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Probing the inner structure and dynamics of pH-sensitive block copolymer nanoparticles with nitroxide radicals using scattering and EPR techniques 利用散射和 EPR 技术探测 pH 值敏感嵌段共聚物纳米粒子的内部结构和动力学特性
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-23 DOI: 10.1016/j.eurpolymj.2024.113473
Svetlana Lukáš Petrova , Alessandro Jäger , Ewa Pavlova , Martina Vragović , Eliézer Jäger , Miloš Steinhart , Damir Klepac
This research emphasizes the crucial role of electron paramagnetic resonance (EPR) spectroscopy in nanoparticle analysis, showcasing its distinctive ability to probe molecular-level details. We demonstrate the synthesis and self-assembly of a new class of pH-responsive amphiphilic diblock copolymers, specifically poly[N-(2-hydroxypropyl)-methacrylamide]-block-poly[2-(diisopropylamino)ethyl methacrylate] (PHPMA-b-PDPA), incorporating 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals covalently bound to the hydrophilic PHPMA segment. The copolymer synthesis involved a three-step process, combining reversible addition − fragmentation chain transfer (RAFT) polymerization with carbodiimide (DCC) chemistry. TEMPO radical-containing nanoparticles (RNPs) were created using microfluidic (MF) nanoprecipitation, a technique essential for generating uniform nanoparticles with predictable biodistribution and cellular uptake. Adjusting MF protocol parameters allowed fine-tuning of RNP sizes. EPR spectroscopy confirmed the formation of core–shell RNPs, with features aligning closely with those obtained from scattering techniques like dynamic light scattering (DLS), static light scattering (SLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (cryo-TEM). EPR spectroscopy emerges as a potent tool for molecular-level analysis of colloidal polymer systems. This study highlights the EPR-spin label method’s efficacy in probing the internal structural features and dynamics of core–shell nanoparticles, especially their response to pH-triggered disassembly. The findings open new avenues for the use of pH-responsive TEMPO-labeled diblock copolymers in controlled drug delivery applications.
这项研究强调了电子顺磁共振 (EPR) 光谱在纳米粒子分析中的关键作用,展示了其探测分子级细节的独特能力。我们展示了一类新型 pH 响应型两亲性二嵌段共聚物的合成和自组装,特别是聚[N-(2-羟基丙基)-甲基丙烯酰胺]-嵌段-聚[2-(二异丙基氨基)乙基甲基丙烯酸酯](PHPMA-b-PDPA),其中包含与亲水性 PHPMA 段共价结合的 2,2,6,6-四甲基哌啶-1-氧(TEMPO)自由基。共聚物的合成过程分为三个步骤,将可逆加成-断裂链转移(RAFT)聚合与碳化二亚胺(DCC)化学结合在一起。含 TEMPO 自由基的纳米颗粒(RNPs)是利用微流体(MF)纳米沉淀法制成的,这种技术对于生成具有可预测的生物分布和细胞吸收的均匀纳米颗粒至关重要。调整 MF 方案参数可对 RNP 大小进行微调。EPR 光谱证实了核壳 RNP 的形成,其特征与动态光散射 (DLS)、静态光散射 (SLS)、小角 X 射线散射 (SAXS) 和冷冻透射电子显微镜 (cryo-TEM) 等散射技术所获得的特征非常吻合。EPR 光谱是对胶体聚合物系统进行分子级分析的有效工具。本研究强调了 EPR 自旋标签法在探测核壳纳米粒子内部结构特征和动态方面的功效,尤其是它们对 pH 触发的解体的反应。这些发现为将 pH 响应型 TEMPO 标记的二嵌段共聚物用于可控药物递送应用开辟了新的途径。
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引用次数: 0
Rapid synthesis of solid polycarboxylate superplasticizers via photoinitiated radical polymerization 通过光引发自由基聚合快速合成固体聚羧酸盐超塑化剂
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-23 DOI: 10.1016/j.eurpolymj.2024.113474
Tianfeng Zhou , Haotian Duan , Beibei Li , Yuxia Pang , Hongming Lou , Dongjie Yang , Xueqing Qiu
The synthesis and performance optimization of solid polycarboxylate superplasticizers (PCEs) present significant challenges. In our study, a rapid synthesis of a solid polycarboxylate superplasticizer (IPCE10) was achieved using photoinitiated free radical polymerization. IPCE10 exhibited good dispersibility and improved compressive strength in concrete. Dynamic light scattering tests and molecular dynamics simulations demonstrated that the adsorption conformation of IPCE10 on the calcium silicate hydrate surface was relatively dispersed, with a thicker adsorption layer. This indicates that IPCE10 has stronger steric hindrance, resulting in superior dispersibility. Additionally, density functional theory calculations of the reaction energy barriers for radical generation by photoinitiated and azo-initiated monomers revealed that the energy barrier in the photoinitiated system was significantly lower than that in the azo-initiated system, indicating that photoinitiated polymerization is more feasible. This study proposes a simple and rapid method for the preparation of solid polycarboxylate superplasticizers, providing valuable insights for the development of high-value-added construction materials.
固体聚羧酸盐超塑化剂(PCE)的合成和性能优化是一项重大挑战。在我们的研究中,采用光引发自由基聚合法快速合成了固体聚羧酸盐超塑化剂(IPCE10)。IPCE10 在混凝土中表现出良好的分散性和抗压强度。动态光散射测试和分子动力学模拟表明,IPCE10 在硅酸钙水合物表面的吸附构象相对分散,吸附层较厚。这表明 IPCE10 具有更强的立体阻碍,因而分散性更好。此外,密度泛函理论计算了光引发单体和偶氮引发单体生成自由基的反应能垒,发现光引发体系的能垒明显低于偶氮引发体系,表明光引发聚合更可行。本研究提出了一种简单、快速制备固体聚羧酸盐超塑化剂的方法,为开发高附加值建筑材料提供了宝贵的启示。
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引用次数: 0
Preparation and biological evaluation of a glucose-responsive block copolymer nanoparticle with the ability to ameliorate diabetic kidney damage 具有改善糖尿病肾损伤能力的葡萄糖响应嵌段共聚物纳米粒子的制备与生物学评价
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-21 DOI: 10.1016/j.eurpolymj.2024.113472
Sen Tong , Shicui Luo , Qiuqiong Yang , Bo Song , Renjie Chang , Junzi Wu
In this study, a p(AAPBA-b-Daidzein) block copolymer was designed and synthesised using glucose-responsive 3-acrylamidophenylboronic acid (AAPBA) and esterified daidzein as structural units; this copolymer possessed anti-diabetic pharmacological activity. After confirming the chemical structure of the copolymer, nanoparticles of the copolymer were prepared using the water-in-oil method. The results of the in vitro experiments showed that nanoparticles swelled when the pH was >7 or when the glucose concentration exceeded 1.0 mg/mL. Particle size measurements showed that the size of the nanoparticles was kept in the range of 100–300 nm before and after the glucose response, which helped avoid their clearance by the liver and kidneys. As the nanoparticles swelled, insulin and esterified daidzein were continuously released. The nanoparticles subcutaneously injected into mice with streptozotocin-induced diabetes were able to quickly and continuously reduce the blood sugar levels; significantly improve renal pathological damage and reduce renal function damage, inflammatory factors and oxidative stress indicators. In summary, the p(AAPBA-b-Daidzein) glucose-responsive nanoparticles prepared in the current study possess good pH value and glucose sensitivity, can achieve a precise and controlled release of insulin and exert the pharmacological activity of esterified daidzein. Therefore, it shows potential clinical application value in the treatment of diabetes and its complications.
本研究以葡萄糖反应性 3-丙烯酰胺基苯硼酸(AAPBA)和酯化麦冬苷为结构单元,设计并合成了一种对(AAPBA-b-麦冬苷)嵌段共聚物;该共聚物具有抗糖尿病药理活性。在确认了共聚物的化学结构后,采用油包水法制备了共聚物纳米颗粒。体外实验结果表明,当pH值为7或葡萄糖浓度超过1.0毫克/毫升时,纳米颗粒会膨胀。粒度测量结果表明,在葡萄糖反应前后,纳米颗粒的粒度保持在 100-300 纳米的范围内,这有助于避免它们被肝脏和肾脏清除。随着纳米颗粒的膨胀,胰岛素和酯化地屈孕酮不断释放出来。将纳米颗粒皮下注射到链脲佐菌素诱导的糖尿病小鼠体内,能够快速、持续地降低血糖水平,显著改善肾脏病理损伤,减少肾功能损伤、炎症因子和氧化应激指标。综上所述,本研究制备的p(AAPBA-b-麦冬苷)葡萄糖响应纳米颗粒具有良好的pH值和葡萄糖敏感性,可实现胰岛素的精确控释,并发挥酯化麦冬苷的药理活性。因此,它在治疗糖尿病及其并发症方面具有潜在的临床应用价值。
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引用次数: 0
Efficient and facile dual post-polymerization modification using acetoacetate-acrylate Michael addition 利用乙酰乙酸酯-丙烯酸酯迈克尔加成法进行高效、简便的双重聚合后改性
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-21 DOI: 10.1016/j.eurpolymj.2024.113463
Hongjie Chen, Linlin Wang, Shengyu Feng, Lei Li
Post-polymerization modification (PPM) is a valuable strategy for achieving diversified functional polymers; nonetheless, the pursuit of achieving mild and efficient dual modification along the polymeric backbone remains as a challenge. In this work, the Michael addition reaction of acetoacetates and acrylates have been demonstrated as a robust PPM technique. The reversible addition-fragmentation chain transfer polymerization of commercially available 2-(acetoacetoxy)ethyl methacrylate provides a polymer scaffold with controlled molecular weight and acetoacetate groups. These pendant groups are capable of undergoing efficient double addition reactions with acrylates, leading to an increased density of functional moieties within the polymeric backbone. This PPM reaction exhibits unique advantages such as mild reaction conditions (at 40 °C), rapid kinetics (completion within 1 h), and high atom economy. Consequently, a series of polymers with tunable thermal stability, glass transition temperature, and hydrophilicity have been successfully synthesized. Applications have been demonstrated for both the synthesis of polymers exhibiting aggregation-induced luminescence and the preparation of luminescent materials with adjustable mechanical properties. This pioneering work unveils a robust post-polymerization modification technique, significantly advancing the synthesis of innovative functional polymers.
聚合后改性(PPM)是实现功能聚合物多样化的重要策略;然而,如何在聚合物骨架上实现温和、高效的双重改性仍然是一项挑战。在这项研究中,乙酰乙酸酯和丙烯酸酯的迈克尔加成反应被证明是一种可靠的 PPM 技术。通过对市售 2-(乙酰乙酰氧基)甲基丙烯酸乙酯进行可逆加成-碎片链转移聚合反应,可获得具有可控分子量和乙酰乙酸酯基团的聚合物支架。这些悬垂基团能够与丙烯酸酯发生高效的双加成反应,从而增加聚合物骨架中功能分子的密度。这种 PPM 反应具有独特的优势,如反应条件温和(40 °C)、动力学反应迅速(1 小时内完成)和原子经济性高。因此,我们成功合成了一系列具有可调热稳定性、玻璃化温度和亲水性的聚合物。在合成具有聚合诱导发光特性的聚合物和制备具有可调机械特性的发光材料方面的应用已得到证实。这项开创性工作揭示了一种强大的聚合后改性技术,极大地推动了创新功能聚合物的合成。
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引用次数: 0
Fabrication of multi-responsive dynamic poly(ethylene glycol)-iron oxide nanoparticle nanocomposite hydrogels through interfacial boronate-catechol crosslinking 通过硼酸盐-儿茶酚界面交联制备多响应动态聚乙二醇-氧化铁纳米颗粒纳米复合水凝胶
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-21 DOI: 10.1016/j.eurpolymj.2024.113469
Chen-Cheng Yu , Yu-Chia Su , Yi-Cheun Yeh
Poly(ethylene glycol) (PEG)-based nanocomposite (NC) hydrogel with multiple advantageous properties such as high mechanical strength and stimuli-responsiveness have been demonstrated as promising materials across various fields. Here, an innovative type of PEG-based NC hydrogels is fabricated using phenylboronic acid-polyethyleneimine (PBA-PEI)-functionalized iron oxide nanoparticles (PP-IOPs) to crosslink the dopamine-modified 4arm-PEG (DA-4APEG) through boronate-catechol crosslinking. DA-4APEG/PP-IOP NC hydrogels exhibit tunable microstructures (i.e., pore size) and properties (i.e., rheological, mechanical, and swelling behaviors) by changing the number of PP-IOPs in the hydrogel network. With the dynamic crosslinks and magnetic nanoparticles in the network, DA-4APEG/PP-IOP NC hydrogels are self-healable and also responsive to various stimuli, including temperature, pH, glucose, dopamine, hydrogen peroxide, magnetic field, and near-infrared light. Therefore, a versatile PEG-based hydrogel platform has been developed, featuring customizable properties, multiple stimuli-responsiveness, and dynamic characteristics, making it suitable for advanced applications.
聚乙二醇(PEG)基纳米复合材料(NC)水凝胶具有多种优势特性,如机械强度高、刺激响应性强等,已被证明是各领域具有发展前景的材料。本文利用苯硼酸-聚乙烯亚胺(PBA-PEI)-功能化氧化铁纳米粒子(PP-IOPs),通过硼酸盐-儿茶酚交联多巴胺改性4arm-PEG(DA-4APEG),制备了一种创新型PEG基NC水凝胶。通过改变水凝胶网络中 PP-IOPs 的数量,DA-4APEG/PP-IOP NC 水凝胶显示出可调的微结构(即孔径)和性能(即流变、机械和膨胀行为)。由于网络中存在动态交联和磁性纳米粒子,DA-4APEG/PP-IOP NC 水凝胶具有自愈性,并能对温度、pH 值、葡萄糖、多巴胺、过氧化氢、磁场和近红外线等各种刺激做出反应。因此,我们开发出了一种多功能 PEG 基水凝胶平台,它具有可定制的特性、多种刺激响应性和动态特性,使其适用于高级应用。
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引用次数: 0
Cyclodextrin-activated porphyrin-DNA nanofibers with AS1411/Hemin toehold for enhanced and targeted photodynamic therapy 环糊精激活的卟啉-DNA 纳米纤维,具有 AS1411/Hemin 趾持,可用于增强和靶向光动力疗法
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-20 DOI: 10.1016/j.eurpolymj.2024.113466
Jinyu Gao, Hai Yang, Cheng Deng, Yuting Lv, Simin Liu, Zhiyong Zhao
Targeted photodynamic therapy is considered superior to conventional photodynamic therapy due to the enhanced uptake of photosensitizers by tumor cells. However, porphyrin-based photodynamic therapy is still limited due to the low hydrophilicity, poor biocompatibility and susceptibility to quenching of photosensitizers. Herein, we report cyclodextrin-activated porphyrin-DNA nanofibers with AS1411/Hemin toeholds, which enable targeted cancer cells recognition and catalytic oxygenation for enhanced photodynamic therapy. The nanofibers are formed through the self-assembly of the host–guest complex of cyclodextrin and porphyrin-DNA amphiphiles, and can be further functionalized on the surface with AS1411/Hemin. AS1411/Hemin can specifically target nucleolin-overexpressing cancer cells and catalyze conversion of excessive H2O2 into O2 within tumor cells, thereby alleviating tumor hypoxia and further cascaded enhancing PDT efficacy. These results suggest that the programmable and multifunctional nanofiber provided an effective nanoplatform for enhanced and targeted photodynamic therapy.
由于肿瘤细胞对光敏剂的吸收能力增强,靶向光动力疗法被认为优于传统光动力疗法。然而,由于光敏剂亲水性低、生物相容性差且易淬灭,基于卟啉的光动力疗法仍然受到限制。在此,我们报告了具有 AS1411/Hemin 趾持的环糊精活化卟啉-DNA 纳米纤维,它能识别靶向癌细胞并催化氧合,从而增强光动力疗法。这种纳米纤维是通过环糊精和卟啉-DNA 两性化合物的主客复合物的自组装形成的,并可通过 AS1411/Hemin 在其表面进一步功能化。AS1411/Hemin 可特异性靶向核素表达过高的癌细胞,催化肿瘤细胞内过多的 H2O2 转化为 O2,从而缓解肿瘤缺氧,并进一步级联提高光动力疗法的疗效。这些结果表明,可编程多功能纳米纤维为增强和靶向光动力疗法提供了一个有效的纳米平台。
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引用次数: 0
Metal-free ring-opening polymerization for the synthesis of biocompatible star-shaped block copolymers with controllable architecture 无金属开环聚合法合成结构可控的生物相容性星形嵌段共聚物
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-20 DOI: 10.1016/j.eurpolymj.2024.113471
Wanwanut Chueasupcharoen , Puttinan Meepowpan , Kiattikhun Manokruang , Montira Sriyai , Chawan Manaspon , Brian J. Tighe , Matthew J. Derry , Paul D. Topham , Winita Punyodom
Star-shaped block copolymers (SBCs) have sparked interest as efficient cargo carriers due to their high loading capacity, decreased burst effects through sustained release, and maintained stability in dilute aqueous solution. Despite these advantages, the practical usage of SBCs is hindered by their challenging synthesis processes that often utilize metal-based catalysts at high temperatures. Herein we report the tailored synthesis of 3-, 4-, and 6-arm polycaprolactone-b-poly(ethylene glycol), PCL-b-PEG, SBCs using diphenyl phosphate as a friendlier, more sustainable non-metallic catalyst. Nuclear magnetic resonance (NMR) analysis confirms the molecular architecture of SBCs and gel permeation chromatography (GPC) is used to elucidate trends in molar mass when the number of arms within the SBCs is tuned, while dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) studies provide insights into aggregation behavior. Critical aggregation concentration (CAC) values, as measured by fluorescence spectroscopy, demonstrated that the 4-arm and 6-arm SBCs have greater stability than the 3-arm SBC. Biocompatibility assessment indicated minimal cytotoxicity of the nanoaggregates, even at high concentration, making these PCL-b-PEG SBCs potentially safe and sustainable vehicles for biomedical release applications.
星形嵌段共聚物(SBC)具有装载量高、通过持续释放减少爆裂效应以及在稀释水溶液中保持稳定等优点,因此作为高效货物载体引发了人们的兴趣。尽管具有这些优点,但 SBC 的实际应用却受到其具有挑战性的合成工艺的阻碍,这些工艺通常需要在高温下使用金属催化剂。在此,我们报告了使用磷酸二苯酯作为更友好、更可持续的非金属催化剂,定制合成 3、4 和 6 臂聚己内酯-b-聚乙二醇(PCL-b-PEG)SBC 的情况。核磁共振(NMR)分析证实了 SBC 的分子结构,凝胶渗透色谱法(GPC)用于阐明调整 SBC 中臂的数量时摩尔质量的变化趋势,而动态光散射(DLS)和小角 X 射线散射(SAXS)研究则为聚合行为提供了见解。通过荧光光谱测定的临界聚集浓度(CAC)值表明,4 臂和 6 臂 SBC 比 3 臂 SBC 具有更高的稳定性。生物相容性评估表明,即使在高浓度下,纳米聚集体的细胞毒性也很小,因此这些 PCL-b-PEG SBC 有可能成为生物医学释放应用中安全、可持续的载体。
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引用次数: 0
Recent trends and applications of nanostructure-based drug delivery in alleviating pulmonary fibrosis 基于纳米结构的药物输送在缓解肺纤维化方面的最新趋势和应用
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-19 DOI: 10.1016/j.eurpolymj.2024.113467
Lokesh Nagar , Annu Saini , Sachin Kumar Singh , Gaurav Gupta , Ronan MacLoughlin , Dinesh Kumar Chellappan , Parteek Prasher , Amlan Chakraborty , Kamal Dua , Harish Dureja

Pulmonary fibrosis is an irreversible fatal chronic disease of lungs, characterized by excessive extracellular matrix deposition, epithelial-mesenchymal transition (EMT) imbalance, and scar formation in the lungs, resulting in severe breathing problems, cough, dyspnea, functional failure of the lungs, impaired quality of life and even death. A recent data on pulmonary fibrosis from various countries shows high mortality rates. As of date, there is no effective clinical treatment to completely cure pulmonary fibrosis. However, conventional symptomatic treatment is available. Anti-fibrotic drugs like pirfenidone and nintedanib are available currently as part of the conventional treatment. Novel therapeutic strategies involving targeted drug delivery via nanostructures has been shown to have enormous potential. Based on their unique physical properties, nanostructures have demonstrated the potential to improve the pharmacokinetics of loaded medications. The main goal of this review is to present a complete spectrum of therapeutics based on nanostructures for the treatment and management of pulmonary fibrosis. These include nanoparticles, polymeric nanoparticles, solid-lipid nanoparticles, liposomes, exosomes, and nanoemulsions. This advanced platform may pave a new path to pulmonary fibrosis clinics.

肺纤维化是一种不可逆的致命性慢性肺部疾病,其特点是细胞外基质过度沉积、上皮-间质转化(EMT)失衡和肺部瘢痕形成,导致严重的呼吸困难、咳嗽、呼吸困难、肺部功能衰竭、生活质量下降甚至死亡。最近各国关于肺纤维化的数据显示,肺纤维化的死亡率很高。迄今为止,还没有有效的临床治疗方法可以完全治愈肺纤维化。不过,传统的对症治疗是可行的。目前,吡非尼酮和宁替达尼等抗纤维化药物可作为常规治疗的一部分。通过纳米结构靶向给药的新型治疗策略已被证明具有巨大的潜力。基于其独特的物理特性,纳米结构已显示出改善负载药物的药代动力学的潜力。本综述的主要目的是介绍基于纳米结构的用于治疗和控制肺纤维化的各种疗法。这些药物包括纳米颗粒、聚合物纳米颗粒、固脂纳米颗粒、脂质体、外泌体和纳米乳剂。这一先进的平台可能会为肺纤维化的临床治疗铺平一条新的道路。
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引用次数: 0
Harnessing potential of microwave-assisted ultrafast synthesis of reduced graphene oxide/Mn3O4 bioactive nanocomposite hydrogel for bone tissue engineering 发挥微波辅助超快合成还原氧化石墨烯/Mn3O4 生物活性纳米复合水凝胶在骨组织工程中的潜力
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-18 DOI: 10.1016/j.eurpolymj.2024.113462
Ritu Singhmar , Sumanta Sahoo , Soonmo Choi , Jin Hyeok Choi , Ankur Sood , Sung Soo Han
The development of functional materials with the potential for bone tissue regeneration along with rapid synthesis and cost-effective approach has been challenging. In this regard, hydrogels have been explored as a potent candidate to behave as a 3D scaffold for bone repair. However, poor mechanical attributes impeded their clinical translation. Enthralling demonstration of the potential of carbon-based nanocomposites in bone tissue engineering has been constantly encouraging the fabrication of advanced nanocomposites. Here, we investigated the fabrication of reduced graphene/manganese (II, III) oxide (RGO/Mn3O4) nanocomposites by taking advantage of the microwave-assisted synthesis approach for cost effective, and ultrafast synthesis. Mn3O4 nanoparticles with uniform distribution in RGO sheets and ∼ 1.7 nm size was fabricated using the approach. Further, fine-tuning of the structural interaction and mechanical behavior of the GelMA-based hydrogels upon reinforcement with RGO/Mn3O4 nanocomposites was investigated as a function of different concentrations of the nanocomposites where upto 50 % increment in the compressive stress was observed compared to native GelMA hydrogel. The ability of these hydrogels was further investigated for their osteogenic behaviour on MC3T3-E1 preosteoblast cells where constant cell proliferation for up to 10 days was witnessed for the hybrid hydrogel with the highest concentration of the nanofillers.
开发具有骨组织再生潜力的功能性材料,并采用快速合成和具有成本效益的方法,一直是一项挑战。在这方面,水凝胶作为一种有效的候选材料,已被探索用作骨修复的三维支架。然而,较差的机械属性阻碍了它们的临床应用。碳基纳米复合材料在骨组织工程中的潜力得到了令人振奋的证明,这不断激励着人们制造先进的纳米复合材料。在此,我们研究了还原石墨烯/锰(II、III)氧化物(RGO/Mn3O4)纳米复合材料的制备方法,该方法利用微波辅助合成,成本低、合成速度快。利用这种方法制备出了在 RGO 片材中均匀分布的 Mn3O4 纳米粒子,其尺寸为 1.7 纳米。此外,还研究了用 RGO/Mn3O4 纳米复合材料增强 GelMA 基水凝胶后,其结构相互作用和机械行为的微调,并将其作为不同浓度纳米复合材料的函数,观察到与原生 GelMA 水凝胶相比,压缩应力增加了 50%。进一步研究了这些水凝胶对 MC3T3-E1 前成骨细胞的成骨能力,结果表明,纳米填料浓度最高的混合水凝胶的细胞增殖持续时间长达 10 天。
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引用次数: 0
Largely enhanced damping performance of nitrile rubber/ethylene–vinyl acetate blends via phenolic resin-induced phase separation 通过酚醛树脂诱导相分离大幅提高丁腈橡胶/乙烯-醋酸乙烯共混物的阻尼性能
IF 5.8 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-09-17 DOI: 10.1016/j.eurpolymj.2024.113446
Mai Feng , Chao-qun Wu , Zhu Zeng , Lin Wang , Meng-jie Xiao , De-xiang Sun , Yong Wang
The low glass transition temperature (Tg) and narrow effective damping temperature range (EDTR) greatly restrict the application of common vulcanized rubbers in fields relating to high temperature environmental condition due to the greatly reduced damping performances. In this work, phenolic resin (PR) was incorporated into nitrile rubber/ethylene–vinyl acetate (NBR/EVM) blends through melt-compounding processing, and the microstructure and damping performance changes induced by PR were comparatively investigated. The results show that PR induces the phase separation of the blends and most of PR particles selectively locate in the NBR component. Molecular dynamics simulation confirms that more hydrogen bonds form in the ternary blends, and reduced free volume fraction is also achieved. The ternary blends show good high-temperature damping performances, and apparently enhanced Tg (up to 17.7 °C) and EDTR (82.6 °C, from −2.6 to 80 °C) are also achieved. Additionally, the ternary blends exhibit good mechanical properties, including higher ductility and larger fracture energy, and better energy dissipation ability. This work provides an alternative resolution way to enhance the damping performances of the common vulcanized rubbers at high temperatures.
普通硫化橡胶的玻璃化转变温度(Tg)较低,有效阻尼温度范围(EDTR)较窄,阻尼性能大打折扣,极大地限制了其在高温环境条件下的应用。本研究通过熔融共混工艺将酚醛树脂(PR)加入丁腈橡胶/乙烯-醋酸乙烯(NBR/EVM)共混物中,比较研究了 PR 诱导的微观结构和阻尼性能变化。结果表明,PR 诱导了共混物的相分离,大部分 PR 颗粒选择性地位于丁腈橡胶组分中。分子动力学模拟证实,三元共混物中形成的氢键更多,自由体积分数也有所降低。三元共混物显示出良好的高温阻尼性能,并明显提高了 Tg(高达 17.7 °C)和 EDTR(82.6 °C,从 -2.6 到 80 °C)。此外,三元共混物还表现出良好的机械性能,包括更高的延展性和更大的断裂能,以及更好的能量耗散能力。这项工作为提高普通硫化橡胶在高温下的阻尼性能提供了另一种解决方案。
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引用次数: 0
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European Polymer Journal
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