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Light-Controlled Interfacial Self-Assembly of Bottlebrush Amphiphiles toward Highly Tunable Photonic Materials
Macromolecules ( IF 5.1 ) Pub Date : 2024-08-15 , DOI: 10.1021/acs.macromol.4c01086
Xingzhou Li 1 , Bingyuan Xia 1 , Yuhang Song 2 , Mohan Zheng 1 , Caili Huang 2 , Yuesheng Li 1 , Dong-Po Song 1
Affiliation  

We present a “light-controlled self-assembly” strategy to enhance the interfacial binding strength of amphiphilic bottlebrush block copolymers (BBCPs) at the water/oil (w/o) interface. A minor quantity (0.5–4 wt %) of o-nitrobenzyl ester units is introduced into the hydrophilic block of the BBCPs, leading to the formation of a semiflexible chain conformation. Under UV radiation, carboxylic acid groups are generated in a quantitative manner by changing the exposure time. This results in the strengthened anchoring effect, as made evident by the increase in the elastic modulus of the monolayer BBCP film. Furthermore, the presence of acid groups induces a significant expansion in the hydrophilic block chain when the BBCPs are adsorbed at the w/o interface of an ordered w/o/w complex emulsion system. This expansion results in a decrease in the spherical curvature of the internal droplets, leading to larger pore diameters in the resulting photonic supraballs. By leveraging this approach, we can easily achieve complex self-assembled structures with unprecedented periodicities (142–556 nm) and photonic band gaps (374–1167 nm) using a minimal number of BBCPs as the fundamental building blocks. The resulting photonic pigments hold significant potential for applications as safe colorants in cosmetics, coatings, inks, and more, as well as IR-reflective materials for biomimetic thermoregulation.

中文翻译:


光控界面自组装瓶刷两亲物以实现高度可调谐光子材料



我们提出了一种“光控自组装”策略,以增强两亲性瓶刷嵌段共聚物(BBCP)在水/油(w/o)界面处的界面结合强度。少量(0.5-4 wt%)硝基苄酯单元被引入 BBCP 的亲水性嵌段中,导致形成半柔性链构象。在紫外线辐射下,通过改变曝光时间以定量方式生成羧酸基团。这导致锚固效应增强,单层 BBCP 薄膜弹性模量的增加就证明了这一点。此外,当 BBCP 吸附在有序的 w/o/w 复合乳液系统的 w/o 界面时,酸基的存在会导致亲水性嵌段链显着扩展。这种膨胀导致内部液滴的球面曲率减小,从而导致所得光子超球的孔径更大。通过利用这种方法,我们可以使用最少数量的 BBCP 作为基本构建块,轻松实现具有前所未有的周期性(142-556 nm)和光子带隙(374-1167 nm)的复杂自组装结构。由此产生的光子颜料在化妆品、涂料、油墨等领域作为安全着色剂以及用于仿生温度调节的红外反射材料具有巨大的应用潜力。
更新日期:2024-08-15
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