Pub Date : 2024-10-12DOI: 10.1016/j.eurpolymj.2024.113503
Jiahang Zhang, Zhengtao Jiang, Qixin Zhuang, Peiyuan Zuo, Xiaoyun Liu
High-temperature-resistant polybenzoxazoles (PBOs) have recently become a prominent research area due to their potential applications in aviation and aerospace. However, achieving a balance between thermal stability and processability remains a significant challenge. In this study, a computer-aided method to develop PBOs with high thermal stability and processability is explored. First, thermoset benzoxazoles (CPBOs) are designed using a material genomic approach. Subsequently, their zero shear viscosity, temperature at 50 % thermal weight loss, dielectric constant and dielectric loss are predicted using a computer-aided method. Finally, two screened thermosetting benzoxazoles, CPBO-1 and CPBO-6, are synthesized and experimentally validated. The experiments indicate that their melting points are below 100 °C, with the lowest melt viscosities being 0.5 Pa•s and 1.5 Pa•s, respectively. The corresponding polymers, pCPBO-1 and pCPBO-6, feature high thermal stability. The 5 % weight loss temperature of pCPBO-1 in N2 is 618.9 °C, while the dielectric constant and dielectric loss are 3.1 and 0.0063, respectively. These are excellent values for thermosetting resins. This computer-aided screening method is more efficient and cost-effective compared to conventional trial-and-error methods.
{"title":"Computer-aided design of thermosetting benzoxazoles containing bis-endoalkynyl groups: Low melting points and high thermal stability","authors":"Jiahang Zhang, Zhengtao Jiang, Qixin Zhuang, Peiyuan Zuo, Xiaoyun Liu","doi":"10.1016/j.eurpolymj.2024.113503","DOIUrl":"10.1016/j.eurpolymj.2024.113503","url":null,"abstract":"<div><div>High-temperature-resistant polybenzoxazoles (PBOs) have recently become a prominent research area due to their potential applications in aviation and aerospace. However, achieving a balance between thermal stability and processability remains a significant challenge. In this study, a computer-aided method to develop PBOs with high thermal stability and processability is explored. First, thermoset benzoxazoles (CPBOs) are designed using a material genomic approach. Subsequently, their zero shear viscosity, temperature at 50 % thermal weight loss, dielectric constant and dielectric loss are predicted using a computer-aided method. Finally, two screened thermosetting benzoxazoles, CPBO-1 and CPBO-6, are synthesized and experimentally validated. The experiments indicate that their melting points are below 100 °C, with the lowest melt viscosities being 0.5 Pa•s and 1.5 Pa•s, respectively. The corresponding polymers, pCPBO-1 and pCPBO-6, feature high thermal stability. The 5 % weight loss temperature of pCPBO-1 in N<sub>2</sub> is 618.9 °C, while the dielectric constant and dielectric loss are 3.1 and 0.0063, respectively. These are excellent values for thermosetting resins. This computer-aided screening method is more efficient and cost-effective compared to conventional trial-and-error methods.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113503"},"PeriodicalIF":5.8,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142437911","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 : 2024-10-11DOI: 10.1016/j.eurpolymj.2024.113499
Xin Wang , Dexian Yin , Zhi Chen , Yuqiong Hu , Shikai Hu , Xiuying Zhao
Elastomers provide excellent damping performance owing to their unique viscoelasticity, which are widely used as vibration and noise reduction materials. However, conventional rubber-based elastomers with a low glass transition temperature (Tg) and narrow damping range are difficult to adapt to room-temperature conditions. Additionally, most of petroleum-based elastomers hinder the sustainable development. In this work, a series of novel polyurethane elastomers was synthesized using carbon-fixed CO2-based polycarbonate propylene diol (PPCD). The impact of hard segment (HS) content on the thermal, mechanical, and damping properties of CO2-based polyurethane (PU) was comprehensively investigated. Increasing the HS content from 16 % to 44 % increased the Tg from −3.8 °C to 21.7 °C, covering the entire damping range at room temperature with an adjustable damping performance. Furthermore, the tensile strength increased from 7.2 MPa to 27.0 MPa. The synthesis of CO2-based PU can propel the utilization of PU in damping applications, enabling sustainable advancement of the PU industry.
{"title":"CO2-based polyurethane elastomers with enhanced mechanical and tunable room-temperature damping performances","authors":"Xin Wang , Dexian Yin , Zhi Chen , Yuqiong Hu , Shikai Hu , Xiuying Zhao","doi":"10.1016/j.eurpolymj.2024.113499","DOIUrl":"10.1016/j.eurpolymj.2024.113499","url":null,"abstract":"<div><div>Elastomers provide excellent damping performance owing to their unique viscoelasticity, which are widely used as vibration and noise reduction materials. However, conventional rubber-based elastomers with a low glass transition temperature (<em>T<sub>g</sub></em>) and narrow damping range are difficult to adapt to room-temperature conditions. Additionally, most of petroleum-based elastomers hinder the sustainable development. In this work, a series of novel polyurethane elastomers was synthesized using carbon-fixed CO<sub>2</sub>-based polycarbonate propylene diol (PPCD). The impact of hard segment (HS) content on the thermal, mechanical, and damping properties of CO<sub>2</sub>-based polyurethane (PU) was comprehensively investigated. Increasing the HS content from 16 % to 44 % increased the <em>T<sub>g</sub></em> from −3.8 °C to 21.7 °C, covering the entire damping range at room temperature with an adjustable damping performance. Furthermore, the tensile strength increased from 7.2 MPa to 27.0 MPa. The synthesis of CO<sub>2</sub>-based PU can propel the utilization of PU in damping applications, enabling sustainable advancement of the PU industry.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113499"},"PeriodicalIF":5.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445986","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 : 2024-10-11DOI: 10.1016/j.eurpolymj.2024.113498
Raouhi Sanaa , Daniel Portinha , Raouf Medimagh , Etienne Fleury
In this work, the amine-catalyzed thiol-Michael reaction of isosorbide or isomannide-derived dithiols as Michael-donors, with some diacrylates and dimethacrylates as Michael-acceptors, is reported. In a first part, different amines (1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), dimethylaminopyridine (DMAP), Amberlyst® A-21 and hexylamine (HA)) were tested as catalysts for reactions involving diacrylates and dimethacrylates in acetonitrile, respectively. Molecular weight taken as the relevant criterion, DBU and DMAP were found to be equally efficient for polymerization with acrylates while DBU was the most efficient one with methacrylates. A library of polymers differing from the structure of the used diacrylate (some of them derived from isosorbide or isomannide) or dimethacrylate was prepared, with fair molecular weights and Tg varying from –22 to +32 °C. Then oligomers with controlled molecular weight and good end group fidelity were prepared, and were further used in a two-stage crosslinking reaction to prepare soft and elastic biobased crosslinked polymers via thiol-Michael addition.
{"title":"Synthesis of linear and crosslinked isosorbide-containing poly(β-thioether ester) via amine-catalyzed thiol-Michael addition","authors":"Raouhi Sanaa , Daniel Portinha , Raouf Medimagh , Etienne Fleury","doi":"10.1016/j.eurpolymj.2024.113498","DOIUrl":"10.1016/j.eurpolymj.2024.113498","url":null,"abstract":"<div><div>In this work, the amine-catalyzed thiol-Michael reaction of isosorbide or isomannide-derived dithiols as Michael-donors, with some diacrylates and dimethacrylates as Michael-acceptors, is reported. In a first part, different amines (1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), dimethylaminopyridine (DMAP), Amberlyst® A-21 and hexylamine (HA)) were tested as catalysts for reactions involving diacrylates and dimethacrylates in acetonitrile, respectively. Molecular weight taken as the relevant criterion, DBU and DMAP were found to be equally efficient for polymerization with acrylates while DBU was the most efficient one with methacrylates. A library of polymers differing from the structure of the used diacrylate (some of them derived from isosorbide or isomannide) or dimethacrylate was prepared, with fair molecular weights and Tg varying from –22 to +32 °C. Then oligomers with controlled molecular weight and good end group fidelity were prepared, and were further used in a two-stage crosslinking reaction to prepare soft and elastic biobased crosslinked polymers via thiol-Michael addition.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113498"},"PeriodicalIF":5.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142535952","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 : 2024-10-11DOI: 10.1016/j.eurpolymj.2024.113497
Yiru Li , Zhizhuang Li , Weihong Zeng , Yuxin Shen , Yanian Fang , Yunliang Wang , Heng Li
In this study, a dual catalytic system that merges crown ether with alkali metal alkoxides (AMA) is utilized in the ring-opening alternating polymerization (ROAP) of phthalic anhydride (PA) and propylene oxide (PO). This method streamlines the production of polyesters characterized by a fully alternating sequence, a modifiable molar mass (achieving up to 59.3 kg mol−1), and a narrow molar mass distribution (ÐM < 1.26). Analysis of various commercially available AMAs, notably sodium ethoxide (EtONa), sodium methoxide, and lithium ethoxide, in tandem with crown ethers (15-crown-5 and 18-crown-6), underscores the superior catalytic efficacy of the EtONa and 18-crown-6 pairing. This heightened efficiency is attributed to the coordination of crown ether with alkali metal ions, thereby boosting the nucleophilicity of terminal alkoxide anions. The methodology has been successfully deployed in the ROAP of PA, norbornene anhydride, and multiple epoxides, while also simplifying the creation of aliphatic–aromatic block polyesters from a mixture of PA, PO, and lactide. This strategy presents a straightforward approach to polyester production, thus making significant contributions to the evolution of polyester synthesis technology.
{"title":"Synthesis of alternating polyesters using a dual catalytic system of alkali metal alkoxides and crown ether","authors":"Yiru Li , Zhizhuang Li , Weihong Zeng , Yuxin Shen , Yanian Fang , Yunliang Wang , Heng Li","doi":"10.1016/j.eurpolymj.2024.113497","DOIUrl":"10.1016/j.eurpolymj.2024.113497","url":null,"abstract":"<div><div>In this study, a dual catalytic system that merges crown ether with alkali metal alkoxides (AMA) is utilized in the ring-opening alternating polymerization (ROAP) of phthalic anhydride (PA) and propylene oxide (PO). This method streamlines the production of polyesters characterized by a fully alternating sequence, a modifiable molar mass (achieving up to 59.3 kg mol<sup>−1</sup>), and a narrow molar mass distribution (<em>Ð</em><sub>M</sub> < 1.26). Analysis of various commercially available AMAs, notably sodium ethoxide (EtONa), sodium methoxide, and lithium ethoxide, in tandem with crown ethers (15-crown-5 and 18-crown-6), underscores the superior catalytic efficacy of the EtONa and 18-crown-6 pairing. This heightened efficiency is attributed to the coordination of crown ether with alkali metal ions, thereby boosting the nucleophilicity of terminal alkoxide anions. The methodology has been successfully deployed in the ROAP of PA, norbornene anhydride, and multiple epoxides, while also simplifying the creation of aliphatic–aromatic block polyesters from a mixture of PA, PO, and lactide. This strategy presents a straightforward approach to polyester production, thus making significant contributions to the evolution of polyester synthesis technology.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113497"},"PeriodicalIF":5.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445988","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 : 2024-10-10DOI: 10.1016/j.eurpolymj.2024.113501
Shankarrao V. Avhad , Shakeb N. Choudhari , Ashootosh V. Ambade
A series of dual stimuli-responsive block copolymers with varying content of photocleavable o-nitrobenzyl (ONB) ester group pendent in the hydrophobic poly(ɛ-caprolactone) block and pH-cleavable acetal linkage at the junction with hydrophilic poly(ethylene glycol) block is synthesized. The hydrophobic block is a random copolymer synthesized by ring-opening copolymerization of ɛ-caprolactone and ONB-substituted ɛ-caprolactone containing varying compositions of the two monomers. Kinetics of polymerization shows that ONB-functionalized monomer has lower reactivity than that of the unsubstituted monomer. The series of block copolymers shows self-assembly into well-defined spherical micelles of average size of 150–200 nm in aqueous solution. Photocleavage of ONB groups is studied by NMR and UV–vis spectroscopy, and its extent is determined. The two stimuli viz. UV light and pH are used individually as well as simultaneously to study the controlled release of the encapsulated drug Camptothecin and the synergistic effect of the two stimuli is demonstrated. The effect of varying content of ONB groups is observed on drug release profile. MTT assay showed non-cytotoxic nature of the polymer. Cell uptake and photoinduced release of doxorubicin (DOX) from the micelles in MDA-MB-231 cells is demonstrated.
{"title":"Photo and pH dual stimuli-responsive block copolymer micelles with defined incorporation of o-nitrobenzyl units in poly(ɛ-caprolactone) block for controlled release","authors":"Shankarrao V. Avhad , Shakeb N. Choudhari , Ashootosh V. Ambade","doi":"10.1016/j.eurpolymj.2024.113501","DOIUrl":"10.1016/j.eurpolymj.2024.113501","url":null,"abstract":"<div><div>A series of dual stimuli-responsive block copolymers with varying content of photocleavable o-nitrobenzyl (ONB) ester group pendent in the hydrophobic poly(ɛ-caprolactone) block and pH-cleavable acetal linkage at the junction with hydrophilic poly(ethylene glycol) block is synthesized. The hydrophobic block is a random copolymer synthesized by ring-opening copolymerization of ɛ-caprolactone and ONB-substituted ɛ-caprolactone containing varying compositions of the two monomers. Kinetics of polymerization shows that ONB-functionalized monomer has lower reactivity than that of the unsubstituted monomer. The series of block copolymers shows self-assembly into well-defined spherical micelles of average size of 150–200 nm in aqueous solution. Photocleavage of ONB groups is studied by NMR and UV–vis spectroscopy, and its extent is determined. The two stimuli <em>viz</em>. UV light and pH are used individually as well as simultaneously to study the controlled release of the encapsulated drug Camptothecin and the synergistic effect of the two stimuli is demonstrated. The effect of varying content of ONB groups is observed on drug release profile. MTT assay showed non-cytotoxic nature of the polymer. Cell uptake and photoinduced release of doxorubicin (DOX) from the micelles in MDA-MB-231 cells is demonstrated.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113501"},"PeriodicalIF":5.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433312","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 : 2024-10-10DOI: 10.1016/j.eurpolymj.2024.113502
Yirong Fan, Tao Wang, Hui Sun
Metal ion coordination has critical influence on the self-assembly behavior of amphiphilic polymers and the morphology of the obtained assemblies. Herein, an amphiphilic homopolymer with 2,2′-bipyridine (BPy) as side chain is synthesized (noted as PBPyAA), which can self-assemble into bowl-shaped nanoparticles (BNPs) in tetrahydrofuran (THF)/water. Taking advantage of the coordination interaction between BPy and metal ions, Fe2+ is chosen to regulate the self-assembly behavior and the morphology of the assemblies of PBPyAA in two pathways. (Ⅰ) The aqueous solution of Fe2+ with various concentrations is added to the THF solution of PBPyAA during self-assembly. (Ⅱ) Fe2+ is added into the THF solution of PBPyAA before self-assembly, followed by the addition of deionized water to promote the self-assembly. The results show that the pathway Ⅰ facilitates the coordination of BPy and Fe2+. With the increase of the concentration of Fe2+ aqueous solution, the coordination efficiency of BPy increases from 0.419 % to 7.789 %, leading to the transformation of BNPs to vesicles. Though the coordination efficiency of BPy also increases with the concentration of Fe2+ in pathway Ⅱ, which is still quite low of 0.274 % to 0.366 %, and the morphology of the BNPs barely changes. In addition, ethylene diamine tetraacetic acid (EDTA), a strong chelating agent, is also added to promote the competitive complexation with BPy, resulting in the dissociation of BPy and Fe2+ and the reversible transformation from vesicles to BNPs. Overall, the effect of Fe2+ coordination on the self-assembly behavior of PBPyAA in two pathways is investigated and the reversible transformation of BNPs to vesicles is also achieved.
{"title":"The influence of Fe2+ on the self-assembly of a bipyridine containing homopolymer: From bowl-shaped nanoparticles to vesicles","authors":"Yirong Fan, Tao Wang, Hui Sun","doi":"10.1016/j.eurpolymj.2024.113502","DOIUrl":"10.1016/j.eurpolymj.2024.113502","url":null,"abstract":"<div><div>Metal ion coordination has critical influence on the self-assembly behavior of amphiphilic polymers and the morphology of the obtained assemblies. Herein, an amphiphilic homopolymer with 2,2′-bipyridine (BPy) as side chain is synthesized (noted as PBPyAA), which can self-assemble into bowl-shaped nanoparticles (BNPs) in tetrahydrofuran (THF)/water. Taking advantage of the coordination interaction between BPy and metal ions, Fe<sup>2+</sup> is chosen to regulate the self-assembly behavior and the morphology of the assemblies of PBPyAA in two pathways. (Ⅰ) The aqueous solution of Fe<sup>2+</sup> with various concentrations is added to the THF solution of PBPyAA during self-assembly. (Ⅱ) Fe<sup>2+</sup> is added into the THF solution of PBPyAA before self-assembly, followed by the addition of deionized water to promote the self-assembly. The results show that the pathway Ⅰ facilitates the coordination of BPy and Fe<sup>2+</sup>. With the increase of the concentration of Fe<sup>2+</sup> aqueous solution, the coordination efficiency of BPy increases from 0.419 % to 7.789 %, leading to the transformation of BNPs to vesicles. Though the coordination efficiency of BPy also increases with the concentration of Fe<sup>2+</sup> in pathway Ⅱ, which is still quite low of 0.274 % to 0.366 %, and the morphology of the BNPs barely changes. In addition, ethylene diamine tetraacetic acid (EDTA), a strong chelating agent, is also added to promote the competitive complexation with BPy, resulting in the dissociation of BPy and Fe<sup>2+</sup> and the reversible transformation from vesicles to BNPs. Overall, the effect of Fe<sup>2+</sup> coordination on the self-assembly behavior of PBPyAA in two pathways is investigated and the reversible transformation of BNPs to vesicles is also achieved.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113502"},"PeriodicalIF":5.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445987","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}
Chronic bacterial-infected wound healing is becoming increasingly severe, with high rates of mortality and disability, owing to bacterial film, excessive accumulation of reactive oxygen species (ROS), inflammatory, and traditional therapeutics with poor drug permeability. Herin, a functional Zn-gallic acid nanozyme (Zn-NM) with excellent antibacterial and antioxidant capacity was incorporated with a gelatin-based microneedle patch (Zn-NM@MN) to achieve transdermal and sustained release of the drug at the infected wound site. The Zn-NM displayed the concentration-dependent antibacterial capacity, and 250 μg/mL of Zn-NM simultaneously possessed excellent antibacterial (89.36 ± 0.95 % for Escherichia coli, 92.44 ± 11.03 % for Staphylococcus aureus, and 95.03 ± 1.06 % for Methicillin-resistant Staphylococcus aureus), antioxidant properties and negligible cytotoxicity. After that, Zn-NM@MN could transdermal the epidermis or biofilm to sustain the release of Zn-NM for 3 h (release of 80 % drug). Systematic tissue regeneration assessment on rats’ infected full-thickness skin wounds demonstrated an enhanced wound healing rate. Zn-NM@MN could efficiently kill the bacteria (about 85 %), alleviate oxidant stress, reduce bacterial-induced inflammation, and promote vascular regeneration. This synergetic therapy strategy will pave the way for treating complicated infection wounds.
{"title":"Metal–phenolic nanozyme based microneedle patch with antibacterial and antioxidant for infected wound healing","authors":"Qi Dong , Siyu Xiong , Junjie Ai , Zhaowei Zhang , Yingshan Zhou","doi":"10.1016/j.eurpolymj.2024.113500","DOIUrl":"10.1016/j.eurpolymj.2024.113500","url":null,"abstract":"<div><div>Chronic bacterial-infected wound healing is becoming increasingly severe, with high rates of mortality and disability, owing to bacterial film, excessive accumulation of reactive oxygen species (ROS), inflammatory, and traditional therapeutics with poor drug permeability. Herin, a functional Zn-gallic acid nanozyme (Zn-NM) with excellent antibacterial and antioxidant capacity was incorporated with a gelatin-based microneedle patch (Zn-NM@MN) to achieve transdermal and sustained release of the drug at the infected wound site. The Zn-NM displayed the concentration-dependent antibacterial capacity, and 250 μg/mL of Zn-NM simultaneously possessed excellent antibacterial (89.36 ± 0.95 % for Escherichia coli, 92.44 ± 11.03 % for Staphylococcus aureus, and 95.03 ± 1.06 % for Methicillin-resistant Staphylococcus aureus), antioxidant properties and negligible cytotoxicity. After that, Zn-NM@MN could transdermal the epidermis or biofilm to sustain the release of Zn-NM for 3 h (release of 80 % drug). Systematic tissue regeneration assessment on rats’ infected full-thickness skin wounds demonstrated an enhanced wound healing rate. Zn-NM@MN could efficiently kill the bacteria (about 85 %), alleviate oxidant stress, reduce bacterial-induced inflammation, and promote vascular regeneration. This synergetic therapy strategy will pave the way for treating complicated infection wounds.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113500"},"PeriodicalIF":5.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445983","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 : 2024-10-09DOI: 10.1016/j.eurpolymj.2024.113494
Tiantian Hao , Ya Gao , Enhao Zheng , Huagong Yang , Yitong Pan , Peikai Zhang , Jing Xu , Zhaosheng Hou
Multifunctional polymers are highly desirable for developing smart materials in medical applications. This study proposed a facile strategy to fabricate a new multifunctional poly(ether‐urethane) incorporating disulfide bonds and phenol-urethane bonds (PEU−TS). The distinctive feature of the designed PEU−TS elastomers was the presence of abundant phenolic hydroxyl groups, dynamic aromatic disulfide bonds, phenol-urethane bonds, and multiple H-bonds between urethane groups and tannic acid (TA) molecules, which endowed the materials with superior antibacterial and antioxidative activities, self‐healing capabilities, and shape memory functions. Furthermore, the phenol-carbamate crosslinked networks enhanced the tensile properties and improved the biostability of the elastomers. Biocompatibility evaluation further demonstrated that networked PEU−TS composites possessed favorable cell viability and high cytocompatibility. The multifunctional PEU−TS elastomers with robust tensile properties hold great potential for application in durable implants and chronic wound dressings. This elaborate design could inspire the development of multifunctional PU materials over wide medical applications.
多功能聚合物是开发医疗应用智能材料的理想材料。本研究提出了一种简单易行的策略，用于制造含有二硫键和苯酚-聚氨酯键的新型多功能聚醚-聚氨酯（PEU-TS）。所设计的 PEU-TS 弹性体的显著特点是含有丰富的酚羟基、动态芳香族二硫键、苯酚-氨基甲酸酯键，以及氨基甲酸酯基团与单宁酸（TA）分子之间的多个 H 键，从而使材料具有优异的抗菌和抗氧化活性、自愈合能力和形状记忆功能。此外，苯酚-氨基甲酸酯交联网络还增强了弹性体的拉伸性能，提高了其生物稳定性。生物相容性评估进一步表明，网络化 PEU-TS 复合材料具有良好的细胞活力和高细胞相容性。具有强大拉伸性能的多功能 PEU-TS 弹性体在耐用植入物和慢性伤口敷料方面具有巨大的应用潜力。这一精心设计可为多功能聚氨酯材料在广泛医疗应用领域的开发提供灵感。
{"title":"Multifunctional poly(ether‐urethane) elastomer based on dynamic phenol-urethane and disulfide bonds: Simultaneously showing superior toughness, self-healing, shape memory, antibacterial, and antioxidative properties","authors":"Tiantian Hao , Ya Gao , Enhao Zheng , Huagong Yang , Yitong Pan , Peikai Zhang , Jing Xu , Zhaosheng Hou","doi":"10.1016/j.eurpolymj.2024.113494","DOIUrl":"10.1016/j.eurpolymj.2024.113494","url":null,"abstract":"<div><div>Multifunctional polymers are highly desirable for developing smart materials in medical applications. This study proposed a facile strategy to fabricate a new multifunctional poly(ether‐urethane) incorporating disulfide bonds and phenol-urethane bonds (PEU−TS). The distinctive feature of the designed PEU−TS elastomers was the presence of abundant phenolic hydroxyl groups, dynamic aromatic disulfide bonds, phenol-urethane bonds, and multiple H-bonds between urethane groups and tannic acid (TA) molecules, which endowed the materials with superior antibacterial and antioxidative activities, self‐healing capabilities, and shape memory functions. Furthermore, the phenol-carbamate crosslinked networks enhanced the tensile properties and improved the biostability of the elastomers. Biocompatibility evaluation further demonstrated that networked PEU−TS composites possessed favorable cell viability and high cytocompatibility. The multifunctional PEU−TS elastomers with robust tensile properties hold great potential for application in durable implants and chronic wound dressings. This elaborate design could inspire the development of multifunctional PU materials over wide medical applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113494"},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424823","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 : 2024-10-09DOI: 10.1016/j.eurpolymj.2024.113496
Zhiyong Wang , Baotao Huang , Xinchao Li , Yi Pan , Zhaohui Zheng , Jinni Deng
Because of low surface energy, silicone polymers would easily peel off from polypropylene (PP) substrate as hydrophobic coatings and they are incompatible with PP in melt-blending process as well. Therefore, ethylene polymers modified with both silicone and alkane side-groups were prepared by nucleophilic substitution in this work. It was confirmed that these prepared polymers could migrate and aggregate to the surface of the blends at that melting temperature when blended with PP due to the low surface energy and high entropy of silicone side groups. Meanwhile, chain entanglement was achieved between alky side-groups of silicone polymers and polymer chain of PP by melt-blending process, so that the compatibility of the blends was improved and the bonding force of two polymers increased simultaneously. Accordingly, molding blends with stable and durable hydrophobility were successfully gained based on migration of silicone and entanglement of alkane and PP. It’s noticeable that the water contact angle of the blend remained to be about 106° from 113°, even soaking in acid (pH = 1) and alkali (pH = 14) solutions, deionized water and anhydrous ethanol, or under multiple strong frictions. This will provide a facile and effective strategy to endow general materials with durable antifouling properties directly by injection molding without additional coating.
{"title":"Molding blends of silicone polymer / polypropylene with durable resistant to extreme conditions based on migration and compatibility of molecular chains","authors":"Zhiyong Wang , Baotao Huang , Xinchao Li , Yi Pan , Zhaohui Zheng , Jinni Deng","doi":"10.1016/j.eurpolymj.2024.113496","DOIUrl":"10.1016/j.eurpolymj.2024.113496","url":null,"abstract":"<div><div>Because of low surface energy, silicone polymers would easily peel off from polypropylene (PP) substrate as hydrophobic coatings and they are incompatible with PP in melt-blending process as well. Therefore, ethylene polymers modified with both silicone and alkane side-groups were prepared by nucleophilic substitution in this work. It was confirmed that these prepared polymers could migrate and aggregate to the surface of the blends at that melting temperature when blended with PP due to the low surface energy and high entropy of silicone side groups. Meanwhile, chain entanglement was achieved between alky side-groups of silicone polymers and polymer chain of PP by melt-blending process, so that the compatibility of the blends was improved and the bonding force of two polymers increased simultaneously. Accordingly, molding blends with stable and durable hydrophobility were successfully gained based on migration of silicone and entanglement of alkane and PP. It’s noticeable that the water contact angle of the blend remained to be about 106° from 113°, even soaking in acid (pH = 1) and alkali (pH = 14) solutions, deionized water and anhydrous ethanol, or under multiple strong frictions. This will provide a facile and effective strategy to endow general materials with durable antifouling properties directly by injection molding without additional coating.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113496"},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424822","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 : 2024-10-09DOI: 10.1016/j.eurpolymj.2024.113487
Yun Dou , Elwathig A.M. Hassan , Shoujuan Wang , Magdi E. Gibril , Fangong Kong
The increasing environmental concerns have heightened the pursuit of sustainable materials, with a particular emphasis on biodegradable polymers. Polyvinyl alcohol (PVA), a recognized biodegradable synthetic polymer, faces challenges such as cost, slow biodegradation, and limited UV resistance. This study explores lignin, an abundant and eco-friendly biopolymer, as a cost-effective additive to enhance PVA properties via the copolymerization technique. The Mannich reaction was utilized to effectively alkylate lignin with allylthiourea, leading to the synthesis of a lignin-based macromonomer (LATU). Subsequently, the LATU macromonomer was copolymerized with vinyl acetate, producing Poly(VAc-Co-LATU) copolymer in a reaction conducted at 70 °C for 6 h. Finally, the copolymers were hydrolyzed (saponification) with potassium hydroxide to obtain Poly(VA-Co-LATU) copolymers. Extensive investigations, including FTIR, XPS, XRD, and 1H NMR, effectively validated the synthesis of the copolymers. The high monomer conversion rate above 89 % emphasizes the effectiveness of the synthesis method. The addition of LATU has a direct impact on the crystalline structure of the copolymer. X-ray diffraction patterns indicate a reduction in crystallinity, which in turn affects the other properties of the synthesized copolymers. Consequently, the lignified copolymer, Poly(VA-co-LATU), exhibited slight decrease in molecular weight (Mw), improved UV-blocking effectiveness, and greater solubility in water as comparison to PVA. This study demonstrates the feasibility of using lignin as a monomer to create novel bio-based polymeric materials that exhibit the necessary properties for certain applications.
{"title":"Synthesis and characteristics properties of lignified PVA copolymer with enhanced UV-blocking performance and water solubility","authors":"Yun Dou , Elwathig A.M. Hassan , Shoujuan Wang , Magdi E. Gibril , Fangong Kong","doi":"10.1016/j.eurpolymj.2024.113487","DOIUrl":"10.1016/j.eurpolymj.2024.113487","url":null,"abstract":"<div><div>The increasing environmental concerns have heightened the pursuit of sustainable materials, with a particular emphasis on biodegradable polymers. Polyvinyl alcohol (PVA), a recognized biodegradable synthetic polymer, faces challenges such as cost, slow biodegradation, and limited UV resistance. This study explores lignin, an abundant and eco-friendly biopolymer, as a cost-effective additive to enhance PVA properties via the copolymerization technique. The Mannich reaction was utilized to effectively alkylate lignin with allylthiourea, leading to the synthesis of a lignin-based macromonomer (LATU). Subsequently, the LATU macromonomer was copolymerized with vinyl acetate, producing Poly(VAc-Co-LATU) copolymer in a reaction conducted at 70 °C for 6 h. Finally, the copolymers were hydrolyzed (saponification) with potassium hydroxide to obtain Poly(VA-Co-LATU) copolymers. Extensive investigations, including FTIR, XPS, XRD, and <sup>1</sup>H NMR, effectively validated the synthesis of the copolymers. The high monomer conversion rate above 89 % emphasizes the effectiveness of the synthesis method. The addition of LATU has a direct impact on the crystalline structure of the copolymer. X-ray diffraction patterns indicate a reduction in crystallinity, which in turn affects the other properties of the synthesized copolymers. Consequently, the lignified copolymer, Poly(VA-co-LATU), exhibited slight decrease in molecular weight (<em>Mw</em>), improved UV-blocking effectiveness, and greater solubility in water as comparison to PVA. This study demonstrates the feasibility of using lignin as a monomer to create novel bio-based polymeric materials that exhibit the necessary properties for certain applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113487"},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424824","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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