Less Noble or More Noble: How Strain Affects the Binding of Oxygen on Gold.

Many heterogeneous catalysts exploit strained active layers to modulate reactivity and/or selectivity. It is therefore significant that density functional theory, as well as experimental approaches, find that tensile strain makes the gold surface more binding for oxygen, in other words, less noble. We show that this behavior does not apply when re-structuring of the gold surface is allowed to occur simultaneously with the adsorption of oxygen. In situ cantilever-bending studies show the surface stress to increase when oxygen species adsorb on a (111)-textured gold surface in aqueous H2 SO4 . This implies a positive sign of the electrocapillary coupling parameter and, hence, a trend for weaker oxygen binding in response to tensile strain. These conflicting findings indicate that different electrosorption processes, and specifically oxygen species adsorption on the bulk-terminated surface, exhibit fundamentally different coupling between the chemistry and the mechanics of the surface.

Toward enzyme-responsive polymersome drug delivery.

In drug delivery, enzyme-responsive drug carriers are becoming increasingly relevant because of the growing association of disease pathology with enzyme overexpression. Polymersomes are of interest to such applications because of their tunable properties. While polymersomes open up a wide range of chemical and physical properties to explore, they also present a challenge in developing generalized rules for the synthesis of novel systems. Motivated by this issue, in this perspective, we summarize the existing knowledge on enzyme-responsive polymersomes and outline the main design choices. Then, we propose heuristics to guide the design of novel systems. Finally, we discuss the potential of an integrated approach using computer simulations and experimental studies to streamline this design process and close the existing knowledge gaps.