Molecular approaches to smart materials via interface recognition and conformationally switchable cavitands

In this thesis the molecular level design of functional materials and systems is reported. In the first part, tetraphosphonate cavitand (Tiiii) recognition properties towards amino acids are studied both in the solid state, through single crystal X-ray diffraction, and in solution, via NMR and ITC experiments. The complexation ability of these supramolecular receptors is then applied to the detection of biologically remarkable N-methylated amino acids and peptides using complex dynamic emulsions-based sensing platforms. In the second part, a general supramolecular approach for surface decoration with single-molecule magnets (SMMs) is presented. The self-assembly of SMMs is achieved through the formation of a multiple hydrogen bonds architecture (UPy-NaPy complexation). Finally we explore the possibility to impart auxetic behavior to polymeric material through the introduction of conformationally switchable monomers, namely tetraquinoxaline cavitands (QxCav). Their interconversion from a closed vase conformation to an extended kite form is studied first in solution, then in polymeric matrixes via pH and tensile stimuli by UV-Vis spectroscopy.

Photonic crystal fibers design for 2 μm wavelenght operation

New photonic crystal fiber designs are presented and numerically investigated in order to improve the state of art of high power fiber lasers. The focus of this work is targeted on the region of 2 μm laser emission, which is of high interest due to its eye-safe nature and due to the large amount of applications permitted. Thulium doped fiber amplifiers are suitable for emitting in this region. Different fiber designs have been proposed, both flexible and rod-type, with the aim to enlarge mode area while maintaining robust single mode operation. The analysis of thermal effects, caused by the high thulium quantum defect, have been taken in consideration. Solutions to counteract issues derived by detrimental thermal effects have been implemented.