Chemical Science最新文献_第10页

A Mechanistic Continuum of Nucleophilic Aromatic Substitution Reactions with Azole Nucleophiles 芳族亲核取代反应与唑类亲核试剂的机理连续体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc01856k

Harrison W Toll, Xiaoyi Zhang, Tong Gao, Guilherme Dal Poggetto, Mikhail Reibarkh, Joshua J Lee, Katherine J Yang, Eugene E. Kwan, Amanda Turek

{"title":"A Mechanistic Continuum of Nucleophilic Aromatic Substitution Reactions with Azole Nucleophiles","authors":"Harrison W Toll, Xiaoyi Zhang, Tong Gao, Guilherme Dal Poggetto, Mikhail Reibarkh, Joshua J Lee, Katherine J Yang, Eugene E. Kwan, Amanda Turek","doi":"10.1039/d5sc01856k","DOIUrl":"https://doi.org/10.1039/d5sc01856k","url":null,"abstract":"Nucleophilic aromatic substitution (SNAr) is a broadly used method for generating structural complexity in pharmaceuticals. Although SNAr reactions were long assumed to be stepwise, recent kinetic isotope effect (KIE) studies have shown that many SNAr reactions are actually concerted. However, it remains unclear how variations in substrate structure affect whether a reaction is stepwise, concerted, or borderline. In this paper, we show that reactions between indole and moderately electron-deficient aryl fluorides proceed by a borderline mechanism and are subject to general base catalysis. These findings are consistent with density functional theory (DFT) calculations, which also predict that borderline mechanisms are operative for a broad range of industrially relevant SNAr reactions involving azole nucleophiles. The predicted transition structures vary smoothly independent of the mechanism, suggesting that these SNAr reactions exist on a mechanistic continuum. The findings of widespread general base catalysis and a mechanistic continuum will guide future efforts to devise general models of SNAr reactivity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890235","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

Brush-Modified Fluorescent Organic Nanoparticles by ATRP with Rigidity-Regulated Emission 刚体调控发射的电刷修饰有机荧光纳米颗粒

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc02349a

Rongguan Yin, Lianshun Luo, Xiaolei Hu, Hironobu Murata, Jaepil Jeong, Feng Gao, Zijie Qiu, Ben Zhong Tang, Michael Rainer Bockstaller, Krzysztof Matyjaszewski

{"title":"Brush-Modified Fluorescent Organic Nanoparticles by ATRP with Rigidity-Regulated Emission","authors":"Rongguan Yin, Lianshun Luo, Xiaolei Hu, Hironobu Murata, Jaepil Jeong, Feng Gao, Zijie Qiu, Ben Zhong Tang, Michael Rainer Bockstaller, Krzysztof Matyjaszewski","doi":"10.1039/d5sc02349a","DOIUrl":"https://doi.org/10.1039/d5sc02349a","url":null,"abstract":"Organic nanoparticles provide exceptional intraparticle tailorability, enabling the incorporation of functional molecules for diverse applications. In this study, we present the synthesis and characterization of fluorescent organic nanoparticles (FoNPs) with encapsulated aggregation-induced emission (AIE) luminogens with emission properties regulated by particle rigidity. Atom transfer radical polymerization (ATRP) was employed in dispersed media to develop various fluorescence colors tuned by precise control over particle rigidity. Comprehensive analyses revealed that increased particle rigidity significantly enhanced photoluminescence, achieving quantum yields of up to 22% in selected solvents. The high chain-end fidelity facilitated the grafting of hydrophilic polymer brushes from surfaces of FoNPs used as macroinitiators, enabling their dispersion in aqueous media while maintaining bright fluorescence. These findings highlight the potential of rigidity-regulated FoNPs as versatile platforms for advanced material applications, particularly in fluorescent waterborne films and aqueous-phase sensing systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890234","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

Tailored phenyl ureas eradicate drug-resistant Mycobacterium tuberculosis by targeting mycolic acid cell wall assembly. 量身定制的苯基脲通过靶向霉菌酸细胞壁组装来根除耐药结核分枝杆菌。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-30 DOI: 10.1039/d5sc02565f

Dietrich Mostert, Josef Braun, Matthew D Zimmerman, Curtis A Engelhart, Sara Berndl, Patrick K Quoika, Andreas M Kany, Julianna Proietto, Suyapa Penalva-Lopez, Joshua B Wallach, Anna K H Hirsch, Martin Zacharias, Dirk Schnappinger, Véronique Dartois, Stephan A Sieber

{"title":"Tailored phenyl ureas eradicate drug-resistant Mycobacterium tuberculosis by targeting mycolic acid cell wall assembly.","authors":"Dietrich Mostert, Josef Braun, Matthew D Zimmerman, Curtis A Engelhart, Sara Berndl, Patrick K Quoika, Andreas M Kany, Julianna Proietto, Suyapa Penalva-Lopez, Joshua B Wallach, Anna K H Hirsch, Martin Zacharias, Dirk Schnappinger, Véronique Dartois, Stephan A Sieber","doi":"10.1039/d5sc02565f","DOIUrl":"https://doi.org/10.1039/d5sc02565f","url":null,"abstract":"Treatment of Mycobacterium tuberculosis infections is a challenging task due to long treatment regiments and a growing number of resistant clinical isolates. To identify new antibiotic hits, we screened a focused library of 400 synthetic compounds derived from a recently discovered molecule with promising anti-mycobacterial activity. A suite of more potent hit molecules was deciphered with sub-micromolar activity. Utilising tailored affinity-based probes for chemical proteomic investigations, we successfully pinpointed the mycolic acid transporter MmpL3 and two epoxide hydrolases, EphD and EphF, also linked to mycolic acid biosynthesis, as specific targets of the compounds. These targets were thoroughly and independently validated by activity assays, under- and overexpression, resistance generation, and proteomic studies. Structural refinement of the most potent hit molecules led to the development of a new lead compound that demonstrates enhanced biological activity in M. tuberculosis, low human cytotoxicity, and improved solubility and oral bioavailability - traits that are often challenging to achieve with anti-mycobacterial drugs. Overall, drug-likeness, as well as the dual mode of action, addressing the mycolic acid cell wall assembly at two distinct steps, holds significant potential for further in vivo applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12041881/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143960672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

AIMNet2: a neural network potential to meet your neutral, charged, organic, and elemental-organic needs. AIMNet2：一个神经网络潜力，满足你的中性、带电、有机和基本有机需求。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d4sc08572h

Dylan M Anstine, Roman Zubatyuk, Olexandr Isayev

{"title":"AIMNet2: a neural network potential to meet your neutral, charged, organic, and elemental-organic needs.","authors":"Dylan M Anstine, Roman Zubatyuk, Olexandr Isayev","doi":"10.1039/d4sc08572h","DOIUrl":"https://doi.org/10.1039/d4sc08572h","url":null,"abstract":"Machine learned interatomic potentials (MLIPs) are reshaping computational chemistry practices because of their ability to drastically exceed the accuracy-length/time scale tradeoff. Despite this attraction, the benefits of such efficiency are only impactful when an MLIP uniquely enables insight into a target system or is broadly transferable outside of the training dataset. In this work, we present the 2nd generation of our atoms-in-molecules neural network potential (AIMNet2), which is applicable to species composed of up to 14 chemical elements in both neutral and charged states, making it a valuable method for modeling the majority of non-metallic compounds. Using an exhaustive dataset of 2 × 107 hybrid DFT level of theory quantum chemical calculations, AIMNet2 combines ML-parameterized short-range and physics-based long-range terms to attain generalizability that reaches from simple organics to diverse molecules with \"exotic\" element-organic bonding. We show that AIMNet2 outperforms semi-empirical GFN2-xTB and is on par with reference density functional theory for interaction energy contributions, conformer search tasks, torsion rotation profiles, and molecular-to-macromolecular geometry optimization. Overall, the demonstrated chemical coverage and computational efficiency of AIMNet2 is a significant step toward providing access to MLIPs that avoid the crucial limitation of curating additional quantum chemical data and retraining with each new application.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12057637/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143961475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of bicyclo[3.2.0]heptane lactones via a ligand-enabled Pd-catalyzed C(sp³)-H activation cascade. 配体激活pd催化C(sp3)-H级联合成双环[3.2.0]庚烷内酯

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d5sc00711a

Zhoulong Fan, Xinpei Cai, Tao Sheng, Jin-Quan Yu

引用次数: 0

Electron rearrangement at the crystalline-amorphous heterogeneous interface boosts alkaline hydrogen production. 晶体-非晶非均相界面的电子重排促进了碱性氢的生成。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d5sc02271a

Meihuan Liu, Yuke Gu, Hui Su, Xuanzhi Liu, Juan Luo, Pengfei Tan, Feng Liu, Jun Pan

{"title":"Electron rearrangement at the crystalline-amorphous heterogeneous interface boosts alkaline hydrogen production.","authors":"Meihuan Liu, Yuke Gu, Hui Su, Xuanzhi Liu, Juan Luo, Pengfei Tan, Feng Liu, Jun Pan","doi":"10.1039/d5sc02271a","DOIUrl":"https://doi.org/10.1039/d5sc02271a","url":null,"abstract":"Modifying the platinum (Pt) local reaction microenvironment is a critical and complex challenge in enhancing electrochemical performance. Herein, amorphous Co(OH)2 and crystalline Pt (labeled as ac-Pt@Co(OH)2) featuring abundant crystalline-amorphous (c-a) interfaces are designed to boost the hydrogen evolution reaction (HER). The engineered structure creates an advantageous chemical environment at the local level, enhancing hydrogen adsorption efficiency and resulting in exceptional HER performance. The ac-Pt@Co(OH)2 achieves a low Tafel slope of 28.5 mV dec-1 and requires merely 95 mV overpotential to reach 200 mA cm-2 in alkaline electrolyte (1 M KOH), surpassing those of conventional Pt/C catalysts (39.4 mV dec-1, 256 mV). In situ advanced characterization investigations reveal dynamic electron rearrangement at the c-a interface, where Co species initially accept electrons from Pt to optimize the adsorption of *H species and then donate electrons to Pt for accelerating reduction kinetics. Theoretical calculations reveal that amorphous Co(OH)2 promotes the dissociation of water molecules to produce active *H, and electron rearrangement at the c-a interface downshifts the d-band center, thereby optimizing the *H adsorption strength and enhancing HER activity. The ac-Pt@Co(OH)2-based alkaline anion-exchange membrane water electrolyzer (AEMWE) maintains a current density of 500 mA cm-2 over 500 h.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12056670/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143985712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-performance elastic ferroelectrics via low-temperature carbene crosslinking and high-temperature annealing. 通过低温碳交联和高温退火制备的高性能弹性铁电体。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d5sc01467k

Linping Wang, Liang Gao, Xiaocui Rao, Fangzhou Li, Da Zu, Yunya Liu, Ben-Lin Hu

{"title":"High-performance elastic ferroelectrics via low-temperature carbene crosslinking and high-temperature annealing.","authors":"Linping Wang, Liang Gao, Xiaocui Rao, Fangzhou Li, Da Zu, Yunya Liu, Ben-Lin Hu","doi":"10.1039/d5sc01467k","DOIUrl":"https://doi.org/10.1039/d5sc01467k","url":null,"abstract":"With the increasing demand for wearable electronics, elastic ferroelectrics with high polarization intensity and Curie temperature have become essential. However, balancing high ferroelectric performance with elasticity in polymeric ferroelectrics remains a challenge, as higher crosslinking density to improve elasticity often compromises Curie temperature and remnant polarization. To address this trade-off, we introduce unsaturated bonds into commercial P(VDF-TrFE), forming P(VDF-TrFE-DB) with enhanced crosslinking reactivity while retaining its inherent ferroelectric properties. A novel two-step LT-HT processing strategy is developed to achieve this balance. The low-temperature (LT) step leverages carbene-mediated crosslinking with diazirine-based crosslinkers below the polymer's Curie temperature, preventing premature crystallization and forming amorphous regions essential for mechanical flexibility. The high-temperature (HT) annealing step promotes the formation and alignment of well-ordered ferroelectric crystalline structures, optimizing remnant polarization and Curie temperature while preserving the crosslinked amorphous regions critical for elasticity. This approach enables high elasticity with minimal crosslinker content while maintaining excellent ferroelectric performance. The resulting elastic P(VDF-TrFE-DB) polymer exhibits a significantly elevated Curie temperature (∼140 °C) and high remnant polarization (7.63 μC cm-2), comparable to commercial P(VDF-TrFE). This method offers a versatile pathway for advanced flexible electronics, soft actuators, and wearable devices requiring robust mechanical and ferroelectric properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076213/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144076309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

TRAP: a contrastive learning-enhanced framework for robust TCR–pMHC binding prediction with improved generalizability TRAP：一个对比学习增强框架，用于鲁棒TCR-pMHC结合预测，具有改进的通用性

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d4sc08141b

Jingxuan Ge, Jike Wang, Qing Ye, Liqiang Pan, Yu Kang, Chao Shen, Yafeng Deng, Chang-Yu Hsieh, Tingjun Hou

{"title":"TRAP: a contrastive learning-enhanced framework for robust TCR–pMHC binding prediction with improved generalizability","authors":"Jingxuan Ge, Jike Wang, Qing Ye, Liqiang Pan, Yu Kang, Chao Shen, Yafeng Deng, Chang-Yu Hsieh, Tingjun Hou","doi":"10.1039/d4sc08141b","DOIUrl":"https://doi.org/10.1039/d4sc08141b","url":null,"abstract":"The binding of T cell receptors (TCRs) to peptide-MHC I (pMHC) complexes is critical for triggering adaptive immune responses to potential health threats. Developing highly accurate machine learning (ML) models to predict TCR–pMHC binding could significantly accelerate immunotherapy advancements. However, existing ML models for TCR–pMHC binding prediction often underperform with unseen epitopes, severely limiting their applicability. We introduce TRAP, which leverages contrastive learning to enhance model performance by aligning structural and sequence features of pMHC with TCR sequences. TRAP outperforms previous state-of-the-art models in both random and unseen epitope scenarios, achieving an AUPR of 0.84 (a 22% improvement over the second-best model) and an AUC of 0.92 in the random scenario, and an AUC of 0.75 (almost 11% higher than the second-best model) in the unseen epitope scenario. Furthermore, TRAP demonstrates a noteworthy capability to diagnose potential issues of cross-reactivity between TCRs and similar epitopes. This highly robust performance makes it a suitable tool for large-scale predictions in real-world settings. A specific case study confirmed that TRAP can discover hit TCRs with binding free energies comparable to referenced experimental results. These findings highlight TRAP's potential for practical applications and its role as a powerful tool in developing TCR-based immunotherapies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897807","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

Dynamic and interconnected influence of dissolved iron on the performance of alkaline water electrolysis 溶解铁对碱性水电解性能的动态相互影响

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/d5sc01380a

Fubiao Di, Cong Chen, Junxia Shen, Zhihe Wei, Wen Dong, Yang Peng, Ronglei Fan, Mingrong Shen, Pierre-Yves Olu

{"title":"Dynamic and interconnected influence of dissolved iron on the performance of alkaline water electrolysis","authors":"Fubiao Di, Cong Chen, Junxia Shen, Zhihe Wei, Wen Dong, Yang Peng, Ronglei Fan, Mingrong Shen, Pierre-Yves Olu","doi":"10.1039/d5sc01380a","DOIUrl":"https://doi.org/10.1039/d5sc01380a","url":null,"abstract":"Dissolved iron (Fe) species is an intriguing player in the overall alkaline water electrolysis (AWE) system, considered both as a poison that needs to be avoided and as a precursor for enhancing the water splitting activity. Here, we unveil the intricate mechanisms governing the Fe influence on practical AWE systems, by measuring the dynamic changes in cell voltage and overpotential of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The dissolved Fe will deposit on the cathode, which significantly enhances the HER activity of bare Ni mesh (BN) while showing negligible impact on the porous RANEY® Ni mesh (RN). The dissolved Fe will also improve the OER activity of the BN by a mechanism based on an equilibrium between leaching and incorporation of Fe onto the oxide layer of the anode. The continuous deposition of Fe on the cathode will gradually deplete the electrolyte of dissolved Fe, which will in turn push the anode surface equilibrium towards low density of active Fe sites thus to a decrease of OER activity. Inspired by the above results, by optimizing the addition of Fe(III) salt into the system, an impressively low cell voltage of 1.95 V for a water splitting current density of 0.4 A cm−2 was achieved for a simple, cheap and robust BN cathode//BN anode zero-gap assembly. This performance is equivalent to a power consumption around 19.3% lower compared to the system without Fe(III) addition.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897875","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

Challenges and opportunities for the characterization of electronic properties in halide perovskite solar cells 卤化物钙钛矿太阳能电池电子特性表征的挑战与机遇

IF 7.6 1区化学

Chemical Science Pub Date : 2025-04-29 DOI: 10.1039/D5SC00504C

Thomas Kirchartz

引用次数: 0