La biodisponibilité du fer est un facteur limitant de la production phytoplanctonique dans de nombreuses régions océaniques. Le fer dissous (<0,2 µm) consommé par les micro-organismes est complexé à 99 % par des ligands organiques dont l'origine et la nature chimique restent peu connues. <br /><br />Les porphyrines, molécules ubiquistes synthétisées par tous les organismes, sont capables de chélater le fer, sous la forme de complexes fer-porphyrines. A la mort des organismes, ces complexes pourraient donc être libérés dans l'eau de mer en tant que produits de dégradation cellulaire et pourraient participer à la complexation organique du fer. L'objectif de ce travail de thèse est donc de tester cette hypothèse.<br /><br />La première partie consistait à mettre au point une première méthode de dosage correspondant à une analyse par injection en flux et détection par chimiluminescence (FIA-CL). Un protocole a été développé pour l'analyse d'échantillons d'eau de mer. Des tests d'interférences suggèrent que la FIA-CL est bien spécifique aux complexes fer-porphyrines. Plusieurs tests d'augmentation de la sensibilité ont permis d'atteindre une limite de détection de 0,11 nM d'équivalent hémine (fer-porphyrine de référence). Des premières concentrations en fer-porphyrines ont ainsi pu être déterminées dans différents types d'environnements naturels (eau de mer, eau douce et eau intermédiaire) riches en matière organique.<br /><br />La seconde partie visait à étudier un processus de relarguage des fer-porphyrines, tel que le broutage du phytoplancton par le zooplancton. Lors de cette étude, l'existence d'une interférence provoquée par les radicaux superoxyde générés lors de la croissance du phytoplancton a été mise en évidence, lors de la mesure des fer-porphyrines. Un protocole d'élimination de ces interférences a donc été établi. Par des expériences de culture, avec un modèle simple « phytoplancton-zooplancton », la libération des fer-porphyrines dans l'eau de mer a pu être mise en évidence.<br /><br />Ce travail de thèse pourra permettre d'étudier le devenir des fer-porphyrines dans l'eau de mer et leur rôle dans la complexation organique du fer.

Ce travail concerne la réalisation d'une électrode enzymatique utilisable pour le suivi en ligne (<i>on-line</i>) d'un procédé de fermentation. Cette étude a nécessité la mise au point d'une nouvelle technique d'immobilisation, applicable à différentes enzymes. Elle est basée sur la formation de liaisons covalentes entre l'enzyme et l'agent portant: le glutaraldéhyde. La méthode consiste en une adsorption de l'enzyme suivie du dépôt, par vaporisation, de l'agent réticulant sur l'extrémité sensible des électrodes de pH en verre. Ce procédé d'immobilisation assure un temps de réponse extrêmement court du biocapteur. Cette performance est un avantage indéniable pour des mesures en continu, tel qu'un système d'analyse par injection en flux continu (FIA). Par la suite, nous avons développé des systèmes FIA incorporant trois différents types de cellules de détection appropriées aux besoins analytiques. Des électrodes à pénicillinase et à uréase, préparées selon la méthode décrite ci-dessus, ont été installées et utilisées dans ces cellules. Les systèmes biocapteurs-FIA, ainsi conçus, ne nécessitent alors ni réacteur enzymatique, ni réactif. De plus, le temps de réponse très court du biocapteur allie aux avantages de la FIA et aux spécificités des cellules a permis d'obtenir une cadence de mesure très élevée. Ce système d'analyse a été applique aux mesures en ligne de la concentration de pénicilline au cours de sa production fermentaire et aux mesures automatiques de l'urée dans les échantillons de sérum humain. Pour cela, nous avons automatise le système biocapteur-FIA et conçu une nouvelle cellule a écoulement agite pour l'installation des électrodes à uréase et a pénicillinase. Ce système biocapteur-FIA donne des résultats satisfaisants pour la détermination de l'urée et surtout s'est révélé extrêmement performant pour le suivi hors ligne et en ligne de la concentration de pénicilline pendant plusieurs fermentations d'une durée de 250 heures environ. Dans ce dernier cas, la comparaison des mesures effectuées avec le système biocapteur-FIA et une méthode classique de dosage (HPLC) est favorable à l'analyseur biocapteur-FIA qui assure des mesures en ligne avec une bonne fiabilité et a un moindre cout, mais aussi en raison de sa simplicité. En rendant possible une exploitation immédiate des mesures en ligne de la concentration en pénicilline par l'ordinateur central de l'installation fermentaire, le système biocapteur-FIA présente un pas important dans l'amélioration du contrôle et/ou de la modélisation des bioprocédés.

Made available in DSpace on 2016-06-02T20:34:18Z (GMT). No. of bitstreams: 1 2757.pdf: 3606841 bytes, checksum: 1cbaf9d57ef931332c3b9f278a479c5a (MD5) Previous issue date: 2009-09-04 / Universidade Federal de Sao Carlos / In this work methods for determining minoxidil (MX) in commercial samples and electrolytes of synthetic plasma and urine are presented. The minoxidil is a pharmaceutical whose blood vessel dilation property is used in the treatment of the Arterial Hypertension and in the treatment of the Alopécia Areata. Three commercial samples were analyzed, the Regaine® (Pharmacia, USA) and the magistral formulation (Porto Bianco, Brazil) both are topical use solutions, in a mixture of ethanol and propilenoglicol as vehicle, containing 2 % (20 mg mL-1) and 5 % of minoxidil (50 mg mL-1) respectively, and Loniten® (Rhodia, Brasil) containing 10 mg of MX per tablet. Three proposals for the determination of minoxidil in commercial samples and electrolytes of synthetic plasma and urine were considered. The first procedure was the determination of MX in the samples using flow injection analysis with spectrophotometric detection in two setups. For the setup procedure using single line with a wavelength of 400 nm, which can quantify the MX present in samples, showing recovery values of 99.7 and 104.8 % for Loniten® and the Regaine® respectively, and 102.5 % for the magistral sample. In merging-zones setup, the detection was in 345 nm, the MX was determined in the samples with recovery 101.3 % for Loniten® and 99.8 % to Regaine® and 103.7 % for the magistral. For both configurations, all the results from flow agree with the labeled values and the results from the chromatographic method (comparative method) in 95 % confidence (t-Student test). In the second procedure, an electroanalytical determination of MX is described using two composite electrodes, the graphite-polyurethane (GPUE) and graphite-silicone rubber (GSRE). Cyclic voltammetry was used to study the electroactive area of electrodes (GPUE = 0.093 cm2; GSRE = 0.089 cm2), the diffusion coefficient of MX (in order of 8.0 x10-6 cm2 s-1) and to study the mechanism of electro-oxidation of MX of which involves one electron per proton. With the support of analytical curves were determined the levels of MX in the samples by different voltammetric techniques; cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). The recovery values are in the range between 96.0 and 110 %, depending on the sample and the voltammetric technique. The electrochemical impedance spectroscopy showed that the mass transport is controlled by diffusion and also there is a weak and reversible adsorption that for both the electrodes. The third method describes the determination of MX and furosemide (FR) using high performance liquid chromatography (HPLC) with spectrophotometric detection. The wavelengths of 275 and 285 nm were for the detection of FR and MX respectively. The mobile phase used was methanol/triethylamine (99:1, V/V) in the flow rate of 0.5 mL min-1. The column used was a C18 Supelco®. The recoveries were 97.7 and 102.4 % for Loniten® and Lasix® respectively. Finally is presented the characterization of the product of oxidation of MX. The informations obtained from infrared spectroscopy technique, were compared with results obtained by nuclear proton magnetic resonance. Two structures were proposed as product of redox reaction between the MX and KMnO4, the desoximinoxidil and another new structure. / No presente trabalho, são apresentados métodos para a determinação minoxidil (MX) em amostras comercias e eletrólitos de plasma e urina sintéticos. O MX é um fármaco que, devido à sua propriedade vasodilatadora, é usado no tratamento da Hipertensão Arterial e no tratamento da Alopécia Areata (calvice). Foram analisadas três amostras comerciais, Regaine® (Pharmacia, EUA), formulação de uso tópico manipulada pela Farmácia de Manipulação Porto Bianco (São Carlos, Brasil) e o Loniten® (Rhodia, Brasil), sendo o primeiro e o segundo soluções de uso tópico contendo 2 % (20 mg mL-1 m/v) e 5 % (50 mg mL-1 m/V) de MX, respectivamente; o terceiro medicamento é apresentado em forma de comprimidos contendo 10 mg de minoxidil, o qual é utilizado no tratamento da hipertensão arterial. Também foram analisados os teores de MX contido nos eletrólitos do plasma e da urina artificiais.Nesse trabalho foram propostas três metodologias para a determinação do MX nas amostras. O primeiro procedimento foi a determinação de MX nas amostras usando análise em fluxo com detecção espectrofotométrica em duas configurações diferentes, as quais monitoraram a formação de um produto amarelado formado a partir da reação entre MX e HNO2 formado in situ. A primeira configuração foi de linha única, com detecção no comprimento de onda de 400 nm, na qual foi possível quantificar o MX presente nas amostras, com recuperações de 99,7 e 104,8 % para o Loniten® e o Regaine®, respectivamente, e 102,5 % para a amostra manipulada. Na segunda configuração, de zonas coalescentes e detecção 345 nm, o MX foi determinado nas amostras com recuperação entre 101,3 % para o Loniten®, 99,8 % para o Regaine ® e 103,7 % para o Manipulado. Observou-se, para ambas as configurações, que todos os resultados do método de análise em fluxo concordam com os valores rotulados das amostras analisadas e com os resultados do método cromatográfico (método comparativo), em 95 % de confiança (teste t-Student). No segundo método, é descrita a determinação eletroanalítica de MX usando dois eletrodos compósitos de grafite-poliuretana (GPUE) e grafiteborracha de silicone (GSRE). Foi usada voltametria cíclica para o obtenção da área eletroativa dos eletrodos (GPUE = 0,093 cm2; GSRE = 0,089 cm2), do coeficiente difusão do MX (na ordem de 8,0x10-6 cm2 s-1) e para estudo do mecanismo da eletro-oxidação da MX, que é de um elétron por próton. Com o auxílio das curvas analíticas, foram determinados os teores de MX contidos nas amostras por diferentes técnicas voltamétricas, voltametria cíclica (CV), voltametria de onda quadrada (SWV) e voltametria de pulso diferencial (DPV), usando ambos os eletrodos. Os valores de recuperação estão no intervalo entre 96,0 e 110 %, dependendo da amostra e da técnica voltamétrica. A espectroscopia de impedância eletroquímica descreveu qual o circuito elétrico foi equivalente à eletro-oxidação do minoxidil e, ainda, mostrou que há adsorção fraca e reversível para ambos os eletrodos. O terceiro método descreve a determinação de MX e furosemida (FR), usando cromatografia líquida de alta eficiência (HPLC) com detecção espectrofotométrica. Os comprimentos de onda de detecção foram 275 e 285 nm para a FR e o MX, respectivamente. A fase móvel usada foi metanol/trietilamina (99:1; V/V) na vazão de 0,5 mL min-1. A coluna usada foi uma C18 da Supelco®. As recuperações foram 97,7 e 102,4 % para o Loniten® e o Furosem®, respectivamente. Finalmente, é apresentada a caracterização do produto de oxidação do MX. Para a caracterização, foi usada a espectroscopia de infravermelho e as informações obtidas foram comparadas com os resultados obtidos na ressonância magnética nuclear de prótons. Foram propostas, através da técnicas IR e RMN, duas estruturas resultantes da reação redox entre o MX e o KMnO4, o desoximinoxidil e uma outra estrutura, inédita na literatura o 3,5-dióxido-2,4- dinitro-6-piperidinopirimidina.

Please read the abstract in the section 00front of this document / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

A new Ph.D research project was started early October into the Department of Civil, Environmental and Natural Resources Engineering at Luleå University of Technology (LTU) by Sarah CONRAD under the direction of Johan INGRI. The part of this project in which I participed was the determination of the concentration of Fe (II) by flow injection analysis using chemiluminescence in the Bothnia Bay. The missions were to handle the instrument and the software and to prepare also some sample standards for the calibration of the FIA. The stream water is first sampled and filtered. Then the water, containing either just the natural iron in the water or after addition of artificial iron, is analyzed by flow injection analysis in combination with luminol. The results are saved on the laptop and interpreted later. The experiments were performed on both the field and the laboratory of the University. / <p>Validerat; 20131008 (global_studentproject_submitter)</p>

The Image-based Change Estimation program (ICE) was developed by the US Forest Service Forest Inventory & Analysis (FIA) program and the Geospatial Technology Applications Center in response to the 2014 Farm Bill calling for more timely and accurate estimates of land cover and use change. ICE monitors change throughout the US on a state by state basis by assessing each FIA plot using high resolution imagery from two dates in time. In the western US, FIA measures 10% of the plots each year to report on status, trends, and sustainability of our Nation’s forests. However, this 10 year cycle misses disturbances because a temporal gap occurs from disturbance event to measurement. This study compares field- and image-based observations of land cover and use change to improve sampling procedures in Utah. Image-based data collected from 2011 and 2014 imagery and field-based plots measured between 2011 and 2016 are compared using three methods to compile the ICE data, termed hierarchical, majority, and point center, to determine a standardized system and better understand their relationships. Additionally, ICE change agents were compared with causes of tree mortality observed on FIA forest plots to assess how well ICE evaluates causes of change and the differences of change vs. mortality agents were explored by conducting a second review of the imagery to find trends in data discrepancies. This knowledge can help image interpreters better recognize and identify change.

Anticipated climate change and increasing wood demand require dependable diameter growth models for adaptive forest management. We used a mixed-effects modeling approach with Forest Inventory and Analysis (FIA) data to fit diameter growth models for loblolly pine, other softwood species (slash pine, shortleaf pine, and longleaf pine), sweetgum, and other hardwood (southern red oak, red maple, and water oak) species. Climatic variables coupled with individual tree attributes and competition factors improved climate insensitive models. Growth of loblolly pine and sweetgum was positively correlated with mean temperature of the coldest month. Mean temperature of the warmest month negatively influenced diameter growth of loblolly pine and other hardwood species. Growing season precipitation and summer precipitation balance had negative effects on the growth of softwood and hardwood species, respectively. Inclusion of FIA plot as random effect improved model fit statistics and residual distribution of climate sensitive models. These findings will be useful to managers for recalibrating diameter growth models resulting in improved biomass yield and volume estimates that will better inform decisions.

In the past 15 years, a large amount of public-domain lidar data has been collected over the Southeastern United States. Most of these acquisitions were undertaken by government agencies, primarily for non-forestry purposes. That is, they were collected mostly to aid in the creation of digital terrain models and to support hydrological and engineering assessments. Such data is not ideal for forestry purposes mainly due to the low pulse density per square meter, the high scan angles and low swath overlaps associated with these acquisitions. Nevertheless, the large area of coverage involved motivated this work. In this dissertation, I first look at how such lidar data (from non-forestry acquisitions) can be combined with National Forest Inventory tree height data to generate a large-area canopy height model. A simple linear regression model was developed using two lidar-based metrics as predictors: the 85th percentile of heights of canopy first returns and the coefficient of variation of the heights of canopy first returns. This model had good predictive ability over 76 disparate lidar projects, covering an area of approximately 297,000 square kilometers between them. Factors leading to the residual lack-of-fit of the model were also analyzed and quantified. For example, predictive ability was found to be better for softwood forests, forests with more homogeneous vegetation structure and for terrains with gentler slopes. Given that as much as 30% of the US is covered by public domain non-forestry lidar acquisitions, this is a first step for constructing a national wall-to-wall vertical vegetation structure map, which can then be used to ask important questions regarding forest inventories, carbon sequestration, wildlife habitat suitability and fire risk mitigation. Then, I examined whether such lidar data could be further used to predict understory shrub presence over disparate forest types. The predictability of classification model was low (accuracy = 62%, kappa = 0.23). Canopy occlusion factors and the heterogeneity of the understory layer were implicated as the main reasons for this poor performance. An analysis of the metrics chosen by the modeling framework highlighted the importance of non-understory metrics (metrics related to canopy openness and topographic aspect) in influencing shrub presence. As the proposed set of metrics were developed over a wide range of temperate forest types and topographic conditions of Southeastern US, it is expected that it will be useful for more localized future studies. Lastly, I explored the possibility of combining lidar-derived canopy height maps with Landsat-derived stand-age maps to predict plantation pine site index over large areas (site index is a measure of forest productivity). The model performance was assessed using a Monte Carlo technique (RMSE = 3.8 meters, relative RMSE = 19%). A sample site index map for large areas of Virginia and South Carolina was generated (map coverage area: 832 sq. km) and implications were discussed. Analysis of the resulting map revealed the following: (1) there is an increase in site index in most areas, compared to the 1970s, and (2) approximately 83% of the area surveyed had low levels of productivity (defined as site index < 22.0 meters for base age of 25 years). This work highlights the efficacy of combining lidar-based canopy height maps with other similar remote sensing based datasets to understand aspects of forest productivity over large areas, and to help make policy-relevant recommendations. / Ph. D.

The first aim of this work was to develop copper modified carbon felt electrode for detection of amino acids, which are not electrochemically active on ordinary carbon electrodes. Phenylalanine solution at a concentration 1.0 mmol dm-3 was chosen as the testing solution. Electrode modified with electrochemical deposition of copper from mixture of copper(II) sulphate and sodium sulphate provided very low responses which were decreasing during first measurements, apparently because of insufficient amount of copper. Therefore, further experiments were performed using copper microparticles as a modifier. Copper microparticles activated in nitric acid at a concentration 80 mmol dm-3 were applied at carbon felt by several techniques and in different parts of the felt, i.e. by stirring the felt in microparticles suspension, by dripping of the suspension to the part of the felt in contact with capillary (proximal), between two parts of the carbon felt (sandwich) and at a part of the carbon felt in contact with electrolyte in a measuring cell (distal). Electrodes modified in the distal and in the sandwich arrangement were chosen as the best ones. In the last part, calibration dependences for phenylalanine in concentration range from 0.025 mmol dm-3 to 1.0 mmol dm-3 were measured on the last two electrodes....

Les biocapteurs ampérométriques décrits dans ce travail sont basés sur l'immobilisation d'enzymes oxydo-réductases dans un polymère conducteur déposé à la surface des électrodes. Les performances des biocapteurs sont conditionnées par la méthode d'immobilisation mise en œuvre ainsi que les caractéristiques de la matrice qui en résulte. Une technique de polymérisation électrochimique a été utilisée pour fixer l'enzyme dans un dérivé du polythiophène, le poly(3,4 éthylènedioxythiophène) (PEDT). Les potentialités de cette technique ont été démontrées pour deux enzymes différentes : la glucose oxydase et la polyphénol oxydase. L'optimisation des paramètres opérationnels a été conduite d'abord en système batch, puis étendue au système d'analyse en flux continu (FIA). Ce système biocapteur-FIA est très adapté pour des mesures en continu de glucose dans les échantillons biologiques. La sélectivité de ce biocapteur en présence de composés interférents a été améliorée par la platinisation de l'électrode, qui rehausse la réponse au glucose, ou l'utilisation des médiateurs rédox. Un biocapteur à polyphénol oxydase exploitant l'amplification enzymatique mise en jeu a permis la détection des polluants phénoliques jusqu'à 50nM.