Pub Date : 2025-03-16DOI: 10.1016/j.eurpolymj.2025.113897
Hanyu Ren , Rongli Zhang , Na Wang , Tongtong Li , Zhuo Ge , Chunhui Luo
It remains challenging for traditional cartilage replacements to simultaneously have the antifouling ability, self-adhesion, and adequate mechanical properties in the physiological environment. Here we develop a tri-layer hydrogel to address this issue. The precursor hydrogel was prepared through a three-cycle freezing-thawing process involving a blend of poly vinyl alcohol, chitosan and deionized water, followed by 3 h immerse in 25 wt% aqueous solution of grape seed protein. The top layer was modified with methacryloyl chloride and polymerized with sulfobetaine methacrylate (SBMA). Meanwhile, the bottom layer was coated with the adhesive of gelatin and tannin. On account of the multiple linkages (crystalline domains, hydrogen bonds, and ionic interactions), the compressive stress remained 42 MPa and the swelling ratio was 0.1 g/g even after a week immersion in simulated synovial fluid. Because of the introduction of SBMA, the hydrogel could resist non-specific protein adsorption and the coefficient of friction was 0.023 in simulated synovial fluid. The amino acids and polyphenol groups could form noncovalent interactions with various substrates, resulting in excellent underwater adhesion capability. The synergy of biocompatible materials and environmentally friendly progress led to exceptional biocompatibility, having promising applications in cartilage replacement.
{"title":"An antifouling, robust and adhesive hydrogel for cartilage replacement","authors":"Hanyu Ren , Rongli Zhang , Na Wang , Tongtong Li , Zhuo Ge , Chunhui Luo","doi":"10.1016/j.eurpolymj.2025.113897","DOIUrl":"10.1016/j.eurpolymj.2025.113897","url":null,"abstract":"<div><div>It remains challenging for traditional cartilage replacements to simultaneously have the antifouling ability, self-adhesion, and adequate mechanical properties in the physiological environment. Here we develop a tri-layer hydrogel to address this issue. The precursor hydrogel was prepared through a three-cycle freezing-thawing process involving a blend of poly vinyl alcohol, chitosan and deionized water, followed by 3 h immerse in 25 wt% aqueous solution of grape seed protein. The top layer was modified with methacryloyl chloride and polymerized with sulfobetaine methacrylate (SBMA). Meanwhile, the bottom layer was coated with the adhesive of gelatin and tannin. On account of the multiple linkages (crystalline domains, hydrogen bonds, and ionic interactions), the compressive stress remained 42 MPa and the swelling ratio was 0.1 g/g even after a week immersion in simulated synovial fluid. Because of the introduction of SBMA, the hydrogel could resist non-specific protein adsorption and the coefficient of friction was 0.023 in simulated synovial fluid. The amino acids and polyphenol groups could form noncovalent interactions with various substrates, resulting in excellent underwater adhesion capability. The synergy of biocompatible materials and environmentally friendly progress led to exceptional biocompatibility, having promising applications in cartilage replacement.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113897"},"PeriodicalIF":5.8,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143644037","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 : 2025-03-15DOI: 10.1016/j.eurpolymj.2025.113884
Lei Zeng, Yingle Chen, Song Wang, Chen Hou, Qiqi Huang, Zhihong Wang, Liu Yang
Water scarcity is a critical problem around the world, and superabsorbent hydrogels has attracted growing attention in water management for handling water deficiency during agricultural and forestry practices. Herein, intending to apply gelatin hydrogel as soil conditioner, humic substances (HS) extracted from Chinese medicine residue compost were used to modify gelatin hydrogel through either physical mixing or chemical cross-linking. The results demonstrated that low level of HS could improve the hardness and rheological properties of the hydrogels, however, the gel strength significantly decreased when the concentration of HS rose up to 16 g/L. As revealed by TEM and XRD, chemical cross-linking reaction promoted the development of denser network structures, thereby improving the hardness and rheological properties of the hydrogels. Subsequently, applying HS at a concentration of 3 g/L was found to be preferable for enhancing the swelling ratio of the gelatin hydrogels, and lightweight substrates amended with the resultant hydrogels displayed superior water retention ratio (17.23 ± 0.79 % for GelHS3 and 17.74 ± 1.31 % for GelHS3-EDC). Furthermore, it was proved that HS-incorporated hydrogels can effectively keep moisture for the growth of Melaleuca alternifolia (Maiden & Betche) Cheel saplings under drought stress. These findings suggest that humic substances can be utilized to modify hydrogels for use as soil conditioners.
{"title":"Modification of gelatin hydrogel for soil water retention: Physical blending or chemical combination with humic substance extracted from compost","authors":"Lei Zeng, Yingle Chen, Song Wang, Chen Hou, Qiqi Huang, Zhihong Wang, Liu Yang","doi":"10.1016/j.eurpolymj.2025.113884","DOIUrl":"10.1016/j.eurpolymj.2025.113884","url":null,"abstract":"<div><div>Water scarcity is a critical problem around the world, and superabsorbent hydrogels has attracted growing attention in water management for handling water deficiency during agricultural and forestry practices. Herein, intending to apply gelatin hydrogel as soil conditioner, humic substances (HS) extracted from Chinese medicine residue compost were used to modify gelatin hydrogel through either physical mixing or chemical cross-linking. The results demonstrated that low level of HS could improve the hardness and rheological properties of the hydrogels, however, the gel strength significantly decreased when the concentration of HS rose up to 16 g/L. As revealed by TEM and XRD, chemical cross-linking reaction promoted the development of denser network structures, thereby improving the hardness and rheological properties of the hydrogels. Subsequently, applying HS at a concentration of 3 g/L was found to be preferable for enhancing the swelling ratio of the gelatin hydrogels, and lightweight substrates amended with the resultant hydrogels displayed superior water retention ratio (17.23 ± 0.79 % for GelHS3 and 17.74 ± 1.31 % for GelHS3-EDC). Furthermore, it was proved that HS-incorporated hydrogels can effectively keep moisture for the growth of Melaleuca alternifolia (Maiden & Betche) Cheel saplings under drought stress. These findings suggest that humic substances can be utilized to modify hydrogels for use as soil conditioners.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113884"},"PeriodicalIF":5.8,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642288","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 : 2025-03-14DOI: 10.1016/j.eurpolymj.2025.113895
Jyh-Long Jeng, Yaw-Terng Chern
Materials with low dielectric constant (Dk) and low dissipation factor (Df) values at a high-frequency are highly demanded to achieve low signal transmission loss. Df shows significantly important influence on signal propagation loss rate in comparison with Dk. However, the structure-Df relationships are still poorly understood. We discuss the influence on Df by polymer chain packing and polar group content. Two series of polyimides (PIs) were synthesized from the two diamines with symmetric or asymmetric tert-butyl pendant groups. The 3 series with symmetric tert-butyl pendant groups revealed a significantly decreased dissipation factor in comparison with that of the corresponding analogues of the 4 series with asymmetric tert-butyl pendant groups. It is evident that the introduction of symmetric tert-butyl pendant groups is demonstrated an effective strategy to restrict polymer chain motion, leading to low Df. For the PIs with good packing ability like 3 series, the predominant influence on their Df is polymer chain packing ability to effectively restrict polymer chain motion. For the PIs without good packing ability like 4 series, the predominant influence on their Df is polar group content. Herein, the concept of symmetric tert-butyl pendant groups and an ester group by designing new diamine monomer (2) was successfully incorporated into copolyimide 6, and demonstrated the remarkable low Df (0.0036 at 10 GHz). The record-low Df is ascribed to the strong intermolecular interaction and good packing ability to effectively restrict molecular motion. PI 6 demonstrates well-balanced properties, including very high Tg, low Df, and excellent flame retardancy, making it a promising candidate for new dielectric substrate materials in the next generation of 5G-compatible high-performance flexible printed circuit boards (FPCBs).
{"title":"Concept of symmetric tert-butyl pendant groups toward record-low dissipation factors of polyimides at high frequency","authors":"Jyh-Long Jeng, Yaw-Terng Chern","doi":"10.1016/j.eurpolymj.2025.113895","DOIUrl":"10.1016/j.eurpolymj.2025.113895","url":null,"abstract":"<div><div>Materials with low dielectric constant (D<sub>k</sub>) and low dissipation factor (D<sub>f</sub>) values at a high-frequency are highly demanded to achieve low signal transmission loss. D<sub>f</sub> shows significantly important influence on signal propagation loss rate in comparison with D<sub>k</sub>. However, the structure-D<sub>f</sub> relationships are still poorly understood. We discuss the influence on D<sub>f</sub> by polymer chain packing and polar group content. Two series of polyimides (PIs) were synthesized from the two diamines with symmetric or asymmetric <em>tert</em>-butyl pendant groups. The <strong>3</strong> series with symmetric <em>tert</em>-butyl pendant groups revealed a significantly decreased dissipation factor in comparison with that of the corresponding analogues of the <strong>4</strong> series with asymmetric <em>tert</em>-butyl pendant groups. It is evident that the introduction of symmetric <em>tert</em>-butyl pendant groups is demonstrated an effective strategy to restrict polymer chain motion, leading to low D<sub>f</sub>. For the PIs with good packing ability like 3 series, the predominant influence on their D<sub>f</sub> is polymer chain packing ability to effectively restrict polymer chain motion. For the PIs without good packing ability like 4 series, the predominant influence on their D<sub>f</sub> is polar group content. Herein, the concept of symmetric <em>tert</em>-butyl pendant groups and an ester group by designing new diamine monomer <strong>(2)</strong> was successfully incorporated into copolyimide <strong>6</strong>, and demonstrated the remarkable low D<sub>f</sub> (0.0036 at 10 GHz). The record-low D<sub>f</sub> is ascribed to the strong intermolecular interaction and good packing ability to effectively restrict molecular motion. PI <strong>6</strong> demonstrates well-balanced properties, including very high Tg, low D<sub>f</sub>, and excellent flame retardancy, making it a promising candidate for new dielectric substrate materials in the next generation of 5G-compatible high-performance flexible printed circuit boards (FPCBs).</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113895"},"PeriodicalIF":5.8,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143636444","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 explores the design and optimization of polyrotaxane-based solid polymer electrolytes (SPEs) by adjusting crosslinker, composition, and polyrotaxane coverage ratio. By incorporating poly (ethylene glycol) (PEG) crosslinkers and refining their molecular weight and loading, we developed SPEs exhibiting high ionic conductivity (7.05 × 10−5 S/cm at 30 °C), excellent flexibility (elongation at break over 270 %) and thermal resistance above 150 °C. Investigations into polyrotaxane with reduced coverage ratios revealed limitations in mechanical properties and ionic conductivity, emphasizing the importance of PEG crosslinker and the need of a robust cross-linked network. This study underscores the potential of polyrotaxane cross-linked networks for advanced SPE applications and provides insights for future design strategies in the field.
{"title":"Development of hydroxypropylated polyrotaxane networks with macromolecular PEG crosslinkers: Strategies for enhanced ionic conductivity","authors":"Rui-Dong Wang, Yi-Fei Zhang, Xiao-Long Han, Yu-Kun Gao, Ting-Ting You, Peng-Gang Yin","doi":"10.1016/j.eurpolymj.2025.113893","DOIUrl":"10.1016/j.eurpolymj.2025.113893","url":null,"abstract":"<div><div>This work explores the design and optimization of polyrotaxane-based solid polymer electrolytes (SPEs) by adjusting crosslinker, composition, and polyrotaxane coverage ratio. By incorporating poly (ethylene glycol) (PEG) crosslinkers and refining their molecular weight and loading, we developed SPEs exhibiting high ionic conductivity (7.05 × 10<sup>−5</sup> S/cm at 30 °C), excellent flexibility (elongation at break over 270 %) and thermal resistance above 150 °C. Investigations into polyrotaxane with reduced coverage ratios revealed limitations in mechanical properties and ionic conductivity, emphasizing the importance of PEG crosslinker and the need of a robust cross-linked network. This study underscores the potential of polyrotaxane cross-linked networks for advanced SPE applications and provides insights for future design strategies in the field.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113893"},"PeriodicalIF":5.8,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627957","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 : 2025-03-07DOI: 10.1016/j.eurpolymj.2025.113887
Thi Ha My Phan , Yu-Hsun Yang , Jing-Ting Lin , Yi-Chen Ethan Li , Yi-Jou Chiu , Ling-Huei Wang , Jeng-Shiung Jan
This study investigates the hydrogelation, injectability, and printability of polypeptide-poly(ethylene glycol)-polypeptide triblock copolymer hydrogels derived from poly(O-benzyl-L-serine) (PBLS) and poly(O-benzyl-L-tyrosine) (PBLY) peptide segments. Experimental results demonstrate that the sheet-like PBLS and PBLY segments effectively function as hydrogelators, facilitating hydrogel formation in aqueous solutions. Key parameters such as polymer chain length, block ratio, and sheet-like peptide assemblies significantly influence the molecular packing of the triblock copolymers and the resulting nano-/microstructures of the hydrogel networks, thereby modulating their mechanical properties. Among all the studied samples, the PBLS6.5-PEG20000-PBLS6.5 exhibits the best hydrogelation ability and mechanical property, highlighting the importance of the additional PEG chain entanglement. The d-spacing between peptide assemblies is found to be mainly dictated by PEG chain length. The as-prepared hydrogels exhibit exceptional shear-thinning behavior and rapid recovery, enabling high-fidelity patterning via direct-ink-writing printing (DIWP) technology. This study underscores the utility of PBLS and PBLY segments as hydrogelators when tethered to hydrophilic polymers like PEG. Furthermore, the as-prepared hydrogels, with superior mechanical properties, hold promise as inks for DIWP-based applications. Functional conjugation at the polymer chain ends offers potential for versatile applications in biomedical and engineering fields.
{"title":"Printable Polypeptide-Poly(ethylene glycol)-Polypeptide triblock copolymer hydrogels based on O-benzyl-L-serine and O-benzyl-L-tyrosine Building blocks","authors":"Thi Ha My Phan , Yu-Hsun Yang , Jing-Ting Lin , Yi-Chen Ethan Li , Yi-Jou Chiu , Ling-Huei Wang , Jeng-Shiung Jan","doi":"10.1016/j.eurpolymj.2025.113887","DOIUrl":"10.1016/j.eurpolymj.2025.113887","url":null,"abstract":"<div><div>This study investigates the hydrogelation, injectability, and printability of polypeptide-poly(ethylene glycol)-polypeptide triblock copolymer hydrogels derived from poly(O-benzyl-<sub>L</sub>-serine) (PBLS) and poly(O-benzyl-<sub>L</sub>-tyrosine) (PBLY) peptide segments. Experimental results demonstrate that the sheet-like PBLS and PBLY segments effectively function as hydrogelators, facilitating hydrogel formation in aqueous solutions. Key parameters such as polymer chain length, block ratio, and sheet-like peptide assemblies significantly influence the molecular packing of the triblock copolymers and the resulting nano-/microstructures of the hydrogel networks, thereby modulating their mechanical properties. Among all the studied samples, the PBLS<sub>6.5</sub>-PEG20000-PBLS<sub>6.5</sub> exhibits the best hydrogelation ability and mechanical property, highlighting the importance of the additional PEG chain entanglement. The d-spacing between peptide assemblies is found to be mainly dictated by PEG chain length. The as-prepared hydrogels exhibit exceptional shear-thinning behavior and rapid recovery, enabling high-fidelity patterning via direct-ink-writing printing (DIWP) technology. This study underscores the utility of PBLS and PBLY segments as hydrogelators when tethered to hydrophilic polymers like PEG. Furthermore, the as-prepared hydrogels, with superior mechanical properties, hold promise as inks for DIWP-based applications. Functional conjugation at the polymer chain ends offers potential for versatile applications in biomedical and engineering fields.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113887"},"PeriodicalIF":5.8,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143592631","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 : 2025-03-06DOI: 10.1016/j.eurpolymj.2025.113886
Zengcai Zhao , Qiaolan Fan , Shengqiang Wu , Nengqin Tao , Yangxin Zhou
Among various dielectrics, ferroelectric thin films for capacitors have attracted considerable attention due to the excellent energy storage properties. In this work, the multilayered BaZr0.35Ti0.65O3 (BZT) ferroelectric films were fabricated on p-type silicon substrates via a sol–gel/spin-coating processing. The microstructure and phase composition of BZT multilayer films were evaluated at variable thickness induced by different number of deposits, and their effects on breakdown strength as well as energy storage performance have been systematically investigated. The results show that BZT thin film coated at a single layer ∼ 40 nm crystallized into a dense nanocrystalline structure of the pyrochlore phase, leading to the lowered leakage current and reduced polarization switching hysteresis, while exhibiting a large energy storage density of 80.4 J/cm3 and high energy efficiency of ∼ 90 % simultaneously due to the ultrahigh breakdown strength of 7.75 MV/cm. This work provides a scalable approach towards high-performance eco-friendly ferroelectric film capacitors integrated on silicon.
{"title":"Simultaneously achieved high energy storage density and efficiency in sol–gel derived BZT thin films integrated on Si","authors":"Zengcai Zhao , Qiaolan Fan , Shengqiang Wu , Nengqin Tao , Yangxin Zhou","doi":"10.1016/j.eurpolymj.2025.113886","DOIUrl":"10.1016/j.eurpolymj.2025.113886","url":null,"abstract":"<div><div>Among various dielectrics, ferroelectric thin films for capacitors have attracted considerable attention due to the excellent energy storage properties. In this work, the multilayered BaZr<sub>0.35</sub>Ti<sub>0.65</sub>O<sub>3</sub> (BZT) ferroelectric films were fabricated on <em>p</em>-type silicon substrates via a sol–gel/spin-coating processing. The microstructure and phase composition of BZT multilayer films were evaluated at variable thickness induced by different number of deposits, and their effects on breakdown strength as well as energy storage performance have been systematically investigated. The results show that BZT thin film coated at a single layer ∼ 40 nm crystallized into a dense nanocrystalline structure of the pyrochlore phase, leading to the lowered leakage current and reduced polarization switching hysteresis, while exhibiting a large energy storage density of 80.4 J/cm<sup>3</sup> and high energy efficiency of ∼ 90 % simultaneously due to the ultrahigh breakdown strength of 7.75 MV/cm. This work provides a scalable approach towards high-performance eco-friendly ferroelectric film capacitors integrated on silicon.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113886"},"PeriodicalIF":5.8,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600752","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 : 2025-03-06DOI: 10.1016/j.eurpolymj.2025.113885
Artyom A. Vagin , Maksim S. Borisenko , Mikhail V. Solovskij , Elena B. Tarabukina , Anna S. Krasova , Alexey A. Nikiforov , Artyom M. Klabukov , Daria N. Razgulyaeva , Anna A. Shtro , Evgenij F. Panarin
Poly[(2-acrylamido-2-methylpropane sulfonic acid)–co–(2-hydroxyethyl methacrylate)] were synthesized by free radical copolymerization in alcohols, and the influence of reaction conditions on their physico-chemical properties was estimated. Copolymers structure was characterized by FT-IR and NMR spectroscopy, the composition was determined by elemental analysis on sulfur and potentiometric titration of sulfonic groups, molecular weight and hydrodynamic characteristics were evaluated by static and dynamic light scattering, as well as viscometry. Reactivity ratios of 2-acrylamido-2-methylpropane sulfonic acid and 2-hydroxyethylmethacrylate were assessed at copolymerization in ethanol and DMSO from terminal and penultimate models. Location of the «foreign» monomer as a penultimate unit significantly reduces the probability of block sequences formation and increases the proportion of chains cross-growth reactions, accordingly. Computation of copolymers chains microstructure showed an alternation higher degree of monomer units at synthesis in ethanol than DMSO. Results of copolymers cytotoxicity against Vero and HEp-2 cell cultures demonstrate their low toxicity. The copolymers showed a high level of antiviral activity against human respiratory syncytial virus and were low active against herpes simplex virus type 1.
{"title":"Poly[(2-acrylamido-2-methylpropane sulfonic acid)-co-(2-hydroxyethyl methacrylate)]: Synthesis, properties, chain microstructure and antiviral activity against RSV and HSV-1","authors":"Artyom A. Vagin , Maksim S. Borisenko , Mikhail V. Solovskij , Elena B. Tarabukina , Anna S. Krasova , Alexey A. Nikiforov , Artyom M. Klabukov , Daria N. Razgulyaeva , Anna A. Shtro , Evgenij F. Panarin","doi":"10.1016/j.eurpolymj.2025.113885","DOIUrl":"10.1016/j.eurpolymj.2025.113885","url":null,"abstract":"<div><div>Poly[(2-acrylamido-2-methylpropane sulfonic acid)–<em>co</em>–(2-hydroxyethyl methacrylate)] were synthesized by free radical copolymerization in alcohols, and the influence of reaction conditions on their physico-chemical properties was estimated. Copolymers structure was characterized by FT-IR and NMR spectroscopy, the composition was determined by elemental analysis on sulfur and potentiometric titration of sulfonic groups, molecular weight and hydrodynamic characteristics were evaluated by static and dynamic light scattering, as well as viscometry. Reactivity ratios of 2-acrylamido-2-methylpropane sulfonic acid and 2-hydroxyethylmethacrylate were assessed at copolymerization in ethanol and DMSO from terminal and penultimate models. Location of the «foreign» monomer as a penultimate unit significantly reduces the probability of block sequences formation and increases the proportion of chains cross-growth reactions, accordingly. Computation of copolymers chains microstructure showed an alternation higher degree of monomer units at synthesis in ethanol than DMSO. Results of copolymers cytotoxicity against Vero and HEp-2 cell cultures demonstrate their low toxicity. The copolymers showed a high level of antiviral activity against human respiratory syncytial virus and were low active against herpes simplex virus type 1.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113885"},"PeriodicalIF":5.8,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143610792","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 : 2025-03-05DOI: 10.1016/j.eurpolymj.2025.113883
Danyang Li, Shizhen Zhao, Yuanpeng Cai, Hui Liu
Single chemotherapy lacked controllability, while smart-responsive hydrogel could deliver drug to specific sites in response to different external stimuli. Hyaluronic acid–Chitosan–Thioketal@Chlorin e6 (HA-CS-TK@Ce6) hydrogel with dual response of ROS and hyaluronidase (HAase) was synthesized by electrostatic interaction force. HA-CS-TK@Ce6 hydrogel loaded with chemotherapeutic drug doxorubicin (DOX) and photosensitizer Ce6 successfully achieved the combined anticancer effect of chemotherapy and photodynamic therapy. Experimental results demonstrated that releasing efficiency of the hydrogel toward DOX could reach 90.6 % in pH = 5 H2O2 solution with HAase at T = 40 ℃. Moreover, HA-CS-TK@Ce6 hydrogel was capable of stimulating Ce6 to produce massive ROS under 650 nm laser irradiation, thus leading to breakage of ROS-cleavable TK and realizing degradation of hydrogel. It was worth mentioning that laser confocal results indicated that MCF-7 cells could successfully uptake Ce6 and DOX, which further proved that HA-CS-TK@Ce6 hydrogel could achieve efficient photodynamic-chemotherapeutic treatment. Therefore, dual-responsive HA-CS-TK@Ce6 hydrogel with excellent biocompatibility and degradability enabled selective and intelligent release of DOX, which would be prospective to improve therapeutic effect of cancer through chemo-photodynamic therapy.
{"title":"Dual-responsive hyaluronic acid-based hydrogel as a drug carrier for combined chemo-photodynamic therapy","authors":"Danyang Li, Shizhen Zhao, Yuanpeng Cai, Hui Liu","doi":"10.1016/j.eurpolymj.2025.113883","DOIUrl":"10.1016/j.eurpolymj.2025.113883","url":null,"abstract":"<div><div>Single chemotherapy lacked controllability, while smart-responsive hydrogel could deliver drug to specific sites in response to different external stimuli. Hyaluronic acid–Chitosan–Thioketal@Chlorin e6 (HA-CS-TK@Ce6) hydrogel with dual response of ROS and hyaluronidase (HAase) was synthesized by electrostatic interaction force. HA-CS-TK@Ce6 hydrogel loaded with chemotherapeutic drug doxorubicin (DOX) and photosensitizer Ce6 successfully achieved the combined anticancer effect of chemotherapy and photodynamic therapy. Experimental results demonstrated that releasing efficiency of the hydrogel toward DOX could reach 90.6 % in pH = 5 H<sub>2</sub>O<sub>2</sub> solution with HAase at T = 40 ℃. Moreover, HA-CS-TK@Ce6 hydrogel was capable of stimulating Ce6 to produce massive ROS under 650 nm laser irradiation, thus leading to breakage of ROS-cleavable TK and realizing degradation of hydrogel. It was worth mentioning that laser confocal results indicated that MCF-7 cells could successfully uptake Ce6 and DOX, which further proved that HA-CS-TK@Ce6 hydrogel could achieve efficient photodynamic-chemotherapeutic treatment. Therefore, dual-responsive HA-CS-TK@Ce6 hydrogel with excellent biocompatibility and degradability enabled selective and intelligent release of DOX, which would be prospective to improve therapeutic effect of cancer through chemo-photodynamic therapy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113883"},"PeriodicalIF":5.8,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578296","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 : 2025-03-05DOI: 10.1016/j.eurpolymj.2025.113882
Marwa Hamdi , Haozhi Sun , Lixia Pan , Dandan Wang , Mengxiao Sun , Zhaoning Zeng , Suming Li , Qingkun Dong , Feng Su
Background
Nowadays, the search for new renewable and broad-spectrum natural biopolymers for biotechnological and medical applications has become an absolute necessity. Chitin and its deacetylated derivative, chitosan, are considered interesting and auspicious biopolymers being potentially applied in a wide range of biotechnological sectors, including medicine, food beverages, agriculture, and cosmetics, owing to their enormous ability to undergo changes in structure and mechanical properties to generate new functions (used as a matrix in beads, membranes, gels, etc.) and applications.
Scope and Approach: The current review provides a comprehensive report summarizing research on the routine chemical and greener non-conventional extraction methodologies of chitin and chitosan and focuses on the progress in their application over the past two decades, in terms of challenges, opportunities, and future perspectives.
Key Findings and Conclusions: Chitosan is an effective material with enormous potential for biotechnology and medicine owing to its biocompatible, biodegradable, and non-toxic traits, besides its antimicrobial potential and low immunogenic potency. To standardize applications in the industrial field considering cost-effectiveness and biocompatibility, the search for innovative recovery and production methods for chitin/chitosan-based materials industrialization is required. Conventional chemical chitin extraction approaches present drawbacks and induce numerous environmental issues. Greener extraction technologies have recently perceived considerable advancement in the polymer chemistry field. This review can serve as a guideline for exploring nature-originated biopolymers as innovative feedstocks for several technologies that show highly appealing potential for application in countless fields.
{"title":"Chitosan and its derivatives as potential biomaterials for biomedical and pharmaceutical applications: A comprehensive review on green extraction approaches, recent progresses, and perspectives","authors":"Marwa Hamdi , Haozhi Sun , Lixia Pan , Dandan Wang , Mengxiao Sun , Zhaoning Zeng , Suming Li , Qingkun Dong , Feng Su","doi":"10.1016/j.eurpolymj.2025.113882","DOIUrl":"10.1016/j.eurpolymj.2025.113882","url":null,"abstract":"<div><h3>Background</h3><div>Nowadays, the search for new renewable and broad-spectrum natural biopolymers for biotechnological and medical applications has become an absolute necessity. <strong>Chitin and its deacetylated derivative, chitosan,</strong> are considered interesting and auspicious biopolymers being potentially applied in a wide range of biotechnological sectors, including medicine, food beverages, agriculture, and cosmetics, owing to their enormous ability to undergo changes in structure and mechanical properties to generate new functions (used as a matrix in beads, membranes, gels, etc.) and applications.</div><div><strong><em>Scope and Approach:</em></strong> The current review provides a comprehensive report summarizing research on the routine chemical and greener non-conventional extraction methodologies of chitin and chitosan and focuses on the progress in their application over the past two decades, in terms of challenges, opportunities, and future perspectives.</div><div><strong><em>Key Findings and Conclusions:</em> Chitosan</strong> is an effective material with enormous potential for biotechnology and medicine owing to its biocompatible, biodegradable, and non-toxic traits, besides its antimicrobial potential and low immunogenic potency. To standardize applications in the industrial field considering cost-effectiveness and biocompatibility, the search for innovative recovery and production methods for chitin/chitosan-based materials industrialization is required. Conventional chemical chitin extraction approaches present drawbacks and induce numerous environmental issues. Greener extraction technologies have recently perceived considerable advancement in the polymer chemistry field. This review can serve as a guideline for exploring nature-originated biopolymers as innovative feedstocks for several technologies that show highly appealing potential for application in countless fields.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113882"},"PeriodicalIF":5.8,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143593194","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}
Traditional polyurethane hot-melt adhesives often fall short in achieving high bonding strength and recyclability, and their dependence on non-renewable resources poses a significant hurdle for sustainable development. In this study, a palm oil-based diethanolamide (POEA) containing a long aliphatic chain was synthesized to develop comb thermoplastic polyurethane hot-melt adhesives (POPUs) with high biobased content, superior adhesion strength, and reusability. The microphase separation structure of POPUs was manipulated through the incorporation of dangling fatty acid chains and hydrogen bonds, resulting in the adhesives with excellent mechanical properties, with an optimum tensile strength of 5.37 MPa and an elongation at break of 282 %. As a hot-melt adhesive, it achieved a maximum lap-shear strength of 7.34 MPa on steel and maintained an average strength of 95 % of its initial value across multiple bonding cycles. Moreover, its lap-shear strengths with wood and glass remained at 6.57 MPa and 3.57 MPa respectively, fully meeting the requirements for interior decoration. Additionally, it was unexpectedly discovered that the adhesives possessed fluorescence characteristics, which can be applied in fields such as cultural relic restoration and anti-counterfeiting.
{"title":"Biobased comb polyurethane hot-melt adhesives consisting of dangling fatty acid chains and H-bonds for tailoring bonding strength","authors":"Zhen Huang , Shimin Geng , Yizhen Chen , Ying Li , Mingen Fei , Renhui Qiu , Tingting Chen , Wendi Liu","doi":"10.1016/j.eurpolymj.2025.113880","DOIUrl":"10.1016/j.eurpolymj.2025.113880","url":null,"abstract":"<div><div>Traditional polyurethane hot-melt adhesives often fall short in achieving high bonding strength and recyclability, and their dependence on non-renewable resources poses a significant hurdle for sustainable development. In this study, a palm oil-based diethanolamide (POEA) containing a long aliphatic chain was synthesized to develop comb thermoplastic polyurethane hot-melt adhesives (POPUs) with high biobased content, superior adhesion strength, and reusability. The microphase separation structure of POPUs was manipulated through the incorporation of dangling fatty acid chains and hydrogen bonds, resulting in the adhesives with excellent mechanical properties, with an optimum tensile strength of 5.37 MPa and an elongation at break of 282 %. As a hot-melt adhesive, it achieved a maximum lap-shear strength of 7.34 MPa on steel and maintained an average strength of 95 % of its initial value across multiple bonding cycles. Moreover, its lap-shear strengths with wood and glass remained at 6.57 MPa and 3.57 MPa respectively, fully meeting the requirements for interior decoration. Additionally, it was unexpectedly discovered that the adhesives possessed fluorescence characteristics, which can be applied in fields such as cultural relic restoration and anti-counterfeiting.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113880"},"PeriodicalIF":5.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578294","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}