Covalent organic frameworks (COFs), as a type of porous crystalline materials with designable structures and tuneable properties, have attracted extensive attention in the field of materials science. The exceptional properties of COFs, particularly their high surface area, tuneable pore size, and functionalizable surfaces, make them ideal platforms for sensing applications. The rational design and synthesis of COFs are fundamental to unlocking their full potential in various applications. This review comprehensively summarizes the research progress of COFs, focusing on their common synthesis methods, applications in biosensing and chemical sensing, as well as current challenges and future perspectives. As for synthesis, two-dimensional COFs are prepared via solvothermal, room-temperature, or microwave-assisted methods (with strengths in crystallinity, mild conditions, and efficiency), while three dimensional COFs use solvothermal, ionothermal, or mechanochemical approaches (expanding synthesis scope and enabling large-scale production). In applications, COFs excel in biosensing (enzyme immobilization, protein/nucleic acid detection, biomarker recognition, cellular sensing) and chemical sensing (explosives, metal ions, gases, etc.) due to their high specific surface area, adjustable pores, and chemical stability. Current challenges include high synthesis cost and poor environmental stability, and future work will focus on optimizing large-scale synthesis, enhancing stability, and developing intelligent sensing systems. This review provides a concise reference for further research and application of COFs.
{"title":"Covalent Organic Frameworks: synthesis, biological and chemical sensing","authors":"Liangyu Dong, Leijing Liu, Wenjing Tian","doi":"10.1039/d5py00896d","DOIUrl":"https://doi.org/10.1039/d5py00896d","url":null,"abstract":"Covalent organic frameworks (COFs), as a type of porous crystalline materials with designable structures and tuneable properties, have attracted extensive attention in the field of materials science. The exceptional properties of COFs, particularly their high surface area, tuneable pore size, and functionalizable surfaces, make them ideal platforms for sensing applications. The rational design and synthesis of COFs are fundamental to unlocking their full potential in various applications. This review comprehensively summarizes the research progress of COFs, focusing on their common synthesis methods, applications in biosensing and chemical sensing, as well as current challenges and future perspectives. As for synthesis, two-dimensional COFs are prepared via solvothermal, room-temperature, or microwave-assisted methods (with strengths in crystallinity, mild conditions, and efficiency), while three dimensional COFs use solvothermal, ionothermal, or mechanochemical approaches (expanding synthesis scope and enabling large-scale production). In applications, COFs excel in biosensing (enzyme immobilization, protein/nucleic acid detection, biomarker recognition, cellular sensing) and chemical sensing (explosives, metal ions, gases, etc.) due to their high specific surface area, adjustable pores, and chemical stability. Current challenges include high synthesis cost and poor environmental stability, and future work will focus on optimizing large-scale synthesis, enhancing stability, and developing intelligent sensing systems. This review provides a concise reference for further research and application of COFs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"225 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147358904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photocatalysis has emerged as a green technology for addressing global energy and environmental challenges. Although g-C₃N₄ exhibits potential as a photocatalyst, its efficiency is hindered by poor charge separation and exciton dissociation. In this study, a donor-acceptor (D-A) engineered carbon nitride (CN-UC x ) was systhesis by incorporating UC monomers into the heptazine. Combined theoretical and experimental analyses reveal that the introduced donor units create two new donor levels, facilitating spatial charge separation and exciton dissociation while preserving strong reducibility. KPFM, surface photovoltage analysis, and photoelectrochemical characterizations confirm the presence of an intrinsic potential difference within CN-UC x . As a result, the optimized CN-UC 0.02 sample demonstrates exceptional photocatalytic performance, achieving a hydrogen evolution rate of 171.2 μmol h⁻¹ under visible light (λ > 420 nm), which is 74.4 times higher than that of g-C₃N₄.Remarkably, even in the absence of cocatalysts or sacrificial agents, CN-UC 0.02 maintains hydrogen evolution rates of 18.3 and 2.6 μmol h⁻¹, respectively. Furthermore, CN-UC 0.02 achieves complete (100%) conversion in the photocatalytic oxidation of methyl phenyl sulfide. This work presents an effective strategy for designing high-performance D-A polymeric photocatalysts through the rational integration of donor units.2
{"title":"Tailoring Local Conjugation in Heptazine-Based Polymers through Donor Unit Engineering for Photocatalytic Water Splitting","authors":"Xinyu Zhao, Wenjing Nie, Chunbo Liu, Yingnan Zhao, Renquan Guan, Wenbo Wang, Huaqiao Tan, Zhao Zhao","doi":"10.1039/d5py00894h","DOIUrl":"https://doi.org/10.1039/d5py00894h","url":null,"abstract":"Photocatalysis has emerged as a green technology for addressing global energy and environmental challenges. Although g-C₃N₄ exhibits potential as a photocatalyst, its efficiency is hindered by poor charge separation and exciton dissociation. In this study, a donor-acceptor (D-A) engineered carbon nitride (CN-UC x ) was systhesis by incorporating UC monomers into the heptazine. Combined theoretical and experimental analyses reveal that the introduced donor units create two new donor levels, facilitating spatial charge separation and exciton dissociation while preserving strong reducibility. KPFM, surface photovoltage analysis, and photoelectrochemical characterizations confirm the presence of an intrinsic potential difference within CN-UC x . As a result, the optimized CN-UC 0.02 sample demonstrates exceptional photocatalytic performance, achieving a hydrogen evolution rate of 171.2 μmol h⁻¹ under visible light (λ > 420 nm), which is 74.4 times higher than that of g-C₃N₄.Remarkably, even in the absence of cocatalysts or sacrificial agents, CN-UC 0.02 maintains hydrogen evolution rates of 18.3 and 2.6 μmol h⁻¹, respectively. Furthermore, CN-UC 0.02 achieves complete (100%) conversion in the photocatalytic oxidation of methyl phenyl sulfide. This work presents an effective strategy for designing high-performance D-A polymeric photocatalysts through the rational integration of donor units.2","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"407 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Poly(3-hydroxybutyrate) (P3HB) is a promising sustainable plastic alternative, valued for its inherent biodegradability, biocompatibility, and desirable material properties. While structural modification of P3HB has largely centered on side-chain functionalization, its end-group functionalization remains relatively unexplored. Herein, we demonstrate that modulation with epoxides in the trimetallic-catalyzed ring-opening polymerization of β-butyrolactone has enabled the synthesis of various end-functionalized P3HBs. In the trimetallic aluminum system, epoxides have switched the initiating group from chloride to alkoxide, thus transforming the propagating species from carboxylate to alkoxide. By contrast, the trimetallic chromium system has exhibited a three-fold enhancement in activity (TOF up to 800 h⁻¹) and five-fold rise in molecular weight (Mn = 47.6 kg/mol) upon epoxide addition, while maintaining a narrow dispersity (Đ ~ 1.26). Mechanistic insight reveals that epoxides have converted the chloride to alkoxide initiator, while the propagation still proceeded via a robust carboxylate species with configurational inversion at the methine carbon atom. This strategy offers a new route to prepare high-molecular-weight P3HB products with desired end-functionalization.
{"title":"Epoxide-Modulated Ring-Opening Polymerization of β-Butyrolactone","authors":"Jun Yang, Tie-Ying Zhang, Xiaobing Lu, Ye Liu","doi":"10.1039/d6py00078a","DOIUrl":"https://doi.org/10.1039/d6py00078a","url":null,"abstract":"Poly(3-hydroxybutyrate) (P3HB) is a promising sustainable plastic alternative, valued for its inherent biodegradability, biocompatibility, and desirable material properties. While structural modification of P3HB has largely centered on side-chain functionalization, its end-group functionalization remains relatively unexplored. Herein, we demonstrate that modulation with epoxides in the trimetallic-catalyzed ring-opening polymerization of β-butyrolactone has enabled the synthesis of various end-functionalized P3HBs. In the trimetallic aluminum system, epoxides have switched the initiating group from chloride to alkoxide, thus transforming the propagating species from carboxylate to alkoxide. By contrast, the trimetallic chromium system has exhibited a three-fold enhancement in activity (TOF up to 800 h⁻¹) and five-fold rise in molecular weight (Mn = 47.6 kg/mol) upon epoxide addition, while maintaining a narrow dispersity (Đ ~ 1.26). Mechanistic insight reveals that epoxides have converted the chloride to alkoxide initiator, while the propagation still proceeded via a robust carboxylate species with configurational inversion at the methine carbon atom. This strategy offers a new route to prepare high-molecular-weight P3HB products with desired end-functionalization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"245 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bole Chen, Xinyang Zhao, Yifan Liu, Xiangqi Xu, Luran Chun, Zhouju Zhong, Jun Nie, Jingfang Li
Achieving thick coatings (>200 μm) remains a significant challenge in the field of photopolymerization, primarily due to light attenuation. Despite the use of photobleaching initiators, rapid polymerization frequently results in the formation of a crosslinking gradient and the development of internal stresses, which adversely affect the mechanical properties, particularly the toughness, of the photo-cured materials. In this study, a novel macrocyclic photobleaching initiator [2](BPC)[2](C12) was developed specifically for thick-coating photopolymerization applications. In contrast to the photobleaching mechanism associated with the commercial initiator TPO, [2](BPC)[2](C12) exhibits a deeper color, which reduces light penetration and significantly decelerates the photobleaching rate, thereby generating a distinctive light-gating effect. This effect modulates the polymerization kinetics by inhibiting premature surface gelation and mitigating both the crosslinking density gradient and internal stress. As a result, the curing process is optimized in terms of uniformity, while maintaining a high degree of monomer crosslinking. To further elucidate the underlying mechanisms, this study is based on the density functional theory (DFT) calculations, steady-state photolysis, in situ nuclear magnetic resonance (NMR) analysis, providing an in-depth investigation into the photobleaching behavior and progressive curing mechanism of [2](BPC)[2](C12) in the presence of an EDB system. The findings from compression tests demonstrate that this progressive curing strategy significantly enhances the mechanical toughness of thick coatings. Specifically, for cylindrical poly(TMPTA) specimens (1 cm in diameter × 1 cm in height), the strain energy density increased from 0.6415 MPa to 0.9207 MPa, reflecting a 43.5% improvement. Moreover, the maximum strain exhibited a substantial increase, from 33% to 77%. This research not only introduces a new molecular platform for photopolymerization but also provides critical mechanistic insights that will aid in the rational design of high-performance photocuring systems for thick coatings.
在光聚合领域，实现厚涂层（>200 μm）仍然是一个重大挑战，主要是由于光衰减。尽管使用了光漂白引发剂，但快速聚合经常导致交联梯度的形成和内应力的发展，这对光固化材料的机械性能，特别是韧性产生不利影响。本研究开发了一种专门用于厚涂层光聚合的新型大环光漂白引发剂[2](BPC)[2]（C12）。与商用引发剂TPO相关的光漂白机制相反，[2](BPC)[2]（C12）呈现出更深的颜色，这减少了光穿透并显着减慢了光漂白速率，从而产生了独特的光门效应。这种效应通过抑制过早的表面凝胶化和减轻交联密度梯度和内应力来调节聚合动力学。因此，固化过程在均匀性方面得到了优化，同时保持了较高的单体交联度。为了进一步阐明其潜在机制，本研究基于密度泛函理论（DFT）计算、稳态光解、原位核磁共振（NMR）分析，对[2](BPC)[2]（C12）在EDB体系存在下的光漂白行为和渐进固化机理进行了深入研究。压缩试验结果表明，这种渐进固化策略显著提高了厚涂层的机械韧性。其中，对于直径为1 cm ×高为1 cm的圆柱形聚乙烯（TMPTA）试样，应变能密度从0.6415 MPa提高到0.9207 MPa，提高了43.5%；最大应变从33%增加到77%。这项研究不仅为光聚合提供了一个新的分子平台，而且还提供了关键的机理见解，这将有助于合理设计高性能的厚涂层光固化系统。
{"title":"Progressive Photocuring Approach: A Macrocyclic Photoinitiator Enabling Exceptional Toughness in Poly(TMPTA) Thick Coatings","authors":"Bole Chen, Xinyang Zhao, Yifan Liu, Xiangqi Xu, Luran Chun, Zhouju Zhong, Jun Nie, Jingfang Li","doi":"10.1039/d6py00038j","DOIUrl":"https://doi.org/10.1039/d6py00038j","url":null,"abstract":"Achieving thick coatings (>200 μm) remains a significant challenge in the field of photopolymerization, primarily due to light attenuation. Despite the use of photobleaching initiators, rapid polymerization frequently results in the formation of a crosslinking gradient and the development of internal stresses, which adversely affect the mechanical properties, particularly the toughness, of the photo-cured materials. In this study, a novel macrocyclic photobleaching initiator [2](BPC)[2](C12) was developed specifically for thick-coating photopolymerization applications. In contrast to the photobleaching mechanism associated with the commercial initiator TPO, [2](BPC)[2](C12) exhibits a deeper color, which reduces light penetration and significantly decelerates the photobleaching rate, thereby generating a distinctive light-gating effect. This effect modulates the polymerization kinetics by inhibiting premature surface gelation and mitigating both the crosslinking density gradient and internal stress. As a result, the curing process is optimized in terms of uniformity, while maintaining a high degree of monomer crosslinking. To further elucidate the underlying mechanisms, this study is based on the density functional theory (DFT) calculations, steady-state photolysis, in situ nuclear magnetic resonance (NMR) analysis, providing an in-depth investigation into the photobleaching behavior and progressive curing mechanism of [2](BPC)[2](C12) in the presence of an EDB system. The findings from compression tests demonstrate that this progressive curing strategy significantly enhances the mechanical toughness of thick coatings. Specifically, for cylindrical poly(TMPTA) specimens (1 cm in diameter × 1 cm in height), the strain energy density increased from 0.6415 MPa to 0.9207 MPa, reflecting a 43.5% improvement. Moreover, the maximum strain exhibited a substantial increase, from 33% to 77%. This research not only introduces a new molecular platform for photopolymerization but also provides critical mechanistic insights that will aid in the rational design of high-performance photocuring systems for thick coatings.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"53 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymer binders play a critical role in lithium-ion battery electrodes by providing mechanical cohesion among active materials, conductive additives and current collectors. They help to preserve the structural integrity of the composite and sustain continuous electron/ion migration pathway throughout repeated lithiation-delithiation cycling. Despite their essential role, polymer binders have historically been understudied, and only limited commercial ones, such as polyvinylidene fluoride (PVDF), carboxyl methylcellulose (CMC)/styrene-butadiene rubber (SBR) and polyacrylic acid (PAA), have been adopted. These widely used commercial binders have intrinsic drawbacks including insufficient adhesion, mechanical brittleness, swelling propensity and using toxic solvents, making them inadequate for high-energy-density batteries. This review categorizes binder design strategies according to the specific requirement of various cathode materials and anode materials, with a particular emphasis on those employed in commercial electrodes as well as those reported in academic research. Finally, perspectives on future binders for high-energy-density batteries with extended cycling life and sustainability are presented.
{"title":"Polymer Binders for High-Performance Lithium-Ion Batteries","authors":"Huan Xue, Mengwei Huo, Xuewei Li, Jiaming Huang, Zejia Huang, Boyi Song, Wangqing Zhang","doi":"10.1039/d5py01176k","DOIUrl":"https://doi.org/10.1039/d5py01176k","url":null,"abstract":"Polymer binders play a critical role in lithium-ion battery electrodes by providing mechanical cohesion among active materials, conductive additives and current collectors. They help to preserve the structural integrity of the composite and sustain continuous electron/ion migration pathway throughout repeated lithiation-delithiation cycling. Despite their essential role, polymer binders have historically been understudied, and only limited commercial ones, such as polyvinylidene fluoride (PVDF), carboxyl methylcellulose (CMC)/styrene-butadiene rubber (SBR) and polyacrylic acid (PAA), have been adopted. These widely used commercial binders have intrinsic drawbacks including insufficient adhesion, mechanical brittleness, swelling propensity and using toxic solvents, making them inadequate for high-energy-density batteries. This review categorizes binder design strategies according to the specific requirement of various cathode materials and anode materials, with a particular emphasis on those employed in commercial electrodes as well as those reported in academic research. Finally, perspectives on future binders for high-energy-density batteries with extended cycling life and sustainability are presented.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel, triazine-ring-containing succinonitrile-based mechanophore was designed and synthesized through radical stabilization energy calculations and molecular simulations. This mechanophore exhibits higher thermal stability rather than a classical mechanophore and a clear mechanochromic response via C–C bond cleavage. This enables its incorporation into polymers via radical polymerization. This study advances the design of thermally stable mechanophores and provides new insights into the relationship between structure and properties in radical-based mechanochemistry, offering new opportunities in polymer chemistry.
{"title":"Design of a thermally stable succinonitrile mechanophore featuring electron-withdrawing triazine rings for radical polymerization","authors":"Hajime Sugita, Akira Kodaka, Akira Takahashi, Koichiro Mikami, Hideyuki Otsuka","doi":"10.1039/d5py01088h","DOIUrl":"https://doi.org/10.1039/d5py01088h","url":null,"abstract":"A novel, triazine-ring-containing succinonitrile-based mechanophore was designed and synthesized through radical stabilization energy calculations and molecular simulations. This mechanophore exhibits higher thermal stability rather than a classical mechanophore and a clear mechanochromic response via C–C bond cleavage. This enables its incorporation into polymers via radical polymerization. This study advances the design of thermally stable mechanophores and provides new insights into the relationship between structure and properties in radical-based mechanochemistry, offering new opportunities in polymer chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"43 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report a straightforward synthetic route to silyl ether-based network polymers, enabled by efficient macrocyclization of diols with dichlorosilacyclobutane (DCSB) followed by thermal ring-opening of the silacyclobutane units. This strategy allows well-defined macrocyclic motifs composed of silyl ether linkages to be embedded directly into the polymer backbone. The resulting films are optically transparent and exhibit excellent thermal stability. Mechanical characterization reveals relatively low hardness, reflecting the intrinsic flexibility of the silyl ether framework. Despite the hydrolytic sensitivity of the macrocyclic precursors, the resulting network films demonstrate high acid resistance, which is attributed to their hydrophobic surface properties.
{"title":"Synthesis of network polymers composed of well-defined silyl ether macrocycles","authors":"Chihiro Nakai, Sota Amano, Koh Sugamata, Naoki Watanabe, Hiroaki Imoto, Kensuke Naka, Takahiro Iwamoto","doi":"10.1039/d6py00035e","DOIUrl":"https://doi.org/10.1039/d6py00035e","url":null,"abstract":"We report a straightforward synthetic route to silyl ether-based network polymers, enabled by efficient macrocyclization of diols with dichlorosilacyclobutane (DCSB) followed by thermal ring-opening of the silacyclobutane units. This strategy allows well-defined macrocyclic motifs composed of silyl ether linkages to be embedded directly into the polymer backbone. The resulting films are optically transparent and exhibit excellent thermal stability. Mechanical characterization reveals relatively low hardness, reflecting the intrinsic flexibility of the silyl ether framework. Despite the hydrolytic sensitivity of the macrocyclic precursors, the resulting network films demonstrate high acid resistance, which is attributed to their hydrophobic surface properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"296 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hanyu Zhou, Ying Su, Hao Dong, Xuan Zhang, Xinyu Zhang, Wei Zeng
Polypropylene (PP) is highly flammable and suffers from severe melt dripping. The incorporation of traditional intumescent flame retardants often leads to poor compatibility and deterioration of the mechanical properties. Herein, we report a bio-derived “three-in-one” intumescent flame retardant (PLM), synthesized through a two-step reaction between lignin, melamine, and piperazine pyrophosphate, to integrate acid, carbon, and gas sources within a single molecular structure. When incorporated into PP at 30 wt%, PLM enabled the composite to achieve a UL-94 V-0 rating, increased the limiting oxygen index to 31.8%, and suppressed melt-dripping. Cone calorimetry revealed an 86% reduction in the peak heat-release rate and an 82% decrease in the total smoke production relative to neat PP. Microstructural analysis confirmed that PLM promoted the formation of a continuous and highly graphitized char layer while simultaneously strengthening the interfacial adhesion with the PP matrix. PP-PLM30 exhibited superior tensile strength and impact toughness compared to its physically blended counterpart, effectively mitigating the severe mechanical deterioration typically observed in high-loading flame-retardant systems. This study demonstrates a practical pathway for high-value lignin utilization and sustainable flame-retardant design for polyolefins.
{"title":"A Three-in-One Lignin-Derived Intumescent Flame Retardant towards Fire-Safe and Tough Polypropylene","authors":"Hanyu Zhou, Ying Su, Hao Dong, Xuan Zhang, Xinyu Zhang, Wei Zeng","doi":"10.1039/d5py01124h","DOIUrl":"https://doi.org/10.1039/d5py01124h","url":null,"abstract":"Polypropylene (PP) is highly flammable and suffers from severe melt dripping. The incorporation of traditional intumescent flame retardants often leads to poor compatibility and deterioration of the mechanical properties. Herein, we report a bio-derived “three-in-one” intumescent flame retardant (PLM), synthesized through a two-step reaction between lignin, melamine, and piperazine pyrophosphate, to integrate acid, carbon, and gas sources within a single molecular structure. When incorporated into PP at 30 wt%, PLM enabled the composite to achieve a UL-94 V-0 rating, increased the limiting oxygen index to 31.8%, and suppressed melt-dripping. Cone calorimetry revealed an 86% reduction in the peak heat-release rate and an 82% decrease in the total smoke production relative to neat PP. Microstructural analysis confirmed that PLM promoted the formation of a continuous and highly graphitized char layer while simultaneously strengthening the interfacial adhesion with the PP matrix. PP-PLM30 exhibited superior tensile strength and impact toughness compared to its physically blended counterpart, effectively mitigating the severe mechanical deterioration typically observed in high-loading flame-retardant systems. This study demonstrates a practical pathway for high-value lignin utilization and sustainable flame-retardant design for polyolefins.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"389 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tiantian Miao, Huili Wei, Yudie Shan, Zixuan Sun, Dan Ning, Yinyin Zhu, Chanming Mei, Bingli Jiang, Xueyu Dou, Yongyang Gong
Nonconventional luminescent materials (NLMs) are promising for bioimaging due to their biocompatibility, yet they frequently suffer from negligible emission in dilute solutions and fluorescence quenching in aqueous environments. Herein, we report a novel NLM polymer, AP3-1, synthesized via the condensation of polyethylenimine and acetylacetone. Unlike typical NLMs, AP3-1 exhibits robust fluorescence in dilute media, achieving a quantum yield of 11.64% in ethanol (10 mg/mL). Due to a reinforced intramolecular hydrogen-bonding network, the polymer demonstrates remarkable water-insensitivity and pH-responsive behavior. Furthermore, AP3-1 serves as a highly sensitive and selective "turn-off" fluorescent chemosensor for Fe3+, Co2+, and Cu2+, with limits of detection (0.123–0.981 μmol/L) well within WHO drinking water standards. Successful cellular imaging further confirms its excellent biocompatibility and potential for real-time ion monitoring in biological systems. This work provides a strategy for developing high-efficiency NLMs capable of performing in both dilute and aqueous conditions.
{"title":"Nonconventional Luminescent Materials Exhibiting Water-Insensitive and pH-Sensitive Properties for Cell Imaging and Metal Ion Detection","authors":"Tiantian Miao, Huili Wei, Yudie Shan, Zixuan Sun, Dan Ning, Yinyin Zhu, Chanming Mei, Bingli Jiang, Xueyu Dou, Yongyang Gong","doi":"10.1039/d5py01034a","DOIUrl":"https://doi.org/10.1039/d5py01034a","url":null,"abstract":"Nonconventional luminescent materials (NLMs) are promising for bioimaging due to their biocompatibility, yet they frequently suffer from negligible emission in dilute solutions and fluorescence quenching in aqueous environments. Herein, we report a novel NLM polymer, AP3-1, synthesized via the condensation of polyethylenimine and acetylacetone. Unlike typical NLMs, AP3-1 exhibits robust fluorescence in dilute media, achieving a quantum yield of 11.64% in ethanol (10 mg/mL). Due to a reinforced intramolecular hydrogen-bonding network, the polymer demonstrates remarkable water-insensitivity and pH-responsive behavior. Furthermore, AP3-1 serves as a highly sensitive and selective \"turn-off\" fluorescent chemosensor for Fe3+, Co2+, and Cu2+, with limits of detection (0.123–0.981 μmol/L) well within WHO drinking water standards. Successful cellular imaging further confirms its excellent biocompatibility and potential for real-time ion monitoring in biological systems. This work provides a strategy for developing high-efficiency NLMs capable of performing in both dilute and aqueous conditions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147292729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Irene M. Harmody, Haley P. Macdonald, Orlando Coronell, Frank A. Leibfarth
Per- and polyfluoroalkyl substances (PFAS) are a class of toxic chemicals that are ubiquitous in the environment and have contaminated water sources globally. As regulations limiting PFAS concentrations in drinking water are being established by regulatory agencies globally, there is an urgent demand for robust granular sorbents that remove PFAS from water selectively and are easily regenerated. Here we report a new class of Ionic Fluorogels (IF) that leverage fluoroolefin-vinyl ether (FVE) perfectly alternating copolymers as a polymer matrix for the development of ion exchange resins. The use of 2-chloroethyl vinyl ether as a comonomer provided a partially fluorinated polymer with electrophilic functionality, which was reacted with multivalent amines to install covalent crosslinks and cationic character in a single synthetic step. Systematic variation in the identity of fluoroolefin comonomer and multivalent amine resulted in a library of materials for structure–property evaluation. We found that the synergistic combination of a fluorophilic matrix and cationic charge leads to high PFAS sorption, and that the ratio of quaternary ammonium to tertiary amine is an important design criteria. Performance evaluation showed that the FVE-based IFs have high binding capacity for GenX, up to 770 milligrams GenX per gram IF, facile regeneration with no lapse in performance across five cycles, and higher PFAS selectivity than commercial ion exchange resin in both simulated and natural waters.
{"title":"Fluoroolefin-vinyl ether copolymer ionic fluorogels for PFAS remediation from water","authors":"Irene M. Harmody, Haley P. Macdonald, Orlando Coronell, Frank A. Leibfarth","doi":"10.1039/d5py00795j","DOIUrl":"https://doi.org/10.1039/d5py00795j","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are a class of toxic chemicals that are ubiquitous in the environment and have contaminated water sources globally. As regulations limiting PFAS concentrations in drinking water are being established by regulatory agencies globally, there is an urgent demand for robust granular sorbents that remove PFAS from water selectively and are easily regenerated. Here we report a new class of Ionic Fluorogels (IF) that leverage fluoroolefin-vinyl ether (FVE) perfectly alternating copolymers as a polymer matrix for the development of ion exchange resins. The use of 2-chloroethyl vinyl ether as a comonomer provided a partially fluorinated polymer with electrophilic functionality, which was reacted with multivalent amines to install covalent crosslinks and cationic character in a single synthetic step. Systematic variation in the identity of fluoroolefin comonomer and multivalent amine resulted in a library of materials for structure–property evaluation. We found that the synergistic combination of a fluorophilic matrix and cationic charge leads to high PFAS sorption, and that the ratio of quaternary ammonium to tertiary amine is an important design criteria. Performance evaluation showed that the FVE-based IFs have high binding capacity for GenX, up to 770 milligrams GenX per gram IF, facile regeneration with no lapse in performance across five cycles, and higher PFAS selectivity than commercial ion exchange resin in both simulated and natural waters.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"52 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147292730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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