Towards the Discrimination of Carboxylates by Hydrogen-Bond Donor Anion Receptors

Kadam, S. A., Martin, K., Haav, K., Toom, L., Mayeux, C., Pung, A., Gale, Philip A., Hiscock, Jennifer R., Brooks, Simon J., Kirby, Isabelle L., and others. (2015) Towards the Discrimination of Carboxylates by Hydrogen-Bond Donor Anion Receptors. Chemistry - A European Journal, 21 (13). pp. 5145-5160. ISSN 0947-6539. (doi:10.1002/chem.201405858) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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https://doi.org/10.1002/chem.201405858

Abstract

The binding constants (log?Kass) of small synthetic receptor molecules based on indolocarbazole, carbazole, indole, urea and some others, as well as their combinations were measured for small carboxylate anions of different basicity, hydrophilicity and steric demands, that is, trimethylacetate, acetate, benzoate and lactate, in 0.5?% H2O/[D6]DMSO by using the relative NMR?based measurement method. As a result, four separate binding affinity scales (ladders) including thirty?eight receptors were obtained with the scales anchored to indolocarbazole. The results indicate that the binding strength is largely, but not fully, determined by the strength of the primary hydrogen?bonding interaction. The latter in turn is largely determined by the basicity of the anion. The higher is the basicity of the anion the stronger in general is the binding, leading to the approximate order of increasing binding strength, lactate<benzoate<acetate?trimethylacetate, which holds with all investigated receptors. Nevertheless, there are a number of occasions when the binding order changes with changing of the carboxylate anion, sometimes quite substantially. Principal component analysis (PCA) reveals that this is primarily connected to preferential binding of trimethylacetate, supposedly caused by an additional hydrophobic/solvophobic interaction. These findings enable making better predictions, which receptor framework or cavity is best suited for carboxylate anions in receptor design.

Item Type: Article
DOI/Identification number: 10.1002/chem.201405858
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences
Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Jennifer Hiscock
Date Deposited: 07 Dec 2018 17:30 UTC
Last Modified: 30 May 2019 08:31 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/70843 (The current URI for this page, for reference purposes)
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