Kitayama Yukiya, Takeuchi Toshifumi
Graduate School of Engineering, Kobe University , 1-1, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Langmuir. 2014 Oct 28;30(42):12684-9. doi: 10.1021/la502801t. Epub 2014 Oct 14.
CO2/N2-triggered stability-controllable gold nanoparticles (AuNPs) grafted with poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) layers (PDEAEMA-g-AuNPs) were synthesized by the surface-initiated atom transfer radical polymerization of DEAEMA with AuNPs bearing the bis[2-(2-bromoisobutyryloxy)undecyl] layer (grafting from method). Extension of the PDEAEMA chain length increased the stability of the PDEAEMA-g-AuNPs in CO2-bubbled water because of the electrosteric repulsion of the protonated PDEAEMA layer. The chain-length-dependent stability of PDEAEMA-g-AuNPs was confirmed by DLS and UV-vis spectra by using the localized surface plasmon resonance property of the AuNPs, where the extinction wavelength was shifted toward shorter wavelength with increasing PDEAEMA chain length. The reversible stability change with the gas stimuli of CO2/N2 was also successfully demonstrated. Finally, the transfer across the immiscible interface between water and organic solvent was successfully demonstrated by N2-triggered insolubilization of PDEAEMA layer on AuNPs in the aqueous phase, leading to the successful collection of AuNPs using organic solvent from the aqueous phase. Our "grafting from" method of reversible stability-controllable AuNPs can be applied to develop advanced materials such as reusable optical AuNP-based nanosensors because the molecular recognition layer can be constructed by two-step polymerization.
通过表面引发的原子转移自由基聚合反应,以带有双[2-(2-溴异丁酰氧基)十一烷基]层的金纳米颗粒(从接枝法)引发二乙氨基乙基甲基丙烯酸酯(DEAEMA)的聚合反应,合成了接枝有聚(2-(二乙氨基)乙基甲基丙烯酸酯)(PDEAEMA)层的二氧化碳/氮气触发的稳定性可控金纳米颗粒(PDEAEMA-g-AuNPs)。由于质子化的PDEAEMA层的静电排斥作用,PDEAEMA链长度的增加提高了PDEAEMA-g-AuNPs在通二氧化碳的水中的稳定性。利用金纳米颗粒的局域表面等离子体共振特性,通过动态光散射(DLS)和紫外可见光谱证实了PDEAEMA-g-AuNPs的链长依赖性稳定性,其中随着PDEAEMA链长度的增加,消光波长向较短波长移动。还成功证明了随着二氧化碳/氮气气体刺激的可逆稳定性变化。最后,通过氮气触发水相中金纳米颗粒上PDEAEMA层的不溶性,成功证明了在水和有机溶剂之间的不混溶界面上的转移,从而导致使用有机溶剂从水相中成功收集金纳米颗粒。我们的可逆稳定性可控金纳米颗粒的“接枝法”可应用于开发先进材料,如可重复使用的基于金纳米颗粒的光学纳米传感器,因为分子识别层可以通过两步聚合构建。