학술논문

Intrinsic and Extrinsic Control of the pKaof Thiol Guests inside Yoctoliter Containers
Document Type
Article
Source
Journal of the American Chemical Society; May 2020, Vol. 142 Issue: 18 p8291-8298, 8p
Subject
Language
ISSN
00027863; 15205126
Abstract
Despite decades of research, there are still many open questions surrounding the mechanisms by which enzymes catalyze reactions. Understanding all the noncovalent forces involved has the potential to allow de novocatalysis design, and as a step toward this, understanding how to control the charge state of ionizable groups represents a powerful yet straightforward approach to probing complex systems. Here we utilize supramolecular capsules assembled via the hydrophobic effect to encapsulate guests and control their acidity. We find that the greatest influence on the acidity of bound guests is the location of the acidic group within the yoctoliter space. However, the nature of the electrostatic field generated by the (remote) charged solubilizing groups also plays a significant role in acidity, as does counterion complexation to the outer surfaces of the capsules. Taken together, these results suggest new ways by which to affect reactions in confined spaces.