Complexation of the basic amino acids lysine and arginine by three sulfonatocalix[n]arenes (n = 4, 6 and 8) in water: microcalorimetric determination of the Gibbs energies, enthalpies and entropies of complexation

Douteau‐Guével, Nathalie; Coleman, Anthony W.; Morel, Jean‐Pierre; Morel‐Desrosiers, Nicole

doi:10.1039/a806855k

Cited by 152 publications

(163 citation statements)

References 30 publications

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“…In the present study, the T∆S°values are also plotted against the ∆H°values by using the thermodynamic parameters obtained in this work and the published data for water-soluble calix [4]arenes. [5,7,9,10,12,19,28,29] As can be seen from Figure 6, the plot of ∆H°against T∆S°gives an excellent straight line with a correlation coefficient of 0.95. The obtained slope (α) and the intercept (T∆S°) values for water-soluble calix [4]arenes as well as the corresponding values for some natural and synthetic receptors are summarized in Table 3.…”

Section: Enthalpy-entropy Compensationmentioning

confidence: 89%

Molecular Selective Binding of Pyridinium Guest Ions by Water‐Soluble Calix[4]arenes

et al. 2005

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The complex stability constants (KS) and thermodynamic parameters (ΔG°, ΔH°, and TΔS°) for 1:1 intermolecular complexation of water‐soluble calix[4]arene tetrasulfonate (CAS) and thiacalix[4]arene tetrasulfonate (TCAS) with pyridinium guest ions 1–10 have been determined by means of titration calorimetry in an acidic buffer solution (pH = 2.0) at 298.15 K, and their binding modes have been investigated by NMR spectroscopy. Possessing a smaller cavity and a higher π electron density than TCAS, CAS affords the stronger binding abilities for all guests examined, giving an exciting molecular selectivity of up to 354 for the 2,6‐dimethylpyridine/2,6‐pyridinedicarboxylic acid pair. The high binding affinities, attributed to the favorable enthalpic gains, are comprehensively discussed from the viewpoint of π–π stacking, electronic effect and size‐fit relationship between host and guest. The thermodynamic parameters that have been obtained, together with the NMR results, jointly demonstrate that the position, number, and type of substituent groups introduced onto the guest molecule are the key factors controlling the structural‐energetics correlation for the molecular selective binding of water‐soluble calixarenes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Enthalpy-entropy Compensationmentioning

confidence: 89%

Molecular Selective Binding of Pyridinium Guest Ions by Water‐Soluble Calix[4]arenes

et al. 2005

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“…Like others before us, we observe for unmodified Lys significant up-field shifts for b, g, d, and e methylene groups upon complexation with 1 (Figure 2 A). [24,29] These shifts arise due to a "side-on" binding mode that has previously been observed in an X-ray co-crystal structure of Lys and 1.…”

mentioning

confidence: 89%

“…[19,22,24,25] The maximum reported affinity of 1 for any free amino acid under similar buffered conditions is for Arg (K assoc = 1520 m À1 , pH 8, 10 mm phosphate buffer [24] ). Whether comparing to this literature value or to the value we observe under our slightly more competitive experimental conditions (K assoc = 330 m À1 , pH 7.4, 40 mm phosphate buffer), the affinity of 1 for Lys(Me 3 ) is far higher than for any other amino acid.…”

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confidence: 98%

A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

et al. 2009

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“…[7][8][9] The diversity of the applications employing SCnAs is due to a number of favorable properties, including their water solubility, preorganized framework, fascinating binding ability, and especially biological compatibility. [10] As a class of versatile macrocyclic hosts, the SCnA family can efficiently include various guest molecules inside their three-dimensional, flexible, π-election-rich cavities.…”

Section: Introductionmentioning

confidence: 99%

Effect of Lower‐Rim Alkylation of p‐Sulfonatocalix[4]arene on the Thermodynamics of Host–Guest Complexation

et al. 2010

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The complex stability constants (KS) and thermodynamic parameters (ΔH° and TΔS°) for the 1:1 complexation of two water‐soluble calixarenes, p‐sulfonatocalix[4]arene (SC4A) and 5,11,17,23‐tetrasulfonato‐25,26,27,28‐tetrakis(n‐butyl)calix[4]arene (SC4A‐Bu), with organic ammonium cations and neutral spherical organic molecules, have been determined by means of isothermal titration calorimetry (ITC) in aqueous solutions at 298.15 K. The obtained results indicate that, upon complexation with these guests by SC4A‐Bu, the enthalpy changes become less favorable, whereas the entropy changes become more favorable relative to SC4A complexation. These differences can be attributed to differential degrees of desolvation and removal of high‐energy water as well as the change in conformation or conformational degrees of freedom upon complexation. The calorimetric investigations, accompanied by 1H NMR and UV/Vis spectroscopy and X‐ray crystallography provide a thermodynamic explanation for the different complexation behavior of SC4A and SC4A‐Bu towards charged and neutral organic guests. Binding ability and molecular selectivity are discussed from the viewpoint of the conformational geometry and electronic properties of hosts and guests.

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Complexation of the basic amino acids lysine and arginine by three sulfonatocalix[n]arenes (n = 4, 6 and 8) in water: microcalorimetric determination of the Gibbs energies, enthalpies and entropies of complexation

Cited by 152 publications

References 30 publications

Molecular Selective Binding of Pyridinium Guest Ions by Water‐Soluble Calix[4]arenes

Molecular Selective Binding of Pyridinium Guest Ions by Water‐Soluble Calix[4]arenes

A Simple Calixarene Recognizes Post‐translationally Methylated Lysine

Effect of Lower‐Rim Alkylation of p‐Sulfonatocalix[4]arene on the Thermodynamics of Host–Guest Complexation

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