Parallel Allosteric Inhibition of Shuttling Motion and Catalysis in a Silver(I)-loaded [2]Rotaxane
Sohom Kundu, Debabrata Mondal, Emad Elramadi, Isa Valiyev, Michael Schmittel
Abstract
A dynamic silver(I)-loaded [2]rotaxane shuttle (k298 = 135 kHz) was converted allosterically into a conformationally restricted [2]rotaxane due to the creation of a bulky imine in the center of the axle component. Only the dynamic silver(I)-loaded [2]rotaxane was able to catalyze a 6-endo-cyclization reaction, whereas the static one was catalytically quiet. The mechanism of catalyst deactivation was elucidated.
Topics & Concepts
RotaxaneChemistryAllosteric regulationCatalysisImineMolecular machineStereochemistryAxlePhotochemistryCombinatorial chemistryNanotechnologyMoleculeOrganic chemistryEnzymeSupramolecular chemistryMaterials scienceMechanical engineeringEngineeringSupramolecular Chemistry and ComplexesMolecular Sensors and Ion DetectionDNA and Nucleic Acid Chemistry