2-O-alkylated para-benzamide α-helix mimetics: the role of scaffold curvature

The design and synthesis of a new 2-O-alklyated benzamide α-helix mimetic is described. Comparison with regioisomeric 3-O-alkylated benzamides permits a preliminary evaluation of the role that mimetic curvature has in determining molecular recognition properties.     

Surface tension curvature correction for fluid–vapour interface by thermodynamics of curved boundary layers

Thermodynamics of curved boundary layers is used to study surface properties of Lennard–Jones fluids and an equation is obtained for the surface tension of the spherical interfaces. The work of cavity formation inside a fluid is utilised to calculate the surface tension. The scaled particle theory (SPT) equation of Pierotti and Stillinger are properly modified. The calculations by the modified Stillinger equation predicts the surface tension in any radius of curvature and the results are in good agreement with the experimental data. But for Pierotti equation, due to low sensitivity to temperature, good agreement obtained only at low temperatures.     

A computational study of cation-π interactions in polycyclic systems: exploring the dependence on the curvature and electronic factors

Density functional theory (B3LYP) calculations with double and triple-ζ quality basis sets were performed on the Li⁺ and Na⁺ π-complexes of corannulene 2, sumanene 3CH₂, heterosumanenes 3X, triphenylene 4 and heterotrindenes 5X. The metal ions bind to both convex and concave faces of buckybowls, with a consistent preference to bind to the convex surface by about 1-4 kcal/mol. The metal ion complexation with the π-framework of the central six-membered ring span wider range compared to benzene, indicating the control of size, curvature and electronic perturbations over the strength of cation-π interactions. Computations show that the bowl-to-bowl inversion barriers are only slightly altered upon metal complexation, indicating the continuity of bowl-to-bowl inversion despite metal complexation. We have calculated the binding energies of model systems, triphenylene (4) and heterotrindenes (5X), which indicate that the interaction energies are controlled by electronic factors. While the inversion barrier is dependent mainly on the size of the heteroatom, the extent of binding is independent of the size of the atom or the bowl depth.