Functional photoactive and electroactive nanodevices

Most of current ultra-miniaturized devices are obtained by the top-down approach, in which nanoscale components are fabricated by cutting down larger precursors. Since this physical-engineering method is reaching its limits, especially for components below 30 nm in size, alternative strategies are necessary. Of particular appeal to chemists is the supramolecular bottom-up approach to nanotechnology, a methodology that utilizes the principles of molecular recognition to build materials and devices from molecular components. The subject of this thesis is the photophysical and electrochemical investigation of nanodevices obtained harnessing the principles of supramolecular chemistry. These systems operate in solution-based environments and are investigated at the ensemble level. The majority of the chemical systems discussed here are based on pseudorotaxanes and catenanes. Such supramolecular systems represent prototypes of molecular machines since they are capable of performing simple controlled mechanical movements. Their properties and operation are strictly related to the supramolecular interactions between molecular components (generally photoactive or electroactive molecules) and to the possibility of modulating such interactions by means of external stimuli. The main issues addressed throughout the thesis are: (i) the analysis of the factors that can affect the architecture and perturb the stability of supramolecular systems; (ii) the possibility of controlling the direction of supramolecular motions exploiting the molecular information content; (iii) the development of switchable supramolecular polymers starting from simple host-guest complexes; (iv) the capability of some molecular machines to process information at molecular level, thus behaving as logic devices; (v) the behaviour of molecular machine components in a biological-type environment; (vi) the study of chemically functionalized metal nanoparticles by second harmonic generation spectroscopy.

Potential Analysis for Hypoelliptic Second Order PDEs with Nonnegative Characteristic Form

In this Thesis we consider a class of second order partial differential operators with non-negative characteristic form and with smooth coefficients. Main assumptions on the relevant operators are hypoellipticity and existence of a well-behaved global fundamental solution. We first make a deep analysis of the L-Green function for arbitrary open sets and of its applications to the Representation Theorems of Riesz-type for L-subharmonic and L-superharmonic functions. Then, we prove an Inverse Mean value Theorem characterizing the superlevel sets of the fundamental solution by means of L-harmonic functions. Furthermore, we establish a Lebesgue-type result showing the role of the mean-integal operator in solving the homogeneus Dirichlet problem related to L in the Perron-Wiener sense. Finally, we compare Perron-Wiener and weak variational solutions of the homogeneous Dirichlet problem, under specific hypothesis on the boundary datum.

Musical tension in harmonic intervals: behavioral and neural correlates

Musical tension is what drives our emotional experience in music listening. However, the specific role of the musical elements involved in tension-resolution perception remains largely unclear. This dissertation aims to advance the understanding of tension perception dynamics related to sensory consonance-dissonance. The first experiment aimed to design and validate a new crossmodal proprioceptive device for tension rating that overcomes some of the limitations of known tools. As a result, a psychophysical equation for the matching of physical force and psychological force was presented. The same tool was subsequently used in the second and third experiments to collect ratings of perceived tension and movement in harmonic musical intervals and standard noises. Besides, a visual analog scale (VAS) was used to allow a comparison of these two methods. The results confirmed the close relationship between sensory dissonance and perceived tension. Moreover, stimuli in the higher pitch register were perceived as more tense, confirming the primary role of pitch as a mediator of tension. The comparison between ratings obtained with the proprioceptive device and the VAS highlighted the tendency to give higher tension ratings using the VAS compared to the proprioceptive device. In the last experiment, brain electrical activity was recorded during the presentation of short tension-resolution patterns created using the most tense (perfect unison, fourth, and fifth) and the least tense harmonic intervals (augmented fourth, minor second, and inverted major seventh) to understand how consonance-dissonance can convey meaningful information on perceived tension-resolution. Results showed overall larger effects during the ‘resolution’ condition compare to the ‘tension induction’ condition, indicating that the resolution of harmonic instability towards a state of stability may be more salient than its opposite. A late positive component (LPC) was elicited, possibly reflecting deeper processing of tension-related meaning within a minimal harmonic context.