Toward an understanding of the atmospheric forcing uncertainties in the Mediterranean Sea

The thesis has extensively investigated for the first time the statistical distributions of atmospheric surface variables and heat fluxes for the Mediterranean Sea. After retrieving a 30-year atmospheric analysis dataset, we have captured the spatial patterns of the probability distribution of the relevant atmospheric variables for ocean atmospheric forcing: wind components (U,V), wind amplitude, air temperature (T2M), dewpoint temperature (D2M) and mean sea-level pressure (MSL-P). The study reveals that a two-parameter PDF is not a good fit for T2M, D2M, MSL-P and wind components (U,V) and a three parameter skew-normal PDF is better suited. Such distribution captures properly the data asymmetric tails (skewness). After removing the large seasonal cycle, we show the quality of the fit and the geographic structure of the PDF parameters. It is found that the PDF parameters vary between different regions, in particular the shape (connected to the asymmetric tails) and the scale (connected to the spread of the distribution) parameters cluster around two or more values, probably connected to the different dynamics that produces the surface atmospheric fields in the Mediterranean basin. Moreover, using the atmospheric variables, we have computed the air-sea heat fluxes for a 20-years period and estimated the net heat budget over the Mediterranean Sea. Interestingly, the higher resolution analysis dataset provides a negative heat budget of –3 W/m2 which is within the acceptable range for the Mediterranean Sea heat budget closure. The lower resolution atmospheric reanalysis dataset(ERA5) does not satisfy the heat budget closure problem pointing out that a minimal resolution of the atmospheric forcing is crucial for the Mediterranean Sea dynamics. The PDF framework developed in this thesis will be the basis for a future ensemble forecasting system that will use the statistical distributions to create perturbations of the atmospheric ocean forcing.

Análise voltamétrica da ciprofloxacina – aplicação a medicamentos e a remediação

O presente trabalho tem como objectivo o desenvolvimento de um método analítico, baseado na voltametria de onda quadrada (SWV), para a análise de ciprofloxacina (CIP) em produtos farmacêuticos e em processos de remediação. Para o desenvolvimento do método voltamétrico foram utilizadas duas células voltamétricas: a célula clássica (utilizando um eléctrodo de trabalho de carbono vítreo - GCE) e um eléctrodo de carbono impresso (SPCE). Após a optimização dos parâmetros da SWV, pH (3,04), frequência (400Hz), incremento de potencial (6 mV) e amplitude do impulso de potencial (40 mV), procedeu-se a validação dos métodos, obtendo-se zonas lineares entre a concentração de CIP e a intensidade de corrente de pico de 5,0×10-6 a 6,0×10-5 mol/L (GCE) e de 1,0×10-5 a 4,0×10-5 mol/L (SPCE) e limites de detecção de 9,48×10-6 mol/L (GCE) e 2,13×10-6 mol/L (SPCE). Verificou-se que a sensibilidade, a precisão e a selectividade são superiores para o SPCE, sendo por isso esta a célula mais adequada para proceder à análise da CIP em produtos farmacêuticos. O SPCE foi aplicado com sucesso à análise de CIP num produto farmacêutico. Para o tratamento de soluções aquosas contendo a CIP foram testados dois oxidantes: o permanganato de potássio e o peróxido de hidrogénio. Para o peróxido de hidrogénio os resultados obtidos foram inconclusivos. No caso do permanganato de potássio, os resultados mostram que a degradação da ciprofloxacina depende da concentração do oxidante. Para uma concentração de CIP de 3,00×10-4 mol/L uma degradação rápida foi obtida com o uso de 6,00×10-3 mol/L de permanganato de potássio. Na aplicação do permanganato na remediação de solos verificou-se que no caso de solos húmicos a ciprofloxacina é adsorvida pelo solo, não sendo possível confirmar a ocorrência da reacção de degradação. No caso de solos arenosos verificou-se que a ciprofloxacina foi rapidamente degradada pelo permanganato de potássio.

Betaiinin tuotannon sivujakeiden mikrosuodattaminen teräskeraamisella kalvolla

Betaiini on ammoniumyhdiste, jota käytetään esimerkiksi eläinten rehussa, kosmetiikassa ja lääkkeissä. Danisco Animal Nutrition Finnfeeds Finland Oy:n Naantalin tehdas on maailman johtava betaiinin tuottaja ja raaka-aineena tehtaalla käytetään melassierotuksesta saatavaa betaiinimelassia. Kiteisen betaiinin puhdistusprosessin yhteydessä syntyybetaiinipitoisia sivujakeita, jotka sisältävät huomattavan määrän betaiinia, minkä takia niiden jatkokäsittely on tärkeää. Betaiinin tuotannon sivujakeet ovat erittäin vaikeasti suodattuvia orgaanisia liuoksia, joiden koostumuksia ei täysin tunneta. Tämän työn tarkoituksena oli puhdistaa betaiinin tuotannon sivujakeita mikrosuodattamalla niitä teräskeraamisella kalvolla. Työn kokeellisessa osassa suoritettiin suodatusparametrien eli pH:n, lämpötilan, TMP:n ja betaiiniliuoksen kuiva-ainepitoisuuden optimointi sekä konsentrointikokeita. Mikrosuodatus suoritettiin Graver Technologiesin Scepter-putkimoduulilla, joka toimi ohivirtausperiaatteella ja jonka huokoskoko oli 0,1 ¿m. Scepter-moduuli koostui ruostumattomasta teräksestä sintratuista putkimoduuleista, joissa erottavana kerroksena toimi TiO2. Esikokeiden perusteella todettiin ettei pH:lla ollut suurta vaikutusta suodatukseen. Permeaattivuo kasvoi selvästi lämpötilan ja TMP:nkasvaessa. Vuo taas huononi ja permeaatin sameus lisääntyi selvästi 35 % korkeammissa kuiva-ainepitoisuuksissa. Konsentrointikokeet suoritettiin betaiiniliuoksen refraktrometrisessa kuiva-ainepitoisuudessa, BetRk, 35 %, 80 °C lämpötilassa ja betaiiniliuoksen omassa pH:ssa (pH 8-9,5). Esikokeiden tulosten perusteella konsentrointikokeet suoritettiin TMP:ssa 0,6; 0,8 ja 1,0 bar. Betaiinin tuotannonsivujakeiden konsentrointikokeissa saannoksi saatiin 95 %. Suodatustuloksista havaittiin, että betaiinin tuotannon sivujakeen erä vaikutti voimakkaasti suodatuksen toimivuuteen. Konsentrointikokeissa suodatukset suoritettiin sekäuusilla mikrosuodatusmoduuleilla että vanhalla moduulilla, joka oli jo kulunut.Kulumisen ei kuitenkaan havaittu huonontavan suodatustehokkuutta. Konsentrointikokeiden perusteella voidaan laitteiston pesuväliksi arvioida noin viikko ja pesu tulisi suorittaa sekä emäksisellä että happamalla pesuaineella.

USO DO PLANEJAMENTO EXPERIMENTAL PARA OTIMIZAÇÃO DE UM PROCEDIMENTO VOLTAMÉTRICO PARA DETERMINAÇÃO SIMULTÂNEA DAS CONCENTRAÇÕES DOS METAIS Zn, Cd, Pb E Cu LIVRES EM ÁGUA DE COCO

Optimization of the main parameters of SWASV using boron-doped diamond electrode was described for the simultaneous determination of Zn, Cd, Pb and Cu free in coconut water. The values of electroanalytical parameters studied were optimized with the factorial design and center composite design. The optimized parameters for the preconcentration of metals were -1.50 V for potential, and 240 s for deposition time. For SWV, the optimized value was 11.56 mV for step potential. In addition, frequency and pulse height were defined at 100 Hz and 55 mV, respectively. Furthermore, the concentration of the supporting electrolyte (acetate buffer, pH 4.7) was optimized in 0.206 mol L-1. The optimized procedure was applied in two samples of coconut water: natural and processed. The limits of detection (LOD) obtained for Zn, Cd, Pb and Cu were 7.2; 4.4; 3.3 and 1.5 µg L-1, respectively. The concentrations of Cd and Pb were not detected. On the other hand, the values found for the concentrations of Zn and Cu were: < LOD (29 µg L-1) and (6.8 ± 0.9) µg L-1 for the natural sample; and (85.8 ± 4.2) µg L-1 and (7.7 ± 0.6) µg L-1 for the processed sample, respectively.

Microcracks and Vortices in Superconducting Thin Films

In this work, superconducting YBa₂ Cu₃O_6+x (YBCO) thin films have been studied with the experimental focus on the anisotropy of BaZrO₃ (BZO) doped YBCOthin films and the theoretical focus on modelling flux pinning by numerically solving Ginzburg- Landau equations. Also, the structural properties of undoped YBCO thin films grown on NdGaO₃ (NGO) and MgO substrates were investigated. The thin film samples were made by pulsed laser ablation on single crystal substrates. The structural properties of the thin films were characterized by X-ray diffraction and atomic force microscope measurements. The superconducting properties were investigated with a magnetometer and also with transport measurements in pulsed magnetic field up to 30 T. Flux pinning was modelled by restricting the value of the order parameter inside the columnar pinning sites and then solving the Ginzburg-Landau equations numerically with the restrictions in place. The computations were done with a parallel code on a supercomputer. The YBCO thin films were seen to develop microcracks when grown on NGO or MgO substrates. The microcrack formation was connected to the structure of the YBCO thin films in both cases. Additionally, the microcracks can be avoided by careful optimization of the deposition parameters and the film thickness. The BZO doping of the YBCO thin films was seen to decrease the effective electron mass anisotropy, which was seen by fitting the Blatter scaling to the angle dependence of the upper critical field. The Ginzburg-Landau simulations were able to reproduce the measured magnetic field dependence of the critical current density for BZO doped and undoped YBCO. The simulations showed that in addition to the large density also the large size of the BZO nanorods is a key factor behind the change in the power law behaviour between BZO doped and undoped YBCO. Additionally, the Ginzburg-Landau equations were solved for type I thin films where giant vortices were seen to appear depending on the film thickness. The simulations predicted that singly quantized vortices are stable in type I films up to quite large thicknesses and that the size of the vortices increases with decreasing film thickness, in a way that is similar to the behaviour of the interaction length of Pearl vortices.

Ruthenium oxide hexacyanoferrate modified electrode for hydrogen peroxide detection

A sensor for H2O2 amperometric detection based on a Prussian blue (PB) analogue was developed. The electrocatalytic process allows the determination of hydrogen peroxide at 0.0 V with a limit of detection of 1.3 mu mol L-1 in a flow injection analysis (FIA) configuration. Studies on the optimization of the FIA parameters were performed and under optimal FIA operational conditions the linear response of the method was extended up to 500 mu mol L-1 hydrogen peroxide with good stability. The possibility of using the developed sensor in medium containing sodium ions and the increased operational stability constitute advantages in comparison with PB-based amperometric sensors. The usefulness of the methodology was demonstrated by addition-recovery experiments with rainwater samples and values were in the 98.8 to 103% range.

Antenas planares integradas com FSSs para aplicações em sistemas de comunicações sem fio

This work presents a theoretical and experimental analysis about the properties of microstrip antennas with integrated frequency selective surfaces (Frequency Selective Surface - FSS). The integration occurs through the insertion of the FSS on ground plane of microstrip patch antenna. This integration aims to improve some characteristics of the antennas. The FSS using patch-type elements in square unit cells. Specifically, the simulated results are obtained using the commercial computer program CST Studio Suite® version 2011. From a standard antenna, designed to operate in wireless communication systems of IEEE 802.11 a / b / g / n the dimensions of the FSS are varied to obtain an optimization of some antenna parameters such as impedance matching and selectivity in the operating bands. After optimization of the investigated parameters are built two prototypes of microstrip patch antennas with and without the FSS ground plane. Comparisons are made of the results with the experimental results by 14 ZVB network analyzer from Rohde & Schwarz ®. The comparison aims to validate the simulations performed and show the improvements obtained with the FSS in integrated ground plane antenna. In the construction of prototypes, we used dielectric substrates of the type of Rogers Corporation RT-3060 with relative permittivity equal to 10.2 and low loss tangent. Suggestions for continued work are presented

Avaliação de interface de reação e colisão para eliminar interferências poliatômicas na análise de etanol combustível por ICP-MS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesen von C-glycosylierten Aminosäuren und Peptiden unter Einsatz speziell konstruierter Mikroreaktoren

Die chemische Synthese definierter Glycopeptidstrukturen bildet die Basis einiger vielversprechender Ansätze zur Therapie verschiedener Krankheiten. Die Entwicklung hochaffiner Selektininhibitoren könnte der Behandlung chronischer Entzündungen und zur Unterdrückung der Metastasierung von Tumoren dienen. Vollsynthetische Vakzine auf Basis glycosylierter MUC1-Partialstrukturen sollen das Immunsystem zur Bekämpfung von krankem Gewebe anregen und so perspektivisch eine Impfung gegen Krebs ermöglichen. Da die natürlich vorkommenden O-Glycoside in vivo eine begrenzte Stabilität besitzen, wurde eine Methode entwickelt, welche die modulare Herstellung von stabilen rnC-Glycosylaminosäuren als Mimetika der natürlichen Serin-, Threonin- und Tyrosin-Glycoside ermöglicht. Dazu wurden passend geschützte Kohlenhydrat-Lactone synthetisiert, die in einer mikrowellengestützten Petasis-Olefinierung unter Durchflussbedingungen in die entsprechenden exo-Glycale überführt wurden. Die Reaktionszeit konnte durch diese spezielle Reaktionsführung auf weniger als drei Minuten verringert werden, während konventionell mehrere Stunden benötigt werden. Die C-glycosidische Verknüpfung mit den entsprechenden Aminosäurebausteinen gelang durch eine Hydroborierungs-Suzuki-Kupplungs-Kaskade. Nach umfangreicher Optimierung der Reaktionsparameter ließ sich neben mehreren Monosacchariden auch ein exo-Glycal der Lactose erfolgreich in der Kupplung einsetzen. Nach verschiedenen Schutzgruppenmanipulationen wurden einige der synthetisierten Bausteine zur Synthese C-glycosylierter Partialstrukturen des Mucins MUC1 an der festen Phase herangezogen. In ELISA-Experimenten wurden die C-Glycosylpeptide von an Brustkrebsgewebe bindenden Antikörpern erkannt, die durch Vakzinierung mit ähnlichen Strukturen erhalten worden waren. Zur Synthese zweier Bausteine potenzieller Selektin-Inhibitoren wurde ein Mimetikum des in natürlichen Liganden vorkommenden Tetrasaccharides Sialyl-Lewisx synthetisiert. Bei diesem wurde die terminale Sialinsäure durch (S)-Cyclohexylmilchsäure ersetzt. Die bei der gewählten Syntheseroute notwendige regioselektive Öffnung eines Benzylidenacetals wurde in einem Mikroreaktor durchgeführt, wodurch eine einfache Reaktionsoptimierung mit geringen Substanzmengen möglich war. Die Reaktionszeit liegt mit unter 4 Minuten deutlich unter den üblichen Werten von einer bis mehreren Stunden. In einer Block-Glycosylierung konnte das Pseudotetrasaccharid sowohl an einen C-Lactosyl-Tyrosin-, als auch an einen C-Lactosyl-Serin-Akzeptor angefügt und somit die Synthese der Zielverbindungen abgeschlossen werden. Diese Bausteine können in Zukunft als Bestandteile synthetischer Glycopeptide zum Einsatz kommen, welche Mimetika der natürlichen Selektin-Liganden darstellen sollen.rn

Síntese verde de nanopartículas de prata a partir de extrato aquoso do tubérculo de Curcuma longa associadas à quitosana e avaliação da atividade antitumoral in vitro em câncer de pele não melanoma (linhagem A431)

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Biológicas, Programa de Pós-Graduação Nanociência e Nanobiotecnologia, 2016.

Estimation of the thickness and the optical parameters of several stacked thin films using optimization

The reverse engineering problem addressed in the present research consists of estimating the thicknesses and the optical constants of two thin films deposited on a transparent substrate using only transmittance data through the whole stack. No functional dispersion relation assumptions are made on the complex refractive index. Instead, minimal physical constraints are employed, as in previous works of some of the authors where only one film was considered in the retrieval algorithm. To our knowledge this is the first report on the retrieval of the optical constants and the thickness of multiple film structures using only transmittance data that does not make use of dispersion relations. The same methodology may be used if the available data correspond to normal reflectance. The software used in this work is freely available through the PUMA Project web page (http://www.ime.usp.br/similar to egbirgin/puma/). (C) 2008 Optical Society of America

Optimization of Process Parameters for the Extraction of Gelatin from the Skin of Freshwater Fish and the Evaluation of Physical anal Chemical Characteristics

Faculty of Marine Sciences,Cochin University of Science and Technology

Investigation and optimization of parameters affecting the multiply charged ion yield in AP-MALDI MS

Liquid matrix-assisted laser desorption/ionization (MALDI) allows the generation of predominantly multiply charged ions in atmospheric pressure (AP) MALDI ion sources for mass spectrometry (MS) analysis. The charge state distribution of the generated ions and the efficiency of the ion source in generating such ions crucially depend on the desolvation regime of the MALDI plume after desorption in the AP-tovacuum inlet. Both high temperature and a flow regime with increased residence time of the desorbed plume in the desolvation region promote the generation of multiply charged ions. Without such measures the application of an electric ion extraction field significantly increases the ion signal intensity of singly charged species while the detection of multiply charged species is less dependent on the extraction field. In general, optimization of high temperature application facilitates the predominant formation and detection of multiply charged compared to singly charged ion species. In this study an experimental setup and optimization strategy is described for liquid AP-MALDI MS which improves the ionization effi- ciency of selected ion species up to 14 times. In combination with ion mobility separation, the method allows the detection of multiply charged peptide and protein ions for analyte solution concentrations as low as 2 fmol/lL (0.5 lL, i.e. 1 fmol, deposited on the target) with very low sample consumption in the low nL-range.

Determining the Optimum Processing Parameters of Glass-like Carbon Using Weibull Analysis of its Fracture Behaviour

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optimization of Arq Parameters of Stanag 5066 for the HFDVL Modem

The reliability of bidirectional communication link can be guaranteed with Automatic Repeat Request Procedures (ARQ). The standard STANAG 5066 describes the ARQ procedure for HF communications that can either be applied to existing HF physical layers modems or adapted to future physical layer designs. In this contribution the physical layer parameters of an HF modem (HFDVL), developed by the authors over the last decade, are chosen to optimize the performance of the ARQ procedure described in STANAG 5066. Besides the interleaving length, constellation size and coding type, the OFDM-based HFDVL modem permits the selection of the number of receiver antennas. It will be shown that this parameter gives additional degrees of freedom and permits reliable communication over low SNR HF communication links.