ChemPub Date : 2025-10-08DOI: 10.1016/j.chempr.2025.102758
Asmaa Jrad, Bikash Garai, Samer Aouad, Gobinda Das, Connor M. Duncan, Mark A. Olson, Ali Trabolsi
{"title":"Redefining forever: Advancements, challenges, and opportunities in covalent organic frameworks for the remediation of forever chemicals","authors":"Asmaa Jrad, Bikash Garai, Samer Aouad, Gobinda Das, Connor M. Duncan, Mark A. Olson, Ali Trabolsi","doi":"10.1016/j.chempr.2025.102758","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102758","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS), known as “forever chemicals,” are persistent pollutants with serious environmental and health impacts. Conventional water treatment methods often fall short of removing PFAS, prompting interest in advanced adsorbents such as covalent organic frameworks (COFs). This review explores recent advances in the development of COFs tailored for PFAS removal. The discussion focuses on key adsorption mechanisms, including hydrophobic, fluorophilic, electrostatic, and hydrogen-bonding interactions. In addition, optimizing pore size and particle size to improve the adsorption of PFAS is highlighted. The potential of COFs for practical applications is evaluated through their integration into composites, membranes, and adsorption columns, which enable continuous flow treatment. Despite promising results, challenges remain, including scalability, synthesis complexity, and realistic testing at environmentally relevant PFAS concentrations. The outline of future research directions aims to drive the advancement of COF-based solutions that have the potential to revolutionize PFAS remediation in real-world applications.","PeriodicalId":268,"journal":{"name":"Chem","volume":"349 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241672","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 : 2025-10-08DOI: 10.1016/j.chempr.2025.102752
Maurice P. Biedermann, Athanasios Markos, Ian Warm, Adeline Schmitt, Johannes Heimgärtner, Kathrin Lang, Helma Wennemers
{"title":"The AMI-isonitrile ligation 2.0: Fast, selective, and pH sensitive","authors":"Maurice P. Biedermann, Athanasios Markos, Ian Warm, Adeline Schmitt, Johannes Heimgärtner, Kathrin Lang, Helma Wennemers","doi":"10.1016/j.chempr.2025.102752","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102752","url":null,"abstract":"The bioorthogonal ligation between isonitriles and azomethine imines (AMIs)—the AMI-isonitrile ligation—combines exquisite chemoselectivity with a stable ligation product, a small molecular reporter, and a pH-dependent rate. In this work, we tailored the modular structure of the dipolar AMI to increase Brønsted basicity and electrophilicity. These additive structural modifications increased the ligation rate by more than two orders of magnitude to 14 M<sup>−1</sup>s<sup>−1</sup> at pH 7, 140 M<sup>−1</sup>s<sup>−1</sup> at pH 6, and >1,000 M<sup>−1</sup>s<sup>−1</sup> at pH 5. The faster reaction rate at lower pH values allowed for the preferential labeling of live cells at acidic versus neutral pH. This environmental sensitivity paves the way for <em>in vivo</em> targeting of acidic milieus, such as tumors.","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241787","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":"Nickel-embedded covalent organic frameworks for dual photocatalytic hydrogen evolution and cross-coupling catalysis","authors":"Swati Jindal, Kuntal Pal, Mostafa Zeama, Partha Maity, Tian Jin, Mickaele Bonneau, Rajesh Kancherla, Omar F. Mohammed, Osama Shekhah, Magnus Rueping, Mohamed Eddaoudi","doi":"10.1016/j.chempr.2025.102751","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102751","url":null,"abstract":"This work reports the design and synthesis of a novel imine-linked 2D covalent organic framework (COF), <strong>TPDA-BiPy-COF</strong>, constructed from [3,3′-bipyridine]-6,6′-dicarboxaldehyde (3,3′-<strong>BiPy</strong>) as an electron acceptor and tetrakis(4-aminophenyl)-1,4-phenylenediamine (<strong>TPDA</strong>) as a donor. The COF features pyridyl-imine linkages, i.e., N<sub>imine</sub>-Ni-N<sub>bipyridine</sub>, with active nitrogen sites that facilitate proton reduction to hydrogen. To improve photocatalytic hydrogen evolution performance, Ni(II) centers were introduced via post-synthetic metalation, forming <strong>TPDA-BiPy@NiX₂</strong> COF (X = Cl, Br). The coordination of Ni(II) with the imine and bipyridine nitrogen atoms enhanced framework planarity and conjugation, thereby boosting photocatalytic activity. Notably, <strong>TPDA-BiPy@Ni(II)</strong> COF achieved an excellent hydrogen evolution rate of 34.13 mmol g⁻¹ h⁻¹ under visible light, without requiring a cocatalyst. Furthermore, the metallaphotoredox activity of TPDA-BiPy@Ni(II) displayed its promise for photocatalyzed C–S cross-coupling reaction. This dual-functional catalyst highlights the advantage of incorporating nickel into COFs, offering a cost-effective and sustainable alternative to noble-metal-based systems for photocatalysis and synthetic transformations.","PeriodicalId":268,"journal":{"name":"Chem","volume":"84 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241673","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 : 2025-10-06DOI: 10.1016/j.chempr.2025.102754
Kinga Gołąbek, Yuchen Chang, Lauren R. Mellinger, Mariana V. Rodrigues, Cauê de Souza Coutinho Nogueira, Fabio B. Passos, Yutao Xing, Aline Ribeiro Passos, Mohammed H. Saffarini, Austin B. Isner, David S. Sholl, Carsten Sievers
{"title":"Spatially resolved reaction environments in mechanochemical upcycling of polymers","authors":"Kinga Gołąbek, Yuchen Chang, Lauren R. Mellinger, Mariana V. Rodrigues, Cauê de Souza Coutinho Nogueira, Fabio B. Passos, Yutao Xing, Aline Ribeiro Passos, Mohammed H. Saffarini, Austin B. Isner, David S. Sholl, Carsten Sievers","doi":"10.1016/j.chempr.2025.102754","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102754","url":null,"abstract":"Mechanochemical processing is an attractive and scalable approach for the upcycling of polymers. The complex and dynamic environment in ball milling, however, makes gaining insight into the physicochemical nature of the collisions driving mechanochemistry challenging, which, in turn, hampers the optimization of these processes. We used controlled single impacts followed by multiple spatially resolved analytical methods (focused ion beam microscopy, Raman spectro-microscopy, and small-angle X-ray scattering) and material point method simulations to gain unprecedented information about mechanochemical depolymerization of poly(ethylene terephthalate). These measurements highlight the contributions of plastic deformation, amorphization, and depolymerization during the transfer of kinetic energy in collisions relevant to ball mills and will enable reactor models based on fundamental kinetics.","PeriodicalId":268,"journal":{"name":"Chem","volume":"31 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229455","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":"Photolysis-generated sulfenylnitrenes enable site-selective nitrogen-atom insertion into N-heterocycles","authors":"Prakash Kafle, Prabhat Kharel, Daniel Nilson, Deacon Herndon, Shuhei Yasuda, Indrajeet Sharma","doi":"10.1016/j.chempr.2025.102753","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102753","url":null,"abstract":"This research delineates a photochemical methodology for generating sulfenylnitrenes from bench-stable precursors via blue-light irradiation without photosensitizers or additives. The resultant sulfenylnitrenes facilitate chemo- and site-selective incorporation of nitrogen atoms into <em>N</em>-heterocycles under mild, aqueous conditions. This approach transforms readily accessible pyrroles, indoles, and imidazoles into synthetically challenging pyrimidines, quinazolines, and triazines with high regioselectivity. Mechanistic investigations and density functional theory calculations provide insight into the origins of the observed regioselectivity. The reaction is compatible with a variety of oxidation-sensitive functional groups. It applies to the late-stage functionalization of bioactive molecules, including natural products, amino acids, <em>C</em>-glycosides, <em>N</em>-nucleosides, and pharmaceuticals. The operational simplicity, functional group tolerance, and extensive substrate scope emphasize the utility of this methodology and augment the repertoire of blue-light-mediated transformations, thereby contributing to the exploration of new chemical space for applications in medicinal chemistry and drug discovery.","PeriodicalId":268,"journal":{"name":"Chem","volume":"17 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209870","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 : 2025-10-03DOI: 10.1016/j.chempr.2025.102742
Joaquin Baixeras Buye, James M. Gallagher, David A. Leigh
{"title":"Structure-performance relationships for catalysis-driven molecular machinery","authors":"Joaquin Baixeras Buye, James M. Gallagher, David A. Leigh","doi":"10.1016/j.chempr.2025.102742","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102742","url":null,"abstract":"Chemically fueled molecular motors are key to life’s most fundamental processes. In recent years, theoretical and experimental insights garnered from chemistry, biology, and physics have led to an understanding of the molecular basis of catalysis-driven motor mechanisms. Unlike their biological counterparts, for which evolutionary baggage and complexity often preclude a complete untangling of the reasons behind particular aspects of their mechanisms, artificial small-molecule motors operate with mechanisms that are entirely knowable. Here, we outline how key performance indicators, such as speed, stalling force, and fuel efficiency, are related to distinct structural and mechanistic features, contextualizing the analysis with both biological and small-molecule examples. These provide rational design principles for functional chemically fueled molecular machinery and benchmarking comparisons with biomolecular machinery. We have made available as a Jupyter notebook an interactive visualization tool that highlights how the key performance indicators change and depend upon the underlying kinetics of chemical fueling: <span><span>https://github.com/JoaquinBaixerasBuye/Performance-Characteristics-of-Motors</span><svg aria-label=\"Opens in new window\" focusable=\"false\" height=\"20\" viewbox=\"0 0 8 8\"><path d=\"M1.12949 2.1072V1H7V6.85795H5.89111V2.90281L0.784057 8L0 7.21635L5.11902 2.1072H1.12949Z\"></path></svg></span>.","PeriodicalId":268,"journal":{"name":"Chem","volume":"99 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209869","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 : 2025-10-01DOI: 10.1016/j.chempr.2025.102750
Jiamin Ye, Yueyue Fan, Gaoli Niu, Yong Kang, Jiacheng Shi, Ruiyan Li, Yiwen Yang, Xiaoyuan Ji
{"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}
ChemPub Date : 2025-09-26DOI: 10.1016/j.chempr.2025.102783
Merve Temel, Stefano Crespi
{"title":"Lighting up dark reactions: An imine network ratchets a coupled equilibrium","authors":"Merve Temel, Stefano Crespi","doi":"10.1016/j.chempr.2025.102783","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102783","url":null,"abstract":"In this issue of <em>Chem</em>, Wu and Greenfield demonstrate how a light-fueled information ratchet in a photoswitchable imine pair shifts the composition of free amines to drive a non-photoresponsive transimination out of equilibrium. The ratchet thus establishes a nonequilibrium steady state in homogeneous solution and provides a blueprint for light-controlled reaction cascades.","PeriodicalId":268,"journal":{"name":"Chem","volume":"60 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141060","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 : 2025-09-26DOI: 10.1016/j.chempr.2025.102743
Jiahan Zhao, Bin Qin, Zhenghan Zhang, Siqi Zhu, Guangjun Wu, Jian Li, Yuchao Chai, Landong Li
{"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}
{"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}