Pub Date : 2026-03-11Epub Date: 2026-01-27DOI: 10.1016/j.eurpolymj.2026.114542
Samir M.M. Morsi , Morsi M. Morsi , Mahmoud E. Abd El-Aziz
Synthetic recognition polymers (SRPs) are functional materials engineered to selectively bind target molecules through molecular imprinting, where a template directs the arrangement of monomers to form complementary binding cavities. Their synthesis relies on key components: a template, a functional monomer, a crosslinker, and an initiator, which collectively create a stable network capable of mimicking the recognition behavior of antibodies and enzymes. Depending on template monomer interactions, SRPs can be prepared using covalent, non-covalent, or semi-covalent imprinting strategies. Advances in polymer chemistry and fabrication methods have expanded SRP applications in chromatography, sensing, separation membranes, catalysis, drug delivery, and environmental remediation. Increasing attention is given to smart, stimuli-responsive SRPs that modulate binding in response to temperature, pH, ions, light, magnetic fields, or biomolecules. This review summarizes the principles of molecular imprinting, recent technological progress, and emerging trends, highlighting how modern design approaches enable SRPs with improved selectivity, faster response, and tunable functionality. It also outlines future challenges and opportunities in developing next-generation adaptive SRP materials.
{"title":"Advances in molecularly imprinted synthetic polymers: from structural principles to functional technologies","authors":"Samir M.M. Morsi , Morsi M. Morsi , Mahmoud E. Abd El-Aziz","doi":"10.1016/j.eurpolymj.2026.114542","DOIUrl":"10.1016/j.eurpolymj.2026.114542","url":null,"abstract":"<div><div>Synthetic recognition polymers (SRPs) are functional materials engineered to selectively bind target molecules through molecular imprinting, where a template directs the arrangement of monomers to form complementary binding cavities. Their synthesis relies on key components: a template, a functional monomer, a crosslinker, and an initiator, which collectively create a stable network capable of mimicking the recognition behavior of antibodies and enzymes. Depending on template monomer interactions, SRPs can be prepared using covalent, non-covalent, or semi-covalent imprinting strategies. Advances in polymer chemistry and fabrication methods have expanded SRP applications in chromatography, sensing, separation membranes, catalysis, drug delivery, and environmental remediation. Increasing attention is given to smart, stimuli-responsive SRPs that modulate binding in response to temperature, pH, ions, light, magnetic fields, or biomolecules. This review summarizes the principles of molecular imprinting, recent technological progress, and emerging trends, highlighting how modern design approaches enable SRPs with improved selectivity, faster response, and tunable functionality. It also outlines future challenges and opportunities in developing next-generation adaptive SRP materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"245 ","pages":"Article 114542"},"PeriodicalIF":6.3,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-11Epub Date: 2026-02-01DOI: 10.1016/j.eurpolymj.2026.114545
Lijiu Cao , Zongxing Yu , Xu Ma , Danrui Wei , Yue Hu , Yunpeng Gong , Shuai Wang , Jian Huang , Yufang Chen
Melamine (M) is a nitrogen-rich triazine heterocyclic organic compound. Currently, it is primarily utilized in the preparation of melamine–formaldehyde resin (MF), which is widely used in adhesives, molding compounds, coating additives and other fields. However, some problems are associated with MF, such as the release of free formaldehyde in its use, which is hazardous to safety production and human health. In this study, melamine (M) and acrylic acid (AA) are used as raw materials to synthesize the monoacrylamidotriazine (MAT) through dehydration reaction. Subsequently, MAT is polymerized through free radical polymerization to prepare polyacrylamide triazine polymer (PMAT) and the structure and properties of PMAT are characterized and tested. The results show that PMAT was successfully polymerized at 100℃ for 8.0 h, with ethylene glycol used as the solvent and 2,2-azobisisobutyronitrile (AIBN) as the initiator. The chemical structure and morphological characteristics of PMAT were systematically verified by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetry (TG), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Additionally, the adhesion of the PMAT −based coating reached 13.09 MPa, and exhibited resistance to chemical corrosion and wear. This research has preliminarily established a technical route for the synthesis of melamine-based polymers through free radical polymerization. It holds important practical significance for promoting the technological development of novel functional melamine-based polymers and facilitating the technical iteration, optimization, and upgrading of the melamine industry chain.
{"title":"Synthesis, polymerization and properties of monoacrylamidotriazine","authors":"Lijiu Cao , Zongxing Yu , Xu Ma , Danrui Wei , Yue Hu , Yunpeng Gong , Shuai Wang , Jian Huang , Yufang Chen","doi":"10.1016/j.eurpolymj.2026.114545","DOIUrl":"10.1016/j.eurpolymj.2026.114545","url":null,"abstract":"<div><div>Melamine (M) is a nitrogen-rich triazine heterocyclic organic compound. Currently, it is primarily utilized in the preparation of melamine–formaldehyde resin (MF), which is widely used in adhesives, molding compounds, coating additives and other fields. However, some problems are associated with MF, such as the release of free formaldehyde in its use, which is hazardous to safety production and human health. In this study, melamine (M) and acrylic acid (AA) are used as raw materials to synthesize the monoacrylamidotriazine (MAT) through dehydration reaction. Subsequently, MAT is polymerized through free radical polymerization to prepare polyacrylamide triazine polymer (P<sub>MAT</sub>) and the structure and properties of P<sub>MAT</sub> are characterized and tested. The results show that P<sub>MAT</sub> was successfully polymerized at 100℃ for 8.0 h, with ethylene glycol used as the solvent and 2,2-azobisisobutyronitrile (AIBN) as the initiator. The chemical structure and morphological characteristics of P<sub>MAT</sub> were systematically verified by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetry (TG), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Additionally, the adhesion of the P<sub>MAT</sub> −based coating reached 13.09 MPa, and exhibited resistance to chemical corrosion and wear. This research has preliminarily established a technical route for the synthesis of melamine-based polymers through free radical polymerization. It holds important practical significance for promoting the technological development of novel functional melamine-based polymers and facilitating the technical iteration, optimization, and upgrading of the melamine industry chain.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"245 ","pages":"Article 114545"},"PeriodicalIF":6.3,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-11Epub Date: 2026-01-28DOI: 10.1016/j.eurpolymj.2026.114519
Xu Hu , Kok Hoong Wong , Nai Yeen Gavin Lai , Juan Li , Haibin Yu , Long Wang
To develop a sustainable and compatible plasticizer for polylactide (PLA), lactide oligomers (LOs) with full biocarbon were synthesized through bulk ring-opening polymerization, initiated by tetrahydrogeraniol. The effects of lactic acid chain length (4, 12, 24 theoretical repeating units) and terminal group (tetrahydrogeranyl and ethyl) on plasticization efficiency were studied. It was determined that the plasticization efficiency decreased with the increase in repeating units and the decrease in terminal alkyl chain length, which could be explained by the strengthened interactions. The LOs have good compatibility with PLA, which can be seen from the high transparent appearance of PLA blends, no phase separation in morphology, one glass transition temperature, low migration rate (<1 % in water, n-hexane and 70 °C) and good durability (performance can be maintained more than 90 days). Tetrahydrogeraniol-initiated lactide oligomer with 4 repeating lactic acid units (TLO4) exhibits higher plasticization efficiency and better durability than commercial acetyl-tri-n-butyl citrate. The elongation at break of the PLA blend is remarkably increased by adding 10 wt% TLO4 (323.9 %) and can further reach 453.1 % (20 wt% loading), with a low glass transition temperature at 32 °C. The crystallization ability of PLA was enhanced by a small amount of LOs, without a noticeable increase in crystallization rate. The molecular dynamics simulation was used to help understand the plasticization mechanism of LOs. This study adds a new choice to the environmentally friendly plasticizers for PLA and may be helpful for the further development of sustainable additives for PLA.
{"title":"Green and facile synthesis of tetrahydrogeraniol-initiated lactide oligomers for plasticizing polylactide","authors":"Xu Hu , Kok Hoong Wong , Nai Yeen Gavin Lai , Juan Li , Haibin Yu , Long Wang","doi":"10.1016/j.eurpolymj.2026.114519","DOIUrl":"10.1016/j.eurpolymj.2026.114519","url":null,"abstract":"<div><div>To develop a sustainable and compatible plasticizer for polylactide (PLA), lactide oligomers (LOs) with full biocarbon were synthesized through bulk ring-opening polymerization, initiated by tetrahydrogeraniol. The effects of lactic acid chain length (4, 12, 24 theoretical repeating units) and terminal group (tetrahydrogeranyl and ethyl) on plasticization efficiency were studied. It was determined that the plasticization efficiency decreased with the increase in repeating units and the decrease in terminal alkyl chain length, which could be explained by the strengthened interactions. The LOs have good compatibility with PLA, which can be seen from the high transparent appearance of PLA blends, no phase separation in morphology, one glass transition temperature, low migration rate (<1 % in water, n-hexane and 70 °C) and good durability (performance can be maintained more than 90 days). Tetrahydrogeraniol-initiated lactide oligomer with 4 repeating lactic acid units (TLO4) exhibits higher plasticization efficiency and better durability than commercial acetyl-tri-n-butyl citrate. The elongation at break of the PLA blend is remarkably increased by adding 10 wt% TLO4 (323.9 %) and can further reach 453.1 % (20 wt% loading), with a low glass transition temperature at 32 °C. The crystallization ability of PLA was enhanced by a small amount of LOs, without a noticeable increase in crystallization rate. The molecular dynamics simulation was used to help understand the plasticization mechanism of LOs. This study adds a new choice to the environmentally friendly plasticizers for PLA and may be helpful for the further development of sustainable additives for PLA.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"245 ","pages":"Article 114519"},"PeriodicalIF":6.3,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymeric nanoparticles (PNPs) are recognized as a potent platform for cancer therapy and provide hope for personalized medicine and targeted therapy. Many polymers are used in PNPs, including polycaprolactone (PCL), polyethylene glycol–polycaprolactone (PEG-PCL), poly(n-butyl cyanoacrylate) (PBCA), poly(ethylene oxide)-poly(butylene oxide), pullulan, poly(lactic-co-glycolic acid) (PLGA), poly(lactic acid) (PLA), methoxypoly(ethylene glycol)-poly(l-lactic acid) (MPEG-PLA), D-α-tocopheryl polyethylene glycol 1000 succinate-poly(lactic acid) (TPGS-PLA), and chitosan. PNPs have gained attention, owing to their biocompatibility, tunable properties, and value in drug formulation, to improve drug delivery. This technology was originally developed to increase drug effectiveness, improve stability, and reduce systemic exposure. PNPs can take advantage of two different types of targeting: passive targeting using enhanced permeability and, or active targeting via functionalizing ligands that enable drug delivery of components. Furthermore, recent studies also show PNPs can provide solutions to drug resistance, improve patient survival, and enable highly effective drug delivery to solid tumors. It is important to note that PNPs are a transformative innovation in oncology, as they improve drug delivery and therapeutics. Furthermore, PNPs are changing the way we can administer cancer therapy through multidimensional therapeutic approaches since they possess the selectivity, versatility, and biocompatibility potential to make them more powerful enablers of future cancer nanomedicine.
{"title":"Emerging Roles of polymeric nanoparticles in cancer Therapy: Design, Targeting, and clinical integration","authors":"Seyedeh Elaheh Sheykholeslami , Saba Halimi , Fatemeh Ahangari , Azadeh Mohammadgholi , Afsoun Mansouri , Hamed Mirzaei Dehaghi , Maliheh Khaleghi Eynakchi , Sara Hosseini , Seyed Kasra Sadr Tahouri , Zahra Shahbazi , Hassan Noorbazargan","doi":"10.1016/j.eurpolymj.2025.114447","DOIUrl":"10.1016/j.eurpolymj.2025.114447","url":null,"abstract":"<div><div>Polymeric nanoparticles (PNPs) are recognized as a potent platform for cancer therapy and provide hope for personalized medicine and targeted therapy. Many polymers are used in PNPs, including polycaprolactone (PCL), polyethylene glycol–polycaprolactone (PEG-PCL), poly(n-butyl cyanoacrylate) (PBCA), poly(ethylene oxide)-poly(butylene oxide), pullulan, poly(lactic-co-glycolic acid) (PLGA), poly(lactic acid) (PLA), methoxypoly(ethylene glycol)-poly(l-lactic acid) (MPEG-PLA), D-α-tocopheryl polyethylene glycol 1000 succinate-poly(lactic acid) (TPGS-PLA), and chitosan. PNPs have gained attention, owing to their biocompatibility, tunable properties, and value in drug formulation, to improve drug delivery. This technology was originally developed to increase drug effectiveness, improve stability, and reduce systemic exposure. PNPs can take advantage of two different types of targeting: passive targeting using enhanced permeability and, or active targeting via functionalizing ligands that enable drug delivery of components. Furthermore, recent studies also show PNPs can provide solutions to drug resistance, improve patient survival, and enable highly effective drug delivery to solid tumors. It is important to note that PNPs are a transformative innovation in oncology, as they improve drug delivery and therapeutics. Furthermore, PNPs are changing the way we can administer cancer therapy through multidimensional therapeutic approaches since they possess the selectivity, versatility, and biocompatibility potential to make them more powerful enablers of future cancer nanomedicine.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114447"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-20Epub Date: 2026-01-16DOI: 10.1016/j.eurpolymj.2026.114509
Adalet Nur Altunkaya , Binnur Aydogan Temel , Muhammet U. Kahveci
Single-chain polymer nanoparticles (SCNPs) have garnered significant attention due to their ability to mimic the folding behavior of proteins and their potential in applications such as drug delivery, catalysis, and sensing. Herein, we present a novel approach for preparation of SCNPs using a photo-induced inverse electron-demand Diels-Alder (photo-IEDDA) reaction. The base polymer, P(MMA-co-HEMA), synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, was functionalized with dihydrotetrazine (dHTz) and norbornene (Nb) moieties through esterification over HEMA units. Upon irradiation of a dilute solution of the modified polymer, P(MMA-co-HEMA)-M−PPA−dHTz/Nb, in the presence of a photosensitizer, dihydrotetrazine groups were in situ converted to reactive tetrazine moieties, enabling intramolecular crosslinking via the photo-IEDDA reaction. This process yielded sub-10 nm SCNPs with high precision and control. The integration of light-triggered reactivity with efficient click chemistry highlights the potential of this method for the scalable production of well-defined SCNPs with tailored properties for advanced applications in nanotechnology and materials science.
{"title":"Fabrication of single-chain polymer nanoparticles by light-induced inverse electron demand diels-alder (Photo-IEDDA) reaction","authors":"Adalet Nur Altunkaya , Binnur Aydogan Temel , Muhammet U. Kahveci","doi":"10.1016/j.eurpolymj.2026.114509","DOIUrl":"10.1016/j.eurpolymj.2026.114509","url":null,"abstract":"<div><div>Single-chain polymer nanoparticles (SCNPs) have garnered significant attention due to their ability to mimic the folding behavior of proteins and their potential in applications such as drug delivery, catalysis, and sensing. Herein, we present a novel approach for preparation of SCNPs using a photo-induced inverse electron-demand Diels-Alder (photo-IEDDA) reaction. The base polymer, P(MMA-<em>co</em>-HEMA), synthesized <em>via</em> reversible addition-fragmentation chain transfer (RAFT) polymerization, was functionalized with dihydrotetrazine (dHTz) and norbornene (Nb) moieties through esterification over HEMA units. Upon irradiation of a dilute solution of the modified polymer, P(MMA-<em>co</em>-HEMA)-<em>M</em>−PPA−dHTz/Nb, in the presence of a photosensitizer, dihydrotetrazine groups were <em>in situ</em> converted to reactive tetrazine moieties, enabling intramolecular crosslinking <em>via</em> the photo-IEDDA reaction. This process yielded sub-10 nm SCNPs with high precision and control. The integration of light-triggered reactivity with efficient click chemistry highlights the potential of this method for the scalable production of well-defined SCNPs with tailored properties for advanced applications in nanotechnology and materials science.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114509"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035776","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-20Epub Date: 2026-01-10DOI: 10.1016/j.eurpolymj.2026.114504
Lauren E. Ball , Bennie Motloung , Michael-Phillip Smith , Rueben Pfukwa , Bert Klumperman
Stimuli responsive double hydrophilic block copolymers (DHBCs) are ubiquitous in water-based applications, such as drug/gene delivery, nanoreactor and sensor development, photocatalysis, 3D inkjet printing, etc. DHBC-based gels, cross-linked with calcium ions, are particularly valuable for the development of biomedically relevant materials (such as wound dressings or injectable formulations), due to the benignity of Ca2+ in biological systems. Therefore, gels formed via the calcium-mediated crosslinking of poly(4-tert-butylstyrene-alt-maleic acid)-block-poly(N-acryloylmorpholine) (PtBuSMA-b-PNAM), which in itself constitutes polymers with established biomedical relevance, are promising candidates for the development of the aforementioned biomedical materials. To this end, PtBuSMA-b-PNAM diblock copolymers were synthesized with different block ratios (1:1, 1:2 and 2:1) and treated with Ca2+, whereby the concentration of the two constituents, the pH or the block copolymer architecture was varied, in order to tune the mechanical properties of the PtBuSMA-b-PNAM/Ca2+ gels. PtBuSMA-b-PNAM/Ca2+ with the lowest PtBuSMA composition (1:2 block ratio) could not form gels and rather formed micelles, whereas PtBuSMA-b-PNAM/Ca2+ with the highest PtBuSMA composition (2:1 block ratio) exhibited enhanced mechanical properties compared to the 1:1 block ratio. The overall amphiphilic balance of the PtBuSMA-b-PNAM/Ca2+ complexes was therefore proven vital for the design and formation of gels with desirable mechanical properties. PtBuSMA-b-PNAM/Ca2+ gels exhibited shear thinning when subjected to high shear conditions and demonstrated some self-healing properties, suggesting these materials have value in the formulation of injectable gels.
{"title":"Mechanistic insights into the calcium-mediated gelation of poly(4-tert-butylstyrene-alt-maleic acid)-block-poly(N-acryloylmorpholine) double hydrophilic block copolymers","authors":"Lauren E. Ball , Bennie Motloung , Michael-Phillip Smith , Rueben Pfukwa , Bert Klumperman","doi":"10.1016/j.eurpolymj.2026.114504","DOIUrl":"10.1016/j.eurpolymj.2026.114504","url":null,"abstract":"<div><div>Stimuli responsive double hydrophilic block copolymers (DHBCs) are ubiquitous in water-based applications, such as drug/gene delivery, nanoreactor and sensor development, photocatalysis, 3D inkjet printing, etc. DHBC-based gels, cross-linked with calcium ions, are particularly valuable for the development of biomedically relevant materials (such as wound dressings or injectable formulations), due to the benignity of Ca<sup>2+</sup> in biological systems. Therefore, gels formed <em>via</em> the calcium-mediated crosslinking of poly(4-<em>tert</em>-butylstyrene-<em>alt</em>-maleic acid)-<em>block</em>-poly(<em>N</em>-acryloylmorpholine) (P<em>t</em>BuSMA-<em>b</em>-PNAM), which in itself constitutes polymers with established biomedical relevance, are promising candidates for the development of the aforementioned biomedical materials. To this end, P<em>t</em>BuSMA-<em>b</em>-PNAM diblock copolymers were synthesized with different block ratios (1:1, 1:2 and 2:1) and treated with Ca<sup>2+</sup>, whereby the concentration of the two constituents, the pH or the block copolymer architecture was varied, in order to tune the mechanical properties of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> gels. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> with the lowest P<em>t</em>BuSMA composition (1:2 block ratio) could not form gels and rather formed micelles, whereas P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> with the highest P<em>t</em>BuSMA composition (2:1 block ratio) exhibited enhanced mechanical properties compared to the 1:1 block ratio. The overall amphiphilic balance of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> complexes was therefore proven vital for the design and formation of gels with desirable mechanical properties. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca<sup>2+</sup> gels exhibited shear thinning when subjected to high shear conditions and demonstrated some self-healing properties, suggesting these materials have value in the formulation of injectable gels.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114504"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-20Epub Date: 2026-01-17DOI: 10.1016/j.eurpolymj.2026.114518
Kun Xu , Haina Mi , Xinyi Zong , Yunji Xie , Zhaoyan Sun , Baijun Liu , Xiaobo Liu , Wei Hu
Since phosphoric acid (PA) has a critical effect on HT-PEM performance, a porous aromatic framework with triazine and –OH groups (PAF-225) was synthesized, and sulfonation was utilized for generating sPAF-225 in this work. On the other hand, OPBI was modified by quaternary ammonium (QA) to prepare QAOPBI containing QA groups. The acid-base effect of QA+⋅⋅H2PO4− ion pairs resulted by the charge interaction between cations and bisphosphonates, can successfully prevent the loss of PA. Furthermore, the –OH, triazine groups and −SO3H of sPAF-225 can form hydrogen bonds with QAOPBI and PA, this can improve the proton conduction efficiency by the increasing proton transport sites and PA retention rate. The PA retention rate of sPAF-225-6/QAOPBI-30 was 34.7 %, which was considerably greater than OPBI (31.4 %) and sPAF-225-6/OPBI (31.4 %), confirming the effect of QA group on the retention of PA. The peak power density of the H2/O2 fuel cells assembled with sPAF-225-6/QAOPBI-30 membrane reached 688.75 mW cm−2 with low Pt loading of 0.3 mg cm−2 at 200 °C without additional humidification, effectively optimizing the capability of fuel cell.
由于磷酸（PA）对HT-PEM的性能有重要影响，本文合成了含三嗪和-OH基团的多孔芳香骨架（PAF-225），并利用磺化法制备了sPAF-225。另一方面，用季铵（QA）修饰OPBI，制备含有QA基团的QAOPBI。阳离子与双膦酸盐之间的电荷相互作用所产生的QA+ H2PO4−离子对的酸碱效应可以成功地防止PA的损失。此外，sPAF-225的-OH、三嗪基团和- SO3H可以与QAOPBI和PA形成氢键，这可以通过增加质子传递位点和PA保留率来提高质子传导效率。sPAF-225-6/QAOPBI-30的PA保留率为34.7%，明显高于OPBI（31.4%）和sPAF-225-6/OPBI(31.4%)，证实了QA组对PA保留率的影响。采用sPAF-225-6/QAOPBI-30膜制备的H2/O2燃料电池在200℃条件下的峰值功率密度达到688.75 mW cm -2， Pt负载低，为0.3 mg cm -2，无需额外加湿，有效地优化了燃料电池的性能。
{"title":"sPAF-225/QAOPBI composite high-temperature proton exchange membrane with robust acid-base interaction and controlled phosphoric acid","authors":"Kun Xu , Haina Mi , Xinyi Zong , Yunji Xie , Zhaoyan Sun , Baijun Liu , Xiaobo Liu , Wei Hu","doi":"10.1016/j.eurpolymj.2026.114518","DOIUrl":"10.1016/j.eurpolymj.2026.114518","url":null,"abstract":"<div><div>Since phosphoric acid (PA) has a critical effect on HT-PEM performance, a porous aromatic framework with triazine and –OH groups (PAF-225) was synthesized, and sulfonation was utilized for generating sPAF-225 in this work. On the other hand, OPBI was modified by quaternary ammonium (QA) to prepare QAOPBI containing QA groups. The acid-base effect of QA<sup>+</sup>⋅⋅H<sub>2</sub>PO<sub>4</sub><sup>−</sup> ion pairs resulted by the charge interaction between cations and bisphosphonates, can successfully prevent the loss of PA. Furthermore, the –OH, triazine groups and −SO<sub>3</sub>H of sPAF-225 can form hydrogen bonds with QAOPBI and PA, this can improve the proton conduction efficiency by the increasing proton transport sites and PA retention rate. The PA retention rate of sPAF-225-6/QAOPBI-30 was 34.7 %, which was considerably greater than OPBI (31.4 %) and sPAF-225-6/OPBI (31.4 %), confirming the effect of QA group on the retention of PA. The peak power density of the H<sub>2</sub>/O<sub>2</sub> fuel cells assembled with sPAF-225-6/QAOPBI-30 membrane reached 688.75 mW cm<sup>−2</sup> with low Pt loading of 0.3 mg cm<sup>−2</sup> at 200 °C without additional humidification, effectively optimizing the capability of fuel cell.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114518"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paracetamol based benzoxazines (PA-Bz) were synthesized using structurally different amines namely 4-aminoacetanilide (AAC), aniline (AN), adamantylamine (AM) and 1,12-diaminododecane (DAD) through Mannich condensation (PA-AAC, PA-AN, PA-AM, PA-DAD). The molecular structure of the synthesized benzoxazines was confirmed through spectroscopic techniques. DSC studies showed that curing temperature of the synthesized benzoxazines are ranged between 205 and 232°C. TGA results showed that poly(PA-DAD) showed the highest maximum degradation temperature of 452°C. Contact angle measurement revealed that poly(PA-AM) exhibited the maximum water contact angle value of 142°. The contact angle studies clearly showed that the resulting polymer can be used for the coating purpose as a hydrophobic sealant. Both PA-AM and its corresponding polymer demonstrated the higher antimicrobial activity. All the synthesized compounds showed 99% corrosion inhibition efficiency. The swelling ratio and high gel content of poly(PA-AN) and poly(PA-DAD) proved its higher crosslinking density. The results obtained on different analysis indicated that the synthesized benzoxazines can be used effectively in coating application, oil–water separation process and also to inhibit the microbial growth on the surface.
{"title":"Paracetamol-based benzoxazines for surface protection applications: Hydrophobicity, antimicrobial activity and corrosion resistance","authors":"Praba Nagarajan , Latha Govindraj , Balaji Krishnasamy , Subramanian Sathy Srikandan","doi":"10.1016/j.eurpolymj.2026.114523","DOIUrl":"10.1016/j.eurpolymj.2026.114523","url":null,"abstract":"<div><div>Paracetamol based benzoxazines (PA-Bz) were synthesized using structurally different amines namely 4-aminoacetanilide (AAC), aniline (AN), adamantylamine (AM) and 1,12-diaminododecane (DAD) through Mannich condensation (PA-AAC, PA-AN, PA-AM, PA-DAD). The molecular structure of the synthesized benzoxazines was confirmed through spectroscopic techniques. DSC studies showed that curing temperature of the synthesized benzoxazines are ranged between 205 and 232°C. TGA results showed that poly(PA-DAD) showed the highest maximum degradation temperature of 452°C. Contact angle measurement revealed that poly(PA-AM) exhibited the maximum water contact angle value of 142°. The contact angle studies clearly showed that the resulting polymer can be used for the coating purpose as a hydrophobic sealant. Both PA-AM and its corresponding polymer demonstrated the higher antimicrobial activity. All the synthesized compounds showed 99% corrosion inhibition efficiency. The swelling ratio and high gel content of poly(PA-AN) and poly(PA-DAD) proved its higher crosslinking density. The results obtained on different analysis indicated that the synthesized benzoxazines can be used effectively in coating application, oil–water separation process and also to inhibit the microbial growth on the surface.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114523"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-20Epub Date: 2026-01-14DOI: 10.1016/j.eurpolymj.2026.114500
Martina Vragović , Jan Pankrác , Peter Páral , Martin Báječný , Alessandro Jäger , Vladimir Sincari , Jan Kučka , Martin Hrubý , Marcela Filipová , Rafał Konefał , Fernando Carlos Giacomelli , Luděk Šefc , Eliézer Jäger
Nanomedicines have shown significant potential in advancing treatment for a variety of cancer types. Despite these advances, further research is essential to improve the efficacy and selectivity of anticancer nanomedicines, particularly by developing delivery systems capable of achieving high efficacy with minimal off-target toxicity. We herein report novel pH-responsive block copolymer-drug conjugates based on poly(N-(2-hydroxypropyl)methacrylamide) (PHPMAm) and benzoic imine linkages, uniquely combining stealth performance with tunable, acid-triggered drug release. By engineering block and random copolymer architectures with controlled hydrophilic shell length, we systematically evaluated how polymer structure governs self-assembly, release kinetics, and therapeutic outcomes. The conjugates achieve up to 10–12 wt% doxorubicin loading, with pH-selective release half-live spanning within 2–40 h. In contrast to most Schiff base polymer-drug systems limited to in vitro data, the synthesized polymer-drug conjugates demonstrated outstanding antitumor efficacy and 100 % survival for spherical assemblies in aggressive murine lymphoma models, with superior safety. Unlike conventional PEG systems, PHPMAm-based copolymers can potentially avoid anti-PEG immunogenicity and exhibit exceptional in vivo stability and tumor accumulation.
{"title":"Morphology control in benzoic imine-linked polymer-drug conjugates for adaptive drug delivery and enhanced in vivo efficacy","authors":"Martina Vragović , Jan Pankrác , Peter Páral , Martin Báječný , Alessandro Jäger , Vladimir Sincari , Jan Kučka , Martin Hrubý , Marcela Filipová , Rafał Konefał , Fernando Carlos Giacomelli , Luděk Šefc , Eliézer Jäger","doi":"10.1016/j.eurpolymj.2026.114500","DOIUrl":"10.1016/j.eurpolymj.2026.114500","url":null,"abstract":"<div><div>Nanomedicines have shown significant potential in advancing treatment for a variety of cancer types. Despite these advances, further research is essential to improve the efficacy and selectivity of anticancer nanomedicines, particularly by developing delivery systems capable of achieving high efficacy with minimal off-target toxicity. We herein report novel pH-responsive block copolymer-drug conjugates based on poly(<em>N</em>-(2-hydroxypropyl)methacrylamide) (PHPMAm) and benzoic imine linkages, uniquely combining stealth performance with tunable, acid-triggered drug release. By engineering block and random copolymer architectures with controlled hydrophilic shell length, we systematically evaluated how polymer structure governs self-assembly, release kinetics, and therapeutic outcomes. The conjugates achieve up to 10–12 wt% doxorubicin loading, with pH-selective release half-live spanning within 2–40 h. In contrast to most Schiff base polymer-drug systems limited to <em>in vitro</em> data, the synthesized polymer-drug conjugates demonstrated outstanding antitumor efficacy and 100 % survival for spherical assemblies in aggressive murine lymphoma models, with superior safety. Unlike conventional PEG systems, PHPMAm-based copolymers can potentially avoid anti-PEG immunogenicity and exhibit exceptional <em>in vivo</em> stability and tumor accumulation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114500"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035777","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-20Epub Date: 2026-01-08DOI: 10.1016/j.eurpolymj.2026.114506
Anastasia E. Gater , Mitchell A. Nascimento , Malachy M. Gilbert , Erin M. Leitao
Polyphosphoramidates are polymers featuring phosphorus-nitrogen bonds within their side or main chain, which impart unique characteristics such as acid-lability and flame retardancy. However, polyphosphoramidates generally require clever design of (P-N)-containing monomers which can then be linked together through conventional polymerisation strategies. Herein, we report the synthesis and characterisation of tyrosine-based polyphosphoramidates with up to ca. 30 repeat units via solvent-free mechanochemically-assisted polycondensation. This polymer synthesis takes advantage of the bifunctional amino and phenolic moieties of tyrosine to form a random copolymer of N-P-N, N-P-O, and O-P-O bonding motifs between tyrosine methyl ester and phenyldichlorophosphate. While polycondensation routes to polyphosphoramidates have been reported previously, this work also represents the first example of a mechanochemical synthesis of a polyphosphoramidate. The use of solid phase synthesis enables the formation of high molecular weight linear species unobtainable under traditional solution phase methods. The obtained polymer exhibits a Tg of ca. 81 ℃, resists degradation up to 250 ℃, and has a char yield of 45.0% remaining at 700 ℃ in N2. These results demonstrate a solvent-free mechanochemical route to partially bio-based polyphosphoramidates.
{"title":"Solvent-free mechanochemical polycondensation to generate tyrosine-based polyphosphoramidates","authors":"Anastasia E. Gater , Mitchell A. Nascimento , Malachy M. Gilbert , Erin M. Leitao","doi":"10.1016/j.eurpolymj.2026.114506","DOIUrl":"10.1016/j.eurpolymj.2026.114506","url":null,"abstract":"<div><div>Polyphosphoramidates are polymers featuring phosphorus-nitrogen bonds within their side or main chain, which impart unique characteristics such as acid-lability and flame retardancy. However, polyphosphoramidates generally require clever design of (P-N)-containing monomers which can then be linked together through conventional polymerisation strategies. Herein, we report the synthesis and characterisation of tyrosine-based polyphosphoramidates with up to ca. 30 repeat units via solvent-free mechanochemically-assisted polycondensation. This polymer synthesis takes advantage of the bifunctional amino and phenolic moieties of tyrosine to form a random copolymer of <strong>N-P-N</strong>, <strong>N-P-O</strong>, and <strong>O-P-O</strong> bonding motifs between tyrosine methyl ester and phenyldichlorophosphate. While polycondensation routes to polyphosphoramidates have been reported previously, this work also represents the first example of a mechanochemical synthesis of a polyphosphoramidate. The use of solid phase synthesis enables the formation of high molecular weight linear species unobtainable under traditional solution phase methods. The obtained polymer exhibits a <em>T<sub>g</sub></em> of ca. 81 ℃, resists degradation up to 250 ℃, and has a char yield of 45.0% remaining at 700 ℃ in N<sub>2</sub>. These results demonstrate a solvent-free mechanochemical route to partially bio-based polyphosphoramidates.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114506"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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