Pub Date : 2024-10-09DOI: 10.1016/j.eurpolymj.2024.113494
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":"","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":null,"pages":null},"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
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":"","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":null,"pages":null},"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.2024.113493
Curdlan is produced by fermentation of microorganisms, which is an insoluble β-(1 → 3)-D-glucans. To better effectively utilize native curdlan, firstly, a derivative from curdlan, carboxymethylated curdlan (CMCD), with different degrees of substitution (DS) DS ∼ 0.20, DS ∼ 0.43 and DS ∼ 0.82 were prepared in this study. Carboxymethylation increases solubility in water more than native curdlan. Moreover, CMCDs were investigated to be hydrolyzed by CcGluE, an endo-β-1 → 3-glucanase and generated the degradation products were oligosaccharides with degrees of polymerization (DP) mainly ranging from 2 to 7. CcGluE also showed high thermal and pH stability when CMCD ∼ 0.43 was used as a substrate. Then these oligosaccharides generated by different CMCDs were applied to Arabidopsis and the activity in inducing defense responses were detected after being treated by the pathogen of Pseudomonas syringae pv tomato DC3000 (Pst DC3000). CMCD (DS ∼ 0.20) degradation oligosaccharide (CMCD ∼ 0.20 OS) pre-treatment was the just one that significantly enhanced the disease resistance to Pst DC3000, which is mediated by the salicylic acid (SA) signaling pathway in plants. The findings offer new insights into the application of curdlan, demonstrating that carboxymethylation enhances its solubility in water. Additionally, the oligosaccharide products derived from CMCD degradation show promising prospects for controlling plant diseases in agriculture.
{"title":"Preparation of carboxymethylated curdlan oligosaccharides and application on plant disease control","authors":"","doi":"10.1016/j.eurpolymj.2024.113493","DOIUrl":"10.1016/j.eurpolymj.2024.113493","url":null,"abstract":"<div><div>Curdlan is produced by fermentation of microorganisms, which is an insoluble β-(1 → 3)-D-glucans. To better effectively utilize native curdlan, firstly, a derivative from curdlan, carboxymethylated curdlan (CMCD), with different degrees of substitution (DS) DS ∼ 0.20, DS ∼ 0.43 and DS ∼ 0.82 were prepared in this study. Carboxymethylation increases solubility in water more than native curdlan. Moreover, CMCDs were investigated to be hydrolyzed by <em>Cc</em>GluE, an <em>endo</em>-β-1 → 3-glucanase and generated the degradation products were oligosaccharides with degrees of polymerization (DP) mainly ranging from 2 to 7. <em>Cc</em>GluE also showed high thermal and pH stability when CMCD ∼ 0.43 was used as a substrate. Then these oligosaccharides generated by different CMCDs were applied to Arabidopsis and the activity in inducing defense responses were detected after being treated by the pathogen of <em>Pseudomonas syringae pv tomato</em> DC3000 (<em>Pst</em> DC3000). CMCD (DS ∼ 0.20) degradation oligosaccharide (CMCD ∼ 0.20 OS) pre-treatment was the just one that significantly enhanced the disease resistance to <em>Pst</em> DC3000, which is mediated by the salicylic acid (SA) signaling pathway in plants<em>.</em> The findings offer new insights into the application of curdlan, demonstrating that carboxymethylation enhances its solubility in water. Additionally, the oligosaccharide products derived from CMCD degradation show promising prospects for controlling plant diseases in agriculture.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424818","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
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":"","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":null,"pages":null},"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}
Pub Date : 2024-10-09DOI: 10.1016/j.eurpolymj.2024.113492
The design of novel hybrid magnetoactive scaffolds based on biocompatible piezopolymers and magnetic nanoparticles is of interest for medicine, mainly for tissue regeneration, because application of an external either static or alternating magnetic field to cells that settled on a magnetoactive scaffold offers an opportunity for remote control of cellular functions. This study describes fabrication of electrospun magnetoactive poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] scaffolds highly doped with 20 wt% of magnetite nanoparticles modified with citric acid (Fe3O4-CA). The electrospun P(VDF-TrFE)/Fe3O4-CA scaffolds have defect-free morphology with a fiber diameter of approximately 1 μm and contain both an electroactive β-phase (predominantly) and a lesser amount of an γ-phase. A high content of uniformly distributed Fe3O4-CA nanoparticles within P(VDF-TrFE) fibrous scaffolds resulted in a high saturation magnetization of 12.1 emu/g and ferrimagnetic behavior of the composite P(VDF-TrFE)/Fe3O4-CA scaffolds. They were proved to be biocompatible with normal human cells: normal human fibroblasts and human mesenchymal stem cells adhered to the scaffold and retained their viability. According to high-throughput RNA-sequencing data, the adhesion of fibroblasts to the scaffolds upregulated genes related to key stages of tissue regeneration such as coagulation (genes THBD and SERPINB2) and wound healing (IL24, PDGFB, F3, and PLAU) and affected TGFβ, BMP, and Wnt signaling pathways. Alternating-magnetic-field exposure of the magnetoactive P(VDF-TrFE)/Fe3O4-CA scaffolds with fibroblasts settled on the surface activated extracellular and intracellular cell signaling pathways.
{"title":"Changes in gene expression profile of normal human fibroblasts on P(VDF-TrFE) scaffolds highly doped with Fe3O4-CA nanoparticles under alternating magnetic field stimulation","authors":"","doi":"10.1016/j.eurpolymj.2024.113492","DOIUrl":"10.1016/j.eurpolymj.2024.113492","url":null,"abstract":"<div><div>The design of novel hybrid magnetoactive scaffolds based on biocompatible piezopolymers and magnetic nanoparticles is of interest for medicine, mainly for tissue regeneration, because application of an external either static or alternating magnetic field to cells that settled on a magnetoactive scaffold offers an opportunity for remote control of cellular functions. This study describes fabrication of electrospun magnetoactive poly(vinylidene fluoride-<em>co</em>-trifluoroethylene) [P(VDF-TrFE)] scaffolds highly doped with 20 wt% of magnetite nanoparticles modified with citric acid (Fe<sub>3</sub>O<sub>4</sub>-CA). The electrospun P(VDF-TrFE)/Fe<sub>3</sub>O<sub>4</sub>-CA scaffolds have defect-free morphology with a fiber diameter of approximately 1 μm and contain both an electroactive β-phase (predominantly) and a lesser amount of an γ-phase. A high content of uniformly distributed Fe<sub>3</sub>O<sub>4</sub>-CA nanoparticles within P(VDF-TrFE) fibrous scaffolds resulted in a high saturation magnetization of 12.1 emu/g and ferrimagnetic behavior of the composite P(VDF-TrFE)/Fe<sub>3</sub>O<sub>4</sub>-CA scaffolds. They were proved to be biocompatible with normal human cells: normal human fibroblasts and human mesenchymal stem cells adhered to the scaffold and retained their viability. According to high-throughput RNA-sequencing data, the adhesion of fibroblasts to the scaffolds upregulated genes related to key stages of tissue regeneration such as coagulation (genes <em>THBD</em> and <em>SERPINB2</em>) and wound healing (<em>IL24</em>, <em>PDGFB</em>, <em>F3</em>, and <em>PLAU</em>) and affected TGFβ, BMP, and Wnt signaling pathways. Alternating-magnetic-field exposure of the magnetoactive P(VDF-TrFE)/Fe<sub>3</sub>O<sub>4</sub>-CA scaffolds with fibroblasts settled on the surface activated extracellular and intracellular cell signaling pathways.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424821","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.2024.113491
Poly(vinylpyrrolidone) (PVP) hydrogels were obtained by green light irradiation of aqueous PVP/ammonium persulfate solutions modified with gold nanoparticles (AuNPs). The increase in temperature produced through the activation of the photothermal effect of AuNPs triggers the decomposition of ammonium persulfate producing radicals that, by attacking the polymer main chain and generating macro-radicals, induce the crosslinking of the polymer via recombination paths. Irradiation from the top of the solutions in an open configuration produced water evaporation and a concomitant increase in temperature during curing, giving rise to dry materials with high aspect ratio and moderate swelling anisotropy. Pads that reversibly adhere to different substrates, including human skin, were produced by simple contact of the final materials with water. Impregnation of gauze wound dressings with PVP-Au-ammonium persulfate dispersions, followed by direct “in situ” photothermal crosslinking, enabled the fabrication of supported functional pads with potential applications as reversible adhesive skin wound dressings. Infusion of the hydrogels with Rose Bengal (RB) provides the materials with photosensitizing properties useful for the photodynamic inactivation of Staphylococcus aureus. A decrease in cell viability of 99.9% was attained after 30 min of irradiation with a low-power green LED source, which demonstrates the efficient singlet oxygen production by RB in the hydrogels and paves the way towards the design of new stimulus-activated bactericidal supplies for biomedical uses.
{"title":"Soft hydrogels obtained by photothermal curing of poly(vinylpyrrolidone)/gold nanoparticles dispersions showing anisotropic swelling and photo-activated antimicrobial properties","authors":"","doi":"10.1016/j.eurpolymj.2024.113491","DOIUrl":"10.1016/j.eurpolymj.2024.113491","url":null,"abstract":"<div><div>Poly(vinylpyrrolidone) (PVP) hydrogels were obtained by green light irradiation of aqueous PVP/ammonium persulfate solutions modified with gold nanoparticles (AuNPs). The increase in temperature produced through the activation of the photothermal effect of AuNPs triggers the decomposition of ammonium persulfate producing radicals that, by attacking the polymer main chain and generating macro-radicals, induce the crosslinking of the polymer via recombination paths. Irradiation from the top of the solutions in an open configuration produced water evaporation and a concomitant increase in temperature during curing, giving rise to dry materials with high aspect ratio and moderate swelling anisotropy. Pads that reversibly adhere to different substrates, including human skin, were produced by simple contact of the final materials with water. Impregnation of gauze wound dressings with PVP-Au-ammonium persulfate dispersions, followed by direct “in situ” photothermal crosslinking, enabled the fabrication of supported functional pads with potential applications as reversible adhesive skin wound dressings. Infusion of the hydrogels with Rose Bengal (RB) provides the materials with photosensitizing properties useful for the photodynamic inactivation of <em>Staphylococcus aureus</em>. A decrease in cell viability of 99.9% was attained after 30 min of irradiation with a low-power green LED source, which demonstrates the efficient singlet oxygen production by RB in the hydrogels and paves the way towards the design of new stimulus-activated bactericidal supplies for biomedical uses.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424819","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 : 2024-10-05DOI: 10.1016/j.eurpolymj.2024.113490
Effective methods of multi-functionalization of nanomaterials are essential for fabricating effective targeted drug delivery systems. Herein, we disclose the fabrication of polymer brush-coated magnetic nanoparticles that could be functionalized with drugs and targeting ligands through orthogonal click reactions. In particular, polymers containing electron-rich furan groups as functionalization handles are grown from the surface of magnetic nanoparticles using the ‘graft-from’ approach. Furthermore, azide groups are installed at the chain end of polymer brushes to furnish an orthogonally functionalizable system. The attachment of maleimide-containing fluorescent dyes and cytotoxic drugs using the Diels-Alder reaction is demonstrated. Drug-conjugated nanoparticles functionalized with integrin-targeting peptide using the azide-alkyne cycloaddition reaction undergo preferential uptake in cancer cells and show dose-dependent cytotoxicity. We envision that the modularly functionalizable system disclosed here could target various cancer cells using an appropriate combination of drugs and targeting groups.
{"title":"‘Clickable’ polymer brush coated magnetic nanoparticles: Employing Diels-Alder and azide-alkyne cycloaddition for modular targeted drug delivery platforms","authors":"","doi":"10.1016/j.eurpolymj.2024.113490","DOIUrl":"10.1016/j.eurpolymj.2024.113490","url":null,"abstract":"<div><div>Effective methods of multi-functionalization of nanomaterials are essential for fabricating effective targeted drug delivery systems. Herein, we disclose the fabrication of polymer brush-coated magnetic nanoparticles that could be functionalized with drugs and targeting ligands through orthogonal click reactions. In particular, polymers containing electron-rich furan groups as functionalization handles are grown from the surface of magnetic nanoparticles using the ‘graft-from’ approach. Furthermore, azide groups are installed at the chain end of polymer brushes to furnish an orthogonally functionalizable system. The attachment of maleimide-containing fluorescent dyes and cytotoxic drugs using the Diels-Alder reaction is demonstrated. Drug-conjugated nanoparticles functionalized with integrin-targeting peptide using the azide-alkyne cycloaddition reaction undergo preferential uptake in cancer cells and show dose-dependent cytotoxicity. We envision that the modularly functionalizable system disclosed here could target various cancer cells using an appropriate combination of drugs and targeting groups.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424817","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 : 2024-10-03DOI: 10.1016/j.eurpolymj.2024.113489
An economical and efficient approach for synthesizing high-fidelity PEGn-Alds through a substitution and oxidation process has been developed, providing a new pathway for obtaining high-purity PEGn-Alds, particularly addressing the issue of peroxidation and breakage of PEG main chains in the oxidation step. The synthesis of a series of high-fidelity PEGn-Alds with different functional groups or topological structures further proves the versatility of this new method. Additionally, PEGn-Alds also exhibit good biocompatibility, and potential ability to modify peptides and self-assembly to micelles, this lays a foundation for synthesizing high-quality drugs and developing novel therapeutics.
{"title":"High-fidelity propionaldehyde functionalized Poly(ethylene glycol): Synthesis and applications","authors":"","doi":"10.1016/j.eurpolymj.2024.113489","DOIUrl":"10.1016/j.eurpolymj.2024.113489","url":null,"abstract":"<div><div>An economical and efficient approach for synthesizing high-fidelity PEG<sub>n</sub>-Alds through a substitution and oxidation process has been developed, providing a new pathway for obtaining high-purity PEG<sub>n</sub>-Alds, particularly addressing the issue of peroxidation and breakage of PEG main chains in the oxidation step. The synthesis of a series of high-fidelity PEG<sub>n</sub>-Alds with different functional groups or topological structures further proves the versatility of this new method. Additionally, PEG<sub>n</sub>-Alds also exhibit good biocompatibility, and potential ability to modify peptides and self-assembly to micelles, this lays a foundation for synthesizing high-quality drugs and developing novel therapeutics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424814","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 : 2024-10-02DOI: 10.1016/j.eurpolymj.2024.113488
Boronic acid (BA) moieties confer a variety of stimuli-response properties upon polymers. PISA is the most efficient technique for the preparation of core–shell nanoparticles (NPs), however aqueous dispersion PISA of free BA-containing monomers is complicated by the formation of the boroxine anhydride at the hydrophobic core. In the present work, dispersion reversible addition-fragmentation chain transfer (RAFT) copolymerization of a free BA-containing derivative of N-phenylacrylamide yields NP morphologies which are different to those formed from the equivalent PISA homopolymerization without BA. Depending on conditions, PISA results in spheres, rods, and worms with colloidal stability improved by using a higher fraction of the non-stimuli responsive monomer to give large compound micelles. Post-polymerization stimuli-response from the resultant PISA dispersion through hydrolysis of boroxine-rich copolymer NPs by dilution with the aqueous dispersion solvent or with water yields micron-sized worms, lamellae, and vesicles. Self-assembly to higher order morphologies is driven by the extent of hydrolysis. The resultant free BA-containing NPs becoming smaller and spherical upon basification and glucose addition.
硼酸（BA）分子赋予聚合物多种刺激响应特性。PISA 是制备核壳纳米粒子（NPs）最有效的技术，但含游离硼酸单体的水分散 PISA 会因疏水核形成硼氧酐而变得复杂。在本研究中，N-苯基丙烯酰胺的游离含 BA 衍生物的分散可逆加成-断裂链转移（RAFT）共聚产生的 NP 形貌不同于不含 BA 的等效 PISA 均聚形成的 NP 形貌。根据条件的不同，PISA 会产生球状、棒状和蠕虫状的 NP，通过使用较高比例的非刺激响应单体来产生大的复合胶束，可以提高胶体稳定性。用水性分散溶剂或水稀释富含硼氧的共聚物 NPs，水解产生的 PISA 分散体的聚合后刺激响应可产生微米大小的蠕虫、薄片和囊泡。高阶形态的自组装受水解程度的影响。由此产生的游离含 BA 的 NPs 在碱化和添加葡萄糖后会变小并呈球形。
{"title":"Stimuli-responsive nanoparticles from RAFT dispersion polymerization-induced self-assembly (PISA) of N-phenylacrylamide copolymerized with a boronic acid-substituted derivative","authors":"","doi":"10.1016/j.eurpolymj.2024.113488","DOIUrl":"10.1016/j.eurpolymj.2024.113488","url":null,"abstract":"<div><div>Boronic acid (BA) moieties confer a variety of stimuli-response properties upon polymers. PISA is the most efficient technique for the preparation of core–shell nanoparticles (NPs), however aqueous dispersion PISA of free BA-containing monomers is complicated by the formation of the boroxine anhydride at the hydrophobic core. In the present work, dispersion reversible addition-fragmentation chain transfer (RAFT) copolymerization of a free BA-containing derivative of <em>N</em>-phenylacrylamide yields NP morphologies which are different to those formed from the equivalent PISA homopolymerization without BA. Depending on conditions, PISA results in spheres, rods, and worms with colloidal stability improved by using a higher fraction of the non-stimuli responsive monomer to give large compound micelles. Post-polymerization stimuli-response from the resultant PISA dispersion through hydrolysis of boroxine-rich copolymer NPs by dilution with the aqueous dispersion solvent or with water yields micron-sized worms, lamellae, and vesicles. Self-assembly to higher order morphologies is driven by the extent of hydrolysis. The resultant free BA-containing NPs becoming smaller and spherical upon basification and glucose addition.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424815","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 : 2024-10-01DOI: 10.1016/j.eurpolymj.2024.113486
Carbon-based materials demonstrate unique physical structures and chemical properties, thus used as effective functional fillers to enhance the properties of intumescent fire-retardant coatings. This review first introduces the classification, composition, and mechanisms of intumescent fire-retardant coatings. Then recent research advancements in carbon-based materials, such as carbon nanotubes, graphene, expandable graphite, and fullerenes applied in the intumescent fire-retardant coatings are summarized. Finally, this review presents future development prospects for carbon-based materials in areas such as early warning systems, self-healing, anti-corrosion, and anti-explosion.
{"title":"Research progress of carbon-based materials in intumescent fire-retardant coatings: A review","authors":"","doi":"10.1016/j.eurpolymj.2024.113486","DOIUrl":"10.1016/j.eurpolymj.2024.113486","url":null,"abstract":"<div><div>Carbon-based materials demonstrate unique physical structures and chemical properties, thus used as effective functional fillers to enhance the properties of intumescent fire-retardant coatings. This review first introduces the classification, composition, and mechanisms of intumescent fire-retardant coatings. Then recent research advancements in carbon-based materials, such as carbon nanotubes, graphene, expandable graphite, and fullerenes applied in the intumescent fire-retardant coatings are summarized. Finally, this review presents future development prospects for carbon-based materials in areas such as early warning systems, self-healing, anti-corrosion, and anti-explosion.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424873","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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