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Interaction Energies and Dynamics of Acid-Base Pairs Isolated in Cavitands.

  作者 Purse, Byron W.;Butterfield, Sara M.;Ballester, Pablo;Shivanyuk, Alexander;Rebek, Julius, Jr.;  
  选自 期刊  Journal of Organic Chemistry;  卷期  2008年73-17;  页码  6480-6488  
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[摘要]reviewed, and their application to the study of salt bridges is introduced. Carboxylate/ammonium ion pairs are generated within an environment that more or less surrounds the functional groups within a synthetic fixed introverted solvent sphere. This is provided by cavitands that fold around amines and present them with a carboxylic acid function. Both org. and water-sol. versions were prepd., and their equil. affinities with quinuclidine bases were detd. by NMR methods. The assocn. consts. range from approx. 103 M-1 in water to more than 105 M-1 in org. solvents. Studies of nitrogen inversion and tumbling of [2.2.2]-diazabicyclooctane within the introverted acids also illustrate the strength of the acid-base interactions. The barriers to in-out exchange of several amine guests were detd. to be in the range from 15 to 24 kcal mol-1. Some parallels with enzymes are drawn: the receptor folds around the guest species, presents them with inwardly directed functionality, and provides a generally hydrophobic environment and a periphery of secondary amide bonds.

 
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