Molecular balances for quantifying non-covalent interactions.
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Dispersion interactions in density-functional theory. Hydrogen-bonding and van der Waals complexes studied by ZEKE and REMPI spectroscopy. Strong solute–solute dispersive interactions in a protein–ligand complex. Van der Waals interactions dominate ligand–protein association in a protein binding site occluded from solvent water. Cyclodextrin inclusion complexes: studies of the variation in the size of alicyclic guests. Evidence for the importance of polarizability in biomimetic catalysis involving cyclophane receptors. Additivity and quantification of dispersive interactions-from cyclopropyl to nitro groups: measurements on porphyrin derivatives. van der Waals interactions in non-polar liquids. Binding mechanisms in supramolecular complexes. Interfaces and the driving force of hydrophobic assembly.
Van der Waals picture of liquids, solids, and phase transformations. Quantifying intermolecular interactions: guidelines for the molecular recognition toolbox. Evidence for van der Waals adhesion in gecko setae. Physicochemical aspects of the action of general anaesthetics. Direct measurement of critical Casimir forces. Hertlein, C., Helden, L., Gambassi, A., Dietrich, S. The Casimir effect in microstructured geometries. Ultrastrong adhesion of graphene membranes. Radial deformation of carbon nanotubes by van der Waals forces.
Overcoming lability of extremely long alkane carbon–carbon bonds through dispersion forces. Storage of methane and freon by interstitial van der Waals confinement. Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals. Similar energetic contributions of packing in the core of membrane and water-soluble proteins. Uber einige Eigenschaften und Anwendungen der Molekularkräfte. The results suggest that theoretical models that implicate important roles for dispersion forces in molecular recognition events should be interpreted with caution in solvent-accessible systems. Instead, it was found that cohesive solvent–solvent interactions are the major driving force behind apolar association in solution. The experimental interaction energies are an order of magnitude smaller than estimates of dispersion forces between alkyl chains that have been derived from vaporization enthalpies and dispersion-corrected calculations. Here, we have used synthetic molecular balances to measure interactions between apolar alkyl chains in 31 organic, fluorous and aqueous solvent environments. Gas-phase measurements and computational methods point to the dominance of dispersion forces in molecular association, but solvent effects complicate the unambiguous quantification of these forces in solution. The emergent properties that arise from self-assembly and molecular recognition phenomena are a direct consequence of non-covalent interactions.
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