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通过表面引发的水相 Cu(0)介导的活性自由基聚合制备的热响应性聚(N-异丙基丙烯酰胺)接枝鸡毛角蛋白:合成与性能。

Thermal responsive poly(N-isopropylacrylamide) grafted chicken feather keratin prepared via surface initiated aqueous Cu(0)-mediated RDRP: Synthesis and properties.

机构信息

Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan.

Graduate School of life and environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577, Japan.

出版信息

Int J Biol Macromol. 2020 Jun 15;153:364-372. doi: 10.1016/j.ijbiomac.2020.02.277. Epub 2020 Feb 25.

Abstract

Poultry chicken feather keratin was extracted and then modified for the fabrication of keratin-graft-PNIPAM copolymers. The keratin was well extracted from feather fiber and powdered. Subsequently, it underwent the surficial functionalization process with initiator groups. After the study conducted full disproportionation of Cu(I)Br/MeTren into Cu(0) and Cu(II)Br in the solvent, surface initiated aqueous Cu(0)-mediated reversible-deactivation radical polymerization (RDRP) of N-isopropylacrylamide (NIPAM) was performed in a methanol/water mixture solvent. The reaction was performed rapidly and efficiently, during which over 100% graft rate was achieved at 60 min. After 6 h reaction, 200% graft rate could be achieved. High graft rate (up to 287%) was achieved, and graft rate could be regulated by controlling the reaction time and the addition of monomer. The fabricated keratin-g-PNIPAM exhibited a rough surface. As revealed from the results of thermal analysis, the thermal stability of keratin-g-PNIPAM was enhanced noticeably compared with the original keratin. Besides, grafted PNIPAM chains exhibited a higher glass transition temperature. The grafted keratin particles displayed enhanced hydrophilicity. Keratin-g-PNIPAMs exhibit a lower LCST comparing to homopolymer and the flocculation in hot water behavior could be controlled by regulating graft rate.

摘要

从鸡毛中提取并修饰角蛋白,以制备角蛋白接枝 PNIPAM 共聚物。角蛋白从羽毛纤维中被很好地提取出来并进行了粉末化处理。随后,它经历了引发剂基团的表面功能化过程。在溶剂中对 Cu(I)Br/MeTren 进行完全歧化反应,生成 Cu(0)和 Cu(II)Br 后,在甲醇/水混合溶剂中进行表面引发的水相 Cu(0)介导的可逆失活自由基聚合(RDRP)反应。该反应快速高效地进行,在 60 分钟内即可达到超过 100%的接枝率。6 小时后,接枝率可达 200%。接枝率高达 287%,通过控制反应时间和单体添加量可以调节接枝率。制备的角蛋白-g-PNIPAM 呈现出粗糙的表面。从热分析结果可知,与原始角蛋白相比,角蛋白-g-PNIPAM 的热稳定性明显增强。此外,接枝的 PNIPAM 链表现出更高的玻璃化转变温度。接枝的角蛋白颗粒显示出增强的亲水性。与均聚物相比,角蛋白-g-PNIPAMs 的 LCST 更低,通过调节接枝率可以控制在热水中的絮凝行为。

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