Pub Date : 2025-12-19DOI: 10.1016/j.eurpolymj.2025.114462
Soumya Shuvra Smita, Krishna Pramanik
The study aims to develop a biomimetic polymeric matrix consisting of silk fibroin, gelatin, and polycaprolactone polymers with antioxidant and antimicrobial properties by adding different concentrations ranging 1–10 mM of curcumin resulting SGPC1, SGPC2.5, SGPC5, and SGPC10 respectively. All the fabricated mats exhibited morphological similarity and peak shifts in FTIR spectra confirming the interaction between curcumin and SGP mats. SGPC10 and SGPC5 mat possess higher tensile strength of 4.9 ± 0.14 MPa and 4.3 ± 0.2 MPa. An insignificant decrease in transparency was observed as compared to control with the addition of curcumin. Moreover, SGPC5 and SGPC10 mats demonstrated a respective controlled degradation rate of 43.66 ± 1.52 % and 42.66 ± 2.08 %. An enhanced antimicrobial and antioxidant properties achieved with SGPC5 and SGPC10 mats. The cytocompatibility of the mats ensured that the curcumin does not negatively affect the cellular growth and attachment of SIRC (Statens Seruminstitut rabbit cornea) cell line. SGPC5 construct exhibited higher cell viability, cell attachment, and denser cytoskeleton arrangement, indicating its potentiality for regeneration of ocular surface.
{"title":"Curcumin improvised antibacterial and antioxidant activities of silk fibroin/gelatin/polycaprolactone composite nanofibrous matrix performing superior ocular surface regeneration","authors":"Soumya Shuvra Smita, Krishna Pramanik","doi":"10.1016/j.eurpolymj.2025.114462","DOIUrl":"10.1016/j.eurpolymj.2025.114462","url":null,"abstract":"<div><div>The study aims to develop a biomimetic polymeric matrix consisting of silk fibroin, gelatin, and polycaprolactone polymers with antioxidant and antimicrobial properties by adding different concentrations ranging 1–10 mM of curcumin resulting SGPC<sub>1</sub>, SGPC<sub>2.5</sub>, SGPC<sub>5</sub>, and SGPC<sub>10</sub> respectively. All the fabricated mats exhibited morphological similarity and peak shifts in FTIR spectra confirming the interaction between curcumin and SGP mats. SGPC<sub>10</sub> and SGPC<sub>5</sub> mat possess higher tensile strength of 4.9 ± 0.14 MPa and 4.3 ± 0.2 MPa. An insignificant decrease in transparency was observed as compared to control with the addition of curcumin. Moreover, SGPC<sub>5</sub> and SGPC<sub>10</sub> mats demonstrated a respective controlled degradation rate of 43.66 ± 1.52 % and 42.66 ± 2.08 %. An enhanced antimicrobial and antioxidant properties achieved with SGPC<sub>5</sub> and SGPC<sub>10</sub> mats. The cytocompatibility of the mats ensured that the curcumin does not negatively affect the cellular growth and attachment of SIRC (Statens Seruminstitut rabbit cornea) cell line. SGPC<sub>5</sub> construct exhibited higher cell viability, cell attachment, and denser cytoskeleton arrangement, indicating its potentiality for regeneration of ocular surface.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114462"},"PeriodicalIF":6.3,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839545","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}
Pub Date : 2025-12-19DOI: 10.1016/j.eurpolymj.2025.114456
Qi Wang, Zhuo Dang, Yijie Dong, Xiaoyu Guo, Lin Lei
The light sources utilized in photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization (PET-RAFT) investigations primarily focus on high-intensity ultraviolet (UV) and blue light, which may induce biological toxicity and side reactions. In this study, we have developed a carbon-doped orange polymerized carbon nitride (OPCN) material that extends the light absorption range of carbon nitride up to 600 nm. This material was employed as a catalyst for PET-RAFT polymerization under long-wavelength light sources ranging from blue to red without the need for any additives. The OPCN-catalyzed PET-RAFT polymerization can proceed without pre-deoxygenation. Furthermore, oxygen not only accelerates the rate of polymerization but also regulates the molecular weight of the resulting polymers. Additionally, we discovered that sodium salts significantly enhance the rate of OPCN-catalyzed PET-RAFT polymerization, demonstrating a “sodium salt-accelerated” behavior alongside its “oxygen-accelerated” counterpart. The combined effects of “oxygen-acceleration” and pronounced “sodium salt-acceleration” enable efficient implementation of OPCN-catalyzed PET-RAFT under long-wavelength light sources.
{"title":"Orange polymerized carbon nitride (OPCN) catalyzed PET-RAFT polymerization under long wavelength light irradiation with “oxygen-acceleration” and “ sodium salt-acceleration” behavior","authors":"Qi Wang, Zhuo Dang, Yijie Dong, Xiaoyu Guo, Lin Lei","doi":"10.1016/j.eurpolymj.2025.114456","DOIUrl":"10.1016/j.eurpolymj.2025.114456","url":null,"abstract":"<div><div>The light sources utilized in photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization (PET-RAFT) investigations primarily focus on high-intensity ultraviolet (UV) and blue light, which may induce biological toxicity and side reactions. In this study, we have developed a carbon-doped orange polymerized carbon nitride (OPCN) material that extends the light absorption range of carbon nitride up to 600 nm. This material was employed as a catalyst for PET-RAFT polymerization under long-wavelength light sources ranging from blue to red without the need for any additives. The OPCN-catalyzed PET-RAFT polymerization can proceed without pre-deoxygenation. Furthermore, oxygen not only accelerates the rate of polymerization but also regulates the molecular weight of the resulting polymers. Additionally, we discovered that sodium salts significantly enhance the rate of OPCN-catalyzed PET-RAFT polymerization, demonstrating a “sodium salt-accelerated” behavior alongside its “oxygen-accelerated” counterpart. The combined effects of “oxygen-acceleration” and pronounced “sodium salt-acceleration” enable efficient implementation of OPCN-catalyzed PET-RAFT under long-wavelength light sources.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114456"},"PeriodicalIF":6.3,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836393","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}
Pub Date : 2025-12-18DOI: 10.1016/j.eurpolymj.2025.114454
Davide Illari, Xiangyu Zhu, Mark A. Hempenius, Frederik R. Wurm
This study addresses the challenge of directly polymerizing furfural, a renewable platform chemical, by cationic copolymerization of furfural and 3,4-dihydro-2H-pyran (DHP), which can be derived from furfural, using GaCl3/EtSO3H/1,4-dioxane. This approach achieves higher yields (up to 72 %) and improved dispersity (Mw/Mn = 1.29–1.45) compared to BF3·OEt2, yielding fully bio-based, predominantly alternating poly(furfural-co-DHP) copolymers with high glass transition temperatures (Tg > 160 °C). These materials, thoroughly characterized by 1H, 13C NMR and FTIR spectroscopy, GPC, TGA, and DSC, demonstrate a new pathway towards sustainable polyacetals. Further, we show that the materials undergo acid-triggered degradation, facilitated by the acetal linkages, and exhibit biodegradation in activated sludge (wastewater treatment) of ca. 52 % after 28 days (following OECD 301F), indicating their potential for reducing plastic waste accumulation and environmental persistence.
{"title":"Cationic copolymerization of furfural and furfural-derived 3,4-dihydropyran: biobased and biodegradable polyacetals with high glass transition temperatures","authors":"Davide Illari, Xiangyu Zhu, Mark A. Hempenius, Frederik R. Wurm","doi":"10.1016/j.eurpolymj.2025.114454","DOIUrl":"10.1016/j.eurpolymj.2025.114454","url":null,"abstract":"<div><div>This study addresses the challenge of directly polymerizing furfural, a renewable platform chemical, by cationic copolymerization of furfural and 3,4-dihydro-2H-pyran (DHP), which can be derived from furfural, using GaCl<sub>3</sub>/EtSO<sub>3</sub>H/1,4-dioxane. This approach achieves higher yields (up to 72 %) and improved dispersity (<em>M</em><sub>w</sub>/<em>M</em><sub>n</sub> = 1.29–1.45) compared to BF<sub>3</sub>·OEt<sub>2</sub>, yielding fully bio-based, predominantly alternating poly(furfural-<em>co</em>-DHP) copolymers with high glass transition temperatures (<em>T</em><sub>g</sub> > 160 °C). These materials, thoroughly characterized by <sup>1</sup>H, <sup>13</sup>C NMR and FTIR spectroscopy, GPC, TGA, and DSC, demonstrate a new pathway towards sustainable polyacetals. Further, we show that the materials undergo acid-triggered degradation, facilitated by the acetal linkages, and exhibit biodegradation in activated sludge (wastewater treatment) of ca. 52 % after 28 days (following OECD 301F), indicating their potential for reducing plastic waste accumulation and environmental persistence.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114454"},"PeriodicalIF":6.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836392","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}
Pub Date : 2025-12-17DOI: 10.1016/j.eurpolymj.2025.114451
Martina Meazzo , Stefan Schroeder , Jan Philippe Kretzer , Fabrizio Barberis , Catherine Van Der Straeten , Peter Dubruel
The menisci, essential fibrocartilaginous structures within the knee joint, play a critical role in load distribution, stability, and shock absorption. Meniscal injuries can result from acute trauma, degeneration, or arise as secondary consequences of other knee pathologies. Meniscus regeneration has emerged as a promising approach to address these challenges by developing biomimetic replacements that restore native function. The mechanical properties of scaffold materials are pivotal in the success of meniscus regeneration, given the complex and dynamic loading environment within the knee joint.
This study presents a comprehensive mechanical characterization of a novel scaffold material—acrylate end-capped urethane-based poly(ethylene glycol) (AUP)—designed specifically for meniscus regeneration applications. AUP is a synthetic polymer that demonstrates remarkable potential due to its tuneable mechanical and structural properties. This work focuses on evaluating AUP’s mechanical performance and its implications for fabricating functional meniscal constructs. Key mechanical properties analyzed include the tensile Young’s modulus (3.19–3.49 MPa), compressive modulus (2–3.32 MPa), storage modulus (5.76–8.2 MPa), loss modulus (0.08–0.14 MPa), swelling degree (200–295 %), gel fraction (>88 %), and fatigue durability (target 200,000 cycles). Utilizing advanced 3D printing techniques, the AUP hydrogel scaffold structure is customized to replicate the mechanical behavior of distinct meniscal zones.
This paper underscores the critical importance of mechanical characterization in developing AUP-based scaffolds for effective meniscus regeneration. The integration of mechanically optimized scaffolds offers a pathway toward restoring joint function, alleviating pain, and improving the overall quality of life for patients affected by meniscal damage.
{"title":"Customizable 3D-printed scaffolds for meniscal replacement: Mechanical insights into urethane-based poly(ethylene glycol) polymer","authors":"Martina Meazzo , Stefan Schroeder , Jan Philippe Kretzer , Fabrizio Barberis , Catherine Van Der Straeten , Peter Dubruel","doi":"10.1016/j.eurpolymj.2025.114451","DOIUrl":"10.1016/j.eurpolymj.2025.114451","url":null,"abstract":"<div><div>The menisci, essential fibrocartilaginous structures within the knee joint, play a critical role in load distribution, stability, and shock absorption. Meniscal injuries can result from acute trauma, degeneration, or arise as secondary consequences of other knee pathologies. Meniscus regeneration has emerged as a promising approach to address these challenges by developing biomimetic replacements that restore native function. The mechanical properties of scaffold materials are pivotal in the success of meniscus regeneration, given the complex and dynamic loading environment within the knee joint.</div><div>This study presents a comprehensive mechanical characterization of a novel scaffold material—acrylate end-capped urethane-based poly(ethylene glycol) (AUP)—designed specifically for meniscus regeneration applications. AUP is a synthetic polymer that demonstrates remarkable potential due to its tuneable mechanical and structural properties. This work focuses on evaluating AUP’s mechanical performance and its implications for fabricating functional meniscal constructs. Key mechanical properties analyzed include the tensile Young’s modulus (3.19–3.49 MPa), compressive modulus (2–3.32 MPa), storage modulus (5.76–8.2 MPa), loss modulus (0.08–0.14 MPa), swelling degree (200–295 %), gel fraction (>88 %), and fatigue durability (target 200,000 cycles). Utilizing advanced 3D printing techniques, the AUP hydrogel scaffold structure is customized to replicate the mechanical behavior of distinct meniscal zones.</div><div>This paper underscores the critical importance of mechanical characterization in developing AUP-based scaffolds for effective meniscus regeneration. The integration of mechanically optimized scaffolds offers a pathway toward restoring joint function, alleviating pain, and improving the overall quality of life for patients affected by meniscal damage.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114451"},"PeriodicalIF":6.3,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797221","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}
Pub Date : 2025-12-16DOI: 10.1016/j.eurpolymj.2025.114450
Anzar Khan
It has been more than two centuries that selenium was discovered. Similarly, cationic polyelectrolytes employing nitrogen, phosphorous, and sulfur atoms are also known for a long time. However, it is only recently that selenium ions are exploited in the preparation of selenonium polyelectrolytes. Herein, we discuss differences between sulfur and selenium which underline the distinctiveness of polyselenoethers. The recent advances in the synthesis of organoselenium polymers are then discussed. Subsequently, polyselenoium salts are introduced along with their capability to be antibacterial. Finally, the progress in the field is summarized and future goals are identified.
{"title":"An update on selenium-containing polymers and introduction to polyselenonium salts","authors":"Anzar Khan","doi":"10.1016/j.eurpolymj.2025.114450","DOIUrl":"10.1016/j.eurpolymj.2025.114450","url":null,"abstract":"<div><div>It has been more than two centuries that selenium was discovered. Similarly, cationic polyelectrolytes employing nitrogen, phosphorous, and sulfur atoms are also known for a long time. However, it is only recently that selenium ions are exploited in the preparation of selenonium polyelectrolytes. Herein, we discuss differences between sulfur and selenium which underline the distinctiveness of polyselenoethers. The recent advances in the synthesis of organoselenium polymers are then discussed. Subsequently, polyselenoium salts are introduced along with their capability to be antibacterial. Finally, the progress in the field is summarized and future goals are identified.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114450"},"PeriodicalIF":6.3,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797213","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}
Pub Date : 2025-12-15DOI: 10.1016/j.eurpolymj.2025.114449
Dongsheng Xie , Anjie Yang , Liangwei Li , Haitian Wei , Yameng Shi , Na Li , Xiang Gao
Photoresists are critical materials for patterning high-resolution features in semiconductor manufacturing. ArF photoresist polymers, which are predominantly multicomponent acrylate copolymers, cannot be synthesized via living anionic polymerization. Consequently, conventional free radical polymerization (FRP) remains the predominant method for their production. However, FRP struggles to meet the stringent requirements for high-performance photoresists, which demand well-defined molecular weights, narrow polydispersity (Đ), and excellent batch-to-batch consistency. Herein, we report a robust synthesis of ArF photoresist polymers by integrating continuous-flow technology with reversible addition–fragmentation chain transfer (RAFT) polymerization. This process maintains high output quality stability and controllability, yielding polymers with well-defined molecular weights and narrow polydispersity (Đ < 1.2). It achieves over 90 % conversion within 200 min and is applicable to microchannel systems with solids content exceeding 40 wt%, meeting commercially viable polymerization results. Furthermore, we introduce an efficient and green method for removing thiocarbonylthio end groups via aqueous hydrogen peroxide treatment under mild conditions. This approach prevents the degradation of thermal stability and lithographic sensitivity performance typically caused by residual RAFT terminal groups. The RAFT-derived, desulfurized photoresist produced patterns with significantly lower line-edge roughness than the FRP-based material, demonstrating superior lithographic performance. This end group removal strategy offers high throughput, excellent efficiency, and seamless compatibility with continuous-flow processes, highlighting its strong potential for industrial adoption.
{"title":"Synthesis of ArF photoresist polymers via continuous-flow RAFT polymerization with an efficient strategy for their thiocarbonylthio end group removal","authors":"Dongsheng Xie , Anjie Yang , Liangwei Li , Haitian Wei , Yameng Shi , Na Li , Xiang Gao","doi":"10.1016/j.eurpolymj.2025.114449","DOIUrl":"10.1016/j.eurpolymj.2025.114449","url":null,"abstract":"<div><div>Photoresists are critical materials for patterning high-resolution features in semiconductor manufacturing. ArF photoresist polymers, which are predominantly multicomponent acrylate copolymers, cannot be synthesized via living anionic polymerization. Consequently, conventional free radical polymerization (FRP) remains the predominant method for their production. However, FRP struggles to meet the stringent requirements for high-performance photoresists, which demand well-defined molecular weights, narrow polydispersity (<em>Đ</em>), and excellent batch-to-batch consistency. Herein, we report a robust synthesis of ArF photoresist polymers by integrating continuous-flow technology with reversible addition–fragmentation chain transfer (RAFT) polymerization. This process maintains high output quality stability and controllability, yielding polymers with well-defined molecular weights and narrow polydispersity (<em>Đ</em> < 1.2). It achieves over 90 % conversion within 200 min and is applicable to microchannel systems with solids content exceeding 40 wt%, meeting commercially viable polymerization results. Furthermore, we introduce an efficient and green method for removing thiocarbonylthio end groups via aqueous hydrogen peroxide treatment under mild conditions. This approach prevents the degradation of thermal stability and lithographic sensitivity performance typically caused by residual RAFT terminal groups. The RAFT-derived, desulfurized photoresist produced patterns with significantly lower line-edge roughness than the FRP-based material, demonstrating superior lithographic performance. This end group removal strategy offers high throughput, excellent efficiency, and seamless compatibility with continuous-flow processes, highlighting its strong potential for industrial adoption.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114449"},"PeriodicalIF":6.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797216","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}
Pub Date : 2025-12-14DOI: 10.1016/j.eurpolymj.2025.114443
Yue Ding , Shuai Liu , Qintang Li , Dan Huang , Junhui Ji
Commercialized poly(butylene adipate -co- butylene terephthalate) (PBAT) was a high-performance biodegradable polyester. However, the limited tensile strength, poor gas barrier properties, and insufficient fracture toughness restricted the broader application of PBAT. Herein, the incorporation of bis-amide structure into the PBAT main chain strengthened the hydrogen bonding interaction, obtaining the high mechanical strength (∼65 MPa) and excellent toughness (∼1000 %) of PBAT plastic. The enhancement of inter-chain interactions through hydrogen bonding reduced free volume of the chains, thereby improving the gas barrier performance of PBAT. Moreover, PBAT plastic retained good biodegradability under composting conditions, emphasizing its significant potential for expanding the application of in the packaging and agricultural film industries. The introduction of multiple hydrogen bonding interactions offered a promising strategy for the development of high-performance and controllably degradable plastic.
{"title":"Simultaneous improvement of mechanical strength, toughness and barrier properties of PBAT plastics enabled by H-bond interaction","authors":"Yue Ding , Shuai Liu , Qintang Li , Dan Huang , Junhui Ji","doi":"10.1016/j.eurpolymj.2025.114443","DOIUrl":"10.1016/j.eurpolymj.2025.114443","url":null,"abstract":"<div><div>Commercialized poly(butylene adipate -co- butylene terephthalate) (PBAT) was a high-performance biodegradable polyester. However, the limited tensile strength, poor gas barrier properties, and insufficient fracture toughness restricted the broader application of PBAT. Herein, the incorporation of bis-amide structure into the PBAT main chain strengthened the hydrogen bonding interaction, obtaining the high mechanical strength (∼65 MPa) and excellent toughness (∼1000 %) of PBAT plastic. The enhancement of inter-chain interactions through hydrogen bonding reduced free volume of the chains, thereby improving the gas barrier performance of PBAT. Moreover, PBAT plastic retained good biodegradability under composting conditions, emphasizing its significant potential for expanding the application of in the packaging and agricultural film industries. The introduction of multiple hydrogen bonding interactions offered a promising strategy for the development of high-performance and controllably degradable plastic.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114443"},"PeriodicalIF":6.3,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797222","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}
Pub Date : 2025-12-13DOI: 10.1016/j.eurpolymj.2025.114445
Tianwen Liu , Yiming Wang , Xuelei Dong , Yanwei Zhang , Min Wang , Xiongwei Qu , Shengli Chen
The construction of three-dimensional (3D) nanostructures via block copolymer self-assembly remains challenging due to insufficient thermodynamic driving forces and limitations in scalable fabrication. Herein, we report a robust polymerization-induced crystallization-driven self-assembly (PI-CDSA) strategy for the in situ synthesis and hierarchical self-assembly of poly(ethylene glycol monomethyl ether)-block-poly(L-lactide) (mPEG-b-PLLA) diblock copolymers in γ-butyrolactone at room temperature. By synergizing ring-opening polymerization with crystallization-driven assembly, we achieved the scalable fabricated well-defined 3D multilayer rhombic nanosheets with high morphological uniformity and macroscopic dispersibility. The geometry of the nanosheets, including edge length, surface area, and layer number, can be precisely controlled by tuning the degrees of polymerization of the PLLA block and mPEG macroinitiator. Systematic investigations using TEM, SEM, AFM, and OM revealed a clear morphological evolution from spherical micelles to 2D rhombic lamellae and ultimately to 3D multilayered stacked nanosheets. This work not only demonstrates the potential of PI-CDSA as a scalable and programmable platform for constructing complex 3D nanoparticles but also provides mechanistic insights into hierarchical self-assembly, with promising applications in nanomedicine and energy storage.
{"title":"Scalable Polymerization-Induced Crystallization-Driven Self-Assembly toward 3D multilayer rhombic nanosheets","authors":"Tianwen Liu , Yiming Wang , Xuelei Dong , Yanwei Zhang , Min Wang , Xiongwei Qu , Shengli Chen","doi":"10.1016/j.eurpolymj.2025.114445","DOIUrl":"10.1016/j.eurpolymj.2025.114445","url":null,"abstract":"<div><div>The construction of three-dimensional (3D) nanostructures via block copolymer self-assembly remains challenging due to insufficient thermodynamic driving forces and limitations in scalable fabrication. Herein, we report a robust polymerization-induced crystallization-driven self-assembly (PI-CDSA) strategy for the <em>in situ</em> synthesis and hierarchical self-assembly of poly(ethylene glycol monomethyl ether)-<em>block</em>-poly(<em>L-</em>lactide) (mPEG-<em>b</em>-PLLA) diblock copolymers in <em>γ</em>-butyrolactone at room temperature. By synergizing ring-opening polymerization with crystallization-driven assembly, we achieved the scalable fabricated well-defined 3D multilayer rhombic nanosheets with high morphological uniformity and macroscopic dispersibility. The geometry of the nanosheets, including edge length, surface area, and layer number, can be precisely controlled by tuning the degrees of polymerization of the PLLA block and mPEG macroinitiator. Systematic investigations using TEM, SEM, AFM, and OM revealed a clear morphological evolution from spherical micelles to 2D rhombic lamellae and ultimately to 3D multilayered stacked nanosheets. This work not only demonstrates the potential of PI-CDSA as a scalable and programmable platform for constructing complex 3D nanoparticles but also provides mechanistic insights into hierarchical self-assembly, with promising applications in nanomedicine and energy storage.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114445"},"PeriodicalIF":6.3,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797215","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}
Pub Date : 2025-12-13DOI: 10.1016/j.eurpolymj.2025.114446
Apollinariya Yu. Konyakhina , Akmal Z. Umarov , Jessica Garcia , Foad Vashahi , Evgeniy V. Dubrovin , Elena N. Subcheva , Aleksandr I. Buglakov , Sergei S. Sheiko , Dimitri A. Ivanov
Thermosensitive bottlebrush triblock copolymers combining poly(N-isopropylacrylamide) (PNIPAM) and poly(ethylene glycol) (PEG) represent a promising class of responsive soft materials. We investigate their molecular morphology and gelation behavior using direct-space imaging, synchrotron small-angle X-ray scattering (SAXS), and coarse-grained simulations. Atomic Force Microscopy (AFM) revealed wormlike bottlebrush backbones, while PNIPAM end blocks were detected under specific conditions using modified substrates. Transmission and scanning transmission electron microscopy (TEM/STEM) with negative staining corroborated AFM observations and provided consistent contour-length distributions. Variable-temperature SAXS revealed fully reversible structural reorganization upon heating above the PNIPAM LCST. This transition was marked by the emergence of an ordered gel network, evidenced by an interference peak corresponding to interdomain spacing and form-factor oscillations associated with PNIPAM micelles. Analysis indicated modest micelle growth while the interdomain spacing remained constant. Complementary dissipative particle dynamics simulations reproduced these features and revealed a crossover at ϕpol ≈ 0.04, where bridging subchains dominate network formation. Together, these results provide a multiscale understanding of bottlebrush copolymer gelation and identify key parameters controlling their responsive behavior.
{"title":"Structure and gelation properties of thermoresponsive bottlebrush hydrogels","authors":"Apollinariya Yu. Konyakhina , Akmal Z. Umarov , Jessica Garcia , Foad Vashahi , Evgeniy V. Dubrovin , Elena N. Subcheva , Aleksandr I. Buglakov , Sergei S. Sheiko , Dimitri A. Ivanov","doi":"10.1016/j.eurpolymj.2025.114446","DOIUrl":"10.1016/j.eurpolymj.2025.114446","url":null,"abstract":"<div><div>Thermosensitive bottlebrush triblock copolymers combining poly(N-isopropylacrylamide) (PNIPAM) and poly(ethylene glycol) (PEG) represent a promising class of responsive soft materials. We investigate their molecular morphology and gelation behavior using direct-space imaging, synchrotron small-angle X-ray scattering (SAXS), and coarse-grained simulations. Atomic Force Microscopy (AFM) revealed wormlike bottlebrush backbones, while PNIPAM end blocks were detected under specific conditions using modified substrates. Transmission and scanning transmission electron microscopy (TEM/STEM) with negative staining corroborated AFM observations and provided consistent contour-length distributions. Variable-temperature SAXS revealed fully reversible structural reorganization upon heating above the PNIPAM LCST. This transition was marked by the emergence of an ordered gel network, evidenced by an interference peak corresponding to interdomain spacing and form-factor oscillations associated with PNIPAM micelles. Analysis indicated modest micelle growth while the interdomain spacing remained constant. Complementary dissipative particle dynamics simulations reproduced these features and revealed a crossover at ϕ<sub>pol</sub> ≈ 0.04, where bridging subchains dominate network formation. Together, these results provide a multiscale understanding of bottlebrush copolymer gelation and identify key parameters controlling their responsive behavior.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"242 ","pages":"Article 114446"},"PeriodicalIF":6.3,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797225","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}
Pub Date : 2025-12-13DOI: 10.1016/j.eurpolymj.2025.114448
Ismail Omrani, Mohammad Taghizadeh, Ali Salimi, Azizollah Nodehi
In this study, a waterborne polyurethane (WPU) adhesive with self-healing and self-crosslinking capabilities was developed via an encapsulation-based strategy, exhibiting exceptional chemical and physical properties. The encapsulation system employed in this study utilized a furan-functionalized crosslinker in combination with an unsaturated WPU, enabling uniform dispersion under aqueous conditions. A reversibly cross-linked WPU adhesive was achieved, exhibiting remarkable recyclability and outstanding self-healing performance via the Diels–Alder (DA) reaction. Using dynamic light scattering (DLS) and transmission electron microscopy (TEM), it was confirmed that the crosslinker-containing synthesized WPU particles have a particle size of 150 nm with a narrow size distribution. The thermal and mechanical properties of the resulting films were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile testing. The incorporation of the crosslinker led to a significant enhancement in mechanical performance. Notably, when the three-functionalized crosslinker (WPU3) was employed, the Young’s modulus increased markedly from 23 MPa to 81 MPa. Reversible cross-linked WPUs exhibit remarkable recyclability and a notable self-healing capability, achieving an initial tensile strength of up to 85 %. Due to its rich polar functionality, crosslinked WPU demonstrates robust bonding capabilities across a variety of substrates, including aluminum, steel, carbon steel, and epoxy composites. Thanks to specific structural design, the newly synthesized WPU showed reliable reusability, i.e., retaining 87 % of its original shear strength after multiple repair cycles. This study presents an effective method for self-curing WPU, enabling the development of high-performance, rapidly self-healing, and environmentally friendly adhesives.
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