Intramolecular Electrostatic Interactions Regulate Reactivity of Zwitterionic Functionalities in Amphiphilic Assemblies.
Angew Chem Int Ed Engl
; : e202405868, 2024 Jul 08.
Article
in En
| MEDLINE
| ID: mdl-38977413
ABSTRACT
Consequences of intramolecular ionic interactions in determining the reactivity of functional groups are of interest because they provide insights into how nature deploys seemingly reactive functionalities to be rather ubiquitous. Of specific interest are the quaternary ammonium ions in lipids. In this work, we investigate the effect of intramolecular electrostatic interactions in zwitterionic functionalities by judiciously incorporating them as leaving groups at the α-position of an α,ß-unsaturated ester-based lipid headgroup. We find that electrostatic stabilization indeed plays a critical role in both the reaction kinetics with nucleophiles and the thermodynamics of lipid formation. We further leverage these findings to fabricate both triggerable assembly and disassembly of liposomal supramolecular assemblies in the presence of nucleophiles.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2024
Document type:
Article
Affiliation country:
Estados Unidos