External and Internal Guest Binding of a Highly Charged Supramolecular Host in Water: Deconvoluting the Very Different Thermodynamics

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NMR, UV-vis and isothermal titration calorimetry (ITC) measurements probe different aspects of competing host-guest equilibria as simple alkylammonium guest molecules interact with both the exterior (ion-association) and interior (encapsulation) of the [Ga{sub 4}L{sub 6}]{sup 12-} supramolecular assembly in water. Data obtained by each independent technique measure different components of the host-guest equilibria and only when analyzed together does a complete picture of the solution thermodynamics emerge. Striking differences between the internal and external guest binding are found. External binding is enthalpy driven and mainly due to attractive interactions between the guests and the exterior surface of the assembly while encapsulation ... continued below

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Sgarlata, Carmelo; Mugridge, Jeffrey; Pluth, Michael; Tiedemann,, Bryan; Zito, Valeria; Arena, Giuseppe et al. July 22, 2009.

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NMR, UV-vis and isothermal titration calorimetry (ITC) measurements probe different aspects of competing host-guest equilibria as simple alkylammonium guest molecules interact with both the exterior (ion-association) and interior (encapsulation) of the [Ga{sub 4}L{sub 6}]{sup 12-} supramolecular assembly in water. Data obtained by each independent technique measure different components of the host-guest equilibria and only when analyzed together does a complete picture of the solution thermodynamics emerge. Striking differences between the internal and external guest binding are found. External binding is enthalpy driven and mainly due to attractive interactions between the guests and the exterior surface of the assembly while encapsulation is entropy driven as a result of desolvation and release of solvent molecules from the host cavity.

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  • Journal Name: Journal of the American Chemical Society; Journal Volume: 132

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  • Report No.: LBNL-3415E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 1001081
  • Archival Resource Key: ark:/67531/metadc833186

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  • July 22, 2009

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  • May 19, 2016, 3:16 p.m.

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  • July 26, 2016, 5:43 p.m.

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Sgarlata, Carmelo; Mugridge, Jeffrey; Pluth, Michael; Tiedemann,, Bryan; Zito, Valeria; Arena, Giuseppe et al. External and Internal Guest Binding of a Highly Charged Supramolecular Host in Water: Deconvoluting the Very Different Thermodynamics, article, July 22, 2009; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc833186/: accessed August 19, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.