Entropy/enthalpy compensation in anion binding: Biotin[6]uril and biotin-L-sulfoxide[6]uril reveal strong solvent dependency

Nicolaj N. Andersen; Kristina Eriksen; Micke Lisbjerg; Mille E. Ottosen; Birgitte Olai Milhøj; Stephan P. A. Sauer; Michael Pittelkow

doi:10.1021/acs.joc.8b02797

Entropy/enthalpy compensation in anion binding: Biotin[6]uril and biotin-L-sulfoxide[6]uril reveal strong solvent dependency

Nicolaj N. Andersen, Kristina Eriksen, Micke Lisbjerg, Mille E. Ottosen, Birgitte Olai Milhøj, Stephan P. A. Sauer, Michael Pittelkow

Department of Chemistry

7 Citations (Scopus)

Abstract

Binding of anions using macrocyclic structures with a nonpolar interior using the CH···anion interaction as the recognition motif has gained popularity in the past few years, and such receptors often rely on a subtle interplay between enthalpic and entropic factors. For these types of receptors solvation of both the anion and the binding pocket of the macrocyclic host play important roles in the overall energetic picture of the binding event. Systematic chemical modifications of synthetic receptors that are able to bind anions in a variety of solvents is an important tool to gain understanding of the factors that determine the supramolecular chemistry of anions. Here we present the chiral macrocyclic structure biotin-l-sulfoxide[6]uril as a host molecule that binds anions in both water and in organic solvents. Biotin-l-sulfoxide[6]uril is prepared in a highly diastereoselective one-pot synthesis from the macrocycle biotin[6]uril. We compare the binding properties with that of biotin[6]uril, also studied in acetonitrile and in aqueous buffer at neutral pH. The biotin-l-sulfoxide[6]uril generally exhibits stronger recognition of anions in acetonitrile, but weaker binding in water as compared to the biotin[6]uril macrocycle. We have studied the binding events using a combination of NMR spectroscopy, isothermal titration calorimetry (ITC), and computational methods.

Original language	English
Journal	The Journal of Organic Chemistry
Volume	84
Issue number	5
Pages (from-to)	2577-2584
Number of pages	8
ISSN	0022-3263
DOIs	https://doi.org/10.1021/acs.joc.8b02797
Publication status	Published - 1 Mar 2019

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@article{1a035d84cf3f4d89838c5cc0cade9c7c,

title = "Entropy/enthalpy compensation in anion binding: Biotin[6]uril and biotin-L-sulfoxide[6]uril reveal strong solvent dependency",

abstract = "Binding of anions using macrocyclic structures with a nonpolar interior using the CH···anion interaction as the recognition motif has gained popularity in the past few years, and such receptors often rely on a subtle interplay between enthalpic and entropic factors. For these types of receptors solvation of both the anion and the binding pocket of the macrocyclic host play important roles in the overall energetic picture of the binding event. Systematic chemical modifications of synthetic receptors that are able to bind anions in a variety of solvents is an important tool to gain understanding of the factors that determine the supramolecular chemistry of anions. Here we present the chiral macrocyclic structure biotin-l-sulfoxide[6]uril as a host molecule that binds anions in both water and in organic solvents. Biotin-l-sulfoxide[6]uril is prepared in a highly diastereoselective one-pot synthesis from the macrocycle biotin[6]uril. We compare the binding properties with that of biotin[6]uril, also studied in acetonitrile and in aqueous buffer at neutral pH. The biotin-l-sulfoxide[6]uril generally exhibits stronger recognition of anions in acetonitrile, but weaker binding in water as compared to the biotin[6]uril macrocycle. We have studied the binding events using a combination of NMR spectroscopy, isothermal titration calorimetry (ITC), and computational methods.",

author = "Andersen, {Nicolaj N.} and Kristina Eriksen and Micke Lisbjerg and Ottosen, {Mille E.} and Milh{\o}j, {Birgitte Olai} and {P. A. Sauer}, Stephan and Michael Pittelkow",

year = "2019",

month = mar,

day = "1",

doi = "10.1021/acs.joc.8b02797",

language = "English",

volume = "84",

pages = "2577--2584",

journal = "The Journal of Organic Chemistry",

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publisher = "American Chemical Society",

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T1 - Entropy/enthalpy compensation in anion binding

T2 - Biotin[6]uril and biotin-L-sulfoxide[6]uril reveal strong solvent dependency

AU - Andersen, Nicolaj N.

AU - Eriksen, Kristina

AU - Lisbjerg, Micke

AU - Ottosen, Mille E.

AU - Milhøj, Birgitte Olai

AU - P. A. Sauer, Stephan

AU - Pittelkow, Michael

PY - 2019/3/1

Y1 - 2019/3/1

N2 - Binding of anions using macrocyclic structures with a nonpolar interior using the CH···anion interaction as the recognition motif has gained popularity in the past few years, and such receptors often rely on a subtle interplay between enthalpic and entropic factors. For these types of receptors solvation of both the anion and the binding pocket of the macrocyclic host play important roles in the overall energetic picture of the binding event. Systematic chemical modifications of synthetic receptors that are able to bind anions in a variety of solvents is an important tool to gain understanding of the factors that determine the supramolecular chemistry of anions. Here we present the chiral macrocyclic structure biotin-l-sulfoxide[6]uril as a host molecule that binds anions in both water and in organic solvents. Biotin-l-sulfoxide[6]uril is prepared in a highly diastereoselective one-pot synthesis from the macrocycle biotin[6]uril. We compare the binding properties with that of biotin[6]uril, also studied in acetonitrile and in aqueous buffer at neutral pH. The biotin-l-sulfoxide[6]uril generally exhibits stronger recognition of anions in acetonitrile, but weaker binding in water as compared to the biotin[6]uril macrocycle. We have studied the binding events using a combination of NMR spectroscopy, isothermal titration calorimetry (ITC), and computational methods.

AB - Binding of anions using macrocyclic structures with a nonpolar interior using the CH···anion interaction as the recognition motif has gained popularity in the past few years, and such receptors often rely on a subtle interplay between enthalpic and entropic factors. For these types of receptors solvation of both the anion and the binding pocket of the macrocyclic host play important roles in the overall energetic picture of the binding event. Systematic chemical modifications of synthetic receptors that are able to bind anions in a variety of solvents is an important tool to gain understanding of the factors that determine the supramolecular chemistry of anions. Here we present the chiral macrocyclic structure biotin-l-sulfoxide[6]uril as a host molecule that binds anions in both water and in organic solvents. Biotin-l-sulfoxide[6]uril is prepared in a highly diastereoselective one-pot synthesis from the macrocycle biotin[6]uril. We compare the binding properties with that of biotin[6]uril, also studied in acetonitrile and in aqueous buffer at neutral pH. The biotin-l-sulfoxide[6]uril generally exhibits stronger recognition of anions in acetonitrile, but weaker binding in water as compared to the biotin[6]uril macrocycle. We have studied the binding events using a combination of NMR spectroscopy, isothermal titration calorimetry (ITC), and computational methods.

U2 - 10.1021/acs.joc.8b02797

DO - 10.1021/acs.joc.8b02797

M3 - Journal article

C2 - 30721069

SN - 0022-3263

VL - 84

SP - 2577

EP - 2584

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 5

ER -

Entropy/enthalpy compensation in anion binding: Biotin[6]uril and biotin-L-sulfoxide[6]uril reveal strong solvent dependency

Abstract

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