Sintesi e caratterizzazione di sistemi nanostrutturati per il trattamento del Glioblastoma multiforme

Nanomedicine is a science based on the preparation of nanosystems for biomedical application. The drugs can be entrapped inside the nanocarriers to improve the drug concentration in the diseased issue through a drug delivery approach; polimeric materials as PLGA-b-PEG has been revealed good properties for this purpose. To improve the nanosystem efficiency it is possible to bind a targeting agent on the carrier surface. In this thesis work silver nanoparticles or drugs as Temsirolimus and Alisertib have been entrapped in PLGA-b-PEG carriers. Chlorotoxin has been linked on the carrier surface as a specific targeting agent for brain tumors. Citotoxicity in vitro of the nanosystems on Glioblastoma cells has been studied.

Oxidative properties of the Iron - Thymine-1-acetic acid - Hydrogen peroxide catalytic system

The oxidation of alcohols and olefins is a pivotal reaction in organic synthesis. However, traditional oxidants are toxic and they often release a considerable amounts of by-products. Here, two IronIII-based systems are shown as oxidative catalyst, working in mild conditions with hydrogen peroxide as primary oxidant. An efficient catalytic system for the selective oxidation of several alcohols to their corresponding aldehydes and ketones was developed and characterized, [Fe(phen)2Cl2]NO3 (phen=1,10-Phenantroline). It was demonstrated that the adoption of a buffered aqueous solution is of crucial importance to ensure both considerable activity and selectivity.The Iron - Thymine-1-acetic acid in-situ complex was studied as catalyst in alcohol oxidations and C-H oxidative functionalization, involving hydrogen peroxide as primary oxidant in mild reaction conditions. The catalytic ability in alcohol oxidations was investigated by Density Functional Theory calculations, however the catalyst still has uncertain structure. The system shows satisfactory activity in alcohol oxidation and aliphatic rings functionalization. The Fe-THA system was studied in cyclohexene oxidation and oxidative halogenations. Halide salts such as NBu4X and NH4X were introduced in the catalytic system as halogens source to obtain cyclohexene derivatives such as halohydrins, important synthetic intermediates.The purpose of this dissertation is to contribute in testing new catalytic systems for alcohol oxidations and C-H functionalization. In particular, most of the efforts in this work focus on studying the Iron - Thymine-1-acetic acid (THA) systems as non-heme oxidative model, which present: ���an iron metal centre(s) as a coordinative active site, ���hydrogen peroxide as a primary oxidant, ���THA as an eco-friendly, biocompatible, low cost coordinating ligand.

Investigation of heterogeneous catalysts for the synthesis of fine chemicals

In order to match the more stringent environmental regulations, heterogenization of traditional homogeneous processes is one of the main challenges of the modern chemical industry. Great results have been achieved in the fields of petrochemicals and base chemicals, whereas in fine chemical industry most of the synthetic procedures are based on multistep processes catalyzed by homogeneous catalysts mainly used in stoichiometric amounts. In the fine chemicals manufacture not so much efforts have been devoted to the investigation of suitable solid catalysts for the development of greener processes, then this sector represent a very attractive field of research. In this context, the present work deals with the extensive investigation of the possibility to heterogenize existing processes, in particular two different classes of reactions have been studied: alkylation of aromatic and heteroaromatic compounds and selective oxidation of aromatic alcohols. Traditional solid acid catalysts, such as zeolites, clays and alumina have been tested in the gas phase alkylation of 1,2-methylendioxybenzene, core building block of many drugs, pesticides and fragrances. The observed reactivity were clarified through a deep FTIR investigation complemented by ab initio calculation. The same catalysts were tested in the gas phase isopropylation of thiophene with the aim of clearly attribute the role of the reaction parameters in the reaction proceeding and verify the possibility to enhance the selectivity of one of the two possible isomers. Finally various Au/CeO2 catalysts were tested in the synthesis of benzaldehyde and piperonal, two aldehydes largely employed in the manufacture of fine chemical products, through liquid phase oxidation of the corresponding alcohols in very mild conditions.

Ingegnerizzazione di nanocosmetici

This study led to the development of new synthesis process to obtain "nano delivery" system like aquasome, suitable to enhance the affinity between dyes and human hair for cosmetic formulation. These systems has been based on silver nanoparticles stabilized by different kind of polymers as PVP or celluloses. The research has been conducted in two steps: the first involved the study and optimization of the nano delivery system synthesis conditions as concentrations, pH and temperature. The second concerned the preparation of a stable, low hazard and with antibacterial and antifungal properties formulation containing the aquasome and a colorant already used in cosmetics (i.e. Basic Red 51) for hair dyeing application.

The synthesis of maleic anhydride: study of a new process and improvement of the industrial catalyst

Maleic anhydride is an important chemical intermediate mainly produced by the selective oxidation of n-butane, an industrial process catalyzed by vanadyl pyrophosphate-based materials, (VO)2P2O7. The first topic was investigated in collaboration with a company specialized in the production of organic anhydrides (Polynt SpA), with the aim of improving the performance of the process for the selective oxidation of n-butane to maleic anhydride, comparing the behavior of an industrial vanadyl pyrophosphate catalysts when utilized either in the industrial plant or in lab-scale reactor. The study was focused on how the catalyst characteristics and reactivity are affected by the reaction conditions and how the addition of a dopant can enhance the catalytic performance. Moreover, the ageing of the catalyst was studied, in order to correlate the deactivation process with the modifications occurring in the catalyst. The second topic was produced within the Seventh Framework (FP7) European Project ���EuroBioRef���. The study was focused on a new route for the synthesis of maleic anhydride starting from an alternative reactant produced by fermentation of biomass:���bio-1-butanol���. In this field, the different possible catalytic configurations were investigated: the process was divided into two main reactions, the dehydration of 1-butanol to butenes and the selective oxidation of butenes to maleic anhydride. The features needed to catalyze the two steps were analyzed and different materials were proposed as catalysts, namely Keggin-type polyoxometalates, VOPO4���2H2O and (VO)2P2O7. The reactivity of 1-butanol was tested under different conditions, in order to optimize the performance and understand the nature of the interaction between the alcohol and the catalyst surface. Then, the key intermediates in the mechanism of 1-butanol oxidehydration to MA were studied, with the aim of understanding the possible reaction mechanism. Lastly, the reactivity of the chemically sourced 1-butanol was compared with that one of different types of bio-butanols produced by biomass fermentation.

An Investigation of the Properties of some of the White Metal Alloys

Although there is no standardized list of alloys, most investigators have, to avoid confusion, concurred in at least grouping the metals under several general heads. Precious metals: gold, silver and the platinum group; the light metals: aluminum and magnesium; the non-ferrous metals (excluding all steels and iron-base alloys); and the antifriction metals.

Coal in Montana

Coal was first mined in Montana in the year 1880. For the last thirty years the mining of coal in this state has been very important-with few people realizing its value. In the mineral industry, the value of the annual production of coal is exceeded by none of the non-metallics, and only by gold, silver, and copper in the metallics. At the present time the coal production of Montana is valued at about 41000,000.00 annually.

A Mineral Dressing Study of the U.S. Grant Ore

This investigation concerns the development of a satis��factory method or extracting or concentrating gold and silver from the ores of the U. S. Grant Mine. The choice between applying an extractive process and one by which the valuable mineral constituents are concentrated depends on more than one factor.

Benefication of an Oxidized Lead Ore from the Franklin Mine Lewis and Clark County

This thesis is concerned with the beneficiation of an oxidized lead ore. Emphasis was placed upon concentration by flotation rather than by gravity methods, although some investigation was made with the Wilfley shaking table. The concentration of lead minerals received most consideration in the problem, but wherever possible attempts were made to increase the silver and gold concentration along with the lead.

Body composition and fuel metabolism after kidney grafting

Kidney transplant patients display decreased muscle mass and increased fat mass. Whether this altered body composition is due to glucocorticoid induced altered fuel metabolism is unclear. To answer this question, 16 kidney transplant patients were examined immediately after kidney transplantation (12 +/- 4 days, mean +/- SEM) and then during months 2, 5, 11 and 16, respectively, by whole body dual energy X-ray absorptiometry (Hologic QDR 1000W) and indirect calorimetry. Results were compared with those of 16 age, sex and body mass index matched healthy volunteers examined only once. All patients received dietary counselling with a step 1 diet of the American Heart Association and were advised to restrict their caloric intake to the resting energy expenditure plus 30%. Immediately after transplantation, lean mass of the trunk was higher by 7 +/- 1% (P < 0.05) and that of the limbs was lower by more than 10% (P < 0.01) in patients than in controls. In contrast, no difference in fat mass and resting energy expenditure could be detected between patients and controls. During the 16 months of observation, total fat mass increased in male (+4.9 +/- 1.5 kg), but not in female patients (0.1 +/- 0.8 kg). The change in fat mass observed in men was due to an increase in all subregions of the body analysed (trunk, arms+legs as well as head+neck), whereas in women only an increase in head+neck by 9 +/- 2% (P = 0.05) was detected. Body fat distribution remained unchanged in both sexes over the 16 months of observation. Lean mass of the trunk mainly decreased between days 11 and 42 (P < 0.01) and remained stable thereafter. After day 42, lean mass of arms and legs (mostly striated muscle) and head+neck progressively increased over the 14 months of observation by 1.6 +/- 0.6 kg (P < 0.05) and 0.4 +/- 0.1 kg (P < 0.01), respectively. Resting energy expenditure was similar in controls and patients at 42 days (30.0 +/- 0.7 vs. 31.0 +/- 0.9 kcal kg-1 lean mass) and did not change during the following 15 months of observation. However, composition of fuel used to sustain resting energy expenditure in the fasting state was altered in patients when compared with normal subjects, i.e. glucose oxidation was higher by more than 45% in patients (P < 0.01) during the second month after grafting, but gradually declined (P < 0.01) over the following 15 months to values similar to those observed in controls. Protein oxidation was elevated in renal transplant patients on prednisone at first measurement, a difference which tended to decline over the study period. In contrast to glucose and protein oxidation, fat oxidation was lower in patients 42 days after grafting (P < 0.01), but increased by more than 100% reaching values similar to those observed in controls after 16 months of study. Mean daily dose of prednisone per kg body weight correlated with the three components of fuel oxidation (r > 0.93, P < 0.01), i.e. protein, glucose and fat oxidation. These results indicate that in prednisone treated renal transplant patients fuel metabolism is regulated in a dose-dependent manner. Moreover, dietary measures, such as caloric and fat intake restriction as well as increase of protein intake, can prevent muscle wasting as well as part of the usually observed fat accumulation. Furthermore, the concept of preferential upper body fat accumulation as consequence of prednisone therapy in renal transplant patients has to be revised.

Efficient management of available technologies. Aplication to mining operations for industry supplies

Nowadays, processing Industry Sector is going through a series of changes, including right management and reduction of environmental affections. Any productive process which looks for sustainable management is incomplete if Cycle of Life of mineral resources sustainability is not taken into account. Raw materials for manufacturing are provided by mineral resources extraction processes, such as copper, aluminum, iron, gold, silver, silicon, titanium? Those elements are necessary for Mankind development and are obtained from the Earth through mineral extractive processes. Mineral extraction processes are operations which must take care about the environmental consequences. Extraction of huge volumes of rock for their transformation into raw materials for industry must be optimized to reduce ecological cost of the final product as l was possible. Reducing the ecological balance on a global scale has no sense to design an efficient manufacturing in secondary industry (transformation), if in first steps of the supply chain (extraction) impact exceeds the savings of resources in successive phases. Mining operations size suggests that it is an environmental aggressive activity, but precisely because of its great impact must be the first element to be considered. That idea implies that a new concept born: Reduce economical and environmental cost This work aims to make a reflection on the parameters that can be modified to reduce the energy cost of the process without an increasing in operational costs and always ensuring the same production capacity. That means minimize economic and environmental cost at same time. An efficient design of mining operation which has taken into account that idea does not implies an increasing of the operating cost. To get this objective is necessary to think in global operation view to make that all departments involved have common guidelines which make you think in the optimization of global energy costs. Sometimes a single operational cost must be increased to reduce global cost. This work makes a review through different design parameters of surface mining setting some key performance indicators (KPIs) which are estimated from an efficient point of view. Those KPIs can be included by HQE Policies as global indicators. The new concept developed is that a new criteria has to be applied in company policies: improve management, improving OPERATIONAL efficiency. That means, that is better to use current resources properly (machinery, equipment,?) than to replace them with new things but not used correctly. As a conclusion, through an efficient management of current technologies in each extractive operation an important reduction of the energy can be achieved looking at downstream in the process. That implies a lower energetic cost in the whole cycle of life in manufactured product.

Thermally tunable polarization by nanoparticle plasmonic resonance in photonic crystal fibers

A photonic crystal fiber selectively filled with silver nanoparticles dispersed in polydimethylsiloxane has been numerically studied via finite elements analysis. These nanoparticles possess a localized surface plasmon resonance in the visible region which depends on the refractive index of the surrounding medium. The refractive index of polydimethylsiloxane can be thermally tuned leading to the design of polarization tunable filters. Filters found with this setup show anisotropic attenuation of the x-polarization fundamental mode around ?x = 1200dB/cm remarkably higher than the y-polarization mode. Moreover, high fiber birefringence and birefringence reversal is observed in the spectral region of the plasmon.

Avalia����o de massa e rugosidade superficial de pastilhas de Ti-6Al-4V com aplica����o de nanopart��culas de prata submetidos ao teste de escova����o

Este estudo teve por objetivo avaliar a varia����o da massa e rugosidade de pastilhas de Ti-6Al-4V com e sem aplica����o superficial de nanopart��culas de prata coloidal (BSafe��) de dimens��es 1,5 cm; 0,5 cm e 0,2 cm, submetidas �� teste de escova����o e imers��o pelo per��odo experimental de 10 anos. No teste de escova����o, quinze esp��cimes de Ti-6Al-4V (TE), quinze com B-Safe�� (BE) e quinze de PMMA (PE) como controle foram subdivididos em tr��s condi����es de escova����o: dentifr��cio comum (DC), dentifr��cio experimental (DE) e controle com ��gua destilada (H2O) por 200 mil ciclos em m��quina de escova����o. Os resultados foram submetidos ao teste ANOVA a 2 crit��rios (condi����o de escova����o e ciclos) e teste de Tukey (&#x3B1;=0,05) para compara����es m��ltiplas. Foi observada varia����o de massa apenas quando a condi����o de escova����o foi DC nos esp��cimes do grupo PE e TE. Houve diferen��a estatisticamente significante nos valores da varia����o de rugosidade no grupo TE e PE quando a condi����o de escova����o foi DC; no grupo BE, houve diferen��a quando a condi����o foi DC e DE, por��m em DE houve redu����o dos valores m��dios. No teste de imers��o, objetivando analisar a a����o dos dentifr��cios sem o atrito das cerdas, seis esp��cimes de Ti-6Al-4V (TI) e seis com B-Safe�� (BI) foram subdivididos em tr��s condi����es de imers��o: DC, DE e H2O pelo per��odo de 244 horas. Os resultados foram submetidos ao teste t de student pareado. N��o foi observada diferen��a estat��stica entre as varia����es de massa e rugosidade de nenhum dos corpos de prova ap��s o teste. Complementar aos ensaios, foi realizado um protocolo de desinfec����o com terapia fotodin��mica com azul de metileno pelo per��odo de 4 semanas nos esp��cimes escovados. Ap��s todos os testes, foi realizada espectrometria de energia dispersiva de raios-X (EDS) para caracteriza����o dos elementos qu��micos presentes nos esp��cimes, onde n��o se observou varia����es. Os resultados sugerem que o DE �� mais indicado para utiliza����o com implantes, enquanto DC apresenta um poder abrasivo capaz de danificar a superf��cie do Ti-6Al- 4V. N��o foi observado nenhum ind��cio de corros��o em nenhum grupo testado.

An��lisis de las relaciones morfolog��a-propiedades en nanocompuestos basados en matrices de copol��meros de bloque

El objetivo principal de la presente investigaci��n ha sido desarrollar una nueva clase de materiales nanocompuestos org��nicos-inorg��nicos basados en la capacidad de los copol��meros de bloque de auto-organizarse promoviendo la dispersi��n de nanopart��culas, as�� como relacionar las diferentes morfolog��as obtenidas con las propiedades finales de los nanocompuestos. Para generar la nanoestructuraci��n de estos nanocompuestos basados en copol��meros de bloque, como el poli(estireno-b-isopreno-b-estireno) (SIS) y el poli(estireno-b-butadieno-b-estireno) (SBS) en nanopart��culas de plata, se han utilizado los conceptos de compatibilizaci��n y confinamiento. Es decir, las nanopart��culas inorg��nicas se confinaron en una sola fase del copol��mero de bloque mediante tratamientos superficiales y su funcionalizaci��n f��sica. En particular, se utilizaron surfactantes (el cloruro de tetrametilamonio, TMAC, y el dodecanotiol, DT) para favorecer la interacci��n entre las nanopart��culas inorg��nicas y la matriz polim��rica. Teniendo en cuenta los c��lculos te��ricos de los par��metros de solubilidad obtenidos mediante la teor��a de Hoftizer-Van Krevelen, y la electronegatividad propia de los diferentes elementos, los dos surfactantes elegidos tienen una muy buena compatibilidad con el bloque de estireno favoreciendo la localizaci��n de las nanopart��culas de plata en este bloque.

Preliminary report on a uranium occurrence in the Atlanta area, Lincoln County, Nevada /

Surface and airborne prospecting of the Ely Springs dolomite is recommended in this region, especially near silicified breccia pipes.