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The role of RuPhos in a Kumada polymerization: revealing the control in catalyst transfer polymerization RuPhos在熊田聚合中的作用:揭示催化剂转移聚合的控制
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-20 Epub Date: 2026-01-13 DOI: 10.1016/j.eurpolymj.2026.114512
Cynthia Verduyckt , Hanne Broux , Julien De Winter , Pascal Gerbaux , Guy Koeckelberghs
In recent years, the controlled nature of catalyst transfer polymerizations (CTP) has been significantly investigated and enhanced. Recent studies on Suzuki-Miyaura CTP (SMCTP) revealed that water converts the process into a chain-growth polymerization, while additional Buchwald ligands, particularly RuPhos, further enhance control. This improvement is attributed to the formation of Pd(RuPhos)2 upon catalyst detachment, a bulky species with no affinity for water, which limits catalyst diffusion and suppresses transfer reactions. Despite extensive research on SMCTP, Buchwald ligands remain unexplored in other CTPs, except for RuPhos in Negishi-mediated polymerization, where transfer steps occur, even in a large extent. Kumada CTP (KCTP) has not been investigated in this context.
Here, we report the first KCTP using a Buchwald ligand-based external palladium initiator, 4-methyl benzoate-Pd(RuPhos)-iodine. First, the controlled nature of the polymerization was investigated and chain transfer and some termination was found. Second, the influence of extra equivalents of ligand severely worsens the controlled nature of the polymerization. These findings elucidate the mechanism of CTP and the role of additional ligand. It is shown that, if the catalysts detaches from the growing polymer chain, the controlled nature of CTP depends on Pd(RuPhos)2 (de)formation and its diffusion. Poor solvent affinity to the ligated Pd-catalyst, as in aqueous mixtures (SMCTP), restricts diffusion and maintains control. In contrast, other (dry) organic solvents allow diffusion, reducing control despite inactive species formation. This work offers a mechanistic framework that may be extended to other catalyst–ligand–polymer combinations, although its broader generalization will require further experimental validation.
近年来,催化剂转移聚合(CTP)的可控性得到了极大的研究和加强。最近对Suzuki-Miyaura CTP (SMCTP)的研究表明,水将该过程转化为链式生长聚合,而附加的Buchwald配体,特别是RuPhos,进一步增强了控制。这一改进归功于催化剂分离后形成的Pd(RuPhos)2,这是一种体积庞大的物质,对水没有亲和力,限制了催化剂的扩散并抑制了转移反应。尽管对SMCTP进行了广泛的研究,但除了在negishi介导的聚合中发生转移步骤的RuPhos外,Buchwald配体在其他ctp中仍未被探索。Kumada CTP (KCTP)尚未在此背景下进行研究。在这里,我们报道了第一个使用布赫瓦尔德配体为基础的外部钯引发剂的KCTP, 4-甲基苯甲酸酯- pd (RuPhos)-碘。首先,研究了聚合的可控性质,发现了链转移和一些终止。其次,配体的额外等价物的影响严重恶化了聚合的可控性。这些发现阐明了CTP的作用机制和附加配体的作用。结果表明,当催化剂与生长中的聚合物链分离时,CTP的受控性质取决于Pd(RuPhos)2的生成及其扩散。对连接的pd -催化剂的溶剂亲和力较差,如在水相混合物(SMCTP)中,限制了扩散并保持控制。相比之下,其他(干燥)有机溶剂允许扩散,减少控制,尽管非活性物种的形成。这项工作提供了一个可以扩展到其他催化剂-配体-聚合物组合的机制框架,尽管其更广泛的推广将需要进一步的实验验证。
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引用次数: 0
Electro-spun biodegradable non-woven nano-fibers and moringa oil extract for knee cartilage regeneration: anti-inflammatory, antibacterial, and antioxidant activity 电纺可生物降解的无纺布纳米纤维和辣木油提取物用于膝关节软骨再生:抗炎、抗菌和抗氧化活性
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-20 Epub Date: 2026-01-12 DOI: 10.1016/j.eurpolymj.2026.114510
Marwa Y. Abdel Tawwab , Bothaina M. Abdel-Hady , Rizk Abd El-Moneim Rizk , Amal I. Hassan , Abdul Aziz M. Gad , Amira A. Gamal , Medhat W. Shafaa
Polycaprolactone/gelatin polymer nanofiber mats (PCL/GT) were fabricated using an electro-spinning technique. Moringa oleifera seed oil (M. oleifera) was loaded onto the mats using the post-spinning sorption method. The electro-spun nanofiber mat loaded with M. oleifera exhibited sustained release of the oil, with 85.3 % cumulative release after 28 days. The experimental data on M. oleifera and electro-spun mats loaded with oil ensure that they exhibit strong antibacterial, antioxidant, and anti-inflammatory activities. During the 48 h incubation, oil-loaded mats P5G5 O7C3 exhibited an increase in bacterial inhibition compared to those of free oil electro-spun mats P5G5 C3 (Staphylococcus aureus; 86.62 ± 0.05 % and Escherichia coli; 90.23 ± 0.04 %). For electro-spun oil loaded mats, the antioxidant activity was increased with increasing the incubation time. The degradation products of an electro-spun polycaprolactone/gelatin nanofiber mat loaded with M. oleifera stimulated cell proliferation and migration. It rapidly reduced the levels of pro-inflammatory cytokines in rat serum such as tumor necrosis factor and Interleukin 6 after mat implantation by increasing the mass of the oil-loaded mat. The histological examination of inflamed and treated knee rat tissue at the second and fourth weeks after sample implantation indicated that the oil-loaded mat has a good effect on the healing of knee synovial membrane and cartilage tissue after inflammation.
采用静电纺丝技术制备了聚己内酯/明胶聚合物纳米纤维垫。采用纺丝后吸附法将辣木籽油吸附到垫子上。负载油棕的电纺丝纳米纤维垫具有缓释性,28 d后的累积释放量为85.3%。油葵和载油电纺垫的实验数据表明,油葵和载油电纺垫具有很强的抗菌、抗氧化和抗炎活性。在48小时的孵育过程中,与游离油电纺丝毡P5G5 C3相比,油纺丝毡P5G5 O7C3对细菌的抑制作用增强(金黄色葡萄球菌86.62±0.05%,大肠杆菌90.23±0.04%)。电纺负载油毡的抗氧化活性随培养时间的延长而增强。电纺聚己内酯/明胶纳米纤维垫的降解产物可刺激细胞增殖和迁移。通过增加载油垫的质量,可迅速降低植入后大鼠血清中肿瘤坏死因子、白细胞介素6等促炎细胞因子的水平。样品植入后第2周和第4周对炎症和治疗的大鼠膝关节组织的组织学检查表明,载油垫对炎症后膝关节滑膜和软骨组织的愈合有良好的作用。
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引用次数: 0
Tailoring tensile properties of polymer nanocomposites with randomly dispersed multi-thread carbon nanothreads 随机分散多线程碳纳米线聚合物纳米复合材料的裁剪拉伸性能
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-20 Epub Date: 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114503
Chengkai Li , Bonan Li , Yilin Gui , Haifei Zhan
Understanding interfacial load transfer is the key challenge in developing high-performance polymer nanocomposites reinforced by one-dimensional nanothreads (NTHs). Here, large-scale molecular dynamics simulations are employed to elucidate how random dispersion of NTHs, the number of aggregated threads, functionalization, and cross-linking influence the tensile performance of poly (methyl methacrylate) (PMMA) nanocomposites. Without cross-linking, tightly aggregated NTHs enhance Young’s modulus and tensile strength by reducing void formation and promoting stronger filler-filler interactions. Quad-thread pristine NTHs yields ∼ 7 % enhancement in Young’s modulus compared with individually dispersed NTHs as reinforcements. Meanwhile, –COOH functionalization provides the highest reinforcement effect. Covalent cross-linking at the filler-matrix interface markedly improves load transfer efficiency. However, increasing the number of cross-linking filler-matrix bonds disrupts the multi-thread architecture, resulting in excessive voids and weakening the non-bonded filler-filler interactions, leading to a reduction in the reinforcement efficiency. In this regard, adding inter-filler bonds between adjacent NTHs can stabilize the multi-thread architecture and further improve the mechanical properties of polymer nanocomposites. Both internal and external cross-linked multi-thread samples show average ∼ 10 % enhancement of Young’s modulus and UTS than non-internally and externally cross-linked counterparts. These findings unveil the interplay between filler architectures, aggregation and interface modification in determining overall load transfer and reinforcement efficiency, which is beneficial for the development of high-performance polymer nanocomposites.
了解界面载荷传递是开发高性能一维纳米线增强聚合物纳米复合材料的关键挑战。本文采用大规模分子动力学模拟来阐明NTHs的随机分散、聚合线的数量、功能化和交联如何影响聚甲基丙烯酸甲酯(PMMA)纳米复合材料的拉伸性能。在没有交联的情况下,紧密聚集的NTHs通过减少空隙形成和促进更强的填料-填料相互作用来提高杨氏模量和抗拉强度。与单独分散的NTHs作为增强材料相比,四线程原始NTHs的杨氏模量提高了7%。同时-COOH功能化的强化效果最高。填料与基体界面的共价交联显著提高了载荷传递效率。然而,增加交联填料-基体键的数量会破坏多线程结构,导致空隙过多,削弱非键合填料-填料的相互作用,导致增强效率降低。因此,在相邻nth之间添加填充间键可以稳定多线程结构,进一步提高聚合物纳米复合材料的力学性能。内部和外部交联的多线程样品与非内部和外部交联的样品相比,杨氏模量和UTS平均提高了10%。这些发现揭示了填料结构、聚集和界面修饰之间的相互作用,决定了总体负载传递和增强效率,这有利于高性能聚合物纳米复合材料的发展。
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引用次数: 0
How chain stereoconfiguration and molecular weight influence Poly(propylene oxide) crystallization 链的立体构型和分子量如何影响聚环氧丙烷的结晶
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-24 DOI: 10.1016/j.eurpolymj.2025.114464
Juan Torres-Rodríguez , Charlotte Fornaciari , Ricardo A. Pérez-Camargo , Agurtzane Mugica , Manuela Zubitur , Giovanni Preda , Dario Pasini , Olivier Coulembier , Alejandro J. Müller
We report on the synthesis and crystallization behavior of poly(propylene oxide) (PPO) with tunable molar masses and defined stereoconfiguration (PPO-R and PPO-S), obtained through controlled oxyanionic ring-opening polymerization using hexaethylene glycol (EG6) as the initiator, with an equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6). This method provides access to well-defined enantiopure PPO samples across a broad range of number-average molecular weights (Mn), allowing for the independent evaluation of how molecular weight and stereoconfiguration influence crystallization. Morphology, thermal transitions, structural features, and crystallization kinetics were analyzed using Polarized Light Optical Microscopy (PLOM), Differential Scanning Calorimetry (DSC), in situ Wide- and Small-angle X-ray Scattering (WAXS/SAXS), and, for the first time in PPO, thermal fractionation via Successive Self-nucleation and Annealing (SSA). Both PPO-R and PPO-S display increasing thermal transitions with Mn, eventually reaching a plateau. Although they crystallize into identical orthorhombic unit cells, the two enantiomers show small yet consistent and reproducible kinetic differences across all techniques used: PPO-R crystallizes faster at low Mn, while PPO-S does so at high Mn. This crossover, related to a specific Mn value, though unexpected for two enantiomeric polymers forming identical lattices, was consistently observed by different experimental techniques across nucleation, spherulitic growth, overall crystallization rate, and SSA fractionation. This confirms the effect is real and experimentally reliable. We provide a mechanistic interpretation suggesting that stereoconfiguration could be influencing melt dynamics, likely through subtle differences in chain diffusion and entanglement onset. Racemic PPO-R:S blends were prepared at both low and high Mn. No stereocomplexation was observed; however, these blends exhibited lower melting transitions and slower crystallization kinetics than the enantiopure samples, possibly due to packing frustration between chains of opposite helicities. Overall, molecular weight and stereoconfiguration are effective parameters for tuning PPO crystallization kinetics, thereby enabling PPO-based blends and copolymers with controlled crystallization rates and expanded processability in biodegradable polymer systems.
本文报道了以六甘醇(EG6)为引发剂,乙酸钾(KOAc)和18-冠-6醚(18C6)为等摩尔混合物,通过可控氧阴离子开环聚合,合成了摩尔质量可调、立体构型可确定的聚环氧丙烷(PPO) (PPO- r和PPO- s)的结晶行为。该方法提供了在广泛的数平均分子量(Mn)范围内访问定义良好的对映不纯PPO样品的途径,允许独立评估分子量和立体构型如何影响结晶。利用偏振光光学显微镜(PLOM)、差示扫描量热法(DSC)、原位宽角和小角x射线散射(WAXS/SAXS)分析了形貌、热转变、结构特征和结晶动力学,并首次在PPO中通过连续自核和退火(SSA)进行了热分馏。随着Mn的增加,PPO-R和PPO-S的热跃迁逐渐增加,最终达到平稳期。尽管它们结晶成相同的正交晶胞,但两种对映体在所有使用的技术中表现出微小但一致且可重复的动力学差异:PPO-R在低锰下结晶更快,而PPO-S在高锰下结晶更快。这种交叉与特定的Mn值有关,尽管对于形成相同晶格的两种对映体聚合物来说是意想不到的,但通过不同的实验技术,在成核、球晶生长、总体结晶速率和SSA分选中一致地观察到了这种交叉。这证实了该效应是真实的,实验上是可靠的。我们提供了一个机制解释,表明立体构型可能会影响熔体动力学,可能是通过链扩散和纠缠开始的细微差异。在低锰和高锰条件下制备了外消旋聚丙烯- r:S共混物。未观察到立体络合;然而,与对映纯样品相比,这些共混物表现出较低的熔融转变和较慢的结晶动力学,可能是由于相反螺旋链之间的包装挫折。总的来说,分子量和立体构型是调整PPO结晶动力学的有效参数,从而使基于PPO的共混物和共聚物在可生物降解聚合物体系中具有可控的结晶速率和扩大的可加工性。
{"title":"How chain stereoconfiguration and molecular weight influence Poly(propylene oxide) crystallization","authors":"Juan Torres-Rodríguez ,&nbsp;Charlotte Fornaciari ,&nbsp;Ricardo A. Pérez-Camargo ,&nbsp;Agurtzane Mugica ,&nbsp;Manuela Zubitur ,&nbsp;Giovanni Preda ,&nbsp;Dario Pasini ,&nbsp;Olivier Coulembier ,&nbsp;Alejandro J. Müller","doi":"10.1016/j.eurpolymj.2025.114464","DOIUrl":"10.1016/j.eurpolymj.2025.114464","url":null,"abstract":"<div><div>We report on the synthesis and crystallization behavior of poly(propylene oxide) (PPO) with tunable molar masses and defined stereoconfiguration (PPO-<em>R</em> and PPO-<em>S</em>), obtained through controlled oxyanionic ring-opening polymerization using hexaethylene glycol (EG6) as the initiator, with an equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6). This method provides access to well-defined enantiopure PPO samples across a broad range of number-average molecular weights (<em>M<sub>n</sub></em>), allowing for the independent evaluation of how molecular weight and stereoconfiguration influence crystallization. Morphology, thermal transitions, structural features, and crystallization kinetics were analyzed using Polarized Light Optical Microscopy (PLOM), Differential Scanning Calorimetry (DSC), in situ Wide- and Small-angle X-ray Scattering (WAXS/SAXS), and, for the first time in PPO, thermal fractionation via Successive Self-nucleation and Annealing (SSA). Both PPO-<em>R</em> and PPO-<em>S</em> display increasing thermal transitions with <em>M<sub>n</sub></em>, eventually reaching a plateau. Although they crystallize into identical orthorhombic unit cells, the two enantiomers show small yet consistent and reproducible kinetic differences across all techniques used: PPO-<em>R</em> crystallizes faster at low <em>M<sub>n</sub></em>, while PPO-<em>S</em> does so at high <em>M<sub>n</sub></em>. This crossover, related to a specific <em>M<sub>n</sub></em> value, though unexpected for two enantiomeric polymers forming identical lattices, was consistently observed by different experimental techniques across nucleation, spherulitic growth, overall crystallization rate, and SSA fractionation. This confirms the effect is real and experimentally reliable. We provide a mechanistic interpretation suggesting that stereoconfiguration could be influencing melt dynamics, likely through subtle differences in chain diffusion and entanglement onset. Racemic PPO-<em>R:S</em> blends were prepared at both low and high <em>M<sub>n</sub></em>. No stereocomplexation was observed; however, these blends exhibited lower melting transitions and slower crystallization kinetics than the enantiopure samples, possibly due to packing frustration between chains of opposite helicities. Overall, molecular weight and stereoconfiguration are effective parameters for tuning PPO crystallization kinetics, thereby enabling PPO-based blends and copolymers with controlled crystallization rates and expanded processability in biodegradable polymer systems.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114464"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939768","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 nanocarrier: Chitosan- polydeoxyribonucleotide (PDRN) nanoparticles for transdermal nucleic acid therapy ph响应纳米载体:壳聚糖-聚脱氧核糖核苷酸(PDRN)纳米颗粒用于透皮核酸治疗
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114499
Yuxin Liu , Wenxin Hu , Caiyun Zhao , Chengke Zhao , Yan Liu , Xiaojing Pei , Jun Zhu , Yongbo Lyu , Zhaohui Qu
Polydeoxyribonucleotide (PDRN) has been demonstrated to possess pharmacological activities, including tissue repair and anti-inflammation, thus rendering it a promising ingredient in both regenerative medicine and cosmetics. However, its application is limited by issues including poor cell membrane permeability due to negative charge, susceptibility to nuclease degradation, and impaired transdermal delivery by the skin barrier. Herein, we constructed the pH-responsive PDRN nanocarrier (CP-NPs) using chitosan (CS) via electrostatic self-assembly. By regulating the molar ratio of CS amino groups to PDRN phosphate groups and optimizing the preparation process, uniform CP-NPs with an average particle size of 161.1 ± 6.2 nm were obtained. PDRN aggregation and protection against nuclease degradation was confirmed through a combination of characterization techniques, including dynamic light scattering, scanning electron microscopy, and infrared spectroscopy, in conjunction with agarose gel electrophoresis. The pH-responsive properties of the material were confirmed through zeta potential and UV analysis. Furthermore, experimental findings demonstrated that CP-NPs exhibit excellent stability and biocompatibility, significantly enhancing antioxidant performance and hydration capacity. Further results proved that CP-NPs promoted the proliferation and migration of human dermal fibroblasts (HDFs), with the migration rate increased by 174.16 %, enhancing in vitro transdermal delivery capacity by 55.3 %, and improving in vivo penetration ability by 167.6 %. Human trials confirmed that CP-NPs could improve skin moisture content, transepidermal water loss (TEWL), glossiness, and elasticity without adverse reactions. This study provides a viable PDRN transdermal delivery approach, advancing “non-invasive nucleic acid therapy” in regenerative medicine and cosmetics and laying a foundation for topical PDRN clinical translation.
聚脱氧核糖核苷酸(PDRN)已被证明具有包括组织修复和抗炎症在内的药理活性,因此使其成为再生医学和化妆品中有前景的成分。然而,它的应用受到一些问题的限制,包括由于负电荷导致的细胞膜渗透性差,对核酸酶降解的易感性以及皮肤屏障的透皮递送受损。本研究以壳聚糖(CS)为原料,通过静电自组装构建ph响应型PDRN纳米载体(CP-NPs)。通过调节CS氨基与PDRN磷酸基的摩尔比,优化制备工艺,可制得均匀的CP-NPs,平均粒径为161.1±6.2 nm。通过动态光散射、扫描电子显微镜、红外光谱以及琼脂糖凝胶电泳等表征技术的结合,证实了PDRN的聚集和对核酸酶降解的保护作用。通过zeta电位和UV分析证实了材料的ph响应性能。此外,实验结果表明,CP-NPs具有良好的稳定性和生物相容性,显著提高了抗氧化性能和水合能力。进一步的结果证明,CP-NPs促进了人真皮成纤维细胞(HDFs)的增殖和迁移,其迁移率提高了174.16%,体外透皮递送能力提高了55.3%,体内渗透能力提高了167.6%。人体试验证实,CP-NPs可以改善皮肤含水量、经皮失水(TEWL)、光泽度和弹性,没有不良反应。本研究提供了一种可行的PDRN经皮给药途径,推进了再生医学和化妆品领域的“无创核酸治疗”,为局部PDRN临床转化奠定了基础。
{"title":"pH-responsive nanocarrier: Chitosan- polydeoxyribonucleotide (PDRN) nanoparticles for transdermal nucleic acid therapy","authors":"Yuxin Liu ,&nbsp;Wenxin Hu ,&nbsp;Caiyun Zhao ,&nbsp;Chengke Zhao ,&nbsp;Yan Liu ,&nbsp;Xiaojing Pei ,&nbsp;Jun Zhu ,&nbsp;Yongbo Lyu ,&nbsp;Zhaohui Qu","doi":"10.1016/j.eurpolymj.2026.114499","DOIUrl":"10.1016/j.eurpolymj.2026.114499","url":null,"abstract":"<div><div>Polydeoxyribonucleotide (PDRN) has been demonstrated to possess pharmacological activities, including tissue repair and anti-inflammation, thus rendering it a promising ingredient in both regenerative medicine and cosmetics. However, its application is limited by issues including poor cell membrane permeability due to negative charge, susceptibility to nuclease degradation, and impaired transdermal delivery by the skin barrier. Herein, we constructed the pH-responsive PDRN nanocarrier (CP-NPs) using chitosan (CS) via electrostatic self-assembly. By regulating the molar ratio of CS amino groups to PDRN phosphate groups and optimizing the preparation process, uniform CP-NPs with an average particle size of 161.1 ± 6.2 nm were obtained. PDRN aggregation and protection against nuclease degradation was confirmed through a combination of characterization techniques, including dynamic light scattering, scanning electron microscopy, and infrared spectroscopy, in conjunction with agarose gel electrophoresis. The pH-responsive properties of the material were confirmed through zeta potential and UV analysis. Furthermore, experimental findings demonstrated that CP-NPs exhibit excellent stability and biocompatibility, significantly enhancing antioxidant performance and hydration capacity. Further results proved that CP-NPs promoted the proliferation and migration of human dermal fibroblasts (HDFs), with the migration rate increased by 174.16 %, enhancing <em>in vitro</em> transdermal delivery capacity by 55.3 %, and improving <em>in vivo</em> penetration ability by 167.6 %. Human trials confirmed that CP-NPs could improve skin moisture content, transepidermal water loss (TEWL), glossiness, and elasticity without adverse reactions. This study provides a viable PDRN transdermal delivery approach, advancing “non-invasive nucleic acid therapy” in regenerative medicine and<!--> <!-->cosmetics and laying a foundation for topical PDRN clinical translation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114499"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939769","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
Water-based polyimide binders with dual functional groups for enhanced electrochemical performance of silicon anodes 具有双官能团的水基聚酰亚胺粘合剂用于提高硅阳极的电化学性能
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-25 DOI: 10.1016/j.eurpolymj.2025.114474
Minji Choi , Nam-Ho You , Hee Jeung Oh , Youngjae Yoo
Silicon-based anodes are promising materials for next-generation lithium-ion batteries due to their high theoretical capacity. However, their practical application is hindered by drastic volume expansion during cycling, which leads to particle fracture, capacity fading, and instability of the electrode structure. In addition, most conventional binders require toxic organic solvents, raising environmental and safety concerns. To address these issues, a water-based polyimide binder with high mechanical robustness was synthesized through an aqueous process by combining 3,5-diaminobenzoic acid (DABA) and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA) in different ratios. The –COOH groups in DABA enhanced adhesion and structural stability, while the –O– linkages in TTDDA improved flexibility and Li+ transport. Among the synthesized binders, D8T2-PI exhibited the best balance between mechanical strength and elasticity, achieving superior cycling performance and higher capacity compared with conventional PAA and CMC binders. The flexible polymer network improved electrode–electrolyte interfacial contact and facilitated Li+ diffusion, thereby enhancing electrochemical performance. These results demonstrate that a sustainable, water-processable polyimide binder can effectively enhance both the mechanical and electrochemical stability of silicon anodes, providing a practical and design strategy for high-performance lithium-ion batteries.
硅基阳极具有较高的理论容量,是下一代锂离子电池的理想材料。然而,它们的实际应用受到循环过程中剧烈的体积膨胀的阻碍,这会导致颗粒断裂、容量衰减和电极结构不稳定。此外,大多数传统粘合剂需要有毒的有机溶剂,这引起了环境和安全问题。为解决上述问题,以3,5-二氨基苯甲酸(DABA)和4,7,10-三氧基-1,13-三胺(TTDDA)为原料,采用水相法合成了一种机械强度高的水基聚酰亚胺粘合剂。DABA中的- cooh基团增强了黏附性和结构稳定性,而TTDDA中的- o -键提高了柔韧性和Li+的运输。在合成的粘结剂中,D8T2-PI在机械强度和弹性之间表现出最好的平衡,与常规PAA和CMC粘结剂相比,具有更好的循环性能和更高的容量。柔性聚合物网络改善了电极-电解质界面接触,促进了Li+扩散,从而提高了电化学性能。这些结果表明,一种可持续的、可水处理的聚酰亚胺粘合剂可以有效地提高硅阳极的机械和电化学稳定性,为高性能锂离子电池的设计提供了一种实用的策略。
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引用次数: 0
Redox-Responsive and mucoadhesive nanoparticles: An overlooked synergy in modern drug delivery 氧化还原反应和黏附纳米颗粒:在现代药物输送中被忽视的协同作用
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-27 DOI: 10.1016/j.eurpolymj.2025.114475
Sibel Küçükertuğrul Çelik , Sema Şentürk , Kevser Bal , Özlem Kaplan , Mehmet Koray Gök
The continuous advancement of therapeutic technologies has intensified the pursuit of drug delivery systems that respond intelligently to physiological and pathological stimuli, thereby enabling precise, localized, and sustained therapeutic outcomes. Among redox-based approaches, systems responsive to intracellular glutathione (GSH) have attracted particular attention due to their ability to trigger disulfide bond cleavage and controlled release within diseased tissues. Mucoadhesive systems, on the other hand, prolong residence time on mucosal surfaces through non-covalent interactions and covalent bond formation, thereby facilitating increased absorption and decreased clearance. Despite their individual successes, the integration of these two mechanisms remains underexplored. This review critically examines the coupling of redox sensitivity and mucoadhesion, highlighting how disulfide-based bonds can simultaneously function as both redox-cleavable and mucoadhesive moieties.
治疗技术的不断进步加强了对药物传递系统的追求,这些系统可以对生理和病理刺激做出智能反应,从而实现精确、局部和持续的治疗结果。在基于氧化还原的方法中,对细胞内谷胱甘肽(GSH)反应的系统由于其在病变组织中触发二硫键切割和控制释放的能力而引起了特别的关注。另一方面,黏附系统通过非共价相互作用和共价键的形成延长了在粘膜表面的停留时间,从而促进吸收增加和清除减少。尽管它们各自取得了成功,但这两种机制的整合仍未得到充分探索。这篇综述严格审查了氧化还原敏感性和黏附性的耦合,强调了二硫基键如何同时作为氧化还原可切割和黏附的部分。
{"title":"Redox-Responsive and mucoadhesive nanoparticles: An overlooked synergy in modern drug delivery","authors":"Sibel Küçükertuğrul Çelik ,&nbsp;Sema Şentürk ,&nbsp;Kevser Bal ,&nbsp;Özlem Kaplan ,&nbsp;Mehmet Koray Gök","doi":"10.1016/j.eurpolymj.2025.114475","DOIUrl":"10.1016/j.eurpolymj.2025.114475","url":null,"abstract":"<div><div>The continuous advancement of therapeutic technologies has intensified the pursuit of drug delivery systems that respond intelligently to physiological and pathological stimuli, thereby enabling precise, localized, and sustained therapeutic outcomes. Among redox-based approaches, systems responsive to intracellular glutathione (GSH) have attracted particular attention due to their ability to trigger disulfide bond cleavage and controlled release within diseased tissues. Mucoadhesive systems, on the other hand, prolong residence time on mucosal surfaces through non-covalent interactions and covalent bond formation, thereby facilitating increased absorption and decreased clearance. Despite their individual successes, the integration of these two mechanisms remains underexplored. This review critically examines the coupling of redox sensitivity and mucoadhesion, highlighting how disulfide-based bonds can simultaneously function as both redox-cleavable and mucoadhesive moieties.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114475"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882474","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
Isosorbide-based copolymers poly(isosorbide carbonate-co-alkylene naphthalate): Synthesis, properties and fluorescence Regulation 基于异山梨酯的共聚物聚(碳酸异山梨酯-萘二甲酸亚烷基酯):合成、性能和荧光调控
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-29 DOI: 10.1016/j.eurpolymj.2025.114477
Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li
Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.
在日益增长的环境问题的推动下,生物基聚合物近年来得到了广泛的研究。在这项工作中,通过生物基单体异山梨酯(Is)与脂肪二醇(1,4-丁二醇(BDO)、1,6-己二醇(HDO)或1,8-辛二醇(ODO))、碳酸二甲酯(DMC)和2,6-萘二羧酸二甲酯(DMN)两步缩聚合成了一系列聚碳酸酯(Is)。合成的聚碳酸异山梨酯-邻萘二甲酸亚烷基酯(PICANs)在体态下具有本质荧光,并且具有387nm至455nm的可调谐发射波长。此外,PICANs共聚物还表现出强大的热稳定性和可观的拉伸性,使其成为生物基荧光柔性塑料的有吸引力的材料。
{"title":"Isosorbide-based copolymers poly(isosorbide carbonate-co-alkylene naphthalate): Synthesis, properties and fluorescence Regulation","authors":"Ming-Xuan Du,&nbsp;Chang-Hao Han,&nbsp;Hong-Jian Lv,&nbsp;Kai-Xuan Li,&nbsp;Yao-Nan Xiao,&nbsp;Shao-Hua Wu,&nbsp;Jia-Jian Liu,&nbsp;Chun-Cheng Li","doi":"10.1016/j.eurpolymj.2025.114477","DOIUrl":"10.1016/j.eurpolymj.2025.114477","url":null,"abstract":"<div><div>Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114477"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882471","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
Modern theoretical and practical approaches to development, research and processing of thermoplastic elastomers and their filled composites. review 热塑性弹性体及其填充复合材料开发、研究和加工的现代理论和实践方法。审查
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-24 DOI: 10.1016/j.eurpolymj.2025.114463
Kh.V. Allahverdiyeva , N.T. Kakhramanov , F.A. Mustafayeva , A.A. Hasanova , L.M. Afandiyeva , R.V. Gurbanova , H.B. Bafadarova , E.I. Suleymanova , A.G. Habibova , T.M. Babayeva , O.M. Guliyeva
The article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.
本文考虑了具有独特结构和性能组合的新型热塑性弹性体(TPE)的当前发展趋势。介绍了选择增容剂提高热塑性塑料与弹性体组分相容性的基本原则。以聚烯烃和极性合成弹性体为例,讨论了获得具有改进的物理、机械物理和化学性能的TPE的可能性。使用现代物理方法来分析TPE及其改性,如扫描电镜和x射线相分析,衍生法,步进膨胀法,使得获得聚合物-聚合物和聚合物-填料体系中结构-性能关系的信息成为可能。研究了不同类型的分散填料和纤维填料以及纳米颗粒对填充TPE的主要物理、力学和热特性的影响。使用积分热变形分析方法(Kanavets),以及应力-应变依赖关系,可以确定弹性体成分的含量,在此阶段发生相变,形成橡胶的高弹性变形特征区域。首次研究了交联剂硫和过氧化二氨基(DCP)对填充和交联TPE复合材料物理力学性能变化规律的影响。重点研究了动态硫化TPE的相关技术问题,研究了反应挤出和注射成型的温度和压力对复合材料质量的影响。
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引用次数: 0
Shape memory polymers: From materials to emerging biomedical applications 形状记忆聚合物:从材料到新兴的生物医学应用
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-23 DOI: 10.1016/j.eurpolymj.2025.114460
Nusrat Hassan Khan , Mohamed Sultan Mohamed Ali , Mohammed Nazibul Hasan
Shape Memory Polymers (SMPs) have emerged as adaptable and promising biomaterials in biomedical engineering, enabling innovative solutions for minimally invasive procedures and personalized therapies. This review presents a comprehensive overview of SMPs, focusing on their unique shape memory effects, tuneable material properties, and emerging biomedical applications. Unlike previous reviews that primarily focused on performance enhancement through conductive fillers or crosslinking strategies, this work highlights both the tailored modification of SMP characteristics and their functional integration within biomedical contexts. Key SMP types, such as poly(lactic acid), polycaprolactone, polyurethane, poly(methyl methacrylate) and bile acid-based polymers are critically evaluated with respect to their biocompatibility, biodegradability, and responsiveness to external stimuli. Moreover, biomedical applications such as controlled drug delivery, vascular stenting, dental devices, and tissue engineering are also discussed, with particular attention to recent advances and persisting challenges. Furthermore, the review identifies essential considerations for SMP selection, including mechanical robustness, physiological compatibility, and regulatory requirements. By synthesizing current developments and outlining emerging research directions, this article provides a framework to guide both researchers and clinicians in leveraging the full potential of SMPs for next-generation biomedical devices and therapeutic platforms.
形状记忆聚合物(SMPs)已成为生物医学工程中适应性强、前景广阔的生物材料,为微创手术和个性化治疗提供了创新的解决方案。这篇综述介绍了SMPs的全面概述,重点是其独特的形状记忆效应,可调谐的材料特性,以及新兴的生物医学应用。与之前主要关注通过导电填料或交联策略提高性能的综述不同,这项工作强调了SMP特征的定制修改及其在生物医学背景下的功能整合。关键的SMP类型,如聚乳酸、聚己内酯、聚氨酯、聚甲基丙烯酸甲酯和胆汁酸基聚合物的生物相容性、生物可降解性和对外部刺激的反应性进行了严格评估。此外,生物医学应用,如控制药物输送,血管支架植入,牙科设备和组织工程也进行了讨论,特别关注最近的进展和持续的挑战。此外,该综述确定了SMP选择的基本考虑因素,包括机械稳健性、生理相容性和监管要求。通过综合当前的发展和概述新兴的研究方向,本文提供了一个框架,以指导研究人员和临床医生充分利用SMPs的下一代生物医学设备和治疗平台的潜力。
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引用次数: 0
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European Polymer Journal
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