Deep penetration of nanocarriers into solid tumours remains a major obstacle in cancer nanomedicine due to the complex tumour microenvironment (TME) and associated physiological barriers. This review provides a comprehensive analysis to guide the design of stimuli-responsive nanocarriers capable of overcoming these transport limitations and enhancing therapeutic efficacy. It begins by examining key nanocarrier classes, including lipid-based, polymeric, inorganic, biomacromolecular, and hydrogel systems, highlighting their structural features, advantages, and limitations. Special focus is given to charge-reversal nanoparticles, which leverage TME-specific triggers such as acidic pH, redox gradients, and enzymatic activity to enhance tumour infiltration and cellular uptake. The review also evaluates complementary strategies including size and shape transformation, surface ligand modification, propulsion-based delivery, and pharmacological modulation of the TME. Collectively, these approaches offer a promising framework for engineering nanocarrier systems capable of targeted delivery, enhanced tumour penetration, and precise spatiotemporal control of drug release.
{"title":"Nanocarrier strategies for deep tumour penetration","authors":"Jinbo Zhang, Guanjiang Wu and Valentin A. Bobrin","doi":"10.1039/D5LP00154D","DOIUrl":"https://doi.org/10.1039/D5LP00154D","url":null,"abstract":"<p >Deep penetration of nanocarriers into solid tumours remains a major obstacle in cancer nanomedicine due to the complex tumour microenvironment (TME) and associated physiological barriers. This review provides a comprehensive analysis to guide the design of stimuli-responsive nanocarriers capable of overcoming these transport limitations and enhancing therapeutic efficacy. It begins by examining key nanocarrier classes, including lipid-based, polymeric, inorganic, biomacromolecular, and hydrogel systems, highlighting their structural features, advantages, and limitations. Special focus is given to charge-reversal nanoparticles, which leverage TME-specific triggers such as acidic pH, redox gradients, and enzymatic activity to enhance tumour infiltration and cellular uptake. The review also evaluates complementary strategies including size and shape transformation, surface ligand modification, propulsion-based delivery, and pharmacological modulation of the TME. Collectively, these approaches offer a promising framework for engineering nanocarrier systems capable of targeted delivery, enhanced tumour penetration, and precise spatiotemporal control of drug release.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 6","pages":" 1403-1427"},"PeriodicalIF":0.0,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00154d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carlo Kurt F. Osorio, Christine Joy M. Omisol, Dan Michael A. Asequia, Blessy Joy M. Aguinid, Daisy Jane D. Erjeno, Kassandra Jayza Gift D. Tejas, Roger G. Dingcong, Tomas Ralph B. Tomon, Renzo Miguel R. Hisona, Andrei E. Etom, Ann Pearl G. Triana, Gerard G. Dumancas, Arnold C. Alguno, Joshua B. Zoleta, Roberto M. Malaluan and Arnold A. Lubguban
High-strength, bio-based rigid polyurethane foam (RPUF) was synthesized using coconut oil-based polyol reinforced with green silica nanoparticles (SNP) derived from rice husk ash (RHA). The SNPs were carbon-doped using κ-carrageenan to enhance their functional properties. Comprehensive characterization of the synthesized SNP and SNP-enhanced RPUF was conducted using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). X-ray photoelectron spectroscopy (XPS) confirmed successful κ-carrageenan-mediated carbon doping, improving SNP reactivity. The incorporation of SNP (up to 0.3% by mass) significantly enhanced the compressive strength of RPUF by 92.42%, attributed to hydrogen bonding and induced crosslinking interactions between the SNP and amine groups in the bio-polyol, as evidenced by FTIR, SEM, and pycnometric analyses. Thermogravimetric analysis (TGA) demonstrated that SNP integration improved the thermal stability of RPUF without compromising its thermal conductivity, meeting industrial standards. This study highlights the potential of sustainably derived nanomaterials to improve the mechanical and thermal properties of bio-based composites. Furthermore, the SNP-reinforced RPUF offers promising applications in environmentally friendly materials for thermal insulation, structural components, and environmental remediation, contributing to the development of high-performance, sustainable materials for various industrial applications.
{"title":"Synthesis of green-based carbon-doped nanosilica for enhanced mechanical properties of coconut oil-based rigid polyurethane foam","authors":"Carlo Kurt F. Osorio, Christine Joy M. Omisol, Dan Michael A. Asequia, Blessy Joy M. Aguinid, Daisy Jane D. Erjeno, Kassandra Jayza Gift D. Tejas, Roger G. Dingcong, Tomas Ralph B. Tomon, Renzo Miguel R. Hisona, Andrei E. Etom, Ann Pearl G. Triana, Gerard G. Dumancas, Arnold C. Alguno, Joshua B. Zoleta, Roberto M. Malaluan and Arnold A. Lubguban","doi":"10.1039/D5LP00161G","DOIUrl":"https://doi.org/10.1039/D5LP00161G","url":null,"abstract":"<p >High-strength, bio-based rigid polyurethane foam (RPUF) was synthesized using coconut oil-based polyol reinforced with green silica nanoparticles (SNP) derived from rice husk ash (RHA). The SNPs were carbon-doped using κ-carrageenan to enhance their functional properties. Comprehensive characterization of the synthesized SNP and SNP-enhanced RPUF was conducted using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). X-ray photoelectron spectroscopy (XPS) confirmed successful κ-carrageenan-mediated carbon doping, improving SNP reactivity. The incorporation of SNP (up to 0.3% by mass) significantly enhanced the compressive strength of RPUF by 92.42%, attributed to hydrogen bonding and induced crosslinking interactions between the SNP and amine groups in the bio-polyol, as evidenced by FTIR, SEM, and pycnometric analyses. Thermogravimetric analysis (TGA) demonstrated that SNP integration improved the thermal stability of RPUF without compromising its thermal conductivity, meeting industrial standards. This study highlights the potential of sustainably derived nanomaterials to improve the mechanical and thermal properties of bio-based composites. Furthermore, the SNP-reinforced RPUF offers promising applications in environmentally friendly materials for thermal insulation, structural components, and environmental remediation, contributing to the development of high-performance, sustainable materials for various industrial applications.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1356-1365"},"PeriodicalIF":0.0,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00161g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Vojtěch Musil, Dominik Laa, Mojtaba Ahmadi, Jürgen Stampfl, Robert Liska, Jan Merna and Katharina Ehrmann
Conventional photopolymers used in light-based additive manufacturing are typically brittle materials with thermoset characteristics. Here we introduce a one-step synthesis of hyperbranched polyethylene rubbers functionalized with pendant methacrylic groups and their application as tougheners of a model brittle photopolymer based on non-volatile styrene and maleimide derivatives. The rubber tougheners can be tailored to tune their compatibility with the matrix, influencing the morphology and the thermomechanical properties of the final printed resins. The resulting polymer structures were analysed by atomic force microscopy, revealing various degrees of phase separation related to the rubber molar mass and methacrylate functionalization. Further, the analysis of the prepared toughened materials revealed the ability of functionalized hyperbranched polyethylene rubbers to improve the mechanical properties significantly (doubled stress at break and improvement of strain at break by a factor of 103 compared to the matrix), while glass transition temperatures around 100 °C could be maintained. Notably, even tensile behaviour mimicking typical thermoplastic yield strain comparable to ABS was observed in one of the prepared materials. This monomer/rubber system appeared to be the most promising and was therefore selected for in-depth analysis of the curing process using photo-rheology and photo-DSC. Finally, this material was used for hot lithography and several highly detailed objects were prepared, demonstrating the good printability of this toughened material.
{"title":"Thermoplastic-like mechanical performance of heterogeneous photopolymers for additive manufacturing with tailored hyperbranched rubbers","authors":"Vojtěch Musil, Dominik Laa, Mojtaba Ahmadi, Jürgen Stampfl, Robert Liska, Jan Merna and Katharina Ehrmann","doi":"10.1039/D5LP00138B","DOIUrl":"https://doi.org/10.1039/D5LP00138B","url":null,"abstract":"<p >Conventional photopolymers used in light-based additive manufacturing are typically brittle materials with thermoset characteristics. Here we introduce a one-step synthesis of hyperbranched polyethylene rubbers functionalized with pendant methacrylic groups and their application as tougheners of a model brittle photopolymer based on non-volatile styrene and maleimide derivatives. The rubber tougheners can be tailored to tune their compatibility with the matrix, influencing the morphology and the thermomechanical properties of the final printed resins. The resulting polymer structures were analysed by atomic force microscopy, revealing various degrees of phase separation related to the rubber molar mass and methacrylate functionalization. Further, the analysis of the prepared toughened materials revealed the ability of functionalized hyperbranched polyethylene rubbers to improve the mechanical properties significantly (doubled stress at break and improvement of strain at break by a factor of 10<small><sup>3</sup></small> compared to the matrix), while glass transition temperatures around 100 °C could be maintained. Notably, even tensile behaviour mimicking typical thermoplastic yield strain comparable to ABS was observed in one of the prepared materials. This monomer/rubber system appeared to be the most promising and was therefore selected for in-depth analysis of the curing process using photo-rheology and photo-DSC. Finally, this material was used for hot lithography and several highly detailed objects were prepared, demonstrating the good printability of this toughened material.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1165-1176"},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00138b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qi Li, Dong Wang, Tianjiao Wang, Yang Zhang, Shiyang Liu, Shiwei Zhang, Zhufeng Hu, Liying Li, Guoyong Wang and Yingmin Zhao
The development of recyclable and self-repairable vitrimer materials featuring reversible B–O bonds has garnered increasing attention. However, their stability and thermomechanical properties remain insufficient for engineering applications in reusable carbon fiber-reinforced composites (CFRCs). Herein, we report a high-performance epoxy vitrimer containing boronic ester bond-based dynamic exchange networks, to which a small amount of N-donating imidazole has been added for introducing intermolecular N–B coordination interactions. The obtained vitrimer (E51-NBO-IMZ) possessed a high glass transition temperature (Tg) of 198 °C and tensile modulus of 3.71 GPa. Compared to the system without imidazole, it exhibited significantly improved solvent resistance due to the stabilization effect of N–B coordination on the B-center atoms. Moreover, stress relaxation tests also indicated a lower activation energy (Ea = 151.31 kJ mol−1) of the E51-NBO-IMZ vitrimer, suggesting better dynamic exchange activity. Despite the high stability and improved thermomechanical properties, the self-repairing, recycling and degradation of the vitrimer and its CFRCs were successfully achieved under heating, stress or chemical environmental conditions, showing outstanding potential for practical applications.
{"title":"Reversible B–O bond-based epoxy vitrimers with high thermomechanical and dynamic properties enhanced by intermolecular B–N coordination","authors":"Qi Li, Dong Wang, Tianjiao Wang, Yang Zhang, Shiyang Liu, Shiwei Zhang, Zhufeng Hu, Liying Li, Guoyong Wang and Yingmin Zhao","doi":"10.1039/D5LP00144G","DOIUrl":"https://doi.org/10.1039/D5LP00144G","url":null,"abstract":"<p >The development of recyclable and self-repairable vitrimer materials featuring reversible B–O bonds has garnered increasing attention. However, their stability and thermomechanical properties remain insufficient for engineering applications in reusable carbon fiber-reinforced composites (CFRCs). Herein, we report a high-performance epoxy vitrimer containing boronic ester bond-based dynamic exchange networks, to which a small amount of N-donating imidazole has been added for introducing intermolecular N–B coordination interactions. The obtained vitrimer (<strong>E51-NBO-IMZ</strong>) possessed a high glass transition temperature (<em>T</em><small><sub>g</sub></small>) of 198 °C and tensile modulus of 3.71 GPa. Compared to the system without imidazole, it exhibited significantly improved solvent resistance due to the stabilization effect of N–B coordination on the B-center atoms. Moreover, stress relaxation tests also indicated a lower activation energy (<em>E</em><small><sub>a</sub></small> = 151.31 kJ mol<small><sup>−1</sup></small>) of the <strong>E51-NBO-IMZ</strong> vitrimer, suggesting better dynamic exchange activity. Despite the high stability and improved thermomechanical properties, the self-repairing, recycling and degradation of the vitrimer and its CFRCs were successfully achieved under heating, stress or chemical environmental conditions, showing outstanding potential for practical applications.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1183-1192"},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00144g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Baskaran Mohan Dass, Ramya Padmanaban, Aparna Mahalingam, Neeshma Maniprakundil, Harshal Agarwal, Sreekuttan M. Unni, Vishal M. Dhavale and Santoshkumar D. Bhat
This study reports the fabrication of composite membranes based on short-side-chain perfluorosulfonic acid (SSC-PFSA) polymers reinforced with polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (PABS-f-SWCNTs) for enhanced polymer electrolyte membrane fuel cell (PEMFC) performance. The dual-functionalized SWCNTs, enriched with –SO3H and –NH2 groups, were uniformly dispersed within the SSC-PFSA matrix, promoting dipolar interactions and efficient proton conduction pathways. Comprehensive characterization confirmed improved ion exchange capacity, water uptake, thermal stability, and proton conductivity, with the 0.5 wt% PABS-f-SWCNT composite membrane exhibiting optimal performance. Under fuel cell operating conditions, this membrane demonstrated a peak power density of 1707 mW cm−2 at 100% RH and sustained high current density at reduced humidity, outperforming the pristine SSC-PFSA membrane. The findings highlight the synergistic role of zwitterionic functional groups and nanotube reinforcement in advancing next-generation PEMFC membrane technology.
本研究报道了基于短侧链全氟磺酸(SSC-PFSA)聚合物和聚氨基苯磺酸功能化单壁碳纳米管(PABS-f-SWCNTs)增强的复合膜的制备,用于增强聚合物电解质膜燃料电池(PEMFC)的性能。富含-SO3H和-NH2基团的双功能化SWCNTs均匀分散在SSC-PFSA基质中,促进了偶极相互作用和有效的质子传导途径。综合表征证实了离子交换能力、吸水性、热稳定性和质子电导率的提高,其中0.5 wt%的PABS-f-SWCNT复合膜表现出最佳性能。在燃料电池工作条件下,该膜在100%相对湿度下的峰值功率密度为1707 mW cm - 2,在降低湿度时保持高电流密度,优于原始SSC-PFSA膜。这些发现强调了两性离子官能团和纳米管增强在推进下一代PEMFC膜技术中的协同作用。
{"title":"Short-side-chain composite membranes with polyaminobenzene sulfonic acid-enriched single-walled carbon nanotubes for polymer electrolyte fuel cells","authors":"Baskaran Mohan Dass, Ramya Padmanaban, Aparna Mahalingam, Neeshma Maniprakundil, Harshal Agarwal, Sreekuttan M. Unni, Vishal M. Dhavale and Santoshkumar D. Bhat","doi":"10.1039/D5LP00172B","DOIUrl":"https://doi.org/10.1039/D5LP00172B","url":null,"abstract":"<p >This study reports the fabrication of composite membranes based on short-side-chain perfluorosulfonic acid (SSC-PFSA) polymers reinforced with polyaminobenzene sulfonic acid-functionalized single-walled carbon nanotubes (PABS-f-SWCNTs) for enhanced polymer electrolyte membrane fuel cell (PEMFC) performance. The dual-functionalized SWCNTs, enriched with –SO<small><sub>3</sub></small>H and –NH<small><sub>2</sub></small> groups, were uniformly dispersed within the SSC-PFSA matrix, promoting dipolar interactions and efficient proton conduction pathways. Comprehensive characterization confirmed improved ion exchange capacity, water uptake, thermal stability, and proton conductivity, with the 0.5 wt% PABS-f-SWCNT composite membrane exhibiting optimal performance. Under fuel cell operating conditions, this membrane demonstrated a peak power density of 1707 mW cm<small><sup>−2</sup></small> at 100% RH and sustained high current density at reduced humidity, outperforming the pristine SSC-PFSA membrane. The findings highlight the synergistic role of zwitterionic functional groups and nanotube reinforcement in advancing next-generation PEMFC membrane technology.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1376-1384"},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00172b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In recent years, taking inspiration from mussel, an underwater organism, various packaging alternatives including adhesive coatings have been developed for food preservation to ensure food availability for everyone. The extraordinary adhesion exhibited by mussel is mainly offered by mussel foot proteins containing catechol groups. This catechol-based chemistry not only improves adhesion but also helps in imparting antimicrobial, antioxidant, and UV-blocking properties to packaging materials for increasing the shelf-life of food items. Herein, we first present an overview of catechol-based chemistry followed by a discussion involving a combination of catechol and its derivatives with various biodegradable polymers and nanomaterials. Further, we summarize the recent efforts made for developing mussel-inspired catechol-based coatings for food preservation, keeping minimum environmental impact in mind. Finally, we discuss various challenges and opportunities existing in this area for the successful commercial utilization of such biomimetic coatings in the future.
{"title":"Mussel-inspired biomimetic adhesive coatings for food preservation: a review","authors":"Deepika Gupta, Dimpy Bhardwaj, Ruchir Priyadarshi, Saurav Kumar and Garima Agrawal","doi":"10.1039/D5LP00173K","DOIUrl":"https://doi.org/10.1039/D5LP00173K","url":null,"abstract":"<p >In recent years, taking inspiration from mussel, an underwater organism, various packaging alternatives including adhesive coatings have been developed for food preservation to ensure food availability for everyone. The extraordinary adhesion exhibited by mussel is mainly offered by mussel foot proteins containing catechol groups. This catechol-based chemistry not only improves adhesion but also helps in imparting antimicrobial, antioxidant, and UV-blocking properties to packaging materials for increasing the shelf-life of food items. Herein, we first present an overview of catechol-based chemistry followed by a discussion involving a combination of catechol and its derivatives with various biodegradable polymers and nanomaterials. Further, we summarize the recent efforts made for developing mussel-inspired catechol-based coatings for food preservation, keeping minimum environmental impact in mind. Finally, we discuss various challenges and opportunities existing in this area for the successful commercial utilization of such biomimetic coatings in the future.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1145-1164"},"PeriodicalIF":0.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00173k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Le Tang, Paul Schweng, Joseph J. Dale and Robert T. Woodward
The selective removal of oil and oil-based contaminants from water remains a critical challenge in environmental remediation. Here, we report a series of hypercrosslinked polymers with high surface areas and tuneable chemistries, achieving exceptional adsorption capacities for a variety of organic solvents, with a maximum capacity of >15 g g−1 for chlorinated solvents. We describe how the adsorption capacities of the materials in pure organic solvents are governed by porosity rather than sample fluorine content and its associated hydrophobicity, challenging conventional design strategies. Oil/water separation tests of the most promising networks demonstrated the effective removal of toluene from water, achieving separation efficiencies of >99%. The polymers also exhibit exceptional stability in organic solvents, allowing repeated use. This work establishes hypercrosslinked polymers as robust, scalable materials for efficient oil–water separation and advanced wastewater treatment.
选择性去除水中的油和油基污染物仍然是环境修复中的一个关键挑战。在这里,我们报道了一系列具有高表面积和可调化学性质的超交联聚合物,对各种有机溶剂具有优异的吸附能力,对氯化溶剂的最大吸附能力为15 g g−1。我们描述了材料在纯有机溶剂中的吸附能力是如何由孔隙率而不是样品氟含量及其相关的疏水性决定的,挑战了传统的设计策略。对最有前途的油水分离网络进行的测试表明,该网络可以有效地从水中去除甲苯,分离效率达到99%。该聚合物在有机溶剂中也表现出优异的稳定性,允许重复使用。这项工作确立了超交联聚合物作为高效油水分离和高级废水处理的坚固、可扩展材料。
{"title":"Hypercrosslinked polymers for oil adsorption: the influence of porosity and fluorine incorporation","authors":"Le Tang, Paul Schweng, Joseph J. Dale and Robert T. Woodward","doi":"10.1039/D5LP00081E","DOIUrl":"https://doi.org/10.1039/D5LP00081E","url":null,"abstract":"<p >The selective removal of oil and oil-based contaminants from water remains a critical challenge in environmental remediation. Here, we report a series of hypercrosslinked polymers with high surface areas and tuneable chemistries, achieving exceptional adsorption capacities for a variety of organic solvents, with a maximum capacity of >15 g g<small><sup>−1</sup></small> for chlorinated solvents. We describe how the adsorption capacities of the materials in pure organic solvents are governed by porosity rather than sample fluorine content and its associated hydrophobicity, challenging conventional design strategies. Oil/water separation tests of the most promising networks demonstrated the effective removal of toluene from water, achieving separation efficiencies of >99%. The polymers also exhibit exceptional stability in organic solvents, allowing repeated use. This work establishes hypercrosslinked polymers as robust, scalable materials for efficient oil–water separation and advanced wastewater treatment.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1315-1324"},"PeriodicalIF":0.0,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00081e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Plastic waste materials in the environment degrade and release smaller particles called microplastic and nanoplastic particles. In this study, a series of polyaramides (PAs) are prepared with different structural features and used to remove plastic nanoparticles and dissolved dyes. The prepared PAs showed good thermal stability, high surface area, and negative zeta surface potential, which were useful for the extraction of pollutants. Among the six PAs studied, PA3 showed the highest adsorption capacity of 342.54 mg g−1 towards cationic polyvinyl chloride nanoparticles (PVC NPs) and dissolved dyes such as neutral red (NR, 323.57 mg g−1) and methylene blue (MB, 312.23 mg g−1). The PA adsorbents were also able to remove multiple pollutants successively from water. The adsorption isotherms, kinetics, mechanism, and reusability were also thoroughly investigated. The anionic PVC NPs or dyes were not adsorbed on the surface of the PAs and showed poor adsorption efficiency. The cationic pollutants were removed from water due to strong electrostatic attraction with the negatively charged PA adsorbents. To understand the adsorption mechanism, the adsorption efficiencies of the branched PAs (1–3; A3B2) are compared with linear PAs (4, 5; A2B2) and a model triamide molecule (TA). PA3 showed high adsorption efficiencies compared to other polymers. After extraction of pollutants, all used adsorbents were regenerated using dilute acid washings and reused for pollutant removal from water with a minimum loss of efficiency. As a proof of concept, plastic particles from a commercial facial scrubber were removed efficiently using PA adsorbents. Synthetic functional polymers offer potential solutions for removing emerging pollutants such as plastic micro- and nanoparticles from water.
塑料废物在环境中降解并释放出更小的颗粒,称为微塑料和纳米塑料颗粒。在本研究中,制备了一系列具有不同结构特征的聚酰胺(PAs),并将其用于去除塑料纳米颗粒和溶解染料。制备的PAs具有良好的热稳定性、高的比表面积和负的zeta表面电位,有利于污染物的提取。在所研究的6种PAs中,PA3对阳离子聚氯乙烯纳米粒子(PVC NPs)和溶解染料如中性红(NR, 323.57 mg g - 1)和亚甲基蓝(MB, 312.23 mg g - 1)的吸附量最高,为342.54 mg g - 1。PA吸附剂还能连续去除水中的多种污染物。研究了吸附等温线、吸附动力学、吸附机理和可重复使用性。阴离子聚氯乙烯NPs或染料不吸附在PAs表面,吸附效率较差。由于带负电荷的PA吸附剂具有很强的静电吸引力,可以去除水中的阳离子污染物。为了了解吸附机理,将支链PAs (1-3; A3B2)与线性PAs (4,5; A2B2)和模型三酰胺分子(TA)的吸附效率进行了比较。与其他聚合物相比,PA3具有较高的吸附效率。在提取污染物后,所有使用过的吸附剂都使用稀酸洗涤再生,并以最小的效率损失重新用于水中的污染物去除。作为概念验证,使用PA吸附剂有效地去除了商用面部洗涤器中的塑料颗粒。合成功能聚合物为从水中去除塑料微粒和纳米颗粒等新出现的污染物提供了潜在的解决方案。
{"title":"Structure–function correlation of branched and linear polyaramides for the removal of pollutants from water","authors":"Gomathi Mahadevan and Suresh Valiyaveettil","doi":"10.1039/D5LP00114E","DOIUrl":"https://doi.org/10.1039/D5LP00114E","url":null,"abstract":"<p >Plastic waste materials in the environment degrade and release smaller particles called microplastic and nanoplastic particles. In this study, a series of polyaramides (PAs) are prepared with different structural features and used to remove plastic nanoparticles and dissolved dyes. The prepared PAs showed good thermal stability, high surface area, and negative zeta surface potential, which were useful for the extraction of pollutants. Among the six PAs studied, PA3 showed the highest adsorption capacity of 342.54 mg g<small><sup>−1</sup></small> towards cationic polyvinyl chloride nanoparticles (PVC NPs) and dissolved dyes such as neutral red (NR, 323.57 mg g<small><sup>−1</sup></small>) and methylene blue (MB, 312.23 mg g<small><sup>−1</sup></small>). The PA adsorbents were also able to remove multiple pollutants successively from water. The adsorption isotherms, kinetics, mechanism, and reusability were also thoroughly investigated. The anionic PVC NPs or dyes were not adsorbed on the surface of the PAs and showed poor adsorption efficiency. The cationic pollutants were removed from water due to strong electrostatic attraction with the negatively charged PA adsorbents. To understand the adsorption mechanism, the adsorption efficiencies of the branched PAs (1–3; A3B2) are compared with linear PAs (4, 5; A2B2) and a model triamide molecule (TA). PA3 showed high adsorption efficiencies compared to other polymers. After extraction of pollutants, all used adsorbents were regenerated using dilute acid washings and reused for pollutant removal from water with a minimum loss of efficiency. As a proof of concept, plastic particles from a commercial facial scrubber were removed efficiently using PA adsorbents. Synthetic functional polymers offer potential solutions for removing emerging pollutants such as plastic micro- and nanoparticles from water.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 6","pages":" 1508-1530"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00114e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Álvaro Hidalgo-Yerga, Leonor Resina, Jordi Casanovas, Hamidreza Enshaei, Francesc Estrany, José I. Iribarren, Maria M. Pérez-Madrigal and Carlos Alemán
A clinical need still exists for advanced therapeutics to improve the recovery of patients suffering from large-gap peripheral nerve injuries (PNI). In this study, tubular constructs of submicrometric thickness (<1 μm) are prepared using shape-memory 50 : 50, 70 : 30 and 90 : 10 poly(lactic acid) (PLA)/polycaprolactone (PCL) blends, which are filled with a hyaluronic acid (HA)-based hydrogel. The hydrogel is crosslinked in situ by click chemistry using a 3-arm alkyne-functionalized polyethylene glycol and thiol-modified HA. The Young's moduli of the hydrogels confined inside the different cylindrical constructs are similar to that of the free hydrogel, the tubular shell mainly affecting the tensile strength and deformability. On the other hand, cell adhesion and proliferation assays demonstrate that the cytocompatibility of the blends, the hydrogel and the filled tubular constructs is similar to or even higher than that of the tissue culture polystyrene used as the control. Furthermore, the scaffold derived from the 70 : 30 PLA/PCL blend provides a 3D cell-friendly mechanical environment that promotes the directional migration of cells towards the confined hydrogel. The engineered scaffolds may have important implications in the repairing of directional tissues.
{"title":"Hydrogel-filled tubular scaffolds for directional tissue regeneration combining shape-memory polyester blends with hyaluronic acid click-hydrogels†","authors":"Álvaro Hidalgo-Yerga, Leonor Resina, Jordi Casanovas, Hamidreza Enshaei, Francesc Estrany, José I. Iribarren, Maria M. Pérez-Madrigal and Carlos Alemán","doi":"10.1039/D5LP00098J","DOIUrl":"https://doi.org/10.1039/D5LP00098J","url":null,"abstract":"<p >A clinical need still exists for advanced therapeutics to improve the recovery of patients suffering from large-gap peripheral nerve injuries (PNI). In this study, tubular constructs of submicrometric thickness (<1 μm) are prepared using shape-memory 50 : 50, 70 : 30 and 90 : 10 poly(lactic acid) (PLA)/polycaprolactone (PCL) blends, which are filled with a hyaluronic acid (HA)-based hydrogel. The hydrogel is crosslinked <em>in situ</em> by click chemistry using a 3-arm alkyne-functionalized polyethylene glycol and thiol-modified HA. The Young's moduli of the hydrogels confined inside the different cylindrical constructs are similar to that of the free hydrogel, the tubular shell mainly affecting the tensile strength and deformability. On the other hand, cell adhesion and proliferation assays demonstrate that the cytocompatibility of the blends, the hydrogel and the filled tubular constructs is similar to or even higher than that of the tissue culture polystyrene used as the control. Furthermore, the scaffold derived from the 70 : 30 PLA/PCL blend provides a 3D cell-friendly mechanical environment that promotes the directional migration of cells towards the confined hydrogel. The engineered scaffolds may have important implications in the repairing of directional tissues.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1340-1355"},"PeriodicalIF":0.0,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00098j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ugur Aslan, Maninderjeet Singh, Akhtar Gul, Jack F. Douglas and Alamgir Karim
Block copolymer (BCP) films hold significant promise for a wide array of technological applications, including nanopatterning, nanophotonics, polymer electrolytes, and optical waveguides. However, the practical realization of these applications is often hindered by the slow kinetics of the ordering of block copolymers, attributed to the inherently glassy dynamics of polymeric soft materials under standard processing conditions. The diverse range of BCP morphologies further highlights the unique self-assembly characteristics of polymeric materials. In this study, we employ a microwave annealing method that generates a high substrate heating rate (18 °C s−1) to rapidly order lamellar BCP thin films on a high-resistivity boron-doped silicon substrate. This substrate efficiently absorbs microwave energy, creating a rapid and substantial z-temperature gradient in the BCP film. The high-temperature annealing facilitated by microwave heating generates 1L0 surface terraces composed of unconventional rim-like morphologies with a 0.5L0 (half domain spacing) height, forming half-domain height island-on-island and hole-in-hole topographies. We hypothesize that these topographies are related to the highly dynamic through-film thickness temperature gradient. Notably, reducing the substrate heating rate to 13.5 °C s−1 only produces interesting 0.5L0 top surface structures. Additionally, the elevated high temperatures of microwave annealing significantly increase the vertical lamellar domain size, L0, of the BCP film surface topography, which we believe corresponds to an “intermediate segregation” regime of chain stretching. This domain size enhancement is due to the synergy of the reduced interaction parameter between blocks and improved interlayer diffusional dynamics resulting from the sharp temperature spike and rapid vitrification. These unique morphological effects, exclusive to microwave annealing, are not seen in conventional thermal or solvent annealing and open new avenues for microwave substrate-directed self-assembly (MS-DSA) to create unique surface and internal BCP morphologies for specialized applications.
{"title":"Concentric half-domain spacing morphologies and anomalous domain stretching in microwave annealed block copolymer thin films†","authors":"Ugur Aslan, Maninderjeet Singh, Akhtar Gul, Jack F. Douglas and Alamgir Karim","doi":"10.1039/D5LP00116A","DOIUrl":"https://doi.org/10.1039/D5LP00116A","url":null,"abstract":"<p >Block copolymer (BCP) films hold significant promise for a wide array of technological applications, including nanopatterning, nanophotonics, polymer electrolytes, and optical waveguides. However, the practical realization of these applications is often hindered by the slow kinetics of the ordering of block copolymers, attributed to the inherently glassy dynamics of polymeric soft materials under standard processing conditions. The diverse range of BCP morphologies further highlights the unique self-assembly characteristics of polymeric materials. In this study, we employ a microwave annealing method that generates a high substrate heating rate (18 °C s<small><sup>−1</sup></small>) to rapidly order lamellar BCP thin films on a high-resistivity boron-doped silicon substrate. This substrate efficiently absorbs microwave energy, creating a rapid and substantial <em>z</em>-temperature gradient in the BCP film. The high-temperature annealing facilitated by microwave heating generates 1<em>L</em><small><sub><em>0</em></sub></small> surface terraces composed of unconventional rim-like morphologies with a 0.5<em>L</em><small><sub><em>0</em></sub></small> (half domain spacing) height, forming half-domain height island-on-island and hole-in-hole topographies. We hypothesize that these topographies are related to the highly dynamic through-film thickness temperature gradient. Notably, reducing the substrate heating rate to 13.5 °C s<small><sup>−1</sup></small> only produces interesting 0.5<em>L</em><small><sub><em>0</em></sub></small> top surface structures. Additionally, the elevated high temperatures of microwave annealing significantly increase the vertical lamellar domain size, <em>L</em><small><sub><em>0</em></sub></small>, of the BCP film surface topography, which we believe corresponds to an “intermediate segregation” regime of chain stretching. This domain size enhancement is due to the synergy of the reduced interaction parameter between blocks and improved interlayer diffusional dynamics resulting from the sharp temperature spike and rapid vitrification. These unique morphological effects, exclusive to microwave annealing, are not seen in conventional thermal or solvent annealing and open new avenues for microwave substrate-directed self-assembly (MS-DSA) to create unique surface and internal BCP morphologies for specialized applications.</p>","PeriodicalId":101139,"journal":{"name":"RSC Applied Polymers","volume":" 5","pages":" 1325-1339"},"PeriodicalIF":0.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lp/d5lp00116a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}