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Title: High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions

Abstract

Isotope effects (IEs) are a powerful tool for examining the reactivity of, and interactions between, molecules. Recently, secondary IEs have been used to probe the nature of noncovalent interactions between guest and host molecules in supramolecular systems. While these studies can provide valuable insight into the specific interactions governing guest recognition and binding properties, IEs on noncovalent interactions are often very small and difficult to measure precisely. The Perrin group has developed an NMR titration method capable of determining ratios of equilibrium constants with remarkable precision. They have used this technique to study small, secondary equilibrium isotope effects (EIEs) on the acidity of carboxylic acids and phenols and on the basicity of amines, measuring differences down to thousandths of a pK{sub a} unit. It occurred to us that this titration method can in principle measure relative equilibrium constants for any process which is fast on the NMR timescale and for which the species under comparison are distinguishable by NMR. Here we report the application of this method to measure very small EIEs on noncovalent host-guest interactions in a supramolecular system.

Authors:
; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
1001080
Report Number(s):
LBNL-3416E
Journal ID: ISSN 0002-7863; JACSAT; TRN: US201101%%821
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 132; Related Information: Journal Publication Date: 2011; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37; ACCURACY; AMINES; CARBOXYLIC ACIDS; ISOTOPE EFFECTS; PH VALUE; PHENOLS; PROBES; TITRATION

Citation Formats

Mugridge, Jeffrey S, Bergman, Robert G, and Raymond, Kenneth N. High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions. United States: N. p., 2009. Web.
Mugridge, Jeffrey S, Bergman, Robert G, & Raymond, Kenneth N. High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions. United States.
Mugridge, Jeffrey S, Bergman, Robert G, and Raymond, Kenneth N. 2009. "High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions". United States. https://www.osti.gov/servlets/purl/1001080.
@article{osti_1001080,
title = {High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions},
author = {Mugridge, Jeffrey S and Bergman, Robert G and Raymond, Kenneth N},
abstractNote = {Isotope effects (IEs) are a powerful tool for examining the reactivity of, and interactions between, molecules. Recently, secondary IEs have been used to probe the nature of noncovalent interactions between guest and host molecules in supramolecular systems. While these studies can provide valuable insight into the specific interactions governing guest recognition and binding properties, IEs on noncovalent interactions are often very small and difficult to measure precisely. The Perrin group has developed an NMR titration method capable of determining ratios of equilibrium constants with remarkable precision. They have used this technique to study small, secondary equilibrium isotope effects (EIEs) on the acidity of carboxylic acids and phenols and on the basicity of amines, measuring differences down to thousandths of a pK{sub a} unit. It occurred to us that this titration method can in principle measure relative equilibrium constants for any process which is fast on the NMR timescale and for which the species under comparison are distinguishable by NMR. Here we report the application of this method to measure very small EIEs on noncovalent host-guest interactions in a supramolecular system.},
doi = {},
url = {https://www.osti.gov/biblio/1001080}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = ,
volume = 132,
place = {United States},
year = {Tue Jun 23 00:00:00 EDT 2009},
month = {Tue Jun 23 00:00:00 EDT 2009}
}