Pub Date : 2026-02-11Epub Date: 2025-12-29DOI: 10.1016/j.eurpolymj.2025.114477
Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li
Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.
{"title":"Isosorbide-based copolymers poly(isosorbide carbonate-co-alkylene naphthalate): Synthesis, properties and fluorescence Regulation","authors":"Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li","doi":"10.1016/j.eurpolymj.2025.114477","DOIUrl":"10.1016/j.eurpolymj.2025.114477","url":null,"abstract":"<div><div>Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114477"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882471","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}
The article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.
{"title":"Modern theoretical and practical approaches to development, research and processing of thermoplastic elastomers and their filled composites. review","authors":"Kh.V. Allahverdiyeva , N.T. Kakhramanov , F.A. Mustafayeva , A.A. Hasanova , L.M. Afandiyeva , R.V. Gurbanova , H.B. Bafadarova , E.I. Suleymanova , A.G. Habibova , T.M. Babayeva , O.M. Guliyeva","doi":"10.1016/j.eurpolymj.2025.114463","DOIUrl":"10.1016/j.eurpolymj.2025.114463","url":null,"abstract":"<div><div>The article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114463"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882475","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 : 2026-02-11Epub Date: 2026-01-02DOI: 10.1016/j.eurpolymj.2026.114496
Yangyang Hu , Ammara Aslam , Runsha Zhai , Yinan Zeng , Silu Wang , Haofei Yang , Anjie Dong , Jianhua Zhang
Due to the advantages of precisely spatiotemporal control and noninvasive manner, the photo-activated micelles derived from photo-responsive block copolymers have found extensive applications in controllable drug delivery systems. However, their practical utility is often constrained, due to the commercial unavailability and high difficulty in synthesis of polymerizable photosensitive monomers, tough challenge in integration of robust blood circulation ability, high toxicity of the metabolite of conventional photo-sensitive O-nitrobenzyl and azobenzene molecules. Herein, a methacryloyl-carrying, polymerizable photoacid generator (MAPDST) was synthesized and used as monomer to prepare amphiphilic photo-responsive block copolymers (PPMT) by RAFT copolymerization with acid-cleavable monomer (TTMA) in the presence of hydrophilic PEGlyated macro-RAFT agent. The structure and physicochemical characteristics of PPMT and corresponding photo-responsive micelles (PPMT NPs) were characterized. The results demonstrated that the PPMT NPs can not only have a high stability for storage and blood circulation as well as good biocompatibility, but also can quickly generate protons and thus strong acidity under UV irradiation, leading to a significant swelling and disassembly by hydrolysis of acid-cleavable TTMA segment and thus achieving a photo-switchable on–off drug release profile. This study indicated the synergistic integration of photoacid and acid-cleavable groups in polymers can provide a facile and promising strategy to endow acid-sensitive polymers and corresponding nanocarriers with desirable photo-responsiveness by photo-triggered cascade reactions. Apparently, considering the multifarious acid-sensitive groups, this new strategy can expand the substrate range of photo-responsive polymer materials and offer alternatives to develop photo-sensitive materials without the limitations associated with conventional photosensitive reagents.
{"title":"Synergistic integration of photoacid and acid-cleavable groups in polymers: An alternative approach to photo-responsive micelles for photo-switchable drug release","authors":"Yangyang Hu , Ammara Aslam , Runsha Zhai , Yinan Zeng , Silu Wang , Haofei Yang , Anjie Dong , Jianhua Zhang","doi":"10.1016/j.eurpolymj.2026.114496","DOIUrl":"10.1016/j.eurpolymj.2026.114496","url":null,"abstract":"<div><div>Due to the advantages of precisely spatiotemporal control and noninvasive manner, the photo-activated micelles derived from photo-responsive block copolymers have found extensive applications in controllable drug delivery systems. However, their practical utility is often constrained, due to the commercial unavailability and high difficulty in synthesis of polymerizable photosensitive monomers, tough challenge in integration of robust blood circulation ability, high toxicity of the metabolite of conventional photo-sensitive O-nitrobenzyl and azobenzene molecules. Herein, a methacryloyl-carrying, polymerizable photoacid generator (MAPDST) was synthesized and used as monomer to prepare amphiphilic photo-responsive block copolymers (PPMT) by RAFT copolymerization with acid-cleavable monomer (TTMA) in the presence of hydrophilic PEGlyated macro-RAFT agent. The structure and physicochemical characteristics of PPMT and corresponding photo-responsive micelles (PPMT NPs) were characterized. The results demonstrated that the PPMT NPs can not only have a high stability for storage and blood circulation as well as good biocompatibility, but also can quickly generate protons and thus strong acidity under UV irradiation, leading to a significant swelling and disassembly by hydrolysis of acid-cleavable TTMA segment and thus achieving a photo-switchable on–off drug release profile. This study indicated the synergistic integration of photoacid and acid-cleavable groups in polymers can provide a facile and promising strategy to endow acid-sensitive polymers and corresponding nanocarriers with desirable photo-responsiveness by photo-triggered cascade reactions. Apparently, considering the multifarious acid-sensitive groups, this new strategy can expand the substrate range of photo-responsive polymer materials and offer alternatives to develop photo-sensitive materials without the limitations associated with conventional photosensitive reagents.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114496"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939772","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}
This work presents a novel strategy for developing a UV-curable bio-based eugenol-derived benzoxazine resin for 4D printing of shape-memory polymers (SMPs) via vat photopolymerization (VPP). The methacrylate group of 2-isocyanatoethyl methacrylate (IEM) was grafted onto the benzoxazine monomer through an isocyanate–hydroxyl reaction, introducing urethane linkages and a methacrylate functional group that enhances hydrogen bonding, improves chain segmental mobility, and imparts UV-reactive functionality. The resulting photoreactive resin exhibits moderate viscosity (25.0 Pa·s at 25 °C and at a shear rate of 30 s−1) and high UV reactivity. After dual UV/thermal curing, the polymer shows high stiffness (storage modulus 2.2 GPa), thermal stability (Td5 = 256 °C), and excellent shape memory performance, with shape fixity and shape recovery ratios ∼ 99 % over 30 cycles. In comparison with conventional benzoxazine-based SMPs, the developed 4D printing SMPs polymer also supports larger temporary shape deformation. Structure–property analyses using solubility testing and DMA indicate a relatively low crosslink density (gel content 56.6 %), suggesting that the thermo-mechanical and shape memory performance primarily arises from the dense hydrogen bonding network within the dual-cured polymer. This study establishes a molecular-design strategy for hydrogen-bonding-rich UV-curable benzoxazine systems and demonstrates the critical role of hydrogen bonding in governing the thermo-mechanical and shape memory properties. The 4D-printed structures produced in this work exhibit large deformation capability and excellent shape memory stability, highlighting their potential for durable and flexible high-performance 4D printing applications.
{"title":"Synthesis and vat-photopolymerization of hydrogen bonding-rich eugenol-based benzoxazine resins for 4D printing of shape memory polymers","authors":"Nuttinan Boonnao , Minwook Jeon , Krittapas Charoensuk , Ibrahim Lawan , Cheol-Hee Ahn , Sarawut Rimdusit","doi":"10.1016/j.eurpolymj.2025.114465","DOIUrl":"10.1016/j.eurpolymj.2025.114465","url":null,"abstract":"<div><div>This work presents a novel strategy for developing a UV-curable bio-based eugenol-derived benzoxazine resin for 4D printing of shape-memory polymers (SMPs) via vat photopolymerization (VPP). The methacrylate group of 2-isocyanatoethyl methacrylate (IEM) was grafted onto the benzoxazine monomer through an isocyanate–hydroxyl reaction, introducing urethane linkages and a methacrylate functional group that enhances hydrogen bonding, improves chain segmental mobility, and imparts UV-reactive functionality. The resulting photoreactive resin exhibits moderate viscosity (25.0 Pa·s at 25 °C and at a shear rate of 30 s<sup>−1</sup>) and high UV reactivity. After dual UV/thermal curing, the polymer shows high stiffness (storage modulus 2.2 GPa), thermal stability (T<sub>d5</sub> = 256 °C), and excellent shape memory performance, with shape fixity and shape recovery ratios ∼ 99 % over 30 cycles. In comparison with conventional benzoxazine-based SMPs, the developed 4D printing SMPs polymer also supports larger temporary shape deformation. Structure–property analyses using solubility testing and DMA indicate a relatively low crosslink density (gel content 56.6 %), suggesting that the thermo-mechanical and shape memory performance primarily arises from the dense hydrogen bonding network within the dual-cured polymer. This study establishes a molecular-design strategy for hydrogen-bonding-rich UV-curable benzoxazine systems and demonstrates the critical role of hydrogen bonding in governing the thermo-mechanical and shape memory properties. The 4D-printed structures produced in this work exhibit large deformation capability and excellent shape memory stability, highlighting their potential for durable and flexible high-performance 4D printing applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114465"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839546","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 : 2026-02-11Epub Date: 2025-12-24DOI: 10.1016/j.eurpolymj.2025.114471
Osama Younis , Faten M. Taher , Marwa M. Sayed, Mostafa Sayed, Mostafa Ahmed
This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, Mono-BenzOx and Mono-NaphthOx, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While Poly-BenzOx showed residual excimer emission, Poly-NaphthOx displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with Poly-NaphthOx exhibiting a higher decomposition temperature (Td5 = 275 °C) and a significantly greater char yield (27 %) than Poly-BenzOx (Td5 = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts Poly-NaphthOx as a premier multifunctional material for advanced optoelectronic and high-performance applications.
{"title":"Naphthoxazine outperforms benzoxazine: carbazole-based polymers with enhanced blue luminescence and high thermal stability","authors":"Osama Younis , Faten M. Taher , Marwa M. Sayed, Mostafa Sayed, Mostafa Ahmed","doi":"10.1016/j.eurpolymj.2025.114471","DOIUrl":"10.1016/j.eurpolymj.2025.114471","url":null,"abstract":"<div><div>This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, <strong>Mono-BenzOx</strong> and <strong>Mono-NaphthOx</strong>, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While <strong>Poly-BenzOx</strong> showed residual excimer emission, <strong>Poly-NaphthOx</strong> displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with <strong>Poly-NaphthOx</strong> exhibiting a higher decomposition temperature (T<sub>d5</sub> = 275 °C) and a significantly greater char yield (27 %) than <strong>Poly-BenzOx</strong> (T<sub>d5</sub> = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts <strong>Poly-NaphthOx</strong> as a premier multifunctional material for advanced optoelectronic and high-performance applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114471"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839548","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 : 2026-02-11Epub Date: 2026-01-02DOI: 10.1016/j.eurpolymj.2025.114491
Yuya Kaneko, Aohan Wang
Innovative coumarin-based π-conjugated polymers have been successfully developed, possessing remarkable solubility and reversible alteration of fluorescence in response to changes in acid and base. Through meticulous molecular design, we synthesized two novel dibromo coumarin monomers: 3,7-dibromo-4-methyl-8-octyloxycoumarin and 3,6-dibromo-7,8-dioctyloxy-4-methylcoumarin. By strategically introducing the alkoxy side chains into the benzene ring, rather than the α-pyrone ring of the coumarin backbone, we achieved exceptional ring-opening and ring-closing properties within the polymer mainchain. The resulting coumarin polymers exhibit high molecular weight and reversible turn-on/off fluorescence. Moreover, the effects of the position of the alkoxy side chain on the ring-opening and ring-closing properties were investigated by using coumarin-based model compounds. Our research involved the synthesis of models featuring methyl, methoxy, and octyloxy moieties at the C4 position, along with an octyloxy chain at the C8 position. The results revealed that the positioning of the alkoxy chain plays a pivotal role that directly influences the ring-opening and ring-closing mechanism in the coumarin unit. Furthermore, the chemical structures of the ring-opened coumarin polymer in the basic state and the ring-closed coumarin polymer in the acidic state were examined. We found clear evidence in the ring-opened form that the C=O double bonds in the lactone ring converted to the COO− chelate structure in FT-IR spectra, and potassium was detected in XPS spectra.
{"title":"A definitive molecular design strategy towards coumarin-based polymers exhibiting reversible acid/base responsivity and high solubility −Exploring the effects of substituent groups at the C4 position of asymmetric coumarin monomer on their ring-opening and closing properties-","authors":"Yuya Kaneko, Aohan Wang","doi":"10.1016/j.eurpolymj.2025.114491","DOIUrl":"10.1016/j.eurpolymj.2025.114491","url":null,"abstract":"<div><div>Innovative coumarin-based π-conjugated polymers have been successfully developed, possessing remarkable solubility and reversible alteration of fluorescence in response to changes in acid and base. Through meticulous molecular design, we synthesized two novel dibromo coumarin monomers: 3,7-dibromo-4-methyl-8-octyloxycoumarin and 3,6-dibromo-7,8-dioctyloxy-4-methylcoumarin. By strategically introducing the alkoxy side chains into the benzene ring, rather than the α-pyrone ring of the coumarin backbone, we achieved exceptional ring-opening and ring-closing properties within the polymer mainchain. The resulting coumarin polymers exhibit high molecular weight and reversible turn-on/off fluorescence. Moreover, the effects of the position of the alkoxy side chain on the ring-opening and ring-closing properties were investigated by using coumarin-based model compounds. Our research involved the synthesis of models featuring methyl, methoxy, and octyloxy moieties at the C4 position, along with an octyloxy chain at the C8 position. The results revealed that the positioning of the alkoxy chain plays a pivotal role that directly influences the ring-opening and ring-closing mechanism in the coumarin unit. Furthermore, the chemical structures of the ring-opened coumarin polymer in the basic state and the ring-closed coumarin polymer in the acidic state were examined. We found clear evidence in the ring-opened form that the C=O double bonds in the lactone ring converted to the COO<sup>−</sup> chelate structure in FT-IR spectra, and potassium was detected in XPS spectra.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114491"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939778","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}
Erlotinib therapy for non-small cell lung cancer is limited by poor solubility and a lack of targeted delivery, leading to systemic adverse effects. To address this, a novel near-infrared (NIR) light-triggered nanoplatform was developed using a pH- and thermoresponsive polymer functionalized with sericin-grafted strontium hexaferrite/graphene quantum dots. The drug adsorption process was optimized using response surface methodology, and the Langmuir isotherm and pseudo-second-order kinetic models confirmed monolayer sorption on a homogeneous surface. Under acidic conditions at high temperature, the system demonstrated a controlled release of 63.10 % of the erlotinib, which was best described by the Korsmeyer-Peppas model, indicating a non-Fickian diffusion mechanism. The significance of this platform was highlighted by its dramatic response to external stimuli, achieving a 100 % drug release rate upon NIR laser irradiation for 45 min. This on-demand capability translated to potent biological effects, while the blank nanocarrier was non-cytotoxic, the erlotinib-loaded nanocomposite induced significant cell death in A549 lung cancer cells, with flow cytometry confirming an apoptosis/necrosis rate of 7.07 %. Biocompatibility of the novel nanocomposite has been extensively verified through platelet adhesion, hemolysis assay, and partial thromboplastin time test. This study presents a highly promising and stimuli-responsive strategy for the precise and effective delivery of erlotinib.
{"title":"pH-and NIR-responsive sericin-coated magnetic graphene quantum dots for enhanced lung cancer therapy","authors":"Farimah Alidousti , Habib Razmi , Homayon Ahmad Panahi , Elham Moniri","doi":"10.1016/j.eurpolymj.2025.114455","DOIUrl":"10.1016/j.eurpolymj.2025.114455","url":null,"abstract":"<div><div>Erlotinib therapy for non-small cell lung cancer is limited by poor solubility and a lack of targeted delivery, leading to systemic adverse effects. To address this, a novel near-infrared (NIR) light-triggered nanoplatform was developed using a pH- and thermoresponsive polymer functionalized with sericin-grafted strontium hexaferrite/graphene quantum dots. The drug adsorption process was optimized using response surface methodology, and the Langmuir isotherm and pseudo-second-order kinetic models confirmed monolayer sorption on a homogeneous surface. Under acidic conditions at high temperature, the system demonstrated a controlled release of 63.10 % of the erlotinib, which was best described by the Korsmeyer-Peppas model, indicating a non-Fickian diffusion mechanism. The significance of this platform was highlighted by its dramatic response to external stimuli, achieving a 100 % drug release rate upon NIR laser irradiation for 45 min. This on-demand capability translated to potent biological effects, while the blank nanocarrier was non-cytotoxic, the erlotinib-loaded nanocomposite induced significant cell death in A549 lung cancer cells, with flow cytometry confirming an apoptosis/necrosis rate of 7.07 %. Biocompatibility of the novel nanocomposite has been extensively verified through platelet adhesion, hemolysis assay, and partial thromboplastin time test. This study presents a highly promising and stimuli-responsive strategy for the precise and effective delivery of erlotinib.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114455"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882472","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 : 2026-02-11Epub Date: 2025-12-30DOI: 10.1016/j.eurpolymj.2025.114479
Baoyun Cao, Chuanzheng Ren, Jianjun Bao
Conventional photocurable polyurethanes possess permanently crosslinked networks that impede recyclability, thereby raising significant environmental concerns. In this work, a general molecular strategy is proposed to impart dynamic reversibility to photocurable systems by incorporating dynamic covalent bonds into both the prepolymer and crosslinker domains. Tert-Butylaminoethyl methacrylate (TBEMA) was utilized to construct a dynamic urea-based crosslinker (HTB) and to end-cap polyurethane prepolymers, ensuring chemical compatibility within the system. By combining these components with flexible (CTFA) or rigid (IBMA) active diluents, a series of UV-curable formulations suitable for digital light processing (DLP) were developed. The cured flexible and rigid resins exhibited tensile strengths of approximately 12 MPa and over 45 MPa, respectively, along with excellent printing fidelity. Rheological analysis revealed a persistent long relaxation process within the networks, which fundamentally governs their thermomechanical behavior and directly guided the selection of hot-pressing as the optimal reprocessing technique. Leveraging this dynamic character, the crosslinked networks were successfully reprocessed via hot-pressing. Furthermore, a practical recycling route for mixed polyurethane waste was established by blending the reprocessed resins with virgin thermoplastic polyurethane (TPU), affording homogeneous composites with well-preserved mechanical integrity. This study provides a versatile molecular design paradigm for recyclable thermosetting resins and contributes to advancing the sustainability of photocurable 3D printing materials.
{"title":"Reprocessable and 3D-printable polyurethane thermosets with dynamic covalent urea networks","authors":"Baoyun Cao, Chuanzheng Ren, Jianjun Bao","doi":"10.1016/j.eurpolymj.2025.114479","DOIUrl":"10.1016/j.eurpolymj.2025.114479","url":null,"abstract":"<div><div>Conventional photocurable polyurethanes possess permanently crosslinked networks that impede recyclability, thereby raising significant environmental concerns. In this work, a general molecular strategy is proposed to impart dynamic reversibility to photocurable systems by incorporating dynamic covalent bonds into both the prepolymer and crosslinker domains. Tert-Butylaminoethyl methacrylate (TBEMA) was utilized to construct a dynamic urea-based crosslinker (HTB) and to end-cap polyurethane prepolymers, ensuring chemical compatibility within the system. By combining these components with flexible (CTFA) or rigid (IBMA) active diluents, a series of UV-curable formulations suitable for digital light processing (DLP) were developed. The cured flexible and rigid resins exhibited tensile strengths of approximately 12 MPa and over 45 MPa, respectively, along with excellent printing fidelity. Rheological analysis revealed a persistent long relaxation process within the networks, which fundamentally governs their thermomechanical behavior and directly guided the selection of hot-pressing as the optimal reprocessing technique. Leveraging this dynamic character, the crosslinked networks were successfully reprocessed via hot-pressing. Furthermore, a practical recycling route for mixed polyurethane waste was established by blending the reprocessed resins with virgin thermoplastic polyurethane (TPU), affording homogeneous composites with well-preserved mechanical integrity. This study provides a versatile molecular design paradigm for recyclable thermosetting resins and contributes to advancing the sustainability of photocurable 3D printing materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114479"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882467","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}
Aliphatic polycarbonates have attracted significant attention for their biodegradability and biocompatibility, yet there are also limitations impacting their applications, which usually need to be further optimized by post modification. Carbene polymerization of diazocompounds is an alternative method to undergo further modification for the aliphatic polycarbonates, due to its unique advantage of synthesizing highly functionalized polymers. In this work, the copolymerization of cyclic carbonates with diazoacetates was achieved through a post-addition strategy with the sequence of “cyclic monomer first added, followed by diazoacetate” catalyzed by Sn(Oct)2. Notably, the resulting nonconventional cyclic carbonate-diazoacetate copolymers exhibit novel fluorescence property despite lacking traditionally known conjugated fluorescent chromophores. In addition, its thermal stability can also be adjusted conveniently via multiple approaches by varying the monomers, or altering the feed ratio of the two kinds of monomers, or regulating the molecular weight of the copolymers.
{"title":"Nonconventional fluorescent copolymers synthesized from cyclic carbonates and diazoacetates via a post-addition strategy","authors":"Xiang-Xiang Jia, Hong-Lei Li, Xiao-Jie Lu, Xiao-Chi Li, Zhi-Ling Ye, Xu Wang, Jun-Chuan Wang, Hui Wang, Xiang-Feng Wu","doi":"10.1016/j.eurpolymj.2025.114492","DOIUrl":"10.1016/j.eurpolymj.2025.114492","url":null,"abstract":"<div><div>Aliphatic polycarbonates have attracted significant attention for their biodegradability and biocompatibility, yet there are also limitations impacting their applications, which usually need to be further optimized by post modification. Carbene polymerization of diazocompounds is an alternative method to undergo further modification for the aliphatic polycarbonates, due to its unique advantage of synthesizing highly functionalized polymers. In this work, the copolymerization of cyclic carbonates with diazoacetates was achieved through a post-addition strategy with the sequence of “cyclic monomer first added, followed by diazoacetate” catalyzed by Sn(Oct)<sub>2</sub>. Notably, the resulting nonconventional cyclic carbonate-diazoacetate copolymers exhibit novel fluorescence property despite lacking traditionally known conjugated fluorescent chromophores. In addition, its thermal stability can also be adjusted conveniently via multiple approaches by varying the monomers, or altering the feed ratio of the two kinds of monomers, or regulating the molecular weight of the copolymers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114492"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939773","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}