Electrostatic spray of liquid : Study on the charged particles in the condensed phase

由于缺乏合适的方法，离子溶剂化的研究一直是一个相当困难的课题。在这项工作中，提取溶解在液体中的离子进入气相通过施加强电场的液体进行了研究，并在凝聚相中的离子的物理化学行为的信息进行了详细的调查。这将导致溶剂效应，在凝聚相中的离子的化学反应性，溶剂化的电子等的说明，为了研究离子溶剂化的机制，热化学稳定性，结构和稳定性进行了研究，使用高压质谱仪。发现F^-离子与溶剂分子反应性很强，经常与溶剂分子形成共价键。相比之下，其他卤离子（Cl^-、Br^-、I^-）仅通过溶剂分子静电溶剂化。水是各种离子的上级溶剂。我们指出这是由于相互极化. ...更多信息 n属于不同溶剂化壳层的水配体，这加强了它们之间的相互作用（增强效应）。第一层中的醇分子比水分子与离子的相互作用更强。对于B =烷基取代的H_2O和NH_3，共轭碱B的气相质子亲合能与共轭离子BH^+的水合自由能之间存在近似的线性关系。这意味着如果共轭碱B具有较高的质子亲合性，则其共轭酸离子BH更容易从凝聚相萃取到气相。因此，电喷雾技术在医药、农业等领域的溶剂化离子分析中具有重要的应用价值。所有检测到的主要离子被发现是伪分子离子。这表明离子提取过程非常温和。少

The study on the ion solvation is a rather difficult task because of the lack of suitable methodology. In this work, the extraction of ions dissolved in the liquid into the gas phase by applying a strong electric field to the liquid are studied, and an information on the physicochemical behavior of ions in the condensed phase is investigated in detail. This will lead to the elucidation of the solvent effect, chemical reactivity of ions in the condensed phase, solvated electron, etc.In order to investigate the mechanism of ion solvation, the thermochemical stabilities, structures, and stabilities were studied using the high-pressure mass spectrometer. It was found that the F^- ion is highly reactive toward the solvent molecules and often forms the covalent bodn with them. In contrast, other halide ions (Cl^-, Br^-, I^-) are solvated only electrostatically by solvent molecules. Water is a superior solvent toward a variety of ions. We pointed out that this is due to the mutual polarizatio … More n of water ligands belonging to the different solvation shells which strengthens the interaction between them (enhancement effect). The alcohol molecules in the first shell experience stronger interaction with ions than watermolecules. However, the enhancement effect for alcohols is weaker than that for water, and thus alcohols are generally poorer solvents than water toward ions.An approximate linear relationship was found between gas-phase proton affinities of conjugate bases B's and free energies of hydration of conjugate ions BH^+'s for B = alkyl-substituted H_2O and NH_3. This means that if the conjugate base B has a higher proton affinity, its conjugate acid ion BH is easier to be extracted from the condensed phase to the gas phase. Thus the electrospray could be a useful tool for the analysis of solvated ions in the fields of medicine, pharmacy, and agriculture.The ions in solution were electrosprayed and mass-analysed. All of the detected major ions are found to be pseudo-molecular ions. This indicates that the ion extraction process is very mild. Less