Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Towards Rapid Environmental Assessment and Coastal Forecasting in the Northern Adriatic Sea

A new Coastal Rapid Environmental Assessment (CREA) strategy has been developed and successfully applied to the Northern Adriatic Sea. CREA strategy exploits the recent advent of operational oceanography to establish a CREA system based on an operational regional forecasting system and coastal monitoring networks of opportunity. The methodology wishes to initialize a coastal high resolution model, nested within the regional forecasting system, blending the large scale parent model fields with the available coastal observations to generate the requisite field estimates. CREA modeling system consists of a high resolution, O(800m), Adriatic SHELF model (ASHELF) implemented into the Northern Adriatic basin and nested within the Adriatic Forecasting System (AFS) (Oddo et al. 2006). The observational system is composed by the coastal networks established in the framework of ADRICOSM (ADRiatic sea integrated COastal areaS and river basin Managment system) Pilot Project. An assimilation technique exerts a correction of the initial field provided by AFS on the basis of the available observations. The blending of the two data sets has been carried out through a multi-scale optimal interpolation technique developed by Mariano and Brown (1992). Two CREA weekly exercises have been conducted: the first, at the beginning of May (spring experiment); the second in middle August (summer experiment). The weeks have been chosen looking at the availability of all coastal observations in the initialization day and one week later to validate model results, verifying our predictive skills. ASHELF spin up time has been investigated too, through a dedicated experiment, in order to obtain the maximum forecast accuracy within a minimum time. Energetic evaluations show that for the Northern Adriatic Sea and for the forcing applied, a spin-up period of one week allows ASHELF to generate new circulation features enabled by the increased resolution and its total kinetic energy to establish a new dynamical balance. CREA results, evaluated by mean of standard statistics between ASHELF and coastal CTDs, show improvement deriving from the initialization technique and a good model performance in the coastal areas of the Northern Adriatic basin, characterized by a shallow and wide continental shelf subject to substantial freshwater influence from rivers. Results demonstrate the feasibility of our CREA strategy to support coastal zone management and wish an additional establishment of operational coastal monitoring activities to advance it.

Energy-efficient Communication and Estimation in Wireless Sensor Networks

This thesis focuses on the energy efficiency in wireless networks under the transmission and information diffusion points of view. In particular, on one hand, the communication efficiency is investigated, attempting to reduce the consumption during transmissions, while on the other hand the energy efficiency of the procedures required to distribute the information among wireless nodes in complex networks is taken into account. For what concerns energy efficient communications, an innovative transmission scheme reusing source of opportunity signals is introduced. This kind of signals has never been previously studied in literature for communication purposes. The scope is to provide a way for transmitting information with energy consumption close to zero. On the theoretical side, starting from a general communication channel model subject to a limited input amplitude, the theme of low power transmission signals is tackled under the perspective of stating sufficient conditions for the capacity achieving input distribution to be discrete. Finally, the focus is shifted towards the design of energy efficient algorithms for the diffusion of information. In particular, the endeavours are aimed at solving an estimation problem distributed over a wireless sensor network. The proposed solutions are deeply analyzed both to ensure their energy efficiency and to guarantee their robustness against losses during the diffusion of information (against information diffusion truncation more in general).

Reproductive and developmental toxicity study using Sprague-Dawley rats exposed under various calendars to the weedkiller Glyphosate and commercial formulations Glyphosate-based

Glyphosate-based herbicides (GBHs) are the most globally used herbicides raising the risk of environmental exposition. Carcinogenic effects are only one component of the multiple adverse health effects of Glyphosate and GBHs that have been reported. Questions related to hazards and corresponding risks identified in relation to endocrine disrupting effects are rising. The present study investigated the possible reproductive/developmental toxicity of GBHs administered to male and female Sprague-Dawley rats under various calendar of treatment. Assessments included maternal and reproductive outcome of F0 and F1 dams exposed to GBHs throughout pregnancy and lactation and developmental landmarks and sexual characteristics of offspring. The study was designed in two stages. In the first stage Glyphosate, or its commercial formulation Roundup Bioflow, was administered to rats at the dose of 1.75 mg/kg bw/day (Glyphosate US Acceptable Daily Intake) from the prenatal period until adulthood. In the second stage, multiple toxicological parameters were simultaneously assessed, including multigeneration reproductive/developmental toxicity of Glyphosate and two GBHs (Roundup Bioflow and Ranger Pro). Man-equivalent doses, beginning from 0.5 mg/kg bw/day (ADI Europe) up to 50 mg/kg bw/day (NOAEL Glyphosate), were administered to male and female rats, covering specific windows of biological susceptibility. The results of stage 1 and preliminary data from stage 2 experiments characterize GBHs as probable endocrine disruptors as suggested by: 1) androgen-like effects of Roundup Bioflow, including a significant increase of anogenital distances in both males and females, delay of first estrous and increased testosterone in females; 2) slight puberty onset anticipation in the high dose of Ranger Pro group, observed in the F1 generation treated from in utero life until adulthood; 3) a delayed balano-preputial separation achievement in the high dose of Ranger Pro-treated males exposed only during the peri-pubertal period, indicating a direct and specific effect of GBHs depending on the timing of exposure.