European Polymer Journal最新文献_第10页

Recent advances in composite materials integrating molecularly imprinted polymers for targeted drug delivery systems 靶向给药系统中分子印迹聚合物复合材料的研究进展

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-12 DOI: 10.1016/j.eurpolymj.2025.113825

Wenjun Guo , Jinyu Ji , Yingying Shi , Na Li , Zechen Yan , Qiuzheng Du

Molecular imprinting technology (MIT) is a method for creating molecular locks that complement specific molecular bonds. This technology yields molecularly imprinted polymers (MIPs), which feature specific binding sites that emulate interactions observed in enzyme-substrate or antigen–antibody binding. The distinctive recognition specificity, structural predictability, and high stability of MIPs have positioned them as key areas of interest within drug delivery systems (DDS). Here, we comprehensively review the recent advancements in composite materials integrating MIPs for DDS (MIPs-DDS). Firstly, we provide a brief introduction to MIPs based on the types of forces acting between templates and functional monomers, then classify and introduce MIPs-DDS based on the types of doped nanomaterials, including metal–organic frameworks (MOFs), quantum dots (QDs), carbon nanotubes (CNTs), siloxane, up-conversion nanoparticles (UCNPs), metallic nanoclusters and magnetic nanoparticles (MNPs). We then delve into the delivery modes and release mechanisms of MIPs-DDS, encompassing factors such as pH, light response, temperature, magnetic response, glutathione, and multi-responsive mechanisms. Additionally, we emphasized the application of MIPs-DDS in cancer, diabetes, eye diseases and other diseases, as well as in the selection and delivery of stereoisomeric drugs. Finally, we outline the existing challenges and future perspectives for MIPs-DDS, aiming to accelerate the development of MIT and facilitate the creation of innovative multifunctional DDS for diverse applications.

分子印迹技术（MIT）是一种创建分子锁以补充特定分子键的方法。该技术产生分子印迹聚合物（MIPs），其特征是特定的结合位点，模拟酶-底物或抗原-抗体结合中观察到的相互作用。MIPs独特的识别特异性、结构可预测性和高稳定性使其成为药物输送系统（DDS）中的关键研究领域。本文全面综述了近年来集成MIPs的DDS复合材料（MIPs-DDS）的研究进展。首先，我们根据模板和功能单体之间的作用力类型对MIPs进行了简要介绍，然后根据掺杂纳米材料的类型对MIPs- dds进行了分类和介绍，包括金属有机框架（MOFs）、量子点（QDs）、碳纳米管（CNTs）、硅氧烷、上转换纳米粒子（UCNPs）、金属纳米团簇和磁性纳米粒子（MNPs）。然后，我们深入研究了MIPs-DDS的递送模式和释放机制，包括pH、光响应、温度、磁响应、谷胱甘肽和多响应机制等因素。此外，我们还强调了MIPs-DDS在癌症、糖尿病、眼病等疾病中的应用，以及在立体异构体药物的选择和递送中的应用。最后，我们概述了MIPs-DDS存在的挑战和未来的展望，旨在加速MIT的发展，促进创新多功能DDS的创建。

{"title":"Recent advances in composite materials integrating molecularly imprinted polymers for targeted drug delivery systems","authors":"Wenjun Guo , Jinyu Ji , Yingying Shi , Na Li , Zechen Yan , Qiuzheng Du","doi":"10.1016/j.eurpolymj.2025.113825","DOIUrl":"10.1016/j.eurpolymj.2025.113825","url":null,"abstract":"<div><div>Molecular imprinting technology (MIT) is a method for creating molecular locks that complement specific molecular bonds. This technology yields molecularly imprinted polymers (MIPs), which feature specific binding sites that emulate interactions observed in enzyme-substrate or antigen–antibody binding. The distinctive recognition specificity, structural predictability, and high stability of MIPs have positioned them as key areas of interest within drug delivery systems (DDS). Here, we comprehensively review the recent advancements in composite materials integrating MIPs for DDS (MIPs-DDS). Firstly, we provide a brief introduction to MIPs based on the types of forces acting between templates and functional monomers, then classify and introduce MIPs-DDS based on the types of doped nanomaterials, including metal–organic frameworks (MOFs), quantum dots (QDs), carbon nanotubes (CNTs), siloxane, up-conversion nanoparticles (UCNPs), metallic nanoclusters and magnetic nanoparticles (MNPs). We then delve into the delivery modes and release mechanisms of MIPs-DDS, encompassing factors such as pH, light response, temperature, magnetic response, glutathione, and multi-responsive mechanisms. Additionally, we emphasized the application of MIPs-DDS in cancer, diabetes, eye diseases and other diseases, as well as in the selection and delivery of stereoisomeric drugs. Finally, we outline the existing challenges and future perspectives for MIPs-DDS, aiming to accelerate the development of MIT and facilitate the creation of innovative multifunctional DDS for diverse applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113825"},"PeriodicalIF":5.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444334","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

Oxidation-responsive phenylboronate-bridged block copolymer for targeted cancer drug delivery 氧化响应苯硼酸桥接嵌段共聚物用于靶向癌症药物递送

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-12 DOI: 10.1016/j.eurpolymj.2025.113784

Hanchen Ding , Shiqun Shao , Youqing Shen , Jiajia Xiang

Nanomedicine has revolutionized cancer therapy by improving targeted drug delivery while mitigating systemic side effects. An effective delivery system must maintain stability in physiological environments while enabling precise and rapid drug release in tumors. The primary challenge lies in designing nanocarriers that are responsive to tumor-specific stimuli. Here, we introduce a novel amphiphilic block copolymer, PEG-Blink-PCL, featuring a phenylboronic ester linker that selectively degrades, responding to reactive oxygen species (ROS), allowing for controlled, site-specific drug release. Our study demonstrates that DOX-loaded PEG-Blink-PCL micelles (B/DOX-M) exhibit excellent stability in the bloodstream yet quickly shed their PEG corona upon exposure to elevated ROS levels, leading to micelle disassembly and efficient DOX release in tumors. This ROS-triggered “shell-removal” strategy significantly augments tumor inhibition while minimizing systemic toxicity in the MDA-MB-231 tumor model. Overall, this study highlights the potential of ROS-responsive PEG-Blink-PCL as a promising platform for effective and precise cancer drug delivery.

纳米医学通过改善靶向药物输送，同时减轻全身副作用，彻底改变了癌症治疗。一个有效的给药系统必须在生理环境中保持稳定，同时能够在肿瘤中精确、快速地释放药物。主要的挑战在于设计对肿瘤特异性刺激有反应的纳米载体。在这里，我们介绍了一种新的两亲性嵌段共聚物PEG-Blink-PCL，其特点是苯硼酯连接物选择性降解，响应活性氧（ROS），允许控制，位点特异性药物释放。我们的研究表明，负载DOX的PEG- blink - pcl胶束（B/DOX- m）在血液中表现出优异的稳定性，但在暴露于ROS水平升高时迅速脱落其PEG冕，导致胶束分解和肿瘤中有效的DOX释放。在MDA-MB-231肿瘤模型中，这种ros触发的“去壳”策略显著增强了肿瘤抑制作用，同时最小化了全身毒性。总的来说，这项研究强调了ros反应性PEG-Blink-PCL作为有效和精确的癌症药物递送的有前途的平台的潜力。

{"title":"Oxidation-responsive phenylboronate-bridged block copolymer for targeted cancer drug delivery","authors":"Hanchen Ding , Shiqun Shao , Youqing Shen , Jiajia Xiang","doi":"10.1016/j.eurpolymj.2025.113784","DOIUrl":"10.1016/j.eurpolymj.2025.113784","url":null,"abstract":"<div><div>Nanomedicine has revolutionized cancer therapy by improving targeted drug delivery while mitigating systemic side effects. An effective delivery system must maintain stability in physiological environments while enabling precise and rapid drug release in tumors. The primary challenge lies in designing nanocarriers that are responsive to tumor-specific stimuli. Here, we introduce a novel amphiphilic block copolymer, PEG-Blink-PCL, featuring a phenylboronic ester linker that selectively degrades, responding to reactive oxygen species (ROS), allowing for controlled, site-specific drug release. Our study demonstrates that DOX-loaded PEG-Blink-PCL micelles (B/DOX-M) exhibit excellent stability in the bloodstream yet quickly shed their PEG corona upon exposure to elevated ROS levels, leading to micelle disassembly and efficient DOX release in tumors. This ROS-triggered “shell-removal” strategy significantly augments tumor inhibition while minimizing systemic toxicity in the MDA-MB-231 tumor model. Overall, this study highlights the potential of ROS-responsive PEG-Blink-PCL as a promising platform for effective and precise cancer drug delivery.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113784"},"PeriodicalIF":5.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429311","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

Ivy-like electrospun block copolymer fibers supported polymer solid electrolytes with wide electrochemical stability window for all-solid-state Li-metal battery 常青藤状电纺嵌段共聚物纤维支撑的聚合物固体电解质具有宽的电化学稳定窗口，用于全固态锂金属电池

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-12 DOI: 10.1016/j.eurpolymj.2025.113808

Shanshan Gao , Wenshuo Wang , Dayang Yu , Pengju Pan , Yongzhong Bao

All-solid-state lithium metal batteries (ASSLMBs) are considered as next-generation energy storage devices due to their high specific energy density and safety, and solid polymer electrolytes (SPEs) are an important component of ASSLMBs. Poly(ethylene oxide) (PEO) is the most prevalent matrix of SPE but is criticized for its poor mechanical properties and a narrow electrochemical stability window. To address this issue, poly(vinylidene fluoride)-b-poly(poly(ethylene glycol) methyl ether methacrylate (PVDF-b-PPEGMA) copolymer fibers with an ivy-like morphology were prepared by electrospinning and used to support PEO/lithium salt electrolytes. The electrospun PVDF-b-PPEGMA copolymer fiber membrane provides an uncial hierarchical structure with large pore size, good compatibility and adhesion with PEO due to side ethylene oxide units in the PPEGMA segment. The ivy-like fibers supported SPE exhibited good thermal stability and high mechanical strength. Furthermore, ASSLMBs assembled using the above SPE, LiFePO₄ cathode, and lithium metal anode possessed a wide electrochemical stable window (5.58 V vs. Li/Li⁺) and good initial discharge capabilities at 60 °C.

全固态锂金属电池（asslmb）因其高比能密度和安全性被认为是下一代储能器件，而固体聚合物电解质（spe）是其重要组成部分。聚环氧乙烷（PEO）是SPE最常用的基质，但其力学性能差，电化学稳定性窗口窄。为了解决这一问题，采用静电纺丝法制备了具有常春藤状形态的聚偏氟乙烯-聚乙二醇甲基丙烯酸甲酯（PVDF-b-PPEGMA）共聚物纤维，并将其用于支撑PEO/锂盐电解质。静电纺丝PVDF-b-PPEGMA共聚物纤维膜具有独特的层次结构，孔径大，与PEO具有良好的相容性和附着力，因为PPEGMA段中的侧环氧乙烷单元。藤状固相萃取纤维具有良好的热稳定性和较高的机械强度。此外，使用上述SPE、LiFePO4阴极和锂金属阳极组装的asslmb具有宽的电化学稳定窗口（5.58 V vs. Li/Li+）和良好的60°C初始放电能力。

{"title":"Ivy-like electrospun block copolymer fibers supported polymer solid electrolytes with wide electrochemical stability window for all-solid-state Li-metal battery","authors":"Shanshan Gao , Wenshuo Wang , Dayang Yu , Pengju Pan , Yongzhong Bao","doi":"10.1016/j.eurpolymj.2025.113808","DOIUrl":"10.1016/j.eurpolymj.2025.113808","url":null,"abstract":"<div><div>All-solid-state lithium metal batteries (ASSLMBs) are considered as next-generation energy storage devices due to their high specific energy density and safety, and solid polymer electrolytes (SPEs) are an important component of ASSLMBs. Poly(ethylene oxide) (PEO) is the most prevalent matrix of SPE but is criticized for its poor mechanical properties and a narrow electrochemical stability window. To address this issue, poly(vinylidene fluoride)-<em>b-</em>poly(poly(ethylene glycol) methyl ether methacrylate (PVDF-<em>b-</em>PPEGMA) copolymer fibers with an ivy-like morphology were prepared by electrospinning and used to support PEO/lithium salt electrolytes. The electrospun PVDF-<em>b-</em>PPEGMA copolymer fiber membrane provides an uncial hierarchical structure with large pore size, good compatibility and adhesion with PEO due to side ethylene oxide units in the PPEGMA segment. The ivy-like fibers supported SPE exhibited good thermal stability and high mechanical strength. Furthermore, ASSLMBs assembled using the above SPE, LiFePO<sub>4</sub> cathode, and lithium metal anode possessed a wide electrochemical stable window (5.58 V vs. Li/Li<sup>+</sup>) and good initial discharge capabilities at 60 °C.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113808"},"PeriodicalIF":5.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429440","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

Multi-functional bioactive hydrogel based on CCM-Co-ZIF-8 nanoparticles for chronic wound healing: Synergistic antibacterial, antioxidant, and anti-inflammatory therapy 基于CCM-Co-ZIF-8纳米颗粒的多功能生物活性水凝胶用于慢性伤口愈合：协同抗菌，抗氧化和抗炎治疗

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-11 DOI: 10.1016/j.eurpolymj.2025.113824

Qi Tao , Hang Yao , Zehao Gu , Xiaofei Yang , Junli Shi , Dong-An Wang , Hui Chong

The treatment of chronic wounds are characterized by a local tissue with issues such as the accumulation of free radicals and persistent inflammation, which contribute to delayed wound healing. Thus, it has emerged as a significant global challenge, profoundly impacting patients’ quality of life and even posing threats to their lives. In this study, we fabricted a CCM (Curcumin)–Co-ZIF-8 nanoparticle (CCZ)@oxidized ammonium alginate (OSA)/carboxymethyl chitosan (CMCS)/tannic acid (TA) composite multifunctional bioactive hydrogel. This nanocomposited double-crosslinked network hydrogel dressing exhibits excellent mechanical properties and self-healing abilities. Additionally, the hydrogel shows good biocompatibility. Due to the formation of dynamic Schiff base bonds between oxidized sodium alginate and CMCS, the hydrogel-TA spray system possesses injectability upon applied to a wound model in mice, allowing better adaptation to irregular wound shapes. Furthermore, it could promote synergistic antibacterial, antioxidant, and anti-inflammatory effects, thereby accelerating wound healing. Our findings highlight the potential of this multifunctional hydrogel system as an advanced therapeutic option for chronic wound management.

慢性伤口的治疗特点是局部组织的问题，如自由基的积累和持续的炎症，这有助于延迟伤口愈合。因此，它已成为一项重大的全球挑战，深刻影响患者的生活质量，甚至对他们的生命构成威胁。本研究制备了一种CCM (Curcumin) -Co-ZIF-8纳米颗粒（CCZ）@氧化海藻酸铵(OSA)/羧甲基壳聚糖(CMCS)/单宁酸（TA）复合多功能生物活性水凝胶。该纳米复合双交联网络水凝胶敷料具有优异的力学性能和自愈能力。此外，该水凝胶具有良好的生物相容性。由于氧化海藻酸钠与CMCS之间形成动态席夫碱键，水凝胶- ta喷雾系统应用于小鼠伤口模型后具有可注射性，可以更好地适应不规则伤口形状。此外，它还能促进协同抗菌、抗氧化和抗炎作用，从而加速伤口愈合。我们的研究结果强调了这种多功能水凝胶系统作为慢性伤口管理的先进治疗选择的潜力。

{"title":"Multi-functional bioactive hydrogel based on CCM-Co-ZIF-8 nanoparticles for chronic wound healing: Synergistic antibacterial, antioxidant, and anti-inflammatory therapy","authors":"Qi Tao , Hang Yao , Zehao Gu , Xiaofei Yang , Junli Shi , Dong-An Wang , Hui Chong","doi":"10.1016/j.eurpolymj.2025.113824","DOIUrl":"10.1016/j.eurpolymj.2025.113824","url":null,"abstract":"<div><div>The treatment of chronic wounds are characterized by a local tissue with issues such as the accumulation of free radicals and persistent inflammation, which contribute to delayed wound healing. Thus, it has emerged as a significant global challenge, profoundly impacting patients’ quality of life and even posing threats to their lives. In this study, we fabricted a CCM (Curcumin)–Co-ZIF-8 nanoparticle (CCZ)@oxidized ammonium alginate (OSA)/carboxymethyl chitosan (CMCS)/tannic acid (TA) composite multifunctional bioactive hydrogel. This nanocomposited double-crosslinked network hydrogel dressing exhibits excellent mechanical properties and self-healing abilities. Additionally, the hydrogel shows good biocompatibility. Due to the formation of dynamic Schiff base bonds between oxidized sodium alginate and CMCS, the hydrogel-TA spray system possesses injectability upon applied to a wound model in mice, allowing better adaptation to irregular wound shapes. Furthermore, it could promote synergistic antibacterial, antioxidant, and anti-inflammatory effects, thereby accelerating wound healing. Our findings highlight the potential of this multifunctional hydrogel system as an advanced therapeutic option for chronic wound management.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113824"},"PeriodicalIF":5.8,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478981","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

Polyurethane hot-melt adhesives for strong and tough adhesion 聚氨酯热熔胶，附着力强而坚韧

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-11 DOI: 10.1016/j.eurpolymj.2025.113814

Jinxing Shi , Xuewei Li , Axiang Li , Haixia Wei , Enyang Zhang , Wangqing Zhang

With the features of easy-operation, fast-bonding and convenient recycling, thermoplastic polyurethane hot-melt adhesives are widely used in daily life and industry. However, thermoplastic polyurethane hot-melt adhesives face the deficiency of poor adhesion strength. Herein, we demonstrate a thermoplastic polyurethane hot-melt adhesive with high adhesion strength on a variety of substrates including metals and plastics under moderate operation conditions. Ascribed to the synergistic effect of the furan moieties in the backbone and the 2-ureido-4-pyrimidinone moieties in the side-chains, the synthesized polyurethane hot-melt adhesive realizes a high adhesion strength of 12.63 MPa. Meanwhile, this adhesive can maintain about 89% original adhesion strength after five recycling use. Besides, such adhesive has favorable tolerance to harsh conditions such as diverse liquids at extremely low temperature of −196 °C. It is expected that this polyurethane hot-melt adhesive has promising application.

热塑性聚氨酯热熔胶具有操作简单、粘接快速、回收方便等特点，在日常生活和工业中得到了广泛的应用。然而，热塑性聚氨酯热熔胶面临着粘接强度差的不足。在此，我们展示了一种热塑性聚氨酯热熔胶，在中等操作条件下，在各种基材（包括金属和塑料）上具有高粘附强度。由于主链上的呋喃基团与侧链上的2-脲基-4-嘧啶酮基团的协同作用，合成的聚氨酯热熔胶的粘接强度达到12.63 MPa。同时，该胶经五次循环使用后，仍能保持89%左右的原有附着力。此外，该粘合剂在- 196°C的极低温度下对各种液体等恶劣条件具有良好的耐受性。预计该聚氨酯热熔胶具有广阔的应用前景。

引用次数: 0

Synthesis and characterization of aromatic polyketones and polyetherketones derived from divanillic acid via Friedel–Crafts acylation 由二苯甲酸经Friedel-Crafts酰化反应合成芳香族聚酮和聚醚酮及表征

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-10 DOI: 10.1016/j.eurpolymj.2025.113823

Takaaki Kamishima , Kouji Inagaki , Akira Nukazuka , Tadahisa Iwata , Yukiko Enomoto

The present paper describes the synthesis and characterization of aromatic polyketones (PKs) and polyetherketones (PEKs) derived from divanillic acid (DVA) via Friedel–Crafts acylation. Various alkyl side-chains with carbon numbers of 2–8 were introduced into the hydroxyl groups of DVA units. Polyketones (PKs) were synthesized from DVA monomers and 2,2′-dimethoxybiphenyl, and polyetherketones (PEKs and PEKOMes; PEKOMes = polyetherketones with methoxy groups) were synthesized from DVA monomers and diphenylether and 3,3′-oxybis(methoxybenzene), respectively. Unexpectedly, some alkyl side-chains were eliminated during polymerization under Friedel–Crafts conditions in a polar solvent, and elimination was suppressed in a non-polar solvent. Longer alkyl side-chains were eliminated more easily. The molecular weights of the PKs, PEKs, and PEKOMes were 12.5–32.7 × 10³, 4.1–6.3 × 10³, and 10.6–15.3 × 10³ g/mol, respectively. DVA-based PKs and PEKs with relatively high molecular weights compared with those obtained by the previously reported method were obtained via Friedel–Crafts acylation. The aryl comonomers with methoxy moieties produced polymers with higher molecular weights, likely owing to their electron-donating properties. These polymers were all amorphous; their glass transition temperatures were 181–252 °C (PKs), 105–152 °C (PEKs), and 149–218 °C (PEKOMes).

本文介绍了芳聚酮（PKs）和聚醚酮（PEKs）的合成和表征，它们是由双苯乙烯酸（DVA）经Friedel-Crafts酰化反应合成的。在DVA单元的羟基上引入了碳数为2-8的各种烷基侧链。以DVA单体和2,2′-二甲氧基联苯、聚醚酮（PEKs）和聚醚酮（PEKs）为原料合成聚酮（PKs）；以DVA单体、二苯醚和3,3′-氧双（甲氧基苯）分别合成了PEKOMes（含甲氧基的聚醚酮）。出乎意料的是，在极性溶剂中，一些烷基侧链在Friedel-Crafts条件下被消除，而在非极性溶剂中被抑制。较长的烷基侧链更容易被消除。PKs、PEKs和PEKOMes的分子量分别为12.5 ~ 32.7 × 103、4.1 ~ 6.3 × 103和10.6 ~ 15.3 × 103 g/mol。通过Friedel-Crafts酰化得到了分子量相对较高的基于dva的PKs和PEKs。具有甲氧基部分的芳基共聚物产生的聚合物具有较高的分子量，可能是由于它们的供电子特性。这些聚合物都是无定形的；它们的玻璃化转变温度分别为181 ~ 252°C （PKs）、105 ~ 152°C （PEKs）和149 ~ 218°C （PEKOMes）。

{"title":"Synthesis and characterization of aromatic polyketones and polyetherketones derived from divanillic acid via Friedel–Crafts acylation","authors":"Takaaki Kamishima , Kouji Inagaki , Akira Nukazuka , Tadahisa Iwata , Yukiko Enomoto","doi":"10.1016/j.eurpolymj.2025.113823","DOIUrl":"10.1016/j.eurpolymj.2025.113823","url":null,"abstract":"<div><div>The present paper describes the synthesis and characterization of aromatic polyketones (PKs) and polyetherketones (PEKs) derived from divanillic acid (DVA) <em>via</em> Friedel–Crafts acylation. Various alkyl side-chains with carbon numbers of 2–8 were introduced into the hydroxyl groups of DVA units. Polyketones (PKs) were synthesized from DVA monomers and 2,2′-dimethoxybiphenyl, and polyetherketones (PEKs and PEKOMes; PEKOMes = polyetherketones with methoxy groups) were synthesized from DVA monomers and diphenylether and 3,3′-oxybis(methoxybenzene), respectively. Unexpectedly, some alkyl side-chains were eliminated during polymerization under Friedel–Crafts conditions in a polar solvent, and elimination was suppressed in a non-polar solvent. Longer alkyl side-chains were eliminated more easily. The molecular weights of the PKs, PEKs, and PEKOMes were 12.5–32.7 × 10<sup>3</sup>, 4.1–6.3 × 10<sup>3</sup>, and 10.6–15.3 × 10<sup>3</sup> g/mol, respectively. DVA-based PKs and PEKs with relatively high molecular weights compared with those obtained by the previously reported method were obtained via Friedel–Crafts acylation. The aryl comonomers with methoxy moieties produced polymers with higher molecular weights, likely owing to their electron-donating properties. These polymers were all amorphous; their glass transition temperatures were 181–252 °C (PKs), 105–152 °C (PEKs), and 149–218 °C (PEKOMes).</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113823"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419122","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

Correlation of molecular weight diversity and colloidal disability performance of anionic lignin derived polymer 阴离子木质素衍生聚合物分子量多样性与胶体失能性能的相关性研究

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-10 DOI: 10.1016/j.eurpolymj.2025.113820

Farzad Gholami , Weijue Gao , Ehsan Behzadfar , Pedram Fatehi

Polymerization is considered one of the valorization techniques of lignin for various applications. Generally, polymerization techniques affect the molecular structure of polymers. In this work, we evaluated a hypothesis that the polymerization strategy and, thus, the molecular weight distribution of lignin-derived polymers would impact their effectiveness as a colloidal disability agent (i.e., flocculant) for a suspension system. To achieve our goal, different lignin-polymethacrylic acid (PMAA) polymers were synthesized via free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) techniques. The experiments were designed such that two sets of polymers with different molecular polydispersities but similar average molecular weights, charge densities, radii of gyration, and hydrodynamic diameters were obtained. Both systems developed colloidal destabilization mainly via bridging phenomenon. The flocculation performance of the ATRP-synthesized samples with narrower molecular weight distribution was notably better than that of FRP-induced samples. The rheological and flocculation analyses under different shear rates confirmed that the ATRP-induced sample promoted the entanglement of particles and had a higher flocculation efficiency. The flocculant prepared using the ATRP technique demonstrated a significantly lower optimal dosage, requiring only 0.4 mg per gram, compared to 25.6 mg per gram for the samples produced using the FRP method. Also, this sample produced stronger flocs with more re-flocculation tendency under different shear rates, while it generated larger flocs under stirring conditions. Such ATRP-derived flocs had an average chord length of approximately 60 μm, and those of FRP-based ones had a 30 μm chord length, while both FRP and ATRP polymers had 500 Da molecular weight. The results of this work confirmed that, while lignin-derived polymers can be an effective flocculant, strategies must be taken into account for generating lignin-derived polymers with a controlled and preferably narrow molecular weight distribution.

聚合被认为是木质素增值技术之一，具有广泛的应用前景。一般来说，聚合技术影响聚合物的分子结构。在这项工作中，我们评估了一个假设，即木质素衍生聚合物的聚合策略和分子量分布将影响它们作为悬浮系统的胶体失能剂（即絮凝剂）的有效性。为了实现这一目标，采用自由基聚合（FRP）和原子转移自由基聚合（ATRP）技术合成了不同的木质素-聚甲基丙烯酸（PMAA）聚合物。实验设计了两组分子多分散度不同但平均分子量、电荷密度、旋转半径和流体动力直径相似的聚合物。两种体系的胶体失稳主要是通过桥接现象发生的。分子量分布较窄的atrp合成样品的絮凝性能明显优于frp诱导样品。不同剪切速率下的流变学和絮凝分析证实，atrp诱导的样品促进了颗粒的缠结，具有较高的絮凝效率。使用ATRP技术制备的絮凝剂显示出明显较低的最佳用量，仅需要0.4 mg / g，而使用FRP方法生产的样品需要25.6 mg / g。在不同剪切速率下，该样品产生的絮凝体更强，重絮凝倾向更强，而在搅拌条件下，该样品产生的絮凝体较大。ATRP衍生絮凝体的平均弦长约为60 μm， FRP基絮凝体的平均弦长为30 μm，而FRP和ATRP聚合物的分子量均为500 Da。这项工作的结果证实，虽然木质素衍生聚合物可以是一种有效的絮凝剂，但必须考虑到生产木质素衍生聚合物的策略，使其具有可控的和优选的窄分子量分布。

{"title":"Correlation of molecular weight diversity and colloidal disability performance of anionic lignin derived polymer","authors":"Farzad Gholami , Weijue Gao , Ehsan Behzadfar , Pedram Fatehi","doi":"10.1016/j.eurpolymj.2025.113820","DOIUrl":"10.1016/j.eurpolymj.2025.113820","url":null,"abstract":"<div><div>Polymerization is considered one of the valorization techniques of lignin for various applications. Generally, polymerization techniques affect the molecular structure of polymers. In this work, we evaluated a hypothesis that the polymerization strategy and, thus, the molecular weight distribution of lignin-derived polymers would impact their effectiveness as a colloidal disability agent (i.e., flocculant) for a suspension system. To achieve our goal, different lignin-polymethacrylic acid (PMAA) polymers were synthesized via free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) techniques. The experiments were designed such that two sets of polymers with different molecular polydispersities but similar average molecular weights, charge densities, radii of gyration, and hydrodynamic diameters were obtained. Both systems developed colloidal destabilization mainly via bridging phenomenon. The flocculation performance of the ATRP-synthesized samples with narrower molecular weight distribution was notably better than that of FRP-induced samples. The rheological and flocculation analyses under different shear rates confirmed that the ATRP-induced sample promoted the entanglement of particles and had a higher flocculation efficiency. The flocculant prepared using the ATRP technique demonstrated a significantly lower optimal dosage, requiring only 0.4 mg per gram, compared to 25.6 mg per gram for the samples produced using the FRP method. Also, this sample produced stronger flocs with more re-flocculation tendency under different shear rates, while it generated larger flocs under stirring conditions. Such ATRP-derived flocs had an average chord length of approximately 60 μm, and those of FRP-based ones had a 30 μm chord length, while both FRP and ATRP polymers had 500 Da molecular weight. The results of this work confirmed that, while lignin-derived polymers can be an effective flocculant, strategies must be taken into account for generating lignin-derived polymers with a controlled and preferably narrow molecular weight distribution.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113820"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419048","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

Krossing’s acid as efficient catalyst for ε-caprolactone polymerization 克罗辛酸作为ε-己内酯聚合的高效催化剂

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-10 DOI: 10.1016/j.eurpolymj.2025.113817

Andrey S. Kozlov , Ping Song , Oleg I. Afanasyev , Klim O. Biriukov , Igor A. Nikovskii , Konstantin L. Boldyrev , Maria I. Godovikova , Saihu Liao , Denis Chusov

A superacid (H(OEt₂)₂)[Al(O^t_fBu)₄] has been demonstrated as a highly active catalyst for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL), which shows the highest catalytic activity among the known Brønsted acid catalysts in this process. With this superacid catalyst, the polymerization can be conducted in solvent and bulk conditions, either at elevated or at room temperature, and synthesis of high molecular weight polymers (> 100 kg/mol) is also successfully achieved.

超强酸（H(OEt2)2）[Al(OtfBu)4]是ε-己内酯（ε-CL）开环聚合（ROP）的高活性催化剂，在已知的Brønsted酸催化剂中具有最高的催化活性。使用这种超强酸催化剂，聚合可以在溶剂和散装条件下进行，无论是在高温还是在室温下，并合成高分子量聚合物(>；100 kg/mol)也成功实现。

引用次数: 0

Thermo- and pH responsive core–shell nanogels: Easy method of synthesis, properties and its use for the loading and releasing of organotin(IV) compounds 热和pH响应核壳纳米凝胶：简单的合成方法，性能及其在有机锡（IV）化合物的装载和释放中的应用

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-10 DOI: 10.1016/j.eurpolymj.2025.113822

Luis Alfonso Valdez-Olea , María Alejandra González-Urías , Angel Licea-Claveríe , Mirian A. González-Ayón , Alejandro Ramírez-Jiménez

In this work, multicomponent responsive core–shell nanogels, based on crosslinked 2-(N,N-diethylamino) ethyl methacrylate (DEAEMA), homo- or copolymerized with N-vinylcaprolactam (NVCL), as the core, and poly(ethylene glycol) methyl ether methacrylate (PEGMA, Mn=950 g mol^-1) as the shell, were synthesized by the Surfactant-Free Emulsion Polymerization (SFEP). Thermo- and pH responsive behavior was revealed by Dynamic Light Scattering (DLS) measurements showing nanogel expansion by decreasing pH and nanogel contraction by increasing temperature taking as reference normal physiological conditions. Nanogels composition was calculated by ¹H NMR, D_h was measured by DLS, thermal transitions were determined by Differential Scanning Calorimetry (DSC). The systems with the best properties were selected for the loading and releasing of diorganotin(IV) complexes which have demonstrated cytotoxic activity against different cancer cells lines. Results showed that the systems have the potential to be used as nanocarriers of metallodrugs towards cancer tissues.

本文采用无表面活性剂乳液聚合（SFEP）法制备了以交联的2-（N，N-二乙基氨基）甲基丙烯酸乙酯（DEAEMA）为核，以N-乙烯基己内酰胺（NVCL）为核，聚乙二醇甲基丙烯酸甲醚（PEGMA, Mn=950 g mol-1）为壳，共聚或共聚的多组分响应性核-壳纳米凝胶。动态光散射（Dynamic Light Scattering， DLS）测量结果显示，在正常生理条件下，纳米凝胶通过降低pH值而膨胀，通过升高温度而收缩。通过1H NMR计算纳米凝胶的组成，DLS测量Dh， DSC（差示扫描量热法）测定热转变。选择了性能最好的系统来装载和释放对不同癌细胞系具有细胞毒活性的重有机锡（IV）复合物。结果表明，该系统具有作为金属药物纳米载体向肿瘤组织转移的潜力。

{"title":"Thermo- and pH responsive core–shell nanogels: Easy method of synthesis, properties and its use for the loading and releasing of organotin(IV) compounds","authors":"Luis Alfonso Valdez-Olea , María Alejandra González-Urías , Angel Licea-Claveríe , Mirian A. González-Ayón , Alejandro Ramírez-Jiménez","doi":"10.1016/j.eurpolymj.2025.113822","DOIUrl":"10.1016/j.eurpolymj.2025.113822","url":null,"abstract":"<div><div>In this work, multicomponent responsive core–shell nanogels, based on crosslinked 2-(<em>N,N-</em>diethylamino) ethyl methacrylate (DEAEMA), homo- or copolymerized with <em>N</em>-vinylcaprolactam (NVCL), as the core, and poly(ethylene glycol) methyl ether methacrylate (PEGMA, <em>Mn</em>=950 g mol<sup>-1</sup>) as the shell, were synthesized by the Surfactant-Free Emulsion Polymerization (SFEP). Thermo- and pH responsive behavior was revealed by Dynamic Light Scattering (DLS) measurements showing nanogel expansion by decreasing pH and nanogel contraction by increasing temperature taking as reference normal physiological conditions. Nanogels composition was calculated by <sup>1</sup>H NMR, <em>D<sub>h</sub></em> was measured by DLS, thermal transitions were determined by Differential Scanning Calorimetry (DSC). The systems with the best properties were selected for the loading and releasing of diorganotin(IV) complexes which have demonstrated cytotoxic activity against different cancer cells lines. Results showed that the systems have the potential to be used as nanocarriers of metallodrugs towards cancer tissues.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113822"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395335","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

Blending strategies for green packaging: Enhancing polyhydroxybutyrate performance for sustainable solutions 绿色包装的混合策略：增强聚羟基丁酸盐性能的可持续解决方案

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-10 DOI: 10.1016/j.eurpolymj.2025.113821

Ramisa Yahyapour , Yusuf Ziya Menceloglu

The rising demand for sustainable alternatives to conventional plastics highlights polyhydroxyalkanoates (PHAs), particularly polyhydroxybutyrate (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), as promising biodegradable thermoplastics. While PHAs offer advantages like non-toxicity and a reduced carbon footprint, their brittleness, narrow processing window, and high production costs limit their broader use, particularly in packaging, the largest source of municipal solid waste. This review provides an overview of PHAs, emphasizing the properties that make them suitable for packaging and the key factors influencing their market longevity. Blending PHAs with natural polymers, such as polylactic acid, cellulose derivatives, and chitin/chitosan improves mechanical, thermal, and barrier properties while enhancing biodegradability by reducing crystallinity or increasing hydrophilicity, thereby facilitating microbial degradation. Additives such as plasticizers, nucleating agents, and compatibilizers, alongside optimized processing conditions and advanced techniques, like reactive blending and the use of block and graft copolymers, improve interfacial adhesion and blend homogeneity, mitigating brittleness and enhancing flexibility and strength. The thermal instability of PHB, which poses challenges during melt processing, can be addressed by incorporating bioplasticizers to lower its glass transition temperature and melt viscosity, allowing processing at lower temperatures and minimizing thermal degradation. Furthermore, in-situ polymerization and bio-based coupling agents further enhance blend uniformity and overall performance. Special attention is given to the potential of PHB/chitosan blends for developing antibacterial, eco-friendly packaging solutions. By reviewing market trends and advances in PHA processing, this review underscores the potential of PHA-based blends to reduce plastic waste and facilitate their commercialization as sustainable, green packaging materials.

对传统塑料可持续替代品的需求日益增长，聚羟基烷酸酯（pha），特别是聚羟基丁酸酯（PHB）和聚（3-羟基丁酸酯-co-3-羟基戊酸酯）（PHBV）作为有前途的可生物降解热塑性塑料。虽然pha具有无毒和减少碳足迹等优点，但它们的脆性、狭窄的加工窗口和高生产成本限制了它们的广泛应用，特别是在包装方面，这是城市固体废物的最大来源。本文综述了pha的概况，强调了使其适合包装的特性以及影响其市场寿命的关键因素。将pha与天然聚合物（如聚乳酸、纤维素衍生物和几丁质/壳聚糖）共混，可以改善机械、热学和屏障性能，同时通过降低结晶度或增加亲水性来提高生物降解性，从而促进微生物降解。增塑剂、成核剂和增容剂等添加剂，以及优化的加工条件和先进的技术，如反应共混、嵌段共聚物和接枝共聚物的使用，改善了界面附着力和共混均匀性，减轻了脆性，提高了柔韧性和强度。PHB的热不稳定性给熔体加工带来了挑战，可以通过加入生物增塑剂来降低其玻璃化转变温度和熔体粘度，从而在更低的温度下进行加工，并最大限度地减少热降解。此外，原位聚合和生物基偶联剂进一步提高了共混物的均匀性和整体性能。特别关注PHB/壳聚糖共混物在开发抗菌、环保包装解决方案方面的潜力。通过回顾PHA加工的市场趋势和进展，本综述强调了PHA基混合物在减少塑料废物和促进其作为可持续绿色包装材料商业化方面的潜力。

{"title":"Blending strategies for green packaging: Enhancing polyhydroxybutyrate performance for sustainable solutions","authors":"Ramisa Yahyapour , Yusuf Ziya Menceloglu","doi":"10.1016/j.eurpolymj.2025.113821","DOIUrl":"10.1016/j.eurpolymj.2025.113821","url":null,"abstract":"<div><div>The rising demand for sustainable alternatives to conventional plastics highlights polyhydroxyalkanoates (PHAs), particularly polyhydroxybutyrate (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), as promising biodegradable thermoplastics. While PHAs offer advantages like non-toxicity and a reduced carbon footprint, their brittleness, narrow processing window, and high production costs limit their broader use, particularly in packaging, the largest source of municipal solid waste. This review provides an overview of PHAs, emphasizing the properties that make them suitable for packaging and the key factors influencing their market longevity. Blending PHAs with natural polymers, such as polylactic acid, cellulose derivatives, and chitin/chitosan improves mechanical, thermal, and barrier properties while enhancing biodegradability by reducing crystallinity or increasing hydrophilicity, thereby facilitating microbial degradation. Additives such as plasticizers, nucleating agents, and compatibilizers, alongside optimized processing conditions and advanced techniques, like reactive blending and the use of block and graft copolymers, improve interfacial adhesion and blend homogeneity, mitigating brittleness and enhancing flexibility and strength. The thermal instability of PHB, which poses challenges during melt processing, can be addressed by incorporating bioplasticizers to lower its glass transition temperature and melt viscosity, allowing processing at lower temperatures and minimizing thermal degradation. Furthermore, in-situ polymerization and bio-based coupling agents further enhance blend uniformity and overall performance. Special attention is given to the potential of PHB/chitosan blends for developing antibacterial, eco-friendly packaging solutions. By reviewing market trends and advances in PHA processing, this review underscores the potential of PHA-based blends to reduce plastic waste and facilitate their commercialization as sustainable, green packaging materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113821"},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395898","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