Studio di metodi di preparazione e caratterizzazione di nanostrutture per la funzionalizzazione di materiali ceramici

This thesis was carried out in the context of a co-tutoring program between Centro Ceramico Bologna (Italy) and Instituto di Tecnologia Ceramica, Castellón de la Plana (Spain). The subject of the thesis is the synthesis of silver nanoparticles and at their likely decorative application in the productive process of porcelain ceramic tiles. Silver nanoparticles were chosen as a case study, because metal nanoparticles are thermally stable, and they have non-linear optical properties when nano-structured, and therefore they develop saturated colours. The nanoparticles were synthesized by chemical reduction in aqueous solution, a method chosen because of its reduced working steps and energy costs. Besides such a synthesis method uses non-expensive and non-toxic raw material. By adopting this synthesis technique, it was also possible to control the dimension and the final shape of the nanoparticles. Several syntheses were carried out during the research work, modifying the molecular weight of the reducing agent and/or the firing temperature, in order to evaluate the influence such parameters have on the Ag-nanoparticles formation. The syntheses were monitored with the use of UV-Vis spectroscopy and the average dimension as well as the morphology of the nanoparticles was analysed by SEM. From the spectroscopic data obtained from each synthesis, a kinetic study was completed, relating the progress of the reaction to the two variables (ie temperature and molecular weight of the reducing agent). The aim was finding equations that allow the establishing of a relationship between the operating conditions during the synthesis and the characteristics of the final product. The next step was finding the best method of synthesis for the decorative application. For such a purpose the amount of nanoparticles, their average particle size, the shape and the agglomeration are considered. An aqueous suspension containing the nanoparticles is then sprayed over the fired ceramic tiles and they are subsequently thermally treated in conditions similar to the industrial one. The colorimetric parameters of the obtained ceramic tiles were studied and the method proved successful, giving the ceramic tiles stable and intense colours.

Biologia di Tuta absoluta (Lepidoptera: Gelechiidae), interazioni con l’ambiente e valutazione di tecniche di contenimento ecocompatibili

Tuta absoluta (Meyrick) è un lepidottero originario dell’America meridionale, infeudato a pomodoro e ad altre solanacee coltivate e spontanee. Con l’attività trofica le larve causano mine fogliari e gallerie nei frutti, con conseguenti ingenti danni alle colture. T. absoluta è stato segnalato per la prima volta in Italia nel 2008 e in Piemonte nel 2009. Pertanto le ricerche sono state condotte per rilevarne la distribuzione in Piemonte, studiarne l’andamento di popolazione in condizioni naturali e controllate, e valutare l’efficacia di differenti mezzi di lotta al fine di definire le strategie di difesa. Il monitoraggio, condotto nel 2010, ha evidenziato come T. absoluta sia ormai largamente diffuso sul territorio regionale già pochi mesi dopo la segnalazione. L’insetto ha mostrato di prediligere condizioni climatiche più miti; infatti è stato ritrovato con maggiore frequenza nelle aree più calde. Il fitofago ha raggiunto densità di popolazione elevate a partire dalla seconda metà dell’estate, a ulteriore dimostrazione che, in una regione a clima temperato come il Piemonte, T. absoluta dà origine a infestazioni economicamente rilevanti solo dopo il culmine della stagione estiva. Per definire le strategie di lotta, sono state condotte prove in laboratorio, semi-campo e campo volte a valutare la tossicità nei confronti del lepidottero di preparati a base di emamectina benzoato, rynaxypyr, spinosad e Bacillus thuringiensis Berliner. In campo è stata verificata anche l’efficacia del miride dicifino Macrolophus pygmaeus (Rambur), reperibile in commercio. In tutte le prove, è stata riscontrata una maggiore efficacia di rynaxypyr ed emamectina benzoato. In campo M. pygmaeus ha mostrato difficoltà d’insediamento ed è stato in grado di contenere efficacemente il fitofago soltanto con bassi livelli d’infestazione. Per contro è stata costantemente osservata la presenza naturale di un altro miride dicifino Dicyphus errans (Wolff), che in laboratorio ha mostrato di non essere particolarmente disturbato dalle sostanze saggiate.

Time-resolved surface enhanced resonance Raman spectro-electrochemistry of heme proteins

The membrane protein Cytochrome c Oxidase (CcO) is one of the most important functional bio-molecules. It appears in almost every eukaryotic cell and many bacteria. Although the different species differ in the number of subunits, the functional differences are merely marginal. CcO is the terminal link in the electron transfer pathway of the mitochondrial respiratory chain. Electrons transferred to the catalytic center of the enzyme conduce to the reduction of molecular oxygen to water. Oxygen reduction is coupled to the pumping of protons into the inter-membrane space and hence generates a difference in electrochemical potential of protons across the inner mitochondrial membrane. This potential difference drives the synthesis of adenosine triphosphate (ATP), which is the universal energy carrier within all biological cells. rnrnThe goal of the present work is to contribute to a better understanding of the functional mechanism of CcO by using time-resolved surface enhanced resonance Raman spectroscopy (TR-SERRS). Despite intensive research effort within the last decades, the functional mechanism of CcO is still subject to controversial discussions. It was the primary goal of this dissertation to initiate electron transfer to the redox centers CuA, heme a, heme a3 and CuB electrochemically and to observe the corresponding redox transitions in-situ with a focus on the two heme structures by using SERRS. A measuring cell was developed, which allowed combination of electrochemical excitation with Raman spectroscopy for the purpose of performing the accordant measurements. Cytochrome c was used as a benchmark system to test the new measuring cell and to prove the feasibility of appropriate Raman measurements. In contrast to CcO the heme protein cc contains only a single heme structure. Nevertheless, characteristic Raman bands of the hemes can be observed for both proteins.rnrnIn order to investigate CcO it was immobilized on top of a silver substrate and embedded into an artificial membrane. The catalytic activity of CcO and therefore the complete functional capability of the enzyme within the biomimetic membrane architecture was verified using cyclic voltammetry. Raman spectroscopy was performed using a special nano-structured silver surface, which was developed within the scope of the present work. This new substrate combined two fundamental properties. It facilitated the formation of a protein tethered bilayer lipid membrane (ptBLM) and it allowed obtaining Raman spectra with sufficient high signal-to-noise ratios.rnSpectro-electrochemical investigations showed that at open circuit potential the enzyme exists in a mixed-valence state, with heme a and and heme a3 in the reduced and oxidized state, respectively. This was considered as an intermediate state between the non-activated and the fully activated state of CcO. Time-resolved SERRS measurements revealed that a hampered electron transfer to the redox center heme a3 characterizes this intermediate state.rn

Selective photo-oxidation of glucose

Biomass transformation into high-value chemicals has attracted attention according to the “green chemistry” principles. Low price and high availability make biomass one of the most interesting renewable resources as it provides the means to create sustainable alternatives to the oil-derived building blocks of the chemical industry In recent year, the need for alternative environmentally friendly routes to drive chemical reactions has in photocatalytic processes an interesting way to obtain valuable chemicals from various sources using the solar light as energy source. The purpose of this work was to use supported noble metal nanoparticles in the selective photo-oxidation of glucose through using visible light. Glucose was chosen as model molecule because it is the cheapest and the most common monosaccharide. Few studies about glucose photo oxidation have been conducted so far, and reaction mechanism is still not totally explained. The aim of this work was to systematically analyze and assess the impact of several parameters (eg. catalyst/substrate ratio, reaction time, effect of the solvent and light source) on the reaction pathway and to monitor the product distribution in order to draw a general reaction scheme for the photo oxidation of glucose under visible light. This study regards the reaction mechanism and the influence of several parameters, such as solvent, light power and substrate concentration. Furthermore, the work focuses on the influence of gold and silver nanoparticles and on the influence of metal loading. The glucose oxidation was monitored through the mass balance and the products selectivity. Reactions were evaluated in terms of glucose conversion, mass balance and selectivities towards arabinose and gluconic acid. In conclusion, this study is able to demonstrate that the photo oxidation of glucose under visible light is feasible; the full identification of the main products allows, for the first time, a comprehensive reaction mechanism scheme.

Some Notes on the Composition of "Copper Pitch"

A supply of so-called "copper pitch" ore was received by the Montana Bureau of Mines and Geology in response to a request by them from a resident of Kalispell, who had previously sent a specimen to the Bureau for a mineralogical analysis. Since this material was little known and had apparently received but little study under a reflec­ting microscope, it was thought that such a study might throw some light on the mineralogical and chemical composition of the material.

The Amplifier - v. 4, no. 8

In this issue...Mines Hockey, Ed Simonich, Faculty Wives Club, convocation, Mineral Research Center, Drama Club, Memoir 36, Montana Bureau of Mines and Geology

Materials-Handling Hazard Controls: Assessment of Haddon’s Injury Control Strategies

This investigation assessed the applicability of Dr. William Haddon’s strategies for controlling hazards involving materials-handling operations in industrial and mining workplaces. Published over 20 years ago, Haddon’s strategies purport to include all strategies for preventing and mitigating harm to people, property, and the environment. Students in an undergraduate class were assigned to find tactical examples of each of Haddon’s strategies applicable to material handling. Haddon’s tenth strategy involving medical care and rehabilitation was not included. Their classifications were analyzed to identify points of confusion as well as points of general agreement. Students found numerous tactics for strategies involving engineering and behavioral strategies. Fewer tactics were identified for strategies involving damage control through effective and timely response.

The Amplifier - v. 5, no. 9

In this issue...Engineering Days, Mine Rescue and First Aid, Chemistry Department, Mineral Club, Anderson-Carlisle Society, Honor Roll, Continental Oil Company, Intramural basketball

The Amplifier - v. 6, no. 9

In this issue...M Days, beard contest, Anderson - Carlisle Society, Honor Roll, South Africa, Magma, International Club, First Aid, Bob Hauck, Continental Oil Company, Montana Power

The Amplifier - v. 7, no. 8

in this issue...Sweetheart Swirl Dance, R J Trio, Air Force Base, Civil Rights, Bill Barry's Boxing Club, International Club, Donald E. Mahagin, Main Hall

Montana Talc; Problems in Physical Properties

General information on talc, including foreign and United States occurrences, origin, and uses is covered. Montana deposits are discussed in greater detail as to location, geology, mineralogy, and mining. Studies of talc by petrographic and x-ray methods and an experiment to determine the porosity are described and discussed.

Up-regulation of the peroxiredoxin-6 related metabolism of reactive oxygen species in skeletal muscle of mice lacking neuronal nitric oxide synthase

Although neuronal nitric oxide synthase (nNOS) plays a substantial role in skeletal muscle physiology, nNOS-knockout mice manifest an only mild phenotypic malfunction in this tissue. To identify proteins that might be involved in adaptive responses in skeletal muscle of knockout mice lacking nNOS, 2D-PAGE with silver-staining and subsequent tandem mass spectrometry (LC-MS/MS) was performed using extracts of extensor digitorum longus muscle (EDL) derived from nNOS-knockout mice in comparison to C57Bl/6 control mice. Six proteins were significantly (P < or = 0.05) more highly expressed in EDL of nNOS-knockout mice than in that of C57 control mice, all of which are involved in the metabolism of reactive oxygen species (ROS). These included prohibitin (2.0-fold increase), peroxiredoxin-3 (1.9-fold increase), Cu(2+)/Zn(2+)-dependent superoxide dismutase (SOD; 1.9-fold increase), heat shock protein beta-1 (HSP25; 1.7-fold increase) and nucleoside diphosphate kinase B (2.6-fold increase). A significantly higher expression (4.1-fold increase) and a pI shift from 6.5 to 5.9 of peroxiredoxin-6 in the EDL of nNOS-knockout mice were confirmed by quantitative immunoblotting. The concentrations of the mRNA encoding five of these proteins (the exception being prohibitin) were likewise significantly (P < or = 0.05) higher in the EDL of nNOS-knockout mice. A higher intrinsic hydrogen peroxidase activity (P < or = 0.05) was demonstrated in EDL of nNOS-knockout mice than C57 control mice, which was related to the presence of peroxiredoxin-6. The treatment of mice with the chemical NOS inhibitor L-NAME for 3 days induced a significant 3.4-fold up-regulation of peroxiredoxin-6 in the EDL of C57 control mice (P < or = 0.05), but did not alter its expression in EDL of nNOS-knockout mice. ESR spectrometry demonstrated the levels of superoxide to be 2.5-times higher (P < or = 0.05) in EDL of nNOS-knockout mice than in C57 control mice while an in vitro assay based on the emission of 2,7-dichlorofluorescein fluorescence disclosed the concentration of ROS to be similar in both strains of mice. We suggest that the up-regulation of proteins that are implicated in the metabolism of ROS, particularly of peroxiredoxin-6, within skeletal muscles of nNOS-knockout mice functionally compensates for the absence of nNOS in scavenging of superoxide.

Is differentiation of frequently encountered foreign bodies in corpses possible by Hounsfield density measurement?

The radiological determination of foreign objects in corpses can be difficult if they are fragmented or deformed. With multislice computed tomography, radiodensities--referred to as Hounsfield units (HU)--can be measured. We examined the possibility of differentiating 21 frequently occurring foreign bodies, such as metals, rocks, and different manmade materials by virtue of their HU values. Gold, steel, and brass showed mean HU values of 30671-30710 (upper measurable limit), mean HU values for steel, silver, copper, and limestone were 20346, 16949, 14033, and 2765, respectively. The group consisting of objects, such as aluminum, tarmac, car front-window glass, and other rocks, displayed mean HU values of 2329-2131 HU. The mean HU value of bottle glass and car side-window glass was 2088, whereas windowpane glass was 493. HU value determination may therefore help in preautopsy differentiation between case-relevant and irrelevant foreign bodies and thus be useful for autopsy planning and extraction of the objects in question.

Metales pesados como indicador de impacto de un sistema ecológico fragmentado por usos de suelo, San Luis Potosí, México

La necesidad de estudiar la presencia de metales pesados en el suelo radica en su impacto como indicador de contaminación ambiental. Se determinó la presencia de Cu, Zn, Pb y Cd en suelos donde se distribuyen especies vegetales en un corredor ecológico. Entre los municipios de Soledad de Graciano Sánchez y San Luis Potosí (México) fueron establecidos 30 puntos distribuidos en cinco prácticas dominantes de usos de suelo: agropecuario, residencial rural, comercio y servicios, residencial urbano y minero. Los muestreos se realizaron en cuatro épocas durante 2009 y 2010 (verano, otoño, invierno y primavera). Se encontró un efecto significativo del uso del suelo en cuanto a los niveles de Cu (p = 0,000), Pb (p = 0,043) y Cd (p = 0,010). En el caso del Zn, el uso del suelo (p = 0,000) y la estación (p = 0,059) fueron significativos. El uso del suelo minero mostró las mayores concentraciones de metales y el agrícola las menores. Los niveles de los cuatro metales se encuentran en el rango marcado como alto por la EPA y por otras fuentes técnicas. En el caso de Pb y Cd no rebasan los estándares NOM-147- SEMARNAT-SSA1. Estos resultados reflejan el potencial indicativo del uso del suelo en la evaluación de la calidad ambiental, sin embargo, se requiere continuar con un monitoreo de metales pesados en la zona.

Vegetación bioindicadora de metales pesados en un sistema semiárido

Evaluar la contaminación por metales pesados en los ecosistemas permite conocer la capacidad bioindicativa de especies vegetativas. El objetivo fue determinar la concentración de metales pesados en Prosopis laevigata, Acacia spp. y Schinus molle bajo el efecto de usos suelo y temporalidad. El área se sitúa en la colindancia de los Municipios de Soledad de Graciano Sánchez y San Luis Potosí fragmentada por usos de suelo: agropecuario, comercio y servicios, residencial urbano y minero. Fueron tomadas muestras de hojas de las tres especies en las estaciones de verano, otoño, invierno y primavera y se evaluó la concentración de metales pesados a través de la técnica de ICP-MS. Los análisis estadísticos indicaron niveles de Aluminio (Al) > Cinc (Zn) > Plomo (Pb) > Cobre (Cu) > Titanio (Ti) > Vanadio (V) > Arsénico (As) > Cromo (Cr) > Cadmio (Cd) > Cobalto (Co). Los elementos Al, As, Cd, Cr, Pb y Ti presentaron niveles por encima del umbral normal en vegetación. El uso de suelo tuvo efecto significativo con Al, Ti, Cd, As y Pb; los árboles ubicados en los usos de suelo minero, comercio y servicios tuvieron la mayor concentración. La especie tuvo efecto significativo con Al y Pb siendo Acacia spp. el que presentó la mayor capacidad de acumulación. La temporada del año impactó significativamente en la acumulación de As, Cd, Co, Cu, Cr y Ti en las tres especies. La dinámica antropogénica de los diferentes usos de suelo genera partículas y residuos con metales pesados impactando en la disponibilidad y acumulación en las especies evaluadas. Se contribuye a evaluar el impacto ambiental en el sistema fragmentado recomendando dar continuidad a este tipo de estudios.