Intrinsic and Extrinsic Control of the pKa of Thiol Guests inside Yoctoliter Containers.
J Am Chem Soc
; 142(18): 8291-8298, 2020 05 06.
Article
en En
| MEDLINE
| ID: mdl-32271561
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 novo catalysis 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.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Año:
2020
Tipo del documento:
Article
País de afiliación:
Estados Unidos