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两性离子磺基甜菜碱的制备及其热性能和纳米结构自组装特性的研究。

Preparation of Zwitterionic Sulfobetaines and Study of Their Thermal Properties and Nanostructured Self-Assembling Features.

作者信息

Amrenova Yenglik, Zhengis Arshyn, Yergesheva Arailym, Abutalip Munziya, Nuraje Nurxat

机构信息

Renewable Energy Laboratory, National Laboratory Astana, Nazarbayev University, Astana 010000, Kazakhstan.

Department of Chemical and Biochemical Engineering, Satbayev University, Almaty 050013, Kazakhstan.

出版信息

Nanomaterials (Basel). 2025 Jan 2;15(1):58. doi: 10.3390/nano15010058.

DOI:10.3390/nano15010058
PMID:39791816
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11722607/
Abstract

Zwitterionic polymers have garnered significant attention for their distinctive properties, such as biocompatibility, antifouling capabilities, and resistance to protein adsorption, making them promising candidates for a wide range of applications, including drug delivery, oil production inhibitors, and water purification membranes. This study reports the synthesis and characterization of zwitterionic monomers and polymers through the modification of linear, vinyl, and aromatic heterocyclic functional groups via reaction with 1,3-propanesultone. Four zwitterionic polymers with varying molecular structures-ranging from linear to five and six membered ring systems-were synthesized: poly(sulfobetaine methacrylamide) (pSBMAm), poly(sulfobetaine-1-vinylimidazole) (pSB1VI), poly(sulfobetaine-2-vinylpyridine) (pSB2VP), and poly(sulfobetaine-4-vinylpyridine) (pSB4VP). Their molecular weights, thermal behavior, and self-assembly properties were analyzed using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and zeta potential measurements. The glass transition temperatures (Tg) ranged from 276.52 °C for pSBMAm to 313.69 °C for pSB4VP, while decomposition temperatures exhibited a similar trend, with pSBMAm degrading at 301.03 °C and pSB4VP at 387.14 °C. The polymers' self-assembly behavior was strongly dependent on pH and their surface charge, particularly under varying pH conditions: spherical micelles were observed at neutral pH, while fractal aggregates formed at basic pH. These results demonstrate that precise modifications of the chemical structure, specifically in the linear, imidazole, and pyridine moieties, enable fine control over the thermal properties and self-assembly behavior of polyzwitterions. Such insights are essential for tailoring polymer properties for targeted applications in filtration membranes, drug delivery systems, and solid polymer electrolytes, where thermal stability and self-assembly play crucial roles.

摘要

两性离子聚合物因其独特的性能,如生物相容性、抗污染能力和抗蛋白质吸附性,而备受关注,这使其成为药物递送、采油抑制剂和水净化膜等广泛应用的有前景的候选材料。本研究报告了通过与1,3 - 丙烷磺内酯反应对线性、乙烯基和芳族杂环官能团进行改性来合成和表征两性离子单体和聚合物。合成了四种具有不同分子结构(从线性到五元环和六元环体系)的两性离子聚合物:聚(甲基丙烯酰氨基磺酸甜菜碱)(pSBMAm)、聚(磺酸甜菜碱 - 1 - 乙烯基咪唑)(pSB1VI)、聚(磺酸甜菜碱 - 2 - 乙烯基吡啶)(pSB2VP)和聚(磺酸甜菜碱 - 4 - 乙烯基吡啶)(pSB4VP)。使用凝胶渗透色谱法(GPC)、热重分析(TGA)、差示扫描量热法(DSC)、透射电子显微镜(TEM)和zeta电位测量对它们的分子量、热行为和自组装性能进行了分析。玻璃化转变温度(Tg)范围从pSBMAm的276.52℃到pSB4VP的313.69℃,而分解温度呈现类似趋势,pSBMAm在301.03℃降解,pSB4VP在387.14℃降解。聚合物的自组装行为强烈依赖于pH值及其表面电荷,特别是在不同的pH条件下:在中性pH下观察到球形胶束,而在碱性pH下形成分形聚集体。这些结果表明,对化学结构进行精确改性,特别是在线性、咪唑和吡啶部分,能够精细控制聚两性离子的热性能和自组装行为。这些见解对于为过滤膜、药物递送系统和固体聚合物电解质等目标应用定制聚合物性能至关重要,在这些应用中热稳定性和自组装起着关键作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/16b0ab1cbb75/nanomaterials-15-00058-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/8ec0932cd762/nanomaterials-15-00058-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/98eff340bc93/nanomaterials-15-00058-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/e7d4188e919d/nanomaterials-15-00058-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/cdfae8a10fc0/nanomaterials-15-00058-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/b8bb154787cc/nanomaterials-15-00058-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/2f5ec5634f8a/nanomaterials-15-00058-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/7d1e89b45eba/nanomaterials-15-00058-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/14faa3bf070e/nanomaterials-15-00058-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/5643255133b9/nanomaterials-15-00058-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/16b0ab1cbb75/nanomaterials-15-00058-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/8ec0932cd762/nanomaterials-15-00058-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/98eff340bc93/nanomaterials-15-00058-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/e7d4188e919d/nanomaterials-15-00058-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/cdfae8a10fc0/nanomaterials-15-00058-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/b8bb154787cc/nanomaterials-15-00058-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/2f5ec5634f8a/nanomaterials-15-00058-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/7d1e89b45eba/nanomaterials-15-00058-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/14faa3bf070e/nanomaterials-15-00058-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/5643255133b9/nanomaterials-15-00058-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4efd/11722607/16b0ab1cbb75/nanomaterials-15-00058-g008.jpg

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