ChemPub Date : 2025-08-05DOI: 10.1016/j.chempr.2025.102693
Christopher K. Lee, Yuanning Feng, Alan E. Enciso, Jake P. Violi, William A. Donald, J. Fraser Stoddart, Dong Jun Kim
{"title":"An aqueous artificial molecular pump","authors":"Christopher K. Lee, Yuanning Feng, Alan E. Enciso, Jake P. Violi, William A. Donald, J. Fraser Stoddart, Dong Jun Kim","doi":"10.1016/j.chempr.2025.102693","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102693","url":null,"abstract":"This work presents an artificial molecular pump designed for efficient operation in water, advancing the integration of synthetic molecular machines into biologically relevant environments. The pump function, demonstrated through the formation of [2]- and [3]rotaxanes, exhibits enhanced efficiency and faster kinetics compared with analogous systems in organic solvents. These improvements stem from radical-radical interactions amplified by water due to its high polarity, emphasizing the solvent’s role in molecular machine performance. The findings underscore the ability of water to strengthen supramolecular interactions essential for pump operation, providing a framework for designing next-generation molecular machines capable of functioning under more biochemically relevant conditions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"287 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144778721","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}
ChemPub Date : 2025-07-30DOI: 10.1016/j.chempr.2025.102667
Fairoosa Poovan, Rajenahally V. Jagadeesh, Matthias Beller
{"title":"A catalytic approach to the valorization of polyesters and biogenic waste for the production of amines","authors":"Fairoosa Poovan, Rajenahally V. Jagadeesh, Matthias Beller","doi":"10.1016/j.chempr.2025.102667","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102667","url":null,"abstract":"Despite the numerous applications of polymers in human life, their excessive use has caused serious environmental hazards. Among polymer recycling methods, chemical recycling offers a streamlined approach to polymer degradation by enabling depolymerization without compromising functionality. Specifically, hydrogenolysis of polymers, a depolymerization technique that utilizes hydrogen to cleave bonds, has emerged as a powerful strategy for depolymerization, facilitating the upcycling of plastics into high-value chemicals. Previous research in this area has predominantly focused on noble metal catalysts, while the potential of base metals remains unexplored. Herein, we propose a cobalt-based hydrogenative amination approach for the depolymerization of polyesters to versatile diamines as well as amino alcohols. This strategy can also be applied to the one-pot synthesis of fatty amines from used cooking oil. The current system opens new avenues for the upcycling of waste into valuable amines, providing a viable solution to plastic pollution and a way to utilize waste as a resource.","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737528","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}
ChemPub Date : 2025-07-29DOI: 10.1016/j.chempr.2025.102685
Hai Zhang, Tianyu Huang, Jianping Zhou, Chunlin Xu, Dongdong Zhang, Lian Duan
{"title":"Fast reverse intersystem crossing over 107 s−1 via near-enantiomeric charge-transfer transitions","authors":"Hai Zhang, Tianyu Huang, Jianping Zhou, Chunlin Xu, Dongdong Zhang, Lian Duan","doi":"10.1016/j.chempr.2025.102685","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102685","url":null,"abstract":"Thermally activated delayed fluorescence (TADF) enables high-efficiency organic light-emitting diodes (OLEDs) through reverse intersystem crossing (RISC) of triplet excitons, yet existing systems struggle to achieve fast RISC rates (<em>k</em><sub>RISC</sub> >10<sup>7</sup> s<sup>−1</sup>), let alone balance a high radiative decay (<em>k</em><sub>r</sub>). Herein, we develop a dual-donor TADF emitter that bypasses the El-Sayed rule restriction by harnessing near-enantiomeric charge-transfer transitions between a high-lying triplet state and the lowest singlet state and that synergizes with heavy atoms to enhance spin-orbit coupling. This design yields a <em>k</em><sub>RISC</sub> of 1.54 × 10<sup>7</sup> s<sup>−1</sup> alongside a <em>k</em><sub>r</sub> of 9.65 × 10<sup>6</sup> s<sup>−1</sup>, reducing the delayed fluorescence lifetime to 1.46 μs. The OLED exhibits a peak external quantum efficiency of 30.6% with minimal roll-off (30.4% at 5,000 cd m<sup>−2</sup>) and an operational lifetime exceeding 1,500 h at 1,000 cd m<sup>−2</sup> before the luminance decays to 95% of its initial value, which extends further to 3,876 h via sensitized narrowband emission. This work bypasses conventional localized triplet-intermediate-dependent RISC mechanisms and establishes a paradigm for designing high-efficiency, stable TADF materials.","PeriodicalId":268,"journal":{"name":"Chem","volume":"24 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720227","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}
ChemPub Date : 2025-07-28DOI: 10.1016/j.chempr.2025.102658
Jonas Spengler, Yvonne Wagenhäuser, Frank Würthner
{"title":"Schwarzite—The holy grail of carbon allotropes","authors":"Jonas Spengler, Yvonne Wagenhäuser, Frank Würthner","doi":"10.1016/j.chempr.2025.102658","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102658","url":null,"abstract":"The discovery of different sp<sup>2</sup>-carbon allotropes such as fullerenes (0D), carbon nanotubes (1D), and graphene (2D) has tremendously impacted molecular materials research. Starting from simple but highly interesting non-planar hydrocarbon building blocks, the logical extension into three dimensions—curved structures called schwarzites—was theoretically predicted by Mackay and Terrones in 1991 but remains elusive, owing to the tremendous synthetic challenge these structures present. In this perspective, we discuss approaches toward schwarzite carbon materials and present our own vision of how atomically precise schwarzites might be synthesized. Key steps of this approach are the template-mediated preorganization of small molecular cutouts of schwarzites and the subsequent formation of the desired, three-dimensionally conjugated carbon allotrope under suitable conditions for C–C bond formation and reorganization.","PeriodicalId":268,"journal":{"name":"Chem","volume":"90 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144715639","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}
ChemPub Date : 2025-07-18DOI: 10.1016/j.chempr.2025.102664
Ryo Tanifuji, Erina Hosono, Hisae Kamakura, Yukiko Muramatsu, Satoshi Yoshida, Sota Sato, Yoshimi Ohashi, Shingo Dan, Hiroyuki Seimiya, Hiroki Oguri
{"title":"Strategic scaffold redesign of ecteinascidins: An approach for generating anticancer macrocycles","authors":"Ryo Tanifuji, Erina Hosono, Hisae Kamakura, Yukiko Muramatsu, Satoshi Yoshida, Sota Sato, Yoshimi Ohashi, Shingo Dan, Hiroyuki Seimiya, Hiroki Oguri","doi":"10.1016/j.chempr.2025.102664","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102664","url":null,"abstract":"Strategies for rational design and scaffold diversification of therapeutically valuable yet synthetically challenging natural products remain elusive, often overshadowed by structural simplification approaches. Herein, we report the molecular redesign of an antitumor drug, ecteinascidin 743, which achieves three pivotal objectives: (1) strategic shift of the bridgehead position from C4 to C5, (2) systematic customization of macrocycle size, and (3) incorporation of functional groups for further modification. Our approach generates diverse 14- to 17-membered macrocyclic frameworks bridged at C5, expanding the accessible chemical space beyond that of conventional C1- to C4-bridged scaffolds, while preserving the core structure essential for covalent DNA interactions. These novel macrocycles induce DNA double-strand breaks and exhibit sub-nanomolar anticancer efficacy comparable to ecteinascidins. This method shortens the conventional 21-step semi-synthetic protocol into a streamlined 6- to 10-step process, cutting the synthetic burden by over 50%.","PeriodicalId":268,"journal":{"name":"Chem","volume":"9 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652626","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}
ChemPub Date : 2025-07-18DOI: 10.1016/j.chempr.2025.102665
Justin O.P. Waters, Elnaz Jamalzade, Hussein T. Abdulrazzaq, Nathaniel Kuch, Sampath R. Gunukula, James A. Dumesic, Philip J. Kersten, Thomas J. Schwartz
{"title":"Production of biorenewable, enantiopure (S)-3-hydroxy-γ-butyrolactone for pharmaceutical applications","authors":"Justin O.P. Waters, Elnaz Jamalzade, Hussein T. Abdulrazzaq, Nathaniel Kuch, Sampath R. Gunukula, James A. Dumesic, Philip J. Kersten, Thomas J. Schwartz","doi":"10.1016/j.chempr.2025.102665","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102665","url":null,"abstract":"Many pharmaceuticals include chiral centers, which are introduced using high-cost building blocks such as (S)-3-hydroxy-γ-butyrolactone, (S)-HBL. This species is used in the synthesis of many important drugs, including statins, antibiotics, and HIV inhibitors, and it is currently produced from fossil resources via a high-cost, high-emission process. Here, we show that a nearly quantitative yield of enantiopure (S)-HBL can be obtained from glucose at ambient temperature, using a combination of biological and chemical catalysis. Whole-cell enzyme catalysis converts glucose to a labile intermediate (denoted as trione) that is subsequently reacted to (S)-HBL by metal-free homogeneous acid/base catalysis. These reactions do not involve the C5 of glucose, leading to enantiopure (S)-HBL, produced at less than half the present cost. This approach can also be used to produce other commercially important building blocks from sustainable feedstocks: the enzymes used for trione production are active in converting xylose, leading to the acrylate co-monomer 3-hydroxypropionic acid.","PeriodicalId":268,"journal":{"name":"Chem","volume":"677 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Chiral C3-symmetric molecule assembly enabling topological nanotoroid, fused nanotoroid, and nanocatenane","authors":"Jinqi Li, Huajie Zhu, Hanxiao Wang, Chenyang Zhao, Guanghui Ouyang, Minghua Liu","doi":"10.1016/j.chempr.2025.102663","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102663","url":null,"abstract":"Although chiral nanostructures have been extensively studied, the fabrication of topological entities such as toroidal assemblies and their higher-order fused or catenated structures remains a formidable challenge. Here, we demonstrate a hierarchical assembly paradigm using a C3-symmetric benzene-1,3,5-tricarboxamide that enables the topological evolution of varied nanoarchitectures, such as discrete nanotoroids, fused super-nanotoroids containing up to 21 toroidal units, and nano-[2]catenanes. Our experimental and calculation results demonstrated that C3 molecules tended to form helical nanofibers with unexpected curvature due to both molecular chirality and bulky side chains. Further longitudinal extension and lateral lamellar packing of primary one-dimensional stacks led to the formation of dominant nanotoroids and stochastic nano-[2]catenanes with chiroptical signals and circularly polarized luminescence through an adaptive templating method. This work presents a cyclization-driven precise assembly of topologically discrete, fused, and catenated nanotoroids, unveiling the synergistic merging of chiral hierarchy and topological architectures in supramolecular self-assembly systems.","PeriodicalId":268,"journal":{"name":"Chem","volume":"21 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Curved anthracenes for visible-light photon energy storage via Dewar isomerization","authors":"Subhayan Chakraborty, Writam S.R. Choudhuri, Junichi Usuba, Qianfeng Qiu, Cijil Raju, Grace G.D. Han","doi":"10.1016/j.chempr.2025.102660","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102660","url":null,"abstract":"We report the design of curved anthracene systems that undergo efficient Dewar isomerization upon visible-light absorption and release heat through thermally triggered reverse isomerization, with high cyclability. These systems achieve remarkably high-energy storage capacities—up to 170 kJ/mol and 0.65 MJ/kg—comparable to the best reported molecular solar thermal (MOST) materials, while offering the added capability of harnessing the standard solar spectrum and presenting chemical robustness. Notably, these curved anthracenes can be fine-tuned to store energy in a neat liquid state, presenting a promising route toward solvent-free solar thermal energy storage devices. This report highlights the potential of fully carbon-based aromatic systems to store a large quantity of solar energy via photo-induced valence isomerization and dearomatization.","PeriodicalId":268,"journal":{"name":"Chem","volume":"35 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630248","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}
ChemPub Date : 2025-07-14DOI: 10.1016/j.chempr.2025.102654
Chensen Li, Minghui Wu, Zheng Zhao, Jacky W.Y. Lam, Bo Xu, Ben Zhong Tang
{"title":"Suppressing molecular motions: A pathway to enhanced organic room temperature phosphorescence","authors":"Chensen Li, Minghui Wu, Zheng Zhao, Jacky W.Y. Lam, Bo Xu, Ben Zhong Tang","doi":"10.1016/j.chempr.2025.102654","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102654","url":null,"abstract":"Organic room-temperature phosphorescence (RTP) emitters have emerged as a compelling research field with broad applications in optoelectronics, anti-counterfeiting, and biomedical imaging. This interest stems from the efficient utilization of the radiative relaxation of the triplet excited state. An efficient intersystem crossing (ISC) process alone is not sufficient for efficient and long-lived RTP emission. It is also crucial to suppress molecular motion, including rotation, vibration, and translation. By rigidifying molecular structures to suppress these motions, triplet excitons are effectively stabilized, and non-radiative transitions are reduced, presenting a viable strategy for developing a variety of efficient and long-lived RTP materials. This review focuses on the current rational engineering efforts to suppress molecular motion for efficient and long-lived RTP generation, enhancing understanding of the interplay between molecular motion and RTP emission, and emphasizing the critical role of restricting molecular motion in the development of efficient and long-lived RTP materials.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622422","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}
ChemPub Date : 2025-07-10DOI: 10.1016/j.chempr.2025.102544
Yisen Yao , Oscar Ávalos-Ovando , Tao Ding , Ramon A. Alvarez-Puebla , Peng Yu , Eric Ashalley , Li Ma , Zhiming Wang , Gil Markovich , Alexander O. Govorov
{"title":"From chiral biomolecules to chiral nanocrystals: A review of the latest developments and emerging concepts","authors":"Yisen Yao , Oscar Ávalos-Ovando , Tao Ding , Ramon A. Alvarez-Puebla , Peng Yu , Eric Ashalley , Li Ma , Zhiming Wang , Gil Markovich , Alexander O. Govorov","doi":"10.1016/j.chempr.2025.102544","DOIUrl":"10.1016/j.chempr.2025.102544","url":null,"abstract":"<div><div>This article reviews the latest developments in the field of chiral nanocrystals (NCs), focusing primarily on plasmonic NCs. Such nanomaterials under illumination concentrate electromagnetic energy in their vicinity, enabling efficient biosensing, asymmetric photocatalysis, and light manipulation. Starting our discussion with Lord Kelvin’s definition of chirality, we describe how enantiomer pairs appear when the molecule becomes progressively more complex. Making a comparison with Pasteur’s chirality of molecules, we discuss nanoscale enantiomers lacking exact mirror symmetry, so-called nonexact enantiomers, and why they should appear fundamentally. Whereas chirality is an intrinsically three-dimensional (3D) concept describing perfect mirror-imaged pairs, a novel property of pseudo-chirality is handy for understanding two-dimensional (2D) systems, including the case of plasmonic growth with circularly polarized light. The topics considered in the review include bio-templated NCs, chiral bio-assemblies, transfer of chirality from biomolecules to NCs, chirality and pseudo-chirality in 3D and 2D systems, growth of NCs under circularly polarized excitation, and more.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 7","pages":"Article 102544"},"PeriodicalIF":19.1,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143890224","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}