Shen Chen, Matsubara Masaki, Yabushita Mizuho, Maki Sachiko, Muramatsu Atsushi, Kanie Kiyoshi
Institute of Multidisciplinary Research for Advanced Material, Tohoku University 2-1-1 Katahira Aoba-ku, Sendai Miyagi 980-8577 Japan
National Institute of Technology, Sendai College 48 Nodayama, Medeshima-Shiote Natori Miyagi 981-1239 Japan.
Nanoscale Adv. 2020 Jan 14;2(2):814-822. doi: 10.1039/c9na00767a. eCollection 2020 Feb 18.
Magnetite (FeO) nanoplates with a hexagonal platelet shape were synthesized by two steps: hydrothermal synthesis of iron(iii) oxide (α-FeO) nanoplates followed by wet chemical reduction of the α-FeO nanoplates. Then, poly(methyl methacrylate) (PMMA) chains were grafted onto the surface of the hexagonal FeO nanoplates (F) surface-initiated atom transfer radical polymerization (SI-ATRP), which ensures dispersion stability in organic solvents and ionic liquids. After mixing with 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Emim][NTf ]), a representative ionic liquid, the resulting PMMA-modified F were found to show good lyotropic liquid-crystalline (LC) behaviour in [Emim][NTf ] and to exhibit a fast response to the application of an external magnetic field. Ultrasmall-angle synchrotron X-ray scattering (USAXS) measurements verified that the PMMA chain length, the weight ratio of the ionic liquid and the external magnetic field could significantly influence the interparticle distance ( ) of the PMMA-modified F in [Emim][NTf ]. In particular, the lyotropic LC phase could be assigned as a nematic phase with a columnar alignment. In addition, the PMMA-modified F maintained a uniaxially aligned nematic columnar structure along the magnetic field direction. Our study also determined the mechanism for the special alignment of the PMMA-modified F under an external magnetic field by analysing the growth axis, the easy magnetic axes, and the interparticle distance of F. The results suggested that the special alignment of the PMMA-modified F was affected by the interparticle interaction caused by the PMMA long chains on F under the magnetic field. Furthermore, the present study revealed that PMMA-modified F exhibited a new magnetic field responsive behaviour that led not only to the formation of a uniaxial alignment structure but also to control of with the help of the PMMA soft corona under the application of a magnetic field. These features could prove to be a promising advance towards novel applications of magnetic nanoparticles (NPs), such as functional magnetic fluids, rewritable magnetic switching devices, and smart magneto-electrochemical nanosensors.
通过两步法合成了具有六边形片状形状的磁铁矿(FeO)纳米片:首先水热合成氧化铁(α-FeO)纳米片,然后对α-FeO纳米片进行湿化学还原。接着,通过表面引发原子转移自由基聚合(SI-ATRP)将聚甲基丙烯酸甲酯(PMMA)链接枝到六边形FeO纳米片(F)的表面,这确保了其在有机溶剂和离子液体中的分散稳定性。与代表性离子液体1-乙基-3-甲基咪唑双(三氟甲磺酰)亚胺([Emim][NTf₂])混合后,发现所得的PMMA修饰的F在[Emim][NTf₂]中表现出良好的溶致液晶(LC)行为,并对外加磁场表现出快速响应。超小角同步加速器X射线散射(USAXS)测量证实,PMMA链长、离子液体的重量比和外加磁场会显著影响PMMA修饰的F在[Emim][NTf₂]中的粒子间距离( )。特别是,溶致液晶相可归为具有柱状排列的向列相。此外,PMMA修饰的F沿磁场方向保持单轴排列的向列柱状结构。我们的研究还通过分析F的生长轴、易磁化轴和粒子间距离,确定了PMMA修饰的F在外部磁场下特殊排列的机制。结果表明,PMMA修饰的F的特殊排列受到磁场作用下F上PMMA长链引起的粒子间相互作用的影响。此外,本研究表明,PMMA修饰的F表现出一种新的磁场响应行为,不仅导致形成单轴排列结构,而且在磁场作用下借助PMMA软冠层控制 。这些特性可能被证明是磁性纳米颗粒(NPs)新应用的一个有前途的进展,如功能磁流体、可重写磁开关装置和智能磁电化学纳米传感器。