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Fabrication of low-shrinkage hydrophilic zwitterionic coating by radical photopolymerization using branched macromonomer as cross-linker for oil/water emulsion separation
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113680
Bin Peng, Liyuan Fan, Jingyu Zhang, Xin Liu, Yicheng Jiang, Qiang Zhang
Fabrication of hydrophilic coatings on membrane surface is one of the best methods to solve membrane fouling caused by oil or other pollutants. Recently, branched macromonomer as cross-linker in polymerization are proved to favor the uniformity and stability of coatings. Herein, we synthesized a branched macromonomer poly(ethylene glycol dimethacrylate) (BP(EGDMA)), which had abundant vinyl groups via catalytic chain transfer polymerization (CCTP), for fabrication of zwitterionic hydrophilic coatings with low volume shrinkage on different surface through photopolymerization. The low molecular weight cross-linkers with different functionality were used as control groups. The results of polymerization on glass plate showed that the hydrophilic coatings cross-linked by BP(EGDMA) was more uniform and stable. The surface chemistry, wettability and permeability of membranes were further investigated. The results showed that coatings which used macromonomer BP(EGDMA) as cross-linker on porous membrane surface was still more uniform than those which used low molecular weight cross-linkers. Meanwhile, the effects of the irradiation time and monomer usage on membrane coatings were explored to choose the best fabrication condition. Under the suitable conditions, the membrane used BP(EGDMA) as cross-linker showed a high oil rejection of >99 % among several oil-in-water emulsion. Moreover, the anti-biofouling experiment revealed that the macromonomer BP(EGDMA) would endow hydrophilic coatings with better fouling resistance by longer irradiation time and larger total monomer usage.
{"title":"Fabrication of low-shrinkage hydrophilic zwitterionic coating by radical photopolymerization using branched macromonomer as cross-linker for oil/water emulsion separation","authors":"Bin Peng,&nbsp;Liyuan Fan,&nbsp;Jingyu Zhang,&nbsp;Xin Liu,&nbsp;Yicheng Jiang,&nbsp;Qiang Zhang","doi":"10.1016/j.eurpolymj.2024.113680","DOIUrl":"10.1016/j.eurpolymj.2024.113680","url":null,"abstract":"<div><div>Fabrication of hydrophilic coatings on membrane surface is one of the best methods to solve membrane fouling caused by oil or other pollutants. Recently, branched macromonomer as cross-linker in polymerization are proved to favor the uniformity and stability of coatings. Herein, we synthesized a branched macromonomer poly(ethylene glycol dimethacrylate) (BP(EGDMA)), which had abundant vinyl groups <em>via</em> catalytic chain transfer polymerization (CCTP), for fabrication of zwitterionic hydrophilic coatings with low volume shrinkage on different surface through photopolymerization. The low molecular weight cross-linkers with different functionality were used as control groups. The results of polymerization on glass plate showed that the hydrophilic coatings cross-linked by BP(EGDMA) was more uniform and stable. The surface chemistry, wettability and permeability of membranes were further investigated. The results showed that coatings which used macromonomer BP(EGDMA) as cross-linker on porous membrane surface was still more uniform than those which used low molecular weight cross-linkers. Meanwhile, the effects of the irradiation time and monomer usage on membrane coatings were explored to choose the best fabrication condition. Under the suitable conditions, the membrane used BP(EGDMA) as cross-linker showed a high oil rejection of &gt;99 % among several oil-in-water emulsion. Moreover, the anti-biofouling experiment revealed that the macromonomer BP(EGDMA) would endow hydrophilic coatings with better fouling resistance by longer irradiation time and larger total monomer usage.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113680"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147595","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}
引用次数: 0
Enhanced detection of explosives: A novel approach using poly(2-oxazoline)s-based molecularly imprinted polymers combined with ambient mass spectrometry
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113704
Michał Cegłowski , Aleksandra Lusina , Tomasz Nazim , Tomasz Otłowski , Błażej Gierczyk , Richard Hoogenboom
Detecting explosives in the environment is essential due to their toxic and mutagenic effects on living organisms. This study presents a novel method for the selective detection and quantification of explosives, including picric acid, 1,3,5-trinitro-1,3,5-triazinane (Research Department Explosive, RDX), and pentaerythritol tetranitrate (PETN), using molecularly imprinted polymers (MIPs) coupled with flowing atmospheric pressure afterglow mass spectrometry (FAPA-MS). MIPs were synthesized via a molecular imprinting process with short-chain poly(2-methoxycarbonylpropyl-2-oxazoline) as the pre-polymer, yielding materials with high affinity for the target compounds. The method achieved detection limits as low as 0.01 µM, representing improvements of two orders of magnitude for picric acid and PETN and one order for RDX compared to direct solution analysis. Spiked river water samples showed high recovery rates, within 8.2 % of true values, confirming the method’s accuracy. Strong linearity with R2 higher than 0.99 and very good precision with RSD not exceeding 8.9 % further validated the system. This approach demonstrates the potential of poly(2-oxazoline)-based MIPs in conjunction with ambient MS for sensitive, accurate, and reliable detection of explosives, offering significant applications in environmental monitoring and screening for illegal manufacturing sites.
{"title":"Enhanced detection of explosives: A novel approach using poly(2-oxazoline)s-based molecularly imprinted polymers combined with ambient mass spectrometry","authors":"Michał Cegłowski ,&nbsp;Aleksandra Lusina ,&nbsp;Tomasz Nazim ,&nbsp;Tomasz Otłowski ,&nbsp;Błażej Gierczyk ,&nbsp;Richard Hoogenboom","doi":"10.1016/j.eurpolymj.2024.113704","DOIUrl":"10.1016/j.eurpolymj.2024.113704","url":null,"abstract":"<div><div>Detecting explosives in the environment is essential due to their toxic and mutagenic effects on living organisms. This study presents a novel method for the selective detection and quantification of explosives, including picric acid, 1,3,5-trinitro-1,3,5-triazinane (Research Department Explosive, RDX), and pentaerythritol tetranitrate (PETN), using molecularly imprinted polymers (MIPs) coupled with flowing atmospheric pressure afterglow mass spectrometry (FAPA-MS). MIPs were synthesized via a molecular imprinting process with short-chain poly(2-methoxycarbonylpropyl-2-oxazoline) as the pre-polymer, yielding materials with high affinity for the target compounds. The method achieved detection limits as low as 0.01 µM, representing improvements of two orders of magnitude for picric acid and PETN and one order for RDX compared to direct solution analysis. Spiked river water samples showed high recovery rates, within 8.2 % of true values, confirming the method’s accuracy. Strong linearity with R<sup>2</sup> higher than 0.99 and very good precision with RSD not exceeding 8.9 % further validated the system. This approach demonstrates the potential of poly(2-oxazoline)-based MIPs in conjunction with ambient MS for sensitive, accurate, and reliable detection of explosives, offering significant applications in environmental monitoring and screening for illegal manufacturing sites.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113704"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147669","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}
引用次数: 0
pH-Responsive amphiphilic homopolymers derived from green solvent CyreneTM
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113686
Javier Delgado-Lijarcio, Juan Carlos Ronda, Gerard Lligadas, Adrian Moreno, Marina Galià
Stimuli-responsive polymers possess the ability to sense external stimuli and translate it into an observable response based on physiochemical changes. However, the development of stimuli-responsive polymers has hitherto been limited to amphiphilic block copolymers, which usually require sequential controlled chain-growth polymerization steps, or amphiphilic homopolymers derived from petroleum sources. Here, we report the preparation of an amphiphilic homopolyacetal derived from green solvent dihydrolevoglucosenone, commercialized under the trade name of Cyrene™. First, an allylic-bearing diol was synthesized using CyreneTM as a starting reagent. Second, a bio-based homopolyacetal was obtained through the polyaddition of the aforementioned diol with 1,4-butanediol divinyl ether (DVE). To introduce amphiphilicity into the homopolymer, a thiol-ene click post-polymerization modification using 2-mercaptoethanol was employed. Thereafter, the self-assembly of the amphiphilic homopolymer in an aqueous solution resulted in the formation of nanostructures capable of loading active cargo molecules and releasing them under relevant biological acidic conditions. Combining a straightforward preparation with ability to self-assemble, this new pH-responsive homopolymer paves the way for the development of bio-based amphiphilic homopolymers for specific applications such as drug delivery.
{"title":"pH-Responsive amphiphilic homopolymers derived from green solvent CyreneTM","authors":"Javier Delgado-Lijarcio,&nbsp;Juan Carlos Ronda,&nbsp;Gerard Lligadas,&nbsp;Adrian Moreno,&nbsp;Marina Galià","doi":"10.1016/j.eurpolymj.2024.113686","DOIUrl":"10.1016/j.eurpolymj.2024.113686","url":null,"abstract":"<div><div>Stimuli-responsive polymers possess the ability to sense external stimuli and translate it into an observable response based on physiochemical changes. However, the development of stimuli-responsive polymers has hitherto been limited to amphiphilic block copolymers, which usually require sequential controlled chain-growth polymerization steps, or amphiphilic homopolymers derived from petroleum sources. Here, we report the preparation of an amphiphilic homopolyacetal derived from green solvent dihydrolevoglucosenone, commercialized under the trade name of Cyrene™. First, an allylic-bearing diol was synthesized using Cyrene<sup>TM</sup> as a starting reagent. Second, a bio-based homopolyacetal was obtained through the polyaddition of the aforementioned diol with 1,4-butanediol divinyl ether (DVE). To introduce amphiphilicity into the homopolymer, a thiol-ene click post-polymerization modification using 2-mercaptoethanol was employed. Thereafter, the self-assembly of the amphiphilic homopolymer in an aqueous solution resulted in the formation of nanostructures capable of loading active cargo molecules and releasing them under relevant biological acidic conditions. Combining a straightforward preparation with ability to self-assemble, this new pH-responsive homopolymer paves the way for the development of bio-based amphiphilic homopolymers for specific applications such as drug delivery.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113686"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146942","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}
引用次数: 0
Anionic terpolymerization of 1,3-pentadiene, para-methyl styrene and para-tert-butylstyrene to produce alternating-random sequence copolymer with tunable composition
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113684
Kun Liu , Qiqi Dai , Jiexun Zhang , Yawen Fu , Xupeng Han , Yao Long , Yanyan Zhang , Yi Yang , Wenjun Yi , Lijun Li
The utilization of the “pentadiene-alternating strategy” offers a unique living anionic polymerization (LAP) routine to synthesize sequence-controlled polymers with well-defined alternating sequences. Moreover, due to the “active” site of the benzyl methyl group, para-methyl styrene (MST) homopolymer and copolymer can provide new approaches for the preparation of functional polymers. Herein, a new class of reactive MST-based copolymers and terpolymers with narrow molecular weight distributions and tunable composition distributions, have been prepared by LAP. The change of the instantaneous compositions in the copolymer throughout the conversion process is tracked by 1H NMR monitoring the characteristic peak change of [PD]/[MST]/[TBS] (i.e. [C=C]/[methyl]/[ter-butyl]) monomer units. Interestingly, by controlling the feed ratio of comonomers (MST, 1,3-pentadiene = PD and para-tert-butylstyrene = TBS), the terpolymers with constant composition and gradient composition distribution can be obtained via a one-pot method. The copolymerization kinetic analysis and copolymer product characteristics are given. At last, the “bond-forming initiation” theory is proposed to interpret this unique terpolymerization behavior. To the best of our knowledge, the combination of “pentadiene alternating modules” and “MST copolymerization strategy” provides a very favorable reaction condition for active benzylmethyl group incorporation to obtain alternating sequences of quantitatively polar functionalized copolymers, as well as comb-shaped copolymers.
{"title":"Anionic terpolymerization of 1,3-pentadiene, para-methyl styrene and para-tert-butylstyrene to produce alternating-random sequence copolymer with tunable composition","authors":"Kun Liu ,&nbsp;Qiqi Dai ,&nbsp;Jiexun Zhang ,&nbsp;Yawen Fu ,&nbsp;Xupeng Han ,&nbsp;Yao Long ,&nbsp;Yanyan Zhang ,&nbsp;Yi Yang ,&nbsp;Wenjun Yi ,&nbsp;Lijun Li","doi":"10.1016/j.eurpolymj.2024.113684","DOIUrl":"10.1016/j.eurpolymj.2024.113684","url":null,"abstract":"<div><div>The utilization of the “pentadiene-alternating strategy” offers a unique living anionic polymerization (LAP) routine to synthesize sequence-controlled polymers with well-defined alternating sequences. Moreover, due to the “active” site of the benzyl methyl group, <em>para</em>-methyl styrene (MST) homopolymer and copolymer can provide new approaches for the preparation of functional polymers. Herein, a new class of reactive MST-based copolymers and terpolymers with narrow molecular weight distributions and tunable composition distributions, have been prepared by LAP. The change of the instantaneous compositions in the copolymer throughout the conversion process is tracked by <sup>1</sup>H NMR monitoring the characteristic peak change of [PD]/[MST]/[TBS] (<em>i.e.</em> [C=C]/[methyl]/[ter-butyl]) monomer units. Interestingly, by controlling the feed ratio of comonomers (MST, 1,3-pentadiene = PD and <em>para</em>-tert-butylstyrene = TBS), the terpolymers with constant composition and gradient composition distribution can be obtained via a one-pot method. The copolymerization kinetic analysis and copolymer product characteristics are given. At last, the “bond-forming initiation” theory is proposed to interpret this unique terpolymerization behavior. To the best of our knowledge, the combination of “pentadiene alternating modules” and “MST copolymerization strategy” provides a very favorable reaction condition for active benzylmethyl group incorporation to obtain alternating sequences of quantitatively polar functionalized copolymers, as well as comb-shaped copolymers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113684"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146943","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}
引用次数: 0
Chain structure comparison of two impact polypropylene copolymers with good balance between stiffness and flowability
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2025.113714
Rui Li , Wei Liu , Yanxiong Pan , Xiangling Ji
Impact polypropylene shows good toughness at low temperatures and has different types, such as high stiffness, high toughness, and high flowability, allowing it to be applied in various scenarios. Two impact polypropylene alloys (F18 and F15) with high stiffness (1828 and 1498 MPa of flexural modulus) and high flowability (54.6 and 61.0 g/10 min of melt flow rate) are separated into nine fractions at specific temperatures using preparative temperature rising elution fractionation (P-TREF). The total content eluted at high temperatures (125 − 140 °C) in F18 is 31.13 wt%, which is 1.2 times higher than 14.26 wt% in F15. Such highly crystalline PP homopolymers provide enough stiffness in the matrix, thus, sample F18 has better stiffness. Two resins both have high flowability. F18 has 9.95 % low molecular weight components (<2 × 104 g/mol) and 4.65 % high molecular weight components (>106 g/mol). The composition of F15 includes 12.72 % low molecular weight components and 2.65 % high molecular weight components. The improved flowability of F15 can be attributed to its higher proportion of low molecular weight components and lower proportion of high molecular weight components. In short, sample F18 has a good stiffness-flowability balance. The toughness and morphological characteristics were also discussed.
{"title":"Chain structure comparison of two impact polypropylene copolymers with good balance between stiffness and flowability","authors":"Rui Li ,&nbsp;Wei Liu ,&nbsp;Yanxiong Pan ,&nbsp;Xiangling Ji","doi":"10.1016/j.eurpolymj.2025.113714","DOIUrl":"10.1016/j.eurpolymj.2025.113714","url":null,"abstract":"<div><div>Impact polypropylene shows good toughness at low temperatures and has different types, such as high stiffness, high toughness, and high flowability, allowing it to be applied in various scenarios. Two impact polypropylene alloys (<strong>F18</strong> and <strong>F15</strong>) with high stiffness (1828 and 1498 MPa of flexural modulus) and high flowability (54.6 and 61.0 g/10 min of melt flow rate) are separated into nine fractions at specific temperatures using preparative temperature rising elution fractionation (P-TREF). The total content eluted at high temperatures (125 − 140 °C) in <strong>F18</strong> is 31.13 wt%, which is 1.2 times higher than 14.26 wt% in <strong>F15</strong>. Such highly crystalline PP homopolymers provide enough stiffness in the matrix, thus, sample <strong>F18</strong> has better stiffness. Two resins both have high flowability. <strong>F18</strong> has 9.95 % low molecular weight components (&lt;2 × 10<sup>4</sup> g/mol) and 4.65 % high molecular weight components (&gt;10<sup>6</sup> g/mol). The composition of <strong>F15</strong> includes 12.72 % low molecular weight components and 2.65 % high molecular weight components. The improved flowability of <strong>F15</strong> can be attributed to its higher proportion of low molecular weight components and lower proportion of high molecular weight components. In short, sample <strong>F18</strong> has a good stiffness-flowability balance. The toughness and morphological characteristics were also discussed.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113714"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147590","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}
引用次数: 0
Zwitterionic thermoresponsive nanocomposites as functional systems for magnetic hyperthermia-activated drug delivery
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113650
Camillo Colli , Nesrine Bali , Chiara Scrocciolani , Bianca Maria Colosimo , Mattia Sponchioni , Emanuele Mauri , Davide Moscatelli , Sulalit Bandyopadhyay
The smart combination of controlled drug delivery and magnetic hyperthermia represents a promising approach for potentiating tumor therapeutic treatments, with minimal adverse effects. Indeed, thermoresponsive nanoparticles enable an on-demand drug release according to their thermal activation, and the polymeric nanosystems characterized by an Upper Critical Solution Temperature (UCST) are leading candidates for hyperthermia-based strategies. Secondly, heating processes promoted by superparamagnetic nanostructures might enable targeted hyperthermic effects, without interfering on healthy cells. In this work, we combined the advantages of the UCST-type nanoparticles and superparamagnetic iron-based nanoclusters to design innovative nanocomposites for tunable drug release, activated by magnetic hyperthermia. The thermoresponsive nanoparticles were obtained via self-assembling of an amphiphilic zwitterionic block copolymer, and the nanoclusters were encapsulated into the polymeric scaffolds via flash nanoprecipitation. The organic and inorganic materials were characterized in terms of composition, size and physicochemical properties, highlighting the potential of the reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization in tuning the copolymer composition and the cloud point of the nanoparticles (investigated range: 30–43 °C). We chose 43 °C as representative temperature of hyperthermia treatment and we validated our nanocomposites as delivery system for paclitaxel, a chemotherapeutic agent, under alternate magnetic field. The combined effect of magnetic hyperthermia and the polymer thermoresponsive behavior ensured an on-demand drug release when the target temperature was achieved, providing an almost complete drug release in the first two hours. Alternatively, without a magnetically-mediated heating, the nanocomposites retained the payload. This could pave the way for the definition of advanced hyperthermia-mediated therapeutic treatments.
{"title":"Zwitterionic thermoresponsive nanocomposites as functional systems for magnetic hyperthermia-activated drug delivery","authors":"Camillo Colli ,&nbsp;Nesrine Bali ,&nbsp;Chiara Scrocciolani ,&nbsp;Bianca Maria Colosimo ,&nbsp;Mattia Sponchioni ,&nbsp;Emanuele Mauri ,&nbsp;Davide Moscatelli ,&nbsp;Sulalit Bandyopadhyay","doi":"10.1016/j.eurpolymj.2024.113650","DOIUrl":"10.1016/j.eurpolymj.2024.113650","url":null,"abstract":"<div><div>The smart combination of controlled drug delivery and magnetic hyperthermia represents a promising approach for potentiating tumor therapeutic treatments, with minimal adverse effects. Indeed, thermoresponsive nanoparticles enable an on-demand drug release according to their thermal activation, and the polymeric nanosystems characterized by an Upper Critical Solution Temperature (UCST) are leading candidates for hyperthermia-based strategies. Secondly, heating processes promoted by superparamagnetic nanostructures might enable targeted hyperthermic effects, without interfering on healthy cells. In this work, we combined the advantages of the UCST-type nanoparticles and superparamagnetic iron-based nanoclusters to design innovative nanocomposites for tunable drug release, activated by magnetic hyperthermia. The thermoresponsive nanoparticles were obtained via self-assembling of an amphiphilic zwitterionic block copolymer, and the nanoclusters were encapsulated into the polymeric scaffolds via flash nanoprecipitation. The organic and inorganic materials were characterized in terms of composition, size and physicochemical properties, highlighting the potential of the reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization in tuning the copolymer composition and the cloud point of the nanoparticles (investigated range: 30–43 °C). We chose 43 °C as representative temperature of hyperthermia treatment and we validated our nanocomposites as delivery system for paclitaxel, a chemotherapeutic agent, under alternate magnetic field. The combined effect of magnetic hyperthermia and the polymer thermoresponsive behavior ensured an on-demand drug release when the target temperature was achieved, providing an almost complete drug release in the first two hours. Alternatively, without a magnetically-mediated heating, the nanocomposites retained the payload. This could pave the way for the definition of advanced hyperthermia-mediated therapeutic treatments.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113650"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146950","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}
引用次数: 0
Bioactive glasses-based nanoenzymes composite double-network hydrogel with ROS scavenging for bone tissue engineering
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2025.113718
Hao Deng , Xiaolu Chen , Wei Zhang , Hulin Yang , Xinyue Yang , Qiyi Zhang , Yonggang Yan
Reactive oxygen species (ROS) plays a crucial role in normal physiological activities. But hypoxia-induced oxidative stress leads to excessive accumulation of ROS in the microenvironment of bone defects, which could hinder tissue repair. Therefore, the regulation of ROS is essential for promoting bone repair. Herein, a mesoporous bioactive glass-based nanoenzyme (MBGNs@PDA@MnO2) with the property to manage ROS was designed and prepared. The MBGNs@PDA@MnO2 powders displayed excellent mineralization properties and antioxidation activity. The hydrogel with double-network structure were constructed and synthesized using oxidized chitosan (OCS) and dopamine-grafted gelatin (Gel-DA) by Schiff-base and oxidative coupling reaction, and then MBGNs@PDA@MnO2 was incorporated into the hydrogel. Cell experiments demonstrated that the composite hydrogels could effectively reduce intracellular ROS level, and had good cytocompatibility and osteogenesis promotion capability. Hence, the composite hydrogels with ROS regulation had the potential to be a new strategy for the treatment of bone defects.
{"title":"Bioactive glasses-based nanoenzymes composite double-network hydrogel with ROS scavenging for bone tissue engineering","authors":"Hao Deng ,&nbsp;Xiaolu Chen ,&nbsp;Wei Zhang ,&nbsp;Hulin Yang ,&nbsp;Xinyue Yang ,&nbsp;Qiyi Zhang ,&nbsp;Yonggang Yan","doi":"10.1016/j.eurpolymj.2025.113718","DOIUrl":"10.1016/j.eurpolymj.2025.113718","url":null,"abstract":"<div><div>Reactive oxygen species (ROS) plays a crucial role in normal physiological activities. But hypoxia-induced oxidative stress leads to excessive accumulation of ROS in the microenvironment of bone defects, which could hinder tissue repair. Therefore, the regulation of ROS is essential for promoting bone repair. Herein, a mesoporous bioactive glass-based nanoenzyme (MBGNs@PDA@MnO<sub>2</sub>) with the property to manage ROS was designed and prepared. The MBGNs@PDA@MnO<sub>2</sub> powders displayed excellent mineralization properties and antioxidation activity. The hydrogel with double-network structure were constructed and synthesized using oxidized chitosan (OCS) and dopamine-grafted gelatin (Gel-DA) by Schiff-base and oxidative coupling reaction, and then MBGNs@PDA@MnO<sub>2</sub> was incorporated into the hydrogel. Cell experiments demonstrated that the composite hydrogels could effectively reduce intracellular ROS level, and had good cytocompatibility and osteogenesis promotion capability. Hence, the composite hydrogels with ROS regulation had the potential to be a new strategy for the treatment of bone defects.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113718"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146475","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}
引用次数: 0
Application of conductive hydrogel based on polyacrylamide/maleic anhydride modified soy protein isolate in flexible sensor
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113688
Yupeng Lv , Yecheng Xu , Wenmin Yang , Changjiang Sun , Guiying Li , Zhen Fang , Zhuhui Qiao
The popularity of conductive hydrogels in flexible sensor research stems from their excellent strain responsiveness and efficient conduction capability. In this study, maleic anhydride (MA)-modified soy protein isolate (MSPI) crosslinked with acrylamide (AM) to form a hydrogel with a tensile strength of 225 kPa at an MSPI content of 16 %. Furthermore, the incorporation of 15 % of lithium chloride (LiCl) significantly enhanced the electrical conductivity of the hydrogel (namely MSPI0.16Li0.15), mechanical strength (tensile stress ∼ 238 kPa with a fracture strain of 241 %) and swelling resistance. MSPI0.16Li0.15 presented a high conductivity of 2.8 S/m, surpassing that of a plethora of bio-based hydrogels. Additionally, MSPI0.16Li0.15 was successfully employed to monitor the movement of fingers, elbows, knees and other joints, and can successfully maintain strain sensing under different pH conditions (pH 1, 3, 5, 9, 11 and 13) and organic solvents. It demonstrated distinct electrical responses to various strains, making it suitable for sensing human motion. This work contributes to the development of hydrogels with enhanced electrical conductivity and mechanical properties, promising applications in the field of flexible sensors.
{"title":"Application of conductive hydrogel based on polyacrylamide/maleic anhydride modified soy protein isolate in flexible sensor","authors":"Yupeng Lv ,&nbsp;Yecheng Xu ,&nbsp;Wenmin Yang ,&nbsp;Changjiang Sun ,&nbsp;Guiying Li ,&nbsp;Zhen Fang ,&nbsp;Zhuhui Qiao","doi":"10.1016/j.eurpolymj.2024.113688","DOIUrl":"10.1016/j.eurpolymj.2024.113688","url":null,"abstract":"<div><div>The popularity of conductive hydrogels in flexible sensor research stems from their excellent strain responsiveness and efficient conduction capability. In this study, maleic anhydride (MA)-modified soy protein isolate (MSPI) crosslinked with acrylamide (AM) to form a hydrogel with a tensile strength of 225 kPa at an MSPI content of 16 %. Furthermore, the incorporation of 15 % of lithium chloride (LiCl) significantly enhanced the electrical conductivity of the hydrogel (namely MSPI<sub>0.16</sub>Li<sub>0.15</sub>), mechanical strength (tensile stress ∼ 238 kPa with a fracture strain of 241 %) and swelling resistance. MSPI<sub>0.16</sub>Li<sub>0.15</sub> presented a high conductivity of 2.8 S/m, surpassing that of a plethora of bio-based hydrogels. Additionally, MSPI<sub>0.16</sub>Li<sub>0.15</sub> was successfully employed to monitor the movement of fingers, elbows, knees and other joints, and can successfully maintain strain sensing under different pH conditions (pH 1, 3, 5, 9, 11 and 13) and organic solvents. It demonstrated distinct electrical responses to various strains, making it suitable for sensing human motion. This work contributes to the development of hydrogels with enhanced electrical conductivity and mechanical properties, promising applications in the field of flexible sensors.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113688"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146947","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}
引用次数: 0
Reactive oxygen species-responsive nanocomposite hydrogels for accurate drug delivery and localized PDT/PTT/chemo synergistic cancer therapy
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113683
Minchae Kim , Ji in Lee , Jongseon Choi , So Yeon Kim
Intratumor local drug delivery systems using injectable hydrogels have received considerable attention due to sustained, controllable drug delivery at target tumor sites and reduced adverse effects of systemic exposure to the drug. To maximize cancer therapeutic efficiency, this study focused on cytotoxic reactive oxygen species (ROS)-cleavable injectable hydrogels that can more accurately control drug delivery as well as photodynamic therapy (PDT)/photothermal therapy (PTT) synergistic combination therapy. Thermo-responsive poly(N-isopropyl acrylamide) (PNIPAAm)-based injectable hydrogels were synthesized using a thioketal crosslinker vulnerable to bond breakage by ROS. In addition, PNIPAAm-based injectable nanocomposite hydrogels containing photosensitizer (PS)-conjugated gold nanorods (GNRs) as a photothermal factor and 1-methyltryptophan (1MT) as a model drug were prepared. PNIPAAm-based injectable nanocomposite hydrogel exhibited a lower critical solution temperature (LCST) in the range of 33.6–36.3 °C, allowing injection through a syringe at room temperature. However, a gel state was achieved through phase transition at a body temperature of 37 °C. ROS generation from PNIPAAm-based injectable nanocomposite hydrogel was controlled by adjusting the feed amount of PS-conjugated GNRs and the 670 nm laser intensity. These hydrogels crosslinked with ROS-cleavable thioketal crosslinker exhibited selective degradation and drug release behavior. In addition, a PNIPAAm-based injectable nanocomposite hydrogel containing GNRs as a photothermal factor and chlorin e6 (Ce6) as a PS showed a PDT/PTT synergistic effect upon laser irradiation. These results indicate that this ROS-sensitive nanocomposite hydrogel would be highly efficient both as an accurate drug delivery platform and as a combinational cancer therapeutic system of localized PDT and PTT.
{"title":"Reactive oxygen species-responsive nanocomposite hydrogels for accurate drug delivery and localized PDT/PTT/chemo synergistic cancer therapy","authors":"Minchae Kim ,&nbsp;Ji in Lee ,&nbsp;Jongseon Choi ,&nbsp;So Yeon Kim","doi":"10.1016/j.eurpolymj.2024.113683","DOIUrl":"10.1016/j.eurpolymj.2024.113683","url":null,"abstract":"<div><div>Intratumor local drug delivery systems using injectable hydrogels have received considerable attention due to sustained, controllable drug delivery at target tumor sites and reduced adverse effects of systemic exposure to the drug. To maximize cancer therapeutic efficiency, this study focused on cytotoxic reactive oxygen species (ROS)-cleavable injectable hydrogels that can more accurately control drug delivery as well as photodynamic therapy (PDT)/photothermal therapy (PTT) synergistic combination therapy. Thermo-responsive poly(N-isopropyl acrylamide) (PNIPAAm)-based injectable hydrogels were synthesized using a thioketal crosslinker vulnerable to bond breakage by ROS. In addition, PNIPAAm-based injectable nanocomposite hydrogels containing photosensitizer (PS)-conjugated gold nanorods (GNRs) as a photothermal factor and 1-methyltryptophan (1MT) as a model drug were prepared. PNIPAAm-based injectable nanocomposite hydrogel exhibited a lower critical solution temperature (LCST) in the range of 33.6–36.3 °C, allowing injection through a syringe at room temperature. However, a gel state was achieved through phase transition at a body temperature of 37 °C. ROS generation from PNIPAAm-based injectable nanocomposite hydrogel was controlled by adjusting the feed amount of PS-conjugated GNRs and the 670 nm laser intensity. These hydrogels crosslinked with ROS-cleavable thioketal crosslinker exhibited selective degradation and drug release behavior. In addition, a PNIPAAm-based injectable nanocomposite hydrogel containing GNRs as a photothermal factor and chlorin e6 (Ce6) as a PS showed a PDT/PTT synergistic effect upon laser irradiation. These results indicate that this ROS-sensitive nanocomposite hydrogel would be highly efficient both as an accurate drug delivery platform and as a combinational cancer therapeutic system of localized PDT and PTT.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113683"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143146949","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}
引用次数: 0
One-step and one-pot synthesis of wrinkled polymer microspheres based on monomer reactivity ratio difference
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-02-06 DOI: 10.1016/j.eurpolymj.2024.113707
Tian Liu, Yungui Ma, Dunxun Yu, Xiaopeng Yang, Zhihua Ma, Ning Liu, Shiyang Shao
Different from conventional multi-step synthesis methods for wrinkled polymer microspheres (WPMs), here we propose a facile one-step and one-pot synthesis strategy for WPMs employing monomer reactivity ratio difference to form linear-crosslinked-linear gradient structure from inside to outside of the microspheres, leading to wrinkled surface by uneven shrinkage of the crosslinked and linear structures. The particle size and surface morphology for WPMs can be easily adjusted by changing monomer types and solvent ratio according to morphological characterization. Meanwhile, this method is universal for synthesizing WPMs having different monomers, supported by the fact that monomers bearing different substituent groups can be successfully used for the synthesis procedure. Finally, fluorescent microspheres with tuned emission colors are synthesized through this strategy by simply adding different fluorescent dyes in polymerization system, demonstrating the potential of such strategy in synthesizing optical-functional materials. These results provide a new perspective on the efficient preparation of WPMs and show its promising application in fabricating functional materials.
{"title":"One-step and one-pot synthesis of wrinkled polymer microspheres based on monomer reactivity ratio difference","authors":"Tian Liu,&nbsp;Yungui Ma,&nbsp;Dunxun Yu,&nbsp;Xiaopeng Yang,&nbsp;Zhihua Ma,&nbsp;Ning Liu,&nbsp;Shiyang Shao","doi":"10.1016/j.eurpolymj.2024.113707","DOIUrl":"10.1016/j.eurpolymj.2024.113707","url":null,"abstract":"<div><div>Different from conventional multi-step synthesis methods for wrinkled polymer microspheres (WPMs), here we propose a facile one-step and one-pot synthesis strategy for WPMs employing monomer reactivity ratio difference to form linear-crosslinked-linear gradient structure from inside to outside of the microspheres, leading to wrinkled surface by uneven shrinkage of the crosslinked and linear structures. The particle size and surface morphology for WPMs can be easily adjusted by changing monomer types and solvent ratio according to morphological characterization. Meanwhile, this method is universal for synthesizing WPMs having different monomers, supported by the fact that monomers bearing different substituent groups can be successfully used for the synthesis procedure. Finally, fluorescent microspheres with tuned emission colors are synthesized through this strategy by simply adding different fluorescent dyes in polymerization system, demonstrating the potential of such strategy in synthesizing optical-functional materials. These results provide a new perspective on the efficient preparation of WPMs and show its promising application in fabricating functional materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"224 ","pages":"Article 113707"},"PeriodicalIF":5.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143147594","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}
引用次数: 0
期刊
European Polymer Journal
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