Physical and Materials Chemistry Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India.
J Phys Chem A. 2013 Mar 28;117(12):2446-54. doi: 10.1021/jp4002934. Epub 2013 Mar 19.
An exhaustive kinetic analysis has been carried out to offer the convincing evidence of the involvement of the oil-water interface in guiding "on water organic reaction" mechanism. We have tuned the interface to prove its indispensable efficacy to make on water reaction a unique type among water mediated organic reactions. Sensitive techniques have established the preferential solvation of polarizable ions at the water surface. The experimental methods have been developed to control the molecular structure of oil-water interface in situ. Temperature-dependent analyses have also been presented to understand the enthalpic and entropic modifications of the interfacial water molecules during a heterogeneous reaction. Both of our kinetic and thermodynamic outcomes have univocally established that the hydrogen-bonding ability of the surface water molecules plays a critical role in deciding the on water organic reaction mechanism. The results have important implications on understanding the role of small water molecules adjacent to the reactants during the reactions discussed in this investigation.
已经进行了详尽的动力学分析,为油-水界面在指导“水上有机反应”机制中的作用提供了令人信服的证据。我们已经调整了界面,证明其在使水上反应成为水相有机反应中独特类型方面具有不可或缺的功效。敏感技术已经确定了可极化离子在水表面的优先溶剂化。已经开发了实验方法来原位控制油水界面的分子结构。还进行了温度依赖性分析,以了解非均相反应过程中界面水分子的焓和熵变化。我们的动力学和热力学结果都一致表明,表面水分子的氢键能力在决定水上有机反应机制方面起着关键作用。这些结果对于理解在本研究中讨论的反应中小分子水在反应物附近的作用具有重要意义。