Vacancies, which inevitably exist in all solids, influence numerous atomic behaviors and material properties and play a crucial role in both synthesis processes and application performance. In this study, we present a successful approach utilizing the flexible transition between [CoO4] and [CoO6] polyhedra to modulate the oxygen vacancies for further controlling the formation of ruthenate pyrochlores and enhancing the electrocatalytic performance for the oxygen evolution reaction. During the formation of the pyrochlore phase, the incorporation of [CoO4] tetrahedra introduces an inherent oxygen deficiency, accompanied by the beneficial transformation of [CoO4] tetrahedra into [CoO6] octahedra. It kinetically accelerates the diffusive reaction rate constant by 164 times. On the other hand, during the oxygen evolution process by the lattice oxygen mediated mechanism, the flexible transformation between [CoO6] octahedra and [CoO4] tetrahedra in pyrochlores can effectively mitigate lattice distortions and suppress the metal-insulator transition induced by atomic rearrangements, thereby significantly enhancing the service life of this multicomponent electrocatalyst in proton and anion exchange membrane water electrolysis applications.
{"title":"Cobalt-mediated structural transition: facilitating rapid synthesis and enhanced performance of pyrochlore materials for efficient water electrolysis.","authors":"Yanzong Huang, Tongtong Liu, Qingren Zhang, Yanfei Wang, Zhengping Zhang, Feng Wang","doi":"10.1039/d5sc09343k","DOIUrl":"10.1039/d5sc09343k","url":null,"abstract":"<p><p>Vacancies, which inevitably exist in all solids, influence numerous atomic behaviors and material properties and play a crucial role in both synthesis processes and application performance. In this study, we present a successful approach utilizing the flexible transition between [CoO<sub>4</sub>] and [CoO<sub>6</sub>] polyhedra to modulate the oxygen vacancies for further controlling the formation of ruthenate pyrochlores and enhancing the electrocatalytic performance for the oxygen evolution reaction. During the formation of the pyrochlore phase, the incorporation of [CoO<sub>4</sub>] tetrahedra introduces an inherent oxygen deficiency, accompanied by the beneficial transformation of [CoO<sub>4</sub>] tetrahedra into [CoO<sub>6</sub>] octahedra. It kinetically accelerates the diffusive reaction rate constant by 164 times. On the other hand, during the oxygen evolution process by the lattice oxygen mediated mechanism, the flexible transformation between [CoO<sub>6</sub>] octahedra and [CoO<sub>4</sub>] tetrahedra in pyrochlores can effectively mitigate lattice distortions and suppress the metal-insulator transition induced by atomic rearrangements, thereby significantly enhancing the service life of this multicomponent electrocatalyst in proton and anion exchange membrane water electrolysis applications.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12863193/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146112377","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}
Philip Kocheril, Haomin Wang, Ryan Eric Leighton, Dongkwan Lee, Noor Naji, Wei Min, Wei Lu
Single-molecule (SM) optical spectroscopy and imaging approaches have proven transformative, allowing for deep insights into molecular dynamics and behaviour. Despite their intrinsically weaker signals, vibrational spectro-microscopies have advanced significantly within the past decade, allowing for far-field vibrational spectroscopy and imaging at the SM level under ambient conditions. In this Perspective, we first discuss the critical insights and advancements that allowed for SM vibrational spectroscopy and imaging to be realized, highlighting the technical developments that have allowed vibrational spectro-microscopies to break the SM barrier with far-field optics. We then discuss the unique and exciting opportunities of these SM vibrational methods.
{"title":"Far-field single-molecule vibrational spectroscopy and imaging","authors":"Philip Kocheril, Haomin Wang, Ryan Eric Leighton, Dongkwan Lee, Noor Naji, Wei Min, Wei Lu","doi":"10.1039/d5sc07076g","DOIUrl":"https://doi.org/10.1039/d5sc07076g","url":null,"abstract":"Single-molecule (SM) optical spectroscopy and imaging approaches have proven transformative, allowing for deep insights into molecular dynamics and behaviour. Despite their intrinsically weaker signals, vibrational spectro-microscopies have advanced significantly within the past decade, allowing for far-field vibrational spectroscopy and imaging at the SM level under ambient conditions. In this Perspective, we first discuss the critical insights and advancements that allowed for SM vibrational spectroscopy and imaging to be realized, highlighting the technical developments that have allowed vibrational spectro-microscopies to break the SM barrier with far-field optics. We then discuss the unique and exciting opportunities of these SM vibrational methods.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098275","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}
Kazuhide Kamiya, Sora Nakasone, Ryo Kurihara, Asato Inoue, Hazuki Irie, Shoko Nakahata, Yuta Nishina, Satoshi Taniguchi, Thuy Thi Hong Nguyen, Sho Kataoka
The conversion of CO2 into multicarbon (C2+) products via electrochemical reduction is considered a key technology for the sustainable production of fuels and chemicals. The performance of high-rate gaseous CO2 electrolysis is governed by interrelated factors such as the electrocatalysts, electrodes, electrolytes, and cell architectures. Despite the intensive focus on catalyst research, systematic studies addressing the other components remain scarce, leaving critical gaps in our understanding toward achieving higher performance in CO2 electrolysis systems. The nanoscale design of catalyst surface electronic structures and the macroscale design of electrodes and electrolyzer architectures both influence the overall activity of the electrochemical system. In designing macroscale components, it is necessary to establish benchmarks based on a comprehensive evaluation of CO2 emissions for the entire electrolysis process, because these parameters are directly linked to output metrics such as current density and cell voltage under practical operating conditions. This review summarizes recent advances in electrodes and electrolyzers, and through life-cycle assessment (LCA), evaluates key performance indicators (KPIs) for achieving negative emissions and assesses the current technology readiness of CO2 electrolysis.
{"title":"Gaseous CO2 Electrolysis: Latest Advances in Electrode and Electrolyzer Technologies toward Abating CO2 Emissions","authors":"Kazuhide Kamiya, Sora Nakasone, Ryo Kurihara, Asato Inoue, Hazuki Irie, Shoko Nakahata, Yuta Nishina, Satoshi Taniguchi, Thuy Thi Hong Nguyen, Sho Kataoka","doi":"10.1039/d5sc08419a","DOIUrl":"https://doi.org/10.1039/d5sc08419a","url":null,"abstract":"The conversion of CO2 into multicarbon (C2+) products via electrochemical reduction is considered a key technology for the sustainable production of fuels and chemicals. The performance of high-rate gaseous CO2 electrolysis is governed by interrelated factors such as the electrocatalysts, electrodes, electrolytes, and cell architectures. Despite the intensive focus on catalyst research, systematic studies addressing the other components remain scarce, leaving critical gaps in our understanding toward achieving higher performance in CO2 electrolysis systems. The nanoscale design of catalyst surface electronic structures and the macroscale design of electrodes and electrolyzer architectures both influence the overall activity of the electrochemical system. In designing macroscale components, it is necessary to establish benchmarks based on a comprehensive evaluation of CO2 emissions for the entire electrolysis process, because these parameters are directly linked to output metrics such as current density and cell voltage under practical operating conditions. This review summarizes recent advances in electrodes and electrolyzers, and through life-cycle assessment (LCA), evaluates key performance indicators (KPIs) for achieving negative emissions and assesses the current technology readiness of CO2 electrolysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"285 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098281","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}
Diva Froim, Hadar Amartely, Jiantong Dong, Eli Pikarsky, Itamar Willner
Allosteric regulation, the modulation of biological macromolecular function through binding of molecules at distant sites distinct from the active site, is a fundamental principle in biology that governs enzyme activity, signaling, and gene expression. In this work, we present allosteric ligand/aptamer complexes, coupled to biocatalytic reaction modules composed of enzymes, DNAzymes, or transcription machineries, regulating the catalytic and transient functions of these frameworks. This principle is exemplified by the assembly of ligand/aptamer subunits supramolecular complexes that allosterically stabilize the Mg2+-dependent DNAzyme, allowing its ribonucleobase cleavage activity, promoting the formation of transcription templates that yield RNA products, and modulating the assembly of thrombin aptamer subunits that inhibit thrombin-induced coagulation. Specifically, melamine (Mel)/aptamer subunits complexes allosterically stabilize the assembly of Mg2+-dependent DNAzyme strands for substrate cleavage, the formation of thrombin aptamer subunits that inhibit the conversion of fibrinogen to fibrin, and the stabilization of a transcription template encoding the Malachite Green (MG) RNA aptamer. Furthermore, coupling an enzyme that depletes the ligand/aptamer complex, which allosterically stabilizes the biocatalytic reaction module, demonstrates the dissipative and transient operation of the catalytic system. This concept is illustrated by the adenosine (Ade)/aptamer subunits supramolecular complex, which stabilizes thrombin aptamer subunits to inhibit thrombin-induced fibrinogenesis, and promotes the formation of an active transcription template for RNA synthesis. In the presence of adenosine deaminase (ADA), Ade is transformed into inosine, which lacks affinity for the aptamer subunits, thereby degrading the Ade/aptamer assemblies and depleting the allosteric complexes. The temporal disassembly of these allosteric stabilizing complexes leads to the transient inhibition of thrombin-induced coagulation or to the transient operation of a transcription machinery.
{"title":"Allosteric ligand–aptamer complexes orchestrate supramolecular or transient catalytic, transcription and fibrinogenesis processes","authors":"Diva Froim, Hadar Amartely, Jiantong Dong, Eli Pikarsky, Itamar Willner","doi":"10.1039/d5sc09098a","DOIUrl":"https://doi.org/10.1039/d5sc09098a","url":null,"abstract":"Allosteric regulation, the modulation of biological macromolecular function through binding of molecules at distant sites distinct from the active site, is a fundamental principle in biology that governs enzyme activity, signaling, and gene expression. In this work, we present allosteric ligand/aptamer complexes, coupled to biocatalytic reaction modules composed of enzymes, DNAzymes, or transcription machineries, regulating the catalytic and transient functions of these frameworks. This principle is exemplified by the assembly of ligand/aptamer subunits supramolecular complexes that allosterically stabilize the Mg<small><sup>2+</sup></small>-dependent DNAzyme, allowing its ribonucleobase cleavage activity, promoting the formation of transcription templates that yield RNA products, and modulating the assembly of thrombin aptamer subunits that inhibit thrombin-induced coagulation. Specifically, melamine (Mel)/aptamer subunits complexes allosterically stabilize the assembly of Mg<small><sup>2+</sup></small>-dependent DNAzyme strands for substrate cleavage, the formation of thrombin aptamer subunits that inhibit the conversion of fibrinogen to fibrin, and the stabilization of a transcription template encoding the Malachite Green (MG) RNA aptamer. Furthermore, coupling an enzyme that depletes the ligand/aptamer complex, which allosterically stabilizes the biocatalytic reaction module, demonstrates the dissipative and transient operation of the catalytic system. This concept is illustrated by the adenosine (Ade)/aptamer subunits supramolecular complex, which stabilizes thrombin aptamer subunits to inhibit thrombin-induced fibrinogenesis, and promotes the formation of an active transcription template for RNA synthesis. In the presence of adenosine deaminase (ADA), Ade is transformed into inosine, which lacks affinity for the aptamer subunits, thereby degrading the Ade/aptamer assemblies and depleting the allosteric complexes. The temporal disassembly of these allosteric stabilizing complexes leads to the transient inhibition of thrombin-induced coagulation or to the transient operation of a transcription machinery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098276","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}
Zinc complexes are attractive candidates for photofunctional materials owing to the low cost and benign nature of Zn, yet directly engaging Zn orbitals in visible-light responses has remained elusive in mononuclear systems. Here, we realize this by engineering an empty C–Zn π orbital as the LUMO in carbene–zincafluorene frameworks, as demonstrated in three newly designed mononuclear Zn complexes. Selective recrystallization of one complex afforded two conformational polymorphs, enabling us to establish a clear correlation among carbene–zincafluorene coplanarity, formation of the empty C–Zn π orbital, LUMO lowering, and visible-light absorption. Natural atomic orbital analyses of the complexes indicate that tuning the carbene scaffold improves C(2p)/Zn(4p) energy-level matching and thereby increases Zn(4p) participation in the LUMO. Additionally, one complex exhibits bright room-temperature phosphorescence in the solid state with a PL quantum yield of 21% and an emission lifetime of 2.0 ms; theoretical calculations including spin–orbit coupling identify the Zn center as a key contributor to the emission. As a proof-of-concept for visible-light responsive photofunctional application, the same complex catalyzes stilbene isomerization under blue-LED irradiation. These results highlight the non-innocent role of Zn in visible-light responses and pave the way toward photoactive mononuclear Zn complexes.
{"title":"Zincafluorene complex with an empty C–Zn π orbital that captures visible light","authors":"Hidemitsu Iwamoto, Yusuke Sunada, Yoshimasa Wada","doi":"10.1039/d5sc09340f","DOIUrl":"https://doi.org/10.1039/d5sc09340f","url":null,"abstract":"Zinc complexes are attractive candidates for photofunctional materials owing to the low cost and benign nature of Zn, yet directly engaging Zn orbitals in visible-light responses has remained elusive in mononuclear systems. Here, we realize this by engineering an empty C–Zn π orbital as the LUMO in carbene–zincafluorene frameworks, as demonstrated in three newly designed mononuclear Zn complexes. Selective recrystallization of one complex afforded two conformational polymorphs, enabling us to establish a clear correlation among carbene–zincafluorene coplanarity, formation of the empty C–Zn π orbital, LUMO lowering, and visible-light absorption. Natural atomic orbital analyses of the complexes indicate that tuning the carbene scaffold improves C(2p)/Zn(4p) energy-level matching and thereby increases Zn(4p) participation in the LUMO. Additionally, one complex exhibits bright room-temperature phosphorescence in the solid state with a PL quantum yield of 21% and an emission lifetime of 2.0 ms; theoretical calculations including spin–orbit coupling identify the Zn center as a key contributor to the emission. As a proof-of-concept for visible-light responsive photofunctional application, the same complex catalyzes stilbene isomerization under blue-LED irradiation. These results highlight the non-innocent role of Zn in visible-light responses and pave the way toward photoactive mononuclear Zn complexes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"67 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098308","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}
Zhi-Xiang Wang, Chun-Li Hu, Chuan-Fu Sun, Jiang-Gao Mao, Fang Kong
The design and synthesis of new ultraviolet nonlinear optical (NLO) materials is challenging due to the constraint relationship between their NLO efficiency and optical bandgap. By functional group modulation strategy, the π-conjugated organic cations and the distorted [SbF4]- anions have been assembled in both antiparallel and parallel arrangement modes, resulting in two new organic-inorganic hybrid fluoroantimonites, namely, centrosymmetric (C4H8N5)(SbF4) and polar (C4H7N4O)(SbF4). The polar (C4H7N4O)(SbF4) demonstrates an excellent comprehensive property, including a strong SHG effect (4.2 × KDP), a wide bandgap (4.40 eV) and a short phase matchable wavelength (248 nm). This SHG intensity is the largest among the organic-inorganic hybrid perfluoroantimonites with the optical band gap > 4.20 eV. The SHG density calculation indicated that the NLO performance of (C4H7N4O)(SbF4) mainly comes from the parallel-arranged organic groups, with its contribution accounting for 89.49%. This work proved that the arrangement of π-conjugated organic ligands can be modulated to a parallel mode by adjusting the number of hydrogen bond donors. Combined with a wide HOMO-LUMO gap, the functional group modulation method is an effective strategy for designing and synthesizing ultraviolet NLO materials.
{"title":"From Centrosymmetric (C4H8N5)(SbF4) to Polar (C4H7N4O)(SbF4): A New UV Nonlinear Optical Material Achieved by Functional Group Modulation","authors":"Zhi-Xiang Wang, Chun-Li Hu, Chuan-Fu Sun, Jiang-Gao Mao, Fang Kong","doi":"10.1039/d5sc09256f","DOIUrl":"https://doi.org/10.1039/d5sc09256f","url":null,"abstract":"The design and synthesis of new ultraviolet nonlinear optical (NLO) materials is challenging due to the constraint relationship between their NLO efficiency and optical bandgap. By functional group modulation strategy, the π-conjugated organic cations and the distorted [SbF4]- anions have been assembled in both antiparallel and parallel arrangement modes, resulting in two new organic-inorganic hybrid fluoroantimonites, namely, centrosymmetric (C4H8N5)(SbF4) and polar (C4H7N4O)(SbF4). The polar (C4H7N4O)(SbF4) demonstrates an excellent comprehensive property, including a strong SHG effect (4.2 × KDP), a wide bandgap (4.40 eV) and a short phase matchable wavelength (248 nm). This SHG intensity is the largest among the organic-inorganic hybrid perfluoroantimonites with the optical band gap > 4.20 eV. The SHG density calculation indicated that the NLO performance of (C4H7N4O)(SbF4) mainly comes from the parallel-arranged organic groups, with its contribution accounting for 89.49%. This work proved that the arrangement of π-conjugated organic ligands can be modulated to a parallel mode by adjusting the number of hydrogen bond donors. Combined with a wide HOMO-LUMO gap, the functional group modulation method is an effective strategy for designing and synthesizing ultraviolet NLO materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098279","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}
Screening small-molecule drugs to suppress both protein aggregation and reactive oxygen species (ROS) generation is critical for developing therapies for neurodegenerative diseases (NDs). However, existing methods are limited to characterizing only a single pathological feature (either aggregation or ROS) in a single measurement. Herein, taking α-synuclein (α-Syn) as the template protein, we developed a dual-mode electrochemical sensing platform for concurrently monitoring protein aggregation and ROS generation characteristics. A gold electrode functionalized with α-Syn via self-assembled monolayers (SAMs) was constructed as the sensing platform, realizing both ordered α-Syn immobilization and monitoring of metal ion (e.g., Cu(II))-driven aggregation. This was accomplished by synchronously recording the electrochemiluminescence (ECL) and cyclic voltammetry (CV) dual-responses of the tris(2,2'-bipyridine) ruthenium(II) (Ru(bpy)32+) reporter in a single integrated assay. The catalysis of DNA oxidation by Ru(bpy)32+ enables the amplification of ECL and CV dual-mode signals, which increased the detection sensitivity for both aggregation and ROS generation accompanied with α-Syn-Cu(II) complex. Machine learning algorithms were then utilized to analyze ECL and CV responses of small molecules with known drug effects. This analysis culminated in the development of a linear discriminant analysis (LDA) screening model, which enabled the assessment of drug efficacy against the two pathological features. The predictive capability of the screening model was verified through transmission electron microscope (TEM), cell viability and intracellular aggregation studies. This model was further successfully applied to assess two previously unexplored small molecules: diethylenetriaminepentaacetic dianhydride (DTPA) and deferiprone. Collectively, this dual-mode sensing platform, integrating DNA-amplified monitoring of protein aggregation and ROS generation, enables the robust establishment of a machine learning-assisted small-molecule drug screening model, offering a novel approach for the in vitro characterization of protein-related pathological features.
{"title":"Machine Learning-Assisted Screening of Small-Molecule Drugs in Protein Aggregation and ROS Generation Based on ECL and CV Dual-Mode Signals Amplified by DNA","authors":"Jiaqi Shi, Wen-Xiu Zhu, Jingyu Yan, Cong Xiao, Huiqin Yao, Lingchen Meng, Hongyun Liu, Lanqun Mao","doi":"10.1039/d5sc08658b","DOIUrl":"https://doi.org/10.1039/d5sc08658b","url":null,"abstract":"Screening small-molecule drugs to suppress both protein aggregation and reactive oxygen species (ROS) generation is critical for developing therapies for neurodegenerative diseases (NDs). However, existing methods are limited to characterizing only a single pathological feature (either aggregation or ROS) in a single measurement. Herein, taking α-synuclein (α-Syn) as the template protein, we developed a dual-mode electrochemical sensing platform for concurrently monitoring protein aggregation and ROS generation characteristics. A gold electrode functionalized with α-Syn via self-assembled monolayers (SAMs) was constructed as the sensing platform, realizing both ordered α-Syn immobilization and monitoring of metal ion (e.g., Cu(II))-driven aggregation. This was accomplished by synchronously recording the electrochemiluminescence (ECL) and cyclic voltammetry (CV) dual-responses of the tris(2,2'-bipyridine) ruthenium(II) (Ru(bpy)32+) reporter in a single integrated assay. The catalysis of DNA oxidation by Ru(bpy)32+ enables the amplification of ECL and CV dual-mode signals, which increased the detection sensitivity for both aggregation and ROS generation accompanied with α-Syn-Cu(II) complex. Machine learning algorithms were then utilized to analyze ECL and CV responses of small molecules with known drug effects. This analysis culminated in the development of a linear discriminant analysis (LDA) screening model, which enabled the assessment of drug efficacy against the two pathological features. The predictive capability of the screening model was verified through transmission electron microscope (TEM), cell viability and intracellular aggregation studies. This model was further successfully applied to assess two previously unexplored small molecules: diethylenetriaminepentaacetic dianhydride (DTPA) and deferiprone. Collectively, this dual-mode sensing platform, integrating DNA-amplified monitoring of protein aggregation and ROS generation, enables the robust establishment of a machine learning-assisted small-molecule drug screening model, offering a novel approach for the in vitro characterization of protein-related pathological features.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098277","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}
Catalytic hydrogenolysis of cellulose into low-carbon alcohols offers a promising route toward sustainable chemical manufacture and carbon-neutral energy systems. Recent advances in aqueous-phase catalysis have progressively clarified the reaction network encompassing cellulose depolymerization, glucose isomerization, retro-aldol C–C scission, and the hydrogenation of key carbonyl intermediates. This review integrates these mechanistic insights with catalyst and process design, highlighting how noble-metal and non-noble bifunctional systems leverage acid–metal cooperation, redox flexibility, and spatial confinement to orchestrate glycosidic, C–O, and C–C bond activation with increasing precision. Kinetic and engineering studies further reveal how reactor configuration, operating conditions, and feedstock pretreatment shape conversion efficiency and carbon utilization in both batch and continuous modes. Emerging opportunities, including single-atom catalysts that maximize atom efficiency and enable precise site control, defect-engineered oxides, machine-learning-assisted discovery for accelerated catalyst optimization, and integrated reaction-separation platforms, hold considerable promise for enabling cost-effective, scalable, and recyclable catalytic systems. Together, these advances establish a coherent framework linking fundamental chemistry with reactor-level engineering, laying the groundwork for practical one-step aqueous-phase routes to bio-derived low-carbon alcohols.
{"title":"Mechanistic insights and catalyst design for the selective hydrogenolysis of cellulose to C2–C3 alcohols","authors":"Yuandong Cui, Dandan Wang, Haoxi Ben, Xiong Su, Xiaoli Yang, Yanqiang Huang","doi":"10.1039/d5sc09595f","DOIUrl":"https://doi.org/10.1039/d5sc09595f","url":null,"abstract":"Catalytic hydrogenolysis of cellulose into low-carbon alcohols offers a promising route toward sustainable chemical manufacture and carbon-neutral energy systems. Recent advances in aqueous-phase catalysis have progressively clarified the reaction network encompassing cellulose depolymerization, glucose isomerization, retro-aldol C–C scission, and the hydrogenation of key carbonyl intermediates. This review integrates these mechanistic insights with catalyst and process design, highlighting how noble-metal and non-noble bifunctional systems leverage acid–metal cooperation, redox flexibility, and spatial confinement to orchestrate glycosidic, C–O, and C–C bond activation with increasing precision. Kinetic and engineering studies further reveal how reactor configuration, operating conditions, and feedstock pretreatment shape conversion efficiency and carbon utilization in both batch and continuous modes. Emerging opportunities, including single-atom catalysts that maximize atom efficiency and enable precise site control, defect-engineered oxides, machine-learning-assisted discovery for accelerated catalyst optimization, and integrated reaction-separation platforms, hold considerable promise for enabling cost-effective, scalable, and recyclable catalytic systems. Together, these advances establish a coherent framework linking fundamental chemistry with reactor-level engineering, laying the groundwork for practical one-step aqueous-phase routes to bio-derived low-carbon alcohols.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"152 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089694","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}
Douglas A. Rose, Zihuan Fu, Mikayla F. Tan, Daniele Vinciguerra, Priera H. Panescu, Heather D. Maynard
Proteins and peptides are an important class of biomolecules employed as therapeutics. Polymer conjugation to therapeutic proteins and peptides can improve their stability and circulation time, as well as reduce aggregation compared to the native biomolecule. However, the steric effect of a large polymer has the potential to drastically reduce or even completely inhibit the bioactivity of the protein. In these cases, traceless and reversible protein–polymer conjugation, in which native protein is released upon exposure to specific stimuli, can be utilized to both mitigate the undesirable effect of conjugation, while also taking advantage of the benefits prior to the cargo delivery. In this review, various linkers used in the reversible conjugations of polymers onto proteins are discussed.
{"title":"Traceless linkers used for reversible protein–polymer conjugations","authors":"Douglas A. Rose, Zihuan Fu, Mikayla F. Tan, Daniele Vinciguerra, Priera H. Panescu, Heather D. Maynard","doi":"10.1039/d5sc05801e","DOIUrl":"https://doi.org/10.1039/d5sc05801e","url":null,"abstract":"Proteins and peptides are an important class of biomolecules employed as therapeutics. Polymer conjugation to therapeutic proteins and peptides can improve their stability and circulation time, as well as reduce aggregation compared to the native biomolecule. However, the steric effect of a large polymer has the potential to drastically reduce or even completely inhibit the bioactivity of the protein. In these cases, traceless and reversible protein–polymer conjugation, in which native protein is released upon exposure to specific stimuli, can be utilized to both mitigate the undesirable effect of conjugation, while also taking advantage of the benefits prior to the cargo delivery. In this review, various linkers used in the reversible conjugations of polymers onto proteins are discussed.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"58 1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089804","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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