MIFT Department, Istituto Sistemi Complessi del CNR, University of Messina, 00185 Rome, Italy.
Department of Chemical, Materials and Production Engineering, University of Naples Federico II, Piazzale Tecchio 80, 80125 Naples, Italy.
Int J Mol Sci. 2023 Jan 19;24(3):2003. doi: 10.3390/ijms24032003.
Interactions between nanoparticles (NPs) determine their self-organization and dynamic processes. In these systems, a quantitative description of the interparticle forces is complicated by the presence of the hydrophobic effect (HE), treatable only qualitatively, and due to the competition between the hydrophobic and hydrophilic forces. Recently, instead, a sort of crossover of HE from hydrophilic to hydrophobic has been experimentally observed on a local scale, by increasing the temperature, in pure confined water and studying the occurrence of this crossover in different water-methanol solutions. Starting from these results, we then considered the idea of studying this process in different nanoparticle solutions. By using photon correlation spectroscopy (PCS) experiments on dendrimer with OH terminal groups (dissolved in water and methanol, respectively), we show the existence of this hydrophobic-hydrophilic crossover with a well defined temperature and nanoparticle volume fraction dependence. In this frame, we have used the mode coupling theory extended model to evaluate the measured time-dependent density correlation functions (ISFs). In this context we will, therefore, show how the measured spectra are strongly dependent on the specificity of the interactions between the particles in solution. The observed transition demonstrates that just the HE, depending sensitively on the system thermodynamics, determines the hydrophobic and hydrophilic interaction properties of the studied nanostructures surface.
纳米粒子 (NPs) 之间的相互作用决定了它们的自组织和动态过程。在这些系统中,由于疏水效应 (HE) 的存在,定量描述粒子间的相互作用力变得很复杂,只能定性处理,而且由于疏水力和亲水力之间的竞争。最近,人们在纯受限水中通过升高温度,在局部尺度上观察到 HE 从亲水到疏水的交叉,在不同的水-甲醇溶液中研究了这种交叉的发生。基于这些结果,我们考虑了在不同的纳米粒子溶液中研究这个过程的想法。通过在具有 OH 端基的树状大分子 (分别溶解在水中和甲醇中) 上进行光子相关光谱 (PCS) 实验,我们证明了这种疏水性-亲水性交叉的存在,其具有明确的温度和纳米粒子体积分数依赖性。在这个框架内,我们使用扩展的模式耦合理论模型来评估测量的时变密度相关函数 (ISFs)。因此,在这个背景下,我们将展示所测量的光谱如何强烈依赖于溶液中粒子之间相互作用的特异性。所观察到的转变表明,正是 HE 强烈依赖于系统热力学,决定了所研究的纳米结构表面的疏水和亲水相互作用特性。