Pub Date : 2025-01-22DOI: 10.1016/j.reactfunctpolym.2025.106173
Heecheol Yun , Sangwoo Park , Jaewon Choi , Se Youn Cho , Hyo Won Kwak
Melamine sponge is widely used in various industrial applications owing to its high specific surface area and excellent mechanical properties. However, its practical use as an oil–water separation material is limited by the complex hydrophobization process and the use of non-renewable additives. Herein, we employed lignin, a wood-based biomass, as an amphiphilic connector to modify melamine foam with alkylated graphene oxide. Lignin was easily coated onto the melamine foam, enhancing its hydrophobicity and allowing for a continuous layer of alkylated graphene oxide. This process considerably improved the hydrophobicity of melamine foam, achieving a contact angle of 132.2°. Consequently, the hydrophobic melamine foam demonstrated selective oil absorption in oil-contaminated environments, with an oil adsorption capacity of 42–158 g/g and an excellent oil absorption efficiency of over 97 % even after 20 cycles. The additional alkylated graphene coating further enhanced flux when used as a filter material, enabling rapid and selective oil removal. Our study presents a straightforward, eco-friendly method for converting hydrophilic materials into hydrophobic surfaces using biomass-derived lignin.
{"title":"Melamine and hydrophobic graphene composite foam with lignin as a green connector for oil–water separation applications","authors":"Heecheol Yun , Sangwoo Park , Jaewon Choi , Se Youn Cho , Hyo Won Kwak","doi":"10.1016/j.reactfunctpolym.2025.106173","DOIUrl":"10.1016/j.reactfunctpolym.2025.106173","url":null,"abstract":"<div><div>Melamine sponge is widely used in various industrial applications owing to its high specific surface area and excellent mechanical properties. However, its practical use as an oil–water separation material is limited by the complex hydrophobization process and the use of non-renewable additives. Herein, we employed lignin, a wood-based biomass, as an amphiphilic connector to modify melamine foam with alkylated graphene oxide. Lignin was easily coated onto the melamine foam, enhancing its hydrophobicity and allowing for a continuous layer of alkylated graphene oxide. This process considerably improved the hydrophobicity of melamine foam, achieving a contact angle of 132.2°. Consequently, the hydrophobic melamine foam demonstrated selective oil absorption in oil-contaminated environments, with an oil adsorption capacity of 42–158 g/g and an excellent oil absorption efficiency of over 97 % even after 20 cycles. The additional alkylated graphene coating further enhanced flux when used as a filter material, enabling rapid and selective oil removal. Our study presents a straightforward, eco-friendly method for converting hydrophilic materials into hydrophobic surfaces using biomass-derived lignin.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"209 ","pages":"Article 106173"},"PeriodicalIF":4.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-22DOI: 10.1016/j.reactfunctpolym.2025.106171
Cangül Gümüş, Emrah Çakmakçi
Anti-smudge coatings are hydrophobic coatings that repel both water and oil. However, preparing substrate-independent, transparent, solvent-free, and easy-to-apply anti-smudge coatings is challenging. In this paper, we report a facile route for the preparation of anti-smudge coatings by using an oxetane-based photocurable formulation. 5 different additives (fluorinated alcohols, poly(dimethyl siloxane), hydrophobic silica nanoparticles, modified hollow silica nanoparticles, and modified polyhedral oligomeric silsesquioxane (POSS) particles were utilized to impart hydrophobicity. Fluorine-modified POSS particle-containing formulations displayed the best properties. The POSS-containing formulations were spray-coated onto different substrates. Coatings displayed high transparency and repelled water, coffee, and ink. Moreover, owing to the low viscosity of the oxetanes, the coating formulations could be sprayed without any solvent. Overall, herein, the advantages of cationic photocuring such as rapid curing and insensitivity to oxygen inhibition are combined with the low viscosity of oxetane monomers, and substrate-independent coatings are prepared. We think there is much room for these coatings to be used for a wide range of applications.
{"title":"Oxetane-based transparent anti-smudge coatings via solvent-free spray-deposition and cationic photopolymerization","authors":"Cangül Gümüş, Emrah Çakmakçi","doi":"10.1016/j.reactfunctpolym.2025.106171","DOIUrl":"10.1016/j.reactfunctpolym.2025.106171","url":null,"abstract":"<div><div>Anti-smudge coatings are hydrophobic coatings that repel both water and oil. However, preparing substrate-independent, transparent, solvent-free, and easy-to-apply anti-smudge coatings is challenging. In this paper, we report a facile route for the preparation of anti-smudge coatings by using an oxetane-based photocurable formulation. 5 different additives (fluorinated alcohols, poly(dimethyl siloxane), hydrophobic silica nanoparticles, modified hollow silica nanoparticles, and modified polyhedral oligomeric silsesquioxane (POSS) particles were utilized to impart hydrophobicity. Fluorine-modified POSS particle-containing formulations displayed the best properties. The POSS-containing formulations were spray-coated onto different substrates. Coatings displayed high transparency and repelled water, coffee, and ink. Moreover, owing to the low viscosity of the oxetanes, the coating formulations could be sprayed without any solvent. Overall, herein, the advantages of cationic photocuring such as rapid curing and insensitivity to oxygen inhibition are combined with the low viscosity of oxetane monomers, and substrate-independent coatings are prepared. We think there is much room for these coatings to be used for a wide range of applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"209 ","pages":"Article 106171"},"PeriodicalIF":4.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1016/j.reactfunctpolym.2025.106168
Jin Huang, Jiajun Ma, Junxiao Yang
Due to its excellent weather resistance, acrylonitrile-styrene-acrylate (ASA) resin is widely utilized. However, one critical challenge is its unsatisfactory impact property, which restricts its further application. Although various studies have been reported on improving the toughening effect of ASA resin, most of them reduce its strength and modulus. It is difficult to strike a balance between the improved toughening effect and the reduced strength and modulus. Herein, we designed a silicone rubber filled acrylate core to synthesize an acrylonitrile-styrene–acrylate@ silicone (Si-ASA) three-layer core-shell nanostructure copolymer via three-step emulsion polymerization. Introducing ductile silicone rubber into the interior of acrylate rubber microparticles can increase and refine the cavitation of the rubber layer upon impact. Meanwhile, the fibrillation of silicone cores can absorb impact energy and bridge cracks. SEM images demonstrated the formation of the three-layer nanostructure of Si-ASA. The mechanical property results showed that the prepared Si-ASA exhibits a significantly increased impact strength of approximately 19.5KJ/m2, which is nearly twice that of the commercial ASA. Considering the much higher impact property of Si-ASA, this slightly higher of modulus is significant. These indicate that the Si-ASA three-layer core-shell nanostructure copolymer, when applied to ASA resin helps in achieving rigid-tough balanced materials.
{"title":"Acrylonitrile-styrene–acrylate@ silicone three layers core-shell nanostructure copolymer with excellent impact toughness and highness-strength balance","authors":"Jin Huang, Jiajun Ma, Junxiao Yang","doi":"10.1016/j.reactfunctpolym.2025.106168","DOIUrl":"10.1016/j.reactfunctpolym.2025.106168","url":null,"abstract":"<div><div>Due to its excellent weather resistance, acrylonitrile-styrene-acrylate (ASA) resin is widely utilized. However, one critical challenge is its unsatisfactory impact property, which restricts its further application. Although various studies have been reported on improving the toughening effect of ASA resin, most of them reduce its strength and modulus. It is difficult to strike a balance between the improved toughening effect and the reduced strength and modulus. Herein, we designed a silicone rubber filled acrylate core to synthesize an acrylonitrile-styrene–acrylate@ silicone (Si-ASA) three-layer core-shell nanostructure copolymer via three-step emulsion polymerization. Introducing ductile silicone rubber into the interior of acrylate rubber microparticles can increase and refine the cavitation of the rubber layer upon impact. Meanwhile, the fibrillation of silicone cores can absorb impact energy and bridge cracks. SEM images demonstrated the formation of the three-layer nanostructure of Si-ASA. The mechanical property results showed that the prepared Si-ASA exhibits a significantly increased impact strength of approximately 19.5KJ/m<sup>2</sup>, which is nearly twice that of the commercial ASA. Considering the much higher impact property of Si-ASA, this slightly higher of modulus is significant. These indicate that the Si-ASA three-layer core-shell nanostructure copolymer, when applied to ASA resin helps in achieving rigid-tough balanced materials.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"209 ","pages":"Article 106168"},"PeriodicalIF":4.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-20DOI: 10.1016/j.reactfunctpolym.2025.106170
Lin Yang , Xueling Liu , Bingyue Song , Sixian Yang , Xiaojie Zhang , Chong Zhao , Yixiao Wu , Lei Zhang , Yanjun Huang
Effective and selective recovery of precious metal silver (Ag(I)) from wastewater can promote resource recycling and mitigate environmental pollution. In this study, dimercaptosuccinic acid (DMSA) functionalized polyhedral oligomeric silsesquioxane (POSS)-based hybrid polymer (DPHP) was synthesized and employed for the adsorption of Ag(I) from aqueous solution. The obtained adsorbent was characterized using SEM-EDS, XPS, solid-state 13C NMR, and 29Si NMR spectra. Batch adsorption experiments were conducted to evaluate the adsorption performance of DPHP for Ag(I). The results revealed that the maximum adsorption capacity of DPHP for Ag(I) was 494.65 mg g−1 at pH 4, and the adsorption process could be well described by pseudo-second-order and Sips models. Thermodynamic studies implied the adsorption of Ag(I) was an endothermic and spontaneous adsorption process in nature. Adsorption and desorption experiments demonstrated that the regeneration efficiency of DPHP remained above 83 % after five cycles and the preconcentration factor of DPHP was determined to be 125. Furthermore, DPHP exhibited selectivity to Ag(I) in solutions containing a variety of competitive metal ions and simulated industrial wastewater. Based on density functional theory (DFT) calculations, as well as XPS, FTIR, and Raman analyses, the interaction between Ag(I) and DPHP involved electrostatic attraction, ion exchange, and coordination, with the coordination mainly between thioether and carboxy groups and Ag(I) ions. Overall, DPHP is a promising adsorbent for the recovery of Ag(I) from aqueous solutions.
{"title":"Selective adsorption of silver(I) by dimercaptosuccinic acid (DMSA) functionalized polyhedral oligomeric silsesquioxane (POSS)-based hybrid polymer: Behavior and mechanism","authors":"Lin Yang , Xueling Liu , Bingyue Song , Sixian Yang , Xiaojie Zhang , Chong Zhao , Yixiao Wu , Lei Zhang , Yanjun Huang","doi":"10.1016/j.reactfunctpolym.2025.106170","DOIUrl":"10.1016/j.reactfunctpolym.2025.106170","url":null,"abstract":"<div><div>Effective and selective recovery of precious metal silver (Ag(I)) from wastewater can promote resource recycling and mitigate environmental pollution. In this study, dimercaptosuccinic acid (DMSA) functionalized polyhedral oligomeric silsesquioxane (POSS)-based hybrid polymer (DPHP) was synthesized and employed for the adsorption of Ag(I) from aqueous solution. The obtained adsorbent was characterized using SEM-EDS, XPS, solid-state <sup>13</sup>C NMR, and <sup>29</sup>Si NMR spectra. Batch adsorption experiments were conducted to evaluate the adsorption performance of DPHP for Ag(I). The results revealed that the maximum adsorption capacity of DPHP for Ag(I) was 494.65 mg g<sup>−1</sup> at pH 4, and the adsorption process could be well described by pseudo-second-order and Sips models. Thermodynamic studies implied the adsorption of Ag(I) was an endothermic and spontaneous adsorption process in nature. Adsorption and desorption experiments demonstrated that the regeneration efficiency of DPHP remained above 83 % after five cycles and the preconcentration factor of DPHP was determined to be 125. Furthermore, DPHP exhibited selectivity to Ag(I) in solutions containing a variety of competitive metal ions and simulated industrial wastewater. Based on density functional theory (DFT) calculations, as well as XPS, FTIR, and Raman analyses, the interaction between Ag(I) and DPHP involved electrostatic attraction, ion exchange, and coordination, with the coordination mainly between thioether and carboxy groups and Ag(I) ions. Overall, DPHP is a promising adsorbent for the recovery of Ag(I) from aqueous solutions.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"209 ","pages":"Article 106170"},"PeriodicalIF":4.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-20DOI: 10.1016/j.reactfunctpolym.2025.106169
Odunayo T. Ore , Ajibola A. Bayode , Adedapo O. Adeola , Stephen Sunday Emmanuel
This study presents an in-depth review of recent developments and advancements in the use of molecularly imprinted polymers (MIPs) for adsorptive denitrogenation and desulphurization of fuel oils, particularly over the last decade. MIPs, known for their specific identification of target molecules, have showed great potential in the removal of nitrogen and sulphur compounds from fuel oils, which are significant contributors to environmental pollution and difficult to eliminate using traditional refining processes, surpassing traditional adsorbents such as activated carbon and zeolites. The review focusses on the synthesis and design methodologies used to optimise MIPs for fuel purification, emphasising their selective adsorption capability, stability, and reusability. In addition, the removal efficiencies demonstrated by MIPs were elucidated in this review. Key challenges, such as MIP scalability, cost-effectiveness, and post-adsorption regeneration, are explored, along with recommendations for future research to overcome these issues. Future research directions include developing innovative imprinting processes, incorporating nanomaterials, and integrating MIPs with enhanced purification technologies to create hybrid systems. The findings from the reviewed studies highlighted the game-changing innovation exhibited by MIPs in the adsorptive denitrogenation and desulphurization of fuel oils, providing a cleaner and more efficient fuel processing solution while minimising environmental effect.
{"title":"Molecularly imprinted polymers for the adsorptive denitrogenation and desulphurization of fuel oils: A review","authors":"Odunayo T. Ore , Ajibola A. Bayode , Adedapo O. Adeola , Stephen Sunday Emmanuel","doi":"10.1016/j.reactfunctpolym.2025.106169","DOIUrl":"10.1016/j.reactfunctpolym.2025.106169","url":null,"abstract":"<div><div>This study presents an in-depth review of recent developments and advancements in the use of molecularly imprinted polymers (MIPs) for adsorptive denitrogenation and desulphurization of fuel oils, particularly over the last decade. MIPs, known for their specific identification of target molecules, have showed great potential in the removal of nitrogen and sulphur compounds from fuel oils, which are significant contributors to environmental pollution and difficult to eliminate using traditional refining processes, surpassing traditional adsorbents such as activated carbon and zeolites. The review focusses on the synthesis and design methodologies used to optimise MIPs for fuel purification, emphasising their selective adsorption capability, stability, and reusability. In addition, the removal efficiencies demonstrated by MIPs were elucidated in this review. Key challenges, such as MIP scalability, cost-effectiveness, and post-adsorption regeneration, are explored, along with recommendations for future research to overcome these issues. Future research directions include developing innovative imprinting processes, incorporating nanomaterials, and integrating MIPs with enhanced purification technologies to create hybrid systems. The findings from the reviewed studies highlighted the game-changing innovation exhibited by MIPs in the adsorptive denitrogenation and desulphurization of fuel oils, providing a cleaner and more efficient fuel processing solution while minimising environmental effect.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106169"},"PeriodicalIF":4.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.reactfunctpolym.2025.106172
Shuang Han , Fei Wang , Fubang Huang , Weidong Zhang
The utility of multiple stimuli to induce reversible deactivation radical polymerizations (RDRPs) is a challenge in synthetic macromolecules. Herein, the quaternary ammonium salt (QAS) generated in situ from methyl bromophenylacetate (MBPA) and N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) is reported for the first time. Moreover, QAS generated in situ serving as radical precursors can be successfully employed to trigger RAFT polymerization in response to light and heat due to high reactivity of C-N bond. The living features are confirmed by polymerization kinetics and chain extension experiments in both cases. More interesting, stimulus-triggered radical release from the in situ formed QAS is able to develop logic-controlled RAFT polymerization with heat and light.
{"title":"Quaternary ammonium salt approach for light and thermo dual stimulus-triggered RAFT polymerization","authors":"Shuang Han , Fei Wang , Fubang Huang , Weidong Zhang","doi":"10.1016/j.reactfunctpolym.2025.106172","DOIUrl":"10.1016/j.reactfunctpolym.2025.106172","url":null,"abstract":"<div><div>The utility of multiple stimuli to induce reversible deactivation radical polymerizations (RDRPs) is a challenge in synthetic macromolecules. Herein, the quaternary ammonium salt (QAS) generated <em>in situ</em> from methyl bromophenylacetate (MBPA) and <em>N,N,N′,N′′,N′′</em>-pentamethyldiethylenetriamine (PMDETA) is reported for the first time. Moreover, QAS generated <em>in situ</em> serving as radical precursors can be successfully employed to trigger RAFT polymerization in response to light and heat due to high reactivity of C-N bond. The living features are confirmed by polymerization kinetics and chain extension experiments in both cases. More interesting, stimulus-triggered radical release from the <em>in situ</em> formed QAS is able to develop logic-controlled RAFT polymerization with heat and light.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106172"},"PeriodicalIF":4.5,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.reactfunctpolym.2025.106166
Klara Jastak, Nicolas Désilles, Fabrice Burel, Laurence Lecamp
This work aimed to develop an original, biobased, semi-aromatic and UV crosslinked unsaturated polyester, synthesized from a pyridine dicarboxylic acid derivative and an unsaturated aliphatic fatty acid derivative having 18 carbon atoms. A prepolymer with a number average molar mass of 1700 g/mol was synthesized and characterized by FTIR and NMR. This liquid prepolymer was then crosslinked under UV using a biobased compound, 7-mercapto-4-methyl coumarin (MMC), in two concomitant steps: the photografting of MMC onto the prepolymer by thiol-ene addition, and the photodimerization of MMC. The optimized conditions for the photochemical reaction were determined by evaluating the influence of formulation composition (thiol/fatty double bonds ratio from 0.1/1 to 1/1), temperature and irradiation time. In the end, relatively soft coatings (König hardness: 14.8 ± 0.8 s, Tg = −34 °C) were produced after 1 h under UV irradiation at 30 °C with 0.1 equivalent of MMC.
{"title":"Photocrosslinking of an original biobased and semi-aromatic unsaturated polyester by combined thiol-ene and cycloaddition routes","authors":"Klara Jastak, Nicolas Désilles, Fabrice Burel, Laurence Lecamp","doi":"10.1016/j.reactfunctpolym.2025.106166","DOIUrl":"10.1016/j.reactfunctpolym.2025.106166","url":null,"abstract":"<div><div>This work aimed to develop an original, biobased, semi-aromatic and UV crosslinked unsaturated polyester, synthesized from a pyridine dicarboxylic acid derivative and an unsaturated aliphatic fatty acid derivative having 18 carbon atoms. A prepolymer with a number average molar mass of 1700 g/mol was synthesized and characterized by FTIR and NMR. This liquid prepolymer was then crosslinked under UV using a biobased compound, 7-mercapto-4-methyl coumarin (MMC), in two concomitant steps: the photografting of MMC onto the prepolymer by thiol-ene addition, and the photodimerization of MMC. The optimized conditions for the photochemical reaction were determined by evaluating the influence of formulation composition (thiol/fatty double bonds ratio from 0.1/1 to 1/1), temperature and irradiation time. In the end, relatively soft coatings (König hardness: 14.8 ± 0.8 s, T<sub>g</sub> = −34 °C) were produced after 1 h under UV irradiation at 30 °C with 0.1 equivalent of MMC.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106166"},"PeriodicalIF":4.5,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
It is still a great challenge to treat oily wastewater and organic dyes in a complex and variable water environment. In this study, polyacrylonitrile (PAN)/polyurethane (PU) was modified by the synthesis of porous nano-zeolite imidazolium skeleton (ZIF-8), and PAN/PU@ZIF-8 composite nanofiber membranes with high hydrophobicity were prepared by electrospinning technology. After the synergistic effect of ZIF-8 and PU, the prepared fibrous membranes showed excellent superhydrophobic properties with a contact angle of 150.5° to water in air. The prepared PAN/PU@ZIF-8 composite nanofiber membranes showed good separation effects on different oil/water mixtures and water-in-oil (W/O) emulsions, with oil fluxes of up to 6391.01 L·m−2·h−1 for different oil/water mixtures and the separation efficiencies were all above 99.15 %. Meanwhile, the separation fluxes of several different W/O emulsions were up to 943.47 L·m−2·h−1, and the separation efficiencies were all above 98.6 %. Not only that, the PAN/PU@ZIF-8 composite nanofiber membrane possessed good adsorption effect on common organic dyes such as rhodamine B (RhB) and methylene blue (MB), and the maximum adsorption amount was up to 93.80 mg/g. Meanwhile, the removal of MB and RhB by the prepared nanofiber membrane was 96.84 % and 83.66 % within 3 h, respectively. In conclusion, we prepared a ZIF-8 doped superhydrophobic PAN/PU@ZIF-8 composite nanofiber membrane by electrospinning technology, which is capable of separating W/O emulsions. It is capable of separating W/O emulsion and adsorbing organic dyes at the same time, which provides a new vision and direction for the treatment of oily wastewater and organic dyes in the complex and variable water environment.
{"title":"Preparation of ZIF-8 modified PAN/PU superhydrophobic-superoleophilic composite nanofiber membranes for oil/water separation and dye adsorption","authors":"Shaokang Fang, Yanan Li, Huizi Yu, Huirong Li, Shida Feng, Shuai Wang, Xiaoyu Chen, Jintong Li, Yushan Yuan, Xue Wang, Yue Yu, Hong Zhang","doi":"10.1016/j.reactfunctpolym.2025.106160","DOIUrl":"10.1016/j.reactfunctpolym.2025.106160","url":null,"abstract":"<div><div>It is still a great challenge to treat oily wastewater and organic dyes in a complex and variable water environment. In this study, polyacrylonitrile (PAN)/polyurethane (PU) was modified by the synthesis of porous nano-zeolite imidazolium skeleton (ZIF-8), and PAN/PU@ZIF-8 composite nanofiber membranes with high hydrophobicity were prepared by electrospinning technology. After the synergistic effect of ZIF-8 and PU, the prepared fibrous membranes showed excellent superhydrophobic properties with a contact angle of 150.5° to water in air. The prepared PAN/PU@ZIF-8 composite nanofiber membranes showed good separation effects on different oil/water mixtures and water-in-oil (W/O) emulsions, with oil fluxes of up to 6391.01 L·m<sup>−2</sup>·h<sup>−1</sup> for different oil/water mixtures and the separation efficiencies were all above 99.15 %. Meanwhile, the separation fluxes of several different W/O emulsions were up to 943.47 L·m<sup>−2</sup>·h<sup>−1</sup>, and the separation efficiencies were all above 98.6 %. Not only that, the PAN/PU@ZIF-8 composite nanofiber membrane possessed good adsorption effect on common organic dyes such as rhodamine B (RhB) and methylene blue (MB), and the maximum adsorption amount was up to 93.80 mg/g. Meanwhile, the removal of MB and RhB by the prepared nanofiber membrane was 96.84 % and 83.66 % within 3 h, respectively. In conclusion, we prepared a ZIF-8 doped superhydrophobic PAN/PU@ZIF-8 composite nanofiber membrane by electrospinning technology, which is capable of separating W/O emulsions. It is capable of separating W/O emulsion and adsorbing organic dyes at the same time, which provides a new vision and direction for the treatment of oily wastewater and organic dyes in the complex and variable water environment.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"209 ","pages":"Article 106160"},"PeriodicalIF":4.5,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chitin, the second most abundant natural polymer after cellulose, is mainly sourced from fungal waste and crustacean exoskeletons. It can be deacetylated to yield chitosan, a biocompatible and renewable material with versatile applications due to its reactive amino groups, allowing modifications like the one presented here, namely the synthesis of a novel chitosan derivative (ChDEEM) through a conjugate addition-elimination reaction with diethylethoxymethylenemalonate (DEEM). The reaction was conducted under various conditions to optimize the degree of substitution (DS) of the chitosan derivative (ChDEEM). Stoichiometry (1:1.5, 1:1.75, 1:2 Ch:DEEM), temperature (60, 70, and 80 °C), and reaction time (1, 2, and 3 h) were varied. ChDEEM was characterized by a range of techniques including Fourier Transform Infrared Spectroscopy (FTIR), Carbon-13 Nuclear Magnetic Resonance (13C NMR), Thermogravimetric analysis (TGA), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Zeta Potential, Contact Angle (CA) and Elemental Analysis (EA). FTIR confirmed the successful modification, with a sharp peak at 805 cm−1 corresponding to the CC bond stretch. 13C NMR analysis showed new chemical shifts (158, 166, 87 and 11 ppm), and in combination with EA, was used to estimate the degree of substitution (DS) as 0.225 and 0.291, respectively. While SEM revealed no significant morphological changes, TGA indicated a decrease in thermal stability and Zeta Potential suggested reduced colloidal stability. Conversely, contact angle measurements showed increased hydrophobicity and decreased surface energy. Finally, XRD analysis revealed a decrease in the crystallinity index (from 79 % to 38 %) of ChDEEM compared to chitosan, likely due to the incorporation of methylenemalonate groups.
{"title":"Synthesis of a chitosan derivative via conjugate addition-elimination with diethylethoxymethylenemalonate and its physicochemical properties","authors":"Samir Leite Mathias , Robson Valentim Pereira , Aparecido Junior de Menezes , Alain Dufresne","doi":"10.1016/j.reactfunctpolym.2025.106167","DOIUrl":"10.1016/j.reactfunctpolym.2025.106167","url":null,"abstract":"<div><div>Chitin, the second most abundant natural polymer after cellulose, is mainly sourced from fungal waste and crustacean exoskeletons. It can be deacetylated to yield chitosan, a biocompatible and renewable material with versatile applications due to its reactive amino groups, allowing modifications like the one presented here, namely the synthesis of a novel chitosan derivative (ChDEEM) through a conjugate addition-elimination reaction with diethylethoxymethylenemalonate (DEEM). The reaction was conducted under various conditions to optimize the degree of substitution (DS) of the chitosan derivative (ChDEEM). Stoichiometry (1:1.5, 1:1.75, 1:2 Ch:DEEM), temperature (60, 70, and 80 °C), and reaction time (1, 2, and 3 h) were varied. ChDEEM was characterized by a range of techniques including Fourier Transform Infrared Spectroscopy (FTIR), Carbon-13 Nuclear Magnetic Resonance (<sup>13</sup>C NMR), Thermogravimetric analysis (TGA), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Zeta Potential, Contact Angle (CA) and Elemental Analysis (EA). FTIR confirmed the successful modification, with a sharp peak at 805 cm<sup>−1</sup> corresponding to the C<img>C bond stretch. <sup>13</sup>C NMR analysis showed new chemical shifts (158, 166, 87 and 11 ppm), and in combination with EA, was used to estimate the degree of substitution (DS) as 0.225 and 0.291, respectively. While SEM revealed no significant morphological changes, TGA indicated a decrease in thermal stability and Zeta Potential suggested reduced colloidal stability. Conversely, contact angle measurements showed increased hydrophobicity and decreased surface energy. Finally, XRD analysis revealed a decrease in the crystallinity index (from 79 % to 38 %) of ChDEEM compared to chitosan, likely due to the incorporation of methylenemalonate groups.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106167"},"PeriodicalIF":4.5,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-13DOI: 10.1016/j.reactfunctpolym.2025.106165
Yifan Zhao , Tong Qiu , Chige Zhuang , Dan Li , Zimin Wan , Hua Zheng , Xueqiong Zhang
In this study, ascorbic acid (HASc)-responsive nano-particles were designed to co-deliver the ferroptosis inducer Baicalin (BAI) and the chemotherapeutic drug cisplatin (Pt(II)) to tumor sites, aiming for a synergistic effect of chemotherapy(CT) and ferroptosis. Using CMCS as the carrier, the small-molecule pro-drug cis-Pt(IV)-COOH was grafted onto the carrier to create an amphiphilic polymer pro-drug. Single-drug nano-particles M(Pt) and dual-drug nano-particles M(BAI/Pt) were obtained by ultrasonically self-assembling BAI encapsulated in hydrophobic cores. The M(BAI/Pt) exhibited an average diameter of 211.37 3.01 nm, a polydispersity index (PDI) of 0.196 0.015, and a surface charge of −14.93 0.72 mV, demonstrating excellent stability. Given that cis-Pt(IV)-COOH is sensitive to HASc, the nanoparticles could quickly release Pt(II) with 83.22 % efficiency in simulated tumor cells. Meanwhile, the nanoparticles disintegrated and released BAI with 84.35 % efficiency as well. BAI can induce the accumulation of lipid peroxides by down-regulating GPX4, while Pt(II) contributes to iron ion accumulation. The combined treatment strategy aims to achieve an effective synergistic approach between chemotherapy and ferroptosis. In vitro toxicity studies indicated that the M(BAI/Pt1–1) exhibited significant cytotoxicity, synergistic impact (CI = 0.94) and strong selectivity (SI = 1.60) against 4 T1 cells. Mitochondrial membrane potential assessments and intracellular ROS and MDA analyses indicated that the M(BAI/Pt1–1) generated substantial ROS, causing mitochondrial structural damage and lipid peroxidation in 4 T1 cells. The M(BAI/Pt1–1) induced ferroptosis in 4 T1 cells by downregulating GPX4 expression and decreasing GSH levels, ultimately inhibiting in vitro tumor cell proliferation effectively. Consequently, these nano-particles provide fresh strategy to cancer treatment by combining chemotherapy with ferroptosis.
{"title":"HASc-responsive dual-drug nano-particles for co-delivery of Pt(II) and BAI for combination therapy of tumors","authors":"Yifan Zhao , Tong Qiu , Chige Zhuang , Dan Li , Zimin Wan , Hua Zheng , Xueqiong Zhang","doi":"10.1016/j.reactfunctpolym.2025.106165","DOIUrl":"10.1016/j.reactfunctpolym.2025.106165","url":null,"abstract":"<div><div>In this study, ascorbic acid (HASc)-responsive nano-particles were designed to co-deliver the ferroptosis inducer Baicalin (BAI) and the chemotherapeutic drug cisplatin (Pt(II)) to tumor sites, aiming for a synergistic effect of chemotherapy(CT) and ferroptosis. Using CMCS as the carrier, the small-molecule pro-drug cis-Pt(IV)-COOH was grafted onto the carrier to create an amphiphilic polymer pro-drug. Single-drug nano-particles M(Pt) and dual-drug nano-particles M(BAI/Pt) were obtained by ultrasonically self-assembling BAI encapsulated in hydrophobic cores. The M(BAI/Pt) exhibited an average diameter of 211.37 <span><math><mo>±</mo></math></span> 3.01 nm, a polydispersity index (PDI) of 0.196 <span><math><mo>±</mo></math></span> 0.015, and a surface charge of −14.93 <span><math><mo>±</mo></math></span> 0.72 mV, demonstrating excellent stability. Given that cis-Pt(IV)-COOH is sensitive to HASc, the nanoparticles could quickly release Pt(II) with 83.22 % efficiency in simulated tumor cells. Meanwhile, the nanoparticles disintegrated and released BAI with 84.35 % efficiency as well. BAI can induce the accumulation of lipid peroxides by down-regulating GPX4, while Pt(II) contributes to iron ion accumulation. The combined treatment strategy aims to achieve an effective synergistic approach between chemotherapy and ferroptosis. <em>In vitro</em> toxicity studies indicated that the M(BAI/Pt<sub>1</sub><sub>–</sub><sub>1</sub>) exhibited significant cytotoxicity, synergistic impact (CI = 0.94) and strong selectivity (SI = 1.60) against 4 T1 cells. Mitochondrial membrane potential assessments and intracellular ROS and MDA analyses indicated that the M(BAI/Pt<sub>1</sub><sub>–</sub><sub>1</sub>) generated substantial ROS, causing mitochondrial structural damage and lipid peroxidation in 4 T1 cells. The M(BAI/Pt<sub>1</sub><sub>–</sub><sub>1</sub>) induced ferroptosis in 4 T1 cells by downregulating GPX4 expression and decreasing GSH levels, ultimately inhibiting <em>in vitro</em> tumor cell proliferation effectively. Consequently, these nano-particles provide fresh strategy to cancer treatment by combining chemotherapy with ferroptosis.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106165"},"PeriodicalIF":4.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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