Pub Date : 2025-02-28DOI: 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}
Pub Date : 2025-02-28DOI: 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 (DPn) 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.
{"title":"Cyclic and linear cationic polymers based on metathesis polymerization for antibacterial and antifungal Applications","authors":"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","doi":"10.1016/j.eurpolymj.2025.113875","DOIUrl":"10.1016/j.eurpolymj.2025.113875","url":null,"abstract":"<div><div>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 (<em>DP<sub>n</sub></em>) of 25 and 100. The azlactone moiety undergoes click aminolysis using <em>N</em>-Boc-ethylenediamine (BEDA) as a cationic precursor and 10 % <em>n</em>-hexylamine or <em>n</em>-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 <sup>1</sup>H NMR spectroscopy. The antibacterial and antifungal properties of these polymers were assessed against a panel of microbial pathogens, including Gram-positive bacteria (methicillin resistant <em>S. aureus</em>), Gram-negative bacteria (<em>E. coli</em>, <em>K. pneumoniae</em>, <em>P. aeruginosa</em>, <em>A. baumannii</em>), and fungi (<em>C. albicans</em>, <em>C. auris</em>, <em>C. krusei</em>, <em>C. tropicalis</em>, <em>C. neoformans</em>, <em>C. deuterogattii</em>, <em>C. gattii</em>). Their cell cytotoxicity against human red blood cells and mammalian HEK293 cells was also investigated.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"230 ","pages":"Article 113875"},"PeriodicalIF":5.8,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600753","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 : 2025-02-26DOI: 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.
{"title":"Amorphous sulfur containing biobased polyamides through a solvent- free protocol: Synthesis and scope","authors":"Maria Diaz-Galbarriatu , Julia Sánchez-Bodón , José Manuel Laza , Isabel Moreno-Benítez , José Luis Vilas-Vilela","doi":"10.1016/j.eurpolymj.2025.113864","DOIUrl":"10.1016/j.eurpolymj.2025.113864","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113864"},"PeriodicalIF":5.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527070","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 : 2025-02-25DOI: 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.
{"title":"Application of a novel anthracene derivative polymer for sensitive voltammetric determination of chloramphenicol in pharmaceutical and food samples","authors":"Serkan Karakaya , İsmet Kaya , Feyza Kolcu , Yusuf Dilgin","doi":"10.1016/j.eurpolymj.2025.113863","DOIUrl":"10.1016/j.eurpolymj.2025.113863","url":null,"abstract":"<div><div>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<sup>−1</sup> cm<sup>−2</sup>) 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.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113863"},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511165","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 : 2025-02-25DOI: 10.1016/j.eurpolymj.2025.113843
Manal Chaib , Suman Thakur , Hicham Ben Youcef , Mohammed Lahcini , Raquel Verdejo
Non-isocyanate polyurethane (NIPU) foams present a safer and more environmentally friendly alternative to conventional polyurethane (PU) foams, which rely on toxic, petrochemical-based isocyanates. Efficient in-situ CO2 generation, achieved through the simultaneous aminolysis and hydrolysis of cyclic carbonates, enables replication of traditional PU foaming processes. This study provides the first systematic investigation of the effect of aromatic and aliphatic epoxy functionalities on these reactions and their quantitative correlation with the self-blowing behavior of NIPU foams. Detailed kinetic analysis of model monomers showed significant differences in activation energy, with aromatic systems exhibiting lower activation energy, leading to faster reaction rates, while aliphatic systems had higher activation energy, indicating slower curing. These differences in reactivity were later revealed in the foaming process, where the aromatic groups contributed to rapid foam formation and improved thermal stability, with a glass transition temperature (Tg) of 60 °C. Conversely, aliphatic substituents provided greater material flexibility but revealed a critical threshold, leading to unsuccessful foaming when their content exceeded 30 %, due to slower reaction kinetics. By integrating kinetic data with foaming behavior, we demonstrate that balancing aromatic and aliphatic functionalities enables precise control over foam properties, including Tg, density, and mechanical performance. This work provides new insights into tailoring NIPU foams through epoxy functionality, advancing their potential for sustainable industrial applications.
{"title":"Achieving rapid foaming in self-blown non-isocyanate polyurethane foams via controlled epoxy functionality in cyclic carbonates","authors":"Manal Chaib , Suman Thakur , Hicham Ben Youcef , Mohammed Lahcini , Raquel Verdejo","doi":"10.1016/j.eurpolymj.2025.113843","DOIUrl":"10.1016/j.eurpolymj.2025.113843","url":null,"abstract":"<div><div>Non-isocyanate polyurethane (NIPU) foams present a safer and more environmentally friendly alternative to conventional polyurethane (PU) foams, which rely on toxic, petrochemical-based isocyanates. Efficient in-situ CO<sub>2</sub> generation, achieved through the simultaneous aminolysis and hydrolysis of cyclic carbonates, enables replication of traditional PU foaming processes. This study provides the first systematic investigation of the effect of aromatic and aliphatic epoxy functionalities on these reactions and their quantitative correlation with the self-blowing behavior of NIPU foams. Detailed kinetic analysis of model monomers showed significant differences in activation energy, with aromatic systems exhibiting lower activation energy, leading to faster reaction rates, while aliphatic systems had higher activation energy, indicating slower curing. These differences in reactivity were later revealed in the foaming process, where the aromatic groups contributed to rapid foam formation and improved thermal stability, with a glass transition temperature (T<sub>g</sub>) of 60 °C. Conversely, aliphatic substituents provided greater material flexibility but revealed a critical threshold, leading to unsuccessful foaming when their content exceeded 30 %, due to slower reaction kinetics. By integrating kinetic data with foaming behavior, we demonstrate that balancing aromatic and aliphatic functionalities enables precise control over foam properties, including T<sub>g</sub>, density, and mechanical performance. This work provides new insights into tailoring NIPU foams through epoxy functionality, advancing their potential for sustainable industrial applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113843"},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527068","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 : 2025-02-25DOI: 10.1016/j.eurpolymj.2025.113849
Carlos Fernández-Clavero , Gonzalo Rivero-Barbarroja , Thais Carmona , Cristina García-Iriepa , Gema Marcelo , Conchita Tros de Ilarduya , Carmen Ortiz Mellet , José M. García Fernández , Juan M. Benito , Francisco Mendicuti
The inclusion complexation of a water soluble bis-azobenzene derivative (bis-Azo) and its monotopic analog (mono-Azo) with α-, β-, and γ-cyclodextrins (CyDs) was investigated as a prototype for light-responsive self-assembling systems. Using spectroscopic techniques (UV–vis, induced circular dichroism, 1H NMR), computational methods (molecular mechanics and dynamics), and thermodynamic analyses, we examined the photoswitching properties, stability, and structural dynamics of these systems. The azobenzene moieties in the E-isomer of mono-Azo and bis-Azo consistently showed strong affinity for the αCyD cavity, characterized by high association constants. In contrast, no complex formation was observed upon photoinduced E-to-Z isomerization. For bis-Azo, this implies the formation of supramolecular αCyD dimers, with the spatial separation between the oppositely oriented host components determined by the connector linking the two azobenzene moieties in the E-configured ditopic guest. This complex disassembles upon photoswitching, driven by the structural disruption associated with the Z-form. Both the E-and Z-isomers fitted in the cavity of βCyD, with moderate selectivity towards the E-form. A similar scenario was found for complexes with γCyD when using low concentrations of the host. Interestingly, at high concentrations γCyD formed low-solubility pseudopolyrotaxane-type supramolecular architectures with bis-Azo, which were disrupted upon Z-isomer photoisomerization. All the complexes demonstrated high fatigue resistance, maintaining structural integrity after multiple isomerization cycles. This work advances the design of stimuli-responsive preorganized supramolecular systems, with potential applications in nucleic acid delivery through dual pH/light-sensitive mechanisms.
{"title":"Light-controlled assembly and disassembly of cyclodextrin-bisazobenzene supramolecular complexes","authors":"Carlos Fernández-Clavero , Gonzalo Rivero-Barbarroja , Thais Carmona , Cristina García-Iriepa , Gema Marcelo , Conchita Tros de Ilarduya , Carmen Ortiz Mellet , José M. García Fernández , Juan M. Benito , Francisco Mendicuti","doi":"10.1016/j.eurpolymj.2025.113849","DOIUrl":"10.1016/j.eurpolymj.2025.113849","url":null,"abstract":"<div><div>The inclusion complexation of a water soluble bis-azobenzene derivative (bis-Azo) and its monotopic analog (mono-Azo) with α-, β-, and γ-cyclodextrins (CyDs) was investigated as a prototype for light-responsive self-assembling systems. Using spectroscopic techniques (UV–vis, induced circular dichroism, <sup>1</sup>H NMR), computational methods (molecular mechanics and dynamics), and thermodynamic analyses, we examined the photoswitching properties, stability, and structural dynamics of these systems. The azobenzene moieties in the <em>E</em>-isomer of mono-Azo and bis-Azo consistently showed strong affinity for the αCyD cavity, characterized by high association constants. In contrast, no complex formation was observed upon photoinduced <em>E</em>-to-<em>Z</em> isomerization. For bis-Azo, this implies the formation of supramolecular αCyD dimers, with the spatial separation between the oppositely oriented host components determined by the connector linking the two azobenzene moieties in the <em>E</em>-configured ditopic guest. This complex disassembles upon photoswitching, driven by the structural disruption associated with the <em>Z</em>-form. Both the <em>E</em>-and <em>Z</em>-isomers fitted in the cavity of βCyD, with moderate selectivity towards the <em>E</em>-form. A similar scenario was found for complexes with γCyD when using low concentrations of the host. Interestingly, at high concentrations γCyD formed low-solubility pseudopolyrotaxane-type supramolecular architectures with bis-Azo, which were disrupted upon <em>Z</em>-isomer photoisomerization. All the complexes demonstrated high fatigue resistance, maintaining structural integrity after multiple isomerization cycles. This work advances the design of stimuli-responsive preorganized supramolecular systems, with potential applications in nucleic acid delivery through dual pH/light-sensitive mechanisms.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113849"},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521305","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 : 2025-02-23DOI: 10.1016/j.eurpolymj.2025.113859
Xiaofei Shen , Wei Fang , Tianci Sun , Yunfeng Yao , Xiangshun Chen , Lei Xia , Longxiang Tang , Bin Xia , Chang-Tong Yang , Tao He , Rupei Tang
Various functional nanoparticle platforms have been used as alternative approaches for tumor treatment such as chemodynamic (CDT) and photothermal therapies (PTT). However, the tumor microenvironment with dense extracellular matrices and increased interstitial fluid pressure is adverse for enrichment and retention of nanoparticles. Herein, a pH-sensitive Cu2-xSe-POED nanoparticles (CS-POED NPs) platform is developed to promote the hydrophilic-hydrophobic transition, that contribute to the formation of CS aggregates with large size in tumor tissue. pH-sensitivity of CS-POED NPs results from modifying the surface with pH-sensitive poly(ethylene glycol)-ortho ester-dihydrolipoic acid (POED). The accumulation of CS-POED NPs led to a Fenton-like reaction, generating considerable amounts of ROS to boost the effectiveness of CDT. Meanwhile, the agglomeration CS-POED NPs prolongs their tumor retention resulting in enhanced PTT. According to in vitro and in vivo studies, CS-POED NPs substantially kills tumor cells with laser irradiation, leading to a significant regression of the tumors. In addition, CS-POED NPs have exhibited a favorable biosafety profile based on their in vitro and in vivo evaluations. The novel pH-sensitive CS-POED nanoparticles platform certainly offers a new strategy for enhanced chemodynamic/photothermal tumor therapy.
{"title":"pH-induced in suit aggregation of Cu2-xSe-POED with extended tumor retention for enhanced chemodynamic /photothermal therapy","authors":"Xiaofei Shen , Wei Fang , Tianci Sun , Yunfeng Yao , Xiangshun Chen , Lei Xia , Longxiang Tang , Bin Xia , Chang-Tong Yang , Tao He , Rupei Tang","doi":"10.1016/j.eurpolymj.2025.113859","DOIUrl":"10.1016/j.eurpolymj.2025.113859","url":null,"abstract":"<div><div>Various functional nanoparticle platforms have been used as alternative approaches for tumor treatment such as chemodynamic (CDT) and photothermal therapies (PTT). However, the tumor microenvironment with dense extracellular matrices and increased interstitial fluid pressure is adverse for enrichment and retention of nanoparticles. Herein, a pH-sensitive Cu<sub>2-x</sub>Se-POED nanoparticles (CS-POED NPs) platform is developed to promote the hydrophilic-hydrophobic transition, that contribute to the formation of CS aggregates with large size in tumor tissue. pH-sensitivity of CS-POED NPs results from modifying the surface with pH-sensitive poly(ethylene glycol)-ortho ester-dihydrolipoic acid (POED). The accumulation of CS-POED NPs led to a Fenton-like reaction, generating considerable amounts of ROS to boost the effectiveness of CDT. Meanwhile, the agglomeration CS-POED NPs prolongs their tumor retention resulting in enhanced PTT. According to <em>in vitro</em> and <em>in vivo</em> studies, CS-POED NPs substantially kills tumor cells with laser irradiation, leading to a significant regression of the tumors. In addition, CS-POED NPs have exhibited a favorable biosafety profile based on their <em>in vitro</em> and <em>in vivo</em> evaluations. The novel pH-sensitive CS-POED nanoparticles platform certainly offers a new strategy for enhanced chemodynamic/photothermal tumor therapy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113859"},"PeriodicalIF":5.8,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487420","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}
Pub Date : 2025-02-23DOI: 10.1016/j.eurpolymj.2025.113860
Mianji Qiu , Zhi Geng , Wangjian Cheng , Chengyuan Hua , Xing Yan , Baoyun Ye , Chongwei An , Jingyu Wang
Solid propellants are essential for rocket engine efficiency and safety. The introduction of energetic self-healing adhesives can improve its energy density, mechanical properties, and safety, while extending its service life. Therefore, this paper proposes a novel energetic self-healing adhesive that utilizes asymmetric alicyclic isophorone diisocyanate (IPDI) and 2-(aminophenyl) disulfide (2-AFD), which has a bent biphenyl ring structure, as hard segments, combined with semicrystalline polymer polycaprolactone (PCL) and energetic adhesive glycidyl azide polymer (GAP) as soft segments to synthesize a series of self-healing adhesives. By adjusting the hard segment content, a balance between mechanical properties and self-healing performance is achieved. Results show that increasing the hard segment content enhances toughness (from 26.60 MJ·m−3 to 58.54 MJ·m−3), but decreases self-healing efficiency (from 90 % to 58 %). GPPU-2 exhibits 38.95 MJ·m−3 toughness and recovers 86 % of its toughness within 90 min at 80 °C via dynamic disulfide and hydrogen bond interactions. The GPPU-2-based propellant, GPPU80, recovers 88.22 % of tensile strength after 24 h at 80 °C, demonstrating effective crack propagation inhibition. Compared to inert adhesive-based propellants, GPPU80 shows superior combustion performance and energy release. This study offers insights for designing high-performance self-healing adhesives to enhance propellant safety and energy density.
{"title":"Construction of a novel GAP/PCL energetic self-healing blend adhesive system for propellants based on the synergistic effect of hydrogen bond reorganization and disulfide bond exchange reactions","authors":"Mianji Qiu , Zhi Geng , Wangjian Cheng , Chengyuan Hua , Xing Yan , Baoyun Ye , Chongwei An , Jingyu Wang","doi":"10.1016/j.eurpolymj.2025.113860","DOIUrl":"10.1016/j.eurpolymj.2025.113860","url":null,"abstract":"<div><div>Solid propellants are essential for rocket engine efficiency and safety. The introduction of energetic self-healing adhesives can improve its energy density, mechanical properties, and safety, while extending its service life. Therefore, this paper proposes a novel energetic self-healing adhesive that utilizes asymmetric alicyclic isophorone diisocyanate (IPDI) and 2-(aminophenyl) disulfide (2-AFD), which has a bent biphenyl ring structure, as hard segments, combined with semicrystalline polymer polycaprolactone (PCL) and energetic adhesive glycidyl azide polymer (GAP) as soft segments to synthesize a series of self-healing adhesives. By adjusting the hard segment content, a balance between mechanical properties and self-healing performance is achieved. Results show that increasing the hard segment content enhances toughness (from 26.60 MJ·m<sup>−3</sup> to 58.54 MJ·m<sup>−3</sup>), but decreases self-healing efficiency (from 90 % to 58 %). GPPU-2 exhibits 38.95 MJ·m<sup>−3</sup> toughness and recovers 86 % of its toughness within 90 min at 80 °C via dynamic disulfide and hydrogen bond interactions. The GPPU-2-based propellant, GPPU80, recovers 88.22 % of tensile strength after 24 h at 80 °C, demonstrating effective crack propagation inhibition. Compared to inert adhesive-based propellants, GPPU80 shows superior combustion performance and energy release. This study offers insights for designing high-performance self-healing adhesives to enhance propellant safety and energy density.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113860"},"PeriodicalIF":5.8,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511166","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 : 2025-02-21DOI: 10.1016/j.eurpolymj.2025.113845
Tim Hoffmann , Florian Behrendt , Lukas Dietz , Caroline T. Holick , Pascal Scharfenberg , Michael Gottschaldt , Bernd W. Sigusch , Ulrich S. Schubert
Herein, we present the synthesis of two poly(2-oxazoline)-based photodegradable cross-linkers. For that 1-(piperazin-1-yl)ethan-1-one-O-methacryloyl oxime (PipOxim) was synthesized as new photocleavable, polymerizable endcapping agent for the termination of the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx), to yield in the bifunctional cross-linker B-Et(10)PipOxim. Secondly, bifunctional poly(2-ethyl-2-oxazoline)s (PEtOx) carrying photocleavable, polymerizable triazene phenyl methacrylate (TAz) ω-end groups were prepared by post-polymerization functionalization (B-Et(10,20,40)TAz). The process of decomposition under UV–Vis irradiation was successfully demonstrated for all cross-linkers that had been produced using UV–Vis spectroscopy. From the photodegradable POx-based cross-linkers, cryogels were prepared with 100% of the two different cross-linkers. Additionally, mixed cryogels made of B-Et(40)TAz and acrylic acid were produced. All cryogels were characterized by thermogravimetric analysis (TGA), solid-state NMR (ssNMR), scanning electron microscopy (SEM) and swelling investigations. Notably, the use of 92 mol% acrylic acid led to the formation of cryogels susceptible to a complete dissolution in water after exposure to UV–Vis light.
{"title":"Photoresponsive cryogels based on poly(2-oxazoline)s","authors":"Tim Hoffmann , Florian Behrendt , Lukas Dietz , Caroline T. Holick , Pascal Scharfenberg , Michael Gottschaldt , Bernd W. Sigusch , Ulrich S. Schubert","doi":"10.1016/j.eurpolymj.2025.113845","DOIUrl":"10.1016/j.eurpolymj.2025.113845","url":null,"abstract":"<div><div>Herein, we present the synthesis of two poly(2-oxazoline)-based photodegradable cross-linkers. For that 1-(piperazin-1-yl)ethan-1-one-<em>O</em>-methacryloyl oxime (<strong>PipOxim</strong>) was synthesized as new photocleavable, polymerizable endcapping agent for the termination of the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx), to yield in the bifunctional cross-linker <strong>B-Et(10)PipOxim</strong>. Secondly, bifunctional poly(2-ethyl-2-oxazoline)s (PEtOx) carrying photocleavable, polymerizable triazene phenyl methacrylate (TAz) ω-end groups were prepared by post-polymerization functionalization (<strong>B-Et(10,20,40)TAz</strong>). The process of decomposition under UV–Vis irradiation was successfully demonstrated for all cross-linkers that had been produced using UV–Vis spectroscopy. From the photodegradable POx-based cross-linkers, cryogels were prepared with 100% of the two different cross-linkers. Additionally, mixed cryogels made of <strong>B-Et(40)TAz</strong> and acrylic acid were produced. All cryogels were characterized by thermogravimetric analysis (TGA), solid-state NMR (ssNMR), scanning electron microscopy (SEM) and swelling investigations. Notably, the use of 92 mol% acrylic acid led to the formation of cryogels susceptible to a complete dissolution in water after exposure to UV–Vis light.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113845"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551746","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}
Pub Date : 2025-02-21DOI: 10.1016/j.eurpolymj.2025.113847
Minghao Sun , Yangke Xiao , Kan Liu , Haitao Wang , Bangban Zhu , Yinlong Chang , Jieyuan Zheng , Xingfen Huang , Shengbin Shi , Pingwei Liu , Wen-Jun Wang
Polyolefins with desired properties can be achieved through precise control of chain structure. This study emphasizes the critical role of monomer feeding strategies in determining chain sequence distribution and topology to enhance the performance of ethylene/propylene rubbers (EPMs). Linear EPMs were synthesized via continuously feeding a fixed composition ethylene/ propylene mixture or through sequential monomer feeding. In contract, long-chain branched (LCB) EPMs (B-EPs) were produced via a tandem catalytic polymerization process, in which macromonomers were first synthesized and subsequently copolymerized with a continuous feed of ethylene/ propylene mixture with fixed composition. The impact of these feeding strategies on the resulting polymer chain structures, as well as their mechanical, thermal, and rheological properties, were systematically investigated. Incorporating 0.7 isotactic polypropylene (iPP) LCBs into the EPM backbone significantly improved the B-EP properties, yielding a high melting point of 141 °C and a low-temperature tensile strength of 52.1 MPa, while having a tensile strength of 8.0 MPa and an elastic recovery of 71.5 %. Furthermore, the B-EP with iPP LCBs demonstrated excellent compatibility with isotactic polypropylene, enhancing the impact resistance of a 30 wt% B-EP/ commercial isotactic polypropylene blend by 23.5 % compared to a similar compound with commercial EPDM. The study provides valuable insights into optimizing EPM performance by tailoring chain structures through controlled monomer feeding strategies.
{"title":"Tailoring chain structures in Ethylene/Propylene copolymers through controlled monomer feeding strategies","authors":"Minghao Sun , Yangke Xiao , Kan Liu , Haitao Wang , Bangban Zhu , Yinlong Chang , Jieyuan Zheng , Xingfen Huang , Shengbin Shi , Pingwei Liu , Wen-Jun Wang","doi":"10.1016/j.eurpolymj.2025.113847","DOIUrl":"10.1016/j.eurpolymj.2025.113847","url":null,"abstract":"<div><div>Polyolefins with desired properties can be achieved through precise control of chain structure. This study emphasizes the critical role of monomer feeding strategies in determining chain sequence distribution and topology to enhance the performance of ethylene/propylene rubbers (EPMs). Linear EPMs were synthesized via continuously feeding a fixed composition ethylene/ propylene mixture or through sequential monomer feeding. In contract, long-chain branched (LCB) EPMs (B-EPs) were produced via a tandem catalytic polymerization process, in which macromonomers were first synthesized and subsequently copolymerized with a continuous feed of ethylene/ propylene mixture with fixed composition. The impact of these feeding strategies on the resulting polymer chain structures, as well as their mechanical, thermal, and rheological properties, were systematically investigated. Incorporating 0.7 isotactic polypropylene (iPP) LCBs into the EPM backbone significantly improved the B-EP properties, yielding a high melting point of 141 °C and a low-temperature tensile strength of 52.1 MPa, while having a tensile strength of 8.0 MPa and an elastic recovery of 71.5 %. Furthermore, the B-EP with iPP LCBs demonstrated excellent compatibility with isotactic polypropylene, enhancing the impact resistance of a 30 wt% B-EP/ commercial isotactic polypropylene blend by 23.5 % compared to a similar compound with commercial EPDM. The study provides valuable insights into optimizing EPM performance by tailoring chain structures through controlled monomer feeding strategies.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113847"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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