CAMARA-CAMPOS, Amaya, MUSUMECI, Daniele, HUNTER, Christopher A. and TUREGA, Simon (2009). Chemical double mutant cycles for the quantification of cooperativity in H-bonded complexes. Journal of the American Chemical Society, 131 (51), 18518-18524.Full text not available from this repository.
Chemical double mutant cycles have been used in conjunction with new H-bonding motifs for the quantification of chelate cooperativity in multiply H-bonded complexes. The double mutant cycle approach specifically deals with the effects of substituents, secondary interactions, and allosteric cooperativity on the free energy contributions from individual H-bond sites and allows dissection of the free energy contribution due to chelate cooperativity associated with the formation of intramolecular noncovalent interactions. Two different doubly H-bonded motifs were investigated in carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane, and cyclohexane, and the results were similar in all cases, with effective molarities of 3−33 M for formation of intramolecular H-bonds. This corresponds to a free energy penalty of 3−9 kJ mol−1 for formation of a bimolecular complex in solution, which is consistent with previous estimates of 6 kJ mol−1. This result can be used in conjunction with the H-bond parameters, α and β, to make a reasonable estimate of the stability constant for formation of a multiply H-bonded complex between two perfectly complementary partners, or to place an upper limit on the stability constant expected for a less complementary system.
|Additional Information:||Publication Date (Web): November 30, 2009|
|Research Institute, Centre or Group:||Biomolecular Sciences Research Centre|
|Depositing User:||Jamie Young|
|Date Deposited:||30 Jun 2015 12:47|
|Last Modified:||30 Jun 2015 12:47|
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