This study presents a sustainable approach to utilizing carbon dioxide (CO2) by converting it into cyclic carbonates, providing a viable strategy to address carbon emissions. A modified polyethersulfone (PES) was developed and applied as a robust heterogeneous catalyst for this transformation under solvent-free conditions. Under optimized conditions (60 °C, 10 atm, 6 h, and 0.05 g of catalyst), the catalyst demonstrated high efficiency, achieving 91–98 % yields. Notably, PES showed excellent reusability, retaining its performance with minimal reduction in yield after 11 consecutive cycles. These results emphasize the catalyst's potential for environmentally friendly applications in CO2 utilization and sustainable chemical processes.
{"title":"ZnBr2/modified polyethersulfone as a new catalytic system for the efficient coupling of CO2 with epoxides","authors":"Mehdi Khalaj , Maryam Bakhtiari , Seyed Mahmoud Musavi Safavi , Majid Ghashang","doi":"10.1016/j.reactfunctpolym.2025.106609","DOIUrl":"10.1016/j.reactfunctpolym.2025.106609","url":null,"abstract":"<div><div>This study presents a sustainable approach to utilizing carbon dioxide (CO<sub>2</sub>) by converting it into cyclic carbonates, providing a viable strategy to address carbon emissions. A modified polyethersulfone (PES) was developed and applied as a robust heterogeneous catalyst for this transformation under solvent-free conditions. Under optimized conditions (60 °C, 10 atm, 6 h, and 0.05 g of catalyst), the catalyst demonstrated high efficiency, achieving 91–98 % yields. Notably, PES showed excellent reusability, retaining its performance with minimal reduction in yield after 11 consecutive cycles. These results emphasize the catalyst's potential for environmentally friendly applications in CO<sub>2</sub> utilization and sustainable chemical processes.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106609"},"PeriodicalIF":5.1,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884674","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 : 2025-12-18DOI: 10.1016/j.reactfunctpolym.2025.106617
Junshuang Zhang , Wenwen Feng , Huizhu Xing , Shufan Chen , Ning Qi , Tong Li , Guan Bai
Traditional membrane materials used for treating oily wastewater from ships often suffer from complex fabrication processes, the use of toxic reagents, and limited capability for efficiently separating emulsified oils under atmospheric conditions. In this study, a natural silkworm cocoon was used as the substrate, onto which a hydrogel coating was constructed through the crosslinking reaction between silk fibroin (SF) and chitosan (CS). Lithium chloride (LiCl) was further incorporated to regulate the membrane properties. Through this strategy, a novel composite separation membrane, cocoon/CS@SF/LiCl (RCSL), was successfully fabricated. The RCSL membrane exhibited superhydrophilic and underwater superoleophobic characteristics, with a water contact angle (WCA) of 0° and an underwater oil contact angle (UOCA) of 152 ± 1°. It achieved separation efficiencies exceeding 98 % for five types of oil-in-water emulsions, including diesel-in-water (D/W) and lubricating oil-in-water (L/W) systems. Moreover, the RCSL membrane demonstrated excellent chemical stability in corrosive environments, such as HCl solution (pH = 3), NaOH solution (pH = 10), and 3.5 wt% NaCl solution, while maintaining a maximum tensile strength of 36.1 MPa—meeting the mechanical requirements for practical applications. This work provides a new strategy for developing efficient, stable, and environmentally friendly membranes for oil–water separation, offering promising potential for applications in the treatment of oily wastewater from ships and related fields.
{"title":"Silk fibroin/chitosan composite cocoon membranes regulated by lithium chloride for atmospheric-pressure oil–water separation","authors":"Junshuang Zhang , Wenwen Feng , Huizhu Xing , Shufan Chen , Ning Qi , Tong Li , Guan Bai","doi":"10.1016/j.reactfunctpolym.2025.106617","DOIUrl":"10.1016/j.reactfunctpolym.2025.106617","url":null,"abstract":"<div><div>Traditional membrane materials used for treating oily wastewater from ships often suffer from complex fabrication processes, the use of toxic reagents, and limited capability for efficiently separating emulsified oils under atmospheric conditions. In this study, a natural silkworm cocoon was used as the substrate, onto which a hydrogel coating was constructed through the crosslinking reaction between silk fibroin (SF) and chitosan (CS). Lithium chloride (LiCl) was further incorporated to regulate the membrane properties. Through this strategy, a novel composite separation membrane, cocoon/CS@SF/LiCl (RCSL), was successfully fabricated. The RCSL membrane exhibited superhydrophilic and underwater superoleophobic characteristics, with a water contact angle (WCA) of 0° and an underwater oil contact angle (UOCA) of 152 ± 1°. It achieved separation efficiencies exceeding 98 % for five types of oil-in-water emulsions, including diesel-in-water (D/W) and lubricating oil-in-water (L/W) systems. Moreover, the RCSL membrane demonstrated excellent chemical stability in corrosive environments, such as HCl solution (pH = 3), NaOH solution (pH = 10), and 3.5 wt% NaCl solution, while maintaining a maximum tensile strength of 36.1 MPa—meeting the mechanical requirements for practical applications. This work provides a new strategy for developing efficient, stable, and environmentally friendly membranes for oil–water separation, offering promising potential for applications in the treatment of oily wastewater from ships and related fields.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106617"},"PeriodicalIF":5.1,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884676","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 : 2025-12-18DOI: 10.1016/j.reactfunctpolym.2025.106613
Jihyun Lee , Ganga Ratnamma Rudru , Kyung-Man Choi , Ildoo Chung
Ultra-stretchable polymeric elastomers with excellent mechanical properties are in high demand for diverse applications, particularly in stretchable electronics. However, achieving both high tensile strength and large elongation remains a major challenge due to the inherent trade-off between strength and stretchability. In this study, highly stretchable polyurethanes were synthesized by incorporating slide-ring polyrotaxanes (PRs) as both chain extenders and crosslinkers. The sliding mechanism of PR crosslinks effectively dissipates stress during deformation while maintaining network integrity, thereby overcoming the conventional limitation between strength and stretchability. PR, a molecularly threaded supramolecular structure, was first synthesized by combining poly(propylene glycol) (PPG) with β-cyclodextrin (β-CD) to form a pseudo-polyrotaxane, which was subsequently end-capped with trityl glycine to prevent dethreading. Using this PR, flexible polyurethanes were synthesized with slide-ring PR as a chain extender, together with 1,4-butanediol (1,4-BD) and β-CD, yielding elastomeric networks with enhanced molecular mobility and flexibility. The synthesized PRs and polyurethanes were characterized by spectroscopic, thermal, and mechanical analyses. Compared with conventional 1,4-BD crosslinked systems, PR-crosslinked polyurethanes exhibited distinct thermal behavior, attributed to the intrinsic mobility of PR crosslinks. Notably, polyurethanes containing 75 % PR achieved ultra-stretchable elongation at break while retaining tensile strength. Furthermore, PR-based polyurethanes simultaneously exhibited enhanced tensile strength, elongation, and toughness compared with chemically crosslinked BDPU, due to the synergistic effects of slide-ring mobility and β-CD supramolecular interactions. These findings establish slide-ring PR-based chain extension and crosslinking as an effective molecular design strategy for next-generation polyurethane elastomers with synergistically improved strength and stretchability.
{"title":"Highly stretchable polyurethanes synthesized via slide-ring polyrotaxanes as chain extenders and crosslinkers with enhanced mechanical properties","authors":"Jihyun Lee , Ganga Ratnamma Rudru , Kyung-Man Choi , Ildoo Chung","doi":"10.1016/j.reactfunctpolym.2025.106613","DOIUrl":"10.1016/j.reactfunctpolym.2025.106613","url":null,"abstract":"<div><div>Ultra-stretchable polymeric elastomers with excellent mechanical properties are in high demand for diverse applications, particularly in stretchable electronics. However, achieving both high tensile strength and large elongation remains a major challenge due to the inherent trade-off between strength and stretchability. In this study, highly stretchable polyurethanes were synthesized by incorporating slide-ring polyrotaxanes (PRs) as both chain extenders and crosslinkers. The sliding mechanism of PR crosslinks effectively dissipates stress during deformation while maintaining network integrity, thereby overcoming the conventional limitation between strength and stretchability. PR, a molecularly threaded supramolecular structure, was first synthesized by combining poly(propylene glycol) (PPG) with β-cyclodextrin (β-CD) to form a pseudo-polyrotaxane, which was subsequently end-capped with trityl glycine to prevent dethreading. Using this PR, flexible polyurethanes were synthesized with slide-ring PR as a chain extender, together with 1,4-butanediol (1,4-BD) and β-CD, yielding elastomeric networks with enhanced molecular mobility and flexibility. The synthesized PRs and polyurethanes were characterized by spectroscopic, thermal, and mechanical analyses. Compared with conventional 1,4-BD crosslinked systems, PR-crosslinked polyurethanes exhibited distinct thermal behavior, attributed to the intrinsic mobility of PR crosslinks. Notably, polyurethanes containing 75 % PR achieved ultra-stretchable elongation at break while retaining tensile strength. Furthermore, PR-based polyurethanes simultaneously exhibited enhanced tensile strength, elongation, and toughness compared with chemically crosslinked BDPU, due to the synergistic effects of slide-ring mobility and β-CD supramolecular interactions. These findings establish slide-ring PR-based chain extension and crosslinking as an effective molecular design strategy for next-generation polyurethane elastomers with synergistically improved strength and stretchability.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106613"},"PeriodicalIF":5.1,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884673","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}
Casein, a sustainable and protein-rich biopolymer derived from milk, has recently exhibited excellent prospects as an efficient building block for the synthesis of eco-friendly materials for water purification. Its abundance of functional groups, intrinsic biocompatibility, and ease of creating composite or hybrid structures render it a potential choice for adsorbents, membranes, and catalytic supports to be employed for the elimination of heavy metals, dyes, drugs, and emerging contaminants. This review critically surveys progress in the design of casein-based materials; chemically modified casein and polymer–casein mixtures to hybrid casein-nanomaterials; and their performance characteristics, regenerability, and environmental impact. Opportunities for innovation, such as newer functionalization strategies, blending with low-cost renewable fillers, and photocatalytic or antimicrobial agent use, are highlighted. Mechanical stability, scalability, and raw casein availability variability issues are discussed alongside environmental and regulatory matters. The review concludes with future directions for valorizing casein in a circular bioeconomy context, aiming to optimize, scale up, and translate laboratory successes into effective water treatment processes.
{"title":"Sustainable casein-derived materials for water purification: opportunities, challenges, progress, and perspectives","authors":"Noureddine El Messaoudi , Youssef Miyah , Jordana Georgin , Dison S.P. Franco , Mesut Yılmazoğlu , Tarek Kouka , Mouslim Messali","doi":"10.1016/j.reactfunctpolym.2025.106612","DOIUrl":"10.1016/j.reactfunctpolym.2025.106612","url":null,"abstract":"<div><div>Casein, a sustainable and protein-rich biopolymer derived from milk, has recently exhibited excellent prospects as an efficient building block for the synthesis of eco-friendly materials for water purification. Its abundance of functional groups, intrinsic biocompatibility, and ease of creating composite or hybrid structures render it a potential choice for adsorbents, membranes, and catalytic supports to be employed for the elimination of heavy metals, dyes, drugs, and emerging contaminants. This review critically surveys progress in the design of casein-based materials; chemically modified casein and polymer–casein mixtures to hybrid casein-nanomaterials; and their performance characteristics, regenerability, and environmental impact. Opportunities for innovation, such as newer functionalization strategies, blending with low-cost renewable fillers, and photocatalytic or antimicrobial agent use, are highlighted. Mechanical stability, scalability, and raw casein availability variability issues are discussed alongside environmental and regulatory matters. The review concludes with future directions for valorizing casein in a circular bioeconomy context, aiming to optimize, scale up, and translate laboratory successes into effective water treatment processes.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106612"},"PeriodicalIF":5.1,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799429","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 : 2025-12-16DOI: 10.1016/j.reactfunctpolym.2025.106615
Longfa Lan , Jiayan Zhou , Hongqing Cheng , Jing Liu , Dongying Hu
The development of eco-friendly wood adhesives from biomass polymers is challenging due to their poor water resistance and low wet bonding strength. To overcome these limitations, a modified guar gum (MGG) adhesive was developed via a combined approach of acrylate grafting, epoxy ring-opening, and silane coupling. This chemical modification established a stable cross-linked network, significantly enhancing cohesive and interfacial adhesion. The viscosity of MGG was reduced to about 900 mPa·s, greatly improving coatability compared to raw GG (6000 mPa·s at 1 % concentration). The optimized adhesive showed a dry bonding strength of 1.67 MPa and a wet bonding strength of 0.84 MPa, outperforming many previously reported biomass-based adhesives. Improved thermal stability and moisture resistance were also confirmed, attributed to introduced aldehyde and ether groups that promote dense crosslinking. This work not only demonstrates a viable pathway to overcome the intrinsic weaknesses of GG, but also highlights MGG as a sustainable and high-performance alternative to conventional formaldehyde-based wood adhesives, providing both practical applicability and scientific significance.
{"title":"Development of chemically modified guar gum adhesives for enhanced wood bonding performance","authors":"Longfa Lan , Jiayan Zhou , Hongqing Cheng , Jing Liu , Dongying Hu","doi":"10.1016/j.reactfunctpolym.2025.106615","DOIUrl":"10.1016/j.reactfunctpolym.2025.106615","url":null,"abstract":"<div><div>The development of eco-friendly wood adhesives from biomass polymers is challenging due to their poor water resistance and low wet bonding strength. To overcome these limitations, a modified guar gum (MGG) adhesive was developed via a combined approach of acrylate grafting, epoxy ring-opening, and silane coupling. This chemical modification established a stable cross-linked network, significantly enhancing cohesive and interfacial adhesion. The viscosity of MGG was reduced to about 900 mPa·s, greatly improving coatability compared to raw GG (6000 mPa·s at 1 % concentration). The optimized adhesive showed a dry bonding strength of 1.67 MPa and a wet bonding strength of 0.84 MPa, outperforming many previously reported biomass-based adhesives. Improved thermal stability and moisture resistance were also confirmed, attributed to introduced aldehyde and ether groups that promote dense crosslinking. This work not only demonstrates a viable pathway to overcome the intrinsic weaknesses of GG, but also highlights MGG as a sustainable and high-performance alternative to conventional formaldehyde-based wood adhesives, providing both practical applicability and scientific significance.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106615"},"PeriodicalIF":5.1,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799428","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 : 2025-12-16DOI: 10.1016/j.reactfunctpolym.2025.106614
Barbara Beiler , Malik H. Mahmood , Dóra Bereczki , Ágnes Sáfrány , Péter Fürjes , Miklós Veres
Porous polymer monoliths with controlled porosity are critical materials for advanced separation technologies. Gamma-radiation initiated polymerization offers a straightforward and robust approach to their synthesis, employing a monomer mixture composed solely of monomers and solvents. Achieving precise control over the pore structure for a given monomer primarily depends on the careful selection of the porogenic solvent. This study presents a comprehensive investigation into how solvent composition affects both the structural characteristics and functional flow performance of diethylene glycol dimethacrylate (DEGDMA) monoliths prepared using binary solvent mixtures via gamma-radiation polymerization. Three binary solvent systems—ethyl acetate/alcohols, acetonitrile/alcohols, and acetone/alcohols—were examined, with alcohol concentrations varying from 0 to 70 vol% in a monomer solution containing 30 vol% DEGDMA. Changes in morphology, porous properties, and flow behavior were characterized by scanning electron microscopy, mercury porosimetry, nitrogen absorption measurements, and liquid flux analyses. Results reveal that binary solvent mixtures enable precise tuning of monolith architecture, ranging from macroporous to microporous and even bulk polymer structures.
{"title":"Tailoring porous properties of polymer monoliths through the composition of the binary solvent mixture","authors":"Barbara Beiler , Malik H. Mahmood , Dóra Bereczki , Ágnes Sáfrány , Péter Fürjes , Miklós Veres","doi":"10.1016/j.reactfunctpolym.2025.106614","DOIUrl":"10.1016/j.reactfunctpolym.2025.106614","url":null,"abstract":"<div><div>Porous polymer monoliths with controlled porosity are critical materials for advanced separation technologies. Gamma-radiation initiated polymerization offers a straightforward and robust approach to their synthesis, employing a monomer mixture composed solely of monomers and solvents. Achieving precise control over the pore structure for a given monomer primarily depends on the careful selection of the porogenic solvent. This study presents a comprehensive investigation into how solvent composition affects both the structural characteristics and functional flow performance of diethylene glycol dimethacrylate (DEGDMA) monoliths prepared using binary solvent mixtures via gamma-radiation polymerization. Three binary solvent systems—ethyl acetate/alcohols, acetonitrile/alcohols, and acetone/alcohols—were examined, with alcohol concentrations varying from 0 to 70 vol% in a monomer solution containing 30 vol% DEGDMA. Changes in morphology, porous properties, and flow behavior were characterized by scanning electron microscopy, mercury porosimetry, nitrogen absorption measurements, and liquid flux analyses. Results reveal that binary solvent mixtures enable precise tuning of monolith architecture, ranging from macroporous to microporous and even bulk polymer structures.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106614"},"PeriodicalIF":5.1,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145885311","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 : 2025-12-15DOI: 10.1016/j.reactfunctpolym.2025.106611
Rizwana Fathima M Kasim, Kalaivizhi Rajappan
The combination of micelles and polymers has produced hybrid polymeric films with embedded micelles, which maintain the nanometric precision of micellar drug carriers while also stabilizing a resilient film matrix that facilitates controlled drug release. The combination of micelles made of block copolymers with high drug-loading capacity, better solubility of hydrophobic payloads, and stimuli-responsive behavior has been facilitated by this system through the mechanical stability and localized delivery capability of thin polymeric matrices. The article provides a detailed discussion of the design principles, fabrication methods, and functional mechanisms of micelle-embedded block copolymer films, focusing on Layer-by-Layer (LBL) assembly, hybrid polymer matrices, and smart stimuli-responsive systems. Their biomedical applications have been reviewed in-depth, including cancer therapy, antimicrobial coatings, wound healing, regenerative medicine, and ocular drug delivery. The multiple functionalities' integration, such as pH, redox, and thermo-responsiveness, results in releasing drugs in the specific area and at the desired time like never before. In conclusion, micelle-embedded polymeric films are a great candidate for the next generation of drug delivery systems, offering personalized, localized, and sustained therapeutic actions through various and diversified clinical fields.
{"title":"Design and functionalization of micelle-embedded polymeric films: Reactive platforms for controlled and targeted drug delivery","authors":"Rizwana Fathima M Kasim, Kalaivizhi Rajappan","doi":"10.1016/j.reactfunctpolym.2025.106611","DOIUrl":"10.1016/j.reactfunctpolym.2025.106611","url":null,"abstract":"<div><div>The combination of micelles and polymers has produced hybrid polymeric films with embedded micelles, which maintain the nanometric precision of micellar drug carriers while also stabilizing a resilient film matrix that facilitates controlled drug release. The combination of micelles made of block copolymers with high drug-loading capacity, better solubility of hydrophobic payloads, and stimuli-responsive behavior has been facilitated by this system through the mechanical stability and localized delivery capability of thin polymeric matrices. The article provides a detailed discussion of the design principles, fabrication methods, and functional mechanisms of micelle-embedded block copolymer films, focusing on Layer-by-Layer (LBL) assembly, hybrid polymer matrices, and smart stimuli-responsive systems. Their biomedical applications have been reviewed in-depth, including cancer therapy, antimicrobial coatings, wound healing, regenerative medicine, and ocular drug delivery. The multiple functionalities' integration, such as pH, redox, and thermo-responsiveness, results in releasing drugs in the specific area and at the desired time like never before. In conclusion, micelle-embedded polymeric films are a great candidate for the next generation of drug delivery systems, offering personalized, localized, and sustained therapeutic actions through various and diversified clinical fields.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106611"},"PeriodicalIF":5.1,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884675","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}
The need for low cost, flexible, and highly sensitive gas sensors is growing rapidly across sectors like environmental monitoring, healthcare, and food safety. Among various sensing materials, polyaniline (PANI) has attracted significant attention due to its reversible redox behaviour, tunable conductivity, and simple room temperature synthesis. However, despite its promise, pristine PANI often falls short in terms of selectivity, mechanical stability, and long term performance. In response, researchers have increasingly focused on blending PANI with other materials such as metal oxides, carbon nanostructures, biopolymers, and green dopants to create multifunctional composites that combine the best of both components. These hybrid systems not only improve sensor sensitivity and selectivity but also enable operation under variable environmental conditions and on flexible platforms. This review provides a comprehensive account of the latest progress in the design, synthesis, and application of PANI based blends and composites for gas sensing. It explores key fabrication strategies, sensing mechanisms, and material performance relationships, while also identifying challenges related to reproducibility, environmental stability, and integration. By compiling comparative data and emerging trends, this review highlights the scientific and practical potential of PANI composites as next generation materials for intelligent and eco-friendly gas sensing technologies.
{"title":"Polyaniline based blends and composites for gas sensing: A comprehensive review on materials, mechanisms, and applications","authors":"Aditi Jain , Mahesh Dhonde , Ankit Soni , Ashok Kumar , Kirti Sahu","doi":"10.1016/j.reactfunctpolym.2025.106610","DOIUrl":"10.1016/j.reactfunctpolym.2025.106610","url":null,"abstract":"<div><div>The need for low cost, flexible, and highly sensitive gas sensors is growing rapidly across sectors like environmental monitoring, healthcare, and food safety. Among various sensing materials, polyaniline (PANI) has attracted significant attention due to its reversible redox behaviour, tunable conductivity, and simple room temperature synthesis. However, despite its promise, pristine PANI often falls short in terms of selectivity, mechanical stability, and long term performance. In response, researchers have increasingly focused on blending PANI with other materials such as metal oxides, carbon nanostructures, biopolymers, and green dopants to create multifunctional composites that combine the best of both components. These hybrid systems not only improve sensor sensitivity and selectivity but also enable operation under variable environmental conditions and on flexible platforms. This review provides a comprehensive account of the latest progress in the design, synthesis, and application of PANI based blends and composites for gas sensing. It explores key fabrication strategies, sensing mechanisms, and material performance relationships, while also identifying challenges related to reproducibility, environmental stability, and integration. By compiling comparative data and emerging trends, this review highlights the scientific and practical potential of PANI composites as next generation materials for intelligent and eco-friendly gas sensing technologies.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106610"},"PeriodicalIF":5.1,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145884678","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 : 2025-12-14DOI: 10.1016/j.reactfunctpolym.2025.106607
Antoni Pagés-Llobet , Fernando Julián , Francesc Xavier Espinach , Mònica Ardanuy , Helena Oliver-Ortega , José Alberto Méndez
Fused Deposition Modelling (FDM) is an additive manufacturing technique that allows the fabrication of complex and customized parts. However, FDM-based pieces exhibit low mechanical performance due to the inherent limitations of this technology: poor interlayer adhesion and internal voids. As a result, the mechanical durability is reduced contributing to the problem of plastic waste generation. In this sense, the introduction of dynamic crosslinkers into the thermoplastic can be particularly beneficial, since they not only reinforce the polymer matrix but also impart self-healing functionality. As a consequence, the service life of FDM components is further extended. Here, we develop a coumarin-modified poly (lactic acid) formulation capable of intrinsic, light-activated self-healing. Upon ultraviolet irradiation under optimized solid-state conditions of irradiance and temperature, coumarin moieties grafted onto the PLA backbone undergo [2π + 2π] cycloaddition, generating photocrosslinked networks. Evidence of photocrosslinking was confirmed by the formation of a gel fraction (9.6 %) and a 72 % increase in storage modulus. Mechanical scratches on FDM specimens were subsequently irradiated, showing accelerated scratch closure and a smaller reduction in storage modulus (9.5 %) compared to neat PLA (32 %). These results suggest that dimerized coumarin units partially undergo reversible cleavage and re-dimerization during the healing process, enabling repeated recovery of mechanical stability. This represents the first demonstration of light-activated self-healing in FDM-printed PLA. Unlike previously reported extrinsic self-healing approaches in PLA, which rely on single-use microcapsule systems, the present work achieves intrinsic, repeatable self-healing within the PLA matrix. By combining biobased composition with extended functionality and durability, this research advances a sustainable strategy for additive manufacturing, addressing both the mechanical limitations of FDM and the broader challenge of reducing plastic waste.
{"title":"Light-activated self-healing poly (lactic acid) for durable FDM 3D printing applications","authors":"Antoni Pagés-Llobet , Fernando Julián , Francesc Xavier Espinach , Mònica Ardanuy , Helena Oliver-Ortega , José Alberto Méndez","doi":"10.1016/j.reactfunctpolym.2025.106607","DOIUrl":"10.1016/j.reactfunctpolym.2025.106607","url":null,"abstract":"<div><div>Fused Deposition Modelling (FDM) is an additive manufacturing technique that allows the fabrication of complex and customized parts. However, FDM-based pieces exhibit low mechanical performance due to the inherent limitations of this technology: poor interlayer adhesion and internal voids. As a result, the mechanical durability is reduced contributing to the problem of plastic waste generation. In this sense, the introduction of dynamic crosslinkers into the thermoplastic can be particularly beneficial, since they not only reinforce the polymer matrix but also impart self-healing functionality. As a consequence, the service life of FDM components is further extended. Here, we develop a coumarin-modified poly (lactic acid) formulation capable of intrinsic, light-activated self-healing. Upon ultraviolet irradiation under optimized solid-state conditions of irradiance and temperature, coumarin moieties grafted onto the PLA backbone undergo [2π + 2π] cycloaddition, generating photocrosslinked networks. Evidence of photocrosslinking was confirmed by the formation of a gel fraction (9.6 %) and a 72 % increase in storage modulus. Mechanical scratches on FDM specimens were subsequently irradiated, showing accelerated scratch closure and a smaller reduction in storage modulus (9.5 %) compared to neat PLA (32 %). These results suggest that dimerized coumarin units partially undergo reversible cleavage and re-dimerization during the healing process, enabling repeated recovery of mechanical stability. This represents the first demonstration of light-activated self-healing in FDM-printed PLA. Unlike previously reported extrinsic self-healing approaches in PLA, which rely on single-use microcapsule systems, the present work achieves intrinsic, repeatable self-healing within the PLA matrix. By combining biobased composition with extended functionality and durability, this research advances a sustainable strategy for additive manufacturing, addressing both the mechanical limitations of FDM and the broader challenge of reducing plastic waste.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106607"},"PeriodicalIF":5.1,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799426","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 : 2025-12-13DOI: 10.1016/j.reactfunctpolym.2025.106605
Farzaneh Qodrati-nasrabadi , Issa Sardivand-chegini , Saeed Zakavi
<div><div>In order to overcome the problem of leaching of porphyrins from solid supports as well as the extensive degradation of porphyrin sensitizers, the tetra sodium salts of <em>meso</em>-tetrakis(4-carboxyphenyl)porphyrin (Na<sub>4</sub>H<sub>2</sub>TCPP) and the corresponding Zn(II) complex (Na<sub>4</sub>ZnTCPP), immobilized into the pores of nanostructured mesoporous Amberlite IRA-900, nanoAmbN(Me)<sub>3</sub>Cl, were synthesized and used as sensitizers in aerobic photooxidation of sulfides in acetonitrile and water. Also, the molecular complex of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and its dication with H<sub>2</sub>SO<sub>4</sub> were prepared and used in photooxidation of sulfides. FESEM, BET, TGA, FT-IR and UV–vis diffuse reflectance spectroscopy (DRS) were used to characterize the nanocomposites. Interestingly, nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was highly stable against leaching of the porphyrin under long-term exposure to acidic conditions at a pH value as low as zero (1.0 M HCl). This finding was attributed to the very low solubility of the peripherally tetra-protonated porphyrins (H<sub>6</sub>TCPP and H<sub>4</sub>ZnTCPP) in water as well as the strong electrostatic interactions between the –COOH groups of the porphyrin and –<sup>+</sup>N(CH<sub>3</sub>)<sub>3</sub> residues of the polymer. The singlet oxygen quantum yield (ϕ<sub>Δ</sub>) of the sensitizers decreased as nanoAmbN(Me)<sub>3</sub>@ZnTCPP (0.73) > > nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP (0.22) ≥ nanoAmbN(Me)<sub>3</sub>@H<sub>4</sub>TCPP(HSO<sub>4</sub>)<sub>2</sub> (0.18) ∼ nanoAmbN(Me)<span><span><sub>3</sub>@H<sub>2</sub>TCPP(DDQ)<sub>2</sub> (0.17</span><svg><path></path></svg></span>). Although a similar photocatalytic activity was observed for nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP and nanoAmbN(Me)<sub>3</sub>@ZnTCPP in the oxidation of more reactive sulfides, the former was significantly more efficient in the oxidation of sulfides with electron-withdrawing and/or sterically demanding substituents at the sulfur atom. This observation was attributed to the higher degree of oxidative degradation of nanoAmbN(Me)<sub>3</sub>@ZnTCPP. The oxidative stability of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was significantly increased due to the formation of the H<sub>2</sub>SO<sub>4</sub> diacid and DDQ molecular complex of H<sub>2</sub>TCPP. However, a two- to three-fold increase in the time required for the completion of the reaction was observed in the presence of the latter sensitizers. The increased steric hindrance around the singlet oxygen generating sites of the sensitizers caused by the presence of HSO<sub>4</sub><sup>−</sup> anions and the DDQ molecules was suggested to explain this observation. Furthermore, a significant decrease in the reactivity of sulfides towards singlet oxygen by increasing steric hindrance around the sulfur atom was observed. The presence CH<sub>3</sub>C
{"title":"Meso-tetrakis(4-carboxyphenyl)porphyrin derivatives anchored to nanostructured amberlite: New porphyrin photosensitizers with unusually high long-term leaching stability, photocatalytic activity and oxidative stability","authors":"Farzaneh Qodrati-nasrabadi , Issa Sardivand-chegini , Saeed Zakavi","doi":"10.1016/j.reactfunctpolym.2025.106605","DOIUrl":"10.1016/j.reactfunctpolym.2025.106605","url":null,"abstract":"<div><div>In order to overcome the problem of leaching of porphyrins from solid supports as well as the extensive degradation of porphyrin sensitizers, the tetra sodium salts of <em>meso</em>-tetrakis(4-carboxyphenyl)porphyrin (Na<sub>4</sub>H<sub>2</sub>TCPP) and the corresponding Zn(II) complex (Na<sub>4</sub>ZnTCPP), immobilized into the pores of nanostructured mesoporous Amberlite IRA-900, nanoAmbN(Me)<sub>3</sub>Cl, were synthesized and used as sensitizers in aerobic photooxidation of sulfides in acetonitrile and water. Also, the molecular complex of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and its dication with H<sub>2</sub>SO<sub>4</sub> were prepared and used in photooxidation of sulfides. FESEM, BET, TGA, FT-IR and UV–vis diffuse reflectance spectroscopy (DRS) were used to characterize the nanocomposites. Interestingly, nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was highly stable against leaching of the porphyrin under long-term exposure to acidic conditions at a pH value as low as zero (1.0 M HCl). This finding was attributed to the very low solubility of the peripherally tetra-protonated porphyrins (H<sub>6</sub>TCPP and H<sub>4</sub>ZnTCPP) in water as well as the strong electrostatic interactions between the –COOH groups of the porphyrin and –<sup>+</sup>N(CH<sub>3</sub>)<sub>3</sub> residues of the polymer. The singlet oxygen quantum yield (ϕ<sub>Δ</sub>) of the sensitizers decreased as nanoAmbN(Me)<sub>3</sub>@ZnTCPP (0.73) > > nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP (0.22) ≥ nanoAmbN(Me)<sub>3</sub>@H<sub>4</sub>TCPP(HSO<sub>4</sub>)<sub>2</sub> (0.18) ∼ nanoAmbN(Me)<span><span><sub>3</sub>@H<sub>2</sub>TCPP(DDQ)<sub>2</sub> (0.17</span><svg><path></path></svg></span>). Although a similar photocatalytic activity was observed for nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP and nanoAmbN(Me)<sub>3</sub>@ZnTCPP in the oxidation of more reactive sulfides, the former was significantly more efficient in the oxidation of sulfides with electron-withdrawing and/or sterically demanding substituents at the sulfur atom. This observation was attributed to the higher degree of oxidative degradation of nanoAmbN(Me)<sub>3</sub>@ZnTCPP. The oxidative stability of nanoAmbN(Me)<sub>3</sub>@H<sub>2</sub>TCPP was significantly increased due to the formation of the H<sub>2</sub>SO<sub>4</sub> diacid and DDQ molecular complex of H<sub>2</sub>TCPP. However, a two- to three-fold increase in the time required for the completion of the reaction was observed in the presence of the latter sensitizers. The increased steric hindrance around the singlet oxygen generating sites of the sensitizers caused by the presence of HSO<sub>4</sub><sup>−</sup> anions and the DDQ molecules was suggested to explain this observation. Furthermore, a significant decrease in the reactivity of sulfides towards singlet oxygen by increasing steric hindrance around the sulfur atom was observed. The presence CH<sub>3</sub>C","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"220 ","pages":"Article 106605"},"PeriodicalIF":5.1,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799425","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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