Graphene has shown tremendous potential in aerospace applications due to its exceptional mechanical and electrical properties. However, transferring graphene’s intrinsic qualities to macroscopic assemblies presents a significant challenge. In this study, we propose a stretching-induced confined assembly strategy to fabricate ultrastrong graphene films and investigate their applications in extreme environments. The resulting graphene films exhibit remarkable tensile strength (1.97 GPa) and Young’s modulus (108 GPa), which are the strongest previously reported graphene films. These superior properties arise from the synergistic interfacial effects of covalent bonds and π–π conjugation formed between graphene nanosheets during the confined assembly process, significantly enhancing interlayer load transfer efficiency. The densely aligned graphene films (with an orientation degree of up to 0.97) maintain stable mechanical and electrical performance under extreme conditions, including cryogenic to high temperatures (−110 to 150 °C) and UV exposure, surpassing conventional carbon fiber composites. Our proposed strategy provides new insights for fabricating macroscopic assemblies of two-dimensional nanomaterials and enhancing their performance in extreme environments.
{"title":"Ultrastrong Graphene Films Through Confined Assembly for Extreme Environmental Applications","authors":"Luping Zheng, Aoxin Qi, Zejun Zhang, Wangwei Lian, Yunfei Tian, Qunfeng Cheng","doi":"10.31635/ccschem.025.202506280","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506280","url":null,"abstract":"Graphene has shown tremendous potential in aerospace applications due to its exceptional mechanical and electrical properties. However, transferring graphene’s intrinsic qualities to macroscopic assemblies presents a significant challenge. In this study, we propose a stretching-induced confined assembly strategy to fabricate ultrastrong graphene films and investigate their applications in extreme environments. The resulting graphene films exhibit remarkable tensile strength (1.97 GPa) and Young’s modulus (108 GPa), which are the strongest previously reported graphene films. These superior properties arise from the synergistic interfacial effects of covalent bonds and π–π conjugation formed between graphene nanosheets during the confined assembly process, significantly enhancing interlayer load transfer efficiency. The densely aligned graphene films (with an orientation degree of up to 0.97) maintain stable mechanical and electrical performance under extreme conditions, including cryogenic to high temperatures (−110 to 150 °C) and UV exposure, surpassing conventional carbon fiber composites. Our proposed strategy provides new insights for fabricating macroscopic assemblies of two-dimensional nanomaterials and enhancing their performance in extreme environments.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"2 1","pages":"3823-3835"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658075","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 : 2025-12-01DOI: 10.31635/ccschem.025.202405209
Henan Li, Suxiang Ma, Qiming Liang, Sang Young Jeong, Qingqing Bai, Ruijie Ma, Qian Liu, Junyi Lu, Bin Liu, Bolin Li, Pei Cheng, Qifan Xue, Agnieszka Iwan, Guangye Zhang, Han Young Woo, Junwu Chen, Xugang Guo, Li Niu, Huiliang Sun
Thiophene and its derivatives have garnered substantial interest in the organic electronics sector, particularly in the development of polymer solar cells (PSCs). Herein, we present the synthesis of a new thiophene derivative, ClE-T, by a simple two-step method, comprising a monothiophene functionalized with a chlorine atom and an ester group. The ClE-T offers unique benefits resulting from the combination of the two groups. The incorporation of ClE-T into a polymer yields a polymer donor poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-chloro-4-(methoxycarbonyl)-2,5-thiophenediyl]] (PBDT-ClET). ClE-T demonstrates synergistic effects that significantly downshift energy levels and enhance the crystallinity of PBDT-ClET. In conclusion, PBDT-ClET is incorporated as a third component in all-polymer solar cells (all-PSCs) to enhance charge transport, reduce energy loss, and achieve more favorable phase separation. Finally, the all-PSCs employing PBDT-ClET achieve a notable power conversion efficiency (PCE) of 19.04%, which is not only among the highest values in all-PSCs but also represents the record PCE achieved for eco-friendly all-PSCs. This work underscores the promising potential of the ClE-T unit as a building block for constructing easily synthesized polymers for high-performance PSCs.
{"title":"A Chlorine and Ester Substituted Monothiophene Enabling New Polymer Donor for High-Performance and Eco-Friendly All-Polymer Solar Cells","authors":"Henan Li, Suxiang Ma, Qiming Liang, Sang Young Jeong, Qingqing Bai, Ruijie Ma, Qian Liu, Junyi Lu, Bin Liu, Bolin Li, Pei Cheng, Qifan Xue, Agnieszka Iwan, Guangye Zhang, Han Young Woo, Junwu Chen, Xugang Guo, Li Niu, Huiliang Sun","doi":"10.31635/ccschem.025.202405209","DOIUrl":"https://doi.org/10.31635/ccschem.025.202405209","url":null,"abstract":"Thiophene and its derivatives have garnered substantial interest in the organic electronics sector, particularly in the development of polymer solar cells (PSCs). Herein, we present the synthesis of a new thiophene derivative, ClE-T, by a simple two-step method, comprising a monothiophene functionalized with a chlorine atom and an ester group. The ClE-T offers unique benefits resulting from the combination of the two groups. The incorporation of ClE-T into a polymer yields a polymer donor poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-chloro-4-(methoxycarbonyl)-2,5-thiophenediyl]] (PBDT-ClET). ClE-T demonstrates synergistic effects that significantly downshift energy levels and enhance the crystallinity of PBDT-ClET. In conclusion, PBDT-ClET is incorporated as a third component in all-polymer solar cells (all-PSCs) to enhance charge transport, reduce energy loss, and achieve more favorable phase separation. Finally, the all-PSCs employing PBDT-ClET achieve a notable power conversion efficiency (PCE) of 19.04%, which is not only among the highest values in all-PSCs but also represents the record PCE achieved for eco-friendly all-PSCs. This work underscores the promising potential of the ClE-T unit as a building block for constructing easily synthesized polymers for high-performance PSCs.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"92 1","pages":"1-13"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619463","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 : 2025-12-01DOI: 10.31635/ccschem.025.202505649
Junlan Liu, Fangfang Xia, Min Li, Weihong Tan
Despite the remarkable advancement of enzyme-free DNA circuits in recent years, their practicality is hindered by fluorometric reporters, which offer limited readout channels and necessitate specialized instrumentation and high-cost fluorophore labeling. Herein, we present a G-quadruplex (G4)-based colorimetric reporter for visible, sensitive, and multiplexed readout of DNA circuits. The colorimetric reporter, generating highly distinguishable visual signal via the peroxidase activity of G4 DNAzyme, shows high specificity cross-validated in eight distinct targets and a low detection limit down to 5.2 nM. It demonstrates high compatibility with established DNA circuits by sharing structural similarities with fluorometric reporters. Absorbance-based kinetics behaviors recorded using the colorimetric reporter show desired performance across various DNA circuits, including Boolean logic gates, cascaded logic circuits, and catalytic circuits. When integrated into an inkjet-printed paper-based analytical chip with user-customizable patterns, the on-paper colorimetric reporter enables multiplexed readouts across eight channels. The colorimetric reporter offers a visualizable, instrument- and modification-free, low-cost solution for real-time, sensitive, qualitative, quantitative, and multiplexed analyses of DNA circuits in a one-pot assay and, as such, will advance DNA-based molecular circuits towards broader applications in various fields.
{"title":"Visualizing DNA Circuits with a G-Quadruplex-Based Colorimetric Reporter","authors":"Junlan Liu, Fangfang Xia, Min Li, Weihong Tan","doi":"10.31635/ccschem.025.202505649","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505649","url":null,"abstract":"Despite the remarkable advancement of enzyme-free DNA circuits in recent years, their practicality is hindered by fluorometric reporters, which offer limited readout channels and necessitate specialized instrumentation and high-cost fluorophore labeling. Herein, we present a G-quadruplex (G4)-based colorimetric reporter for visible, sensitive, and multiplexed readout of DNA circuits. The colorimetric reporter, generating highly distinguishable visual signal via the peroxidase activity of G4 DNAzyme, shows high specificity cross-validated in eight distinct targets and a low detection limit down to 5.2 nM. It demonstrates high compatibility with established DNA circuits by sharing structural similarities with fluorometric reporters. Absorbance-based kinetics behaviors recorded using the colorimetric reporter show desired performance across various DNA circuits, including Boolean logic gates, cascaded logic circuits, and catalytic circuits. When integrated into an inkjet-printed paper-based analytical chip with user-customizable patterns, the on-paper colorimetric reporter enables multiplexed readouts across eight channels. The colorimetric reporter offers a visualizable, instrument- and modification-free, low-cost solution for real-time, sensitive, qualitative, quantitative, and multiplexed analyses of DNA circuits in a one-pot assay and, as such, will advance DNA-based molecular circuits towards broader applications in various fields.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"151 1","pages":"1-11"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619459","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 : 2025-12-01DOI: 10.31635/ccschem.025.202506367
Hai Wang, Liang Wang, Feng-Shou Xiao
Supported metal catalysts are essential for industrial processes like energy conversion, chemical synthesis, and pollutant removal, yet they often suffer from low activity, poor selectivity, and deactivation. Matching zeolites with metal species is an effective method for synthesizing highly efficient heterogeneous catalysts, where the zeolite crystals not only stabilize the metal species against sintering/leaching, but also enhance the catalytic activity and product selectivity. In this minireview, we briefly summarize recent advances in matching zeolites with metal species for efficient catalysis, highlighting the synergistic effects between zeolites and metal species to improve the catalytic performance. Multiple functions of zeolites with respect to the metal species are highlighted, including the regulation of reactant/product diffusion for increasing the catalytic activity, the control of steric adsorption of reactant for changing the product selectivity, and the modulation of dynamic structural change of metal species for enhancing catalytic stability. Additionally, future challenges and opportunities in rational metal-zeolite catalyst design are discussed to inspire further innovations in catalytic applications. We believe that this minireview will open up novel pathways for the widespread utilization of metal-zeolite catalysts in diverse catalytic processes.
{"title":"Matching Zeolites with Metal Species for Efficient Catalysis","authors":"Hai Wang, Liang Wang, Feng-Shou Xiao","doi":"10.31635/ccschem.025.202506367","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506367","url":null,"abstract":"Supported metal catalysts are essential for industrial processes like energy conversion, chemical synthesis, and pollutant removal, yet they often suffer from low activity, poor selectivity, and deactivation. Matching zeolites with metal species is an effective method for synthesizing highly efficient heterogeneous catalysts, where the zeolite crystals not only stabilize the metal species against sintering/leaching, but also enhance the catalytic activity and product selectivity. In this minireview, we briefly summarize recent advances in matching zeolites with metal species for efficient catalysis, highlighting the synergistic effects between zeolites and metal species to improve the catalytic performance. Multiple functions of zeolites with respect to the metal species are highlighted, including the regulation of reactant/product diffusion for increasing the catalytic activity, the control of steric adsorption of reactant for changing the product selectivity, and the modulation of dynamic structural change of metal species for enhancing catalytic stability. Additionally, future challenges and opportunities in rational metal-zeolite catalyst design are discussed to inspire further innovations in catalytic applications. We believe that this minireview will open up novel pathways for the widespread utilization of metal-zeolite catalysts in diverse catalytic processes.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"328 1","pages":"3540-3552"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651331","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 : 2025-12-01DOI: 10.31635/ccschem.025.202506418
Mark L. Verheijden, Jurriaan Huskens, Pascal Jonkheijm
Understanding how multivalency contributes to targeting dynamic lipid membranes is challenging. We show superselectivity in the multiple weak interactions formed between vesicles displaying nickel(II)-complexing nitrilotriacetic acid (NTA(Ni)) and histidine (His)-displaying supported lipid bilayers (SLBs). The lateral mobility of receptors on the SLBs led to receptor recruitment inside the contact area between vesicle and SLB and depletion outside of the contact area in the case of low receptor density at the SLB and high ligand density in the targeting vesicles.
{"title":"Superselectivity in Weakly Multivalent Targeting of Supported Lipid Bilayers","authors":"Mark L. Verheijden, Jurriaan Huskens, Pascal Jonkheijm","doi":"10.31635/ccschem.025.202506418","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506418","url":null,"abstract":"Understanding how multivalency contributes to targeting dynamic lipid membranes is challenging. We show superselectivity in the multiple weak interactions formed between vesicles displaying nickel(II)-complexing nitrilotriacetic acid (NTA(Ni)) and histidine (His)-displaying supported lipid bilayers (SLBs). The lateral mobility of receptors on the SLBs led to receptor recruitment inside the contact area between vesicle and SLB and depletion outside of the contact area in the case of low receptor density at the SLB and high ligand density in the targeting vesicles.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"32 1","pages":"1-8"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619454","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}
Nanocrystal scintillators are redefining the landscape of radiation detection and biomedical imaging, offering a highly tunable, scalable, and multifunctional platform for next-generation diagnostics and therapy. Their bottom-up synthesis enables low-temperature, cost-effective fabrication of large-area detectors with high spatial resolution and structural flexibility. Through precise control over crystal phase, dimensionality, and surface chemistry, nanocrystal scintillators achieve customizable emission properties, fast response times, and seamless integration with flexible substrates and photonic devices. These features are particularly advantageous for advanced biomedical applications, including high-resolution in vivo imaging, radiotherapy of deep-seated lesions, biosensing, and optogenetic modulation. Here, we present a minireview that outlines the fundamental mechanisms of X-ray-induced luminescence, highlights recent advances in nanocrystal scintillator development—from halide perovskites and lanthanide-doped systems to lead-free analogs—and discusses the key material and engineering challenges that remain. Looking ahead, innovations in surface passivation, hybrid architectures, and biocompatibility will be critical for translating these materials from proof-of-concept demonstrations to real-world clinical and industrial applications.
{"title":"Advances in Nanocrystal Scintillators for X-Ray Imaging and Biomedical Applications","authors":"Zhijian Yang, Chen Chen, Yu He, Lili Xie, Qiushui Chen, Huanghao Yang","doi":"10.31635/ccschem.025.202506233","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506233","url":null,"abstract":"Nanocrystal scintillators are redefining the landscape of radiation detection and biomedical imaging, offering a highly tunable, scalable, and multifunctional platform for next-generation diagnostics and therapy. Their bottom-up synthesis enables low-temperature, cost-effective fabrication of large-area detectors with high spatial resolution and structural flexibility. Through precise control over crystal phase, dimensionality, and surface chemistry, nanocrystal scintillators achieve customizable emission properties, fast response times, and seamless integration with flexible substrates and photonic devices. These features are particularly advantageous for advanced biomedical applications, including high-resolution in vivo imaging, radiotherapy of deep-seated lesions, biosensing, and optogenetic modulation. Here, we present a minireview that outlines the fundamental mechanisms of X-ray-induced luminescence, highlights recent advances in nanocrystal scintillator development—from halide perovskites and lanthanide-doped systems to lead-free analogs—and discusses the key material and engineering challenges that remain. Looking ahead, innovations in surface passivation, hybrid architectures, and biocompatibility will be critical for translating these materials from proof-of-concept demonstrations to real-world clinical and industrial applications.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"29 1","pages":"1-16"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619450","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 : 2025-12-01DOI: 10.31635/ccschem.025.202506292
Yu Qi, Fuxiang Zhang
Particulate photocatalytic overall water splitting (OWS) represents a promising way to generate green hydrogen for solar energy storage, attracting considerable attention due to its low operational cost, simplicity, and potential for scalable application. To construct efficient systems capable of achieving reasonable energy efficiency amenable to the economic feasibility, it is a prerequisite that the band gap of photocatalysts used should be narrow to guarantee the efficient absorption of incident light. However, the sluggish charge separation remains the main challenge due to the reduced driving force caused by the decreased band gap. This minireview summarizes the latest advances (over the past 5 years) of inorganic photocatalysts with visible-light response beyond 500 nm to construct powder-suspended OWS systems. Additionally, various strategies to improve charge separation and suppress the backward reaction are elaborated, including defect and morphological control, cocatalyst design and surface engineering strategies. Furthermore, challenges and prospects in the developing efficient OWS systems are discussed to inspire future research toward the rational design of photocatalytic OWS systems.
{"title":"Recent Progress on Overall Water Splitting Using Particulate Inorganic Photocatalysts with Wide Visible Light Utilization","authors":"Yu Qi, Fuxiang Zhang","doi":"10.31635/ccschem.025.202506292","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506292","url":null,"abstract":"Particulate photocatalytic overall water splitting (OWS) represents a promising way to generate green hydrogen for solar energy storage, attracting considerable attention due to its low operational cost, simplicity, and potential for scalable application. To construct efficient systems capable of achieving reasonable energy efficiency amenable to the economic feasibility, it is a prerequisite that the band gap of photocatalysts used should be narrow to guarantee the efficient absorption of incident light. However, the sluggish charge separation remains the main challenge due to the reduced driving force caused by the decreased band gap. This minireview summarizes the latest advances (over the past 5 years) of inorganic photocatalysts with visible-light response beyond 500 nm to construct powder-suspended OWS systems. Additionally, various strategies to improve charge separation and suppress the backward reaction are elaborated, including defect and morphological control, cocatalyst design and surface engineering strategies. Furthermore, challenges and prospects in the developing efficient OWS systems are discussed to inspire future research toward the rational design of photocatalytic OWS systems.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"21 1","pages":"1-15"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619453","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}
Poly(lactic-co-glycolic acid) (PLGA) copolymers exhibit exceptional biodegradability and biocompatibility, showcasing significant potential for biomedical applications. While PLG and high molecular weight PLGA emerges as one of the most prominent PLGAs with promising thermal-mechanical performance, its utility in medical applications is limited by catalyst’s metal residue and weakened crystallinity/mechanical properties caused by increased molecular weight. Herein, we report the first high-performance metal-free alternating PLGA developed by using new highly active and selective organic catalysts and fine-tuning the PLGA crystallization. Specifically, we designed a series of guanidine-based catalysts with variable steric hindrance, facilitating high activity and suppressed side reactions: The catalyzed ring-opening polymerization of 3-methyl glycolic acid produced PLGA with high regioselectivity (up to 97%), minimal racemization, very high molecular weight (up to 168 kg/mol—ten times higher than the best previous selective organocatalytic systems), and narrow dispersity. We further efficiently reinforced the obtained PLGA materials by fine-tuning their crystallization with nucleating agents and unconventional non-stoichiometric stereocomplexation. In this way, we for the first time realize full PLLGA crystallization after melting treatment and the highest tensile strength (108.7 MPa) for alternating PLGA. This study informs the future alternating PLGA copolymers with potential applications in medical materials.
{"title":"Metal-Free Regioselective Ring-Opening Polymerization of Methyl Glycolide and Crystallization-Controlled Tuning of Poly(lactic-co-glycolic Acid) Performance","authors":"Guanyu Liu, Linyao Zhou, Yanlong Liu, Xinchao Bian, Tianchang Wang, Jinbo Hu, Wenbo Wang, Yeqi Du, Ranlong Duan, Xuesi Chen","doi":"10.31635/ccschem.025.202506204","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506204","url":null,"abstract":"Poly(lactic-<i>co</i>-glycolic acid) (PLGA) copolymers exhibit exceptional biodegradability and biocompatibility, showcasing significant potential for biomedical applications. While PLG and high molecular weight PLGA emerges as one of the most prominent PLGAs with promising thermal-mechanical performance, its utility in medical applications is limited by catalyst’s metal residue and weakened crystallinity/mechanical properties caused by increased molecular weight. Herein, we report the first high-performance metal-free alternating PLGA developed by using new highly active and selective organic catalysts and fine-tuning the PLGA crystallization. Specifically, we designed a series of guanidine-based catalysts with variable steric hindrance, facilitating high activity and suppressed side reactions: The catalyzed ring-opening polymerization of 3-methyl glycolic acid produced PLGA with high regioselectivity (up to 97%), minimal racemization, very high molecular weight (up to 168 kg/mol—ten times higher than the best previous selective organocatalytic systems), and narrow dispersity. We further efficiently reinforced the obtained PLGA materials by fine-tuning their crystallization with nucleating agents and unconventional non-stoichiometric stereocomplexation. In this way, we for the first time realize full PLLGA crystallization after melting treatment and the highest tensile strength (108.7 MPa) for alternating PLGA. This study informs the future alternating PLGA copolymers with potential applications in medical materials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"368 1","pages":"1-14"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619460","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 : 2025-12-01DOI: 10.31635/ccschem.025.202506277
Letian Wang, Wencan Wang, Xinyi Zhu, Chenming Tang, Xiaodong Jing, Yahui He, Justin Amengual, Yao Lin, Zhixiang Yu, Hua Lu
Poly-l-hydroxyproline (PHyp) represents an important model for comprehending the polyproline II helix and holds immense potential for broad biomedical applications. The synthesis of PHyp, however, involves inefficient protection-deprotection steps and has been restricted to low molecular weight (MW) and linear topology. Here, we report the first ring-opening polymerization (ROP) of unprotected hydroxyproline N-carboxyanhydride (Hyp-NCA) for the facile synthesis of PHyp with tunable linear or branching topologies. While linear PHyp was readily prepared with control via water-assisted polymerization in minutes, tertiary amine-mediated ROP of Hyp-NCA affords branched PHyp (B-PHyp) for the first time with MW up to 438 kDa, ∼40 times higher than the previous record. Experimental and computational studies collectively uncovered fresh insights into the general mechanism regarding the hydroxy/amine selectivity. Postpolymerization modification of B-PHyp affords injectable hydrogels with a critical gelization concentration as low as 1.0%. This study provides an approach that may inspire the development of novel synthetic collagen-like biomaterials.
{"title":"Ring-Opening Polymerization of Unprotected Hydroxyproline N-Carboxyanhydride for the Facile Synthesis of Linear and Branched Poly-l-hydroxyproline","authors":"Letian Wang, Wencan Wang, Xinyi Zhu, Chenming Tang, Xiaodong Jing, Yahui He, Justin Amengual, Yao Lin, Zhixiang Yu, Hua Lu","doi":"10.31635/ccschem.025.202506277","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506277","url":null,"abstract":"Poly-<span>l</span>-hydroxyproline (PHyp) represents an important model for comprehending the polyproline II helix and holds immense potential for broad biomedical applications. The synthesis of PHyp, however, involves inefficient protection-deprotection steps and has been restricted to low molecular weight (MW) and linear topology. Here, we report the first ring-opening polymerization (ROP) of unprotected hydroxyproline <i>N</i>-carboxyanhydride (Hyp-NCA) for the facile synthesis of PHyp with tunable linear or branching topologies. While linear PHyp was readily prepared with control via water-assisted polymerization in minutes, tertiary amine-mediated ROP of Hyp-NCA affords branched PHyp (B-PHyp) for the first time with MW up to 438 kDa, ∼40 times higher than the previous record. Experimental and computational studies collectively uncovered fresh insights into the general mechanism regarding the hydroxy/amine selectivity. Postpolymerization modification of B-PHyp affords injectable hydrogels with a critical gelization concentration as low as 1.0%. This study provides an approach that may inspire the development of novel synthetic collagen-like biomaterials.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"32 1","pages":"3807-3822"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651334","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 : 2025-12-01DOI: 10.31635/ccschem.025.202506113
Shi-Xiong Tang, Guan-Wang Huang, Jin-Kai Cheng, Fei Wang
meta-Phenylenediamines serve as privileged structural motifs in numerous bioactive compounds and organic materials. However, conventional electrophilic amination of aryl amines and their derivatives inherently favors ortho/para substitution, leaving the meta-selective C–H amination of aryl amines a formidable challenge. We report here an acid-promoted radical-mediated C–H amination of aryl amines to directly afford meta-phenylenediamines. The reaction takes advantage of the high reactivity of cationic nitrogen centered radicals and protonation-enabled polarity inversion of aryl amines. This method is applicable to both ammoniumyl and pyridinium radicals, and accommodates primary, secondary, and tertiary aryl amines, furnishing meta-phenylenediamines with great structural diversity. Synthetic utility of this protocol is demonstrated through concisely synthesizing the intermediates of several bioactive molecules.
{"title":"meta-Selective C–H Amination of Aryl Amines via Protonation-Enabled Polarity Inversion in Homolytic Aromatic Substitution","authors":"Shi-Xiong Tang, Guan-Wang Huang, Jin-Kai Cheng, Fei Wang","doi":"10.31635/ccschem.025.202506113","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506113","url":null,"abstract":"<i>meta</i>-Phenylenediamines serve as privileged structural motifs in numerous bioactive compounds and organic materials. However, conventional electrophilic amination of aryl amines and their derivatives inherently favors <i>ortho</i>/<i>para</i> substitution, leaving the <i>meta</i>-selective C–H amination of aryl amines a formidable challenge. We report here an acid-promoted radical-mediated C–H amination of aryl amines to directly afford <i>meta</i>-phenylenediamines. The reaction takes advantage of the high reactivity of cationic nitrogen centered radicals and protonation-enabled polarity inversion of aryl amines. This method is applicable to both ammoniumyl and pyridinium radicals, and accommodates primary, secondary, and tertiary aryl amines, furnishing <i>meta</i>-phenylenediamines with great structural diversity. Synthetic utility of this protocol is demonstrated through concisely synthesizing the intermediates of several bioactive molecules.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"175 1","pages":"1-10"},"PeriodicalIF":11.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145619452","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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