Evidence for partially bound states in cooperative molecular recognition interfaces

CHEKMENEVA, Elena, HUNTER, Christopher A., PACKER, Martin J. and TUREGA, Simon M. (2008). Evidence for partially bound states in cooperative molecular recognition interfaces. Journal of the American Chemical Society, 130 (52), 17718-17725.

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Official URL: http://dx.doi.org/10.1021/ja803434z
Link to published version:: 10.1021/ja803434z

Abstract

A zinc porphyrin equipped with four amide H-bonding sites provides a rigid molecular receptor for the study of cooperative multipoint binding interactions. The interaction of this receptor with a variety of pyridine ligands bearing zero, one, and two H-bonding sites has been studied using UV/vis absorption, 1H and 31P NMR spectroscopy, and isothermal titration calorimetry in five different solvents. The results are analyzed in terms of a bound state that populates an ensemble of different complexes in which zero, one, or two of the potential H-bond interactions are formed. The key parameter that determines the behavior of the system is the product of the association constant for the H-bond interaction, KH, and the effective molarity for the intramolecular interaction, EM. In the system reported here, EM is 0.1−1 M for all of the intramolecular interactions. For strong H-bonds (large KH in nonpolar solvents), all of the interactions are formed in the complex and the fully bound state dominates. In this case, additional binding interactions produce incremental increases in complex stability. However, for weaker H-bonds (small KH in polar solvents), the formation of additional interactions does not lead to an increase in the overall stability of the complex, due to the population of partially bound states.

Item Type: Article
Research Institute, Centre or Group: Biomolecular Sciences Research Centre
Identification Number: 10.1021/ja803434z
Depositing User: Jamie Young
Date Deposited: 30 Jun 2015 12:39
Last Modified: 30 Jun 2015 12:39
URI: http://shura.shu.ac.uk/id/eprint/10024

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