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A redox switchable smart anti-cancer polymer coated nano-surface 一种氧化还原可切换智能抗癌聚合物包覆纳米表面
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-06 DOI: 10.1016/j.eurpolymj.2026.114501
Moumita Dhara , Vidya Chitta Voina , Somdatta Rudra , Anand K. Kondapi , Tushar Jana
Smart nano-surfaces with switchable properties are emerging as promising candidates for next-generation biomedical applications. Here we report a simple fabrication strategy for a poly(ferrocenyl methacrylate)-functionalized nano-surface that is externally redox-switchable and exhibits strong cytotoxicity toward cancer cells. Strategic positioning of poly(ferrocenyl methacrylate) on the interface of a nano-surface rather than in solution or nanoparticle cores, we envision spatially localized and tunable biological responses. The surface design is based on well-defined poly(2-(methacryloyloxy)ethylferrocenecarboxylate) (pFcMA) brushes tethered to silica nanoparticles (SiNPs) via surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization. Transmission electron microscopy (TEM) revealed polymer grafted SiNP core size varies in the range of 46–70 nm, while the grafting density of pFcMA brushes could be systematically tuned between 0.103 and 0.045 chains nm−2. Variation in monomer loading allowed systematic modulation of chain conformation from “mushroom” to “brush” regimes as confirmed by thermal and microscopic studies. The surface attached pFcMA shells displayed reversible redox behaviour, validated by cyclic voltammetry (CV), UV–visible spectroscopy, and dynamic light scattering (DLS) analysis. In human neuroblastoma and embryonic kidney cell lines, the redox-switchable poly(ferrocenyl methacrylate) coatings exhibited substantial cytotoxicity, presenting as redox-responsive nano-surface with potential applicability in stimuli-regulated guest loading and release under control. This innovative fusion of redox regulation, anticancer activity, and interfacial design reveals promising prospects in biosensing, on-demand therapeutic interfaces, and smart implant coatings.
具有可切换特性的智能纳米表面正在成为下一代生物医学应用的有前途的候选者。在这里,我们报告了一种简单的制造策略,聚(二茂铁甲基丙烯酸酯)功能化纳米表面是外部氧化还原可切换的,并对癌细胞表现出很强的细胞毒性。将聚二茂铁甲基丙烯酸酯战略性地定位在纳米表面的界面上,而不是在溶液或纳米颗粒核心中,我们设想空间定位和可调的生物反应。表面设计是基于定义良好的聚(2-(甲基丙烯氧基)乙基二茂铁羧酸酯)(pFcMA)刷,通过表面引发的可逆加成-破碎链转移(SI-RAFT)聚合,将其拴在二氧化硅纳米颗粒(SiNPs)上。透射电镜(TEM)显示,聚合物接枝的SiNP芯尺寸在46 ~ 70 nm之间,而pFcMA刷的接枝密度可以在0.103 ~ 0.045链nm−2之间系统调节。单体负载的变化允许从“蘑菇”到“刷状”的链构象的系统调节,这一点得到了热学和微观研究的证实。通过循环伏安法(CV)、紫外可见光谱和动态光散射(DLS)分析证实,表面附着的pFcMA壳具有可逆的氧化还原行为。在人类神经母细胞瘤和胚胎肾细胞系中,氧化还原可切换的聚二茂铁甲基丙烯酸酯涂层表现出实质性的细胞毒性,表现为氧化还原响应的纳米表面,在刺激调节的客体加载和释放控制下具有潜在的适用性。这种氧化还原调节、抗癌活性和界面设计的创新融合在生物传感、按需治疗界面和智能植入物涂层方面显示出广阔的前景。
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引用次数: 0
Self-initiated copolymer grafting on ground tire rubber for controlled interfacial properties 自引发共聚物接枝在地面轮胎橡胶的界面性能控制
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114497
Reymark D. Maalihan, Eugene B. Caldona
Ground tire rubber (GTR) is a plentiful secondary polymer resource, but its aged, nonpolar surface limits compatibility with polar matrices. This study presents a scalable “graft-from” copolymerization of acrylic acid (AA) and methyl methacrylate (MMA) onto cryo-milled GTR, initiated by mechanoradicals generated during milling, eliminating the need for external initiators. By varying the AA:MMA ratio, copolymer grafts with tunable polarity were obtained and correlated with surface and dispersion properties. Spectroscopy confirmed successful co-grafting, with compositional trends identified by principal component analysis. Electron paramagnetic resonance indicated near-complete radical consumption. Thermogravimetric analysis confirmed surface-limited modification. Increasing AA content transformed fractured carbon-rich surfaces into continuous oxygen-rich films, with greater surface roughness. Contact angle tests showed rapid wetting on AA-rich surfaces versus poor wetting on neat or MMA-rich samples. Dielectric measurements showed that permittivity increased from 4.36 for the neat GTR to ∼11 for AA-rich grafts. The 50:50 AA:MMA composition achieved ∼8.0 at 100 Hz. Kelvin probe force microscopy confirmed increasing surface potential with AA content. Dispersion tests in mixed polar solvents showed that 50:50 and 60:40 grafted GTR remained suspended for over 8 h, while other formulations showed partial stabilization or faster settling, with significantly shorter suspension times for neat or homopolymer-grafted samples. These findings demonstrate a tunable, initiator-free method to enhance interfacial polarity, dielectric response, and colloidal stability of GTR, enabling its use in coatings, adhesives, and dielectric elastomers.
地面轮胎橡胶是一种丰富的二次聚合物资源,但其老化的非极性表面限制了其与极性基质的相容性。该研究提出了一种可扩展的丙烯酸(AA)和甲基丙烯酸甲酯(MMA)在低温铣削GTR上的接枝共聚,由铣削过程中产生的机械自由基引发,无需外部引发剂。通过改变AA:MMA的比例,得到极性可调的接枝共聚物,并与表面和分散性能相关。光谱分析证实共接枝成功,主成分分析确定了成分趋势。电子顺磁共振显示自由基消耗接近完全。热重分析证实了表面限制改性。增加AA含量可使断裂的富碳表面转变为连续的富氧膜,表面粗糙度增大。接触角测试表明,在富含aa的表面快速润湿,而在整洁或富含mma的样品上润湿较差。介电测量表明,纯GTR的介电常数从4.36增加到富aa接枝的介电常数为~ 11。50:50 AA:MMA组合在100 Hz下达到了~ 8.0。开尔文探针力显微镜证实,表面电位随AA含量的增加而增加。在混合极性溶剂中的分散测试表明,50:50和60:40接枝的GTR悬浮时间超过8小时,而其他配方的GTR表现出部分稳定或更快的沉降,纯聚合物或均聚接枝的GTR悬浮时间明显缩短。这些发现证明了一种可调的、无引发剂的方法可以增强GTR的界面极性、介电响应和胶体稳定性,使其能够用于涂料、粘合剂和介电弹性体。
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引用次数: 0
Functionalized crosslinked polyesters incorporating fatty, coumarin, and PEG units: An attractive approach to the fluorescent hydrogels preparation 含有脂肪、香豆素和PEG单元的功能化交联聚酯:一种有吸引力的荧光水凝胶制备方法
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-08 DOI: 10.1016/j.eurpolymj.2026.114508
Andrade-Acuña Daniela , Sanchez A. Susana , Aguilar Joao , Aguilar-Bolados Hector , Dahrouch Mohamed
Fluorescent crosslinking polyesters composed of a siloxane fatty ester, polyethylene glycols, and coumarin units were successfully synthesized via a polytransesterification reaction under melting and high vacuum conditions. Their respective structures were identified by spectroscopic analysis, showing that the different monomers, particularly the coumarin compound, were successfully covalently incorporated. The crosslinking polyesters displayed appropriate thermal properties and hydrogel-forming capabilities, and the incorporation of the fluorescent molecule showed improved swelling properties in water. The results determined by the rheological studies are promising thinking in potential different applications, and these fluorescent crosslinking polyesters showed to be biocompatible. Confocal microscopy revealed that the coumarin units are part of the polymer structure, conferring attractive fluorescent properties to these new crosslinking polyesters and their corresponding hydrogels.
在熔融和高真空条件下,通过多酯交换反应成功合成了由硅氧烷脂肪酯、聚乙二醇和香豆素单元组成的荧光交联聚酯。通过光谱分析鉴定了它们各自的结构,表明不同的单体,特别是香豆素化合物,成功地共价结合。交联聚酯具有良好的热性能和水凝胶形成能力,荧光分子的掺入改善了其在水中的溶胀性能。流变学研究结果表明,这些荧光交联聚酯具有生物相容性,具有潜在的应用前景。共聚焦显微镜显示香豆素单元是聚合物结构的一部分,赋予这些新的交联聚酯及其相应的水凝胶吸引人的荧光特性。
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引用次数: 0
Molecular engineering of fluorene–thiophene architectures toward enhanced conjugation-dependent electrochromic energy storage 面向增强偶联依赖性电致变色储能的芴-噻吩结构的分子工程
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114498
Jianhua Lv , Yuting Song , Yunjiao Jiang , Zibo Wei , Cheng Liu , Wang Zhang , Jian Liu , Beili Lu , Biao Huang , Jiayu Tao
Electrochromic polymers capable of simultaneously delivering optical modulation and energy storage functions are of great interest for next-generation smart energy devices. In particular, precise molecular engineering of conjugated backbones offers an effective strategy to regulate electronic structure, ion transport, and charge storage behavior. A series of fluorene–thiophene conjugated polymers (P3TF, P2TF, and P2TTF) were designed and electrochemically synthesized to investigate the impact of molecular conjugation length and substitution position on electrochromic and energy storage performance. The UV–Vis absorption spectra of three monomers and their corresponding polymer films in the neutral state exhibited a consistent trend of gradual red-shift in the maximum absorption (P2TTF > P2TF > P3TF). This evolution reflects the intrinsic structural effect of increasing thiophene content and optimized substitution position, which collectively enhance the π-conjugation and reduce the electronic bandgap. Electrochromic studies showed that P3TF achieved a high optical contrast of 72 % at 1100 nm. Galvanostatic charge–discharge testing revealed significantly highiest areal capacitances for P2TTF (9.29 mF/cm2 at 0.8 mA/cm2) compared with P3TF and P2TF. Meanwhile, P2TTF shows superior stability in terms of both electrochromic and energy storage performance. The P2TTF-based electrochromic energy storage device, could power a LED light for over 15 s, maintaining over 86 % of its capacitance after 1500 cycles. These results highlight the critical role of molecular engineering in regulating conjugation and morphology to achieve synergistic electrochromic–energy storage performance.
能够同时提供光调制和能量存储功能的电致变色聚合物是下一代智能能源设备的重要研究方向。特别是,共轭骨架的精确分子工程提供了一种有效的策略来调节电子结构、离子传输和电荷存储行为。设计并合成了一系列芴-噻吩共轭聚合物(P3TF、P2TF和P2TTF),研究了分子共轭长度和取代位置对电致变色性能和储能性能的影响。三种单体及其相应的中性态聚合物膜的紫外-可见吸收光谱在最大吸收(P2TTF > P2TF > P3TF)处表现出一致的逐渐红移趋势。这种演变反映了增加噻吩含量和优化取代位置的内在结构效应,共同增强了π共轭性,减小了电子带隙。电致变色研究表明,P3TF在1100nm处实现了72%的高光学对比度。恒流充放电测试显示,与P3TF和P2TF相比,P2TTF在0.8 mA/cm2时的面电容显著高于P2TF (9.29 mF/cm2)。同时,P2TTF在电致变色性能和储能性能方面均表现出优异的稳定性。基于p2ttf的电致变色储能装置可以为LED灯供电超过15秒,在1500次循环后保持超过86%的电容。这些结果强调了分子工程在调节共轭和形态以实现协同电致变色储能性能方面的关键作用。
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引用次数: 0
Poly(2-isopropenyl-2-oxazoline) hydrogels as multipurpose drug delivery systems: Tailoring molecular interactions for controlled loading and release 聚(2-异丙烯-2-恶唑啉)水凝胶作为多用途药物递送系统:为控制装载和释放定制分子相互作用
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-11-19 DOI: 10.1016/j.eurpolymj.2025.114407
Emilian Ghibu , Dumitru Mircea Vuluga , Raluca Stan , Florica Adriana Jerca , Valentin Victor Jerca
Poly(2-isopropenyl-2-oxazoline) (PiPOx) is an established polymer used in the synthesis of a wide range of functional materials with tailored properties designed to meet the demands of specific applications, particularly in the biomedical field. In the present study, we report on the therapeutic potential of PiPOx hydrogels systems by evaluating their drug loading capacity and drug release kinetics using pharmacologically active compounds belonging to diverse therapeutic classes. The exceptional versatility of PiPOx hydrogels as a drug delivery platform arises from their ability to engage in a diverse array of non-covalent interactions such as ionic, cation-π, ion–dipole, hydrophobic, and hydrogen bonding that can be established between the 2-oxazoline rings, crosslinks, and the drugs. Moreover, the weakly basic nature of the 2-oxazoline units allows protonation, enabling pH-responsive control over drug loading and drug release, while the chemical nature of the crosslinker allows further fine-tuning of the release profile through secondary physical interactions with the drug, resulting in sustained drug release profiles. Finally, the identified structure–property relationships enabled the rational use of PiPOx hydrogels as RNA delivery platforms.
聚(2-异丙烯-2-恶唑啉)(PiPOx)是一种成熟的聚合物,用于合成广泛的功能材料,具有定制的特性,旨在满足特定应用的需求,特别是在生物医学领域。在本研究中,我们报告了PiPOx水凝胶系统的治疗潜力,通过评估其载药能力和药物释放动力学,使用属于不同治疗类别的药理活性化合物。PiPOx水凝胶作为药物传递平台的特殊多功能性源于它们能够参与多种非共价相互作用,如离子、阳离子-π、离子偶极子、疏水和氢键,这些键可以在2-恶唑啉环、交联和药物之间建立。此外,2-恶唑啉单元的弱碱性允许质子化,使ph响应控制药物负载和药物释放,而交联剂的化学性质允许通过与药物的二次物理相互作用进一步微调释放谱,从而产生持续的药物释放谱。最后,确定的结构-性质关系使PiPOx水凝胶作为RNA递送平台的合理使用成为可能。
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引用次数: 0
Smart pH-responsive hydrogels: A versatile tool for addressing public health challenges in diagnostic and therapeutic applications 智能ph响应水凝胶:在诊断和治疗应用中解决公共卫生挑战的多功能工具
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-12-21 DOI: 10.1016/j.eurpolymj.2025.114466
Jige Yuan , Yi Wang , Xiaoxia Kang , Conglin Guo , Haiwei ji , Li Wu , Yuling Qin
Hydrogels have garnered substantial attention in biomedical and public health applications due to their high water content, tunable physicochemical properties, excellent biocompatibility, and capacity for functional modification. Among them, pH-responsive hydrogels represent a notably promising category of “smart” materials, which can undergo significant physical or chemical changes in response to slight variations in environmental pH. This inherent responsiveness allows for their application in real-time monitoring and targeted therapy, thereby addressing the key limitations of conventional diagnostic and therapeutic approaches, including poor sensitivity, lack of real-time feedback, non-specific drug release, and systemic side effects. In the field of public health, alterations in pH often serve as critical indicators of pathological states, such as wound infection, food spoilage, and the acidic tumor microenvironment. While traditional methods for pH detection or pH-triggered drug delivery face challenges in terms of portability, continuous monitoring, selectivity, and adaptability to dynamic physiological conditions, pH-responsive hydrogels offer a versatile platform that can be engineered for specific public health scenarios. However, their broader application is constrained by several challenges, including the need for precise response range tuning, stability under physiological conditions, long-term biocompatibility, and scalable fabrication. This review systematically summarizes recent advances in the design and application of pH-responsive hydrogels in public health, with a focus on diagnostic tools (e.g., wound pH monitoring, food freshness detection, disease biomarker sensing) and therapeutic strategies (e.g., antimicrobial wound dressings, tumor-targeted drug delivery, tissue engineering). Unlike prior reviews that often emphasize material synthesis or single applications, this work uniquely integrates public health perspectives, highlighting how hydrogel design can be tailored to address real-world detection and treatment challenges. We further discuss current limitations and future directions, aiming to provide insightful guidance for the rational development of pH-responsive hydrogels that can be effectively translated into public health practice.
水凝胶由于其高含水量、可调节的物理化学性质、优异的生物相容性和功能修饰能力,在生物医学和公共卫生应用中获得了大量关注。其中,ph响应水凝胶代表了一个非常有前途的“智能”材料类别,它可以对环境ph的轻微变化做出显著的物理或化学变化。这种固有的响应性允许它们在实时监测和靶向治疗中应用,从而解决了传统诊断和治疗方法的关键局限性,包括灵敏度差、缺乏实时反馈、非特异性药物释放、还有全身的副作用。在公共卫生领域,pH值的改变通常是病理状态的关键指标,如伤口感染、食物腐败和酸性肿瘤微环境。虽然传统的pH检测或pH触发药物递送方法在便携性、连续监测、选择性和对动态生理条件的适应性方面面临挑战,但pH响应水凝胶提供了一个多功能平台,可以针对特定的公共卫生场景进行设计。然而,它们的广泛应用受到几个挑战的限制,包括需要精确的响应范围调谐,生理条件下的稳定性,长期生物相容性和可扩展的制造。本文系统总结了pH响应水凝胶在公共卫生领域的设计和应用的最新进展,重点介绍了诊断工具(如伤口pH监测、食品新鲜度检测、疾病生物标志物传感)和治疗策略(如抗菌伤口敷料、肿瘤靶向药物输送、组织工程)。与以往强调材料合成或单一应用的综述不同,这项工作独特地整合了公共卫生观点,强调了如何定制水凝胶设计来解决现实世界的检测和治疗挑战。我们进一步讨论了目前的局限性和未来的发展方向,旨在为ph响应水凝胶的合理开发提供有洞察力的指导,从而有效地转化为公共卫生实践。
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引用次数: 0
Side-chain symmetry and backbone structure as design parameters for transparent cyclic olefin polymer 侧链对称和主链结构作为透明环烯烃聚合物的设计参数
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-11-23 DOI: 10.1016/j.eurpolymj.2025.114415
Minhoo Ku , Huikyung Kim , Ashmita Jaishi , Kyosun Ku , Hyosun Lee , Sang-Ho Lee , Hyeonuk Yeo
Cyclic olefin polymers (COPs) are attractive for transparent coatings, yet balancing optical performance with processability remains challenging. We conducted a systematic structure–property study of oxanorbornene-based COPs with symmetric (OMM, OEE) and asymmetric (OME) ester substituents. Monomers were synthesized, polymerized via ring-opening metathesis polymerization, and hydrogenated to remove backbone unsaturation. NMR confirmed complete conversion and selective saturation without side-chain degradation. Thermal analyses revealed that symmetric, compact substituents increase glass-transition temperature (Tg) and thermal resistance, while asymmetric substitution decreases Tg but enhances chain mobility. Hydrogenation decreased Tg but increased decomposition temperatures (Td) by ∼40 °C, improving stability. Optical analyses revealed that asymmetric P-OME achieves the highest transmittance (>97 %) and the most blue-shifted cutoff, whereas hydrogenated P-OMM gains transparency by eliminating residual double bonds. These findings establish side-chain symmetry and backbone saturation as key molecular design handles, offering guidelines for transparent, processable organic films for optoelectronic and protective applications.
环烯烃聚合物(cop)在透明涂层中很有吸引力,但平衡光学性能和可加工性仍然是一个挑战。我们对对称(OMM, OEE)和不对称(OME)酯取代基的草生冰片烯基cop进行了系统的结构-性能研究。合成单体,通过开环复分解聚合进行聚合,加氢去除主链不饱和。核磁共振证实完全转化和选择性饱和,无侧链降解。热分析表明,对称紧凑取代基提高了玻璃化转变温度(Tg)和热阻,而不对称取代基降低了Tg,但提高了链迁移率。加氢降低了Tg,但使分解温度(Td)提高了~ 40℃,提高了稳定性。光学分析表明,不对称P-OME具有最高的透过率(97%)和最大的蓝移截止,而氢化P-OMM通过消除残余双键而获得透明度。这些发现确立了侧链对称和主链饱和是关键的分子设计手柄,为光电和防护应用的透明、可加工有机薄膜提供了指导。
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引用次数: 0
A review of recent progress in multi-component organic thermochromic materials: mechanisms, performance optimization, and applications 多组分有机热致变色材料的研究进展:机理、性能优化及应用
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-11-21 DOI: 10.1016/j.eurpolymj.2025.114408
Kexin Liu, Guiying Wang
Organic thermochromic materials (OTCMs) have attracted significant research interest within the field of stimulus-responsive materials, due to their reversible response characteristics, environmental friendliness and adjustable functionality. This review summarizes recent research progress in multi-component organic thermochromic materials (MOTCMs) over the past five years. First, this review analyzes the reversible and irreversible thermochromic mechanisms in MOTCMs. This is significant for understanding the thermochromic mechanisms and pathways for performance optimization. Subsequently, addressing key challenges of traditional thermochromic materials (TCMs), including high toxicity, inadequate responsiveness, poor stability, and limited functionality in practical applications, this review provides a comprehensive overview of recent five years (2020–2025) research progress in regulating the performance of MOTCMs, with a focus on the development of non-toxic color developers, optimized responsiveness, enhanced stability, and multifunctional integration. Meanwhile, the practical applications of MOTCMs in fields such as intelligent temperature control, energy-saving materials, anti-counterfeiting, intelligent packaging and temperature indicator are also summarized. Finally, it analyzes the primary challenges in three dimensions of material properties, preparation technology and application, aiming to promote innovative research and the wider application of TCMs in fields such as smart windows, temperature responsive coatings and advanced anti-counterfeiting.
有机热致变色材料(OTCMs)由于其可逆响应特性、环境友好性和可调节功能,在刺激响应材料领域引起了广泛的研究兴趣。本文综述了近五年来多组分有机热致变色材料的研究进展。本文首先分析了motcm的可逆和不可逆热致变色机理。这对于理解热致变色机制和性能优化途径具有重要意义。针对传统热致变色材料在实际应用中存在的毒性大、响应性差、稳定性差和功能有限等问题,本文综述了近5年(2020-2025)热致变色材料性能调控的研究进展,重点介绍了无毒显色剂的开发、响应性优化、稳定性增强和多功能集成等方面的研究进展。同时,总结了motm在智能温控、节能材料、防伪、智能包装、温度指示等领域的实际应用。最后,从材料性能、制备工艺和应用三个方面分析了中药面临的主要挑战,旨在推动中药在智能窗、温度响应涂料和先进防伪等领域的创新研究和广泛应用。
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引用次数: 0
Self-assembly of PEG-fluoroalkyl chains into new generation nanodroplets as histotripsy agent with determinable perfluorocarbon content 聚乙二醇-氟烷基链自组装成具有可测定全氟碳含量的新一代纳米液滴
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-11-30 DOI: 10.1016/j.eurpolymj.2025.114427
Mohammad Abou Chakra , Ibtisam Naser , Sarah Hall , Cemran Toydemir , Dylan Pearson , Eli Vlaisavljeivich , Yasemin Yuksel Durmaz
The development of nanodroplets (NDs) as first-generation agents for nanoparticle-mediated histotripsy (NMH) aimed to overcome the limitations of histotripsy by significantly reducing the cavitation threshold. While effective, conventional NDs present several drawbacks, including complex multistep synthesis, poor long-term stability, and the inability to quantify the perfluorocarbon (PFC) concentration in treatment doses, which limit their clinical utility. To address these issues, a novel advancement has emerged in the form of PEG-fluoroalkyl NDs as new histotripsy agents. These NDs are formed through the self-assembly of PEG-fluoroalkyl chains encapsulating perfluorohexane (PFH), a highly efficient PFC derivative for histotripsy. The resulting NDs possess desirable size, detectable PFH content, and enhanced nanoparticle stability. We hypothesize that the presence and increasing number of fluorine (F) groups enhance PFH encapsulation within the ND core, resulting in a more stable structure. To test this, a library of eight NDs was prepared using two poly(ethylene glycol) chain lengths (PEG550 and PEG2000) and four distinct fluoroalkyl chains, in the presence of PFH. The findings highlight facile production, biocompatibility, and a size smaller than 200 nm, with PEG550-based NDs showing quantifiable PFH encapsulation. Moreover, increasing the fluoroalkyl chain length improved the PFH encapsulation for PEG550 derivatives. All PEG-fluoroalkyl NDs reduced cavitation thresholds, ranging from 11.2 to 17.6 MPa, which could be tuned by varying ND concentration. These results suggest PEG-fluoroalkyl NDs represent a promising next-generation agent for NMH applications.
纳米液滴(NDs)作为纳米颗粒介导的组织切片(NMH)的第一代药物的发展旨在通过显着降低空化阈值来克服组织切片的局限性。传统的NDs虽然有效,但存在一些缺点,包括复杂的多步骤合成、较差的长期稳定性以及无法量化治疗剂量的全氟化碳(PFC)浓度,这限制了它们的临床应用。为了解决这些问题,一种新的进展以peg -氟烷基nd的形式出现,作为新的组织划分剂。这些NDs是通过包裹全氟己烷(PFH)的peg -氟烷基链的自组装形成的,全氟己烷是一种高效的PFC衍生物。所得到的nd具有理想的尺寸、可检测的PFH含量和增强的纳米颗粒稳定性。我们假设氟(F)基团的存在和数量的增加增强了ND核心内PFH的包封,从而导致更稳定的结构。为了验证这一点,在PFH存在的情况下,用两种聚乙二醇链长度(PEG550和PEG2000)和四种不同的氟烷基链制备了8个nd库。研究结果强调了易于生产,生物相容性和尺寸小于200纳米,基于peg550的nd显示可量化的PFH封装。此外,增加氟烷基链长改善了PEG550衍生物的PFH封装。所有聚乙二醇-氟烷基ND都降低了空化阈值,范围从11.2到17.6 MPa,可以通过改变ND浓度来调节。这些结果表明,peg -氟烷基NDs代表了下一代NMH应用的前景。
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引用次数: 0
Structural transformation and charge regulation of natural rubber-derived polymeric anticoagulants 天然橡胶聚合物抗凝剂的结构转化和电荷调节
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-22 Epub Date: 2025-12-05 DOI: 10.1016/j.eurpolymj.2025.114440
Katarzyna Byś , Pablo M. Blanco , Krzysztof Fink , Mateusz Psurski , Honorata Zachary , Miroslav Štěpánek , Peter Košovan , Mariusz Uchman
Heparin-mimicking polyelectrolytes act as anticoagulants in vivo due to their highly negative charge and high charge density. Unlike heparin, these polymers can be structurally tailored to tune chain length, sulfation degree and binding affinity, thereby modulating their therapeutic action. Here, we present two such heparin-mimicking polyelectrolytes, derived from natural rubber as an inexpensive and readily available raw material. These polymers, sodium poly((sulfamate-carboxylate) isoprene) (PISC) and poly((amino-carboxylate) isoprene (PACIS), contain sulfonate groups, as well as weakly acidic and basic groups on adjacent carbons, which enable us to tune their net charge in the biological pH range, while maintaining solubility and anticoagulation activity. Moreover, their activity may be further optimized by adjusting chain length. To test this tunability, we prepared a set of PISC- and PACIS-based copolymers varying in chain length and dispersity by post-polymerization modification of cis-1,4-polyisoprene. We characterized their structure and functionalization degree using various methods, further analyzing with potentiometric titration and computer simulations how their net charge varies with pH and affects aggregation. Despite aggregation, all PISC- and PACIS-based copolymers displayed heparin-mimicking activity, measured as activated partial thromboplastin time, while remaining biocompatible. In this context, the longest-chain copolymers performed best, extending aPTT by more than threefold in comparison with the control at 3.8 μg/mL, while maintaining biocompatibility up to 100 μg/mL across various cell lines. These findings demonstrate that natural rubber-derived polyelectrolytes provide a promising alternative to heparin for antithrombotic therapy.
模拟肝素的聚电解质由于其高负电荷和高电荷密度而在体内起抗凝血作用。与肝素不同,这些聚合物可以在结构上进行调整,以调整链长、磺化程度和结合亲和力,从而调节其治疗作用。在这里,我们提出了两种这样的模拟肝素的聚电解质,从天然橡胶中提取,作为一种廉价和容易获得的原料。这些聚合物,聚((氨基-羧酸)异戊二烯钠)(PISC)和聚(氨基-羧酸)异戊二烯(PACIS),含有磺酸基团,以及相邻碳上的弱酸性和碱性基团,这使我们能够在生物pH范围内调节它们的净电荷,同时保持溶解性和抗凝活性。此外,通过调节链长可以进一步优化其活性。为了测试这种可调节性,我们制备了一组基于PISC和pacis的共聚物,这些共聚物通过顺式-1,4-聚异戊二烯的聚合后改性而改变了链长和分散性。我们用不同的方法表征了它们的结构和功能化程度,并进一步用电位滴定法和计算机模拟分析了它们的净电荷随pH值的变化和对聚集的影响。尽管聚合,所有的pisci -和PACIS-based共聚物显示肝素模拟活性,以活化的部分凝血活素时间来测量,同时保持生物相容性。在这种情况下,长链共聚物表现最好,与3.8 μg/mL的对照相比,aPTT延长了三倍以上,同时在各种细胞系之间保持高达100 μg/mL的生物相容性。这些发现表明,天然橡胶衍生的聚电解质为抗血栓治疗提供了一个有希望的肝素替代品。
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引用次数: 0
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European Polymer Journal
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