Departamento Química Física II, Facultad de Farmacia, Universidad Complutense, 28040 Madrid, Spain.
Langmuir. 2010 May 18;26(10):7101-6. doi: 10.1021/la904452c.
We investigate in a hybrid material the interactions existing between magnetic nanoparticles of gamma-Fe(2)O(3) and the polymer matrix constituted by core-shell poly(N-isopropylacrylamide-sodium acrylate) microgels. These interactions provoke the shifting of the microgel volume phase transition to higher temperatures when the amount of gamma-Fe(2)O(3) increases. The study was performed using different techniques such as incoherent quasi-elastic neutron scattering (IQNS), infrared spectroscopy (FTIR-ATR), and dynamic light scattering (DLS). Below the low critical solution temperature (LCST) of the polymer, the IQNS data confirm that the presence of inorganic nanoparticles affects the PNIPAM chain motions. Thus, in the swollen state both the mean-square displacement of the polymer segments and the diffusive motion of the polymer chains decrease as the iron oxide content increases. The FTIR-ATR study indicates that the reduction of vibrational and diffusional motions of the polymer chains is due to the formation of hydrogen bonds between the amide groups of the polymer matrix and the OH groups of the magnetic nanoparticles. The creation of this hybrid complex would explain the reduction of the swelling capacity with increasing the iron content in the microgels. Furthermore, this interaction could also explain the shift of the polymer LCST to higher temperatures as due to the extra energy required by the system to break the hydrogen bonds prior to the PNIPAM collapse.
我们研究了一种混合材料中 γ-Fe(2)O(3) 磁性纳米粒子与由核壳型聚(N-异丙基丙烯酰胺-丙烯酸钠)微凝胶构成的聚合物基质之间存在的相互作用。当 γ-Fe(2)O(3) 的含量增加时,这些相互作用会导致微凝胶体积相转变向更高的温度移动。这项研究使用了不同的技术,如非相干准弹性中子散射(IQNS)、傅里叶变换衰减全反射红外光谱(FTIR-ATR)和动态光散射(DLS)。在聚合物的低临界溶液温度(LCST)以下,IQNS 数据证实了无机纳米粒子的存在会影响 PNIPAM 链的运动。因此,在溶胀状态下,随着氧化铁含量的增加,聚合物链段的均方根位移和聚合物链的扩散运动都会减小。FTIR-ATR 研究表明,聚合物链振动和扩散运动的减少是由于聚合物基质中的酰胺基团和磁性纳米粒子的 OH 基团之间形成了氢键。这种杂化复合物的形成可以解释随着微凝胶中铁含量的增加,溶胀能力的降低。此外,这种相互作用还可以解释聚合物 LCST 向更高温度的移动,这是由于系统在 PNIPAM 塌陷之前需要额外的能量来打破氢键。