Chemical Science最新文献

{"title":"Beyond static paradigms: defect dynamic evolution and advanced applications in water electrolysis.","authors":"Xiaojun Wang, Huilin Zhao, Lei Li, Weiping Xiao, Guangrui Xu, Guangying Fu, Lei Wang, Zexing Wu","doi":"10.1039/d6sc01899h","DOIUrl":"https://doi.org/10.1039/d6sc01899h","url":null,"abstract":"<p><p>Electrocatalytic reactions play crucial roles in energy conversion and green chemical synthesis; however, their practical applications are often constrained by sluggish reaction kinetics, high overpotentials, and insufficient operational stability. In recent years, defect engineering has emerged as an effective structural regulation strategy, providing new opportunities to enhance electrocatalytic performance through the deliberate introduction of non-ideal structural features, such as vacancies, heteroatom dopants and interfacial architectures. Accumulating studies have demonstrated that defects not only modulate the electronic structure of catalysts and reaction pathways, but that their dynamic evolution under specific reaction conditions also exerts profound influence on the real working-state structure and long-term catalytic performance. Owing to central importance in green hydrogen production, water-splitting reactions serve as representative model systems for elucidating defect-structure-activity relationships. In this review, we systematically summarize recent advances in defect engineering for electrocatalysis, with particular focus on water electrolysis. Emphasis is placed on defect types and structural characteristics, construction strategies, dynamic evolution behaviors, and their typical applications, while current challenges and future research directions are also discussed, aiming to provide valuable guidance for the rational design and practical implementation of high-performance defect-engineered electrocatalysts.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13147289/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834413","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}

{"title":"Lucigenin: a strongly oxidizing dicationic photocatalyst for the direct azolation of arenes.","authors":"Alexandra Matei, Baptiste Roure, Xiaobing Chen, Sebastian B Beil, Ben L Feringa","doi":"10.1039/d6sc02111e","DOIUrl":"https://doi.org/10.1039/d6sc02111e","url":null,"abstract":"<p><p>The direct oxidative C-H amination of arenes has become an attractive method to bypass the classical multistep and sequential synthesis of arylamines. Most current approaches rely on photocatalysis, using strong photooxidants to generate an arene radical cation <i>in situ</i>, which can then be trapped by a nitrogen nucleophile. In this regard, the development of new photocatalysts capable of accessing oxidation potentials greater than +2.5 V has been a thriving field of research in recent years. Here, we report the use of commercially available Lucigenin-widely used as a fluorescent probe in biology-to achieve this transformation. This strategy features short reaction times, a wide azole scope, and avoids the use of additives or fluorinated solvents, a common limitation of many previous methodologies. Preliminary mechanistic studies are also described, suggesting that the initial formation of an azole radical cation could be involved.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13148268/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147833676","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}

{"title":"Rational regulation of the torsion angle of covalent organic frameworks for enhanced CO₂ photoreduction to ethane.","authors":"Yun Ma, Qian Zhang, Hao Chen, Huiyong Wang, Yunjing Deng, Yingying Guo, Shuaiqi Gao, Jianji Wang","doi":"10.1039/d5sc09241h","DOIUrl":"https://doi.org/10.1039/d5sc09241h","url":null,"abstract":"<p><p>Light-driven CO₂ reduction to hydrocarbon fuels is a green and sustainable technology to alleviate global warming while producing high value-added chemicals. However, highly efficient production of ethane (C₂H₆) remains a great challenge due to insufficient electron deliverability and sluggish C-C coupling kinetics. Herein, a series of β-ketoenamine linked Tp-COFs-Mo with different torsion angles were designed and synthesized for the photocatalytic CO₂ reduction reaction to C₂H₆. It was disclosed that these Tp-COFs-Mo had identical structural active sites of Mo-N₃O, while different torsion angles significantly affected their photocatalytic performance. Significantly, TpPa-COF-Mo exhibited a remarkable C₂H₆ production rate of 262.6 µmol g^-1 h^-1 and a high C₂H₆ electron selectivity of 91.8%, which exceeds that of the most COF-, POP-, and MOF-based photocatalysts reported previously. Mechanism studies revealed that the smaller torsion angle of TpPa-COF-Mo led to electron accumulation within the layers and stronger electron capturing capacity of Mo sites, which improved separation and transfer of photogenerated electrons along the intralayer, enhanced *H adsorption, and reduced the energy barrier for the formation of *CHOCO intermediate species, thus promoting the efficient conversion of CO₂ to C₂H₆. This work opens a new pathway to design efficient COF catalysts by optimizing the torsion angle of COFs.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13142704/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147833656","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}

{"title":"Integrated learning-assisted design of metal-nitrogen-carbon single-atom catalysts: electronegativity regulates the coupling rules of interfacial valence electrons.","authors":"Hang Zhang, Zishan Luo, Xi Sun, Yuhang Zhou, Wenhao Yan, Jiawei Li, Tao Zhang, Hong Cui, Weizhi Tian, Rong Feng, Hongkuan Yuan","doi":"10.1039/d6sc00422a","DOIUrl":"https://doi.org/10.1039/d6sc00422a","url":null,"abstract":"<p><p>Single-atom catalysts (SACs) have demonstrated great potential in the electrochemical nitrogen reduction reaction (NRR). However, the electronic regulation mechanism of intermediate adsorption on SACs remains unclear, and conventional density functional theory (DFT) calculations fail to establish a universal \"structure-performance\" relationship. This study is based on coordinated single-atom structures (M-NnCm-GN), anchored at defect sites of nitrogen-doped graphene (GN), and develops an AdaBoost-XGB integrated model (<i>R</i> ² = 0.95) to analyze the interaction mechanisms between metal active sites and reaction intermediates (O, N, C and H). The results show that the doped metal in the MN4 structure and the adsorbed intermediates follow the 10-valence electron coupling rule, which is extended to different coordination environments. For the N intermediate, average electronegativity values less than 2.8, equal to 2.8 and greater than 2.8 correspond to the 11-, 10- and 10-valence electron coupling rules, respectively, while O follows the 10-valence electron coupling rule. In addition, we used this rule to guide the design of NRR (N₂ → NNH) and OER (OH → O) catalysts. The three-dimensional descriptor of the adsorbate fitted by the SISSO algorithm achieved an <i>R</i> ² of 0.97, further improving predictive accuracy. The metal valence electron number (Ne₁) exhibits a positive correlation with adsorption energy, while the introduction of bond length features (<i>d</i> ₁) enhances the model's predictive accuracy by approximately 17%. The electronegativity-regulated interfacial valence electron coupling rules established in this study successfully unravels the \"structure-activity relationship black box\" challenge of SAC catalysts, providing a quantifiable and transferable approach for the design of high-performance SACs.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13142277/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147833510","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}

{"title":"A robust Au-C[triple bond, length as m-dash]C anchoring group greatly improves the signal stability of electrochemical aptamer-based sensors for <i>in vivo</i> measurements.","authors":"Wanxue Zhang, Bandar Alsuwayni, Jiamei Liu, Qingqing Wu, Ziyin Mei, Songjun Hou, Zishuo Zhang, Xuewei Du, Suyan Yi, Shaoguang Li, Colin Lambert, Hui Li, Fan Xia","doi":"10.1039/d6sc02701f","DOIUrl":"https://doi.org/10.1039/d6sc02701f","url":null,"abstract":"<p><p>The ability to monitor drug pharmacokinetics in real time and directly <i>in vivo</i> is critical to achieve therapeutic efficacy and personalized medicine. Electrochemical aptamer-based (EAB) sensors have emerged as a promising platform for this purpose, yet their long-term stability is compromised by the degradation of the conventional Au-S bond-based bioelectronic interface under continuous interrogation. To address this fundamental limitation, we introduced an approach based on an Au-C[triple bond, length as m-dash]C anchoring group to create a significantly more robust sensing interface. This stable configuration enabled our sensors to retain 92% signal integrity over 72 hours (>6000 scans) in whole blood. Leveraging this exceptional stability, we successfully achieved real-time tracking of drug concentrations in live rats, demonstrating a significant advance toward continuous pharmacokinetic monitoring.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13139930/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834335","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}

{"title":"Correction: Controlled intra- and extracellular localization of bioorthogonal polymeric nanozymes.","authors":"Cristina-Maria Hirschbiegel, Mathangi Shrikanth, Yagiz Anil Cicek, Nourina Nasim, Joe Truong, Junwhee Yang, Alexander Ribbe, Maged Abdelaziz, Vincent M Rotello","doi":"10.1039/d6sc90100j","DOIUrl":"https://doi.org/10.1039/d6sc90100j","url":null,"abstract":"<p><p>[This corrects the article DOI: 10.1039/D5SC07223A.].</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13142841/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834362","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}

{"title":"A reflection on synthesis by extrusion ten years on: achievements, challenges and opportunities for solvent-free, sustainable, continuous chemical manufacturing.","authors":"Deborah E Crawford, Stuart L James","doi":"10.1039/d6sc90085b","DOIUrl":"https://doi.org/10.1039/d6sc90085b","url":null,"abstract":"<p><p>In 2015, we and colleagues published an article reporting that it was possible to synthesise metal organic frameworks (MOFs) and discrete coordination complexes by Twin Screw Extrusion (TSE) - a remarkably efficient, continuous and potentially scalable synthesis technique that required little or no solvent (D. Crawford, J. Casaban, R. Haydon, N. Giri, T. McNallyand S. L. James, <i>Chem. Sci.</i> 2015, <b>6</b>, 1645, https://doi.org/10.1039/C4SC03217A). In the years since its publication, this work has had impact across both academia and industry. Here, we reflect on the origins of that study and its place in the rapidly advancing field of mechanochemical synthesis. We also discuss the challenges and opportunities that lie ahead for the further development and implementation of TSE as an enabling and sustainable method for chemical synthesis and manufacturing.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13133924/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147811698","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}

{"title":"An extrinsic enzyme-activatable fluorescent probe for high-contrast tumor imaging.","authors":"Yifang Guo, Yuwei Du, Liru Heng, Huimin Miao, Chen Chen, Qiang Zhang, Jiayi Wang, Yige Shan, Zhang Chen, Li Li","doi":"10.1039/d6sc00484a","DOIUrl":"https://doi.org/10.1039/d6sc00484a","url":null,"abstract":"<p><p>Malignant tumors pose a major threat to human health, and the effectiveness of treatment largely depends on accurate early diagnosis and complete resection. Although fluorescence imaging offers high sensitivity and enables real-time visualization for intraoperative navigation, conventional fluorescent dyes are limited by photobleaching, poor targeting, and low signal-to-noise (S/N) ratios. These limitations result in false-negative or false-positive outcomes, thereby compromising the precision of surgery and the validity of subsequent treatment decisions. Herein, we developed a fluorescent probe, TMN-CPG, which is specifically activated by carboxypeptidase G2 (CPG2), an enzyme notable for prodrug activation in antibody-directed enzyme prodrug therapy (ADEPT). Upon CPG2-mediated hydrolysis of the TMN-CPG amide bond, the highly fluorescent TMN-NH₂ is released and subsequently internalized by cancer cells, resulting in tumor-specific fluorescence. In a 4T1 tumor-bearing mouse model, this extrinsic enzyme-activated fluorescence system produced high-contrast tumor imaging. These results indicate that this external enzyme-activatable probe can minimize nonspecific activation, thereby improving the accuracy of tumor imaging.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13148267/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834348","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}

{"title":"Rationally designed tetrahedral-configuration-matching methane trap in a metal-organic framework for efficient CH₄/N₂ separation.","authors":"Yating Wang, Feifei Zhang, Yanan Yang, Xiaoqing Wang, Jinping Li, Jiangfeng Yang","doi":"10.1039/d6sc02393b","DOIUrl":"https://doi.org/10.1039/d6sc02393b","url":null,"abstract":"<p><p>The enrichment and purification of CH₄ from coalbed methane by adsorption are important but challenging. We propose a \"tetrahedral-configuration-matching\" metal-organic framework (MOF) methane trap, TUTJ-3Ni, with cyclopropyl groups precisely positioned to create a pre-configured pore structure that is geometrically complementary to tetrahedral CH₄ molecules. TUTJ-3Ni exhibits a substantially higher CH₄ adsorption heat (30.3 kJ mol^-1) than its analogue TUTJ-2Ni (24.0 kJ mol^-1), and this value is the highest among reported adsorbents. Moreover, TUTJ-3Ni exhibits a superior CH₄/N₂ selectivity of 11.1, the highest value reported for hydrophobic MOFs. <i>In situ</i> spectroscopy and theoretical modeling results elucidate that the matched tetrahedral binding pocket, constructed with two hydrogen atoms of the cyclopropyl group along with fluorine and oxygen atoms from the ligand, engages all four hydrogen atoms of CH₄ <i>via</i> synergistic van der Waals interactions. Breakthrough experiment results verify that TUTJ-3Ni delivers high-purity CH₄ (>99.9%) from coalbed methane and that its dynamic CH₄ working capacity in humid environments is the highest among reported adsorbents. Furthermore, TUTJ-3Ni has good thermal and moisture stability and can easily be scaled up, making it promising for potential industrial applications.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13131965/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147811619","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}

{"title":"Nanoarchitectonics of molecular machines, biomolecular machines, and microrobots in their collective behaviour","authors":"Katsuhiko Ariga, Wenyan Lyu, Jingwen Song","doi":"10.1039/d6sc01674j","DOIUrl":"https://doi.org/10.1039/d6sc01674j","url":null,"abstract":"Nanoarchitectonics of small-scale molecular units into functional materials is a key strategy in materials science. The central challenge lies in assembling, integrating, and nanoarchitecting fundamental functional units, such as molecular machines and microrobots to innovate materials. This review examines collective behaviours typical in molecular and biomolecular machines and microrobots. We categorize collective behaviours into six types: (i) small-scale units operating cooperatively or collaboratively (often seen in macroscopic objects such as crystals); (ii) free-moving units in bulk material; (iii) mechanical coupling between units resulting in chain interactions (not unlike gears); (iv) assembly of units to generate macroscopic output functions; (v) macroscopic stimuli controlling individual units; (vi) cooperation between different molecular species to generate functional flows within a single system. After categorizing collective behaviours in molecular machines, we consider examples of material systems exhibiting this behaviour, such as MOFs, COFs and crystals. Furthermore, we examine the collective behaviours of molecular machines at solid surfaces and liquid interfaces. Additionally, we highlight the behaviour of biomolecular machines and microrobots in separate sections. Each section identifies and discusses trends in the relevant examples. This approach to utilize molecular machines is anticipated to create highly functional systems, realizing an ultimate goal of functional materials chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755277","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}