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}
ChemPub Date : 2025-07-16DOI: 10.1016/j.chempr.2025.102687
Haomiao Xie, Kent O. Kirlikovali, Omar K. Farha
{"title":"Blueprints for crystallinity: Coordination templates enable synthesis of atomically resolved covalent-organic frameworks","authors":"Haomiao Xie, Kent O. Kirlikovali, Omar K. Farha","doi":"10.1016/j.chempr.2025.102687","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102687","url":null,"abstract":"Atomic-level characterization of covalent-organic frameworks (COFs) has been constrained by their poor crystallinity. In the June issue of <em>Chem</em>, Zhang et al. report a coordination-templated strategy that guides imine linkage formation to produce single-crystalline metal-organic COF hybrids (MOCOFs) resolvable at sub-angstrom precision by single-crystal X-ray diffraction analysis. This advance enables detailed investigations of framework growth, host-guest chemistry, and chirality transfer.","PeriodicalId":268,"journal":{"name":"Chem","volume":"34 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144640591","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 : 2025-07-14DOI: 10.1016/j.chempr.2025.102455
Yoshiyuki Kageyama
{"title":"Catalyst: Advancing nonequilibrium chemistry by clarifying misconceptions","authors":"Yoshiyuki Kageyama","doi":"10.1016/j.chempr.2025.102455","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102455","url":null,"abstract":"Yoshiyuki Kageyama obtained his PhD in multidisciplinary science from the University of Tokyo in 2006 and is currently an independent assistant professor in the Faculty of Chemistry at Hokkaido University. He has developed autonomous molecular systems and robots measuring tens of micrometers, including a light-driven self-oscillatory flipping microcrystal that exhibits self-propelling motion in water through a novel mechanism and the autocatalytic reproduction of vesicles by modeling self-sustainable cell division.","PeriodicalId":268,"journal":{"name":"Chem","volume":"14 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622423","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}
ChemPub Date : 2025-07-10DOI: 10.1016/j.chempr.2025.102448
Scott Jensen , Brendan T. Sullivan , Daniel A. Hartzler , Irina Kosheleva , Robert W. Henning , Allison Page , Yulia Pushkar
{"title":"Challenges of observing O–O bond formation in the Mn4Ca cluster of photosystem II","authors":"Scott Jensen , Brendan T. Sullivan , Daniel A. Hartzler , Irina Kosheleva , Robert W. Henning , Allison Page , Yulia Pushkar","doi":"10.1016/j.chempr.2025.102448","DOIUrl":"10.1016/j.chempr.2025.102448","url":null,"abstract":"<div><div>Photosystem II (PS II) sustains the biosphere by enabling oxygen evolution in the S<sub>3</sub>-to-S<sub>0</sub> transition (duration ∼1–2 ms) of its catalytic cycle. Using time-resolved Mn K<sub>β</sub> X-ray emission spectroscopy, we observed spectroscopic changes (which were unimpeded in D<sub>2</sub>O buffer) consistent with a modified electronic structure as early as ∼50 μs in the transition. These changes are consistent with the reduction of the Mn centers at the ∼50–200 μs time window in H<sub>2</sub>O and at ∼50–500 μs in D<sub>2</sub>O, ahead of the reduction of the redox-active Tyr<sub>Z</sub><sup>⋅+</sup>. These results indicate the multi-step nature of O–O bond formation and O<sub>2</sub> release by the oxygen-evolving complex (OEC), where an O–O bond is most likely formed prior to the final electron-transfer step. The D<sub>2</sub>O-induced extension of up to ∼500 μs in the lifetime of the early transient state of a possible peroxo nature opens it up to further spectroscopic and structural analysis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 7","pages":"Article 102448"},"PeriodicalIF":19.1,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144588885","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.2025.102614
Jing Zhao , Xiaobo Peng , Lilong Jiang , Kang Cheng , Jincan Kang , Qinghong Zhang , Noritatsu Tsubaki , Ye Wang
{"title":"3D-printing technologies for C1 chemistry","authors":"Jing Zhao , Xiaobo Peng , Lilong Jiang , Kang Cheng , Jincan Kang , Qinghong Zhang , Noritatsu Tsubaki , Ye Wang","doi":"10.1016/j.chempr.2025.102614","DOIUrl":"10.1016/j.chempr.2025.102614","url":null,"abstract":"<div><div>One-carbon (C1) molecules (including carbon dioxide [CO<sub>2</sub>], carbon monoxide [CO], methane [CH<sub>4</sub>], and methanol [CH<sub>3</sub>OH]) are abundant carbon feedstocks and important conversion platforms. To promote the utilization of C1 molecules, three-dimensional (3D)-printing technologies pave an avenue of digital additive manufacturing for the conversion of C1 molecules into high-value-added chemicals. This perspective highlights the progress and challenges of 3D-printing technologies for the conversion of C1 molecules. We systematically analyze the design and preparation of 3D-printed reactors, catalysts, and electrodes in the conversion of C1 molecules. Further, we summarize and discuss their technical features and challenges to reveal the revolutionary nature of 3D-printing technologies. The goal of this perspective is to provide guidance and suggestions for accelerating the development of digitalization, automation, and intelligentization in chemical synthesis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 7","pages":"Article 102614"},"PeriodicalIF":19.1,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219203","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}