Iqbal Muhammad Asif, Younis Muhammad Wasim, Maqbool Muhammad, Goh Hui Hwang, Kurniawan Tonni Agustiono, Amjad Muhammad, Othman Mohd Hafiz Dzarfan
Department of Chemistry, School of Science, University of Management and Technology, C-II, Johar Town, 54770 Lahore, Pakistan.
Department of Chemistry, School of Science, University of Management and Technology, C-II, Johar Town, 54770 Lahore, Pakistan.
Int J Biol Macromol. 2025 Feb;288:138775. doi: 10.1016/j.ijbiomac.2024.138775. Epub 2024 Dec 14.
In this study, we present a groundbreaking approach utilizing metal-free, visible light-mediated organic photoredox catalyzed atom transfer radical polymerization (O-ATRP) to synthesize cellulose-based stimuli-responsive polymers. Our method resulted in the successful synthesis of innovative metal-free poly(N-tertiary-butylacrylamide)-graft-hydroxypropyl cellulose (PNTBAM-g-HPC) polymers with exceptional control over molecular weight and narrow dispersity index (Đ) and explored their applications in organo-photocatalytic reactions. This approach addresses the limitations of traditional atom transfer radical polymerization method, which suffer from metal contamination and toxicity related problems. O-ATRP and organic photoredox catalysts have been sought to address these difficult challenges. In this study, we synthesized organic compound; 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPIPN), which served as an organic photoredox catalyst, enabling the synthesis and application study of PNTBAM-g-HPC polymers via organic photoredox catalysis. Furthermore, by employing 4DPIPN, three different types of PNTBAM-g-HPC polymers were synthesized. Through thorough characterization techniques including FTIR, NMR, UV/Visible spectroscopy, TGA, and GPC analysis, we confirmed the successful synthesis of photocatalyst and three different types of PNTBAM-g-HPC polymers under O-ATRP conditions. By adjusting the molar ratios of PNTBAM side chains, we fine-tuned the LCST of HTA-20 polymers to 37.3 °C, demonstrating their thermoresponsive behavior. This synthetic approach shows great potential for applications in biosensors, pharmaceuticals, biomedical engineering, and drug delivery systems.
在本研究中，我们提出了一种开创性的方法，利用无金属、可见光介导的有机光氧化还原催化原子转移自由基聚合（O-ATRP）来合成基于纤维素的刺激响应聚合物。我们的方法成功合成了创新的无金属聚（N-叔丁基丙烯酰胺）-接枝-羟丙基纤维素（PNTBAM-g-HPC）聚合物，对分子量具有出色的控制，且分散指数（Đ）较窄，并探索了它们在有机光催化反应中的应用。这种方法解决了传统原子转移自由基聚合方法的局限性，传统方法存在金属污染和毒性相关问题。人们一直在寻求O-ATRP和有机光氧化还原催化剂来应对这些艰巨挑战。在本研究中，我们合成了有机化合物；2,4,5,6-四（二苯胺基）间苯二甲腈（4DPIPN），它作为有机光氧化还原催化剂，能够通过有机光氧化还原催化合成和研究PNTBAM-g-HPC聚合物。此外，通过使用4DPIPN，合成了三种不同类型的PNTBAM-g-HPC聚合物。通过包括FTIR、NMR、紫外/可见光谱、TGA和GPC分析在内的全面表征技术，我们证实了在O-ATRP条件下成功合成了光催化剂和三种不同类型的PNTBAM-g-HPC聚合物。通过调整PNTBAM侧链的摩尔比，我们将HTA-20聚合物的低临界溶液温度（LCST）微调至37.3°C，证明了它们的热响应行为。这种合成方法在生物传感器、制药、生物医学工程和药物递送系统中的应用显示出巨大潜力。
