1,3-Dihydroxypropan-2-one (DHA) synthesis from Glycerol for pharmaceutical applications

In the last century the amino alcohol serinol (2-amino-1,3-propanediol) has become a common intermediate for several chemical processes. Since the 40's serinol was used as precursor for synthesis of antibiotics (e.g. chloramphenicol). In the last years, new scopes of application were discovered. Serinol is used as building block in the synthesis of X-ray contrast agents, pharmaceuticals (anti-inflammatory or analgesic drugs) or in the cosmetics industry. It can either be obtained by chemical processes based on 2-nitro-1,3-propanediol, dihydroxiacetone (1,3-Dihydroxypropan-2-one or simply DHA) and ammonia [59]. One way to synthesize Serinol, in fact, is reacting DHA in a catalyzed reaction using Pt supported on carbon as catalyst. The DHA can be synthesized from Glycerol (1,2,3-propanetriol or glycerine) with a selective oxydation of the secondary carbon. The reaction from Glycerol to DHA must be catalyzed and nowadays only one method is well known. The method to obtain DHA uses gluconobacter oxydans as catalyst for the selective glycerol oxydation. Anyway the method presents many drawbacks cost not yet solved such as low productivity and high production. It is fundamental to underline how nowadays glycerol plants are closing and others are opening that use glycerol as a raw material as a result of the large surplus of glycerol that is formed as a byproduct in manufacturing biodiesel fuel by transesterification of seed oils with methanol. Over the last twenty years, indeed, biodiesel emerged as a viable fuel and as a fossil diesel additive to replace sulfur, whose content is being progressively lowered according to tighter environmental legislation. However, the increasing production of biodiesel is not artificially sustained and is predicted to spread and increase, as biodiesel provides sufficient advantages to merit subsidy. Besides the closure of production plants, industry reacted to this situation stimulating research to find new applications of glycerol as a low-cost feedstock for functional derivatives either for mass consumption, such as additives for concrete, or as a precursor of valued fine chemicals [60]. One investigated application of glycerol is exact its possible use as starting material for DHA synthesis (figure 1.4, chapter 1). The aim of this work was to investigate for new possibilities to transform glycerol into DHA, avoinding gluconobacter oxydans utilisation. In particular the attention was posed on new catalytic solutions investigating inorganic catalysts for the selective oxydation of glycerol. Two catalytic system were investigated. An heterogenous solution using noble metal nanoparticles supported on carbonious supports (mono- and bi-metallic systems) and an homogeneous one using an organometallic catalyst based on Pd. The study was approach from experimental and theoretical point of view becasue the reaction mechanism is not still clear. The research bring us to investigate deeply many weakness of the reaction and not still clear in literature, such as an efficient analytical method, problems linked to the catalysts aging, their deactivation and synthesis

A first thermodynamic interpretation of the technology transfer activities

In the last years new interdisciplinary approaches to economics and social science have been developed. A Thermodynamic approach to socio-economics has brought to a new interdisciplinary scientific field called econophysics. Why thermodynamic? Thermodynamic is a statistical theory for large atomic system under constraints of energy[1] and the economy can be considered a large system governed by complex rules. The present job proposes a new application, starting from econophysic, passing throughout the thermodynamic laws to interpret and to described the Technology Transfer (TT) activities. Using the definition of economy (i.e. economy[dictionary def.] = the process or system by which goods and services are produced, sold, and bought in a country or region) the TT can be considered an important sub-domain of the economy and a transversal new area of the scientific research. The TT is the process of transferring knowledge, that uses the results from the research to produce innovation and to ensure that scientific and technological developments could become accessible to a wider range of users. Starting from important Universities (MIT, Stanford, Oxford, etc) nowadays the TT is assuming a central role. It is called the third mission, together with education and research. The importance to provide new theories and tools to describe the TT activities and their behavior, has been retained fundamental to support the social rapid evolution that is involving the TT offices. The presented work uses the thermodynamic theories applying them to Technology Transfer and starting from the concept of entropy, exergy and anergy. The output analysis should become an help to make decision to improve the TT activities and a better resources employment

Synthesis and catalytic application of Pt and Pt-Bi nanoparticles in graphite oxide

The mono- and bi-metallic catalysts based on noble metal nanoparticles (NPs) are the most used for the selective oxidation of organic molecules. The activity of catalysts based on Pt NPs is strongly improved by the Pt/Bi coupled systems, where the presence of Bi prevents the poisoning of Pt by O2 in strong oxidative environment. Using bi-metallic catalysts based, one of the challenges is the synthesis of bi-metallic coupled systems enhancing an uniform distribution of NPs on the support and reducing the metals loading as much as possible without influencing the activity

Sensore e dispositivo per il monitoraggio di fluidi

L’oggetto del brevetto è una soluzione hardware in grado di acquisire contemporaneamente e in una sola misura il dato di pressione e portata di un fluido. Il misuratore possiede una scheda elettronica incorporata che lo rende compatibile con un software in grado di raccogliere i dati in tempo reale, integrabile in una rete di monitoraggio. I bassi consumi e la versatilità lo rendono una soluzione alternativa sul mercato degli smart-meter

Numerical and experimental characterization of a novel modular passive micromixer

This paper reports a new low-cost passive microfluidic mixer design, based on a replication of identical mixing units composed of microchannels with variable curvature (clothoid) geometry. The micromixer presents a compact and modular architecture that can be easily fabricated using a simple and reliable fabrication process. The particular clothoid-based geometry enhances the mixing by inducing transversal secondary flows and recirculation effects. The role of the relevant fluid mechanics mechanisms promoting the mixing in this geometry were analysed using computational fluid dynamics (CFD) for Reynolds numbers ranging from 1 to 110. A measure of mixing potency was quantitatively evaluated by calculating mixing efficiency, while a measure of particle dispersion was assessed through the lacunarity index. The results show that the secondary flow arrangement and recirculation effects are able to provide a mixing efficiency equal to 80 % at Reynolds number above 70. In addition, the analysis of particles distribution promotes the lacunarity as powerful tool to quantify the dispersion of fluid particles and, in turn, the overall mixing. On fabricated micromixer prototypes the microscopic-Laser-Induced-Fluorescence (μLIF) technique was applied to characterize mixing. The experimental results confirmed the mixing potency of the microdevice

Selective oxidation of glycerol to dihidroxyacetone (DHA): a comparison between neocuproine-Pd(OAc)2 based catalyst and an its dimeric form

The behaviour of two different organometallic complexes based on Pd were examined in depth with the aim to obtain the selective oxidation of glycerol to 1,3-dihydroxyacetone (DHA). An high glycerol conversion (93.5%) was obtained in a acetonitrile/water mixture in the presence of oxygen as a terminal oxidant.</b

Selective oxidation of glycerol to dihidroxyacetone (DHA): a comparison between neocuproine-Pd(OAc)2 based catalyst and an its dimeric form

<b>The behaviour of two different organometallic complexes based on Pd were examined in depth with the aim to obtain the selective oxidation of glycerol to 1,3-dihydroxyacetone (DHA). An high glycerol conversion (93.5%) was obtained in a acetonitrile/water mixture in the presence of oxygen as a terminal oxidant.</b

Analysis of mixing of a clothoid based passive micromixer: A numerical study

A computational study of a novel passive micromixer is presented. In this work, we analysed a Clo-plus micromixer designed to achieve efficient mixing and characterized by a process of construction that can use a single planar soft lithography step. Mixing studies were carried out at different Reynolds numbers ranging from 1 to 100. The preliminary results suggest that at Re> 50, the Clo-plus micromixer is characterized by a good mixing because of stronger Dean secondary flow and recirculation effect

iIteratrial shunting through an asymptomatic patent foramen ovale in thoracic surgery

Background: Patent foramen ovale (PFO) is present in as many as 25% of the general population and is considered an irrelevant condition in healthy subjects. Here, we sought to determine an association between an asymptomatic PFO at baseline and postoperative short-term adverse events in patients undergoing major pulmonary resection for lung cancer. In addition, we evaluated for the rate of PFO after pulmonary resections. Methods: This prospective, observational study assessed patients by transcranial Doppler with contrast at baseline and discharge. To confirm interatrial shunting, patients with positive transcranial Doppler at baseline also underwent contrast transthoracic echocardiography. Multivariate logistic regression models were adopted to investigate for independent factors that could have been associated with complications. Backward stepwise procedure was used for model selection. Results: Median age was 67.7 ± 9.2 years (range, 36 to 86), and 67% were men. Overall, 18 patients underwent pneumonectomy, 11 bilobectomy, and 118 lobectomy; 54% underwent right-sided procedure and 46%, left-sided. One perioperative death was recorded, and 34 patients had one or more cardiopulmonary complications. At baseline, PFO was positive in 25% (37 of 147) and negative in 75% (110 of 147); of the latter, 11% were positive at discharge. Detection of PFO at baseline, on multivariate analysis, was significantly associated with a risk of postoperative complications (odds ratio 2.5; 95% confidence interval: 1.1 to 5.8). Specifically, we observed a significant association between atrial fibrillation and positive PFO at baseline (odds ratio 3.5; 95% confidence interval: 1.4 to 9.0). Conclusions: Preoperative asymptomatic PFO was independently associated with postoperative adverse events. Moreover, 11% of patients who had negative transcranial Doppler studies at baseline had asymptomatic PFOs at discharge. Larger prospective studies are needed to further investigate for a prognostic impact of PFO in thoracic surgery