Environmentally Sustainable Design of Innovative Chemical Processes and Synthetic Methods Focused on the Synthesis of Novel Molecular Libraries

Questa tesi è mirata ad essere un lavoro che racchiude alcuni dei vari aspetti rilevanti che collegano la Green Chemistry alla sostenibilità ambientale. La tesi riguarda lo sviluppo sostenibile attraverso capitoli che concorrono alla progettazione di processi chimici eco-compatibili innovativi e approcci verdi per ridurre al minimo e/o rimediare l'inquinamento ambientale. In questo contesto, il mio progetto di dottorato ha affrontato tre temi principali: 1. Progettazione, sintesi e caratterizzazione di nuove molecole di tensioattivo che impiegano materie prime rinnovabili, acido itaconico e ammine lipofile, come materiali di partenza; il Capitolo 2 descrive questo argomento. 2. Sviluppo di una procedura sostenibile finalizzata alla sintesi multicomponente a cascata di biarilcalconi in acqua pura o in condizioni di catalisi micellare; in quest'ultimo caso, uno dei tensioattivi precedentemente sintetizzati è stato ampiamente impiegato; il Capitolo 5 descrive questo argomento. Capitolo 3 e Capitolo 4 descrivono il contesto scientifico e le innovazioni più importanti che hanno aperto la strada a i risultati conseguiti durante il 2 ° anno del corso di dottorato; il primo è una panoramica sull'uso dell'acqua come solvente per reazioni organiche; il secondo è una panoramica sulle reazioni di cross-coupling e lo sfruttamento in questo contesto della catalisi micellare. 3. Progettazione, sintesi e impiego di ligandi di tipo fenantrolinico deuterati per l'ossidazione aerobica palladio catalizzata del metil-glucoside, consentendo un elevato miglioramento della prestazione in questa reazione impegnativa; il Capitolo 7 raccoglie i risultati ottenuti, mentre il capitolo 6 riassume i più importanti progressi ottenuti negli ultimi anni nelle ossidazioni aerobiche di alcoli palladio-catalizzate.This thesis is intended to be a work that encompasses some of the various relevant aspects linking the Green Chemistry practice to environmental sustainability. The thesis covers sustainable development through chapters that contribute to the design of novel environmentally benign chemical processes and green approaches to minimize and/or remediate environmental pollution. In this context, my PhD project has faced three main topics: 1. Design, synthesis and characterization of new surfactant molecules employing renewable feedstocks, itaconic acid and fatty amines, as starting materials; Chapter 2 describes this topic. 2. Development of a sustainable procedure aimed to the multicomponent cascade synthesis of biaryl-based chalcones in pure water or under micellar catalysis conditions; in the latter case, one of the surfactants previously synthesized has been widely employed; Chapter 5 describes this topic. Chapter 3 and Chapter 4 describe the scientific context and the most important innovations that have paved the way to the results achieved during the 2nd year of PhD course; the former is an overview on the use of water as solvent for organic reactions; the latter is an overview on cross-coupling reactions and the exploitation in this context of micellar catalysis. 3. Design, synthesis and exploitation of deuterated phenanthroline-type ligands for the aerobic palladium-catalyzed oxidation of methyl glucoside, allowing a high performance improvement in this challenging reaction; Chapter 7 collects the obtained results, while Chapter 6 summarizes the most important advances obtained in the last years in the palladium-catalyzed aerobic oxidations of alcohols

design of passive ring resonators to be used for sensing applications

In this paper we report on the effects of two optical beams counterpropagating in a passive ring resonator that is the building block of a lot of sensing applications. By using the transfer matrix method in combination with the coupled mode theory, the analytical expressions of the power transfer functions for drop and through port configurations are derived in both cases of single beam and double beams inside the ring. The implemented model has shown some improvements in the resonator performance, such as the increase of the transmission power and the reduction of the linewidth, when the interaction between the two beams is considered, with respect to the single beam ring resonator configuration

Three-dimensional modelling of scattering loss in InGaAsP/InP and silica-on-silicon bent waveguides

A three-dimensional (3D) method for the estimation of scattering loss due to sidewalls roughness in bent optical waveguides is proposed and validated. The approach, based on Volume Current Method (VCM), has been pointed out to accurately calculate the scattering loss as dependent on curvature radius and wavelength. An exponential model has been employed to analytically describe the sidewalls roughness and a 3D mode solver based on mode-matching method has been used to calculate optical field distribution in the bent waveguide cross-section. Scattering loss suffered by two low index contrast waveguides has been investigated by the developed algorithm. For a buried InGaAsP/InP waveguide and a 6 μm x 6 μm Silica-on-Silicon guiding structure scattering loss dependence on bending radius, wavelength, roughness, correlation length and standard deviation has been investigated and discussed. Because of the different index contrast values, InGaAsP/InP waveguide exhibits a scattering loss which is quite six times larger than in Silica-on-Silicon. For both guiding structures, quasi-TM mode shows a larger scattering loss than quasi-TE one

The pattern of structural change: testing the product space framework

The set of available local “capabilities” determines what an economy produces today (its static comparative advantage) and, at the same time, defines the trajectories that the process of structural change may take in the future. The product space (PS) framework developed in recent seminal works by economists and physicists suggests that path-dependence characterizes the evolution of the production basket (Hausmann and Klinger, 2007, Harvard University Center for International Development Working Paper #146; Hidalgo et al., 2007, Science Magazine, 317(5837), 482–487). These authors represent economies as sets of productive capabilities that can be combined in different ways to produce different products. Countries progressively change their production baskets and move toward goods that require capabilities that are already available; on the contrary radical structural change rarely happens. In this article, we analyze the evolution over time of the production baskets in 107 Italian provinces (NUTS 3) and perform the first test on the PS hypothesis of path-dependence. We investigate whether new products entering the provincial production baskets are nonrandomly related to initial production baskets. We confirm the general tendency of path-dependence but highlight at the same time that a sizable share of “new products” are an exception to this general pattern. These “random entries” over the PS are particularly interesting for industrial policy, since they represent radical deviations from the initial comparative advantage. In the final part of the article, we investigate using parametric analysis the product and provincial characteristics that determine these deviations from the PS pattern

Use of recombinant canine granulocyte-colony stimulating factor to increase leukocyte count in dogs naturally infected by canine parvovirus

Canine parvovirus (CPV) is one of the most important cause of mortality in young dogs and no specific treatment exists. Since prolonged leukopenia greatly increases the risk of death in infected pups, strategies to counteract this decline were investigated. The outcomes of CPV naturally infected pups treated with the recombinant canine granulocyte-colony stimulating factor (rcG-CSF), in combination with the routine therapy, were compared with similarly-managed infected pups not treated with rcG-CSF. A non-randomized prospective clinical trial was performed on 62 CPV infected pups with WBC counts <3000 cells/μL and two different groups were selected based on a non-randomized approach. Group A dogs (31/62) received 5 μg/Kg of rcG-CSF daily from the hospitalization day until WBC reached the reference range (3–5 days) and group B (31/62) received 1 ml of placebo injection. All dogs in group A recovered, while five dogs in group B died. The rcG-CSF treatment demonstrated a statistically significant effect on WBC counts (p < 0.0001) and, surprisingly, also on lymphocytes and monocytes counts (p < 0.0001). There was no significant effect of treatment on neutrophil count (p = 0.5502). Although lymphocytes and monocytes are not a specific target for rcG-CSF, our study highlights that rcG-CSF is able to improve haematological parameters compared to untreated dogs and a clear increase in their number was detected, as previously described for humans treated with the homologous molecule

Deuteration enhances catalyst lifetime in palladium-catalysed alcohol oxidation

The catalyst palladium/2,9-CD3-phenanthroline has a 1.8 times higher turnover number than its non-deuterated counterpart in the aerobic alcohol oxidation of methyl glucoside and allows the regioselective oxidation with dioxygen as the terminal oxidant

Evaluation of body composition with bioimpedence. A comparison between athletic and non-athletic children

Purpose: Conventional Bioelectrical Impedance Analysis (BIA) or Bioelectrical Impedance Vector Analysis (BIVA) can provide direct evaluations of body composition. The purpose of this study was to evaluate lean and fat mass (FM), and hydration of children involved in daily competitive sports. Methods: 190 non-athletic [8.2–10.5 years] and 29 competitive children [8.0–10.5 years] were enrolled. They were evaluated: at baseline (t0), 6 months (t1) and one year (t2). Anthropometric, BIA and BIVA, lean and FM, and hydration evaluations were performed. Results: Resistance (R/h) and reactance (Xc/h) were lower at t0 in competitive individuals when compared to controls. Xc/h (+3.28) significantly increases in competitive when compared to non-competitive individuals (+0.66, p for difference: 0.011), while phase angle (PA) was lower at t0 (5.72 vs. 6.17, p < .001) and after 6 months (p = .001). Total body water adjusted for height (TBW/h) significantly increased only in non-athletes (+0.50 ± 0.13, p < .001) between t0 and t1. At t1, extracellular water (ECW) significantly decreased (p = .026) in the two groups: −0.45 ± 0.19% in non-competitive, −1.63 ± 0.49% in competitive subjects, while intracellular water (ICW) increased. At one-year follow-up (t2), there were no statistically significant differences in R/h, Xc/h and PA in competitive individuals when compared to baseline and t1. Furthermore, we observed at t2 that hours/week of training, age, male gender and body mass index can influence FFM/h and FM/h in both competitive and non-competitive subjects. In particular, a direct correlation was for hours/week and FFM/h, inverse for hours/week and FM/h. Conclusions: Body mass index does not allow evaluating differences in lean body mass and FM between athletes and non-athletes. BIA and BIVA can give more reliable details about body composition differences in competitive adolescents and non-competitive, outlining a progressive decline in ECW and increase in ICW without affecting TBW composition of athletes

Surfactants from itaconic acidToxicity to HaCaT keratinocytes in vitro, micellar solubilization, and skin permeation enhancement of hydrocortisone

One of the most widely used approaches for improving drug permeation across the stratum corneum barrier of the skin is the use of chemical penetration enhancers, such as surfactants. In this study, two anionic surfactants, named C12-OPK and C18-OPK, were synthesized via condensation of itaconic acid and fatty amines, with C12 and C18 alkyl chains, respectively. Assessment of impacts on HaCaT keratinocyte cell viability was used as indicator of their potential to cause skin irritation 24 h post exposure (Alamar Blue assay). The LC50 values of C12-OPK and C18-OPK (144 and 85 mg/L, respectively) were lower than LC50 values of the most used commercial surfactants (e.g. SDS). The effect of different surfactant concentrations (up to ten times the critical micellar concentration, CMC) on hydrocortisone (HC) solubility and permeation through porcine skin was also evaluated. Results showed that drug solubility increased linearly with increasing concentrations of both surfactants, as a consequence of the association between drug and micelles. In vitro permeation results showed that the permeability coefficient increased at surfactant concentrations lower than the CMC. In particular, a higher enhancement effect on drug permeation was obtained with C18-OPK, due to its hydrophobic properties that ensured a more effective HC permeation in comparison to C12-OPK