European Polymer Journal最新文献_第5页

Reactive oxygen species-responsive nanocomposite hydrogels for accurate drug delivery and localized PDT/PTT/chemo synergistic cancer therapy

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113683

Minchae Kim , Ji in Lee , Jongseon Choi , So Yeon Kim

Intratumor local drug delivery systems using injectable hydrogels have received considerable attention due to sustained, controllable drug delivery at target tumor sites and reduced adverse effects of systemic exposure to the drug. To maximize cancer therapeutic efficiency, this study focused on cytotoxic reactive oxygen species (ROS)-cleavable injectable hydrogels that can more accurately control drug delivery as well as photodynamic therapy (PDT)/photothermal therapy (PTT) synergistic combination therapy. Thermo-responsive poly(N-isopropyl acrylamide) (PNIPAAm)-based injectable hydrogels were synthesized using a thioketal crosslinker vulnerable to bond breakage by ROS. In addition, PNIPAAm-based injectable nanocomposite hydrogels containing photosensitizer (PS)-conjugated gold nanorods (GNRs) as a photothermal factor and 1-methyltryptophan (1MT) as a model drug were prepared. PNIPAAm-based injectable nanocomposite hydrogel exhibited a lower critical solution temperature (LCST) in the range of 33.6–36.3 °C, allowing injection through a syringe at room temperature. However, a gel state was achieved through phase transition at a body temperature of 37 °C. ROS generation from PNIPAAm-based injectable nanocomposite hydrogel was controlled by adjusting the feed amount of PS-conjugated GNRs and the 670 nm laser intensity. These hydrogels crosslinked with ROS-cleavable thioketal crosslinker exhibited selective degradation and drug release behavior. In addition, a PNIPAAm-based injectable nanocomposite hydrogel containing GNRs as a photothermal factor and chlorin e6 (Ce6) as a PS showed a PDT/PTT synergistic effect upon laser irradiation. These results indicate that this ROS-sensitive nanocomposite hydrogel would be highly efficient both as an accurate drug delivery platform and as a combinational cancer therapeutic system of localized PDT and PTT.

{"title":"Reactive oxygen species-responsive nanocomposite hydrogels for accurate drug delivery and localized PDT/PTT/chemo synergistic cancer therapy","authors":"Minchae Kim , Ji in Lee , Jongseon Choi , So Yeon Kim","doi":"10.1016/j.eurpolymj.2024.113683","DOIUrl":"10.1016/j.eurpolymj.2024.113683","url":null,"abstract":"<div><div>Intratumor local drug delivery systems using injectable hydrogels have received considerable attention due to sustained, controllable drug delivery at target tumor sites and reduced adverse effects of systemic exposure to the drug. To maximize cancer therapeutic efficiency, this study focused on cytotoxic reactive oxygen species (ROS)-cleavable injectable hydrogels that can more accurately control drug delivery as well as photodynamic therapy (PDT)/photothermal therapy (PTT) synergistic combination therapy. Thermo-responsive poly(N-isopropyl acrylamide) (PNIPAAm)-based injectable hydrogels were synthesized using a thioketal crosslinker vulnerable to bond breakage by ROS. In addition, PNIPAAm-based injectable nanocomposite hydrogels containing photosensitizer (PS)-conjugated gold nanorods (GNRs) as a photothermal factor and 1-methyltryptophan (1MT) as a model drug were prepared. PNIPAAm-based injectable nanocomposite hydrogel exhibited a lower critical solution temperature (LCST) in the range of 33.6–36.3 °C, allowing injection through a syringe at room temperature. However, a gel state was achieved through phase transition at a body temperature of 37 °C. ROS generation from PNIPAAm-based injectable nanocomposite hydrogel was controlled by adjusting the feed amount of PS-conjugated GNRs and the 670 nm laser intensity. These hydrogels crosslinked with ROS-cleavable thioketal crosslinker exhibited selective degradation and drug release behavior. In addition, a PNIPAAm-based injectable nanocomposite hydrogel containing GNRs as a photothermal factor and chlorin e6 (Ce6) as a PS showed a PDT/PTT synergistic effect upon laser irradiation. These results indicate that this ROS-sensitive nanocomposite hydrogel would be highly efficient both as an accurate drug delivery platform and as a combinational cancer therapeutic system of localized PDT and PTT.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113683"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146949","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}

引用次数: 0

One-step and one-pot synthesis of wrinkled polymer microspheres based on monomer reactivity ratio difference

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113707

Tian Liu, Yungui Ma, Dunxun Yu, Xiaopeng Yang, Zhihua Ma, Ning Liu, Shiyang Shao

Different from conventional multi-step synthesis methods for wrinkled polymer microspheres (WPMs), here we propose a facile one-step and one-pot synthesis strategy for WPMs employing monomer reactivity ratio difference to form linear-crosslinked-linear gradient structure from inside to outside of the microspheres, leading to wrinkled surface by uneven shrinkage of the crosslinked and linear structures. The particle size and surface morphology for WPMs can be easily adjusted by changing monomer types and solvent ratio according to morphological characterization. Meanwhile, this method is universal for synthesizing WPMs having different monomers, supported by the fact that monomers bearing different substituent groups can be successfully used for the synthesis procedure. Finally, fluorescent microspheres with tuned emission colors are synthesized through this strategy by simply adding different fluorescent dyes in polymerization system, demonstrating the potential of such strategy in synthesizing optical-functional materials. These results provide a new perspective on the efficient preparation of WPMs and show its promising application in fabricating functional materials.

{"title":"One-step and one-pot synthesis of wrinkled polymer microspheres based on monomer reactivity ratio difference","authors":"Tian Liu, Yungui Ma, Dunxun Yu, Xiaopeng Yang, Zhihua Ma, Ning Liu, Shiyang Shao","doi":"10.1016/j.eurpolymj.2024.113707","DOIUrl":"10.1016/j.eurpolymj.2024.113707","url":null,"abstract":"<div><div>Different from conventional multi-step synthesis methods for wrinkled polymer microspheres (WPMs), here we propose a facile one-step and one-pot synthesis strategy for WPMs employing monomer reactivity ratio difference to form linear-crosslinked-linear gradient structure from inside to outside of the microspheres, leading to wrinkled surface by uneven shrinkage of the crosslinked and linear structures. The particle size and surface morphology for WPMs can be easily adjusted by changing monomer types and solvent ratio according to morphological characterization. Meanwhile, this method is universal for synthesizing WPMs having different monomers, supported by the fact that monomers bearing different substituent groups can be successfully used for the synthesis procedure. Finally, fluorescent microspheres with tuned emission colors are synthesized through this strategy by simply adding different fluorescent dyes in polymerization system, demonstrating the potential of such strategy in synthesizing optical-functional materials. These results provide a new perspective on the efficient preparation of WPMs and show its promising application in fabricating functional materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113707"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147594","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}

引用次数: 0

Construction of nanoparticle-based 3D protein microarrays with high protein capacity and controllable density

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113708

Guo Li , Yu Wang , Tao Chen , Haili Zhao

Three-dimensional (3D) substrates have received considerable attention for the fabrication of protein microarrays with high protein capacity owing to their enlarged surface area for the high density immobilization of proteins. In this work, a facile strategy for constructing the protein microarrays with a low background and high signal intensity was developed based on the polystyrene nanoparticles (PS-NPs) assembled substrate. The discontinuous hydrophilic surface with hydrophobic initiators and hydrophilic poly(ethylene glycol) methacrylate (PEGMA) brushes was fabricated in the first step via digital micromirror device (DMD)-mediated photoinduced atom transfer radical polymerization (Photo-ATRP) process, and the hydrophilic interaction between sodium dodecyl sulfate (SDS)-modified PS-NPs and PEGMA brushes enabled the selective assembly of PS-NPs on the PEGMA brush region, resulting in the successful formation of arrayed surface with PS-NPs patterns. Then, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) brushes were grafted surrounding the PS-NPs to eliminate background noise caused by non-specific protein absorption. Compared to the PGMA brushes patterned substrate, the PS-NPs substrate exhibited excellent protein adsorption capability, leading to the 3D protein microarrays with higher protein capacity were easily obtained. Especially, the assembly density could be controlled by adjusting the PS suspension concentration, resulting in the effective regulation on the density of surface-bound proteins. Finally, the spatial control of protein density on the same substrate was achieved through regulating the distribution density of assembled PS-NPs, allowing for a protein microarrays with controllable density. This simple and effective mothed for fabricating nanoparticle-based 3D protein microarrays has tremendous potential in the fields of biomedical detection and high-throughput analysis.

{"title":"Construction of nanoparticle-based 3D protein microarrays with high protein capacity and controllable density","authors":"Guo Li , Yu Wang , Tao Chen , Haili Zhao","doi":"10.1016/j.eurpolymj.2024.113708","DOIUrl":"10.1016/j.eurpolymj.2024.113708","url":null,"abstract":"<div><div>Three-dimensional (3D) substrates have received considerable attention for the fabrication of protein microarrays with high protein capacity owing to their enlarged surface area for the high density immobilization of proteins. In this work, a facile strategy for constructing the protein microarrays with a low background and high signal intensity was developed based on the polystyrene nanoparticles (PS-NPs) assembled substrate. The discontinuous hydrophilic surface with hydrophobic initiators and hydrophilic poly(ethylene glycol) methacrylate (PEGMA) brushes was fabricated in the first step via digital micromirror device (DMD)-mediated photoinduced atom transfer radical polymerization (Photo-ATRP) process, and the hydrophilic interaction between sodium dodecyl sulfate (SDS)-modified PS-NPs and PEGMA brushes enabled the selective assembly of PS-NPs on the PEGMA brush region, resulting in the successful formation of arrayed surface with PS-NPs patterns. Then, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) brushes were grafted surrounding the PS-NPs to eliminate background noise caused by non-specific protein absorption. Compared to the PGMA brushes patterned substrate, the PS-NPs substrate exhibited excellent protein adsorption capability, leading to the 3D protein microarrays with higher protein capacity were easily obtained. Especially, the assembly density could be controlled by adjusting the PS suspension concentration, resulting in the effective regulation on the density of surface-bound proteins. Finally, the spatial control of protein density on the same substrate was achieved through regulating the distribution density of assembled PS-NPs, allowing for a protein microarrays with controllable density. This simple and effective mothed for fabricating nanoparticle-based 3D protein microarrays has tremendous potential in the fields of biomedical detection and high-throughput analysis.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113708"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146474","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}

引用次数: 0

Biobased poly(amido-imide) CANs catalyzed by lanthanide triflates: High creep resistance and superior reprocessability

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113700

Adrià Roig , Jesús Padilla , Silvia De la Flor , Àngels Serra

Here, we report the preparation of a series of dynamic covalent poly(amido-imide) materials where the network architecture and the addition of external catalysts were carefully selected through an in-depth study to fine-tune the thermomechanical properties of the final materials and maximize their possible applicability.

The use of bioderived tricarballylic acid in combination with different proportions of commercially available amines enabled tailoring the thermal and mechanical properties of the final materials. This approach allowed to obtain materials with T_gs ranging from 90 °C to 130 °C, high thermal stability (T_1% > 248 °C) and robust mechanical properties at room temperature (σ_break > 85 MPa, Young Modulus > 3.1 GPa). Moreover, the addition of lanthanide triflates significantly enhanced the dynamicity of the networks by almost one order of magnitude, while still maintaining excellent structural integrity and high creep resistance at service temperatures. This achievement represents a significant step towards highly crosslinked materials with fast reprocessing capabilities and good thermomechanical performance.

The materials also showcased excellent self-welding and shape-memory capabilities, highlighting their versatility, which we envision will open up new advancements in the field of reprocessable thermosetting materials.

{"title":"Biobased poly(amido-imide) CANs catalyzed by lanthanide triflates: High creep resistance and superior reprocessability","authors":"Adrià Roig , Jesús Padilla , Silvia De la Flor , Àngels Serra","doi":"10.1016/j.eurpolymj.2024.113700","DOIUrl":"10.1016/j.eurpolymj.2024.113700","url":null,"abstract":"<div><div>Here, we report the preparation of a series of dynamic covalent poly(amido-imide) materials where the network architecture and the addition of external catalysts were carefully selected through an in-depth study to fine-tune the thermomechanical properties of the final materials and maximize their possible applicability.</div><div>The use of bioderived tricarballylic acid in combination with different proportions of commercially available amines enabled tailoring the thermal and mechanical properties of the final materials. This approach allowed to obtain materials with T<sub>g</sub>s ranging from 90 °C to 130 °C, high thermal stability (T<sub>1%</sub> > 248 °C) and robust mechanical properties at room temperature (σ<sub>break</sub> > 85 MPa, Young Modulus > 3.1 GPa). Moreover, the addition of lanthanide triflates significantly enhanced the dynamicity of the networks by almost one order of magnitude, while still maintaining excellent structural integrity and high creep resistance at service temperatures. This achievement represents a significant step towards highly crosslinked materials with fast reprocessing capabilities and good thermomechanical performance.</div><div>The materials also showcased excellent self-welding and shape-memory capabilities, highlighting their versatility, which we envision will open up new advancements in the field of reprocessable thermosetting materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113700"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147591","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}

引用次数: 0

Microscopic studies on remarkable rheological behavior of single-chain nanoparticles and linear polymer blends

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113687

Yangjing Chen, Zhiyu Hu, Hongting Pu

The incorporation of nanoparticles into linear polymers can significantly alter the rheological properties of the system. Nevertheless, the fundamental mechanisms behind this phenomenon have remained elusive. In present study, the changes in the microstructure, particularly the mesh size (ξ) and relaxation time (τ_d) of entangled chains, in a fully polymer/single chain nanoparticles (SCNPs) nanocomposite (PNC) composed of linear polymethyl methacrylate (PMMA) chains and PMMA SCNPs was investigated by microrheological techniques. This research aims to elucidate the mechanism by which soft nanofillers affects the macroscopic properties of SCNP and linear polymer composite systems from a microstructural perspective. Results reveal that SCNPs demonstrate rapid chain segment relaxation and exhibit low viscosity in solution due to three-dimensional spherical structure. More importantly, the addition of SCNPs to the linear matrix significantly modifies the entanglement behavior of the linear polymer, decreasing the entanglement density (lager mesh size), resulting in a lower viscosity, and quicker relaxation times for the system. Additionally, it is observed that the dispersed nature and high penetrability of SCNPs lead to increased disorder in their conformation in solution as their size grows, which gradually diminishes their impact on the entanglement behavior of the system’s chains. Consequently, the effect of SCNPs on the rheological behavior of the system shows a strong dependence on size.

{"title":"Microscopic studies on remarkable rheological behavior of single-chain nanoparticles and linear polymer blends","authors":"Yangjing Chen, Zhiyu Hu, Hongting Pu","doi":"10.1016/j.eurpolymj.2024.113687","DOIUrl":"10.1016/j.eurpolymj.2024.113687","url":null,"abstract":"<div><div>The incorporation of nanoparticles into linear polymers can significantly alter the rheological properties of the system. Nevertheless, the fundamental mechanisms behind this phenomenon have remained elusive. In present study, the changes in the microstructure, particularly the mesh size (<em>ξ</em>) and relaxation time (<em>τ</em><sub>d</sub>) of entangled chains, in a fully polymer/single chain nanoparticles (SCNPs) nanocomposite (PNC) composed of linear polymethyl methacrylate (PMMA) chains and PMMA SCNPs was investigated by microrheological techniques. This research aims to elucidate the mechanism by which soft nanofillers affects the macroscopic properties of SCNP and linear polymer composite systems from a microstructural perspective. Results reveal that SCNPs demonstrate rapid chain segment relaxation and exhibit low viscosity in solution due to three-dimensional spherical structure. More importantly, the addition of SCNPs to the linear matrix significantly modifies the entanglement behavior of the linear polymer, decreasing the entanglement density (lager mesh size), resulting in a lower viscosity, and quicker relaxation times for the system. Additionally, it is observed that the dispersed nature and high penetrability of SCNPs lead to increased disorder in their conformation in solution as their size grows, which gradually diminishes their impact on the entanglement behavior of the system’s chains. Consequently, the effect of SCNPs on the rheological behavior of the system shows a strong dependence on size.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113687"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146948","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}

引用次数: 0

Balancing flame retardancy and high toughness in solvent-free reactive polyurethane films via P/Si synergistic strategy

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-05 DOI: 10.1016/j.eurpolymj.2025.113810

Jinbiao Zhao , Huimin Duan , Xinxin Xu , Shangchao Ji , Hao Yang , Zhichao Huang , Qi Zhong , Dongming Qi

Reactive polyurethane (RPU) films in a solvent-free medium exhibit exceptional stability and mechanical properties due to their highly cross-linked structure. Achieving inherent fire resistance, waterproofing, and high mechanical performance in RPUs is challenging. Here, we prepared an intrinsic flame retardant, waterproof, and flexible RPU using a P/Si synergistic system with hydroxylated ammonium polyphosphate aAPP/Si-RPU via in-situ polyaddition of NCO-double capped prepolymer and polyol components, including polydimethylsiloxane (PDMS) and aAPP. The aAPP was synthesized through cation exchange between diethylene glycol amine (DGA) and ammonium polyphosphate (APP). Compared to pure RPU, aAPP/Si_15%-RPU showed a 60.3 % reduction in peak heat release rate (pk-HRR) and a 14.1 % reduction in total heat release (THR), with the limiting oxygen index (LOI) increasing from 18.2 % to 27.8 %. Mechanical properties and hydrophobicity improved, with tensile strength at 31.9 ± 1.9 MPa, elongation at break at 522.7 ± 20.3 %, and a water contact angle of 127.1°. The balance of properties was due to ordered microphase separation from the organic–inorganic hybrid structure of aAPP and PDMS, where aAPP particles enhanced microstructure and crosslinked interactions, and the Si-O bond in PDMS provided flexibility and water resistance. This study presents a strategy to resolve the conflict between rigidity and toughness, offering design ideas for intrinsic flame retardant polyurethane.

{"title":"Balancing flame retardancy and high toughness in solvent-free reactive polyurethane films via P/Si synergistic strategy","authors":"Jinbiao Zhao , Huimin Duan , Xinxin Xu , Shangchao Ji , Hao Yang , Zhichao Huang , Qi Zhong , Dongming Qi","doi":"10.1016/j.eurpolymj.2025.113810","DOIUrl":"10.1016/j.eurpolymj.2025.113810","url":null,"abstract":"<div><div>Reactive polyurethane (RPU) films in a solvent-free medium exhibit exceptional stability and mechanical properties due to their highly cross-linked structure. Achieving inherent fire resistance, waterproofing, and high mechanical performance in RPUs is challenging. Here, we prepared an intrinsic flame retardant, waterproof, and flexible RPU using a P/Si synergistic system with hydroxylated ammonium polyphosphate aAPP/Si-RPU via <em>in-situ</em> polyaddition of NCO-double capped prepolymer and polyol components, including polydimethylsiloxane (PDMS) and aAPP. The aAPP was synthesized through cation exchange between diethylene glycol amine (DGA) and ammonium polyphosphate (APP). Compared to pure RPU, aAPP/Si<sub>15%</sub>-RPU showed a 60.3 % reduction in peak heat release rate (pk-HRR) and a 14.1 % reduction in total heat release (THR), with the limiting oxygen index (LOI) increasing from 18.2 % to 27.8 %. Mechanical properties and hydrophobicity improved, with tensile strength at 31.9 ± 1.9 MPa, elongation at break at 522.7 ± 20.3 %, and a water contact angle of 127.1°. The balance of properties was due to ordered microphase separation from the organic–inorganic hybrid structure of aAPP and PDMS, where aAPP particles enhanced microstructure and crosslinked interactions, and the Si-O bond in PDMS provided flexibility and water resistance. This study presents a strategy to resolve the conflict between rigidity and toughness, offering design ideas for intrinsic flame retardant polyurethane.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113810"},"PeriodicalIF":5.8,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378246","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}

引用次数: 0

Acetal-functionalized polyurethane adhesives: A path to debonding-on-demand

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-05 DOI: 10.1016/j.eurpolymj.2025.113807

Tankut Türel , Patrick Schara , Anna M. Cristadoro , Martin Linnenbrink , Željko Tomović

Polyurethanes stand out as remarkably versatile polymers, renowned for their adjustable mechanical and thermal characteristics, making them invaluable across various domains, notably in adhesive applications. Yet conventional polyurethane adhesives typically form permanent bonds, and thus debonding is not possible without harming the bonded substrates. In the light of escalating calls for sustainability, the development of polyurethane adhesives with debonding-on-demand capabilities has become paramount. Such innovations facilitate disassembly, repair, exchange, and recycling of bonded materials. Consequently, herein, we integrate three different linear acetal polyols into one-component, polyether-based polyurethane adhesives. These new systems not only exhibit comparable thermal properties and superior adhesive performance to conventional adhesives but also offer debonding-on-demand capabilities. These findings provide a drop-in solution to the limitations of traditional bonding methods and foster a circular economy, underscoring the pivotal role of adhesive technology in addressing environmental imperatives.

{"title":"Acetal-functionalized polyurethane adhesives: A path to debonding-on-demand","authors":"Tankut Türel , Patrick Schara , Anna M. Cristadoro , Martin Linnenbrink , Željko Tomović","doi":"10.1016/j.eurpolymj.2025.113807","DOIUrl":"10.1016/j.eurpolymj.2025.113807","url":null,"abstract":"<div><div>Polyurethanes stand out as remarkably versatile polymers, renowned for their adjustable mechanical and thermal characteristics, making them invaluable across various domains, notably in adhesive applications. Yet conventional polyurethane adhesives typically form permanent bonds, and thus debonding is not possible without harming the bonded substrates. In the light of escalating calls for sustainability, the development of polyurethane adhesives with debonding-on-demand capabilities has become paramount. Such innovations facilitate disassembly, repair, exchange, and recycling of bonded materials. Consequently, herein, we integrate three different linear acetal polyols into one-component, polyether-based polyurethane adhesives. These new systems not only exhibit comparable thermal properties and superior adhesive performance to conventional adhesives but also offer debonding-on-demand capabilities. These findings provide a drop-in solution to the limitations of traditional bonding methods and foster a circular economy, underscoring the pivotal role of adhesive technology in addressing environmental imperatives.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113807"},"PeriodicalIF":5.8,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of hyperbranched polyethers with diverse structures based on “A1 + B2” ring-opening polymerization

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-05 DOI: 10.1016/j.eurpolymj.2025.113806

Xinkai Zou , Xiaofei Sun , Anxin Xu , Yang Liu , Wei Zhao , Yingxia Zong , Jingjiang Sun , Qingfu Wang

The research on hyperbranched polyethers (HBPEths) currently focused on two main areas: (1) the development of a practical synthesis method and (2) the functionalization of HBPEths. “A₁ + B₂” ring-opening polymerization (“A₁ + B₂”-ROP) offers an efficient approach to access functional HBPEths with controllable structures. In the present study, a series of HBPEths were successfully prepared by employing “A₁ + B₂”-ROP, where the A₁ and B₂ represent a monofunctional primary alcohol and a biepoxy monomer, respectively. The obtained HBPEths possessed molar masses ranging from 2600 to 30000 g/mol. By employing functional A₁ primary alcohol initiators, it is possible to directly introduce a single type or a mixture of functionalities including fluoride, alkyne, alkene, azide, and furfuryl groups into the HBPEths terminal structures, while by adjusting various B₂ monomers with different linkage between both epoxy groups the main chain structures could be well controlled. Moreover, apart from conventional end group modification via esterification, the functionalities can be introduced during the one-pot “A₁ + B₂”-ROP process via ether bonds, which are stable against hydrolysis and redox-reaction.

{"title":"Synthesis of hyperbranched polyethers with diverse structures based on “A1 + B2” ring-opening polymerization","authors":"Xinkai Zou , Xiaofei Sun , Anxin Xu , Yang Liu , Wei Zhao , Yingxia Zong , Jingjiang Sun , Qingfu Wang","doi":"10.1016/j.eurpolymj.2025.113806","DOIUrl":"10.1016/j.eurpolymj.2025.113806","url":null,"abstract":"<div><div>The research on hyperbranched polyethers (HBPEths) currently focused on two main areas: (1) the development of a practical synthesis method and (2) the functionalization of HBPEths. “A<sub>1</sub> + B<sub>2</sub>” ring-opening polymerization (“A<sub>1</sub> + B<sub>2</sub>”-ROP) offers an efficient approach to access functional HBPEths with controllable structures. In the present study, a series of HBPEths were successfully prepared by employing “A<sub>1</sub> + B<sub>2</sub>”-ROP, where the A<sub>1</sub> and B<sub>2</sub> represent a monofunctional primary alcohol and a biepoxy monomer, respectively. The obtained HBPEths possessed molar masses ranging from 2600 to 30000 g/mol. By employing functional A<sub>1</sub> primary alcohol initiators, it is possible to directly introduce a single type or a mixture of functionalities including fluoride, alkyne, alkene, azide, and furfuryl groups into the HBPEths terminal structures, while by adjusting various B<sub>2</sub> monomers with different linkage between both epoxy groups the main chain structures could be well controlled. Moreover, apart from conventional end group modification via esterification, the functionalities can be introduced during the one-pot “A<sub>1</sub> + B<sub>2</sub>”-ROP process via ether bonds, which are stable against hydrolysis and redox-reaction.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113806"},"PeriodicalIF":5.8,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372925","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}

引用次数: 0

UVB protective polyvinyl alcohol/ZnCeO3 nanocomposite Films: Blue luminescent UV leakage detectors

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-05 DOI: 10.1016/j.eurpolymj.2025.113809

S. Sachhidananda , K.S. Nithin , H.B.Vasanth Patil , B.M. Jagajeevan Raj , T.E. Somesh , G.S. Nanjundaswamy , S. Roopa

This work focuses on the development of Polyvinyl Alcohol (PVA) nanocomposite (NC) films for UVB shielding and detection applications. The films, incorporating 0.5, 1.0, 2.0, and 4.0 wt% Zinc-doped Cerium Oxide (ZnCeO₃) nanoparticles, were fabricated using a modified solution casting technique. This method enabled rapid solvent removal and efficient film formation. The resulting NC films were characterized using various analytical tools to evaluate their structural, microstructural, morphological, and optical properties. The UVB shielding performance of the PVA/ZnCeO₃ NC films was subsequently assessed by monitoring UVB-induced DNA denaturation in tender coconut extracts. The DNA degradation kinetics demonstrated that the PVA/ZnCeO₃ NC films effectively preserved DNA stability, protecting it from the harmful photo-oxidative effects of high-energy UVB radiation. Further validation of the UVB protective effects was achieved using UV transilluminator measurements. Additionally, the PVA/ZnCeO₃ NC films exhibited visible fluorescent blue light emission upon UVB exposure, highlighting their potential as UVB protective packaging materials and UVB leakage monitors. Hence, this study demonstrates the potential of these NC films to provide effective UVB protection while simultaneously enabling the detection of UVB radiation.

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引用次数: 0

Photodynamic, UV-curable and fibre-forming polyvinyl alcohol derivative with broad processability and staining-free antibacterial capability

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-04 DOI: 10.1016/j.eurpolymj.2025.113794

Man Li , Charles Brooker , Rucha Ambike , Ziyu Gao , Paul Thornton , Thuy Do , Giuseppe Tronci

Antimicrobial photodynamic therapy (APDT) is a promising antibiotic-free strategy for broad-spectrum infection control in chronic wounds, minimising bacterial resistance risks. However, rapid photosensitiser diffusion, tissue staining, side toxicity, and short-lived antimicrobial effects present significant clinical limitations for integrating APDT into wound dressings. To address these challenges, we present the design of a bespoke polyvinyl alcohol (PVA) derivative conjugated with both phenothiazine and methacrylate functionalities, enabling staining-free antibacterial photodynamic effects, cellular tolerability and processability into various wound dressing formats, including films, textile fibres and nanoscale coatings. Tosylation of PVA is leveraged for the covalent coupling of toluidine blue ([TB]: 0.69 ± 0.03–0.81 ± 0.05 mg per gram of polymer), as confirmed by UV–Vis spectroscopy and the minimal average release of TB (≤ 3 wt%, < 0.4 µg) following 96-hour incubation in vitro. UV-induced network formation is demonstrated by complete solution gelation, rheology, and a high gel content (Ḡ > 95 wt%), and exploited to accomplish cast films and nanoscale integrated wound dressing coatings. UV curing is also successfully coupled with an in-house wet spinning process to realise individual, water-insoluble fibres as the building blocks of fibrous wound dressings. A fluorometric assay supports the generation of reactive oxygen species when the UV-cured samples are exposed to work, but not UV, light, yielding a mean log₁₀ reduction of up to 2.13 in S. aureus, and the complete eradication of P. aeruginosa. Direct and extract cytotoxicity tests with UV-cured films and fibres demonstrate the viability of L929 fibroblasts following 60-min light irradiation and 72-hour cell culture. The bespoke molecular architecture, broad processability and cellular tolerability of this PVA derivative are highly attractive aiming to integrate durable staining-free photodynamic capability in a wide range of healthcare technologies, from chronic wound dressings up to minimally invasive localised therapy.

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引用次数: 0