Polymer最新文献_第7页

Formation and distribution of the mesophase in ultrasonic micro-injection-molded ethylene vinyl alcohol copolymer

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-10 DOI: 10.1016/j.polymer.2025.128388

Ce Shi , Yujing Tang , Jiaqi Zhang , Ying Lu , Yongfeng Men

The formation and distribution of mesophase in ethylene vinyl alcohol copolymer ultrasonic micro-injection-molded at different mold temperature and filling velocity were investigated using wide angle X-ray diffraction (WAXD) technique and dynamic rheological characterizations. The one-dimensional WAXD profiles of unoriented and oriented components was separated to evaluate the fraction of mesophase, orthorhombic crystals and amorphous phase in each part. The results demonstrated that mesophase mostly existed in samples with mold temperature lower than 90 °C. Compared to the mold temperature, the filling velocity had slight influence on the formation of mesophase. With the WAXD mapping experiments along the thickness direction, it was found that mesophase mainly appeared in the core layer of unoriented component, regardless of mold temperature and filling velocity. The formation of the mesophase is found to depend on the competition between the time needed for polymer chain relaxation and crystallization. Only the polymer chains relaxed to a random coil state in the core layer is possible to form mesophase, otherwise polymer chains will crystallize into orthorhombic crystals.

利用广角 X 射线衍射（WAXD）技术和动态流变特性研究了在不同模具温度和填充速度下超声微注塑成型的乙烯-乙烯醇共聚物中介相的形成和分布。对无取向和取向组分的一维 WAXD 曲线进行了分离，以评估各组分中的介相、正交晶相和无定形相的比例。结果表明，介相主要存在于模具温度低于 90 摄氏度的样品中。与模具温度相比，填充速度对介相的形成影响较小。通过沿厚度方向的 WAXD 制图实验发现，无论模具温度和填充速度如何，介相主要出现在无取向部件的芯层中。介相的形成取决于聚合物链松弛和结晶所需的时间之间的竞争。只有聚合物链在芯层中松弛成无规线圈状态时才有可能形成介相，否则聚合物链将结晶成正方晶。

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引用次数: 0

Crystal structure and crystalline morphology of poly(hexamethylene trans-1,4-cyclohexane dicarboxylate)

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-10 DOI: 10.1016/j.polymer.2025.128354

Wenxian Hu , Tianyi Ma , Yong Zhou , Michelina Soccio , Nadia Lotti , Dario Cavallo , Dujin Wang , Guoming Liu

The crystal structure of poly (hexamethylene trans-1, 4-cyclohexane dicarboxylate) (PHCE) was determined by X-ray fiber diffraction. Only one crystal form was observed, independent of the crystallization condition. The PHCE has a triclinic unit cell with the space group

. The cell parameters are: a = 5.47 Å, b = 7.36 Å, c = 15.95 Å, α = 141.14°, β = 113.69°, γ = 60.70°. One chain passes through a unit cell, resulting in a crystal density of 1.203 g/cm³. To study the crystal habit, the morphology of PHCE films was studied by imaging techniques. Depending on film thickness and crystallization temperature (T_c), the morphology varied from single crystals, S-shaped crystals, branched single-layer bent crystals, branched multilayer bent single crystals, and spherulites. By investigating the crystal growth rates, two scenarios were observed, characterized by diffusion-controlled growth or secondary nucleation. The interplay between crystal bending and chain tilting was investigated by electron diffraction.

通过 X 射线纤维衍射测定了聚（反式-1，4-环己烷二羧酸六亚甲基酯）（PHCE）的晶体结构。只观察到一种晶体形态，与结晶条件无关。PHCE 具有空间群为 .晶胞参数为：a = 5.47 Å，b = 7.36 Å，c = 15.95 Å，α = 141.14°，β = 113.69°，γ = 60.70°。一条链穿过一个单位晶胞，因此晶体密度为 1.203 g/cm3。为了研究晶体习性，我们利用成像技术对 PHCE 薄膜的形态进行了研究。根据薄膜厚度和结晶温度（Tc）的不同，其形态有单晶体、S 形晶体、支化单层弯曲晶体、支化多层弯曲单晶体和球状晶体。通过研究晶体生长速率，观察到两种情况，即扩散控制生长或二次成核。通过电子衍射研究了晶体弯曲和链倾斜之间的相互作用。

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引用次数: 0

Reaction kinetics and application of polybutylene terephthalate alcoholysis for the preparation of recycled BHBT 聚对苯二甲酸丁二醇酯醇解制备再生 BHBT 的反应动力学及应用

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-09 DOI: 10.1016/j.polymer.2025.128383

Mei Wang , Zhenlin Jiang , Wenjun Wang , Wanyu Xie , Jizhe Liu , Jiaguo Li , Min Zhu , Jianping Yang , Ling Huang

Polybutylene terephthalate (PBT) is an important synthetic polymer in the plastics industry and is widely used in many fields. However, post-consumer PBT products are difficult to degrade in the natural environment, resulting in environmental pollution. Although traditional physical recycling methods can extend the life of the plastic, they degrade the material properties and cannot completely solve the environmental problems. In this paper, a novel chemical recycling process is proposed to convert waste PBT to bishydroxybutyl terephthalate (BHBT) through a controlled alcoholysis reaction, which is further used to produce high performance recycled PBT and poly(butyleneadipate-co-terephthalate) (PBAT). The process uses 1,4-butanediol (BDO) as a solvent and zinc acetate as a catalyst, which significantly improves the efficiency of alcoholysis. Under optimal conditions (zinc acetate content of 1 wt% PBT, PBT to BDO mass ratio of 1:4, alcoholysis temperature of 213 °C and alcoholysis time of 60 min), the conversion of PBT reached 93.5 % and the yield of BHBT was 65.1 %. The reaction kinetics study showed that the depolymerization reaction of PBT in BDO environment conformed to a first-order reaction kinetics model with an activation energy of 61.79 kJ/mol and a reaction kinetic constant of 0.02588 g (mol·min⁻¹). The quantitative life cycle analysis (LCA) demonstrates that this process achieves a 45–50 % reduction in CO₂ emissions and 30–40 % cost savings. The alcoholysis process proposed in this paper has outstanding environmental and economic advantages. It not only avoids the generation of toxic gases from high-temperature thermal cracking, simplifies product separation and reduces the risk of secondary contamination, but also has mild reaction conditions, low energy consumption and catalyst cost, and is suitable for large-scale industrial application. Recycled BHBT can be used to produce high performance PBT and PBAT, reducing dependence on virgin raw materials and recycling resources. Economically, the process is commercially viable as it reduces raw material and waste disposal costs.

{"title":"Reaction kinetics and application of polybutylene terephthalate alcoholysis for the preparation of recycled BHBT","authors":"Mei Wang , Zhenlin Jiang , Wenjun Wang , Wanyu Xie , Jizhe Liu , Jiaguo Li , Min Zhu , Jianping Yang , Ling Huang","doi":"10.1016/j.polymer.2025.128383","DOIUrl":"10.1016/j.polymer.2025.128383","url":null,"abstract":"<div><div>Polybutylene terephthalate (PBT) is an important synthetic polymer in the plastics industry and is widely used in many fields. However, post-consumer PBT products are difficult to degrade in the natural environment, resulting in environmental pollution. Although traditional physical recycling methods can extend the life of the plastic, they degrade the material properties and cannot completely solve the environmental problems. In this paper, a novel chemical recycling process is proposed to convert waste PBT to bishydroxybutyl terephthalate (BHBT) through a controlled alcoholysis reaction, which is further used to produce high performance recycled PBT and poly(butyleneadipate-co-terephthalate) (PBAT). The process uses 1,4-butanediol (BDO) as a solvent and zinc acetate as a catalyst, which significantly improves the efficiency of alcoholysis. Under optimal conditions (zinc acetate content of 1 wt% PBT, PBT to BDO mass ratio of 1:4, alcoholysis temperature of 213 °C and alcoholysis time of 60 min), the conversion of PBT reached 93.5 % and the yield of BHBT was 65.1 %. The reaction kinetics study showed that the depolymerization reaction of PBT in BDO environment conformed to a first-order reaction kinetics model with an activation energy of 61.79 kJ/mol and a reaction kinetic constant of 0.02588 g (mol·min<sup>−1</sup>). The quantitative life cycle analysis (LCA) demonstrates that this process achieves a 45–50 % reduction in CO<sub>2</sub> emissions and 30–40 % cost savings. The alcoholysis process proposed in this paper has outstanding environmental and economic advantages. It not only avoids the generation of toxic gases from high-temperature thermal cracking, simplifies product separation and reduces the risk of secondary contamination, but also has mild reaction conditions, low energy consumption and catalyst cost, and is suitable for large-scale industrial application. Recycled BHBT can be used to produce high performance PBT and PBAT, reducing dependence on virgin raw materials and recycling resources. Economically, the process is commercially viable as it reduces raw material and waste disposal costs.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128383"},"PeriodicalIF":4.1,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806560","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

Ultra-fast coarsening dynamics in late-stage spinodal decomposition of critical binary polymer mixtures 临界二元聚合物混合物后期旋光分解中的超快粗化动力学

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-09 DOI: 10.1016/j.polymer.2025.128387

Hao Yu, Wei-Che Lin, Po-Da Hong

This work aimed to elucidate the ultra-fast dynamics of late-stage spinodal decomposition in critical polymer mixtures using a home-built time-resolved small-angle light scattering (SALS) apparatus. A crossover from the interfacial-tension-driven linear dynamics

R \propto t

to the ultra-fast dynamics

R \propto t^{3}

was observed when the domain size

R

exceeded the capillary length. According to our hydrodynamic model for late-stage spinodal decomposition, the ultra-fast dynamics is considered induced by the accelerating gravity-driven Stokes flow. At the same time, the acceleration is caused by the interfacial-tension-driven coarsening, which enlarges the size of the falling phase and increases the terminal velocity of the Stokes flow. Although the percolating phase-separating structure grows self-similarly on the xy-plane (normal vector parallel to gravity), we consider that the fluid tubes will elongate along the z-axis, resulting in the failure of the dynamical scaling hypothesis in the 3D space. Finally, SALS data also revealed that the gravitational effects should appear as long as there is a density difference between the phase-separating phases. Apart from a transition from one dynamics to another, it is the competition between the interfacial-tension-driven Poiseuille flow and the gravity-driven Stokes flow that determines the predominant mode of the coarsening dynamics in the late-stage spinodal decomposition process.

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引用次数: 0

A novel dual pH- and temperature-responsive poly (N-isopropylacrylamide)/polyacrylamide/calcium alginate hydrogel with robust mechanical performance and biocompatibility for sustainable drug release 一种新型 pH 和温度双重响应聚（N-异丙基丙烯酰胺）/聚丙烯酰胺/海藻酸钙水凝胶，具有稳定的机械性能和生物相容性，可用于持续释放药物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-09 DOI: 10.1016/j.polymer.2025.128386

Yi-Qi Liu , Hong-Yang Guo , Chang-Ying Hu , Xiaowen Xu

Stimuli-responsive hydrogels show promising potential for drug delivery, but often fall short in complex environments due to their single responsiveness and inadequate mechanical properties. Herein, we introduce a dual thermo-/pH-responsive hydrogel carrier, poly(N-isopropylacrylamide)/polyacrylamide/Ca²⁺-coordinated sodium alginate (PNIPAM/PAM/Alg-Ca²⁺), distinguished by exceptional mechanical performance and biocompatibility. The developed PNIPAM/PAM/Alg-Ca²⁺ hydrogel has demonstrated exceptional performance, with a remarkable breaking elongation reaching 4900 % and a toughness of 6.5 MJ/m³, greatly outperforming traditional PNIPAM hydrogels that usually have an elongation of only 247 % and a toughness of 0.035 MJ/m³. It also showcased outstanding crack resistance, with a tearing energy of 212 J/m², far superior to the average of 10 J/m² for existing hydrogel carriers. Moreover, even hydrogel samples with notches can be stretched beyond 1000 %. Swelling tests revealed dual responsiveness (pH and thermo-responsiveness), along with a highly porous structure that supports high drug loading and cell proliferation. Importantly, the hydrogel showed non-cytotoxicity towards NIH-3T3 cells. In vitro release studies of dexamethasone from the hydrogel demonstrated sustained release at pH 7.0 and 37 °C, showing potential for application in drug delivery. Overall, this work highlights the transformative potential of the dual thermo-/pH-responsive PNIPAM/PAM/Alg-Ca²⁺ hydrogel carrier for advancing next-generation biomaterials with enhanced therapeutic efficacy and safety profiles.

刺激响应型水凝胶在药物递送方面显示出巨大的潜力，但由于其响应性单一和机械性能不足，在复杂环境中往往无法发挥其作用。在本文中，我们介绍了一种热/pH 双响应水凝胶载体--聚（N-异丙基丙烯酰胺）/聚丙烯酰胺/Ca2+配位海藻酸钠（PNIPAM/PAM/Alg-Ca2+），它具有优异的机械性能和生物相容性。所开发的 PNIPAM/PAM/Alg-Ca2+ 水凝胶具有卓越的性能，其断裂伸长率高达 4900%，韧性为 6.5 MJ/m3，大大优于通常伸长率仅为 247%、韧性仅为 0.035 MJ/m3 的传统 PNIPAM 水凝胶。它还具有出色的抗裂性，其撕裂能量为 212 J/m2，远高于现有水凝胶载体的平均 10 J/m2。此外，即使是有缺口的水凝胶样品也能拉伸超过 1000%。膨胀测试表明，这种水凝胶具有双重响应性（pH 值和热响应性）以及高多孔性结构，可支持高药物负载和细胞增殖。重要的是，这种水凝胶对 NIH-3T3 细胞无毒性。水凝胶中地塞米松的体外释放研究表明，在 pH 值为 7.0 和温度为 37 ℃ 的条件下，地塞米松可持续释放，显示了其在药物输送方面的应用潜力。总之，这项工作凸显了热/pH 双响应 PNIPAM/PAM/Alg-Ca2+ 水凝胶载体的变革潜力，可促进下一代生物材料的发展，提高治疗效果和安全性。

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引用次数: 0

Molecular simulations of Poly-4-methyl-1-pentene (PMP) and PMP/Calix[4]arene (PMP/CA) for H2S/CO2 separation 用于分离 H2S/CO2 的聚 4-甲基-1-戊烯 (PMP) 和 PMP/Calix[4]arene (PMP/CA) 的分子模拟

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-09 DOI: 10.1016/j.polymer.2025.128288

Hua You , Xinlu Cheng , Hong Zhang

Efficient separation of H

_{2}

S and CO

_{2}

is crucial for industrial applications. Poly-4-methyl-1-pentene (PMP) membranes, enhanced with Calix[4]arene (CA), show promise in improving separation performance. Herein, Molecular dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulations were used to systematically investigate the gas transport properties of H

_{2}

S over PMP membranes, as well as the performance of mixed matrix membranes (MMMs) with varying CA contents (0–7.75 wt%) in H

_{2}

S/CO

_{2}

gas separation. The results indicate that while CO

_{2}

exhibits a higher diffusion coefficient than H

_{2}

S, it has a lower solubility coefficient and permeability coefficient, suggesting that the permeation process is predominantly governed by solubility. The incorporation of CA significantly enhances the H

_{2}

S/CO

_{2}

separation performance. Notably, the 7.75% CA-doped M5 system exhibits a 93.6% increase in separation factor (

α = 4.28

) compared to pure PMP (

α = 2.21

). In addition, CA doping significantly improves the thermal stability, with the glass transition temperature (

T_{g}

) of M5 rising by 25%, and mechanical properties, as evidenced by a 12.4% increase in Young’s modulus. These findings highlight the dual role of CA in modifying both the thermodynamic and kinetic properties of PMP membranes. In summary, this study provides a theoretical basis for the application of PMP-based composite membranes in gas separation and important guidance for material optimization.

{"title":"Molecular simulations of Poly-4-methyl-1-pentene (PMP) and PMP/Calix[4]arene (PMP/CA) for H2S/CO2 separation","authors":"Hua You , Xinlu Cheng , Hong Zhang","doi":"10.1016/j.polymer.2025.128288","DOIUrl":"10.1016/j.polymer.2025.128288","url":null,"abstract":"<div><div>Efficient separation of H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S and CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> is crucial for industrial applications. Poly-4-methyl-1-pentene (PMP) membranes, enhanced with Calix[4]arene (CA), show promise in improving separation performance. Herein, Molecular dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulations were used to systematically investigate the gas transport properties of H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S over PMP membranes, as well as the performance of mixed matrix membranes (MMMs) with varying CA contents (0–7.75 wt%) in H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S/CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> gas separation. The results indicate that while CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibits a higher diffusion coefficient than H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S, it has a lower solubility coefficient and permeability coefficient, suggesting that the permeation process is predominantly governed by solubility. The incorporation of CA significantly enhances the H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S/CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> separation performance. Notably, the 7.75% CA-doped M5 system exhibits a 93.6% increase in separation factor (<span><math><mrow><mi>α</mi><mo>=</mo><mn>4</mn><mo>.</mo><mn>28</mn></mrow></math></span>) compared to pure PMP (<span><math><mrow><mi>α</mi><mo>=</mo><mn>2</mn><mo>.</mo><mn>21</mn></mrow></math></span>). In addition, CA doping significantly improves the thermal stability, with the glass transition temperature (<span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>) of M5 rising by 25%, and mechanical properties, as evidenced by a 12.4% increase in Young’s modulus. These findings highlight the dual role of CA in modifying both the thermodynamic and kinetic properties of PMP membranes. In summary, this study provides a theoretical basis for the application of PMP-based composite membranes in gas separation and important guidance for material optimization.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128288"},"PeriodicalIF":4.1,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806559","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

Incorporation of cupric sulfate and vanillin empowered poly (vinyl alcohol) hydrogel as flexible sensing device 加入硫酸铜和香兰素赋能的聚（乙烯醇）水凝胶作为柔性传感装置

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-09 DOI: 10.1016/j.polymer.2025.128384

Yuze Zhao , Xiaofeng Song , Junfen Chen , Yueyue Chen , Xingyun Wang , Feng Wang

Poly (vinyl alcohol) (PVA) attracts increasing interest in hydrogel field, but it suffers from some obstacles including multi-component, complex preparation process, inadequate mechanical properties, and poor bacteriostatic properties, which hinder its application such as flexible electric devices. In the study, a novel strategy was put forward to make the conductive hydrogel by a combination of coupling vanillin onto PVA and immersing CuSO₄ solution. Coupled vanillin as an accelerator regulates the formation of hydrophobic microcrystal network to enhance the mechanical properties of the hydrogel. CuSO₄ as conductive medium improves the amorphous network by the salting-out effect to further reinforce the mechanical properties of the hydrogel. The optimized hydrogel is super-tough, and its toughness, tensile strength, and elongation at break are 15.05 MJ∙m⁻³, 4.72 MPa, and 737.80 %, respectively. The conductive hydrogel was assembled into a flexible sensing device and exhibits reliable sensitivity (GF = 2.94, Response time = 0.22 s), stability, and durability for monitoring human activities. In addition, conductive hydrogel possesses frost resistance at −20 °C without the introduction of cryoprotectants, and good antimicrobial activity. It provides a general method and reference example for the development of multifunctional hydrogel electronic materials.

{"title":"Incorporation of cupric sulfate and vanillin empowered poly (vinyl alcohol) hydrogel as flexible sensing device","authors":"Yuze Zhao , Xiaofeng Song , Junfen Chen , Yueyue Chen , Xingyun Wang , Feng Wang","doi":"10.1016/j.polymer.2025.128384","DOIUrl":"10.1016/j.polymer.2025.128384","url":null,"abstract":"<div><div>Poly (vinyl alcohol) (PVA) attracts increasing interest in hydrogel field, but it suffers from some obstacles including multi-component, complex preparation process, inadequate mechanical properties, and poor bacteriostatic properties, which hinder its application such as flexible electric devices. In the study, a novel strategy was put forward to make the conductive hydrogel by a combination of coupling vanillin onto PVA and immersing CuSO<sub>4</sub> solution. Coupled vanillin as an accelerator regulates the formation of hydrophobic microcrystal network to enhance the mechanical properties of the hydrogel. CuSO<sub>4</sub> as conductive medium improves the amorphous network by the salting-out effect to further reinforce the mechanical properties of the hydrogel. The optimized hydrogel is super-tough, and its toughness, tensile strength, and elongation at break are 15.05 MJ∙m<sup>−3</sup>, 4.72 MPa, and 737.80 %, respectively. The conductive hydrogel was assembled into a flexible sensing device and exhibits reliable sensitivity (<em>GF</em> = <em>2.94</em>, <em>Response time = 0.22 s</em>), stability, and durability for monitoring human activities. In addition, conductive hydrogel possesses frost resistance at −20 °C without the introduction of cryoprotectants, and good antimicrobial activity. It provides a general method and reference example for the development of multifunctional hydrogel electronic materials.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128384"},"PeriodicalIF":4.1,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806561","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 hybrid hydrogels reinforced with biomimetic nanocomposites and dual-biomolecular cross-linking for enhanced antibacterial and photothermal therapeutic effects

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-08 DOI: 10.1016/j.polymer.2025.128382

Chenxi Du , Guanghui Gu , Youyin Xu , Zhuang Liu , Yongming Xi , Gang Wei

Bioactive hydrogels hold great promise in advancing biomedical treatments, offering potential solutions for drug delivery, tissue engineering, as well as tumor diagnosis and therapy applications. To extend biomedical applications of hydrogels, enhancing their biocompatibility and structural doping to achieve multifunctional capabilities are key challenges. In this study, we develop a biomimetic bioactive hybrid hydrogels via bioinspired synthesis and dual-biomolecular cross-linking techniques to enable multifunctional biomedical applications, specifically as antibacterial and photothermal therapy (PTT) materials. Initially, peptide-bioinspired silver nanoparticles (PAN) are synthesized through a coordination reaction between peptide molecules and Ag⁺ and then biomimetic synthesis strategy, which are then loaded onto graphene oxide (GO) via electrostatic interactions, forming the GO/PAN nanohybrids (PGA). PGA is subsequently combined with chitosan (CS) and dopamine (DA) to form hybrid hydrogels under the oxidation of ammonium persulfate. Experimental results indicate that the synergistic effects of CS and PAN notably enhance the hydrogel's antibacterial properties. In addition, the hydrogels demonstrate high photothermal conversion efficiency under the NIR laser irradiation, enabling injectable tumor cell ablation through in vitro and in vivo PTT tests. The biomimetic bioactive hybrid hydrogels developed in this work exhibit enhanced antibacterial and PTT properties, offering a novel material candidate for tumor therapy and antibacterial applications.

生物活性水凝胶在推进生物医学治疗方面大有可为，为药物输送、组织工程以及肿瘤诊断和治疗应用提供了潜在的解决方案。要扩展水凝胶的生物医学应用，增强其生物相容性和结构掺杂以实现多功能是关键挑战。在本研究中，我们通过生物启发合成和双生物分子交联技术开发了一种仿生生物活性混合水凝胶，以实现多功能生物医学应用，特别是作为抗菌和光热治疗（PTT）材料。首先，通过肽分子与 Ag+ 的配位反应以及仿生合成策略合成肽生物启发银纳米粒子（PAN），然后通过静电相互作用将其负载到氧化石墨烯（GO）上，形成 GO/PAN 纳米杂化物（PGA）。PGA 随后与壳聚糖（CS）和多巴胺（DA）结合，在过硫酸铵的氧化作用下形成混合水凝胶。实验结果表明，CS 和 PAN 的协同作用显著增强了水凝胶的抗菌性能。此外，该水凝胶在近红外激光照射下具有很高的光热转换效率，通过体外和体内 PTT 试验可实现注射式肿瘤细胞消融。这项研究开发的仿生生物活性混合水凝胶具有更强的抗菌和 PTT 特性，为肿瘤治疗和抗菌应用提供了一种新型候选材料。

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引用次数: 0

Preparation and application of poly(arylamine ketone) materials for electrochromism and lithium-ion batteries

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-08 DOI: 10.1016/j.polymer.2025.128379

Huilin Shen, Qilin Wang, Yuntao Han, Shuo Yang, Yixuan Liu, Zheng Chen, Zhenhua Jiang

The investigation of electrochemical materials with multiple functions is steadily growing. By joining ketone groups to triphenylamine structures via a two-step C–N coupling procedure, PAEK-CzTPAs multiple function copolymers were prepared and used in the electrochromic and battery fields. When the PAK-CzTPA polymer is applied to the electrochromic field, the transmission change has a small attenuation even after 600 s. PAK-CzTPA polymer as cathode active material with a theoretical specific capacity of 122.9 mAh/g, PAK-CzTPA cathode capacity is about 90.0 mAh/g after 50 cycles with 87.9 % capacity retention at 0.2 C current density. 6F-PAEK-CzTPA20 cathode reaches 164.0 mAh/g at 0.1 C current density after 50 cycles with 85.0 % coulombic efficiency, which itself as binder is applied to ternary (NCM811) electrode. Materials with the ability to store energy, exhibit electrochromic characteristics and perform other physical tasks of materials with a wide range of potential uses that could increase energy efficiency, save an important quantity of resources and make the system more sustainable overall.

对具有多种功能的电化学材料的研究正在稳步发展。通过两步 C-N 偶联程序将酮基连接到三苯胺结构上，制备出 PAEK-CzTPAs 多种功能共聚物，并将其应用于电致变色和电池领域。PAK-CzTPA 聚合物作为阴极活性材料，理论比容量为 122.9 mAh/g，在 0.2 C 电流密度下，PAK-CzTPA 阴极容量在 50 个循环后约为 90.0 mAh/g，容量保持率为 87.9%。6F-PAEK-CzTPA20 阴极在 0.1 C 电流密度下循环 50 次后达到 164.0 mAh/g，库仑效率为 85.0%，其本身作为粘合剂应用于三元（NCM811）电极。具有储能、电致变色特性和执行其他物理任务能力的材料具有广泛的潜在用途，可提高能源效率，节约大量资源，并使系统在整体上更具可持续性。

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引用次数: 0

Diffusion-limited free radical mechanisms in peroxide-initiated crosslinking of low-density polyethylene

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-08 DOI: 10.1016/j.polymer.2025.128376

Kai Shang, Jiacai Li, Yifan Wu, Shihang Wang, Yang Feng, Shengtao Li

There have been many attempts to describe the kinetics of the peroxide-initiated crosslinking of low-density polyethylene (LDPE). However, these kinetic models have not comprehensively captured the free radical behavior during LDPE crosslinking. In this study, the evolution of the reduced reaction rate (R_r), derived from the mechanistic kinetic model, is employed to gain detailed insight into free radical behaviors in LDPE during crosslinking. The curve of R_r over time, which follows a bell shape, demonstrates that the complexity of the crosslinking chemistry incorporates diffusional limitation, leading to ineffective free radical terminations. When combined with structural characterization of functional trans-vinylene groups and hydroxyl groups of antioxidants, our analysis highlights a diffusion-limited mechanism associated with a continuous decrease in the effective consumption of peroxide and a sequential increase in radical scavenging. These observations are a result of the intramolecular disproportionation induced by the cage effect in peroxides and the unimolecular termination of LDPE radicals by antioxidants during network formation, respectively. Consequently, a refined kinetic model is proposed, which accounts for the effect of diffusional limitation on free radical terminations, thereby providing an accurate description of the LDPE crosslinking process. This comprehensive understanding of free radical crosslinking mechanisms in LDPE will facilitate the precise control and optimization of the properties of this reaction.

人们曾多次尝试描述过氧化物引发的低密度聚乙烯（LDPE）交联动力学。然而，这些动力学模型并没有全面捕捉到低密度聚乙烯交联过程中的自由基行为。在本研究中，利用机械动力学模型推导出的还原反应速率（Rr）的演变来详细了解交联过程中低密度聚乙烯中的自由基行为。Rr 随时间变化的曲线呈钟形，表明交联化学的复杂性包含了扩散限制，从而导致自由基的无效终止。结合功能性反乙烯基团和抗氧化剂羟基的结构特征，我们的分析强调了一种与过氧化物有效消耗量持续减少和自由基清除量依次增加有关的扩散限制机制。这些观察结果分别是由于过氧化物中的笼效应引起的分子内比例失调，以及网络形成过程中抗氧化剂对低密度聚乙烯自由基的单分子终止。因此，我们提出了一个完善的动力学模型，该模型考虑了自由基终止的扩散限制效应，从而准确地描述了 LDPE 的交联过程。对低密度聚乙烯中自由基交联机理的全面了解将有助于精确控制和优化该反应的特性。

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引用次数: 0