Pub Date : 2025-02-09DOI: 10.1016/j.eurpolymj.2025.113818
Aqila Che Ab Rahman , Siyoung Yang , Sooman Lim
The advancement of microneedle technology offers a promising alternative to conventional drug delivery methods by enhancing drug loading efficiency, controlled release, and patient comfort. In this study, we developed a high-resolution microneedle array fabricated via vat photopolymerization using a biocompatible UV-curable polymer. Engineered indentations were introduced to increase the surface area, enhancing drug loading capacity and improving drug uptake. Additionally, the microneedles were mounted on a mechanically adaptive substrate designed to accommodate dynamic movements and conform to curved or flexible surfaces. Mechanical characterization demonstrated that the microneedle patch withstood up to 46.8 ± 2 % strain without failure while maintaining penetration efficiency in rat skin. Drug release analysis showed an initial burst phase within the first 60 h, followed by a sustained release profile. The optimized microneedle design with a 0.25 mm indentation achieved a drug loading efficiency of 27.5 ± 0.6 % and a cumulative release of 37.6 ± 0.7 % after 25 h. These findings highlight the potential of biomimetic structural modifications and vat photopolymerization in advancing microneedle-based transdermal drug delivery, offering a minimally invasive, efficient, and patient-friendly alternative to conventional drug administration.
{"title":"Biocompatible microneedles with engineered indentation design fabricated via vat photopolymerization for enhanced transdermal drug delivery","authors":"Aqila Che Ab Rahman , Siyoung Yang , Sooman Lim","doi":"10.1016/j.eurpolymj.2025.113818","DOIUrl":"10.1016/j.eurpolymj.2025.113818","url":null,"abstract":"<div><div>The advancement of microneedle technology offers a promising alternative to conventional drug delivery methods by enhancing drug loading efficiency, controlled release, and patient comfort. In this study, we developed a high-resolution microneedle array fabricated via vat photopolymerization using a biocompatible UV-curable polymer. Engineered indentations were introduced to increase the surface area, enhancing drug loading capacity and improving drug uptake. Additionally, the microneedles were mounted on a mechanically adaptive substrate designed to accommodate dynamic movements and conform to curved or flexible surfaces. Mechanical characterization demonstrated that the microneedle patch withstood up to 46.8 ± 2 % strain without failure while maintaining penetration efficiency in rat skin. Drug release analysis showed an initial burst phase within the first 60 h, followed by a sustained release profile. The optimized microneedle design with a 0.25 mm indentation achieved a drug loading efficiency of 27.5 ± 0.6 % and a cumulative release of 37.6 ± 0.7 % after 25 h. These findings highlight the potential of biomimetic structural modifications and vat photopolymerization in advancing microneedle-based transdermal drug delivery, offering a minimally invasive, efficient, and patient-friendly alternative to conventional drug administration.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113818"},"PeriodicalIF":5.8,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419144","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}
Unsaturated polyesters (UPs) are a family of thermoset polymers largely used for glass fiber reinforced composite (GFRC) manufacturing, but their recycling is very challenging due to their crosslinked structure. Here, novel recyclable-by-design model unsaturated polymer resins were redesigned, positioning the C=C acrylic unsaturations as end groups and replacing styrene with alternative reactive diluents bearing –OH groups. The crosslinked polymers showed thermomechanical properties in line with conventional UPs, and the corresponding GFRCs containing 30 %vol of GFs were successfully prepared. Both the crosslinked unsaturated polymers and their composites were effectively solvolyzed in mild conditions (T = 200 °C, atmospheric pressure, t = 1–3 h) using different alcohols and glycols as solvent media, and 1,5,7-trazabicyclo[4.4.0]dec-5-ene as transesterification catalyst. Liberated GFs were found to be clean (as assessed by thermogravimetric analysis) and retained nearly 100 % of their original modulus and strength. The recovered organic recyclate showed a high –OH functional group reactivity and could be reused as hydroxylated binder in the formulation of bicomponent polyurethane coatings. These materials were found to exhibit excellent optical clarity, high Tg (> 100 °C), good substrate adhesion (3.45 MPa on glass), and moderate hydrophilicity (water contact angle of 65°). Finally, the same unsaturated polymer resins were prepared with the addition of the transesterification catalyst directly in the liquid prepolymer formulation. While the base physical properties of the crosslinked material remained unchanged, the resulting network showed a dynamic behavior, with thermally-induced stress-relaxation response clearly dependent on both hydroxyl group content and catalyst concentration, and easy post-cure thermoformability.
{"title":"Revisiting Unsaturated Polyesters: Recyclable-by-Design Vinylester Resins for the Circular Economy","authors":"Giulia Altamura, Eleonora Manarin, Gianmarco Griffini, Stefano Turri","doi":"10.1016/j.eurpolymj.2025.113819","DOIUrl":"10.1016/j.eurpolymj.2025.113819","url":null,"abstract":"<div><div>Unsaturated polyesters (UPs) are a family of thermoset polymers largely used for glass fiber reinforced composite (GFRC) manufacturing, but their recycling is very challenging due to their crosslinked structure. Here, novel recyclable-by-design model unsaturated polymer resins were redesigned, positioning the C=C acrylic unsaturations as end groups and replacing styrene with alternative reactive diluents bearing –OH groups. The crosslinked polymers showed thermomechanical properties in line with conventional UPs, and the corresponding GFRCs containing 30 %vol of GFs were successfully prepared. Both the crosslinked unsaturated polymers and their composites were effectively solvolyzed in mild conditions (T = 200 °C, atmospheric pressure, t = 1–3 h) using different alcohols and glycols as solvent media, and 1,5,7-trazabicyclo[4.4.0]dec-5-ene as transesterification catalyst. Liberated GFs were found to be clean (as assessed by thermogravimetric analysis) and retained nearly 100 % of their original modulus and strength. The recovered organic recyclate showed a high –OH functional group reactivity and could be reused as hydroxylated binder in the formulation of bicomponent polyurethane coatings. These materials were found to exhibit excellent optical clarity, high T<sub>g</sub> (> 100 °C), good substrate adhesion (3.45 MPa on glass), and moderate hydrophilicity (water contact angle of 65°). Finally, the same unsaturated polymer resins were prepared with the addition of the transesterification catalyst directly in the liquid prepolymer formulation. While the base physical properties of the crosslinked material remained unchanged, the resulting network showed a dynamic behavior, with thermally-induced stress-relaxation response clearly dependent on both hydroxyl group content and catalyst concentration, and easy post-cure thermoformability.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113819"},"PeriodicalIF":5.8,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.eurpolymj.2025.113797
Jingwen Lan , Zihan Wei , Rukuan Liu , Airong Xu
Although hydrogel sensors have broad application prospects in wearable devices, biomedical electronic skin, human–computer interaction and other fields, the hydrogel sensor with the synergy of robust mechanical behaviors, super freeze-resistant ability and signal output stability still remain challenged. To overcome the challenge, here, a novel hydrogel sensor AICG were developed using polyvinyl alcohol (PVA), glycidyl trimethyl ammonium chloride (EPTAC), polyethyleneimine (PEI) and ethylene glycol (EG). The effects of PVA, PEI, EPTAC and EG contents in AICG hydrogel on mechanical properties were systematically investigated. The notably boosted mechanical properties (antibreakage performance, fatigue-resistant ability) and super freeze-resistant performance are primarily ascribed to the superhydrogen-bond networks of PVA with PEI, EPTAC and EG. The hydrogel is so strong that it can load a 60 Kg boy and endure super low temperature (−120 ℃). Besides rendering AICG hydrogel good conductivity (5.56 mS·cm−1), EPTAC was used to graft it on the PVA/PEI macromolecular chains of AICG hydrogel via ring-opening reaction of EPTAC, thus impeding the leakage of EPTAC from the hydrogel as much as possible and improving conductive stability. On being used a sensor, it can accurately detect human joint movements and simulate electronic skin due to high sensitivity and stable signal output ability. It is expected that this study can provide valuable information for the design and fabrication of the hydrogel sensor with desired high performances.
{"title":"Ultra-anti-freezing robust hydrogel snesor","authors":"Jingwen Lan , Zihan Wei , Rukuan Liu , Airong Xu","doi":"10.1016/j.eurpolymj.2025.113797","DOIUrl":"10.1016/j.eurpolymj.2025.113797","url":null,"abstract":"<div><div>Although hydrogel sensors have broad application prospects in wearable devices, biomedical electronic skin, human–computer interaction and other fields, the hydrogel sensor with the synergy of robust mechanical behaviors, super freeze-resistant ability and signal output stability still remain challenged. To overcome the challenge, here, a novel hydrogel sensor AICG were developed using polyvinyl alcohol (PVA), glycidyl trimethyl ammonium chloride (EPTAC), polyethyleneimine (PEI) and ethylene glycol (EG). The effects of PVA, PEI, EPTAC and EG contents in AICG hydrogel on mechanical properties were systematically investigated. The notably boosted mechanical properties (antibreakage performance, fatigue-resistant ability) and super freeze-resistant performance are primarily ascribed to the superhydrogen-bond networks of PVA with PEI, EPTAC and EG. The hydrogel is so strong that it can load a 60 Kg boy and endure super low temperature (−120 ℃). Besides rendering AICG hydrogel good conductivity (5.56 mS·cm<sup>−1</sup>), EPTAC was used to graft it on the PVA/PEI macromolecular chains of AICG hydrogel via ring-opening reaction of EPTAC, thus impeding the leakage of EPTAC from the hydrogel as much as possible and improving conductive stability. On being used a sensor, it can accurately detect human joint movements and simulate electronic skin due to high sensitivity and stable signal output ability. It is expected that this study can provide valuable information for the design and fabrication of the hydrogel sensor with desired high performances.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113797"},"PeriodicalIF":5.8,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 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}
Pub Date : 2025-02-07DOI: 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-DMx 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-DMx matrix while preventing its deactivation during functionalization. This property facilitates the transition of CD-DMx 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-DMx 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}
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-PTPNm-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-PTPNm-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}
Pub Date : 2025-02-06DOI: 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}
Pub Date : 2025-02-06DOI: 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}
Pub Date : 2025-02-06DOI: 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}
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}
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