Pub Date : 2025-10-01DOI: 10.1016/j.chempr.2025.102750
Jiamin Ye, Yueyue Fan, Gaoli Niu, Yong Kang, Jiacheng Shi, Ruiyan Li, Yiwen Yang, Xiaoyuan Ji
Colorectal cancer (CRC) remains a major global health challenge due to insufficient tumor penetration and immunosuppressive microenvironments. Herein, we propose a modular train-style nanorobot (TPP-Exo@LOX-Pd-Cu7S4) as a targeted synergistic therapeutic platform for CRC. The exosome “head” enables neutrophil-like tumor homing, while the Cu7S4 “tail” generates thermophoretic propulsion for deep tumor penetration. Under near-infrared region II (NIR-II) laser irradiation, the Pd-Cu7S4 Schottky heterojunction drives highly efficient catalytic cascades, disrupting redox homeostasis and inducing metabolic stress by converting O₂ to ·O₂−, H₂O₂ to ·OH, GSH to GSSG, NADH to NAD+, and lactate to pyruvate. The nanorobot directly targets mitochondria to reprogram tumor metabolism and trigger cuproptosis. Meanwhile, lactate oxidase (LOX), encapsulated within the engineered exosomes, depletes excess lactate to relieve immunosuppression and boost antitumor immunity. In CRC models, these nanorobots exhibit strong barrier penetration, precise targeting, and deep tumor infiltration, offering a multifunctional and metabolically disruptive therapeutic approach.
{"title":"Modular train-style nanorobots for targeted deep penetration and multi-directional collaborative treatment of colorectal cancer","authors":"Jiamin Ye, Yueyue Fan, Gaoli Niu, Yong Kang, Jiacheng Shi, Ruiyan Li, Yiwen Yang, Xiaoyuan Ji","doi":"10.1016/j.chempr.2025.102750","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102750","url":null,"abstract":"Colorectal cancer (CRC) remains a major global health challenge due to insufficient tumor penetration and immunosuppressive microenvironments. Herein, we propose a modular train-style nanorobot (TPP-Exo@LOX-Pd-Cu<sub>7</sub>S<sub>4</sub>) as a targeted synergistic therapeutic platform for CRC. The exosome “head” enables neutrophil-like tumor homing, while the Cu<sub>7</sub>S<sub>4</sub> “tail” generates thermophoretic propulsion for deep tumor penetration. Under near-infrared region II (NIR-II) laser irradiation, the Pd-Cu<sub>7</sub>S<sub>4</sub> Schottky heterojunction drives highly efficient catalytic cascades, disrupting redox homeostasis and inducing metabolic stress by converting O₂ to ·O₂<sup>−</sup>, H₂O₂ to ·OH, GSH to GSSG, NADH to NAD<sup>+</sup>, and lactate to pyruvate. The nanorobot directly targets mitochondria to reprogram tumor metabolism and trigger cuproptosis. Meanwhile, lactate oxidase (LOX), encapsulated within the engineered exosomes, depletes excess lactate to relieve immunosuppression and boost antitumor immunity. In CRC models, these nanorobots exhibit strong barrier penetration, precise targeting, and deep tumor infiltration, offering a multifunctional and metabolically disruptive therapeutic approach.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194962","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}
Pub Date : 2025-09-26DOI: 10.1016/j.chempr.2025.102743
Jiahan Zhao, Bin Qin, Zhenghan Zhang, Siqi Zhu, Guangjun Wu, Jian Li, Yuchao Chai, Landong Li
CuZn-based catalysts like Cu/ZnO/Al2O3 have been extensively investigated for CO2 hydrogenation to methanol, while the active sites and underlying mechanism are hotly debated due to the ultra-high CuZn loadings and the structural complexity thereof. We report herein that zeolite-stabilized trinuclear Zn1Cu2 sites can efficiently catalyze the selective hydrogenation of CO2 to methanol, surpassing the performance of the benchmark CuZn-based catalyst, although the CuZn loading is over an order of magnitude lower. Both experimental evidence and theoretical calculations reveal the formate pathway of CO2 hydrogenation with the involvement of the Cu2+-Cuδ+-Cu2+ redox cycle. Zn ions incorporated into the zeolite framework play an essential role in stabilizing cationic Cu species against overreduction to less active metallic Cu during the reaction. Our results provide new insights into the chemistry of CO2 stepwise hydrogenation to methanol, which are useful for the rational design of catalysts.
{"title":"Zeolite-stabilized trinuclear Zn1Cu2 sites catalyze CO2 hydrogenation to methanol","authors":"Jiahan Zhao, Bin Qin, Zhenghan Zhang, Siqi Zhu, Guangjun Wu, Jian Li, Yuchao Chai, Landong Li","doi":"10.1016/j.chempr.2025.102743","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102743","url":null,"abstract":"CuZn-based catalysts like Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> have been extensively investigated for CO<sub>2</sub> hydrogenation to methanol, while the active sites and underlying mechanism are hotly debated due to the ultra-high CuZn loadings and the structural complexity thereof. We report herein that zeolite-stabilized trinuclear Zn<sub>1</sub>Cu<sub>2</sub> sites can efficiently catalyze the selective hydrogenation of CO<sub>2</sub> to methanol, surpassing the performance of the benchmark CuZn-based catalyst, although the CuZn loading is over an order of magnitude lower. Both experimental evidence and theoretical calculations reveal the formate pathway of CO<sub>2</sub> hydrogenation with the involvement of the Cu<sup>2+</sup>-Cu<sup>δ+</sup>-Cu<sup>2+</sup> redox cycle. Zn ions incorporated into the zeolite framework play an essential role in stabilizing cationic Cu species against overreduction to less active metallic Cu during the reaction. Our results provide new insights into the chemistry of CO<sub>2</sub> stepwise hydrogenation to methanol, which are useful for the rational design of catalysts.","PeriodicalId":268,"journal":{"name":"Chem","volume":"18 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141112","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}
Here, we present a bioinspired oxidative deamination strategy that reverses the polarity of lysine reactivity and thus allows for lysine bioconjugation in peptides and proteins with unprecedented biocompatibility and chemoselectivity. The in-situ-generated aldehyde intermediates facilitate versatile downstream transformations, including 15N/18O-labeling, reductive amination, Pinnick oxidation, and Wittig, Seyferth-Gilbert, and Van Leusen reactions. To demonstrate the broad applicability of our strategy, we successfully conjugated diverse functional payloads onto the backbone of semaglutide, full-length proteins, and therapeutic antibodies.
{"title":"Rewriting lysine reactivity: Lysine-targeted bioconjugation via biomimetic polarity reversal for diversified biomolecule modification","authors":"Lu Wang, Hongxiang Yang, Jianwen Cui, Xiaoping Chen, Biao Yu, Xiaheng Zhang","doi":"10.1016/j.chempr.2025.102744","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102744","url":null,"abstract":"Here, we present a bioinspired oxidative deamination strategy that reverses the polarity of lysine reactivity and thus allows for lysine bioconjugation in peptides and proteins with unprecedented biocompatibility and chemoselectivity. The <em>in</em>-<em>situ</em>-generated aldehyde intermediates facilitate versatile downstream transformations, including <sup>15</sup>N/<sup>18</sup>O-labeling, reductive amination, Pinnick oxidation, and Wittig, Seyferth-Gilbert, and Van Leusen reactions. To demonstrate the broad applicability of our strategy, we successfully conjugated diverse functional payloads onto the backbone of semaglutide, full-length proteins, and therapeutic antibodies.","PeriodicalId":268,"journal":{"name":"Chem","volume":"17 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134501","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}
Doping is a key approach to adjusting the electrical conductivities of polymer devices. However, the disruption to the microstructure of conjugated polymers from counterions of the dopant is the crucial factor limiting performance improvement. Herein, we propose a dual-affinity strategy for dopant design and present a novel n-type dopant, pTAM, with a 2-aminobenzimidazole triaminomethane structure. This pTAM dopant can significantly improve the electrical conductivity of several classic conjugated polymers with a 40%–240% increase in electrical conductivities compared with polymers doped by the widely used dopant 1,3-dimethyl-2-phenylbenzimidazoline (N-DMBI), reaching 83.3 ± 5.1 S cm−1. The enhanced performance is attributed to the matched interaction between pTAM cation and doped conjugated polymer, maintaining a well-ordered microstructure. Our work emphasizes the importance of the dopant-polymer microstructure relationship to the electrical performance, providing a corresponding effective strategy of dopant design for organic electronics and modern semiconductors.
掺杂是调节聚合物器件电导率的关键方法。然而，掺杂剂的反离子对共轭聚合物微观结构的破坏是限制性能提高的关键因素。在此，我们提出了一种双亲和策略来设计掺杂剂，并提出了一种新型的n型掺杂剂，pTAM，具有2-氨基苯并咪唑三胺甲烷结构。与广泛使用的掺杂剂1,3-二甲基-2-苯基苯并咪唑啉（N-DMBI）相比，该pTAM掺杂剂可以显著提高几种经典共轭聚合物的电导率，电导率提高40%-240%，达到83.3±5.1 S cm−1。这种增强的性能是由于pTAM阳离子与掺杂的共轭聚合物之间的匹配相互作用，保持了良好的微观结构。我们的工作强调了掺杂-聚合物微观结构关系对电性能的重要性，为有机电子和现代半导体的掺杂设计提供了相应的有效策略。
{"title":"Achieving well-ordered microstructure and enhanced conductivities in n-doped conjugated polymers via dual-affinity dopant","authors":"Chen-Kai Pan, Yi-Fan Huang, Zi-Di Yu, Ze-Fan Yao, Chi-Yuan Yang, Jie-Yu Wang, Jian Pei","doi":"10.1016/j.chempr.2025.102755","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102755","url":null,"abstract":"Doping is a key approach to adjusting the electrical conductivities of polymer devices. However, the disruption to the microstructure of conjugated polymers from counterions of the dopant is the crucial factor limiting performance improvement. Herein, we propose a dual-affinity strategy for dopant design and present a novel n-type dopant, pTAM, with a 2-aminobenzimidazole triaminomethane structure. This pTAM dopant can significantly improve the electrical conductivity of several classic conjugated polymers with a 40%–240% increase in electrical conductivities compared with polymers doped by the widely used dopant 1,3-dimethyl-2-phenylbenzimidazoline (N-DMBI), reaching 83.3 ± 5.1 S cm<sup>−1</sup>. The enhanced performance is attributed to the matched interaction between pTAM cation and doped conjugated polymer, maintaining a well-ordered microstructure. Our work emphasizes the importance of the dopant-polymer microstructure relationship to the electrical performance, providing a corresponding effective strategy of dopant design for organic electronics and modern semiconductors.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116788","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}
Catalysis is a key strategy for enhancing the yields and selectivities of desired products in both living systems and industry. Catalysts do not affect the reaction outcome of simple reversible reactions; they only accelerate equilibration. Herein, we report that catalysis greatly improves the self-assembly yield. In the presence of ReO4− as the catalyst, the M6L4 square-based pyramid (SP) was almost quantitatively assembled, whereas the yield was only 24% without catalysis. Experimental and theoretical analyses of the self-assembly revealed that M3L3 and M4L3 triangle species were trapped without ReO4−, that in the presence of the catalyst, the conversion of the trapped species was indirectly promoted by greater acceleration of the late stage of the self-assembly, and that local reaction loops involving SP prevented global equilibration to attain a metastable state.
{"title":"Catalytic manipulation of reversibility and irreversibility in a supramolecular reaction network to control the self-assembly outcome","authors":"Tsukasa Abe, Satoshi Takahashi, Runyu Chai, Hirofumi Sato, Shuichi Hiraoka","doi":"10.1016/j.chempr.2025.102741","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102741","url":null,"abstract":"Catalysis is a key strategy for enhancing the yields and selectivities of desired products in both living systems and industry. Catalysts do not affect the reaction outcome of simple reversible reactions; they only accelerate equilibration. Herein, we report that catalysis greatly improves the self-assembly yield. In the presence of ReO<sub>4</sub><sup>−</sup> as the catalyst, the M<sub>6</sub>L<sub>4</sub> square-based pyramid (<strong>SP</strong>) was almost quantitatively assembled, whereas the yield was only 24% without catalysis. Experimental and theoretical analyses of the self-assembly revealed that M<sub>3</sub>L<sub>3</sub> and M<sub>4</sub>L<sub>3</sub> triangle species were trapped without ReO<sub>4</sub><sup>−</sup>, that in the presence of the catalyst, the conversion of the trapped species was indirectly promoted by greater acceleration of the late stage of the self-assembly, and that local reaction loops involving <strong>SP</strong> prevented global equilibration to attain a metastable state.","PeriodicalId":268,"journal":{"name":"Chem","volume":"94 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145072105","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}
Pub Date : 2025-09-16DOI: 10.1016/j.chempr.2025.102740
Finn Gude, Annkathrin Bohne, Maria Dell, Jonathan Franke, Kyle L. Dunbar, Michael Groll, Christian Hertweck
Closthioamide (CTA) is a potent antibiotic with a unique polythioamide scaffold produced by Ruminiclostridium cellulolyticum. Unlike classical non-ribosomal peptide synthetases (NRPSs), which use modular adenylation and condensation domains, CTA biosynthesis proceeds through non-canonical standalone enzymes. Central to this process is the papain-like ligase CtaG, which catalyzes amide bond formation between two distinct peptidyl carrier proteins (PCPs): CtaH, presenting para-hydroxybenzoic acid (PHBA), and CtaE, carrying a tri-β-alanine ((βAla)3) chain. Using biochemical assays, chemical probes, crystallography, and mutational analysis, we show that CtaG operates via a ping-pong mechanism involving an enzyme-bound intermediate. A single substrate tunnel mediates directional transfer, enabling distal chain elongation that mirrors solid-phase peptide synthesis. Structure-based genome mining revealed homologous enzymes in the biosynthetic pathways of petrobactin, butirosin, and methylolanthanin. Together, our findings uncover a previously overlooked class of thiotemplated ligases and provide a mechanistic blueprint for engineering ribosome-independent peptide assembly lines.
{"title":"Distal peptide elongation by a protease-like ligase and two distinct carrier proteins","authors":"Finn Gude, Annkathrin Bohne, Maria Dell, Jonathan Franke, Kyle L. Dunbar, Michael Groll, Christian Hertweck","doi":"10.1016/j.chempr.2025.102740","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102740","url":null,"abstract":"Closthioamide (CTA) is a potent antibiotic with a unique polythioamide scaffold produced by <em>Ruminiclostridium cellulolyticum</em>. Unlike classical non-ribosomal peptide synthetases (NRPSs), which use modular adenylation and condensation domains, CTA biosynthesis proceeds through non-canonical standalone enzymes. Central to this process is the papain-like ligase CtaG, which catalyzes amide bond formation between two distinct peptidyl carrier proteins (PCPs): CtaH, presenting para-hydroxybenzoic acid (PHBA), and CtaE, carrying a tri-β-alanine ((βAla)<sub>3</sub>) chain. Using biochemical assays, chemical probes, crystallography, and mutational analysis, we show that CtaG operates via a ping-pong mechanism involving an enzyme-bound intermediate. A single substrate tunnel mediates directional transfer, enabling distal chain elongation that mirrors solid-phase peptide synthesis. Structure-based genome mining revealed homologous enzymes in the biosynthetic pathways of petrobactin, butirosin, and methylolanthanin. Together, our findings uncover a previously overlooked class of thiotemplated ligases and provide a mechanistic blueprint for engineering ribosome-independent peptide assembly lines.","PeriodicalId":268,"journal":{"name":"Chem","volume":"36 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068133","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}
Pub Date : 2025-09-11DOI: 10.1016/j.chempr.2025.102498
Jingyan Zhang , Zhongxin Song , Xiaozhang Yao , Yi Guan , Ziwei Huo , Ning Chen , Lei Zhang , Xueliang Sun
Triple-atom catalysts (TACs) are promising for surpassing the activity of normal single-atom and dual-atom catalysts. However, the rational design and construction of TACs remain challenging. Herein, we developed asymmetric Pt-Ru-Co triple atoms (TAs) by using selective atomic layer deposition technology. Compared with the corresponding single-atom and dual-atom counterparts, they demonstrate superior electrocatalytic performance in both the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). Operando X-ray absorption spectroscopy (XAS) revealed that the heterogeneous atoms within Pt-Ru-Co TAs have strong interactions and serve as active centers, synergistically accelerating reaction kinetics. Additionally, theoretical calculations indicate that introducing Co atoms effectively optimizes the d orbital electronic structure of Pt and Ru, endowing enhanced catalytic activity of the Pt-Ru-Co TAs. This work presents asymmetric Pt-Ru-Co TAs with excellent electrocatalytic activity and provides new insights into the catalytic mechanism of TACs.
三原子催化剂（TAC）有望超越普通单原子和双原子催化剂的活性。然而，三原子催化剂的合理设计和构建仍具有挑战性。在此，我们利用选择性原子层沉积技术开发了不对称铂-铜-钴三原子（TAs）。与相应的单原子和双原子相比，它们在氢气进化反应（HER）和氢气氧化反应（HOR）中都表现出卓越的电催化性能。操作性 X 射线吸收光谱（XAS）显示，铂-铜-钴 TAs 中的异质原子具有很强的相互作用，可作为活性中心，协同加速反应动力学。此外，理论计算表明，引入 Co 原子可有效优化铂和钌的 d 轨道电子结构，从而增强 Pt-Ru-Co TAs 的催化活性。这项工作提出了具有优异电催化活性的不对称铂-钌-钴 TAs，并为 TACs 的催化机理提供了新的见解。
{"title":"Precisely constructing asymmetric triple atoms for highly efficient electrocatalysis","authors":"Jingyan Zhang , Zhongxin Song , Xiaozhang Yao , Yi Guan , Ziwei Huo , Ning Chen , Lei Zhang , Xueliang Sun","doi":"10.1016/j.chempr.2025.102498","DOIUrl":"10.1016/j.chempr.2025.102498","url":null,"abstract":"<div><div><span>Triple-atom catalysts (TACs) are promising for surpassing the activity of normal single-atom and dual-atom catalysts. However, the rational design and construction of TACs remain challenging. Herein, we developed asymmetric Pt-Ru-Co triple atoms (TAs) by using selective atomic layer deposition technology<span>. Compared with the corresponding single-atom and dual-atom counterparts, they demonstrate superior electrocatalytic performance in both the hydrogen evolution reaction<span> (HER) and hydrogen oxidation reaction (HOR). </span></span></span><span><em>Operando</em></span><span> X-ray absorption spectroscopy (XAS) revealed that the heterogeneous atoms within Pt-Ru-Co TAs have strong interactions and serve as active centers, synergistically accelerating reaction kinetics. Additionally, theoretical calculations indicate that introducing Co atoms effectively optimizes the </span><em>d</em><span><span> orbital electronic structure of Pt and Ru, endowing enhanced catalytic activity of the Pt-Ru-Co TAs. This work presents asymmetric Pt-Ru-Co TAs with excellent </span>electrocatalytic activity and provides new insights into the catalytic mechanism of TACs.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 9","pages":"Article 102498"},"PeriodicalIF":19.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703588","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}
Pub Date : 2025-09-11DOI: 10.1016/j.chempr.2025.102649
Huaiyuan Zhu , Shigeyoshi Inoue
N-heterocyclic carbene-phosphinidene (NHCP) and its anionic counterpart represent one of the most prominent classes of N-heterocyclic carbene (NHC) derivatives featuring phosphorus, distinguished by their efficacy and utility as phosphorus-donor ligands. This perspective showcases the impact of structurally and electronically distinct carbene moieties on the design principles of NHCP ligands, with a spotlight on their pivotal role in synthesizing diverse main-group compounds—especially those featuring low-valent element centers. The end of this perspective provides a detailed outline of several potential future directions for the development of NHCP ligands, including the synthesis of novel NHCP-involved main-group compounds leveraging the tunable electronic and steric properties of NHCPs, as well as the exploration of their applications in small molecule activation, catalysis, and materials science.
n -杂环卡宾-磷二烯（NHCP）及其阴离子对应物是含磷的n -杂环卡宾（NHC）衍生物中最突出的一类，以其作为磷给体的功效和用途而闻名。这一视角展示了结构上和电子上不同的碳基团对NHCP配体设计原则的影响，重点关注了它们在合成各种主基团化合物（特别是那些具有低价元素中心的化合物）中的关键作用。该展望的最后详细概述了未来NHCP配体发展的几个潜在方向，包括利用NHCP的可调电子和空间性质合成新的NHCP主基化合物，以及探索其在小分子活化、催化和材料科学中的应用。
{"title":"N-Heterocyclic carbene-phosphinidenes in main-group chemistry","authors":"Huaiyuan Zhu , Shigeyoshi Inoue","doi":"10.1016/j.chempr.2025.102649","DOIUrl":"10.1016/j.chempr.2025.102649","url":null,"abstract":"<div><div><em>N</em>-heterocyclic carbene-phosphinidene (NHCP) and its anionic counterpart represent one of the most prominent classes of <em>N</em>-heterocyclic carbene (NHC) derivatives featuring phosphorus, distinguished by their efficacy and utility as phosphorus-donor ligands. This perspective showcases the impact of structurally and electronically distinct carbene moieties on the design principles of NHCP ligands, with a spotlight on their pivotal role in synthesizing diverse main-group compounds—especially those featuring low-valent element centers. The end of this perspective provides a detailed outline of several potential future directions for the development of NHCP ligands, including the synthesis of novel NHCP-involved main-group compounds leveraging the tunable electronic and steric properties of NHCPs, as well as the exploration of their applications in small molecule activation, catalysis, and materials science.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 9","pages":"Article 102649"},"PeriodicalIF":19.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533798","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}
Pub Date : 2025-09-11DOI: 10.1016/j.chempr.2025.102583
Bayu I.Z. Ahmad , Kiser Z. Colley , Andrew J. Musser , Phillip J. Milner
Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO2 separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO2, and CO2 release is realized through an intramolecular photodecarboxylation reaction. This system operates isothermally, works with natural sunlight, and facilitates CO2 removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.
{"title":"A fully light-driven approach to separate carbon dioxide from emission streams","authors":"Bayu I.Z. Ahmad , Kiser Z. Colley , Andrew J. Musser , Phillip J. Milner","doi":"10.1016/j.chempr.2025.102583","DOIUrl":"10.1016/j.chempr.2025.102583","url":null,"abstract":"<div><div><span><span>Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by </span>fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO</span><sub>2</sub> separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO<sub>2</sub>, and CO<sub>2</sub> release is realized through an intramolecular photodecarboxylation reaction. This system operates isothermally, works with natural sunlight, and facilitates CO<sub>2</sub> removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 9","pages":"Article 102583"},"PeriodicalIF":19.6,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927096","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}
Pub Date : 2025-09-11DOI: 10.1016/j.chempr.2025.102500
Gautam Mitra , Jueting Zheng , Karen Schaefer , Michael Deffner , Jonathan Z. Low , Luis M. Campos , Carmen Herrmann , Theo A. Costi , Elke Scheer
The Blatter radical has been suggested as a building block in future molecular spintronic devices because of its radical character and expected long spin lifetime. However, whether its radical character is maintained in single-molecule junctions depends on the environment. Here, we demonstrate the ability to retain the open-shell nature of the Blatter radical in a two-terminal device by the appearance of a Kondo resonance in transport spectroscopy. Additionally, a high negative magnetoresistance is observed in junctions that do not reveal a zero-bias anomaly. By combining distance-dependent and magnetic-field-dependent measurements and accompanying quantum-chemical and quantum-transport calculations, we show that both findings, the negative magnetoresistance and the Kondo features, can be consistently explained by a singlet-triplet Kondo model. Our findings provide the possibility of using the Blatter radical in a two-terminal system under cryogenic conditions and also reveal the magnetotransport properties emerging from different configurations of the molecule inside a junction.
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