Pub Date : 2026-01-16DOI: 10.1016/j.eurpolymj.2026.114509
Adalet Nur Altunkaya , Binnur Aydogan Temel , Muhammet U. Kahveci
Single-chain polymer nanoparticles (SCNPs) have garnered significant attention due to their ability to mimic the folding behavior of proteins and their potential in applications such as drug delivery, catalysis, and sensing. Herein, we present a novel approach for preparation of SCNPs using a photo-induced inverse electron-demand Diels-Alder (photo-IEDDA) reaction. The base polymer, P(MMA-co-HEMA), synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, was functionalized with dihydrotetrazine (dHTz) and norbornene (Nb) moieties through esterification over HEMA units. Upon irradiation of a dilute solution of the modified polymer, P(MMA-co-HEMA)-M−PPA−dHTz/Nb, in the presence of a photosensitizer, dihydrotetrazine groups were in situ converted to reactive tetrazine moieties, enabling intramolecular crosslinking via the photo-IEDDA reaction. This process yielded sub-10 nm SCNPs with high precision and control. The integration of light-triggered reactivity with efficient click chemistry highlights the potential of this method for the scalable production of well-defined SCNPs with tailored properties for advanced applications in nanotechnology and materials science.
{"title":"Fabrication of single-chain polymer nanoparticles by light-induced inverse electron demand diels-alder (Photo-IEDDA) reaction","authors":"Adalet Nur Altunkaya , Binnur Aydogan Temel , Muhammet U. Kahveci","doi":"10.1016/j.eurpolymj.2026.114509","DOIUrl":"10.1016/j.eurpolymj.2026.114509","url":null,"abstract":"<div><div>Single-chain polymer nanoparticles (SCNPs) have garnered significant attention due to their ability to mimic the folding behavior of proteins and their potential in applications such as drug delivery, catalysis, and sensing. Herein, we present a novel approach for preparation of SCNPs using a photo-induced inverse electron-demand Diels-Alder (photo-IEDDA) reaction. The base polymer, P(MMA-<em>co</em>-HEMA), synthesized <em>via</em> reversible addition-fragmentation chain transfer (RAFT) polymerization, was functionalized with dihydrotetrazine (dHTz) and norbornene (Nb) moieties through esterification over HEMA units. Upon irradiation of a dilute solution of the modified polymer, P(MMA-<em>co</em>-HEMA)-<em>M</em>−PPA−dHTz/Nb, in the presence of a photosensitizer, dihydrotetrazine groups were <em>in situ</em> converted to reactive tetrazine moieties, enabling intramolecular crosslinking <em>via</em> the photo-IEDDA reaction. This process yielded sub-10 nm SCNPs with high precision and control. The integration of light-triggered reactivity with efficient click chemistry highlights the potential of this method for the scalable production of well-defined SCNPs with tailored properties for advanced applications in nanotechnology and materials science.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114509"},"PeriodicalIF":6.3,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035776","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 : 2026-01-14DOI: 10.1016/j.eurpolymj.2026.114500
Martina Vragović , Jan Pankrác , Peter Páral , Martin Báječný , Alessandro Jäger , Vladimir Sincari , Jan Kučka , Martin Hrubý , Marcela Filipová , Rafał Konefał , Fernando Carlos Giacomelli , Luděk Šefc , Eliézer Jäger
Nanomedicines have shown significant potential in advancing treatment for a variety of cancer types. Despite these advances, further research is essential to improve the efficacy and selectivity of anticancer nanomedicines, particularly by developing delivery systems capable of achieving high efficacy with minimal off-target toxicity. We herein report novel pH-responsive block copolymer-drug conjugates based on poly(N-(2-hydroxypropyl)methacrylamide) (PHPMAm) and benzoic imine linkages, uniquely combining stealth performance with tunable, acid-triggered drug release. By engineering block and random copolymer architectures with controlled hydrophilic shell length, we systematically evaluated how polymer structure governs self-assembly, release kinetics, and therapeutic outcomes. The conjugates achieve up to 10–12 wt% doxorubicin loading, with pH-selective release half-live spanning within 2–40 h. In contrast to most Schiff base polymer-drug systems limited to in vitro data, the synthesized polymer-drug conjugates demonstrated outstanding antitumor efficacy and 100 % survival for spherical assemblies in aggressive murine lymphoma models, with superior safety. Unlike conventional PEG systems, PHPMAm-based copolymers can potentially avoid anti-PEG immunogenicity and exhibit exceptional in vivo stability and tumor accumulation.
{"title":"Morphology control in benzoic imine-linked polymer-drug conjugates for adaptive drug delivery and enhanced in vivo efficacy","authors":"Martina Vragović , Jan Pankrác , Peter Páral , Martin Báječný , Alessandro Jäger , Vladimir Sincari , Jan Kučka , Martin Hrubý , Marcela Filipová , Rafał Konefał , Fernando Carlos Giacomelli , Luděk Šefc , Eliézer Jäger","doi":"10.1016/j.eurpolymj.2026.114500","DOIUrl":"10.1016/j.eurpolymj.2026.114500","url":null,"abstract":"<div><div>Nanomedicines have shown significant potential in advancing treatment for a variety of cancer types. Despite these advances, further research is essential to improve the efficacy and selectivity of anticancer nanomedicines, particularly by developing delivery systems capable of achieving high efficacy with minimal off-target toxicity. We herein report novel pH-responsive block copolymer-drug conjugates based on poly(<em>N</em>-(2-hydroxypropyl)methacrylamide) (PHPMAm) and benzoic imine linkages, uniquely combining stealth performance with tunable, acid-triggered drug release. By engineering block and random copolymer architectures with controlled hydrophilic shell length, we systematically evaluated how polymer structure governs self-assembly, release kinetics, and therapeutic outcomes. The conjugates achieve up to 10–12 wt% doxorubicin loading, with pH-selective release half-live spanning within 2–40 h. In contrast to most Schiff base polymer-drug systems limited to <em>in vitro</em> data, the synthesized polymer-drug conjugates demonstrated outstanding antitumor efficacy and 100 % survival for spherical assemblies in aggressive murine lymphoma models, with superior safety. Unlike conventional PEG systems, PHPMAm-based copolymers can potentially avoid anti-PEG immunogenicity and exhibit exceptional <em>in vivo</em> stability and tumor accumulation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114500"},"PeriodicalIF":6.3,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035777","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 : 2026-01-14DOI: 10.1016/j.eurpolymj.2026.114517
Yichen Tian , Yanan Li , Mengyuan Xu , Wenjie Li , Hailin Cong , Bing Yu
Polyvinyl alcohol (PVA) hydrogels constitute a fundamental material platform in biomedical engineering, distinguished by their inherent hydrophilicity, exceptional biocompatibility, and low cytotoxicity. Their unique molecular architecture, featuring abundant hydroxyl groups, serves as reactive sites for diverse chemical modifications. Strategies such as blending, graft copolymerization, and nanocomposite formation enable the effective incorporation of functional polymers, bioactive molecules, and nanomaterials into the PVA matrix. These strategies mitigate the intrinsic limitations of PVA while introducing tailored functionalities, facilitating the design of advanced hydrogels with enhanced performance. This review presents a systematic overview of modification strategies for PVA hydrogels, with the goal of enhancing their antibacterial properties, mechanical strength, and cell adhesion. It further explores their applications in wound dressings, drug delivery, tissue engineering, strain sensors, and biomedical detection. Finally, the review concludes by summarizing the application prospects and key challenges of PVA hydrogels, aiming to provide new insights for related biomedical applications.
{"title":"Polyvinyl alcohol Hydrogels: Structure, Preparation, Modification Strategies and Biomedical Applications","authors":"Yichen Tian , Yanan Li , Mengyuan Xu , Wenjie Li , Hailin Cong , Bing Yu","doi":"10.1016/j.eurpolymj.2026.114517","DOIUrl":"10.1016/j.eurpolymj.2026.114517","url":null,"abstract":"<div><div>Polyvinyl alcohol (PVA) hydrogels constitute a fundamental material platform in biomedical engineering, distinguished by their inherent hydrophilicity, exceptional biocompatibility, and low cytotoxicity. Their unique molecular architecture, featuring abundant hydroxyl groups, serves as reactive sites for diverse chemical modifications. Strategies such as blending, graft copolymerization, and nanocomposite formation enable the effective incorporation of functional polymers, bioactive molecules, and nanomaterials into the PVA matrix. These strategies mitigate the intrinsic limitations of PVA while introducing tailored functionalities, facilitating the design of advanced hydrogels with enhanced performance. This review presents a systematic overview of modification strategies for PVA hydrogels, with the goal of enhancing their antibacterial properties, mechanical strength, and cell adhesion. It further explores their applications in wound dressings, drug delivery, tissue engineering, strain sensors, and biomedical detection. Finally, the review concludes by summarizing the application prospects and key challenges of PVA hydrogels, aiming to provide new insights for related biomedical applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114517"},"PeriodicalIF":6.3,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035771","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}
Due to the rapid progress in high frequency and high speed communication technologies, there is an urgent demand for polyimide (PI) films that exhibit both low dielectric constant (Dk) and low dielectric loss (Df) at high frequencies. Achieving a reduction in the Dk of PIs at high frequencies is relatively straightforward in accordance with the Clausius–Mossotti equation. However, the optimization of Df is more complex and challenging than that of Dk. From the perspective of polarization mechanisms, suppressing dipolar orientational polarization (Pd) provides an effective way to lower Df. Inspired by liquid crystalline polyesters (LCPs), poly(ester imide)s (PEIs) can achieve ultralow Df (Df < 0.0030) by reducing intermolecular friction, but they still exhibit relatively high Dk (Dk > 3.20). In this work, a high free volume triptycene-based diamine (TPC-NH2) was copolymerized with three ester-containing dianhydrides—phenyl ester (TAHQ), naphthalene ester (NAHQ), and biphenyl ester (BAHQ)—to prepare a series of PEI films with different mesogen units. The influence of the molecular conformations of the mesogen unit on aggregation structure, dielectric properties, thermal properties, mechanical properties, and moisture absorption was systematically evaluated. Wide-angle X-ray diffraction, polarized optical microscopy, and molecular dynamics simulations revealed that phenyl ester dianhydride (TAHQ) and naphthalene ester dianhydride (NAHQ) units yielded amorphous PEIs with low Dk values of 2.62 and 2.55 at 10 GHz, respectively. The “crankshaft-like” para-aromatic ester linkage (Ph–COO–Ph-OCO–Ph) in TPC-TAHQ and TPC-NAHQ restricted imide group deflection through interchain dipole–dipole interactions, thereby lowering Df to 0.0068 and 0.0051 at 10 GHz, respectively. In contrast, biphenyl ester dianhydride BAHQ-based PEI (TPC-BAHQ) promoted the formation of liquid–crystal-like ordered structure, achieving the lowest Df of 0.0047 and a relatively low Dk of 2.84 at 10 GHz. Moreover, TPC-BAHQ exhibited outstanding comprehensive properties, including a 5 wt% decomposition temperature (Td5%) of 502 ℃, a coefficient of thermal expansion (CTE) of 56.3 ppm/℃, a tensile strength (σmax) of 112.2 MPa, and a water absorption (Wa) of 0.24 %.
{"title":"Fluorine-free triptycene-based poly(ester imide) films: Role of mesogen units in balancing free volume and structural order for low Dk and low Df","authors":"Shiying Qi, Yuqing Lu, Chi Zhang, Zengjin Liu, Jiou Zhang, Jianchao Jiang, Yuanrong Cheng","doi":"10.1016/j.eurpolymj.2026.114516","DOIUrl":"10.1016/j.eurpolymj.2026.114516","url":null,"abstract":"<div><div>Due to the rapid progress in high frequency and high speed communication technologies, there is an urgent demand for polyimide (PI) films that exhibit both low dielectric constant (<em>D</em><sub>k</sub>) and low dielectric loss (<em>D</em><sub>f</sub>) at high frequencies. Achieving a reduction in the <em>D</em><sub>k</sub> of PIs at high frequencies is relatively straightforward in accordance with the Clausius–Mossotti equation. However, the optimization of <em>D</em><sub>f</sub> is more complex and challenging than that of <em>D</em><sub>k</sub>. From the perspective of polarization mechanisms, suppressing dipolar orientational polarization (<em>P</em><sub>d</sub>) provides an effective way to lower <em>D</em><sub>f</sub>. Inspired by liquid crystalline polyesters (LCPs), poly(ester imide)s (PEIs) can achieve ultralow <em>D</em><sub>f</sub> (<em>D</em><sub>f</sub> < 0.0030) by reducing intermolecular friction, but they still exhibit relatively high <em>D</em><sub>k</sub> (<em>D</em><sub>k</sub> > 3.20). In this work, a high free volume triptycene-based diamine (TPC-NH<sub>2</sub>) was copolymerized with three ester-containing dianhydrides—phenyl ester (TAHQ), naphthalene ester (NAHQ), and biphenyl ester (BAHQ)—to prepare a series of PEI films with different mesogen units. The influence of the molecular conformations of the mesogen unit on aggregation structure, dielectric properties, thermal properties, mechanical properties, and moisture absorption was systematically evaluated. Wide-angle X-ray diffraction, polarized optical microscopy, and molecular dynamics simulations revealed that phenyl ester dianhydride (TAHQ) and naphthalene ester dianhydride (NAHQ) units yielded amorphous PEIs with low <em>D</em><sub>k</sub> values of 2.62 and 2.55 at 10 GHz, respectively. The “crankshaft-like” <em>para</em>-aromatic ester linkage (Ph–COO–Ph-OCO–Ph) in TPC-TAHQ and TPC-NAHQ restricted imide group deflection through interchain dipole–dipole interactions, thereby lowering <em>D</em><sub>f</sub> to 0.0068 and 0.0051 at 10 GHz, respectively. In contrast, biphenyl ester dianhydride BAHQ-based PEI (TPC-BAHQ) promoted the formation of liquid–crystal-like ordered structure, achieving the lowest <em>D</em><sub>f</sub> of 0.0047 and a relatively low <em>D</em><sub>k</sub> of 2.84 at 10 GHz. Moreover, TPC-BAHQ exhibited outstanding comprehensive properties, including a 5 wt% decomposition temperature (<em>T</em><sub>d5%</sub>) of 502 ℃, a coefficient of thermal expansion (CTE) of 56.3 ppm/℃, a tensile strength (<em>σ</em><sub>max</sub>) of 112.2 MPa, and a water absorption (<em>W</em><sub>a</sub>) of 0.24 %.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114516"},"PeriodicalIF":6.3,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035775","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 : 2026-01-13DOI: 10.1016/j.eurpolymj.2026.114514
Samah Saied-Ahmad, Ofir Binenthal, Keshet Yelin, Michael S. Silverstein
PolyMIPEs are macroporous polymers templated within medium internal phase emulsions (MIPEs), 30 to 74 vol % internal phase. Emulsion-templated biocompatible and biodegradable polycaprolactone (PCL) polyMIPEs, attractive for biomedical applications such as tissue engineering, have been generated using oligomeric polyols. Macroporous, high molecular weight PCLs, advantageous for many applications, can be accessed through the ring-opening polymerization (ROP) of ε-caprolactone (CL) within oil-in-oil (O/O) emulsions. Here, a novel toolset for synthesizing macroporous biodegradable, and even printable polyesters was generated by combining ROP, emulsion templating, and foaming in a versatile design platform to provide enhanced control over the macromolecular architecture, porous structure, properties, and degradation.
Highly interconnected, macroporous PCLs, with densities and moduli suitable for soft tissue scaffolds, were synthesized under various conditions. The relatively low-temperature, metal-free organo-catalysts are of interest for biomedical applications and the room temperature UV catalysis can enable access to additive manufacturing. The introduction of hierarchical porosity through foaming reduced the density and modulus, while enhancing the degradation rate. Poly(l-lactide) polyMIPEs, with densities and moduli similar to those of the PCL polyMIPEs, exhibited significantly higher degradation rates.
{"title":"Porous Degradable Polyesters from Ring-Opening Polymerization within Oil-in-Oil Emulsions: Initiation, Catalysis, and Foaming","authors":"Samah Saied-Ahmad, Ofir Binenthal, Keshet Yelin, Michael S. Silverstein","doi":"10.1016/j.eurpolymj.2026.114514","DOIUrl":"10.1016/j.eurpolymj.2026.114514","url":null,"abstract":"<div><div>PolyMIPEs are macroporous polymers templated within medium internal phase emulsions (MIPEs), 30 to 74 vol % internal phase. Emulsion-templated biocompatible and biodegradable polycaprolactone (PCL) polyMIPEs, attractive for biomedical applications such as tissue engineering, have been generated using oligomeric polyols. Macroporous, high molecular weight PCLs, advantageous for many applications, can be accessed through the ring-opening polymerization (ROP) of ε-caprolactone (CL) within oil-in-oil (O/O) emulsions. Here, a novel toolset for synthesizing macroporous biodegradable, and even printable polyesters was generated by combining ROP, emulsion templating, and foaming in a versatile design platform to provide enhanced control over the macromolecular architecture, porous structure, properties, and degradation.</div><div>Highly interconnected, macroporous PCLs, with densities and moduli suitable for soft tissue scaffolds, were synthesized under various conditions. The relatively low-temperature, metal-free organo-catalysts are of interest for biomedical applications and the room temperature UV catalysis can enable access to additive manufacturing. The introduction of hierarchical porosity through foaming reduced the density and modulus, while enhancing the degradation rate. Poly(<span>l</span>-lactide) polyMIPEs, with densities and moduli similar to those of the PCL polyMIPEs, exhibited significantly higher degradation rates.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"246 ","pages":"Article 114514"},"PeriodicalIF":6.3,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122696","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 : 2026-01-13DOI: 10.1016/j.eurpolymj.2026.114512
Cynthia Verduyckt , Hanne Broux , Julien De Winter , Pascal Gerbaux , Guy Koeckelberghs
In recent years, the controlled nature of catalyst transfer polymerizations (CTP) has been significantly investigated and enhanced. Recent studies on Suzuki-Miyaura CTP (SMCTP) revealed that water converts the process into a chain-growth polymerization, while additional Buchwald ligands, particularly RuPhos, further enhance control. This improvement is attributed to the formation of Pd(RuPhos)2 upon catalyst detachment, a bulky species with no affinity for water, which limits catalyst diffusion and suppresses transfer reactions. Despite extensive research on SMCTP, Buchwald ligands remain unexplored in other CTPs, except for RuPhos in Negishi-mediated polymerization, where transfer steps occur, even in a large extent. Kumada CTP (KCTP) has not been investigated in this context.
Here, we report the first KCTP using a Buchwald ligand-based external palladium initiator, 4-methyl benzoate-Pd(RuPhos)-iodine. First, the controlled nature of the polymerization was investigated and chain transfer and some termination was found. Second, the influence of extra equivalents of ligand severely worsens the controlled nature of the polymerization. These findings elucidate the mechanism of CTP and the role of additional ligand. It is shown that, if the catalysts detaches from the growing polymer chain, the controlled nature of CTP depends on Pd(RuPhos)2 (de)formation and its diffusion. Poor solvent affinity to the ligated Pd-catalyst, as in aqueous mixtures (SMCTP), restricts diffusion and maintains control. In contrast, other (dry) organic solvents allow diffusion, reducing control despite inactive species formation. This work offers a mechanistic framework that may be extended to other catalyst–ligand–polymer combinations, although its broader generalization will require further experimental validation.
{"title":"The role of RuPhos in a Kumada polymerization: revealing the control in catalyst transfer polymerization","authors":"Cynthia Verduyckt , Hanne Broux , Julien De Winter , Pascal Gerbaux , Guy Koeckelberghs","doi":"10.1016/j.eurpolymj.2026.114512","DOIUrl":"10.1016/j.eurpolymj.2026.114512","url":null,"abstract":"<div><div>In recent years, the controlled nature of catalyst transfer polymerizations (CTP) has been significantly investigated and enhanced. Recent studies on Suzuki-Miyaura CTP (SMCTP) revealed that water converts the process into a chain-growth polymerization, while additional Buchwald ligands, particularly RuPhos, further enhance control. This improvement is attributed to the formation of Pd(RuPhos)<sub>2</sub> upon catalyst detachment, a bulky species with no affinity for water, which limits catalyst diffusion and suppresses transfer reactions. Despite extensive research on SMCTP, Buchwald ligands remain unexplored in other CTPs, except for RuPhos in Negishi-mediated polymerization, where transfer steps occur, even in a large extent. Kumada CTP (KCTP) has not been investigated in this context.</div><div>Here, we report the first KCTP using a Buchwald ligand-based external palladium initiator, 4-methyl benzoate-Pd(RuPhos)-iodine. First, the controlled nature of the polymerization was investigated and chain transfer and some termination was found. Second, the influence of extra equivalents of ligand severely worsens the controlled nature of the polymerization. These findings elucidate the mechanism of CTP and the role of additional ligand. It is shown that, if the catalysts detaches from the growing polymer chain, the controlled nature of CTP depends on Pd(RuPhos)<sub>2</sub> (de)formation and its diffusion. Poor solvent affinity to the ligated Pd-catalyst, as in aqueous mixtures (SMCTP), restricts diffusion and maintains control. In contrast, other (dry) organic solvents allow diffusion, reducing control despite inactive species formation. This work offers a mechanistic framework that may be extended to other catalyst–ligand–polymer combinations, although its broader generalization will require further experimental validation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114512"},"PeriodicalIF":6.3,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976414","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 : 2026-01-12DOI: 10.1016/j.eurpolymj.2026.114511
Jia-Le Lu , Jiawei Wang , Jingjing Ning, Rong Chen, Haixia Shen, Guo-Xing Li, Qing Li, Su Chen
Conventional microfluidic chips, fabricated from rigid polymers like polydimethylsiloxane, fail to recapitulate the dynamic and compliant nature of the native extracellular matrix (ECM), limiting their broader applications in biomedicine. In contrast, hydrogel-based microfluidic chips offer a promising alternative. However, their fabrication remains challenging due to the structural fragility, often requiring multi-step processes and secondary bonding. Here, we report a paradigm-shifting strategy for the monolithic fabrication of hydrogel-based microfluidic chips by leveraging the unique spatiotemporal control of aqueous frontal polymerization (FP). We employ 3D-printed polyvinyl alcohol (PVA) as a sacrificial template, which is encapsulated and preserved within a propagating polymerization front. The Transient reaction zone rapidly solidifies the hydrogel matrix within minutes, enabling the sacrificial template in its pristine state without significant deformation. Subsequent removal of the template yields complex, high-fidelity, and leak-free microchannels, avoiding post-fabrication bonding. The resulting hydrogel chip exhibits robust mechanical properties, anti-swelling capacity, antibacterial activity, and superior biocompatibility, providing great potentials for biomedical applications. This FP-directed fabrication method provides great convenience for precise control over channel geometries and sizes, paving a new avenue for creating next-generation all- hydrogel biomimetic microfluidic platforms.
{"title":"Frontal polymerization enabled monolithic fabrication of hydrogel microfluidic chips","authors":"Jia-Le Lu , Jiawei Wang , Jingjing Ning, Rong Chen, Haixia Shen, Guo-Xing Li, Qing Li, Su Chen","doi":"10.1016/j.eurpolymj.2026.114511","DOIUrl":"10.1016/j.eurpolymj.2026.114511","url":null,"abstract":"<div><div>Conventional microfluidic chips, fabricated from rigid polymers like polydimethylsiloxane, fail to recapitulate the dynamic and compliant nature of the native extracellular matrix (ECM), limiting their broader applications in biomedicine. In contrast, hydrogel-based microfluidic chips offer a promising alternative. However, their fabrication remains challenging due to the structural fragility, often requiring multi-step processes and secondary bonding. Here, we report a paradigm-shifting strategy for the monolithic fabrication of hydrogel-based microfluidic chips by leveraging the unique spatiotemporal control of aqueous frontal polymerization (FP). We employ 3D-printed polyvinyl alcohol (PVA) as a sacrificial template, which is encapsulated and preserved within a propagating polymerization front. The Transient reaction zone<!--> <!-->rapidly solidifies the hydrogel matrix within minutes,<!--> <!-->enabling the sacrificial template in its pristine state<!--> <!-->without significant deformation. Subsequent removal of the template yields complex, high-fidelity, and leak-free microchannels, avoiding post-fabrication bonding. The resulting hydrogel chip exhibits robust mechanical properties, anti-swelling capacity, antibacterial activity, and superior biocompatibility, providing great potentials for biomedical applications. This FP-directed fabrication method provides great convenience for precise control over channel geometries and sizes, paving a new avenue for creating next-generation all- hydrogel biomimetic microfluidic platforms.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114511"},"PeriodicalIF":6.3,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035773","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 : 2026-01-12DOI: 10.1016/j.eurpolymj.2026.114510
Marwa Y. Abdel Tawwab , Bothaina M. Abdel-Hady , Rizk Abd El-Moneim Rizk , Amal I. Hassan , Abdul Aziz M. Gad , Amira A. Gamal , Medhat W. Shafaa
Polycaprolactone/gelatin polymer nanofiber mats (PCL/GT) were fabricated using an electro-spinning technique. Moringa oleifera seed oil (M. oleifera) was loaded onto the mats using the post-spinning sorption method. The electro-spun nanofiber mat loaded with M. oleifera exhibited sustained release of the oil, with 85.3 % cumulative release after 28 days. The experimental data on M. oleifera and electro-spun mats loaded with oil ensure that they exhibit strong antibacterial, antioxidant, and anti-inflammatory activities. During the 48 h incubation, oil-loaded mats P5G5 O7C3 exhibited an increase in bacterial inhibition compared to those of free oil electro-spun mats P5G5 C3 (Staphylococcus aureus; 86.62 ± 0.05 % and Escherichia coli; 90.23 ± 0.04 %). For electro-spun oil loaded mats, the antioxidant activity was increased with increasing the incubation time. The degradation products of an electro-spun polycaprolactone/gelatin nanofiber mat loaded with M. oleifera stimulated cell proliferation and migration. It rapidly reduced the levels of pro-inflammatory cytokines in rat serum such as tumor necrosis factor and Interleukin 6 after mat implantation by increasing the mass of the oil-loaded mat. The histological examination of inflamed and treated knee rat tissue at the second and fourth weeks after sample implantation indicated that the oil-loaded mat has a good effect on the healing of knee synovial membrane and cartilage tissue after inflammation.
{"title":"Electro-spun biodegradable non-woven nano-fibers and moringa oil extract for knee cartilage regeneration: anti-inflammatory, antibacterial, and antioxidant activity","authors":"Marwa Y. Abdel Tawwab , Bothaina M. Abdel-Hady , Rizk Abd El-Moneim Rizk , Amal I. Hassan , Abdul Aziz M. Gad , Amira A. Gamal , Medhat W. Shafaa","doi":"10.1016/j.eurpolymj.2026.114510","DOIUrl":"10.1016/j.eurpolymj.2026.114510","url":null,"abstract":"<div><div>Polycaprolactone/gelatin polymer nanofiber mats (PCL/GT)<!--> <!-->were fabricated using an electro-spinning technique.<!--> <em>Moringa oleifera</em> <!-->seed oil (<em>M. oleifera</em>) was loaded onto the mats using the post-spinning sorption method.<!--> <!-->The electro-spun<!--> <!-->nanofiber mat loaded with <em>M. oleifera</em> <!-->exhibited sustained release of the oil, with 85.3 % cumulative release after 28 days.<!--> <!-->The experimental data on <em>M. oleifera</em> and electro-spun mats loaded with oil ensure that they exhibit strong antibacterial, antioxidant, and anti-inflammatory activities. During the 48 h incubation, oil-loaded mats P5G5 O7C3 exhibited an increase in bacterial inhibition compared to those of free oil electro-spun mats P5G5 C3 (<em>Staphylococcus aureus</em>; 86.62 ± 0.05 % and <em>Escherichia coli</em>; 90.23 ± 0.04 %).<!--> <!-->For electro-spun oil loaded mats, the antioxidant activity was increased with increasing the incubation time. The degradation products of an electro-spun polycaprolactone/gelatin nanofiber mat loaded with <em>M. oleifera</em> stimulated cell proliferation and migration. It rapidly reduced the levels of pro-inflammatory cytokines in rat serum such as tumor necrosis factor and Interleukin 6 after mat implantation by increasing the mass of the oil-loaded mat. The histological examination of inflamed and treated knee rat tissue at the second and fourth weeks after sample implantation indicated that the oil-loaded mat has a good effect on the healing of knee synovial membrane and cartilage tissue after inflammation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114510"},"PeriodicalIF":6.3,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976412","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 : 2026-01-10DOI: 10.1016/j.eurpolymj.2026.114504
Lauren E. Ball , Bennie Motloung , Michael-Phillip Smith , Rueben Pfukwa , Bert Klumperman
Stimuli responsive double hydrophilic block copolymers (DHBCs) are ubiquitous in water-based applications, such as drug/gene delivery, nanoreactor and sensor development, photocatalysis, 3D inkjet printing, etc. DHBC-based gels, cross-linked with calcium ions, are particularly valuable for the development of biomedically relevant materials (such as wound dressings or injectable formulations), due to the benignity of Ca2+ in biological systems. Therefore, gels formed via the calcium-mediated crosslinking of poly(4-tert-butylstyrene-alt-maleic acid)-block-poly(N-acryloylmorpholine) (PtBuSMA-b-PNAM), which in itself constitutes polymers with established biomedical relevance, are promising candidates for the development of the aforementioned biomedical materials. To this end, PtBuSMA-b-PNAM diblock copolymers were synthesized with different block ratios (1:1, 1:2 and 2:1) and treated with Ca2+, whereby the concentration of the two constituents, the pH or the block copolymer architecture was varied, in order to tune the mechanical properties of the PtBuSMA-b-PNAM/Ca2+ gels. PtBuSMA-b-PNAM/Ca2+ with the lowest PtBuSMA composition (1:2 block ratio) could not form gels and rather formed micelles, whereas PtBuSMA-b-PNAM/Ca2+ with the highest PtBuSMA composition (2:1 block ratio) exhibited enhanced mechanical properties compared to the 1:1 block ratio. The overall amphiphilic balance of the PtBuSMA-b-PNAM/Ca2+ complexes was therefore proven vital for the design and formation of gels with desirable mechanical properties. PtBuSMA-b-PNAM/Ca2+ gels exhibited shear thinning when subjected to high shear conditions and demonstrated some self-healing properties, suggesting these materials have value in the formulation of injectable gels.
{"title":"Mechanistic insights into the calcium-mediated gelation of poly(4-tert-butylstyrene-alt-maleic acid)-block-poly(N-acryloylmorpholine) double hydrophilic block copolymers","authors":"Lauren E. Ball , Bennie Motloung , Michael-Phillip Smith , Rueben Pfukwa , Bert Klumperman","doi":"10.1016/j.eurpolymj.2026.114504","DOIUrl":"10.1016/j.eurpolymj.2026.114504","url":null,"abstract":"<div><div>Stimuli responsive double hydrophilic block copolymers (DHBCs) are ubiquitous in water-based applications, such as drug/gene delivery, nanoreactor and sensor development, photocatalysis, 3D inkjet printing, etc. DHBC-based gels, cross-linked with calcium ions, are particularly valuable for the development of biomedically relevant materials (such as wound dressings or injectable formulations), due to the benignity of Ca<sup>2+</sup> in biological systems. Therefore, gels formed <em>via</em> the calcium-mediated crosslinking of poly(4-<em>tert</em>-butylstyrene-<em>alt</em>-maleic acid)-<em>block</em>-poly(<em>N</em>-acryloylmorpholine) (P<em>t</em>BuSMA-<em>b</em>-PNAM), which in itself constitutes polymers with established biomedical relevance, are promising candidates for the development of the aforementioned biomedical materials. To this end, P<em>t</em>BuSMA-<em>b</em>-PNAM diblock copolymers were synthesized with different block ratios (1:1, 1:2 and 2:1) and treated with Ca<sup>2+</sup>, whereby the concentration of the two constituents, the pH or the block copolymer architecture was varied, in order to tune the mechanical properties of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> gels. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> with the lowest P<em>t</em>BuSMA composition (1:2 block ratio) could not form gels and rather formed micelles, whereas P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> with the highest P<em>t</em>BuSMA composition (2:1 block ratio) exhibited enhanced mechanical properties compared to the 1:1 block ratio. The overall amphiphilic balance of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> complexes was therefore proven vital for the design and formation of gels with desirable mechanical properties. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> gels exhibited shear thinning when subjected to high shear conditions and demonstrated some self-healing properties, suggesting these materials have value in the formulation of injectable gels.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114504"},"PeriodicalIF":6.3,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976413","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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