IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-29 DOI: 10.1016/j.polymer.2025.128331

Yuanhang Xiao , Yixuan Wang , Keshuai Ren , Chunhua Wang , Jun Sang , Mingjun Ma , Liang Ma , Wei Lin

Amphoteric polymers as leather retanning agents are considered to effectively address the charge imbalance between chrome-free tanned leather and common anionic wet finishing materials, and improve the quality of finished leather. However, the currently existed high chemical dosage and tedious wet finishing process associated with chrome-free tanning inevitably lead to high pollution emission and energy consumption. Herein, an amphoteric acrylic polymer (i.e., AARFA) with retanning and fatliquoring functions was prepared by free radical polymerization, which exhibited broad molecular weight (10−100 kDa) and appropriate particle size (∼200 nm). Molecular dynamics simulations and experiments showed that AARFA exhibited good dispersion in water and its aggregation behavior can be modulated by adjusting pH. We then applied AARFA in the rapid and reduced wet finishing process (RRWF) for two kinds of typical chrome-free tanned leather. Compared with conventional wet finishing (CWF) process (i.e., 10 % retanning agents and 10 % fatliquor), 12 % AARFA afforded leather dispersed collagen fibers, improved physical and sensory properties, and excellent dyeing performance. The RRWF process can effectively save work time by ∼31 %, reduce chemical consumption by ∼35 % and exhibit better wastewater degradability. Our developed RRWF process offer the promise for the chrome-free leather manufacturing towards low energy consumption and less carbon emissions.

{"title":"Engineering design of amphoteric acrylic polymer for rapid and reduced wet-finishing process of eco-leather production towards energy saving and carbon reduction","authors":"Yuanhang Xiao , Yixuan Wang , Keshuai Ren , Chunhua Wang , Jun Sang , Mingjun Ma , Liang Ma , Wei Lin","doi":"10.1016/j.polymer.2025.128331","DOIUrl":"10.1016/j.polymer.2025.128331","url":null,"abstract":"<div><div>Amphoteric polymers as leather retanning agents are considered to effectively address the charge imbalance between chrome-free tanned leather and common anionic wet finishing materials, and improve the quality of finished leather. However, the currently existed high chemical dosage and tedious wet finishing process associated with chrome-free tanning inevitably lead to high pollution emission and energy consumption. Herein, an amphoteric acrylic polymer (i.e., AARFA) with retanning and fatliquoring functions was prepared by free radical polymerization, which exhibited broad molecular weight (10−100 kDa) and appropriate particle size (∼200 nm). Molecular dynamics simulations and experiments showed that AARFA exhibited good dispersion in water and its aggregation behavior can be modulated by adjusting pH. We then applied AARFA in the rapid and reduced wet finishing process (RRWF) for two kinds of typical chrome-free tanned leather. Compared with conventional wet finishing (CWF) process (i.e., 10 % retanning agents and 10 % fatliquor), 12 % AARFA afforded leather dispersed collagen fibers, improved physical and sensory properties, and excellent dyeing performance. The RRWF process can effectively save work time by ∼31 %, reduce chemical consumption by ∼35 % and exhibit better wastewater degradability. Our developed RRWF process offer the promise for the chrome-free leather manufacturing towards low energy consumption and less carbon emissions.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128331"},"PeriodicalIF":4.1,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734214","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

Development of biocompatible azelaic acid-based copolyester plasticizers for PVC applications

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-29 DOI: 10.1016/j.polymer.2025.128322

Wanjing Zhang , Liyan Wang , Yunsheng Chong , Wei Liu , Xin Qian

In this study, the copolyester plasticizers PHNAZ, synthesized from azelaic acid and hexanediol and modified by neopentyl glycol (NPG), was prepared via direct esterification. A series of characterization tests revealed that the number-average molecular weight of the PHNAZ copolyester plasticizers was less than 2000 with a dispersion coefficient of less than 2, demonstrating excellent thermal stability below 250 °C. PVC samples plasticized with PHNAZ showed thermal degradation temperatures above 250 °C, reduced glass transition temperatures to −33 °C, and significantly improved hydrophilicity. Notably, the water contact angle of PHNAZ-50/PVC was smallest, averaging 53.956°. The highlight of the study is the cytotoxicity testing of the prepared PHNAZ copolyester plasticizer at concentrations of 1 μg/mL, 10 μg/mL, and 50 μg/mL, where the average cell survival rate exceeded 100 %, indicating excellent biocompatibility. Additionally, PHNAZ displayed outstanding plasticizing effects, particularly PHNAZ-20/PVC, which achieved an elongation at break of 913.6 % and a plasticizing efficiency of 260.0 %. These results suggest that PHNAZ not only excels in chemical and thermal properties but also exhibits good biocompatibility and high plasticizing capability, indicating broad application prospects.

{"title":"Development of biocompatible azelaic acid-based copolyester plasticizers for PVC applications","authors":"Wanjing Zhang , Liyan Wang , Yunsheng Chong , Wei Liu , Xin Qian","doi":"10.1016/j.polymer.2025.128322","DOIUrl":"10.1016/j.polymer.2025.128322","url":null,"abstract":"<div><div>In this study, the copolyester plasticizers PHNAZ, synthesized from azelaic acid and hexanediol and modified by neopentyl glycol (NPG), was prepared via direct esterification. A series of characterization tests revealed that the number-average molecular weight of the PHNAZ copolyester plasticizers was less than 2000 with a dispersion coefficient of less than 2, demonstrating excellent thermal stability below 250 °C. PVC samples plasticized with PHNAZ showed thermal degradation temperatures above 250 °C, reduced glass transition temperatures to −33 °C, and significantly improved hydrophilicity. Notably, the water contact angle of PHNAZ-50/PVC was smallest, averaging 53.956°. The highlight of the study is the cytotoxicity testing of the prepared PHNAZ copolyester plasticizer at concentrations of 1 μg/mL, 10 μg/mL, and 50 μg/mL, where the average cell survival rate exceeded 100 %, indicating excellent biocompatibility. Additionally, PHNAZ displayed outstanding plasticizing effects, particularly PHNAZ-20/PVC, which achieved an elongation at break of 913.6 % and a plasticizing efficiency of 260.0 %. These results suggest that PHNAZ not only excels in chemical and thermal properties but also exhibits good biocompatibility and high plasticizing capability, indicating broad application prospects.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128322"},"PeriodicalIF":4.1,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734217","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

Impact of UHMW PEO on the ionic speciation and electrochemical properties of EMIC-AlCl3 gel electrolytes

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128327

Ángela Campo , Anand Kunverji , Karl S. Ryder , Gary J. Ellis , Nuria García , Pilar Tiemblo

Polymer gel electrolytes based on EMIC-AlCl₃ (1:1.5) and ultra-high molecular weight polyethylene oxide (UHMW PEO M_v = 8 × 10⁶ g mol⁻¹) were synthesised with PEO concentrations of 2, 3.5, 5, 10 wt% without the use of auxiliary solvents, by melting the polymer into the electrolyte. This method produced elastic gels with progressively increasing elastic modulus. The speciation of the chloroaluminate anions in the gel electrolytes was characterized by NMR and Raman spectroscopy, revealing a decrease in Al₂Cl₇⁻ and corresponding increase in AlCl₄⁻ with rising PEO content. In particular, the gel with 10 wt% PEO showed no detectable Al₂Cl₇⁻. Electrochemical activity of these gels was evaluated using two configurations: a platinum disc electrode and parallel planar aluminium foil electrode, the latter mimicking a practical electrochemical cell operating geometry. Surprisingly, all gels exhibited electrochemical activity, even in the absence of the Al₂Cl₇⁻ species. Increasing PEO concentration led to reduced current densities but enhanced coulombic efficiency. The study discusses the influence of the molecular weight of PEO on ionic speciation and electrochemical performance of the polymer gel electrolytes, providing insights into the interplay between polymer content, ionic speciation, and electrochemical behaviour. These findings contribute to the development of safer, more sustainable aluminium batteries.

{"title":"Impact of UHMW PEO on the ionic speciation and electrochemical properties of EMIC-AlCl3 gel electrolytes","authors":"Ángela Campo , Anand Kunverji , Karl S. Ryder , Gary J. Ellis , Nuria García , Pilar Tiemblo","doi":"10.1016/j.polymer.2025.128327","DOIUrl":"10.1016/j.polymer.2025.128327","url":null,"abstract":"<div><div>Polymer gel electrolytes based on EMIC-AlCl<sub>3</sub> (1:1.5) and ultra-high molecular weight polyethylene oxide (UHMW PEO M<sub>v</sub> = 8 × 10<sup>6</sup> g mol<sup>−1</sup>) were synthesised with PEO concentrations of 2, 3.5, 5, 10 wt% without the use of auxiliary solvents, by melting the polymer into the electrolyte. This method produced elastic gels with progressively increasing elastic modulus. The speciation of the chloroaluminate anions in the gel electrolytes was characterized by NMR and Raman spectroscopy, revealing a decrease in Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> and corresponding increase in AlCl<sub>4</sub><sup>−</sup> with rising PEO content. In particular, the gel with 10 wt% PEO showed no detectable Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup>. Electrochemical activity of these gels was evaluated using two configurations: a platinum disc electrode and parallel planar aluminium foil electrode, the latter mimicking a practical electrochemical cell operating geometry. Surprisingly, all gels exhibited electrochemical activity, even in the absence of the Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> species. Increasing PEO concentration led to reduced current densities but enhanced coulombic efficiency. The study discusses the influence of the molecular weight of PEO on ionic speciation and electrochemical performance of the polymer gel electrolytes, providing insights into the interplay between polymer content, ionic speciation, and electrochemical behaviour. These findings contribute to the development of safer, more sustainable aluminium batteries.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128327"},"PeriodicalIF":4.1,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724013","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

Topological constraint of ring fillers on the lamellar forming ABA-type tri-block copolymers using coarse-grained molecular dynamics simulations

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128334

Katsumi Hagita , Takahiro Murashima

Coarse-grained molecular dynamics simulations were performed under the restriction of chain-crossing prohibition to investigate the effect of topological constraints by ring fillers on the lamellar domain spacing D of ABA tri-block copolymers (BCPs), where A domain is hard, and B domain is soft. Here, we introduced an effective bridge by linking a B component ring filler between two U-shaped loop configurations of the ABA tri-BCPs. For a large fraction (f_add) of the additional ring fillers, we found that D for the linked ring cases became much smaller than that for the unlinked ring cases. It was also confirmed that the reduction effect was greater for smaller sizes of the linked rings. Moreover, we found that normalized domain spacing (D/N_total) was proportional to number of links by ring fillers, where N_total denotes the total number of beads in the system under the periodic boundary conditions. For small f_add, void growth and stretching of fibril-like ring fillers were observed in the soft B domain, whereas for large f_add, temporal void growth in the soft B domain was observed before total fracture in the hard A domain. A bonded ring complex was also considered as an alternative to a simple ring, but it was found that there was little difference. This work will promote syntheses of a linked ring filler with deuterated polymers and observations of the behavior of single-molecules.

在禁止链交叉的限制条件下，我们进行了粗粒度分子动力学模拟，以研究环状填料的拓扑约束对 ABA 三嵌段共聚物（BCPs）层状结构域间距 D 的影响，其中 A 结构域是硬的，B 结构域是软的。在这里，我们通过在 ABA 三嵌段共聚物的两个 U 型环形结构之间连接 B 组分环形填料，引入了一种有效的桥。对于大部分（fadd）的附加环填料，我们发现连接环情况下的 D 值比未连接环情况下的 D 值小得多。我们还证实，连接环的尺寸越小，减小效果越明显。此外，我们还发现归一化畴间距（D/Ntotal）与环形填料的链接数成正比，其中 Ntotal 表示周期性边界条件下系统中珠子的总数。对于较小的 fadd，在软 B 域观察到空隙增长和纤维状环形填料的拉伸，而对于较大的 fadd，在硬 A 域完全断裂之前，在软 B 域观察到时间性空隙增长。此外，还考虑用键合环状复合物来替代简单的环状物，但结果发现两者差别不大。这项工作将促进用氚化聚合物合成连接环填料，并观察单分子的行为。

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引用次数: 0

Biodegradable poly (lactic acid) blends toughened with in situ formed core-shell structure by reactive processing

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128330

Wei Bao , Yunbao Gao , Jianing Zhang , Jing Jin , Na Zhang , Baijun Liu , Mingyao Zhang , Zhaohui Su , Hongwen Liang , Xiangling Ji , Wei Jiang

Biodegradable poly (lactic acid) (PLA) blends toughened with a core-shell structure were successfully prepared by melt-blending PLA with poly (butylene adipate-co-terephthalate) (PBAT) and poly (ether-block-amide) (PEBA). Scanning electron microscopy (SEM) and atomic force microscopy-infrared (AFM-IR) analyses confirmed the presence of core-shell structure in the PLA matrix, in which the core and the shell are PBAT and PEBA, respectively. To enhance the interfacial compatibility between PLA and PEBA, glycidyl methacrylate (GMA) was grafted onto PEBA, yielding the PEBA-GMA copolymer. The epoxy groups in PEBA-GMA reacted with the end groups (-OH, –COOH) of PBAT and PLA, which enhanced the interfacial compatibility of PLA/PEBA and PEBA/PBAT, thereby facilitating the formation of a smaller dispersed phase with core-shell structure. Consequently, a super-toughened PLA/PEBA-GMA/PBAT blend was prepared. The PLA/PEBA-GMA5/PBAT (70/15/15) blends achieved a notched Izod impact strength of 72.9 kJ/m². Moreover, with a fixed PLA matrix content of 80 wt%, the upper limit of core PBAT content in PLA/PEBA-GMA3/PBAT blends was 18 wt%, while the minimum shell PEBA-GMA3 content was 2 wt% to ensure that the blends were ductile fracture. The composite of this blend had a lower stiffness loss, i.e., 26 %, demonstrating a well-balanced toughness and stiffness. Furthermore, the PLA/PEBA-GMA3/PBAT (70/25/5) blend exhibited excellent toughness at low temperatures, achieving a notched Izod impact strength of 47.1 kJ/m² at −20 °C. Enzyme degradation experiments confirmed that the PLA blends retained the biodegradability of PLA, PBAT, and PEBA, ensuring that the blends were environmentally friendly.

通过将聚乳酸与聚己二酸丁二醇酯（PBAT）和聚醚嵌段酰胺（PEBA）熔融混合，成功制备了具有核壳结构的可生物降解聚乳酸（PLA）增韧共混物。扫描电子显微镜（SEM）和原子力显微镜-红外（AFM-IR）分析证实，聚乳酸基质中存在核壳结构，其中核和壳分别为 PBAT 和 PEBA。为了增强聚乳酸和 PEBA 之间的界面相容性，在 PEBA 上接枝了甲基丙烯酸缩水甘油酯（GMA），从而得到 PEBA-GMA 共聚物。PEBA-GMA 中的环氧基团与 PBAT 和 PLA 的端基（-OH、-COOH）发生反应，增强了 PLA/PEBA 和 PEBA/PBAT 的界面相容性，从而促进了具有核壳结构的较小分散相的形成。因此，制备出了超增韧聚乳酸/PEBA-GMA/PBAT 共混物。聚乳酸/PEBA-GMA5/PBAT（70/15/15）混合物的缺口伊佐德冲击强度达到 72.9 kJ/m2。此外，在固定聚乳酸基体含量为 80 wt.%的情况下，聚乳酸/PEBA-GMA3/PBAT 共混物的核心 PBAT 含量上限为 18 wt.%，而外壳 PEBA-GMA3 的最低含量为 2 wt.%，以确保共混物具有韧性断裂。这种混合物的复合材料刚度损失较低，仅为 26%，表明韧性和刚度得到了很好的平衡。此外，聚乳酸/PEBA-GMA3/PBAT（70/25/5）共混物在低温条件下表现出优异的韧性，在-20 °C时的缺口伊佐德冲击强度达到47.1 kJ/m2。酶降解实验证实，聚乳酸共混物保留了聚乳酸、PBAT 和 PEBA 的生物降解性，确保了共混物的环境友好性。

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引用次数: 0

Accelerating polycondensation efficiency through introducing aromatic monofunctional alcohol

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128329

Peixuan Han , Hongjun Yin , Xuhui Zhang, Ting Li, Jing Huang, Yang Wang, Bihua Xia, Shibo Wang, Weifu Dong

Increasing the polycondensation rate of polyester is crucial for energy conservation, cost control, product quality, and improving production efficiency, as the process typically occurs under high temperature and vacuum conditions. To increase the rate, this study proposes a novel approach to accelerate the polycondensation of polybutylene succinate (PBS) by introducing benzyl alcohol as a comonomer. Experimental results show that the addition of benzyl alcohol significantly speeds up the polycondensation reaction. Without benzyl alcohol, the polymerization reaction required 170 min under a high vacuum to reach an intrinsic viscosity of 0.85 dL/g. With benzyl alcohol, the polymer's intrinsic viscosity can reach 1.31 dL/g in just 85 min. The accelerated polycondensation rate was revealed to stem from the high ester exchange activity of the benzyl ester groups and the significantly accelerated chain growth rate. Furthermore, density functional theory calculations further confirmed that the energy required for the removal of benzyl alcohol from the polymer chain was lower than that for 1,4-butanediol. Importantly, this method did not alter the physical properties of the polymer, suggesting the potential for industrial preparation. We believe that this approach holds significant practical value for polyester industrial production, particularly in terms of reducing production costs and improving production efficiency.

{"title":"Accelerating polycondensation efficiency through introducing aromatic monofunctional alcohol","authors":"Peixuan Han , Hongjun Yin , Xuhui Zhang, Ting Li, Jing Huang, Yang Wang, Bihua Xia, Shibo Wang, Weifu Dong","doi":"10.1016/j.polymer.2025.128329","DOIUrl":"10.1016/j.polymer.2025.128329","url":null,"abstract":"<div><div>Increasing the polycondensation rate of polyester is crucial for energy conservation, cost control, product quality, and improving production efficiency, as the process typically occurs under high temperature and vacuum conditions. To increase the rate, this study proposes a novel approach to accelerate the polycondensation of polybutylene succinate (PBS) by introducing benzyl alcohol as a comonomer. Experimental results show that the addition of benzyl alcohol significantly speeds up the polycondensation reaction. Without benzyl alcohol, the polymerization reaction required 170 min under a high vacuum to reach an intrinsic viscosity of 0.85 dL/g. With benzyl alcohol, the polymer's intrinsic viscosity can reach 1.31 dL/g in just 85 min. The accelerated polycondensation rate was revealed to stem from the high ester exchange activity of the benzyl ester groups and the significantly accelerated chain growth rate. Furthermore, density functional theory calculations further confirmed that the energy required for the removal of benzyl alcohol from the polymer chain was lower than that for 1,4-butanediol. Importantly, this method did not alter the physical properties of the polymer, suggesting the potential for industrial preparation. We believe that this approach holds significant practical value for polyester industrial production, particularly in terms of reducing production costs and improving production efficiency.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128329"},"PeriodicalIF":4.1,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723491","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

Effect of Divalent Ions on the Structure of Polyelectrolyte Gels

IF 4.6 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128311

Ferenc Horkay, Jack F. Douglas

We perform an exploratory study of the influence of adding divalent metal ion salts such as CaCl₂ to the structure of model monovalent metal counterion polyelectrolyte gels to test the hypothesis that such counterions lead to a tendency of polyelectrolyte chains to form fiber-like structures. Our experimental methodology is based on osmotic pressure Π measurements and small angle neutron scattering measurements on typical synthetic [poly(acrylic acid) and polystyrene sulfonate] and biopolymer (DNA and hyaluronic acid) polyelectrolyte gels over large polymer and CaCl₂ concentration ranges. The results of the present combined small-angle neutron scattering (SANS) and Π measurements strongly suggest that the Ca²⁺ counterions are causing a tendency of the polyelectrolyte chains to associate all along the chain axis to form semi-flexible fiber structures rather than as randomly positioned physical cross-links between the chains. This form of association is consistent with the added divalent salt giving rise to attractive interactions between the chains that reduce phase stability of such polymers and with the observed scaling properties of the osmotic pressure of the gels and their structure as inferred from small angle neutron scattering. Further studies are required to confirm this structural assignment to this class of hydrogels given the uncertainty in assigning a unique structure by neutron scattering.

{"title":"Effect of Divalent Ions on the Structure of Polyelectrolyte Gels","authors":"Ferenc Horkay, Jack F. Douglas","doi":"10.1016/j.polymer.2025.128311","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128311","url":null,"abstract":"We perform an exploratory study of the influence of adding divalent metal ion salts such as CaCl<sub>2</sub> to the structure of model monovalent metal counterion polyelectrolyte gels to test the hypothesis that such counterions lead to a tendency of polyelectrolyte chains to form fiber-like structures. Our experimental methodology is based on osmotic pressure <em>Π</em> measurements and small angle neutron scattering measurements on typical synthetic [poly(acrylic acid) and polystyrene sulfonate] and biopolymer (DNA and hyaluronic acid) polyelectrolyte gels over large polymer and CaCl<sub>2</sub> concentration ranges. The results of the present combined small-angle neutron scattering (SANS) and <em>Π</em> measurements strongly suggest that the Ca<sup>2+</sup> counterions are causing a tendency of the polyelectrolyte chains to associate all along the chain axis to form semi-flexible fiber structures rather than as randomly positioned physical cross-links between the chains. This form of association is consistent with the added divalent salt giving rise to attractive interactions between the chains that reduce phase stability of such polymers and with the observed scaling properties of the osmotic pressure of the gels and their structure as inferred from small angle neutron scattering. Further studies are required to confirm this structural assignment to this class of hydrogels given the uncertainty in assigning a unique structure by neutron scattering.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734220","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

A photothermal antimicrobial, antioxidant hydrogel for healing of bacterial-infected wounds

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128332

Junqi Zhao , Ying Chen , Qing Zhong , Wenjie Chen , Langhuan Huang , Jingxian Zhang , Ming Lu , Guocong Liu , Shaozao Tan

Skin is an important barrier to protect the body from the external environment. Once damaged, the body becomes vulnerable to external bacterial attacks, which induce wound infection, and excessive accumulation of reactive oxygen species (ROS) at the wound site destroys fibroblasts and thus affects the wound healing process. Therefore, in this study, an OD-Gel-CuTA hydrogel dressing with near-infrared (NIR) photothermal antimicrobial properties was prepared using gelatin (Gel), oxidized dextran (ODex), and copper tannic acid nanosheets (CuTA). The composition and morphology of CuTA and the hydrogel were analyzed by XRD, FTIR and SEM. Additionally, the mechanical, antioxidant, NIR photothermal, and antimicrobial properties of the hydrogel were investigated with varying CuTA contents. The results showed that the addition of CuTA endowed the OD-Gel-CuTA hydrogel with good mechanical, antioxidant, and antimicrobial properties. Furthermore, the hydrogel promoted the healing of bacterial-infected wounds, which is potentially applicable to the treatment of bacterial wounds in combination with photothermal therapy.

{"title":"A photothermal antimicrobial, antioxidant hydrogel for healing of bacterial-infected wounds","authors":"Junqi Zhao , Ying Chen , Qing Zhong , Wenjie Chen , Langhuan Huang , Jingxian Zhang , Ming Lu , Guocong Liu , Shaozao Tan","doi":"10.1016/j.polymer.2025.128332","DOIUrl":"10.1016/j.polymer.2025.128332","url":null,"abstract":"<div><div>Skin is an important barrier to protect the body from the external environment. Once damaged, the body becomes vulnerable to external bacterial attacks, which induce wound infection, and excessive accumulation of reactive oxygen species (ROS) at the wound site destroys fibroblasts and thus affects the wound healing process. Therefore, in this study, an OD-Gel-CuTA hydrogel dressing with near-infrared (NIR) photothermal antimicrobial properties was prepared using gelatin (Gel), oxidized dextran (ODex), and copper tannic acid nanosheets (CuTA). The composition and morphology of CuTA and the hydrogel were analyzed by XRD, FTIR and SEM. Additionally, the mechanical, antioxidant, NIR photothermal, and antimicrobial properties of the hydrogel were investigated with varying CuTA contents. The results showed that the addition of CuTA endowed the OD-Gel-CuTA hydrogel with good mechanical, antioxidant, and antimicrobial properties. Furthermore, the hydrogel promoted the healing of bacterial-infected wounds, which is potentially applicable to the treatment of bacterial wounds in combination with photothermal therapy.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128332"},"PeriodicalIF":4.1,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734221","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

Synergistic effect of PANI nanofibers on MXene sheets for high performance electrodes in supercapacitor applications

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-28 DOI: 10.1016/j.polymer.2025.128328

Nidhi , Nahid Tyagi , Gaurav Sharma , Manoj Kumar Singh

Development of advanced composite materials for supercapacitor electrodes is crucial for achieving high performance energy storage devices. This research presents the electrochemical properties of 2D MXene (Ti₃C₂T_x) sheets by integrating them with polyaniline (PANI) nanofiber using polymerization method. The electrochemical measurements were finding by utilizing of graphite sheet as a current collector. The results demonstrate that the Ti₃C₂T_x/PANI nanocomposite has a remarkable capacitance of 854 F/g at a current density of 1A/g with 1 M H₂SO₄ electrolyte. Moreover, it demonstrates at an immersive retention capacity of 88 % after 2000 cycles of charging and discharging, even at 5 A/g current density. Ti₃C₂T_x/PANI has 48.6 μS/cm ionic conductivity and a diffusion coefficient of 196.1 × 10⁻¹² cm²/s as calculated by EIS measurements. Therefore, Ti₃C₂T_x/PANI nanocomposite can be regarded a promising electrode material for supercapacitor applications.

{"title":"Synergistic effect of PANI nanofibers on MXene sheets for high performance electrodes in supercapacitor applications","authors":"Nidhi , Nahid Tyagi , Gaurav Sharma , Manoj Kumar Singh","doi":"10.1016/j.polymer.2025.128328","DOIUrl":"10.1016/j.polymer.2025.128328","url":null,"abstract":"<div><div>Development of advanced composite materials for supercapacitor electrodes is crucial for achieving high performance energy storage devices. This research presents the electrochemical properties of 2D MXene (Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>) sheets by integrating them with polyaniline (PANI) nanofiber using polymerization method. The electrochemical measurements were finding by utilizing of graphite sheet as a current collector. The results demonstrate that the Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>/PANI nanocomposite has a remarkable capacitance of 854 F/g at a current density of 1A/g with 1 M H<sub>2</sub>SO<sub>4</sub> electrolyte. Moreover, it demonstrates at an immersive retention capacity of 88 % after 2000 cycles of charging and discharging, even at 5 A/g current density. Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>/PANI has 48.6 μS/cm ionic conductivity and a diffusion coefficient of 196.1 × 10<sup>−12</sup> cm<sup>2</sup>/s as calculated by EIS measurements. Therefore, Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>/PANI nanocomposite can be regarded a promising electrode material for supercapacitor applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128328"},"PeriodicalIF":4.1,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734216","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

Tailoring the morphology in partially and fully miscible mixtures of PEEK and PEI

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-03-27 DOI: 10.1016/j.polymer.2025.128315

Arthur Lassus , Daniel Therriault , Basil D. Favis , Nick Virgilio

Over the last three decades, the vast body of work related to the control of the morphology of multiphase polymers has concentrated on systems that are inherently immiscible. On the other hand, detailed morphological studies of phase separation in miscible blends have been limited by the highly unstable nature of the structures generated as a function of time and temperature. In this work, we present one basic polymer system, with a slight variation in chemical structure, that allows for a high level of morphological tailoring and control in the miscible to partially miscible region. Two close isomeric forms of polyetherimides (PEI) yield fundamentally different types of morphologies in polyetheretherketone (PEEK)/PEI melt-processed multiphase systems: a partially miscible, phase-separated microstructure for the barely studied PEEK/para-PEI (p-PEI) system, and the typically reported fully miscible PEEK/meta-PEI system (m-PEI). The PEEK/p-PEI system displays sub-μm, matrix/dispersed phase or co-continuous types of morphologies, with the latter quickly coarsening over tens of μm in length scale under quiescent annealing conditions due to the PEEK/p-PEI interfacial tension, which was measured by the breaking thread method at 0.14 mN/m, one of the lowest values ever reported for a polymer pair. On the other hand, for the PEEK/m-PEI system, controlling the thermal annealing temperature promotes PEEK recrystallization and the formation of a nanostructured PEI-rich phase. Considering both types of blends, it is then possible to control the morphological length scale of PEEK and PEI domains over nearly 4 orders of magnitude, from ≈5 nm to over 15 μm. This is the smallest domain size ever reported for co-continuous systems. The selective extraction of the PEI phase then results in porous PEEK monoliths with full pore interconnectivity, with an average pore size spanning the same considerable range – without any interfacial modifier or block copolymer.

{"title":"Tailoring the morphology in partially and fully miscible mixtures of PEEK and PEI","authors":"Arthur Lassus , Daniel Therriault , Basil D. Favis , Nick Virgilio","doi":"10.1016/j.polymer.2025.128315","DOIUrl":"10.1016/j.polymer.2025.128315","url":null,"abstract":"<div><div>Over the last three decades, the vast body of work related to the control of the morphology of multiphase polymers has concentrated on systems that are inherently immiscible. On the other hand, detailed morphological studies of phase separation in miscible blends have been limited by the highly unstable nature of the structures generated as a function of time and temperature. In this work, we present one basic polymer system, with a slight variation in chemical structure, that allows for a high level of morphological tailoring and control in the miscible to partially miscible region. Two close isomeric forms of polyetherimides (PEI) yield fundamentally different types of morphologies in polyetheretherketone (PEEK)/PEI melt-processed multiphase systems: a partially miscible, phase-separated microstructure for the barely studied PEEK/<em>para</em>-PEI (<em>p</em>-PEI) system, and the typically reported fully miscible PEEK/<em>meta</em>-PEI system (<em>m</em>-PEI). The PEEK/<em>p</em>-PEI system displays sub-μm, matrix/dispersed phase or co-continuous types of morphologies, with the latter quickly coarsening over tens of μm in length scale under quiescent annealing conditions due to the PEEK/<em>p</em>-PEI interfacial tension, which was measured by the breaking thread method at 0.14 mN/m, one of the lowest values ever reported for a polymer pair. On the other hand, for the PEEK/<em>m</em>-PEI system, controlling the thermal annealing temperature promotes PEEK recrystallization and the formation of a nanostructured PEI-rich phase. Considering both types of blends, it is then possible to control the morphological length scale of PEEK and PEI domains over nearly 4 orders of magnitude, from ≈5 nm to over 15 μm. This is the smallest domain size ever reported for co-continuous systems. The selective extraction of the PEI phase then results in porous PEEK monoliths with full pore interconnectivity, with an average pore size spanning the same considerable range – without any interfacial modifier or block copolymer.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128315"},"PeriodicalIF":4.1,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

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