Charge-induced instabilities of droplets containing macromolecular complexes

Abstract

Solvated macromolecular complexes are ubiquitous in nature, notably in biological systems containing proteins and nucleic acids. Studies of the interactions within a macromolecular complex and between the complex and the solvent in droplet environments are critical for understanding the stability of macromolecular complexes in electrospray ionization (ESI) and nanofluidic experiments. In this study, two distinct cases of macromolecular complexes in aqueous nanodrops are examined by using molecular dynamics simulations: (i) a pair of sodiated poly(ethylene) glycol (PEG) macroions and (ii) a double-stranded DNA (dsDNA). PEG represents a case in which the surface energy of the aqueous droplet is larger than the solvent–macromolecule energy. Conversely, in a droplet solvating dsDNA, the solvent–macromolecule interaction energy overcomes the solvent interaction energy. We report that charge-induced instabilities previously identified for single macroions also appear in the case of complexes, but with a higher level of complexity. In the case of a pair of PEG macroions, we found that their conformations on the surface of a droplet “sense” each other. The charged PEGs are each released from a droplet at different times through contiguous extrusion or drying-out mechanisms. In the case of the DNA, the charge-induced instability manifests as a spine droplet morphology. Narrow regions of the spines promote break down of the hydrogen bonds that hold the dsDNA together. The dsDNA separates into two single strands as it is increasingly exposed to vacuum. These findings elucidate charge-induced instabilities of macromolecular complexes in droplets, which are critical intermediates in ESI and nanofluidic experiments.