Development of paper based electrodes: From air-breathing to paintable enzymatic cathodes

This work presents the results from the development of bio-cathodes for the application on paper-based biofuel cells. Our main goal here is to demonstrate the possibility of using different designs of air-breathing bio-cathodes and ink-based bio-cathodes for this new type of paper based electrochemical cell. The electrochemical performance for the bio-electrocatalytic oxygen reduction reaction was studied by using open circuit voltage and amperometry measurements, as well as polarization curves to probe the four-electron reduction reaction of ambient oxygen catalyzed by bilirubin oxidase (BOx). The electrochemical measurements showed that all procedures allowed the direct electron transfer from the active site of the bilirubin oxidase to the electrode surface with a limiting current density of almost 500 mu A cm(-2) for an air-breathing BOx cathode and 150 mu A cm(-2) for an ink based BOx cathode. Under a load of 300 mV a stable current density was obtained for 12 h of continuous operation. (C) 2012 Elsevier Ltd. All rights reserved.

Texture analysis of cold rolled and annealed aluminum alloy produced by twin-roll casting

A 7.4 mm thick strip of 3003 aluminum alloy produced by the industrial twin-roll casting (TRC) process was homogenized at 500 °C for 12 hours, after which it was cold rolled in two conditions: 1) to reduce the strip's thickness by 67%, and 2) to reduce it by 91%. The alloy was annealed at 400 °C for 1 hour in both conditions. The results revealed that a rotated cube texture, the {001}<110> component, predominated in the as-cast condition and was transformed into brass, copper and S type textures during the cold rolling process. There was practically no difference between the deformation textures at the two thickness reductions.

Antioxidative responses of cell suspension cultures of two Coffea arabica varieties to low aluminum levels at pH 5.8

The effects of aluminum (Al) on the activities of antioxidant enzymes and ferritin expression were studied in cell suspension cultures of two varieties of Coffea arabica, Mundo Novo and Icatu, in medium with pH at 5.8. The cells were incubated with 300 µM Al3+, and the Al speciation as Al3+ was 1.45% of the mole fraction. The activities of superoxide dismutase (SOD), catalase (CAT), and glutathione S-transferase (GST) were increased in Mundo Novo, whereas glutathione reductase (GR) and guaiacol peroxidase (GPOX) activities remained unchanged. SOD, GR, and GST activities were increased in Icatu, while CAT activity was not changed, and GPOX activity decreased. The expression of two ferritin genes (CaFer1 and CaFer2) were analyzed by Real-Time PCR. Al caused a downregulation of CaFER1 expression and no changes of CaFER2 expression in both varieties. The Western blot showed no alteration in ferritin protein levels in Mundo Novo and a decrease in Icatu. The differential enzymes responses indicate that the response to Al is variety-dependent.

Modelling coupled physical-biogeochemical processes in ice-covered oceans

The last decades have seen a large effort of the scientific community to study and understand the physics of sea ice. We currently have a wide - even though still not exhaustive - knowledge of the sea ice dynamics and thermodynamics and of their temporal and spatial variability. Sea ice biogeochemistry is instead largely unknown. Sea ice algae production may account for up to 25% of overall primary production in ice-covered waters of the Southern Ocean. However, the influence of physical factors, such as the location of ice formation, the role of snow cover and light availability on sea ice primary production is poorly understood. There are only sparse localized observations and little knowledge of the functioning of sea ice biogeochemistry at larger scales. Modelling becomes then an auxiliary tool to help qualifying and quantifying the role of sea ice biogeochemistry in the ocean dynamics. In this thesis, a novel approach is used for the modelling and coupling of sea ice biogeochemistry - and in particular its primary production - to sea ice physics. Previous attempts were based on the coupling of rather complex sea ice physical models to empirical or relatively simple biological or biogeochemical models. The focus is moved here to a more biologically-oriented point of view. A simple, however comprehensive, physical model of the sea ice thermodynamics (ESIM) was developed and coupled to a novel sea ice implementation (BFM-SI) of the Biogeochemical Flux Model (BFM). The BFM is a comprehensive model, largely used and validated in the open ocean environment and in regional seas. The physical model has been developed having in mind the biogeochemical properties of sea ice and the physical inputs required to model sea ice biogeochemistry. The central concept of the coupling is the modelling of the Biologically-Active-Layer (BAL), which is the time-varying fraction of sea ice that is continuously connected to the ocean via brines pockets and channels and it acts as rich habitat for many microorganisms. The physical model provides the key physical properties of the BAL (e.g., brines volume, temperature and salinity), and the BFM-SI simulates the physiological and ecological response of the biological community to the physical enviroment. The new biogeochemical model is also coupled to the pelagic BFM through the exchange of organic and inorganic matter at the boundaries between the two systems . This is done by computing the entrapment of matter and gases when sea ice grows and release to the ocean when sea ice melts to ensure mass conservation. The model was tested in different ice-covered regions of the world ocean to test the generality of the parameterizations. The focus was particularly on the regions of landfast ice, where primary production is generally large. The implementation of the BFM in sea ice and the coupling structure in General Circulation Models will add a new component to the latters (and in general to Earth System Models), which will be able to provide adequate estimate of the role and importance of sea ice biogeochemistry in the global carbon cycle.

Ectomycorrhizae of sessile oak (Quercus petraea (Matt.) Liebl.)

Investigations were performed during the years 1999 to 2001 on a limed and unlimed plot within a high-elevated sessile oak forest. The oak forest (with 90 years old European beech at the understorey) was 170 to 197 years old. It is located at forest district Merzalben, location 04/0705, which is situated in the Palatinate Forest in south-west Germany. Liming was performed in December 1988 when 6 tons/ha of powdered Dolomite were brought up by the forestry department. Liming was performed to counteract the effects of soil acidification (pH(H2O) at Horizon A (0-10 cm): 3.9), which is induced by long-term (anthropogenic) acidic cloud cover and precipitation. Potentially toxic Al3+ ions, which become solubilized below pH 5, were suspected to be responsible for forest dieback and sudden death of the mature oaks. The most logical entry point for these toxic ions was suspected to occur in the highly absorptive region of the ectomycorrhizae (fungal covered root tips). However, the diversity and abundance of oak-ectomycorrhizal species and their actual roles in aluminum translocation (or blockage) were unknown. It was hypothesized that the ectomycorrhizae of sessile oaks in a limed forest would exhibit greater seasonal diversity and abundance with less evidence of incorporated aluminum than similar oak ectomycorrhizae from unlimed soils. To test this hypothesis, 12 oaks in the limed plot and 12 in an adjacent unlimed plot were selected. Each spring and fall for 2 years (1999 & 2000), 2 sets of soil cylinders (9.9 cm dia.) were extracted from Horizon A (0-10 cm), Horizon B (30-40 cm) and Horizon C (50-60 cm depth) at a distance of 1 meter from each tree base. Roots were extracted from each probe by gentle sieving and rinsing. Soil samples were retained for pH (H2O, CaCl2, and KCl) and moisture analysis. One set of roots was sorted by size and air-dried for biomass analysis. The finest mycorrhizal roots of this set were used for bound and unbound (cytosolic) mineral [Al, Ca, Mg, K, Na, Mn, S, Zn, Fe, Cd and Pb] analysis (by Landwirtschaftliche Untersuchungs- und Forschungsanstalt Rheinland Palatinate (LUFA)). Within 7 days of collection, the mycorrhizal tips from the second set of probes were excised, sorted, identified (using Agerer’s Color Atlas), counted and weighed. Seasonal diversity and abundance was characterized for 50 of the 93 isolates. The location and relative abundance of Al within the fungal and root cell walls was characterized for 68 species using 0.01% Morin dye and fluorescence microscopy. Morin complexes with Al to produce an intense yellow fluorescence. The 4 most common species (Cenococcum geophilum, Quercirhiza fibulocsytidiata, Lactarius subdulcis, Piceirhiza chordata) were prepared for bound Al, Ca, Fe and K mineral analysis by LUFA. The unlimed and limed plots were then compared. Only 46 of the 93 isolated ectomycorrhizal species had been previously associated with oaks in the literature. Mycorrhizal biomass was most abundant in Horizon A, declining with depth, drought and progressive soil acidification. Mycorrhizae were most diverse (32 species) in the limed plot, but individual species abundance was low (R Selection) in comparison to the unlimed plot, where there were fewer species (24) but each species present was abundant (K Selection). Liming increased diversity and altered dominance hierarchy, seasonal distributions and succession trends of ectomycorrhizae at all depths. Despite an expected reduction in Al content, the limed ectomycorrhizae both qualitatively (fluorescence analysis) and quantitatively (mineral analysis) contained more bound Al, especially so in Horizon A. The Al content qualitatively and quantitatively increased with depth in the unlimed and limed plots. The bound Al content fluctuated between 4000-and 20000 ppm while the unbound component was consistently lower (4 -14 ppm). The relative amount of unbound Al declined upon liming implying less availability for translocation to the crown area of the trees. This correspouds with the findings of good crown appearance and lower tree mortality in the limed zone. Each ectomycorrhizal species was unique in its ability to block, sequester (hold) or translocate Aluminum. In several species, Al uptake varied with changes in moisture, pH, depth and liming. According to the fluorescence study, about 48% of the isolated ectomycorrhizal species blocked and/or sequestered (held) Al in their mantle and/or Hartig net walls, qualitatively lowering bound Al in the adjacent root cell walls. Generally, if Al was more concentrated in the fungal walls, it was less evident in the cortex and xylem and conversely, if Al was low or absent from the fungal walls it was frequently more evident in the cortex and xylem.

Determinazione di radicali OH: sintesi di materiali per la modifica di elettrodi di platino e carbone vetroso

Questa tesi descrive lo sviluppo di un elettrodo modificato con un polimero isolante per la determinazione indiretta del radicale OH. I polimeri testati sono stati polifenolo, polipirrolo e polipirrolo sovraoossidato ed il primo è risultato quello con le migliori prestazioni. Il film di modificante è stato depositato per elettropolimerizzazione del fenolo in ambiente acido, su un elettrodo di carbone vetroso (GC) ed è risultato isolante e perfettamente adeso al GC, impedendo il trasferimento di carica alle più comuni sonde redox. L’attacco dei radicali OH, generati dalla reazione di Fenton o dalla fotolisi di H2O2, rimuove parzialmente il polimero dal GC, ripristinando parzialmente il comportamento conduttore dell’elettrodo. L’entità della degradazione del film polifenolico è stata valutata sfruttando la corrente relativa alla sonda redox Ru(NH3)63+, che rappresenta il segnale analitico per la determinazione del radicale OH. L’elettrodo è stato impiegato per stimare le prestazioni di foto catalizzatori a base di nanoparticelle di TiO2, ottenendo risultati correlati a quelli ricavati da un metodo HPLC. Inoltre esso è stato usato per sviluppare una nuova procedura per la determinazione della capacità di scavenging verso i radicali OH, che è stata applicata all’analisi di composti puri e campioni reali. I risultati erano confrontabili con quelli determinati con metodiche standardizzate, comunemente impiegate per la determinazione della capacità antiossidante. Inoltre è stato condotto uno studio riguardante la modifica di un elettrodo di platino con un idrossido misto a strati a base di cobalto e alluminio (LDH). In particolare si sono valutati gli effetti di diversi pretrattamenti del Pt sulle caratteristiche e prestazioni elettrocatalitiche del film di LDH nei confronti dell’ossidazione di anilina, fenolo e acido salicilico. Questi composti possono essere impiegati come molecole sonda per la determinazione del radicale OH e rivestono interesse da un punto di vista elettroanalitico perché portano facilmente alla passivazione della superficie di Pt.

Tunnelkontakte mit Heusler-Elektrode: Spinpolarisation von Co 2Cr 0,6Fe 0,4Al und Einfluss der Barriere

Ziel dieser Arbeit ist die Bestimmung der Spinpolarisation von der Heusler-Verbindung Co2Cr0,6Fe0,4Al. Dieses Ziel wurde durch die sorgfältige Präparation von Co2Cr0,6Fe0,4Al basierten Tunnelkontakten realisiert. Tunnelwiderstandsmessungen an Co2Cr0,6Fe0,4Al-basiertenrnTunnelkontakten ergaben einen Tunnelmagnetowiderstand von 101% bei 4 K. DieserrnTunnelmagnetowiderstand legt eine untere Grenze von 67% für die Spinpolarisation von Co2Cr0,6Fe0,4Al fest.rnrnCo2Cr0,6Fe0,4Al ist eine Heusler-Verbindung, der die Eigenschaften eines halbmetallischen Ferromagneten zugeschrieben werden. Ein halbmetallischer Ferromagnet hat an der Fermikante nur Elektronenspinzustände mit einer Polarisation. Als Folge davon können bei einem spinerhaltenden Tunnelprozess nur Elektronen einer Spinrichtung in den halbmetallischen Ferromagneten tunneln. Mit einem magnetischen Feld und einer durch einen Antiferromagneten fixierten Gegenelektrode, können an einem Tunnelkontakt mit einem spinpolarisierten Ferromagneten deshalb zwei Zustände, eine hohe und eine niedrige Tunnelleitfähigkeit, erzeugt werden. Daher finden spinpolarisierte Tunnelkontakte in Form von MRAM in der Datenspeicherung Verwendung. Bislang wurde jedoch keine Verbindung gefunden, der eine Spinpolarisation von 100% experimentell eindeutig nachgewiesen werden konnte. Für Co2Cr0,6Fe0,4Al lagen die höchsten gemessenen Spinpolarisationen um 50%.rnrnTunnelspektroskopie ist eine zuverlässige und anwendungsnahe Methode zur Untersuchung der Spinpolarisation. Inelastische Tunnelprozesse und eine reduzierte Ordnung an Grenzflächen bewirken einen reduzierten Tunnelmagnetowiderstand. Eine symmetriebrechende Barriere, wie amorphes AlOx, ist Voraussetzung für die Anwendung des Jullière-Modells zur Bestimmung der Spinpolarisation. Das Jullière-Modell verknüpft die Spin-aufgespaltenenrnZustandsdichten der Elektroden mit dem Tunnelmagnetowiderstand. Ohne einernsymmetriebrechende Barriere, zum Beispiel mit MgO als Isolatorschicht, können höhere Tunnelmagnetowiderstände erzwungen werden. Ein eindeutiger Rückschluss auf die Spinpolarisation ist dann jedoch nicht mehr möglich. Mit Aluminiumoxid-basierten Barrieren liefert die Anwendung des einfachen Jullière-Modells eine Untergrenze der Spinpolarisation.rnrnUm die Spinpolarisation von Co2Cr0,6Fe0,4Al durch Tunnelspektroskopie zu bestimmen, musste die Präparation der Tunnelkontakte verbessert werden. Dies wurde ermöglicht durch den Anbau einer neuen Sputterkammer mit besseren UHV-Bedingungen an ein bestehendes Präparationscluster. Co2Cr0,6Fe0,4Al wird mit Hilfe von Radiofrequenz-Kathodenzerstäuben deponiert. Die resultierenden Schichten verfügen nach ihrer Deposition über einen höheren Ordnungsgrad und über eine geordnete Oberfläche. Durch eine Magnesium-Pufferschicht war es möglich, auf diese Oberfläche eine homogene amorphe AlOx-Barriere zu deponieren. Als Gegenelektrode wurde CoFe als Ferromagnet mit MnFe als Antiferromagnet gewählt. Diese Gegenelektrode ermöglicht Tunnelmessungen bis hin zu Raumtemperatur.rnrnMit den in dieser Arbeit vorgestellten optimierten Analyse- und Präparationsmethoden ist es möglich, die Untergrenze der Spinpolarisation von Co2Cr0,6Fe0,4Al auf 67% anzuheben. Dies ist der bisher höchste veröffentlichte Wert der Spinpolarisation von Co2Cr0,6Fe0,4Al.rn

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Thermally reduced Graphene Oxide: a well promising way to transparent flexible electrodes.

L'elaborato tratta dell'ottimizzazione del processo di riduzione termica dell'ossido di grafene in termini di conduttività e trasmittanza ottica. Definiti gli standard di deposizione tramite spin-coating e riduzione termica, i film prodotti vengono caratterizzati tramite XPS, AFM, UPS, TGA, ne vengono testate la conducibilità, con e senza effetto di gate, e la trasmittanza ottica, ne si misura l'elasticità tramite spettroscopia di forza, tutto al fine di comprendere l'evoluzione del processo termico di riduzione e di individuare i parametri migliori al fine di progredire verso la produzione di elettrodi flessibili e trasparenti a base di grafen ossido ridotto.

Microbiologic results after non-surgical erbium-doped:yttrium, aluminum, and garnet laser or air-abrasive treatment of peri-implantitis: a randomized clinical trial

The purpose of this study is to assess clinical and microbiologic effects of the non-surgical treatment of peri-implantitis lesions using either an erbium-doped:yttrium, aluminum, and garnet (Er:YAG) laser or an air-abrasive subgingival polishing method.

A Model to Predict Percolation Threshold and Effective Conductivity of Infiltrated Electrodes for Solid Oxide Fuel Cells

We present a mechanistic modeling methodology to predict both the percolation threshold and effective conductivity of infiltrated Solid Oxide Fuel Cell (SOFC) electrodes. The model has been developed to mirror each step of the experimental fabrication process. The primary model output is the infiltrated electrode effective conductivity which provides results over a range of infiltrate loadings that are independent of the chosen electronically conducting material. The percolation threshold is utilized as a valuable output data point directly related to the effective conductivity to compare a wide range of input value choices. The predictive capability of the model is demonstrated by favorable comparison to two separate published experimental studies, one using strontium molybdate and one using La0.8Sr0.2FeO3-δ as infiltrate materials. Effective conductivities and percolation thresholds are shown for varied infiltrate particle size, pore size, and porosity with the infiltrate particle size having the largest impact on the results.

A Model to Predict Percolation Threshold and Effective Conductivity of Infiltrated Electrodes for Solid Oxide Fuel Cells

We present a mechanistic modeling methodology to predict both the percolation threshold and effective conductivity of infiltrated Solid Oxide Fuel Cell (SOFC) electrodes. The model has been developed to mirror each step of the experimental fabrication process. The primary model output is the infiltrated electrode effective conductivity which provides results over a range of infiltrate loadings that are independent of the chosen electronically conducting material. The percolation threshold is utilized as a valuable output data point directly related to the effective conductivity to compare a wide range of input value choices. The predictive capability of the model is demonstrated by favorable comparison to two separate published experimental studies, one using strontium molybdate and one using La0.8Sr0.2FeO3-delta as infiltrate materials. Effective conductivities and percolation thresholds are shown for varied infiltrate particle size, pore size, and porosity with the infiltrate particle size having the largest impact on the results. (C) 2013 The Electrochemical Society. All rights reserved.

Emergency and elective implantation of covered stent systems in iatrogenic arterial injuries

To evaluate the effectiveness and safety of covered stents for the management of iatrogenic arterial injury.