Pub Date : 2025-04-10DOI: 10.1016/j.chempr.2025.102499
Ruyi Zhou , Jicheng Yu , Zhen Gu
Disrupting redox homeostasis in cancer cells represents a promising strategy for minimizing toxicity and improving chemotherapy outcomes. In Cell Biomaterials, Chen, Ma, and colleagues describe an approach that employs a selenium electrophilic center with rapid electron-shuttle properties to boost mitochondrial electron leakage and thus convert antioxidants into pro-oxidants for cancer therapy.
{"title":"Electrophilic selenium drives electron leakage","authors":"Ruyi Zhou , Jicheng Yu , Zhen Gu","doi":"10.1016/j.chempr.2025.102499","DOIUrl":"10.1016/j.chempr.2025.102499","url":null,"abstract":"<div><div>Disrupting redox homeostasis in cancer cells represents a promising strategy for minimizing toxicity and improving chemotherapy outcomes. In <em>Cell Biomaterials</em>, Chen, Ma, and colleagues describe an approach that employs a selenium electrophilic center with rapid electron-shuttle properties to boost mitochondrial electron leakage and thus convert antioxidants into pro-oxidants for cancer therapy.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102499"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635553","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 : 2025-04-10DOI: 10.1016/j.chempr.2024.10.026
Can Liu , Yan Zhang , Rui Shang
Phenolates are increasingly studied as photocatalysts because of their abundance and easy accessibility. However, their potential as potent and broadly applicable reducing photoredox catalysts is hindered by the high electronegativity of oxygen and the reactivity of phenoxy radicals. Herein, we discovered that renowned 1,1′-Bi-2-naphtholate derivatives (BINOLates) are potent reducing photocatalysts. These catalysts are effective for the activation of inert bonds and the reduction of unsaturated bonds, including selective CF activation of activated –CF3,–CF2H, –C2F5, and aryl fluoride, activation of alkyl and aryl chlorides, detosylation, Birch reduction, and alkene reduction, demonstrating potent reducing ability and catalytic versatility. Defluoroalkylation using PhCF3 as a limiting reagent, a challenging substrate for reported catalysts, proceeded smoothly. BINOLates were applicable as photoredox catalysts even under green light. This work introduces a new catalytic application for the renowned BINOLates, suggesting the potential for future expansion of their applications in the realm of photocatalysis.
{"title":"BINOLates as potent reducing photocatalysts for inert-bond activation and reduction of unsaturated systems","authors":"Can Liu , Yan Zhang , Rui Shang","doi":"10.1016/j.chempr.2024.10.026","DOIUrl":"10.1016/j.chempr.2024.10.026","url":null,"abstract":"<div><div>Phenolates are increasingly studied as photocatalysts because of their abundance and easy accessibility. However, their potential as potent and broadly applicable reducing photoredox catalysts is hindered by the high electronegativity of oxygen and the reactivity of phenoxy radicals. Herein, we discovered that renowned 1,1′-Bi-2-naphtholate derivatives (BINOLates) are potent reducing photocatalysts. These catalysts are effective for the activation of inert bonds and the reduction of unsaturated bonds, including selective CF activation of activated –CF<sub>3</sub>,–CF<sub>2</sub>H, –C<sub>2</sub>F<sub>5</sub>, and aryl fluoride, activation of alkyl and aryl chlorides, detosylation, Birch reduction, and alkene reduction, demonstrating potent reducing ability and catalytic versatility. Defluoroalkylation using PhCF<sub>3</sub> as a limiting reagent, a challenging substrate for reported catalysts, proceeded smoothly. BINOLates were applicable as photoredox catalysts even under green light. This work introduces a new catalytic application for the renowned BINOLates, suggesting the potential for future expansion of their applications in the realm of photocatalysis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102359"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805258","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 : 2025-04-10DOI: 10.1016/j.chempr.2025.102540
Nicholas Ballard , Haritz Sardon
As the recycling of polymer materials becomes a topic of growing societal importance, there is a need to develop robust methods for dealing with plastic waste. In a recent article in Science, Anastasaki and co-workers report a route for the efficient chemical recycling of commercial polymethacrylates via low-temperature depolymerization using visible light.
{"title":"Depolymerizing off-the-shelf polymethacrylates with visible light","authors":"Nicholas Ballard , Haritz Sardon","doi":"10.1016/j.chempr.2025.102540","DOIUrl":"10.1016/j.chempr.2025.102540","url":null,"abstract":"<div><div>As the recycling of polymer materials becomes a topic of growing societal importance, there is a need to develop robust methods for dealing with plastic waste. In a recent article in <em>Science</em>, Anastasaki and co-workers report a route for the efficient chemical recycling of commercial polymethacrylates via low-temperature depolymerization using visible light.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102540"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703516","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 : 2025-04-10DOI: 10.1016/j.chempr.2024.11.014
Johannes Hahmann , Boris N. Schüpp , Aman Ishaqat , Arjuna Selvakumar , Robert Göstl , Frauke Gräter , Andreas Herrmann
Nucleic acids, such as DNA, are integral components of biological systems in that they steer many cellular processes and biotechnological applications. In addition, their monomer-precise sequence and accurately predictable structure render them an excellent model for exploring fundamental problems in nanotechnology and polymer science. In the field of polymer mechanochemistry, predetermined breaking points, called mechanophores, are used to endow macromolecules with chain-scission selectivity when subjected to external forces. However, this approach entails cumbersome chemical synthesis and limited outcome analysis. Here, we show the mechanophore-free, near-nucleotide-precise scission of nicked double-stranded DNA in a combined experimental and computational approach. We leverage next-generation sequencing to achieve monomer-level precision in assessing chain scission. Additionally, we monitor and control the scission distribution on the polymer’s backbone. Our research highlights the potential of DNA as a model polymer in the field of polymer mechanochemistry.
{"title":"Sequence-specific, mechanophore-free mechanochemistry of DNA","authors":"Johannes Hahmann , Boris N. Schüpp , Aman Ishaqat , Arjuna Selvakumar , Robert Göstl , Frauke Gräter , Andreas Herrmann","doi":"10.1016/j.chempr.2024.11.014","DOIUrl":"10.1016/j.chempr.2024.11.014","url":null,"abstract":"<div><div>Nucleic acids, such as DNA, are integral components of biological systems in that they steer many cellular processes and biotechnological applications. In addition, their monomer-precise sequence and accurately predictable structure render them an excellent model for exploring fundamental problems in nanotechnology and polymer science. In the field of polymer mechanochemistry, predetermined breaking points, called mechanophores, are used to endow macromolecules with chain-scission selectivity when subjected to external forces. However, this approach entails cumbersome chemical synthesis and limited outcome analysis. Here, we show the mechanophore-free, near-nucleotide-precise scission of nicked double-stranded DNA in a combined experimental and computational approach. We leverage next-generation sequencing to achieve monomer-level precision in assessing chain scission. Additionally, we monitor and control the scission distribution on the polymer’s backbone. Our research highlights the potential of DNA as a model polymer in the field of polymer mechanochemistry.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102376"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912261","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 : 2025-04-10DOI: 10.1016/j.chempr.2024.11.015
Sheng-Yi Yang , Cheng Liu , Fei Wang , Ben Zhong Tang
In this issue of Chem, Jiang and colleagues utilized a spiro-fluorene unit as a π-bridge to construct a series of π-stacked multi-resonance thermally activated delayed fluorescence emitters. By introducing different heavy atoms through chemical bonding, they revealed the impact of the intramolecular through-space heavy-atom effect on the optoelectronic properties of the molecules.
{"title":"Intramolecular through-space heavy-atom effect in π-stacked MR-TADF emitters","authors":"Sheng-Yi Yang , Cheng Liu , Fei Wang , Ben Zhong Tang","doi":"10.1016/j.chempr.2024.11.015","DOIUrl":"10.1016/j.chempr.2024.11.015","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Jiang and colleagues utilized a spiro-fluorene unit as a π-bridge to construct a series of π-stacked multi-resonance thermally activated delayed fluorescence emitters. By introducing different heavy atoms through chemical bonding, they revealed the impact of the intramolecular through-space heavy-atom effect on the optoelectronic properties of the molecules.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102377"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608742","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 : 2025-04-10DOI: 10.1016/j.chempr.2025.102536
Chang Long (隆昶) , Zhiyong Tang (唐智勇)
In this issue of Chem, Strasser and co-workers introduce an electrolyte design that leverages the alkali-metal enhancement effect for the sustainable electrosynthesis of H2O2 from oxygen. This little electrolyte alteration, combined with a cost-effective commercial carbon-based gas-diffusion electrode, represents a significant advancement toward the green production of H2O2.
{"title":"Electrolyte: The cornerstone of commercializing the electrosynthesis of H2O2","authors":"Chang Long (隆昶) , Zhiyong Tang (唐智勇)","doi":"10.1016/j.chempr.2025.102536","DOIUrl":"10.1016/j.chempr.2025.102536","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Strasser and co-workers introduce an electrolyte design that leverages the alkali-metal enhancement effect for the sustainable electrosynthesis of H<sub>2</sub>O<sub>2</sub> from oxygen. This little electrolyte alteration, combined with a cost-effective commercial carbon-based gas-diffusion electrode, represents a significant advancement toward the green production of H<sub>2</sub>O<sub>2</sub>.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102536"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695861","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 : 2025-04-10DOI: 10.1016/j.chempr.2025.102535
Alexander J. Norquist
In this issue of Chem, Harel and co-workers report a chemical-space-property descriptor model capable of predicting chemical compositions of metal halide perovskites by using fast optical analyses. This model is designed to enable facile monitoring of chemical composition and assessment of material properties in industrial-scale syntheses.
{"title":"Flipping the script: Predicting chemical composition in metal-halide perovskites from optical spectroscopy","authors":"Alexander J. Norquist","doi":"10.1016/j.chempr.2025.102535","DOIUrl":"10.1016/j.chempr.2025.102535","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Harel and co-workers report a chemical-space-property descriptor model capable of predicting chemical compositions of metal halide perovskites by using fast optical analyses. This model is designed to enable facile monitoring of chemical composition and assessment of material properties in industrial-scale syntheses.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102535"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713535","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 : 2025-04-10DOI: 10.1016/j.chempr.2025.102502
Sophie R. Thomas, Nina Willnhammer, Angela Casini, Guillermo Moreno-Alcántar
Metallacages (MCgs) are three-dimensional (3D)-supramolecular coordination complexes (SCCs) obtained by the self-assembly of metal ions with donor ligands, which are arranged to delimit a cavity. Recently, the number of structural studies using gold ions in the construction of metallacages and the first efforts to design these systems for diverse applications have shed light on the potential of gold MCgs to become useful supramolecular systems in sensing and separation, catalysis, and medicine. This work critically revises the design principles of gold MCgs and their early applications, highlighting the main challenges and opportunities for developing functional assemblies.
{"title":"Gold metallacages: Design principles and applications","authors":"Sophie R. Thomas, Nina Willnhammer, Angela Casini, Guillermo Moreno-Alcántar","doi":"10.1016/j.chempr.2025.102502","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102502","url":null,"abstract":"Metallacages (MCgs) are three-dimensional (3D)-supramolecular coordination complexes (SCCs) obtained by the self-assembly of metal ions with donor ligands, which are arranged to delimit a cavity. Recently, the number of structural studies using gold ions in the construction of metallacages and the first efforts to design these systems for diverse applications have shed light on the potential of gold MCgs to become useful supramolecular systems in sensing and separation, catalysis, and medicine. This work critically revises the design principles of gold MCgs and their early applications, highlighting the main challenges and opportunities for developing functional assemblies.","PeriodicalId":268,"journal":{"name":"Chem","volume":"183 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143814148","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}
Lead-halide perovskites exhibit highly tunable optical properties, making them suitable for applications in photovoltaics and optoelectronics. Although considerable effort has gone into the development of methods that accurately predict the optical properties of perovskite materials based on structure, the reverse—predicting composition from optical data—is far less explored. In this study, high-throughput approaches were employed to synthesize and spectroscopically analyze a wide array of perovskites composed of mono-halide, di-halide, and tri-halides with a general formula, MAxCs1−xPb(ClxBryI1−x−y)3. The spectroscopic data were used to train an artificial neural network (ANN)-based chemical space-property predictor model designed to work with multiple responses and multiple predictors. The model predicted the chemical composition of perovskites from terahertz (THz) Raman spectroscopic data with approximately 85% accuracy. When the dataset also incorporated UV-visible spectroscopic data, the accuracy increased to nearly 92%. This study opens the possibility of real-time monitoring and defect detection, degradation analysis, and streamlined material selection and optimization of perovskite materials in industrial production.
{"title":"Chemical space-property predictor model of perovskite materials by high-throughput synthesis and artificial neural networks","authors":"Md. Ataur Rahman , Md. Shahjahan , Yaqing Zhang , Rihan Wu , Elad Harel","doi":"10.1016/j.chempr.2024.10.027","DOIUrl":"10.1016/j.chempr.2024.10.027","url":null,"abstract":"<div><div>Lead-halide perovskites exhibit highly tunable optical properties, making them suitable for applications in photovoltaics and optoelectronics. Although considerable effort has gone into the development of methods that accurately predict the optical properties of perovskite materials based on structure, the reverse—predicting composition from optical data—is far less explored. In this study, high-throughput approaches were employed to synthesize and spectroscopically analyze a wide array of perovskites composed of mono-halide, di-halide, and tri-halides with a general formula, MA<sub>x</sub>Cs<sub>1−x</sub>Pb(Cl<sub>x</sub>Br<sub>y</sub>I<sub>1−x−y</sub>)<sub>3</sub>. The spectroscopic data were used to train an artificial neural network (ANN)-based chemical space-property predictor model designed to work with multiple responses and multiple predictors. The model predicted the chemical composition of perovskites from terahertz (THz) Raman spectroscopic data with approximately 85% accuracy. When the dataset also incorporated UV-visible spectroscopic data, the accuracy increased to nearly 92%. This study opens the possibility of real-time monitoring and defect detection, degradation analysis, and streamlined material selection and optimization of perovskite materials in industrial production.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102360"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783066","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 : 2025-04-10DOI: 10.1016/j.chempr.2025.102436
Senfeng Zhao , Qian Chen , Qimanguli Saiding , Soohwan An , Zhuoming Zhou , Na Kong , Yujing J. Heng , Reza Abdi , Wei Tao
Live bacteria-based living materials have gained unprecedented attention in the biomedical landscape due to their natural host compatibility and unique dynamic accommodation. In recent decades, the strategic application of live bacteria has yielded revolutionary biomedical outcomes that standardized methods cannot achieve. However, misusing live bacteria may lead to infections, toxicity, or even biochemical dangers for patients. Fortunately, bacteria’s nature as single-celled organisms with relatively well-defined chemical compositions is advantageous. Leveraging our deep understanding of live bacterial chemistry and using chemical tools for management allows us to customize live bacterial behaviors and functions on demand. In this perspective, we will summarize the programmable chemical sites on live bacteria and the potential physical, chemical, or biological functions achievable through chemical engineering. We will focus on chemical approaches to live bacteria-based biomedicine to discuss and highlight how a more defined application of engineered live bacteria concepts could accelerate future clinical transformation.
{"title":"Live bacterial chemistry in biomedicine","authors":"Senfeng Zhao , Qian Chen , Qimanguli Saiding , Soohwan An , Zhuoming Zhou , Na Kong , Yujing J. Heng , Reza Abdi , Wei Tao","doi":"10.1016/j.chempr.2025.102436","DOIUrl":"10.1016/j.chempr.2025.102436","url":null,"abstract":"<div><div>Live bacteria-based living materials have gained unprecedented attention in the biomedical landscape due to their natural host compatibility and unique dynamic accommodation. In recent decades, the strategic application of live bacteria has yielded revolutionary biomedical outcomes that standardized methods cannot achieve. However, misusing live bacteria may lead to infections, toxicity, or even biochemical dangers for patients. Fortunately, bacteria’s nature as single-celled organisms with relatively well-defined chemical compositions is advantageous. Leveraging our deep understanding of live bacterial chemistry and using chemical tools for management allows us to customize live bacterial behaviors and functions on demand. In this perspective, we will summarize the programmable chemical sites on live bacteria and the potential physical, chemical, or biological functions achievable through chemical engineering. We will focus on chemical approaches to live bacteria-based biomedicine to discuss and highlight how a more defined application of engineered live bacteria concepts could accelerate future clinical transformation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 4","pages":"Article 102436"},"PeriodicalIF":19.1,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776225","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}
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