European Polymer Journal最新文献_第7页

Highly conductive, low detection limit and durable hydrogel sensors based on PSBMA-IA-PPy/Fe3+ composite materials for mechanosensing

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-07 DOI: 10.1016/j.eurpolymj.2025.113813

Shaoju Fu , Tiantian Li , Linghui Zhou , Zhining Huang , Mengfan Hu , Yuen Hu , Peixin Tang , Yang Si

Hydrogels are hydrophilic polymeric materials that are typically distinguished by their excellent biocompatibility, flexibility, and environmental friendliness. However, most hydrogels exhibit high swelling rates, poor mechanical stability, and low durability, which restrict their utilization in sensor applications. Herein, conductive hydrogels with a low swelling rate were fabricated by incorporating polypyrrole (PPy)/ ferric ion (Fe³⁺) into poly(sulfobetaine methacrylate)/itaconic acid (PSBMA-IA) based hydrogels. The abundance of unsaturated bonds on SBMA and IA macromolecules enables them to undergo addition polymerization and form their respective long chains. The carbon–carbon double bonds at both ends of Methylenebisacrylamide (MBA) can also undergo addition reactions with the double bonds of SBMA and IA, resulting in the formation of a three-dimensional interconnective network. This ultimately improves the mechanical properties of the composite hydrogel (maximum compressive stress of 66.7 kPa). Furthermore, Fe³⁺ ions and pyrrole monomers facilitate the formation of an additional conductive macromolecular network on the hydrogel skeleton through in situ polymerization. This dual network structure confers enhanced anti-swelling properties (minimum swelling rate of 33 %), and excellent electrical conductivity (>0.2 S/m). As a result, the PSBMA-IA-PPy/Fe³⁺ based hydrogel sensors exhibit low detection (0.543 ∼ 2.717 kPa), high sensitivity (1.4853 ∼ 1.8316), and excellent response and recovery times (<106 ms).

{"title":"Highly conductive, low detection limit and durable hydrogel sensors based on PSBMA-IA-PPy/Fe3+ composite materials for mechanosensing","authors":"Shaoju Fu , Tiantian Li , Linghui Zhou , Zhining Huang , Mengfan Hu , Yuen Hu , Peixin Tang , Yang Si","doi":"10.1016/j.eurpolymj.2025.113813","DOIUrl":"10.1016/j.eurpolymj.2025.113813","url":null,"abstract":"<div><div>Hydrogels are hydrophilic polymeric materials that are typically distinguished by their excellent biocompatibility, flexibility, and environmental friendliness. However, most hydrogels exhibit high swelling rates, poor mechanical stability, and low durability, which restrict their utilization in sensor applications. Herein, conductive hydrogels with a low swelling rate were fabricated by incorporating polypyrrole (PPy)/ ferric ion (Fe<sup>3+</sup>) into poly(sulfobetaine methacrylate)/itaconic acid (PSBMA-IA) based hydrogels. The abundance of unsaturated bonds on SBMA and IA macromolecules enables them to undergo addition polymerization and form their respective long chains. The carbon–carbon double bonds at both ends of Methylenebisacrylamide (MBA) can also undergo addition reactions with the double bonds of SBMA and IA, resulting in the formation of a three-dimensional interconnective network. This ultimately improves the mechanical properties of the composite hydrogel (maximum compressive stress of 66.7 kPa). Furthermore, Fe<sup>3+</sup> ions and pyrrole monomers facilitate the formation of an additional conductive macromolecular network on the hydrogel skeleton through in situ polymerization. This dual network structure confers enhanced anti-swelling properties (minimum swelling rate of 33 %), and excellent electrical conductivity (>0.2 S/m). As a result, the PSBMA-IA-PPy/Fe<sup>3+</sup> based hydrogel sensors exhibit low detection (0.543 ∼ 2.717 kPa), high sensitivity (1.4853 ∼ 1.8316), and excellent response and recovery times (<106 ms).</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113813"},"PeriodicalIF":5.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372924","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

pH triggered polycarvacrol-based antibacterial microspheres: Integrated offensive and defensive platform

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-07 DOI: 10.1016/j.eurpolymj.2025.113811

Xiangbin Sun, Xiaobing Ma, Yufeng He, Pengfei Song, Rongmin Wang

The natural plant essential oil carvacrol exhibits substantial antimicrobial properties. However, its efficacy is significantly compromised following functionalization, thereby limiting its optimal application in polymer science. In this study, a quaternary ammonium carvacrol ester ionic liquid monomer was synthesized utilizing the ionic liquid technique. Subsequently, a series of cyclodextrin-grafted poly(quaternary ammonium carvacrol ester) polymer nanospheres were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The controllability offered by RAFT polymerization enables precise loading of carvacrol small molecules, representing a significant breakthrough for the incorporation of carvacrol into polymers. Particularly noteworthy is the CD-DM_x formulation, which demonstrates exceptional antibacterial efficacy against both E. coli and S. aureus. This is attributed to the synergistic interaction between carvacrol and cationic components, resulting in a 100% antibacterial ratio. Additionally, the labile nature of the betaine ester bonds with carvacrol and cations facilitates the controlled release of carvacrol from the CD-DM_x matrix while preventing its deactivation during functionalization. This property facilitates the transition of CD-DM_x from exhibiting antibacterial properties (offense mode) to demonstrating anti-protein adhesion properties (defense mode). Furthermore, cytotoxicity assessments and electrospinning studies have demonstrated the biocompatibility and potential applications of CD-DM_x in medical protective equipment. In summary, we have not only proposed a strategy for the efficient utilization of natural carvacrol essential oil but has also developed a green, environmentally friendly cationic essential oil-based antibacterial agent that is well-suited for medical applications.

{"title":"pH triggered polycarvacrol-based antibacterial microspheres: Integrated offensive and defensive platform","authors":"Xiangbin Sun, Xiaobing Ma, Yufeng He, Pengfei Song, Rongmin Wang","doi":"10.1016/j.eurpolymj.2025.113811","DOIUrl":"10.1016/j.eurpolymj.2025.113811","url":null,"abstract":"<div><div>The natural plant essential oil carvacrol exhibits substantial antimicrobial properties. However, its efficacy is significantly compromised following functionalization, thereby limiting its optimal application in polymer science. In this study, a quaternary ammonium carvacrol ester ionic liquid monomer was synthesized utilizing the ionic liquid technique. Subsequently, a series of cyclodextrin-grafted poly(quaternary ammonium carvacrol ester) polymer nanospheres were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The controllability offered by RAFT polymerization enables precise loading of carvacrol small molecules, representing a significant breakthrough for the incorporation of carvacrol into polymers. Particularly noteworthy is the CD-DM<sub>x</sub> formulation, which demonstrates exceptional antibacterial efficacy against both <em>E. coli</em> and <em>S. aureus</em>. This is attributed to the synergistic interaction between carvacrol and cationic components, resulting in a 100% antibacterial ratio. Additionally, the labile nature of the betaine ester bonds with carvacrol and cations facilitates the controlled release of carvacrol from the CD-DM<sub>x</sub> matrix while preventing its deactivation during functionalization. This property facilitates the transition of CD-DM<sub>x</sub> from exhibiting antibacterial properties (offense mode) to demonstrating anti-protein adhesion properties (defense mode). Furthermore, cytotoxicity assessments and electrospinning studies have demonstrated the biocompatibility and potential applications of CD-DM<sub>x</sub> in medical protective equipment. In summary, we have not only proposed a strategy for the efficient utilization of natural carvacrol essential oil but has also developed a green, environmentally friendly cationic essential oil-based antibacterial agent that is well-suited for medical applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113811"},"PeriodicalIF":5.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372926","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

Role of acid hydrocarbon chain length on the cure kinetics and thermal degradation of epoxy- dicarboxylic acid vitrimers

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-07 DOI: 10.1016/j.eurpolymj.2025.113812

Shouqi Shen, Alexandros A Skordos

This study investigates the cure kinetics and thermal degradation of epoxy-dicarboxylic acid vitrimers, focusing on the effect of methylene chain length. A diffusion-controlled, modified autocatalytic kinetics model was applied, based on Differential Scanning Calorimetry (DSC) data, whilst Thermogravimetric Analysis (TGA) was used to assess degradation. Increasing the methylene chain length enhanced thermal stability, with decomposition temperatures ranging from 430 °C for the hexanedioic acid formulation to 500 °C for the tetradecanedioic acid formulation. The curing process transitioned through three distinct kinetics regimes: an initial non-catalysed phase, followed by an autocatalytic stage, and finally, a diffusion-limited phase at high crosslink density. This shift leads to a 30 %-70 % reduction in apparent activation energy during the early stages. The activation energy displays a complex behaviour, initially decreasing with longer methylene sequences before rising due to competing effects of chain flexibility and reduced reactivity. Kissinger and isoconversional analyses confirmed reliable activation energy values. Despite some discrepancies in the dodecanedioic acid formulation due to secondary reactions, the model exhibits a good approximation, with an average goodness-of-fit of 84.4 %. This analysis improves understanding of vitrimer cure kinetics and thermal behaviour, providing insights for optimising industrial applications.

{"title":"Role of acid hydrocarbon chain length on the cure kinetics and thermal degradation of epoxy- dicarboxylic acid vitrimers","authors":"Shouqi Shen, Alexandros A Skordos","doi":"10.1016/j.eurpolymj.2025.113812","DOIUrl":"10.1016/j.eurpolymj.2025.113812","url":null,"abstract":"<div><div>This study investigates the cure kinetics and thermal degradation of epoxy-dicarboxylic acid vitrimers, focusing on the effect of methylene chain length. A diffusion-controlled, modified autocatalytic kinetics model was applied, based on Differential Scanning Calorimetry (DSC) data, whilst Thermogravimetric Analysis (TGA) was used to assess degradation. Increasing the methylene chain length enhanced thermal stability, with decomposition temperatures ranging from 430 °C for the hexanedioic acid formulation to 500 °C for the tetradecanedioic acid formulation. The curing process transitioned through three distinct kinetics regimes: an initial non-catalysed phase, followed by an autocatalytic stage, and finally, a diffusion-limited phase at high crosslink density. This shift leads to a 30 %-70 % reduction in apparent activation energy during the early stages. The activation energy displays a complex behaviour, initially decreasing with longer methylene sequences before rising due to competing effects of chain flexibility and reduced reactivity. Kissinger and isoconversional analyses confirmed reliable activation energy values. Despite some discrepancies in the dodecanedioic acid formulation due to secondary reactions, the model exhibits a good approximation, with an average goodness-of-fit of 84.4 %. This analysis improves understanding of vitrimer cure kinetics and thermal behaviour, providing insights for optimising industrial applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113812"},"PeriodicalIF":5.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143454778","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

Effects of side-chain flexibility on properties of azatriphenylene discotic liquid-crystalline ionomers

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113685

Qian Yang, Xiao-Ping Xiong, Chao-Min Yan, Long Li, Hong-Mei Chen, Hai-Liang Ni, Chun Feng, Ke-Qing Zhao, Ping Hu, Yu-Jie Ma, Wen-Hao Yu

To investigate the influence of side-chain flexibility on the properties of discotic liquid-crystalline ionomers (DLCIs), a series of side-chain azatriphenylene ionic copolymers, denoted as C-PTPN_m-X (where X = Br⁻ or TFSI⁻ and m = 3, 5, 7, 15), were synthesised via ring-opening metathesis polymerisation. These copolymers comprise a polycyclooctene backbone connected to discotic mesogenic units via flexible spacers of different lengths. Monomers and ionomers containing bis(trifluoromethanesulfonyl)imide ions (TFSI⁻) displayed columnar liquid-crystalline phases, whereas those with bromide anions exhibited non-mesogenic properties. Both the monomers and copolymers emitted yellow fluorescence with wavelengths ranging from 515 to 561 nm in both the solution and film states. Notably, replacing bromide anions with TFSI⁻ significantly enhanced the absolute quantum yield in both monomers and copolymers. Additionally, the mechanical properties of the ionomers were dependent on the spacer length, with the stress and Young’s modulus of C-PTPN_m-TFSI being approximately 30 times lower than those of H-PCOE, a cycloolefin homopolymer, thereby facilitating solution spinning. All the DLCIs demonstrated rapid thermal responsiveness and excellent shape memory characteristics. Flexible spacers in ionic monomers and copolymers enhance their thermal stability and mechanical properties while also influencing their clearing points and mesogenic temperature ranges. The type of anion significantly improved the thermal stability and affected the luminescence properties, whereas the spacer length had less impact on these attributes. The ionic conductivity of the DLCIs was strongly temperature-dependent and only slightly affected by the spacer chain length.

{"title":"Effects of side-chain flexibility on properties of azatriphenylene discotic liquid-crystalline ionomers","authors":"Qian Yang, Xiao-Ping Xiong, Chao-Min Yan, Long Li, Hong-Mei Chen, Hai-Liang Ni, Chun Feng, Ke-Qing Zhao, Ping Hu, Yu-Jie Ma, Wen-Hao Yu","doi":"10.1016/j.eurpolymj.2024.113685","DOIUrl":"10.1016/j.eurpolymj.2024.113685","url":null,"abstract":"<div><div>To investigate the influence of side-chain flexibility on the properties of discotic liquid-crystalline ionomers (DLCIs), a series of side-chain azatriphenylene ionic copolymers, denoted as <strong>C-PTPN<em><sub>m</sub></em>-X</strong> (where X = Br<sup>−</sup> or TFSI<sup>−</sup> and <em>m</em> = 3, 5, 7, 15), were synthesised via ring-opening metathesis polymerisation. These copolymers comprise a polycyclooctene backbone connected to discotic mesogenic units via flexible spacers of different lengths. Monomers and ionomers containing bis(trifluoromethanesulfonyl)imide ions (TFSI<sup>−</sup>) displayed columnar liquid-crystalline phases, whereas those with bromide anions exhibited non-mesogenic properties. Both the monomers and copolymers emitted yellow fluorescence with wavelengths ranging from 515 to 561 nm in both the solution and film states. Notably, replacing bromide anions with TFSI<sup>−</sup> significantly enhanced the absolute quantum yield in both monomers and copolymers. Additionally, the mechanical properties of the ionomers were dependent on the spacer length, with the stress and Young’s modulus of <strong>C-PTPN<em><sub>m</sub></em>-TFSI</strong> being approximately 30 times lower than those of <strong>H-PCOE</strong>, a cycloolefin homopolymer, thereby facilitating solution spinning. All the DLCIs demonstrated rapid thermal responsiveness and excellent shape memory characteristics. Flexible spacers in ionic monomers and copolymers enhance their thermal stability and mechanical properties while also influencing their clearing points and mesogenic temperature ranges. The type of anion significantly improved the thermal stability and affected the luminescence properties, whereas the spacer length had less impact on these attributes. The ionic conductivity of the DLCIs was strongly temperature-dependent and only slightly affected by the spacer chain length.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113685"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146944","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

Supramolecular microgel from cellulose and gelatin via host–guest interaction: Formation and sustained release application

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113690

Kexin Hao , Shuo Yu , Ying Xue , Miao Wang , Hailiang Wu , Yingxiong Wang , Yijun Yao

Herein, β-cyclodextrin-coupled cellulose (β-CD-Cel) copolymer microgel was synthesized by cross-linking copolymerization in the NaOH/urea water system. Then, cellulose/gelatin supramolecular microgel (CGSM) with vesicle morphology was obtained by utilizing the host–guest interaction between β-CD cavity and phenylalanine, tryptophan, and tyrosine of gelatin structure. Furthermore, the hydrophobic active substance vanillin was encapsulated into CGSM supramolecular microgel by ultrasonic method to obtain a long-lasting fragrance-released microgel. FTIR, XRD, UV–vis, fluorescence spectra, and ¹H NMR provided evidences for the formation of CGSM supramolecular microgel and the supramolecular interaction between cellulose and gelatin molecules. SEM and DLS confirmed the formation of supramolecular microgel with vesicle structure. Benefiting from the core, residual β-CD cavity, and rich network structure of CGSM supramolecular microgel, the efficient loading and long-lasting release for vanillin was achieved. Compared with β-CD-Cel microgel, CGSM supramolecular microgel showed a higher loading efficiency (98.58 %) for vanillin, and the vanillin retention rate still reached 53.87 % after 196 h of release. After being sprayed on the fabric surface, the fragrance release time of long-lasting fragrance-released CGSM microgel is more than 60 days, and 20 % vanillin is still retained on fabric after washing ten times.

{"title":"Supramolecular microgel from cellulose and gelatin via host–guest interaction: Formation and sustained release application","authors":"Kexin Hao , Shuo Yu , Ying Xue , Miao Wang , Hailiang Wu , Yingxiong Wang , Yijun Yao","doi":"10.1016/j.eurpolymj.2024.113690","DOIUrl":"10.1016/j.eurpolymj.2024.113690","url":null,"abstract":"<div><div>Herein, <em>β</em>-cyclodextrin-coupled cellulose (<em>β</em>-CD-Cel) copolymer microgel was synthesized by cross-linking copolymerization in the NaOH/urea water system. Then, cellulose/gelatin supramolecular microgel (CGSM) with vesicle morphology was obtained by utilizing the host–guest interaction between <em>β</em>-CD cavity and phenylalanine, tryptophan, and tyrosine of gelatin structure. Furthermore, the hydrophobic active substance vanillin was encapsulated into CGSM supramolecular microgel by ultrasonic method to obtain a long-lasting fragrance-released microgel. FTIR, XRD, UV–vis, fluorescence spectra, and <sup>1</sup>H NMR provided evidences for the formation of CGSM supramolecular microgel and the supramolecular interaction between cellulose and gelatin molecules. SEM and DLS confirmed the formation of supramolecular microgel with vesicle structure. Benefiting from the core, residual <em>β</em>-CD cavity, and rich network structure of CGSM supramolecular microgel, the efficient loading and long-lasting release for vanillin was achieved. Compared with <em>β</em>-CD-Cel microgel, CGSM supramolecular microgel showed a higher loading efficiency (98.58 %) for vanillin, and the vanillin retention rate still reached 53.87 % after 196 h of release. After being sprayed on the fabric surface, the fragrance release time of long-lasting fragrance-released CGSM microgel is more than 60 days, and 20 % vanillin is still retained on fabric after washing ten times.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113690"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146945","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

Paving the way toward reactive self-assembly-induced colloidal covalent organic frameworks: Elaboration of macromolecular growth-blocking agents

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113711

Axelle Larrieu , William Lafargue-Dit-Hauret , Pierre Marcasuzaa , Didier Bégué , Laurent Billon

Herein, we develop an original strategy to limit rapid precipitation in solution of Covalent Organic Frameworks (COFs), permitting both the control of their morphology and processing. The enhance COF dispersibility can be implemented and controlled by growth-blocking macromolecular agent concepts. This macromolecular agent limits the growth of COFs and stabilized the COF in a colloidal shape. We propose the synthesis of a hydrophilic end-chain functional Poly(DiMethylAmino)Ethyl MethAcrylate (PDMAEMA) as a macromolecular growth-blocking agent, designed to stabilize imine-COF in aqueous media. Its reactivity with a tri-functional imine-COF blockbuilder (Tpa) is investigated via two different strategies: grafting from and grafting to. This concept is followed by several characterization techniques in solution and in solid states. Depending on the PDMAEMA/Tpa ratios and the grafting strategy, several populations, from mono- to tri-functionalized Tpa are synthesized, and the colloids size and morphology can be tuned. A concomitant DFT calculations provide a better understanding of the self-assembly of the building blocks, shedding the light on the Tpa stacking effects. This study finally provides a first step toward the synthesis of electrostatically/sterically stabilized colloidal COF in water media, for photo hydrogen evolution reaction.

{"title":"Paving the way toward reactive self-assembly-induced colloidal covalent organic frameworks: Elaboration of macromolecular growth-blocking agents","authors":"Axelle Larrieu , William Lafargue-Dit-Hauret , Pierre Marcasuzaa , Didier Bégué , Laurent Billon","doi":"10.1016/j.eurpolymj.2024.113711","DOIUrl":"10.1016/j.eurpolymj.2024.113711","url":null,"abstract":"<div><div>Herein, we develop an original strategy to limit rapid precipitation in solution of Covalent Organic Frameworks (COFs), permitting both the control of their morphology and processing. The enhance COF dispersibility can be implemented and controlled by growth-blocking macromolecular agent concepts. This macromolecular agent limits the growth of COFs and stabilized the COF in a colloidal shape. We propose the synthesis of a hydrophilic end-chain functional Poly(DiMethylAmino)Ethyl MethAcrylate (PDMAEMA) as a macromolecular growth-blocking agent, designed to stabilize imine-COF in aqueous media. Its reactivity with a tri-functional imine-COF blockbuilder (Tpa) is investigated <em>via</em> two different strategies: <em>grafting from</em> and <em>grafting to</em>. This concept is followed by several characterization techniques in solution and in solid states. Depending on the PDMAEMA/Tpa ratios and the grafting strategy, several populations, from mono- to tri-functionalized Tpa are synthesized, and the colloids size and morphology can be tuned. A concomitant DFT calculations provide a better understanding of the self-assembly of the building blocks, shedding the light on the Tpa stacking effects. This study finally provides a first step toward the synthesis of electrostatically/sterically stabilized colloidal COF in water media, for photo hydrogen evolution reaction.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113711"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147589","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

Ketone constructed by alkyl bridge strategy for LED-sensitive free radical photopolymerization

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113681

Jingfang Li , Qilu Deng , Xianju Zhou , Jiaxin Yu , Xiaoqun Zhu , Jun Nie

To enhance the photosensitivity of ketones, which are prone to side isomerization reactions during free radical photopolymerization, a novel strategy involving the use of an alkyl bridge was introduced. This approach was assessed by comparing the performance of two ketone photoinitiators: (E)-2-((1H-pyrrol-2-yl)methylene)-4-methyl-3,4-dihydronaphthalen-1(2H)-one (PDN) and (2E,2′E)-2,2′-((octane-1,8-diylbis(1H-pyrrole-1,2-diyl))bis(methaneylylidene))bis(4-methyl-3,4-dihydronaphthalen-1(2H)-one) (bis-PDN). The synthesis of bis-PDN involved linking two PDN molecules via a long alkyl chain derived from 1,8-dibromooctane. It was shown that this alkyl bridge not only provides steric hindrance that limits the isomerization of PDN but also imparts a significant increase in the molar extinction coefficient of the newly synthesized bis-PDN to 43,779 M⁻¹cm⁻¹ by following the strategy of multiple chromophores. Consequently, bis-PDN demonstrated a notably high initiating efficiency for LED-sensitive polymerization. The efficacy of this alkyl bridge modification was further validated through DFT calculations, steady-state photolysis, NMR testing, polymerization kinetics analysis, and 3D printing experiments. The alkyl bridge technique offers considerable promise for the development of ketone compounds with enhanced photo-activity.

{"title":"Ketone constructed by alkyl bridge strategy for LED-sensitive free radical photopolymerization","authors":"Jingfang Li , Qilu Deng , Xianju Zhou , Jiaxin Yu , Xiaoqun Zhu , Jun Nie","doi":"10.1016/j.eurpolymj.2024.113681","DOIUrl":"10.1016/j.eurpolymj.2024.113681","url":null,"abstract":"<div><div>To enhance the photosensitivity of ketones, which are prone to side isomerization reactions during free radical photopolymerization, a novel strategy involving the use of an alkyl bridge was introduced. This approach was assessed by comparing the performance of two ketone photoinitiators: (E)-2-((1H-pyrrol-2-yl)methylene)-4-methyl-3,4-dihydronaphthalen-1(2H)-one (PDN) and (2E,2′E)-2,2′-((octane-1,8-diylbis(1H-pyrrole-1,2-diyl))bis(methaneylylidene))bis(4-methyl-3,4-dihydronaphthalen-1(2H)-one) (bis-PDN). The synthesis of bis-PDN involved linking two PDN molecules via a long alkyl chain derived from 1,8-dibromooctane. It was shown that this alkyl bridge not only provides steric hindrance that limits the isomerization of PDN but also imparts a significant increase in the molar extinction coefficient of the newly synthesized bis-PDN to 43,779 M<sup>−1</sup>cm<sup>−1</sup> by following the strategy of multiple chromophores. Consequently, bis-PDN demonstrated a notably high initiating efficiency for LED-sensitive polymerization. The efficacy of this alkyl bridge modification was further validated through DFT calculations, steady-state photolysis, NMR testing, polymerization kinetics analysis, and 3D printing experiments. The alkyl bridge technique offers considerable promise for the development of ketone compounds with enhanced photo-activity.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113681"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146946","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

Development of a functionalized polystyrene platform from packaging waste via Friedel-Craft acylation

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113676

Daniela Porcu , Emiliano Carretti , Raffaella Fontana , David Chelazzi , Damiano Bandelli

Through a circular economy approach, expanded polystyrene (EPS) waste can address the need to develop new low-impact materials suitable for packaging, adhesives, and even protective coatings needed for buildings and works of art. In this study, waste Polystyrene (PS) has been chemically modified with increasing feeds of maleic anhydride (MA), using a Lewis acid as a cationic activator (AlCl₃) via Friedel-Crafts acylation. As a result, a novel library of polymer, renamed PS-MA, was synthesized by developing a “one pot” acylation reaction protocol. Nuclear Magnetic Resonance (NMR) and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) assessed the functionalization of PS with MA. PS-MA physicochemical properties were investigated through Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA), and Size Exclusion Chromatography (SEC), linking the characterization of the crosslinked structure with the functionalization degree. Finally, solubility tests yielded the Hansen Solubility Parameters (HSP) and Teas Triangle solubility windows of the new materials. Noticeably, the new PS-MA can be solubilized in green solvents, making its processability in chemical and industrial applications more sustainable than traditional PS. Overall, a new platform of PS-MA with tunable properties was formulated, which stands as an example of functionalized materials obtained from waste through a sustainable synthetic path, with promising impact in numerous industrial and processing sectors.

{"title":"Development of a functionalized polystyrene platform from packaging waste via Friedel-Craft acylation","authors":"Daniela Porcu , Emiliano Carretti , Raffaella Fontana , David Chelazzi , Damiano Bandelli","doi":"10.1016/j.eurpolymj.2024.113676","DOIUrl":"10.1016/j.eurpolymj.2024.113676","url":null,"abstract":"<div><div>Through a circular economy approach, expanded polystyrene (EPS) waste can address the need to develop new low-impact materials suitable for packaging, adhesives, and even protective coatings needed for buildings and works of art. In this study, waste Polystyrene (PS) has been chemically modified with increasing feeds of maleic anhydride (MA), using a Lewis acid as a cationic activator (AlCl<sub>3</sub>) via Friedel-Crafts acylation. As a result, a novel library of polymer, renamed PS-MA, was synthesized by developing a “one pot” acylation reaction protocol. Nuclear Magnetic Resonance (NMR) and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) assessed the functionalization of PS with MA. PS-MA physicochemical properties were investigated through Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA), and Size Exclusion Chromatography (SEC), linking the characterization of the crosslinked structure with the functionalization degree. Finally, solubility tests yielded the Hansen Solubility Parameters (HSP) and Teas Triangle solubility windows of the new materials. Noticeably, the new PS-MA can be solubilized in green solvents, making its processability in chemical and industrial applications more sustainable than traditional PS. Overall, a new platform of PS-MA with tunable properties was formulated, which stands as an example of functionalized materials obtained from waste through a sustainable synthetic path, with promising impact in numerous industrial and processing sectors.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113676"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146952","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

Bio-based dual dynamic covalent adaptive networks based on itaconic acid with superior degradability, reprocessability, and mechanical properties

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113709

Genzheng Sha, Fangfang Kong, Minghui Cui, Mengqiu Quan, Yuqing Wang, Fenglong Li, Jin Zhu, Jing Chen

Thermosetting polymers are increasingly integral to diverse industrial applications due to their superior mechanical robustness and dimensional stability. However, challenges associated with their recyclability and reprocessability persist, limiting their environmental sustainability. Covalent Adaptive Networks (CANs) present a promising pathway to overcoming these limitations by introducing dynamic covalent bonds, which facilitate enhanced recyclability and reprocessability of thermoset resins, Additionally, the use of bio-based feedstocks offers a promising route to mitigate the environmental impacts of polymer production. Herein, we report the development of an innovative thermosetting polyurethane synthesized from bio-derived itaconic acid and vanillin, featuring dual dynamic covalent bonds: imine linkages and disulfide linkages. These bonds endow the polyurethane network with inherent recyclability, reprocessability, degradability, and shape memory characteristics. After three thermal reshaping cycles, the material exhibited significant tensile strength recovery, exceeding 70 %, and demonstrated rapid degradability within 5 h at 50 °C. These findings represent a strategic advancement in polyurethane technology, offering a potential route to address the environmental challenges associated with traditional thermosets. The development of this multifunctional, sustainable material aligns with the growing emphasis on designing polymers that foster both resource sustainability and a reduced environmental footprint.

{"title":"Bio-based dual dynamic covalent adaptive networks based on itaconic acid with superior degradability, reprocessability, and mechanical properties","authors":"Genzheng Sha, Fangfang Kong, Minghui Cui, Mengqiu Quan, Yuqing Wang, Fenglong Li, Jin Zhu, Jing Chen","doi":"10.1016/j.eurpolymj.2024.113709","DOIUrl":"10.1016/j.eurpolymj.2024.113709","url":null,"abstract":"<div><div>Thermosetting polymers are increasingly integral to diverse industrial applications due to their superior mechanical robustness and dimensional stability. However, challenges associated with their recyclability and reprocessability persist, limiting their environmental sustainability. Covalent Adaptive Networks (CANs) present a promising pathway to overcoming these limitations by introducing dynamic covalent bonds, which facilitate enhanced recyclability and reprocessability of thermoset resins, Additionally, the use of bio-based feedstocks offers a promising route to mitigate the environmental impacts of polymer production. Herein, we report the development of an innovative thermosetting polyurethane synthesized from bio-derived itaconic acid and vanillin, featuring dual dynamic covalent bonds: imine linkages and disulfide linkages. These bonds endow the polyurethane network with inherent recyclability, reprocessability, degradability, and shape memory characteristics. After three thermal reshaping cycles, the material exhibited significant tensile strength recovery, exceeding 70 %,and demonstrated rapid degradability within 5 h at 50 °C. These findings represent a strategic advancement in polyurethane technology, offering a potential route to address the environmental challenges associated with traditional thermosets. The development of this multifunctional, sustainable material aligns with the growing emphasis on designing polymers that foster both resource sustainability and a reduced environmental footprint.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113709"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147592","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

Electrospinning of microspheres with ectodermal mesenchymal stem cells for vascular regeneration

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2025.113716

Jiangnan Yu , Min Ni , Kai Liu , Pengfei Pan , Xiaoli Li , Jin Zhang , Tianwen Deng , Qilong Wang , Ximing Xu , Xia Cao

The goal of vascular tissue engineering (VTE) is to cure various vascular illnesses by utilizing biomaterials, cells, and growth factors to construct functional vascular structures. In this study, we fabricated hydrogel microspheres encapsulating ectodermal mesenchymal stem cells (EMSCs) by electrostatic spraying and assessed their potential for VTE. To achieve homogenous and highly viable hydrogel microspheres with a diameter of about 150 µm, an internal pore size of approximately 50 µm, a porosity of approximately 45 %, and a degradation duration of approximately 28 days, we improved the electrostatic spraying settings. The hydrogel microspheres supported the adhesion, expansion and proliferation of EMSCs. We induced the microspheres to differentiate into endothelial cells and form vascular-like structures in vitro. We also confirmed the microspheres promoted neovascularization and tissue integration, resulting in a high vascular density in vivo. Electrospun GelMA microspheres loaded with EMSCs offer a promising strategy for VTE. By regulating the composition and structure of microspheres, the directional release of EMSCs and cell signal transduction can be realized, and the therapeutic effect and biocompatibility can be improved. In addition, this technology can also avoid ischemia and hypoxia during cell transplantation and improve the survival rate and functional performance of cells. Their unique properties and angiogenic ability make them a valuable addition to the field. Further investigations are needed to optimize their performance and clinical translation.

{"title":"Electrospinning of microspheres with ectodermal mesenchymal stem cells for vascular regeneration","authors":"Jiangnan Yu , Min Ni , Kai Liu , Pengfei Pan , Xiaoli Li , Jin Zhang , Tianwen Deng , Qilong Wang , Ximing Xu , Xia Cao","doi":"10.1016/j.eurpolymj.2025.113716","DOIUrl":"10.1016/j.eurpolymj.2025.113716","url":null,"abstract":"<div><div>The goal of vascular tissue engineering (VTE) is to cure various vascular illnesses by utilizing biomaterials, cells, and growth factors to construct functional vascular structures. In this study, we fabricated hydrogel microspheres encapsulating ectodermal mesenchymal stem cells (EMSCs) by electrostatic spraying and assessed their potential for VTE. To achieve homogenous and highly viable hydrogel microspheres with a diameter of about 150 µm, an internal pore size of approximately 50 µm, a porosity of approximately 45 %, and a degradation duration of approximately 28 days, we improved the electrostatic spraying settings. The hydrogel microspheres supported the adhesion, expansion and proliferation of EMSCs. We induced the microspheres to differentiate into endothelial cells and form vascular-like structures <em>in vitro</em>. We also confirmed the microspheres promoted neovascularization and tissue integration, resulting in a high vascular density <em>in vivo</em>. Electrospun GelMA microspheres loaded with EMSCs offer a promising strategy for VTE. By regulating the composition and structure of microspheres, the directional release of EMSCs and cell signal transduction can be realized, and the therapeutic effect and biocompatibility can be improved. In addition, this technology can also avoid ischemia and hypoxia during cell transplantation and improve the survival rate and functional performance of cells. Their unique properties and angiogenic ability make them a valuable addition to the field. Further investigations are needed to optimize their performance and clinical translation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113716"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147593","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