Inclusion complexes of alcohols with ?-cyclodextrin

Experimental Binding Energies in Supramolecular Complexes

“…Because the hydrophobic influence was eliminated by use of accurate experimental solvation free energies, it can be unambiguously concluded that dispersion interactions are energetically important in supramolecular complexes, even for poorly polarizable hosts, contrasting molecular-balance based studies with empirical solvent-effect corrections that reported the opposite. 226,466 Binding studies with a series of open-chain alcohols binding to α-cyclodextrin (α-CD) gave a free energy binding increment for a methylene group of ΔΔG = −3.0 kJ/mol (ΔΔH = −3.8 kJ/mol and Δ(−TΔS) = 0.8 kJ/mol); 596,644 similar correlations were found with alkanesulfonate ions, aliphatic amines, and α-amino acids. 645 CH 2 -binding increments ΔΔG determined for the larger host β-CD and ionized and nonionized carboxylic acids are very similar, 2.5 and 3.3 kJ/mol, respectively.…”

“…Binding studies with a series of open-chain alcohols binding to α-cyclodextrin (α-CD) gave a free energy binding increment for a methylene group of ΔΔ G = −3.0 kJ/mol (ΔΔ H = −3.8 kJ/mol and Δ­(− T Δ S ) = 0.8 kJ/mol); , similar correlations were found with alkanesulfonate ions, aliphatic amines, and α-amino acids . CH 2 -binding increments ΔΔ G determined for the larger host β-CD and ionized and nonionized carboxylic acids are very similar, 2.5 and 3.3 kJ/mol, respectively .…”

Energetic and Kinetic Control Aspects to Explain the Performances and Elucidate the Mechanisms of Oriented Membrane Processes for Extraction and Recovery of Glycerol Compound

“…But the movement associated with the migration of the substrate molecules across each of the adopted PIM membranes is conducted by successive equilibrium reactions (association/dissociation): Understanding the phenomenon related to the host–guest complexes has been a long and important aspect of chemistry physics and of course in many related fields where this phenomenon plays an important role. Because of the large number of particles forming these systems and to the variety of different interactions established, computer simulations represent particularly adequate theoretical tools for understanding and predicting the physicochemical properties of these complexes at the microscopic level. , Possible interactions between the glycerol molecules and the used extractive agents are numerous, whereas the capacity of the extractive agent (host) to react selectively with the glycerol molecule (guest) in solution is an important operation for the search of selective processes. It is known that chemical structure of an extractive agent plays a major role in selectivity processes by influencing the stability and the nature of “host–guest” complexes formed in the membrane phase.…”

“…Because of the large number of particles forming these systems and to the variety of different interactions established, computer simulations represent particularly adequate theoretical tools for understanding and predicting the physicochemical properties of these complexes at the microscopic level. 42,43 Possible interactions between the glycerol molecules and the used extractive agents are numerous, whereas the capacity of the extractive agent (host) to react selectively with the glycerol molecule (guest) in solution is an important operation for the search of selective processes. It is known that chemical structure of an extractive agent plays a major role in selectivity processes by influencing the stability and the nature of "host− guest" complexes formed in the membrane phase.…”

Thermodynamics of Supramolecular Structure Formation in Water

“…According to the classical theory of hydrophobic interactions (Frank & Evans, 1945), the driving force of the attractive interaction should be entropic gain due to increased freedoms of water molecules. It is puzzling, however, that hydrophobic effects are enthalpy-driven in some cases (Ross & Subramanian, 1981;Gelb et al, 1981;Smithrud et al, 1991;Spencer et al, 1995;Arena et al, 2000) and entropy-driven in others (Hooley et al, 2007;Iwamoto et al, 2007;Whitesides & Krishnamurthy, 2005, Sgarlata et. al., 2010.…”