Microcalorimetric titration of a tetra-p-sulfonated calix[4]arene with alkylammonium ions in aqueous solution

Stödeman, Magnus; Dhar, N.S.

doi:10.1039/a708413g

Cited by 38 publications

(19 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The sign of the differential heat capacity indicates formally that the transfer of the monovalent cation from the aqueous solution to the macrocycle is an order‐forming or order‐destroying process 48. Both positive and negative values have been reported for guest binding by macrocycles 49. It is generally assumed that hydration of a polar or charged solute is associated with a negative heat capacity, while for the dehydration of polar or ionic groups a positive heat capacity is expected 50.…”

Section: Resultsmentioning

confidence: 99%

“…[48] Both positive and negative values have been reported for guest binding by macrocycles. [49] It is generally assumed that hydration of a polar or charged solute is associated with a negative heat capacity, while for the dehydration of polar or ionic groups a positive heat capacity is expected. [50] Therefore, we attribute the positive heat capacity in the complexation of the alkali metal cations with SC4 tentatively to dehydration of the sulfonato group of the calixarene and the cation itself.…”

Section: Ion-exchange Model For the Complexation Of Other Cationsmentioning

confidence: 99%

See 1 more Smart Citation

The “True” Affinities of Metal Cations to p‐Sulfonatocalix[4]arene: A Thermodynamic Study at Neutral pH Reveals a Pitfall Due to Salt Effects in Microcalorimetry

Francisco¹,

Piñeiro

Nau

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

A microcalorimetric study on the inclusion of monovalent and divalent metal cations by p-sulfonatocalix[4]arene was performed. The thermodynamic parameters for the complexation of alkali metal cations and Ag(+) were obtained for the first time at neutral pH. The Na(+) cation is routinely present as counterion of the calixarene in neutral aqueous solution, and this must be taken into account in the determination of the thermodynamic parameters for the complexation of Na(+) and the other cations by considering a sequential or a competitive binding scheme. The ΔH° and ΔS° values show that the inclusion process is entropically driven, although an influence of the temperature on the complexation reaction indicates that the enthalpic term is also an important contributor. The results also reveal that enthalpy/entropy compensation balances the gain in one contribution against a corresponding loss in the other. The obtained thermodynamic data are in contrast to the results from previous microcalorimetric studies, which showed binding constants that were orders of magnitude smaller and complexations, which were in part enthalpically driven but which neglected the influence of the alkali metal counterions.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Ion-exchange Model For the Complexation Of Other Cationsmentioning

confidence: 99%

The “True” Affinities of Metal Cations to p‐Sulfonatocalix[4]arene: A Thermodynamic Study at Neutral pH Reveals a Pitfall Due to Salt Effects in Microcalorimetry

Francisco¹,

Piñeiro

Nau

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…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%

“…Among these recognition processes, the molecular recognition of calixarenes in aqueous solution seems to be more important because most biological processes occur in aqueous solution. Arena, [5] Stödeman [6,7] and Morel-Desrosiers [8,9] et al have successively investigated the binding behaviors of some p-sulfonatocalix [4]arenes with organic ammonium cations by NMR spectroscopy and microcalorimetry, finding that the sulfonate groups of hosts appear to serve as anchoring points for positively charged guests to give a more stable inclusion complex. Coleman et al [10] examined the binding thermodynamics of p-sulfonatocalix[n]arenes (n = 4, 6 and 8) with amino acids and polypeptides to understand the nature and manner of interactions between the synthetic receptors and glycosylaminoglycan (GAG) receptor sequences.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2005

View full text Add to dashboard Cite

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)

show abstract

“…[25,26] These arise from partial desolvation of the ion groups (ion-pairing). Associated endothermic enthalpies of binding have been ascribed to the energetic cost required to desolvate the charged groups.…”

Section: The Influence Of Tether Chargementioning

confidence: 99%

Complexation of Charged Porphyrins by Charged and Metal‐Chelated EDTA‐Tethered β‐Cyclodextrin Dimers: A Thermodynamic Study on the Influence of Tether Charge and Flexibility on Binding Affinity

Mulder¹,

Huskens²,

Reinhoudt³

2005

Eur J Org Chem

View full text Add to dashboard Cite

Keywords: Cyclodextrins / Molecular recognition / Host-guest systems / PorphyrinoidsComplex formation between charged porphyrin guests and charged or neutral β-cyclodextrin (CD) host dimers linked by ethylenediamine-N,N,NЈ,NЈ-tetraacetate (EDTA) tethers was assessed by microcalorimetry. Two EDTA-tethered CD dimers (1 and 2) were employed to obtain a series of structurally similar CD dimers with different tether charges and flexibilities through either (partial) protonation or metal chelation (with Ca II or Eu III ) of the EDTA tether. Both the tether charge and the flexibility of the CD dimers strongly influenced the binding properties, giving rise to binding constants differing by factors of up to 22. The effect of tether charge was elucidated by the complexation of tetraanionic meso-tetrakis(4-sulfonatophenyl)porphyrin (TSPP) by the different forms of CD dimer 1. Tether charge-dependent complex (de)solvation gave rise to large systematic and counteracting changes in binding enthalpy and entropy, resulting in a binding affinity

show abstract

Microcalorimetric titration of a tetra-p-sulfonated calix[4]arene with alkylammonium ions in aqueous solution

Cited by 38 publications

References 8 publications

The “True” Affinities of Metal Cations to p‐Sulfonatocalix[4]arene: A Thermodynamic Study at Neutral pH Reveals a Pitfall Due to Salt Effects in Microcalorimetry

The “True” Affinities of Metal Cations to p‐Sulfonatocalix[4]arene: A Thermodynamic Study at Neutral pH Reveals a Pitfall Due to Salt Effects in Microcalorimetry

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

Complexation of Charged Porphyrins by Charged and Metal‐Chelated EDTA‐Tethered β‐Cyclodextrin Dimers: A Thermodynamic Study on the Influence of Tether Charge and Flexibility on Binding Affinity

Contact Info

Product

Resources

About