Journal of the American Chemical Society最新文献_第9页

Redox-Selective Macromolecular Electrolysis for Sequential Functionalization and Deconstruction

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-03 DOI: 10.1021/jacs.4c16333

Graham C. Gilchrist, Rhys W. Hughes, Sean R. Gitter, Joshua D. Marquez, Brent S. Sumerlin, Austin M. Evans

{"title":"Redox-Selective Macromolecular Electrolysis for Sequential Functionalization and Deconstruction","authors":"Graham C. Gilchrist, Rhys W. Hughes, Sean R. Gitter, Joshua D. Marquez, Brent S. Sumerlin, Austin M. Evans","doi":"10.1021/jacs.4c16333","DOIUrl":"https://doi.org/10.1021/jacs.4c16333","url":null,"abstract":"This study demonstrates that selective macromolecular electrolysis can be achieved on copolymers containing redox-orthogonal targets by controlling the externally applied voltage. We designed macromolecules containing phthalimide (E1/2 = −1.8 V vs Ag/AgNO3) and tetrachlorophthalimide (E1/2 = −1.3 V vs Ag/AgNO3) (meth)acrylates that have significantly different reduction potentials such that they are separately redox-addressable. The polymer-centered radicals generated by decarboxylation can either undergo (1) hydrogen atom transfer to form olefinic repeat units or (2) β-scission to deconstruct the polymer backbone. Our results reveal selective electrochemical control over postpolymerization modifications, which enables sequential transformations that tune the glass transition temperature of electrochemically generated copolymers over a range of −54 to 125 °C. This method was also shown to maintain its selectivity in a polymer blend and provided access to copolymers (poly(styrene-co-propylene-co-ethylene)) that would be challenging to prepare in other ways. These results demonstrate the potential of macromolecular electrolysis for selective material functionalization and degradation. This approach expands the toolbox for postpolymerization modification and targeted polymer degradation with applications in macromolecular information processing, spatiotemporal patterning, and producing materials with complex architectures that are driven by external stimuli.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"52 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532622","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

Revealing the Relationship between Publication Bias and Chemical Reactivity with Contrastive Learning 通过对比学习揭示出版偏差与化学反应性之间的关系

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.5c01120

Wenhao Gao, Priyanka Raghavan, Ron Shprints, Connor W. Coley

{"title":"Revealing the Relationship between Publication Bias and Chemical Reactivity with Contrastive Learning","authors":"Wenhao Gao, Priyanka Raghavan, Ron Shprints, Connor W. Coley","doi":"10.1021/jacs.5c01120","DOIUrl":"https://doi.org/10.1021/jacs.5c01120","url":null,"abstract":"A synthetic method’s substrate tolerance and generality are often showcased in a “substrate scope” table. However, substrate selection exhibits a frequently discussed publication bias: unsuccessful experiments or low-yielding results are rarely reported. In this work, we explore more deeply the relationship between such a publication bias and chemical reactivity beyond the simple analysis of yield distributions using a novel neural network training strategy, substrate scope contrastive learning. By treating reported substrates as positive samples and nonreported substrates as negative samples, our contrastive learning strategy teaches a model to group molecules within a numerical embedding space, based on historical trends in published substrate scope tables. Training on 20,798 aryl halides in the CAS Content CollectionTM, spanning thousands of publications from 2010 to 2015, we demonstrate that the learned embeddings exhibit a correlation with physical organic reactivity descriptors through both intuitive visualizations and quantitative regression analyses. Additionally, these embeddings are applicable to various reaction modeling tasks like yield prediction and regioselectivity prediction, underscoring the potential to use historical reaction data as a pretraining task. This work not only presents a chemistry-specific machine learning training strategy to learn from literature data in a new way but also represents a unique approach to uncover trends in chemical reactivity reflected by trends in substrate selection in publications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"15 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143528224","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

Pd-Catalyzed Strain-Releasing Dyotropic Rearrangement: Ring-Expanding Amidofluorination of Methylenecyclobutanes

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.5c01108

Baochao Yang, Guoqiang Yang, Qian Wang, Jieping Zhu

引用次数: 0

Tracking the Fate of Therapeutic Proteins Using Ratiometric Imaging of Responsive Shortwave Infrared Probes

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.4c15614

Pradeep Shrestha, Nimit L. Patel, Joseph D. Kalen, Syed Muhammad Usama, Martin J. Schnermann

{"title":"Tracking the Fate of Therapeutic Proteins Using Ratiometric Imaging of Responsive Shortwave Infrared Probes","authors":"Pradeep Shrestha, Nimit L. Patel, Joseph D. Kalen, Syed Muhammad Usama, Martin J. Schnermann","doi":"10.1021/jacs.4c15614","DOIUrl":"https://doi.org/10.1021/jacs.4c15614","url":null,"abstract":"Monoclonal antibodies (mAbs) are essential agents for cancer treatment and diagnosis. Advanced optical imaging strategies have the potential to address specific questions regarding their complex in vivo life cycle. This study presents responsive shortwave infrared (SWIR) probes and an associated imaging scheme to assess mAb biodistribution, cellular uptake, and proteolysis. Specifically, we identify a Pegylated benzo-fused norcyanine derivative (Benz-NorCy7) that is activated in acidic environments and can be appended to mAbs without significant changes in optical properties. As a mAb conjugate, this agent shows high tumor specificity in a longitudinal imaging study in a murine model. To enable independent tracking of mAb uptake and lysosomal uptake and retention, a two-color ratiometric imaging strategy was employed using an “always-ON” heptamethine cyanine dye (λex = 785 nm) and the pH-responsive Benz-NorCy7 (λex = 890 nm). To assess proteolytic catabolism, we append a cleavable carbamate to Benz-NorCy7 to create turn-ON probes. These agents facilitate the comparison of two common peptide linkers and provide insights into their in vivo properties. Overall, these studies provide a strategy to assess the fate of protein-based therapeutics using optical imaging.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532623","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

Synthesis and Structure of Uranium Disilyl-Substituted Alkylidene Complexes

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.5c01486

Yafei Li, Chengxiang Ding, Qianyi Zhao, Shuao Wang, Jin Xie, Sudip Pan, Congqing Zhu

引用次数: 0

Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.4c16508

Fenglei Qiu, Xinting Zhang, Wenjing Wang, Kongzhao Su, Daqiang Yuan

{"title":"Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages","authors":"Fenglei Qiu, Xinting Zhang, Wenjing Wang, Kongzhao Su, Daqiang Yuan","doi":"10.1021/jacs.4c16508","DOIUrl":"https://doi.org/10.1021/jacs.4c16508","url":null,"abstract":"The development of new chiral building blocks for constructing complex chiral architectures, such as macrocycles and cages, is both crucial and challenging. Although concave-shaped calixarenes have been established as versatile building blocks for the synthesis of cage compounds, there are no reports on cages constructed from chiral calix[4]arene derivatives. Herein, we present a straightforward and effective method for gram-scale synthesis of a new member of chiral calix[4]arene macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As a proof of concept, we functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via the Duff reaction to construct chiral porous organic cages (CPOCs) using polyamine synthons. Specifically, we employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine and tris(4-aminophenyl)amine, to assemble with PC[4]ACHO enantiomers, resulting in [2 + 4] lantern-shaped and [6 + 8] truncated octahedral CPOCs, respectively. These structures have been unambiguously characterized by single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy. Notably, the [6 + 8] truncated CPOCs exhibit internal diameters of approximately 3.1 nm, a cavity volume of around 5300 Å3, and high specific surface areas of up to 1300 m2 g–1 after desolvation, making them among the largest CPOCs reported. Additionally, investigations into their chiral sensing performance demonstrate that these PC[4]A-based CPOCs enable the enantioselective recognition of amino acids and their derivatives. This work strongly suggests that PC[4]A can serve as an excellent building block for the rational design of chiral materials with practical applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"67 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532672","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

Efficient Metabolomics Profiling from Plasma Extracellular Vesicles Enables Accurate Diagnosis of Early Gastric Cancer

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.4c18110

Fanqin Bu, Xinyi Shen, Haosu Zhan, Duanda Wang, Li Min, Yongyang Song, Shutao Wang

{"title":"Efficient Metabolomics Profiling from Plasma Extracellular Vesicles Enables Accurate Diagnosis of Early Gastric Cancer","authors":"Fanqin Bu, Xinyi Shen, Haosu Zhan, Duanda Wang, Li Min, Yongyang Song, Shutao Wang","doi":"10.1021/jacs.4c18110","DOIUrl":"https://doi.org/10.1021/jacs.4c18110","url":null,"abstract":"Accurate diagnosis of early gastric cancer is valuable for asymptomatic populations, while current endoscopic examination combined with pathological tissue biopsy often encounters bottlenecks for early-stage cancer and causes pain to patients. Liquid biopsy shows promise for noninvasive diagnosis of early gastric cancer; however, it remains a challenge to achieve accurate diagnosis due to the lack of highly sensitive and specific biomarkers. Herein, we propose a protocol combining metabolomics profiling from plasma extracellular vesicles (EVs) and machine learning to identify the metabolomics discrepancies of early gastric cancer individuals from other populations. Efficient metabolomics profiling is achieved by efficient, high-purity, and damage-free plasma EVs separation using elaborately designed nanotrap-structured microparticles (NanoFisher) by taking advantage of stereoscopic interaction and affinity interaction. Significant metabolomics discrepancies are obtained from 150 early gastric cancer (50), benign gastric disease (50), and non-disease control (50) plasma samples. Machine learning enables ideal distinction between early gastric cancer and non-disease control samples with an area under the curve (AUC) of 1.000, achieves an AUC of 0.875–0.975 for differentiating early gastric cancer from benign gastric diseases, and demonstrates an overall accuracy of 92% in directly classifying these three categories. The plasma EV metabolomics profiling enabled by NanoFisher materials, integrated with machine learning, holds considerable promise for broad clinical acceptance, enhancing gastric cancer screening outcomes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"26 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143528203","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

Precision Self-assembly of 3D DNA Crystals Using Microfluidics

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.4c17455

Xugen Chen, Pan Fu, Karol Woloszyn, Yuemeng Zhang, Huanhuan Hu, Likai Hou, Xiaoyu Li, Jia Liu, Wenting Jiang, Lebing Wang, Simon Vecchioni, Yoel P. Ohayon, Ruojie Sha, Jianping Zheng, Feng Zhou

{"title":"Precision Self-assembly of 3D DNA Crystals Using Microfluidics","authors":"Xugen Chen, Pan Fu, Karol Woloszyn, Yuemeng Zhang, Huanhuan Hu, Likai Hou, Xiaoyu Li, Jia Liu, Wenting Jiang, Lebing Wang, Simon Vecchioni, Yoel P. Ohayon, Ruojie Sha, Jianping Zheng, Feng Zhou","doi":"10.1021/jacs.4c17455","DOIUrl":"https://doi.org/10.1021/jacs.4c17455","url":null,"abstract":"Controlling the uniformity in size and quantity of macroscopic three-dimensional (3D) DNA crystals is essential for their integration into complex systems and broader applications. However, achieving such control remains a major challenge in DNA nanotechnology. Here, we present a novel strategy for synthesizing monodisperse 3D DNA single crystals using microfluidic double-emulsion droplets as nanoliter-scale microreactors. These uniformly sized droplets can shrink and swell without leaking their inner contents, allowing the concentration of the DNA solution inside to be adjusted. The confined volume ensures that, once a crystal seed forms, it rapidly consumes the available DNA material, preventing the formation of additional crystals within the same droplet. This approach enables precise control over crystal growth, resulting in a yield of one DNA single crystal per droplet, with a success rate of up to 98.6% ± 0.9%. The resulting DNA crystals exhibit controlled sizes, ranging from 19.3 ± 0.9 μm to 56.8 ± 2.6 μm. Moreover, this method can be applied to the controlled growth of various types of DNA crystals. Our study provides a new pathway for DNA crystal self-assembly and microengineering.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532673","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

Mechanoluminescence from Amorphous Organic Luminogens

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.5c00894

Zongliang Xie, Huangjun Deng, Xiangyu Ge, Zhenguo Chi, Bin Liu

引用次数: 0

Energy Threshold of Nonlinear Sulfur Solubility for Li–S Batteries

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-02 DOI: 10.1021/jacs.4c17438

Keying Guo, Xiaosheng Song, Zhengyuan Shen, Xuebing Zhu, Jun Wei, Qing Han, Xueping Qian, Zhaoqing Jin, Jianhao Lu, Weikun Wang, Yong Zhao

{"title":"Energy Threshold of Nonlinear Sulfur Solubility for Li–S Batteries","authors":"Keying Guo, Xiaosheng Song, Zhengyuan Shen, Xuebing Zhu, Jun Wei, Qing Han, Xueping Qian, Zhaoqing Jin, Jianhao Lu, Weikun Wang, Yong Zhao","doi":"10.1021/jacs.4c17438","DOIUrl":"https://doi.org/10.1021/jacs.4c17438","url":null,"abstract":"Unclear regulation mechanisms of solid solubility make it difficult to accurately control its concentration, posing challenges for accelerating chemical reactions. Herein, we use a model system to determine the effects of solvent type and ratio, concentration, and type of lithium salt on sulfur solubility. Our findings reveal a nonlinear relationship between sulfur solubility and both lithium salt concentration and the ratio of different solvents in composite solutions. Importantly, significant differences in sulfur solubility are discovered with changes in the solvation structure regulated by the type of salt anion. Quantitative evaluation of nonlinear sulfur solubility is illustrated to be breaking the threshold value of the interaction energy between the solute and solvent molecules. Based on these findings, simultaneous regulation of sulfur and lithium polysulfide concentrations in ether electrolytes can be achieved by controlling the concentration and type of salts. As a result, a liquid–liquid–solid reaction pathway is supported for lithium–sulfur batteries with a finite amount of electrolyte in the coin cell, and the pouch cell shows an energy density of 554 Wh kg–1, ranking at the top level of the reported system.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"38 8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532670","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