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Germanium ligand redox cooperativity: A key to ambiphilicity and switchable two- and four-electron transfer 锗配体氧化还原协同性:两亲性和可切换的二电子和四电子转移的关键
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-07-06 DOI: 10.1016/j.chempr.2026.103127
Sung Gyu Kim, Jinrok Oh, Dae Eui Choi, Seung Jun Hwang
{"title":"Germanium ligand redox cooperativity: A key to ambiphilicity and switchable two- and four-electron transfer","authors":"Sung Gyu Kim,&nbsp;Jinrok Oh,&nbsp;Dae Eui Choi,&nbsp;Seung Jun Hwang","doi":"10.1016/j.chempr.2026.103127","DOIUrl":"10.1016/j.chempr.2026.103127","url":null,"abstract":"<div><div>Controlling electron count in small molecule activation, toggling between two- and four-electron pathways, remains a fundamental challenge typically addressed using distinct catalysts. Here, we report germanium complex <strong>1,</strong> which achieves this control within a single molecular framework through synergy between germanium’s orbital energetics and atomic parameters with a redox-active, structurally constraining ligand scaffold. GeK <strong>(1)</strong> performs four-electron activation of elemental chalcogens (S<sub>8</sub>, O<sub>2</sub>), with spectroscopic detection of key intermediates. Selective methylation provides access to the two-electron intermediate GeMe <strong>(4)</strong> or the four-electron product GeMe<sub>2</sub>I <strong>(7)</strong> through controlled stepwise oxidation. Remarkably, GeMe <strong>(4)</strong> exhibits single-site ambiphilicity, capable of both nucleophilic attack and electrophilic activation at the germanium center. Computational and spectroscopic analyses reveal that conjugative aromaticity arising from germanium-ligand π-orbital overlap stabilizes otherwise fleeting intermediates and enables this dual reactivity. Practical utility emerges through efficient dehalogenation of vicinal dihalides under ambient conditions, demonstrating that rationally designed main-group complexes can achieve transition-metal-like versatility.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103127"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718885","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
Design and organocatalytic enantioselective assembly of axially chiral boracyclohexylidenes and chiral boraspiranes 轴向手性硼环己基醚和手性硼aspiranes的设计和有机催化对映选择性组装
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-03-27 DOI: 10.1016/j.chempr.2026.102990
Shuai Wang, Jianbo Liu, Wangyang Li, Ying Li, Yanying Huang, Wenyue Ma, Qiuling Song
{"title":"Design and organocatalytic enantioselective assembly of axially chiral boracyclohexylidenes and chiral boraspiranes","authors":"Shuai Wang,&nbsp;Jianbo Liu,&nbsp;Wangyang Li,&nbsp;Ying Li,&nbsp;Yanying Huang,&nbsp;Wenyue Ma,&nbsp;Qiuling Song","doi":"10.1016/j.chempr.2026.102990","DOIUrl":"10.1016/j.chempr.2026.102990","url":null,"abstract":"<div><div>Chiral tetracoordinate boron compounds have garnered significant attention in organoboron chemistry, asymmetric synthesis, and material sciences. However, the synthesis of chiral tetracoordinate boron compounds with backbones remains elusive and challenging. Herein, we disclose the synthesis of axially chiral boracyclohexylidenes featuring boron atoms as spiro centers and chiral boraspiranes with boron atoms as stereogenic centers. Of note, the latter could be achieved from the newly built former one via a highly stereoselective Beckmann rearrangement, enabling the transformation of axial chirality to central chirality. Our strategy showcases structures with excellent enantioselectivity, high efficiency, and a broad substrate scope, and the resulting chiral borons demonstrate significant fluorescent properties, which will further enhance and promote the development of chiral optoelectronic materials.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 102990"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147535871","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
Alcoholysis of nylon 6 waste to ε-caprolactam promoted by phosphoric acid 磷酸促进尼龙6废醇解制ε-己内酰胺的研究
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-03-30 DOI: 10.1016/j.chempr.2026.102966
Xianyuan Wu, Rahul Prasad Bangalore Ashok, Xiao Wang, Matthew S. Webber, Anna E. Brenner, Griffin Drake, Joel Miscall, Clarissa Lincoln, Elisabeth Van Roijen, Stefan J. Haugen, Jason S. DesVeaux, Taylor Uekert, Yang Shao-Horn, Shannon S. Stahl, Gregg T. Beckham, Yuriy Román-Leshkov
{"title":"Alcoholysis of nylon 6 waste to ε-caprolactam promoted by phosphoric acid","authors":"Xianyuan Wu,&nbsp;Rahul Prasad Bangalore Ashok,&nbsp;Xiao Wang,&nbsp;Matthew S. Webber,&nbsp;Anna E. Brenner,&nbsp;Griffin Drake,&nbsp;Joel Miscall,&nbsp;Clarissa Lincoln,&nbsp;Elisabeth Van Roijen,&nbsp;Stefan J. Haugen,&nbsp;Jason S. DesVeaux,&nbsp;Taylor Uekert,&nbsp;Yang Shao-Horn,&nbsp;Shannon S. Stahl,&nbsp;Gregg T. Beckham,&nbsp;Yuriy Román-Leshkov","doi":"10.1016/j.chempr.2026.102966","DOIUrl":"10.1016/j.chempr.2026.102966","url":null,"abstract":"<div><div>Nylon 6 is widely used in high-performance materials. However, the inherent structural rigidity of nylon 6 inhibits catalytic depolymerization to its monomer, ε-caprolactam. Here, we demonstrate an acid-catalyzed alcoholysis process that depolymerizes nylon 6 to ε-caprolactam, achieving yields up to 74% using <em>n</em>-propanol as solvent and phosphoric acid as catalyst at 220°C for 2 h. We further applied the process to commercial nylon-containing products, demonstrating ε-caprolactam yields of 67% to 76%. Process modeling and techno-economic analysis estimated a minimum selling price of recycled nylon 6 at $1.79/kg, 30% lower than the 5-year average market price of virgin nylon 6. These estimates depend on assumed costs and process performance and may vary with future conditions. Life cycle assessment indicated that nylon 6 produced via alcoholysis can reduce greenhouse gas emissions by up to 63% compared with primary production. Overall, this study demonstrates a facile, cost-effective, and environmentally beneficial process for nylon 6 chemical recycling.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 102966"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147586286","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
Reaction: Navigating the path to reasoning laboratories 反应:探索推理实验室之路
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-07-30 DOI: 10.1016/j.chempr.2026.103147
Joshua W. Sin, David Ming Segura, Ramon Winkler, Philippe Schwaller
{"title":"Reaction: Navigating the path to reasoning laboratories","authors":"Joshua W. Sin,&nbsp;David Ming Segura,&nbsp;Ramon Winkler,&nbsp;Philippe Schwaller","doi":"10.1016/j.chempr.2026.103147","DOIUrl":"10.1016/j.chempr.2026.103147","url":null,"abstract":"<div><div>Joshua W. Sin holds bachelor’s and master’s degrees in chemistry from Oxford and is a joint PhD student at Roche and EPFL’s Laboratory of Artificial Chemical Intelligence (LIAC), where he focuses on automation and large language models (LLMs) for chemistry. David Ming Segura received his master’s degree from EPFL after earning a bachelor’s degree from the University of Geneva and completing an internship at Roche. He is now a PhD student at LIAC, where he works on LLMs and agentic workflows for chemistry. Ramon Winkler is a technical R&amp;D senior associate scientist at Roche, and his decade of pharmaceutical experience bridges wet-lab chemistry, automation, and machine learning. Philippe Schwaller is a tenure-track assistant professor at EPFL, where he leads LIAC and is a core principal investigator of NCCR Catalysis and NCCR Separations. He previously worked at IBM Research Europe, earned his PhD from the University of Bern, and received the Novartis Early Career Award and the University Latsis Prize.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103147"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148624230","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
Catalyst: When self-driving labs begin to reason 催化剂:当自动驾驶实验室开始推理
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-07-30 DOI: 10.1016/j.chempr.2026.103108
Milad Abolhasani
{"title":"Catalyst: When self-driving labs begin to reason","authors":"Milad Abolhasani","doi":"10.1016/j.chempr.2026.103108","DOIUrl":"10.1016/j.chempr.2026.103108","url":null,"abstract":"<div><div>Milad Abolhasani is the Dr. R.J. Polge Professor and a university faculty scholar in the Department of Chemical and Biomolecular Engineering at North Carolina State University, where he serves as director of accelerated technologies within the Integrative Sciences Initiative. He received his PhD from the University of Toronto and completed postdoctoral training at the Massachusetts Institute of Technology. His research focuses on integrating flow chemistry, robotics, automation, and artificial intelligence to develop self-driving laboratories for the accelerated discovery, development, and manufacturing of materials and molecules. He has received honors including the NSF CAREER Award, AIChE Colburn Award, Dreyfus Machine Learning Award, and ACS Sustainable Chemistry &amp; Engineering Lectureship Award.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103108"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148624234","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
Chem at 10: Jihye Park 10点化学课:济惠公园
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 DOI: 10.1016/j.chempr.2026.103144
Jihye Park
{"title":"Chem at 10: Jihye Park","authors":"Jihye Park","doi":"10.1016/j.chempr.2026.103144","DOIUrl":"10.1016/j.chempr.2026.103144","url":null,"abstract":"<div><div>At the University of Minnesota, Dr. Jihye Park runs a materials chemistry lab centered on metal-organic frameworks (MOFs) and the untapped potential of organic linker design. In this interview with <em>Chem</em>, she reflects on her journey into MOF chemistry, what she has learned about mentoring students, and the value of embracing unexpected outcomes in research.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103144"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718574","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
Chem at 10: Guangbin Dong 化学10点:董广斌
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 DOI: 10.1016/j.chempr.2026.103156
Guangbin Dong
{"title":"Chem at 10: Guangbin Dong","authors":"Guangbin Dong","doi":"10.1016/j.chempr.2026.103156","DOIUrl":"10.1016/j.chempr.2026.103156","url":null,"abstract":"<div><div>In this interview with <em>Chem</em>, Prof. Guangbin Dong describes the non-scientific conversations he enjoys, offers advice to young scientists, and shares key aspects of his approach to mentorship. He also presents his perspective on exciting developments in synthetic chemistry, the impact of AI on scholarly publishing, and his overall experience with <em>Chem</em>.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103156"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718851","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
Fabrication of corrugated halogen 2D metal-organic frameworks by means of F···Au coordination 利用F···Au配位制备波纹卤素二维金属有机骨架
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-03-26 DOI: 10.1016/j.chempr.2026.102967
Jorge Labella, Adriana E. Candia, Jonas Björk, Tomás Torres, Jorge Lobo-Checa
{"title":"Fabrication of corrugated halogen 2D metal-organic frameworks by means of F···Au coordination","authors":"Jorge Labella,&nbsp;Adriana E. Candia,&nbsp;Jonas Björk,&nbsp;Tomás Torres,&nbsp;Jorge Lobo-Checa","doi":"10.1016/j.chempr.2026.102967","DOIUrl":"10.1016/j.chempr.2026.102967","url":null,"abstract":"<div><div>Halogens have generally been discarded in the design of two-dimensional metal-organic frameworks (2D MOFs) due to their weak coordination ability. Here, this gap is closed by depositing bowl-shaped molecules on Au(111) under ultra-high-vacuum conditions to produce a monodomain, extended, and periodic halogen 2D MOF. By means of high-resolution scanning tunneling microscopy, two distinct molecular arrangements formed at room temperature are disclosed, the first revealing a compact phase (kinetic product) and the second forming a porous, chiral phase comprising hexameric units via F···Au coordination (thermodynamic product). Notably, annealing to 470 K yields an ordered 2D MOF, in which native Au adatoms coordinate with six fluorine atoms. Bond-resolved atomic force microscopy confirms a non-planar geometry induced by the bowl-shaped precursors. Despite this corrugation and unconventional coordination, scanning tunneling spectroscopy and theoretical calculations reveal electronic conjugation. Altogether, this work introduces new concepts for the design of non-planar yet electronically conjugated 2D nanostructures.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 102967"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147524524","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
Reimagining amine chemistry 重新构想胺化学
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 DOI: 10.1016/j.chempr.2026.103202
Xiaheng Zhang
{"title":"Reimagining amine chemistry","authors":"Xiaheng Zhang","doi":"10.1016/j.chempr.2026.103202","DOIUrl":"10.1016/j.chempr.2026.103202","url":null,"abstract":"<div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (321KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span>Xiaheng Zhang completed his undergraduate degree in chemistry at Sichuan University in 2009, then his PhD in organic chemistry at Shanghai Institute of Organic Chemistry in 2015 under the supervision of Professor Biao Yu, focusing on the total synthesis of the complex oligosaccharides. From 2015 to 2020, he conducted postdoctoral research at Princeton University under the mentorship of Professor David MacMillan, working on the development of novel cross-coupling methodologies. In early 2021, he started his independent career at Fudan University. In the same year, he moved to Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, as a research group leader. His current research interests focus on the development of novel synthetic methodologies, with an emphasis on the efficient transformation of carbon–nitrogen bonds in amines.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103202"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718569","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
Site-specific integration of reversibly taggable furylalanine into nonribosomal peptides 可逆标记糠丙氨酸与非核糖体肽的位点特异性整合
IF 19.1 1区 化学
Chem Pub Date : 2026-08-13 Epub Date: 2026-04-20 DOI: 10.1016/j.chempr.2026.103034
Friedrich J. Ehinger, Alexander Hoff, Maximilian Müll, Ingrid Richter, Benjamin Bartels, Annika Blum, Maria Hoernke, Hajo Kries, Christian Hertweck
{"title":"Site-specific integration of reversibly taggable furylalanine into nonribosomal peptides","authors":"Friedrich J. Ehinger,&nbsp;Alexander Hoff,&nbsp;Maximilian Müll,&nbsp;Ingrid Richter,&nbsp;Benjamin Bartels,&nbsp;Annika Blum,&nbsp;Maria Hoernke,&nbsp;Hajo Kries,&nbsp;Christian Hertweck","doi":"10.1016/j.chempr.2026.103034","DOIUrl":"10.1016/j.chempr.2026.103034","url":null,"abstract":"<div><div>Diverse chemical biology applications, including targeted drug delivery and fluorescent labeling, rely on the site-selective functionalization of peptides. Nonribosomal peptide synthetases (NRPSs) install reactive building blocks directly into bioactive scaffolds, but current methods rely on externally supplied substrates and irreversible conjugation reactions. Here, we establish an integrated system for the <em>de novo</em> biosynthesis of nonribosomal peptides bearing the Diels-Alder (DA)-reactive amino acid 3-furylalanine (Fua). Rational engineering revealed mutations that switched specificity from phenylalanine to Fua across adenylation (A) domains. In a full assembly line context, the engineered gramicidin S synthetase site-specifically recruited biosynthetically provided Fua, forming Fua-modified gramicidin S. This analog exhibits enhanced antibacterial potency and reduced hemolytic activity. As intended, the Fua residue enabled DA-mediated fluorescent labeling of peptides integrated into cell membranes. This work introduces a <em>de novo</em> biosynthesis strategy of reversibly taggable natural products, expanding the interface between biosynthetic pathway engineering and bioorthogonal chemistry.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 8","pages":"Article 103034"},"PeriodicalIF":19.1,"publicationDate":"2026-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718884","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
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