://doi.org/10.1021/jacs.4c18440","url":null,"abstract":"Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li₂FeS₂, composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al³⁺ for Fe²⁺ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g^–1) and energy density (≳1000 Wh·kg^–1). We show that Al³⁺ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"16 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546929","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":"Modular Access from Acrylate to a Sustainable Polyester Platform with Large-Span Tunability and Chemical Circularity under Mild Conditions","authors":"Haoyu Fan, Chenyang Hu, Mingxin Niu, Qi Zhang, Bokun Li, Xuan Pang, Xuesi Chen","doi":"10.1021/jacs.5c00044","DOIUrl":"https://doi.org/10.1021/jacs.5c00044","url":null,"abstract":"Making polyesters with conventional vinyl monomers is one of the most economical ways to develop sustainable polymeric materials. For polar vinyls, while their transformation into lactones has been studied extensively, there exists no further access to synthesizing polyesters, presumably due to the nonstrained and nonpolymerizable nature of the obtained lactones. Herein, we report the first facile synthesis of polyesters that originated from one of the most critical classes of polar vinyls-acrylates. Specifically, a series of modular six-membered lactones were rationally designed and synthesized from methyl acrylate together with malonic esters containing diverse functional groups and formaldehyde. The monomers underwent ring-opening polymerization (ROP) to yield the first acrylate-derived polyesters, which further constitute a unique polymer platform with a large scope of potential functionalities and performances as well as easy chemical circularity under mild conditions. Notably, the obtained polyesters are a rare example featuring tunable functionalities on the side ester groups whose impact on certain material properties (e.g., glass transition temperature) is similar to that of polyacrylates, implying potential replacement between polyesters and polyacrylates. In addition, by presenting the special geminal disubstitutions originally from the monomers’ γ-position for the first time, polyesters also exhibited unprecedentedly enhanced thermal and recycling properties: Variation of the geminal disubstitutions offers a unique access to large-span modulation from completely amorphous to high-level crystalline materials, and the melting temperature of the polymer with high crystallinity was drastically increased by 84 °C compared with the reported monosubstituted counterpart. At the same time, compared with polyesters synthesized from other six-membered lactones whose chemical recycling required harsh conditions (&gt;150 °C and high vacuum), the gem-disubstituted polyesters in this work can undergo complete chemical recycling to monomers under much milder conditions (80 °C and ambient pressure). This study informs the design of future high-performance polyesters derived from polar vinyls.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547065","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":"Giant Enhancement of Optical Nonlinearity by Manipulating Guest Molecular Stacking Modes in Metal–Organic Frameworks","authors":"Kangshuai Geng, Yupei Sun, Yujie Zhao, Zhichao Shao, Yi Wei, Jing Huang, Yang Cui, Xiaoyan Xu, Hongwei Hou","doi":"10.1021/jacs.5c00081","DOIUrl":"https://doi.org/10.1021/jacs.5c00081","url":null,"abstract":"The influence of guest stacking interactions in host–guest (H–G) MOF composites on third-order nonlinear optical (NLO) performance remains largely unknown. Herein, we propose for the first time a noncovalent aggregate confinement strategy for synthesizing H–G MOF composites with different guest stacking modes. And [perylene₂]_<i>n</i> (α-Pe) and [perylene]_<i>n</i> (β-Pe) were selected as guests and confined into a novel Ca-based MOF {[Ca(TBAPy)(DMA)₂]·3DMA·[N(CH₃)₂]·H₂O}_<i>n</i> (Ca-MOF-pts). The NLO results showed that compared to β-Pe@Ca-MOF-pts, the saturable absorption (SA) and self-defocusing properties of α-Pe@Ca-MOF-pts were increased by 2.71-fold and 3.82-fold, respectively. Interestingly, α/β-Pe@Ca-MOF-pts can be transformed into α/β-Pe@Ca-MOF-flu (Ca-MOF-flu = {[Ca_1.5(TBAPy)(H₂O)₂]·DMA·[N(CH₃)₂]·2H₂O}_<i>n</i>) through self-adaptive topological evolution, and the corresponding NLO absorption signal change from SA to reverse saturable absorption (RSA). As expected, compared to β-Pe@Ca-MOF-flu, the RSA and self-defocusing properties of α-Pe@Ca-MOF-flu are improved by 2.94-fold and 4.07-fold, respectively, demonstrating the importance of guest stacking modes. Theoretical calculation and transient absorption spectra indicated the enhancement of NLO performance was attributed to the large π–π overlap of α-Pe, which promoted the electron delocalization/transfer and optimized the cross-sectional of the ground state and excited state. This study provides a new strategy for developing H–G MOF composites with excellent NLO properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"84 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546867","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":"Advances in Organic Small Molecule-Based Fluorescent Probes for Precision Detection of Liver Diseases: A Perspective on Emerging Trends and Challenges","authors":"Luling Wu, Zilu Li, Kun Wang, Robin R. Groleau, Xiaodi Rong, Xueting Liu, Caiyun Liu, Simon E. Lewis, Baocun Zhu, Tony D. James","doi":"10.1021/jacs.4c17092","DOIUrl":"https://doi.org/10.1021/jacs.4c17092","url":null,"abstract":"Liver disease poses a significant challenge to global health, and its early diagnosis is crucial for improving treatment outcomes and patient prognosis. Since fluctuation of key biomarkers during the onset and progression of liver diseases can directly reflect liver health and normal/abnormal function, biomarker-based assays are vital tools for the early detection of liver disease. In this context, small molecule fluorescent probes have undeniably emerged as indispensable tools for diagnosis and analysis, with an ever-growing number of small molecule-based fluorescent probes being developed over recent years, with the sole aim of monitoring relevant biomarkers of liver disease. This perspective will focus on the development and application of probes developed primarily over the last 10 years for diagnosing a range liver disease-related processes. It will outline the foundational design strategies for developing promising probes, their optical response to key biomarkers, and how they have been demonstrated in proof-of-concept imaging applications. Current challenges and new developments in the field will be discussed, with the aim of providing insights and highlighting opportunities in the field.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539191","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":"A Library of Polymetallic Alloy Nanotubes: From Binary to Septenary","authors":"Cheng Yang, Jiasai Yao, Senyao Meng, Ping Wang, Miao He, Pangen Li, Peng Xiao, Jianyang Xiao, Yunpeng Liu, Zhenxing Li","doi":"10.1021/jacs.5c00597","DOIUrl":"https://doi.org/10.1021/jacs.5c00597","url":null,"abstract":"The polymetallic alloy nanostructure has received widespread attention in electrocatalytic reactions due to the variability in composition and excellent performance. However, the controllable synthesis of one-dimensional (1D) polymetallic alloy nanomaterials remains a significant challenge. Herein, we propose a new and general low-temperature method to prepare a library of binary to septenary polymetallic alloy nanotubes, and this method can be used to synthesize 18 kinds of polymetallic alloy nanotube (NT), including eight kinds of high-entropy alloy (HEA) NT. A representative Cu₃₀Ni₂₆Co₁₉Ru₁₄Ir₁₁ HEA NT demonstrates efficient and stable catalytic performance for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Cu₃₀Ni₂₆Co₁₉Ru₁₄Ir₁₁ HEA NT exhibits an overpotential of only 121 mV for the HER and 272 mV for the OER, respectively, when measured at a current density of 100 mA cm^–2. In addition, the two-electrode system comprising the Cu₃₀Ni₂₆Co₁₉Ru₁₄Ir₁₁ HEA NT exhibits an impressive efficiency of 100 mA cm^–2 during overall water splitting, requiring only a potential of 1.67 V. The high catalytic activity of the Cu₃₀Ni₂₆Co₁₉Ru₁₄Ir₁₁ HEA NT is attributed to the downward shift of the <i>d</i>-band center. In the HER, the downward shift of the <i>d</i>-band center can reduce the binding energy with *H, which is beneficial for the desorption process of hydrogen. In the OER, the downward shift can also reduce the reaction energy barrier associated with the rate-determining step from *O to *OOH. This work seeks to offer a new and general method for synthesizing polymetallic alloy nanotubes with controllable structures and compositions under mild conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"43 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546868","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":"Noninvasive Vagus Nerve Electrical Stimulation for Immune Modulation in Sepsis Therapy","authors":"Cam-Hoa Mac, Giang Le Thi Nguyen, Dien Thi My Nguyen, Sheng-Min Huang, Hsu-Hsia Peng, Yen Chang, Shih-Kai Lo, Hui-Hua Kenny Chiang, Yuan-Zhen Yang, Hsiang-Lin Song, Wei-Tso Chia, Yu-Jung Lin, Hsing-Wen Sung","doi":"10.1021/jacs.4c16367","DOIUrl":"https://doi.org/10.1021/jacs.4c16367","url":null,"abstract":"Sepsis presents a significant medical challenge due to its intense inflammatory response to infection, often resulting in high mortality rates. A promising therapeutic strategy targets the cholinergic anti-inflammatory pathway (CAIP), which regulates immune responses. This study investigates the ingestion of piezoelectric particles that adhere to the stomach lining, specifically targeting TRPV1 receptors. In a mouse model of sepsis, these particles, when activated by low-intensity pulsed ultrasound, generate mild electrical pulses. These pulses stimulate vagal afferent fibers, transmitting signals to the brain and modulating the neural-immune network via the CAIP. Consequently, this leads to a reduction in systemic inflammation, mitigating weight loss, alleviating multiple tissue injuries, and preventing death by modulating immune cells in the spleen. This approach addresses the critical need for noninvasive sepsis therapies, potentially improving patient outcomes. Utilizing portable ultrasound equipment with minimal thermal effects, this technique offers a safe and convenient treatment option, even for home use.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539084","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}