Molecular modeling has revealed that the presence of charged macromolecules (macroions) in liquid droplets dramatically changes the pathways of droplet fission. These mechanisms are not captured by the traditional theories such as ion-evaporation and charge-residue models. We review the general mechanisms by which macroions emerge from droplets and the factors that determine the droplet fission. These mechanisms include counter-intuitive "star" droplet formations and extrusion of linear macroions from droplets. These findings may play a direct role in determining macromolecule charge states in electrospray mass spectrometry experiments. (C) 2016 Elsevier B.V. All rights reserved.