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How much do van der Waals dispersion forces contribute to molecular recognition in solution?
Lixu Yang1, Catherine Adam, Gary S Nichol
11] EaStCHEM School of Chemistry, University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, UK [2].
Nature Chemistry
|November 22, 2013
Summary
Apolar association in solution is driven by solvent cohesion, not dispersion forces. Experimental data reveals interaction energies are much smaller than predicted, challenging current theoretical models for molecular recognition.
Area of Science:
- Supramolecular Chemistry
- Physical Chemistry
- Chemical Thermodynamics
Background:
- Non-covalent interactions govern self-assembly and molecular recognition.
- Dispersion forces are theoretically dominant in molecular association, but solvent effects are complex.
- Quantifying forces in solution requires accounting for solvent interactions.
Purpose of the Study:
- To experimentally measure interaction energies between apolar alkyl chains in various solvents.
- To compare experimental results with theoretical predictions of dispersion forces.
- To elucidate the primary driving forces for apolar association in solution.
Main Methods:
- Utilized synthetic molecular balances for precise interaction measurements.
- Investigated 31 diverse solvent environments, including organic, fluorous, and aqueous media.
- Compared experimental data with dispersion force estimates from vaporization enthalpies and calculations.
Main Results:
- Experimental interaction energies were significantly smaller (by an order of magnitude) than predicted dispersion forces.
- Cohesive solvent-solvent interactions were identified as the dominant driving force for apolar association.
- Dispersion force contributions in solvent-accessible systems are less significant than previously assumed.
Conclusions:
- Solvent cohesive forces, not alkyl chain dispersion, primarily drive apolar association in solution.
- Theoretical models emphasizing dispersion forces in molecular recognition need re-evaluation for solution-phase systems.
- Understanding solvent effects is crucial for accurate predictions of molecular interactions.
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