Department of Applied Mathematics, Research School of Physics and Engineering, The Australian National University, Canberra ACT 0200, Australia.
Langmuir. 2010 May 4;26(9):6478-83. doi: 10.1021/la9039495.
Specific ion effects are ubiquitous in soft matter systems and are most readily observed at high salt concentrations where long-range electrostatic forces are screened. In biological systems, ion-specificity is universal and is necessary to introduce the complexity required to carry out the processes of life. Many specific ion effects fall within the Hofmeister paradigm, whereby the strengths of action of the anions and cations follow a well-defined order, independent of the counterion. In contrast, specific ion effects evident in bubble coalescence inhibition depend on the combination of ions, and this phenomenon can be codified using simple ion-combining rules not evident in the Hofmeister systems. Here we show that these disparate specific ion effects have the same origin: They result from the variation in ion affinity for the solution interface. Equilibrium affinities explain Hofmeister effects, whereas we argue that the cation/anion combination controls bubble coalescence inhibition because of dynamic interfacial processes occurring at the more deformable gas-water interface.
特定离子效应在软物质体系中普遍存在,在高盐浓度下最容易观察到,因为长程静电相互作用被屏蔽。在生物系统中,离子特异性是普遍存在的,这对于引入执行生命过程所需的复杂性是必要的。许多特定离子效应属于 Hofmeister 效应范畴,其中阴离子和阳离子的作用强度遵循明确的顺序,与抗衡离子无关。相比之下,在气泡聚并抑制中观察到的特定离子效应取决于离子的组合,并且可以使用 Hofmeister 体系中不明显的简单离子组合规则对这种现象进行编码。在这里,我们表明这些不同的特定离子效应具有相同的起源:它们是由离子对溶液界面的亲和力的变化引起的。平衡亲和力可以解释 Hofmeister 效应,而我们认为,由于在更可变形的气-水界面上发生的动态界面过程,阳离子/阴离子组合控制气泡聚并抑制。