Contribution of Non-Covalent Interactions and Electronic Effects on the Conformational Landscape and Tautomeric Equilibria of Molecules and Molecular Complexes: Structural and Dynamical Data from Rotational Spectroscopy

This thesis concerns the study of complex conformational surfaces and tautomeric equilibria of molecules and molecular complexes by quantum chemical methods and rotational spectroscopy techniques. In particular, the focus of this research is on the effects of substitution and noncovalent interactions in determining the energies and geometries of different conformers, tautomers or molecular complexes. The Free-Jet Absorption Millimeter Wave spectroscopy and the Pulsed-Jet Fourier Transform Microwave spectroscopy have been applied to perform these studies and the obtained results showcase the suitability of these techniques for the study of conformational surfaces and intermolecular interactions. The series of investigations of selected medium-size molecules and complexes have shown how different instrumental setups can be used to obtain a variety of results on molecular properties. The systems studied, include molecules of biological interest such as anethole and molecules of astrophysical interest such as N-methylaminoethanol. Moreover halogenation effects have been investigated on halogen substituted tautomeric systems (5-chlorohydroxypyridine and 6-chlorohydroxypyridine), where it has shown that the position of the inserted halogen atom affects the prototropic equilibrium. As for fluorination effects, interesting results have been achieved investigating some small complexes where a molecule of water is used as a probe to reveal the changes on the electrostatic potential of different fluorinated compounds: 2-fluoropyridine, 3-fluoropyridine and penta-fluoropyridine. While in the case of the molecular complex between water and 2-fluoropyridine and 3-fluoropyridine the geometry of the complex with one water molecule is analogous to that of pyridine with the water molecule linked to the pyridine nitrogen, the case of pentafluoropyridine reveals the effect of perfluorination and the water oxygen points towards the positive center of the pyridine ring. Additional molecular adducts with a molecule of water have been analyzed (benzylamine-water and acrylic acid-water) in order to reveal the stabilizing driving forces that characterize these complexes.

Landscape and well-being: a scoping study on the health-promoting impact of outdoor environments

OBJECTIVES: The present literature review conceptualises landscape as a health resource that promotes physical, mental, and social well-being. Different health-promoting landscape characteristics are discussed. METHODS: This article is based on a scoping study which represents a special kind of qualitative literature review. Over 120 studies have been reviewed in a five-step-procedure, resulting in a heuristic device. RESULTS: A set of meaningful pathways that link landscape and health have been identified. Landscapes have the potential to promote mental well-being through attention restoration, stress reduction, and the evocation of positive emotions; physical well-being through the promotion of physical activity in daily life as well as leisure time and through walkable environments; and social well-being through social integration, social engagement and participation, and through social support and security. CONCLUSION: This scoping study allows us to systematically describe the potential of landscape as a resource for physical, mental and social well-being. A heuristic framework is presented that can be applied in future studies, facilitating systematic and focused research approaches and informing practical public health interventions.