Raman Research Institute, Sadashivanagar, Bangalore 560080, India.
J Chem Phys. 2010 Jul 28;133(4):044701. doi: 10.1063/1.3465575.
Langmuir monolayer of a novel molecule containing dimer of disk shaped moiety, viz., terephtalic acid bis-[6-(3,6,7,10,11-pentahexyloxy-triphenylen-2-yloxyl)-hexyl] ester (tp-dimer), was studied at air-water interface. The monolayer of the tp-dimer at air-water interface exhibited the coexistence of condensed and gas phases at large area per molecule which on compression transformed to a uniform condensed phase at lower area per molecule (1.80 nm(2)) and then collapsed at 1.67 nm(2). The monolayer film transferred by Langmuir-Blodgett technique onto a hydrophilic silicon substrate was studied using an atomic force microscope. The topography image showed the film to be of height of about 1.5 nm corresponding to the edge-on configuration of the triphenylene moieties. We have studied the collapse of monolayer at air-water interface as a function of compression rate and temperature. We find that the collapse pressure increased with increase in the compression rate. The surface pressure of the monolayer is considered as stress and compression as strain. The strain rate is related to the collapse pressure by a power law similar to that found in the dendrimers. Our studies on the effect of temperature on the collapse pressure of tp-dimer monolayer showed that the collapse pressure decreased with increase in temperature. We have considered the Arrhenius temperature dependence of the strain rate and calculated the activation energy for the collapse of monolayer. Our analysis of the relative area loss as a function of time in the collapse region suggests that the monolayer collapses by the formation of nuclei of three-dimensional crystallites.
一种新型分子的朗缪尔单分子层,其中包含双碟状部分,即对苯二甲酸双-[6-(3,6,7,10,11-五己氧基-三联苯-2-基氧代)-己基]酯(tp-二聚体),在气液界面进行了研究。在大面积分子面积下,tp-二聚体在气液界面的单分子层表现出凝聚相和气相的共存,而在较小的面积分子面积(1.80nm^2)下则转变为均匀的凝聚相,然后在 1.67nm^2 下坍塌。通过 Langmuir-Blodgett 技术将单层膜转移到亲水硅衬底上,使用原子力显微镜进行了研究。形貌图像显示该膜的高度约为 1.5nm,对应于三联苯部分的边缘配置。我们研究了单分子层在气液界面的坍塌作为压缩率和温度的函数。我们发现,随着压缩率的增加,坍塌压力增加。单分子层的表面压力被视为应力,压缩为应变。应变率与崩溃压力之间的关系类似于树枝状聚合物中的关系。我们对温度对 tp-二聚体单分子层坍塌压力的影响的研究表明,坍塌压力随温度的升高而降低。我们考虑了应变率的 Arrhenius 温度依赖性,并计算了单分子层坍塌的活化能。我们对坍塌区域中相对面积损失随时间的分析表明,单分子层通过形成三维晶体的核而坍塌。