European Polymer Journal最新文献_第2页

Compatibilisation of immiscible soft segments in self-healing thermoplastic polyurethane elastomers via Diels-Alder cycloaddition

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-03-04 DOI: 10.1016/j.eurpolymj.2025.113881

Jennifer C. Hughes , James A. Wilson , N. Hawkins , Yi. Zhang , Chris Holland , Andrew T. Slark

In this work, Diels-Alder (DA) chemistry has been used for the first time to make dual-soft segment thermoplastic polyurethane (TPU) elastomers (M_n = 34,000–42,000 g.mol⁻¹) with superior properties from incompatible precursors. Immiscible poly(1,4-butadiene) and poly(ɛ-caprolactone) polyols were used to prepare maleimide and furan-terminated poly(butadiene urethane) (PBU) and poly(ɛ-caprolactone urethane) (PEU) prepolymers (M_n = 7000–8000 g.mol⁻¹) from isocyanate terminated intermediates. These prepolymers were subsequently copolymerised via DA-cycloaddition reactions to prepare DA-(PBU-co-PEU) multiblock copolymers comprising 25, 50 and 75 wt.% PBU and PEU segments, which were compared to DA-100PBU or DA-100PEU copolymers containing 100 wt.% PBU or PEU segments. The morphology and thermomechanical properties of the DA-TPUs can be systematically controlled via altering PBU : PEU composition. Copolymers containing ≥75 wt.% PEU segments display predominantly semi-crystalline behaviour, whilst those containing ≤50 wt.% PEU segments exhibit amorphous behaviour. Copolymerisation via DA-cycloaddition enables soft segment compatibilisation providing the composition DA-(50PBU-co-50PEU) with excellent elastomeric properties (increased toughness by a factor of 7 over DA-100PBU and enhanced elastic recovery over DA-100PEU). The elastomers also display excellent thermal reprocessing and healing abilities under mild conditions (≤130 °C), retaining high stress recovery ratios over 85 % and rapidly healing 50 µm defects. The facile methodology established in this study could be applied to compatibilise other immiscible soft segments to obtain recyclable, self-healing materials with unique properties.

{"title":"Compatibilisation of immiscible soft segments in self-healing thermoplastic polyurethane elastomers via Diels-Alder cycloaddition","authors":"Jennifer C. Hughes , James A. Wilson , N. Hawkins , Yi. Zhang , Chris Holland , Andrew T. Slark","doi":"10.1016/j.eurpolymj.2025.113881","DOIUrl":"10.1016/j.eurpolymj.2025.113881","url":null,"abstract":"<div><div>In this work, Diels-Alder (DA) chemistry has been used for the first time to make dual-soft segment thermoplastic polyurethane (TPU) elastomers (<em>M</em><sub>n</sub> = 34,000–42,000 g.mol<sup>−1</sup>) with superior properties from incompatible precursors. Immiscible poly(1,4-butadiene) and poly(ɛ-caprolactone) polyols were used to prepare maleimide and furan-terminated poly(butadiene urethane) (PBU) and poly(ɛ-caprolactone urethane) (PEU) prepolymers (<em>M</em><sub>n</sub> = 7000–8000 g.mol<sup>−1</sup>) from isocyanate terminated intermediates. These prepolymers were subsequently copolymerised <em>via</em> DA-cycloaddition reactions to prepare DA-(PBU<em>-co-</em>PEU) multiblock copolymers comprising 25, 50 and 75 wt.% PBU and PEU segments, which were compared to DA-100PBU or DA-100PEU copolymers containing 100 wt.% PBU or PEU segments. The morphology and thermomechanical properties of the DA-TPUs can be systematically controlled <em>via</em> altering PBU : PEU composition. Copolymers containing ≥75 wt.% PEU segments display predominantly semi-crystalline behaviour, whilst those containing ≤50 wt.% PEU segments exhibit amorphous behaviour. Copolymerisation <em>via</em> DA-cycloaddition enables soft segment compatibilisation providing the composition DA-(50PBU<em>-co-</em>50PEU) with excellent elastomeric properties (increased toughness by a factor of 7 over DA-100PBU and enhanced elastic recovery over DA-100PEU). The elastomers also display excellent thermal reprocessing and healing abilities under mild conditions (≤130 °C), retaining high stress recovery ratios over 85 % and rapidly healing 50 µm defects. The facile methodology established in this study could be applied to compatibilise other immiscible soft segments to obtain recyclable, self-healing materials with unique properties.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113881"},"PeriodicalIF":5.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578295","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

Amidinium pyridinolate ion pair organocatalyst for ring-opening polymerizations of cyclic esters

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-03-03 DOI: 10.1016/j.eurpolymj.2025.113848

Fengzhen Guo, Yaling Yin, Zhenjiang Li, Yue Xu, Shaoju Cao, Ziqi Liu, Yanqi Shi, Chunyu Li, Kai Guo

Ion pair organocatalyst composed of a positively charged hydrogen-bond donor (HBD⁺) and a nucleophilic anion (A⁻) was proposed for ring-opening polymerizations (ROPs) of cyclic esters. The HBD⁺/A⁻ ion pair catalyst was readily accessible by mixing stoichiometric of super strong nitrogen bases (i.e. DBU, TBD, and MTBD) with 2-, 3-, and 4-pyridinols (4-PyOH). Nine ion pair catalysts were evaluated in bulk ROPs of L-lactide (LLA) by ratios of 25 : 1 : 1 of the monomer to the initiator and to the catalyst at 140 °C, in which the DBUH⁺/4-PyO⁻ pair showed optimal performances in producing polylactide (PLLA) by high conversion (95 %) in 15 min. Under the catalysis of DBUH⁺/4-PyO⁻ ion pair, PLLA of predicted molecular weights (M_n,NMR = 3.3–23.9 kg·mol⁻¹) and narrow dispersity (Ð = 1.10–1.25) was prepared; ROPs of trimethylene carbonate (TMC), δ-valerolactone, and ε-caprolactone, as well as diblock-copolymers of TMC and LLA were all successful in the bulk. Bifunctional catalytic mechanism of the ion pair via activation of the monomer with the cationic HBD⁺ and activation of the initiator/chain-end with anion A⁻ was suggested and validated by NMR titrations. The design principle of H-bonding cation and nucleophilic anion ion pair organocatalyst featured easy access and multiple combinations paved avenues to wider scope of catalytic polymerizations.

{"title":"Amidinium pyridinolate ion pair organocatalyst for ring-opening polymerizations of cyclic esters","authors":"Fengzhen Guo, Yaling Yin, Zhenjiang Li, Yue Xu, Shaoju Cao, Ziqi Liu, Yanqi Shi, Chunyu Li, Kai Guo","doi":"10.1016/j.eurpolymj.2025.113848","DOIUrl":"10.1016/j.eurpolymj.2025.113848","url":null,"abstract":"<div><div>Ion pair organocatalyst composed of a positively charged hydrogen-bond donor (HBD<sup>+</sup>) and a nucleophilic anion (A<sup>−</sup>) was proposed for ring-opening polymerizations (ROPs) of cyclic esters. The HBD<sup>+</sup>/A<sup>−</sup> ion pair catalyst was readily accessible by mixing stoichiometric of super strong nitrogen bases (i.e. DBU, TBD, and MTBD) with 2-, 3-, and 4-pyridinols (4-PyOH). Nine ion pair catalysts were evaluated in bulk ROPs of L-lactide (LLA) by ratios of 25 : 1 : 1 of the monomer to the initiator and to the catalyst at 140 °C, in which the DBUH<sup>+</sup>/4-PyO<sup>−</sup> pair showed optimal performances in producing polylactide (PLLA) by high conversion (95 %) in 15 min. Under the catalysis of DBUH<sup>+</sup>/4-PyO<sup>−</sup> ion pair, PLLA of predicted molecular weights (<em>M</em><sub>n,NMR</sub> = 3.3–23.9 kg·mol<sup>−1</sup>) and narrow dispersity (<em>Ð</em> = 1.10–1.25) was prepared; ROPs of trimethylene carbonate (TMC), <em>δ</em>-valerolactone, and <em>ε</em>-caprolactone, as well as diblock-copolymers of TMC and LLA were all successful in the bulk. Bifunctional catalytic mechanism of the ion pair <em>via</em> activation of the monomer with the cationic HBD<sup>+</sup> and activation of the initiator/chain-end with anion A<sup>−</sup> was suggested and validated by NMR titrations. The design principle of H-bonding cation and nucleophilic anion ion pair organocatalyst featured easy access and multiple combinations paved avenues to wider scope of catalytic polymerizations.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113848"},"PeriodicalIF":5.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143593147","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

The polyhydrogen bond stretchable waterborne polyurethane film with excellent self-healing properties

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-03-03 DOI: 10.1016/j.eurpolymj.2025.113879

Liyang Yao, Miaomiao Qian, Lin Chen, Yanchao Zhu

The fabrication of self-healing dielectric elastomers that are capable of effective recovery from both electrical breakdown and mechanical damage represents a valuable advancement in the field of actuators. However, the mechanical and dielectric properties of the materials may be compromised during the repair process, which has thus far limited their application as dielectric elastomers. In this work, we have developed a self-healing polyurethane film based on hydrogen bonding interactions by incorporating tannic acid (TA), which has been shown to retain high mechanical properties and excellent dielectric performance. The incorporation of TA has been demonstrated to enhance the efficiency of the damage in question is mechanical or electrical breakdown. The tensile strength of WPU/TA_0.42 that had been subjected to mechanical damage was restored by up to 97.51 % after 48 h. Following an electrical breakdown, a 60 % ethanol solution was applied to the damaged surface of the samples in order to remove the deposited carbides. The breakdown strength of WPU/TA_0.42 recovered close to 100 %, and it was demonstrated to be capable of being re-braked stably at 80MV/m. It is noteworthy that WPU/TA_0.42 exhibits enhanced mechanical and dielectric properties which can be attributed to the increased formation hydrogen bonds at crosslinking sites and interfacial polarization. This work presents a straightforward approach to fabricating dielectric elastomers with enhanced mechanical and dielectric properties capable of efficient self-healing following mechanical damage and electric breakdown.

{"title":"The polyhydrogen bond stretchable waterborne polyurethane film with excellent self-healing properties","authors":"Liyang Yao, Miaomiao Qian, Lin Chen, Yanchao Zhu","doi":"10.1016/j.eurpolymj.2025.113879","DOIUrl":"10.1016/j.eurpolymj.2025.113879","url":null,"abstract":"<div><div>The fabrication of self-healing dielectric elastomers that are capable of effective recovery from both electrical breakdown and mechanical damage represents a valuable advancement in the field of actuators. However, the mechanical and dielectric properties of the materials may be compromised during the repair process, which has thus far limited their application as dielectric elastomers. In this work, we have developed a self-healing polyurethane film based on hydrogen bonding interactions by incorporating tannic acid (TA), which has been shown to retain high mechanical properties and excellent dielectric performance. The incorporation of TA has been demonstrated to enhance the efficiency of the damage in question is mechanical or electrical breakdown. The tensile strength of WPU/TA<sub>0.42</sub> that had been subjected to mechanical damage was restored by up to 97.51 % after 48 h. Following an electrical breakdown, a 60 % ethanol solution was applied to the damaged surface of the samples in order to remove the deposited carbides. The breakdown strength of WPU/TA<sub>0.42</sub> recovered close to 100 %, and it was demonstrated to be capable of being re-braked stably at 80MV/m. It is noteworthy that WPU/TA<sub>0.42</sub> exhibits enhanced mechanical and dielectric properties which can be attributed to the increased formation hydrogen bonds at crosslinking sites and interfacial polarization. This work presents a straightforward approach to fabricating dielectric elastomers with enhanced mechanical and dielectric properties capable of efficient self-healing following mechanical damage and electric breakdown.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113879"},"PeriodicalIF":5.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563072","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

Evaluation of the effect of coupling agent on the kinetic and mechanical properties of a 3D printable dual curing epoxy/acrylate system

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-03-02 DOI: 10.1016/j.eurpolymj.2025.113878

A.A. Escriba-Flores , X. Fernández-Francos , F. Ferrando , A. Fabregat-Sanjuan

In recent years, the use of vat photopolymerization in additive manufacturing technology has created a prominent potential in the world manufacturing industry due to its adaptability and quick production capabilities. However, a challenge faced by this technology is creating large-sized parts and ensuring the geometric versatility of processed parts. The physical and mechanical properties of existing materials limit their processing, affecting their final applications. Moreover, dual-curing systems allow new possibilities to 3D printing if shape geometry is changed after the first curing stage and fixed in the second curing stage. This study aims to address these challenges by developing a dual-curing system involving epoxy/acrylic resins. We assess the kinetic and mechanical behavior, focusing on variations in the network coupling agent. The initial curing stage of a low viscous formulation, achieved through processing on a DLP 3D printer (partially cured), produces a flexible material allowing deformations up to 160 %. The second curing stage, achieved through thermal treatment, transforms the material into a rigid system with an impressive maximum tensile strength close to 80 MPa. We compare the contribution of the bonding agent in partial and total cured states. Comprehensive mechanical tests have been performed, including tension and shear evaluations. Results have been favorably aligned with relevant literature. The dual-curing approach shows promise in expanding 3D printing vat photopolymerization applications, providing new design and manufacturing possibilities by enhancing material availability. Our findings emphasize the benefits of the dual-curing system, including low viscosity, shape manipulation during intermediate curing that allows complex geometries with fast procedures and without the need of supports and exceptional strength and durability achieved in the final curing phase. Results on mechanical characterization in joints show that dual curing resins could be attractive in applications where different parts must be joined and precise alignment and structural integrity are crucial. The main reason for that is the interaction with the bonding agent in each state of the dual curing.

{"title":"Evaluation of the effect of coupling agent on the kinetic and mechanical properties of a 3D printable dual curing epoxy/acrylate system","authors":"A.A. Escriba-Flores , X. Fernández-Francos , F. Ferrando , A. Fabregat-Sanjuan","doi":"10.1016/j.eurpolymj.2025.113878","DOIUrl":"10.1016/j.eurpolymj.2025.113878","url":null,"abstract":"<div><div>In recent years, the use of vat photopolymerization in additive manufacturing technology has created a prominent potential in the world manufacturing industry due to its adaptability and quick production capabilities. However, a challenge faced by this technology is creating large-sized parts and ensuring the geometric versatility of processed parts. The physical and mechanical properties of existing materials limit their processing, affecting their final applications. Moreover, dual-curing systems allow new possibilities to 3D printing if shape geometry is changed after the first curing stage and fixed in the second curing stage. This study aims to address these challenges by developing a dual-curing system involving epoxy/acrylic resins. We assess the kinetic and mechanical behavior, focusing on variations in the network coupling agent. The initial curing stage of a low viscous formulation, achieved through processing on a DLP 3D printer (partially cured), produces a flexible material allowing deformations up to 160 %. The second curing stage, achieved through thermal treatment, transforms the material into a rigid system with an impressive maximum tensile strength close to 80 MPa. We compare the contribution of the bonding agent in partial and total cured states. Comprehensive mechanical tests have been performed, including tension and shear evaluations. Results have been favorably aligned with relevant literature. The dual-curing approach shows promise in expanding 3D printing vat photopolymerization applications, providing new design and manufacturing possibilities by enhancing material availability. Our findings emphasize the benefits of the dual-curing system, including low viscosity, shape manipulation during intermediate curing that allows complex geometries with fast procedures and without the need of supports and exceptional strength and durability achieved in the final curing phase. Results on mechanical characterization in joints show that dual curing resins could be attractive in applications where different parts must be joined and precise alignment and structural integrity are crucial. The main reason for that is the interaction with the bonding agent in each state of the dual curing.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113878"},"PeriodicalIF":5.8,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563073","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

Amphiphilic block copolymer conjugated with cell-penetrating-peptides derived from Influenza A H1N1 virus as a biocompatible scaffold for enhanced cell-uptake

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-03-01 DOI: 10.1016/j.eurpolymj.2025.113876

Carolina Ventura-Hunter , David Pretzel , Carolin Kellner , Stephanie Hoeppener , Nicole C. Roesner , Patricia Quintana-Owen , Ulrich S. Schubert , Guadalupe Ayora-Talavera , Enrique Saldívar-Guerra , Stefano Fedeli , Carlos Guerrero-Sanchez

Amphiphilic copolymers prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization are versatile and biocompatible scaffolds for multiple drug delivery applications. Decorating these structures with biomolecules and targeting moieties is a proven approach to enhance the cell uptake of polymers. In particular, spike proteins on the surface of the influenza A H1N1 virus are biomacromolecules highly evolved to promote cell adhesion and uptake, leading to effective cell-penetrating processes. We harnessed this uptake ability by selecting the peptide sequences responsible for the cell uptake and grafting them on a methacrylate copolymer. The adopted polymeric scaffold included glycerol, butyl, and N-hydroxy succinimide ester (NHS-ester) groups. This polymer resulted in a water-dispersible and biocompatible structure. Moreover, the reactivity of NHS-ester units enabled the modular insertion of the peptide in post-polymerization reactions. Through this approach, we combined the cell penetration efficiency of influenza A H1N1 virus with the easy manipulation of polymers and small biomolecules. The resulting bioconjugate was demonstrated to be a modular, safe, and effective platform for potential intracellular delivery applications.

{"title":"Amphiphilic block copolymer conjugated with cell-penetrating-peptides derived from Influenza A H1N1 virus as a biocompatible scaffold for enhanced cell-uptake","authors":"Carolina Ventura-Hunter , David Pretzel , Carolin Kellner , Stephanie Hoeppener , Nicole C. Roesner , Patricia Quintana-Owen , Ulrich S. Schubert , Guadalupe Ayora-Talavera , Enrique Saldívar-Guerra , Stefano Fedeli , Carlos Guerrero-Sanchez","doi":"10.1016/j.eurpolymj.2025.113876","DOIUrl":"10.1016/j.eurpolymj.2025.113876","url":null,"abstract":"<div><div>Amphiphilic copolymers prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization are versatile and biocompatible scaffolds for multiple drug delivery applications. Decorating these structures with biomolecules and targeting moieties is a proven approach to enhance the cell uptake of polymers. In particular, spike proteins on the surface of the influenza A H1N1 virus are biomacromolecules highly evolved to promote cell adhesion and uptake, leading to effective cell-penetrating processes. We harnessed this uptake ability by selecting the peptide sequences responsible for the cell uptake and grafting them on a methacrylate copolymer. The adopted polymeric scaffold included glycerol, butyl, and N-hydroxy succinimide ester (NHS-ester) groups. This polymer resulted in a water-dispersible and biocompatible structure. Moreover, the reactivity of NHS-ester units enabled the modular insertion of the peptide in post-polymerization reactions. Through this approach, we combined the cell penetration efficiency of influenza A H1N1 virus with the easy manipulation of polymers and small biomolecules. The resulting bioconjugate was demonstrated to be a modular, safe, and effective platform for potential intracellular delivery applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113876"},"PeriodicalIF":5.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578293","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

Microsphere-integrated hydrogel microneedle patch for sustained methotrexate delivery in the long-term management of atopic dermatitis 用于长期治疗特应性皮炎的甲氨蝶呤持续给药的微球集成水凝胶微针贴片

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-28 DOI: 10.1016/j.eurpolymj.2025.113877

Yanan Shi , Zhiming Li , Shaojie Lu , Puxuan Zhao , Xin Wang , Fei Jia , Hao Chang

Atopic dermatitis (AD) is a chronic inflammatory skin condition requiring long-term management. Methotrexate (MTX) is an effective treatment for moderate-to-severe AD, but traditional administration methods suffer from low bioavailability, frequent dosing, and side effects. This study presents a microsphere-integrated hydrogel microneedle (MP-HMN) patch for localized and sustained MTX delivery. Fabricated using a two-casting micromolding, this patch consisting of microneedle arrays made from MTX-loaded poly (lactic-co-glycolic acid) microspheres and photo-crosslinked gelatin methacryloyl (GelMA), supported by a hyaluronic acid (HA) backing. The integration of microspheres enhances mechanical strength of microneedles, while crosslinked GelMA minimizes the burst release of MTX. The MP-HMNs penetrates the skin easily and separates from the HA backing as the HA rapidly dissolves on contact with skin interstitial fluid. The implanted MP-HMNs degrades gradually within the skin, allowing for a 12-day release of MTX. In an AD mouse model, this patch demonstrated superior therapeutic efficacy and reduced dosing frequency, compared to oral and subcutaneous MTX administration, offering a promising strategy for long-term management of AD and other chronic skin diseases.

{"title":"Microsphere-integrated hydrogel microneedle patch for sustained methotrexate delivery in the long-term management of atopic dermatitis","authors":"Yanan Shi , Zhiming Li , Shaojie Lu , Puxuan Zhao , Xin Wang , Fei Jia , Hao Chang","doi":"10.1016/j.eurpolymj.2025.113877","DOIUrl":"10.1016/j.eurpolymj.2025.113877","url":null,"abstract":"<div><div>Atopic dermatitis (AD) is a chronic inflammatory skin condition requiring long-term management. Methotrexate (MTX) is an effective treatment for moderate-to-severe AD, but traditional administration methods suffer from low bioavailability, frequent dosing, and side effects. This study presents a microsphere-integrated hydrogel microneedle (MP-HMN) patch for localized and sustained MTX delivery. Fabricated using a two-casting micromolding, this patch consisting of microneedle arrays made from MTX-loaded poly (lactic-co-glycolic acid) microspheres and photo-crosslinked gelatin methacryloyl (GelMA), supported by a hyaluronic acid (HA) backing. The integration of microspheres enhances mechanical strength of microneedles, while crosslinked GelMA minimizes the burst release of MTX. The MP-HMNs penetrates the skin easily and separates from the HA backing as the HA rapidly dissolves on contact with skin interstitial fluid. The implanted MP-HMNs degrades gradually within the skin, allowing for a 12-day release of MTX. In an AD mouse model, this patch demonstrated superior therapeutic efficacy and reduced dosing frequency, compared to oral and subcutaneous MTX administration, offering a promising strategy for long-term management of AD and other chronic skin diseases.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113877"},"PeriodicalIF":5.8,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143529828","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

Fluorescent gels: Immobilization of non-fluorescence molecules beyond the aggregation induced emission

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-28 DOI: 10.1016/j.eurpolymj.2025.113865

Victor Vazquez-Villar , Ana Sousa-Herves , Antonio Cuesta-Casas , M. Paz Fernández-Liencres , Philippe J. Mésini , Amparo Ruiz-Carretero , Amparo Navarro , Juan Tolosa , Joaquín C. García-Martínez

Aggregation Induced Emission (AIE) has aroused the interest of the scientific community, revealing the mechanisms behind this phenomenon. The most common ones are the avoidance of electronic couplings which could quench the emission or non-radiative deactivation through vibrational modes, intramolecular rotations, photoisomerization, etc. This type of knowledge can be applied to the rational design of molecules that are trapped in an environment that prevents those non-radiative processes. Here we present oligo(styryl)benzene and bis(styryl)-4-(dicyanomethylene)-4H-pyran molecules designed to be non-fluorescence either in solution or in the solid/aggregate state, but they reach in some cases quantum yields of 50 % and 60 % when trapped in a gel matrix. These compounds deactivate in solution by vibrational relaxation and photoisomerization, the latter favored by the incorporation of cyano groups. The complete spectroscopic characterization of the gels together with quantum chemical calculations have allowed us to explain their photophysical behavior. In addition, compounds 1 and 4 were interacted with β-cyclodextrin and bacterial DNA (plasmid pUC19). An increase in fluorescence was observed which suggests an interaction between the dye and the supramolecular structure that blocks intramolecular motions and prevents aggregation. A more selective functionalization would allow the design of more fluorescent, higher contrast and more specific sensors.

{"title":"Fluorescent gels: Immobilization of non-fluorescence molecules beyond the aggregation induced emission","authors":"Victor Vazquez-Villar , Ana Sousa-Herves , Antonio Cuesta-Casas , M. Paz Fernández-Liencres , Philippe J. Mésini , Amparo Ruiz-Carretero , Amparo Navarro , Juan Tolosa , Joaquín C. García-Martínez","doi":"10.1016/j.eurpolymj.2025.113865","DOIUrl":"10.1016/j.eurpolymj.2025.113865","url":null,"abstract":"<div><div>Aggregation Induced Emission (AIE) has aroused the interest of the scientific community, revealing the mechanisms behind this phenomenon. The most common ones are the avoidance of electronic couplings which could quench the emission or non-radiative deactivation through vibrational modes, intramolecular rotations, photoisomerization, etc. This type of knowledge can be applied to the rational design of molecules that are trapped in an environment that prevents those non-radiative processes. Here we present oligo(styryl)benzene and bis(styryl)-4-(dicyanomethylene)-4H-pyran molecules designed to be non-fluorescence either in solution or in the solid/aggregate state, but they reach in some cases quantum yields of 50 % and 60 % when trapped in a gel matrix. These compounds deactivate in solution by vibrational relaxation and photoisomerization, the latter favored by the incorporation of cyano groups. The complete spectroscopic characterization of the gels together with quantum chemical calculations have allowed us to explain their photophysical behavior. In addition, compounds 1 and 4 were interacted with β-cyclodextrin and bacterial DNA (plasmid pUC19). An increase in fluorescence was observed which suggests an interaction between the dye and the supramolecular structure that blocks intramolecular motions and prevents aggregation. A more selective functionalization would allow the design of more fluorescent, higher contrast and more specific sensors.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113865"},"PeriodicalIF":5.8,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551747","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

Cyclic and linear cationic polymers based on metathesis polymerization for antibacterial and antifungal Applications

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-28 DOI: 10.1016/j.eurpolymj.2025.113875

Clément Gonnot , Muhammad Bilal Hassan Mahboob , Melvin Aumond , Jessica R. Tait , Kevin Nay , Katayoun Nazemi , Holly Floyd , Johannes Zuegg , Fabien Boeda , Cornelia B Landersdorfer , John F. Quinn , Laurent Fontaine , Michael R. Whittaker , Véronique Montembault

Cationic polymers have emerged as a significant class of materials in the fight against antimicrobial resistance. The macromolecular topology, polymer size, cationic and hydrophobic moieties and their distribution within these polymers, play crucial roles in determining their antimicrobial properties and selectivity. In this study, we report the synthesis of cyclic cationic polymers via the combination of ring-expansion metathesis polymerization (REMP) and click chemistry, using a single cyclic poly(norbornenyl azlactone) platform. Notably, this methodology, recently reported by our group, has also been successfully applied to producing glycopolymers with lectin-binding ability. Herein, we employ a double post-polymerization modification (PPM) of these scaffolds, with number-average degrees of polymerization (DP_n) of 25 and 100. The azlactone moiety undergoes click aminolysis using N-Boc-ethylenediamine (BEDA) as a cationic precursor and 10 % n-hexylamine or n-dodecylamine as lipophilic side chains, in a one-pot process followed by Boc deprotection. This approach enabled the synthesis of a library of six cyclic and six linear cationic polymer analogues, which were characterized in detail using size-exclusion chromatography (SEC), FT-IR, and ¹H NMR spectroscopy. The antibacterial and antifungal properties of these polymers were assessed against a panel of microbial pathogens, including Gram-positive bacteria (methicillin resistant S. aureus), Gram-negative bacteria (E. coli, K. pneumoniae, P. aeruginosa, A. baumannii), and fungi (C. albicans, C. auris, C. krusei, C. tropicalis, C. neoformans, C. deuterogattii, C. gattii). Their cell cytotoxicity against human red blood cells and mammalian HEK293 cells was also investigated.

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引用次数: 0

Amorphous sulfur containing biobased polyamides through a solvent- free protocol: Synthesis and scope

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-26 DOI: 10.1016/j.eurpolymj.2025.113864

Maria Diaz-Galbarriatu , Julia Sánchez-Bodón , José Manuel Laza , Isabel Moreno-Benítez , José Luis Vilas-Vilela

In this study a series of sulfur containing semi-aromatic polyamides has been successfully synthetized employing the biobased compound eugenol as starting material. The so-obtained polymers have been characterized through various techniques, including Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FT-IR) and Gel Permeation Chromatography (GPC). Furthermore, the thermal properties of the synthesized polyamides have been studied by means of Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA) providing valuable insights into their potential applications and performance under varying conditions. Moreover, it has been demonstrated the great influence of the diamine counterpart not only in the success of the polymerization reaction but also in the properties of the synthetized polymers. The obtained materials have demonstrated excellent thermal stability, dimensional integrity and favorable processing properties.

引用次数: 0

Application of a novel anthracene derivative polymer for sensitive voltammetric determination of chloramphenicol in pharmaceutical and food samples

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-25 DOI: 10.1016/j.eurpolymj.2025.113863

Serkan Karakaya , İsmet Kaya , Feyza Kolcu , Yusuf Dilgin

The application of new polymers for the preparation of modified electrodes is an interesting research area, which is highly significant in the electrochemical antibiotic drug sensors for food safety and environmental sides. Herein, we successfully report the synthesis of a new anthracene-based monomer (N1, N4-bis(anthracene-9-yl-methylene)-2,5-dichlorobenzene-1,4-diamine (ADCA) and Poly(ADCA) modified carbon-based electrode has been used in sensitive and selective differential pulse voltammetric determination of chloramphenicol (CPNL) for the first time. In this platform, the proposed monomer was successfully electro-polymerized onto a cheap, low-cost, and disposable pencil graphite electrode (PGE). The cyclic and differential pulse voltammetric experiments proved that the polymer-modified electrode Poly(ADCA)/PGE) has great electrocatalytic efficiency on the reduction of CPNL. The proposed platform shows a comparable performance in terms of wide linear ranges (2.0–100 and 100–1000 µM), a low detection limit (0.55 µM) and high sensitivity (11405 µA mM⁻¹ cm⁻²) by differential pulse voltammetry (DPV). Additionally, the Poly(ADCA)/PGE exhibited high selectivity and anti-interference facilities for the CPNL. The fabricated sensor showed a promising potential for the determination of CPNL in food (honey, and milk), bottled water, and pharmaceutical (eye ointment) samples with acceptable accuracies and precisions.

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引用次数: 0