O aminociclopiraclor é o primeiro herbicida sintetizado do grupo químico ácido pirimidinocarboxílico, pertence à classe das auxinas sintéticas, atua em um amplo espectro de plantas daninhas, e está em fase de registro junto a ANVISA. A literatura sobre o aminociclopiraclor ainda é limitada, mas sabe-se que suas principais vantagens são o amplo espectro de controle de plantas daninhas, elevada eficácia em baixas doses de aplicação, e baixa toxicidade a organismos não alvo. Estudos como degradação, sorção - dessorção e lixiviação de herbicidas em diferentes tipos de solos são indispensáveis para revelar a dinâmica do seu comportamento no solo promovendo subsídios para evitar efeitos prejudiciais ao ambiente e as culturas subsequentes. O presente trabalho teve como objetivo a avaliação da dinâmica do herbicida aminociclopiraclor através de ensaios de degradação e mineralização, sorção-dessorção e lixiviação em três solos brasileiros: Latossolo Vermelho distrófico (LVd - textura arenosa), Plintossolo Pétrico concrecionário (FFc - textura argilosa) e Latossolo Vermelho eutrófico (LVe - textura muito argilosa). Os estudos foram realizados no Laboratório de Ecotoxicologia do CENA/USP seguindo as normas da \"Organisation For Economic Co-operation and Development\" (OECD). As taxas de mineralização do aminociclopiraclor nos solos avaliados foram inferiores a 10%, e seguem a seguinte ordem: FFc < LVd < LVe. A concentração extraível do aminociclopiraclor foi reduzida em 37% após 126 dias, indicando a tendência à formação de resíduos ligados. O sistema de eluição utilizado na técnica de cromatografia em camada delgada não foi adequado para separar e qualificar a presença de metabólitos extraíveis. O modelo de Freundlich apresentou ajuste adequado para a sorção e dessorção do aminociclopiraclor, com coeficientes de correlação superiores a 0,99 para os três solos avaliados. Os coeficientes de sorção variaram entre 0,37 e 1,34 enquanto os de dessorção variaram entre 3,62 a 5,36. Os coeficientes de sorção apresentam correlação positiva significativa com os teores de argila, o mesmo comportamento não foi verificado em relação ao pH. Nos solos de textura argilosa (FFc e LVe), o aminociclopiraclor apresentou médias de lixiviação inferiores a 1%, e no solo de textura arenosa (LVd) superior a 3%. As concentrações do herbicida na primeira camada do solo (0-5 cm) apresentaram correlação positiva significativa com os teores de argila e capacidade de troca catiônica, o mesmo não foi observado em relação a matéria orgânica / The aminocyclopyrachlor is the first herbicide of the chemical group pyrimidinecarboxylic acid, belongs to the class of synthetic auxin, acts in a broad spectrum of weeds and is under registration at ANVISA. The literature on the aminocyclopyrachlor is still limited, but it is known that its main advantages are the broad spectrum of weed control, high efficacy at low application rates, and low toxicity to non-target organisms. Studies such as degradation, sorption-desorption and leaching of herbicides in different types of soils are essential to reveal the dynamics of its behavior in the soil promoting subsidies to avoid adverse environmental effects and the subsequent cultures. This study aimed to evaluate the dynamics of herbicide aminociclopiraclor by testing degradation and mineralization, sorption-desorption and leaching in three Brazilian soils: Latossolo Vermelho distrofico (LVd - sandy texture), Plintossolo Petrico concrecionãrio (FFc - clay texture) and Latossolo Vermelho eutrofico (LVe - clay texture). The studies were conducted at the Laboratory of Ecotoxicology CENA/USP, following the rules of the Organisation For Economic Co-operation and Development (OECD). Mineralization rates in the aminocyclopyrachlor evaluated soils were lower than 10%, and follow the following order: FFc <LVd <LVe. The concentration of extractable aminocyclopyrachlor was reduced by 37% after 126 days, indicating the tendency to formation of bound residues. The system elution technique used in thin layer chromatography was inadequate to separate and qualify the presence of extractable metabolites. The Freundlich model showed an adequate fit for the sorption and desorption of aminocyclopyrachlor, with correlation coefficients higher than 0.99 for the three test soils. The sorption coefficients ranged from 0.37 to 1.34 while the desorption ranged from 3.62 to 5.36. The sorption coefficients showed a significant positive correlation with the clay, the same behavior was not observed in relation to pH. In clay soils (FFc and LVe), the aminocyclopyrachlor presented averages less than 1% leaching, and sandy soil (LVd) exceeding 3%. The concentrations of the herbicide in the topsoil (0-5 cm) showed significant positive correlation with clay content and cation exchange capacity, the same was not observed for organic matter

<p>U disertaciji je izvr&scaron;ena optimizacija detektorskog IZ&nbsp;&nbsp; sistema Quantulus 1220^TM radi razvoja metoda za određivanje pojedinačnih radionuklida ³H,²²²Rn i⁹⁰Sr, kao i ukupne alfa/beta aktivnosti u vodama. Predstavljeni su eksperimenti u svrhu kalibracije sistema, istraživanja uticaja relevantnih parametara na rezultate određivanja aktivnosti alfa i beta emitera, i pode&scaron;avanja optimalnih vrednosti ovih parametara.&nbsp;Posebna pažnja je posvećena variranju&nbsp; PSA diskriminatora, odnosno pode&scaron;avanju analizatora oblika impulsa na optimalnu vrednost u svrhu optimalnog razdvajanja alfa od beta događaja, kao i ispitivanju efekata prigu&scaron;enja u uzorcima i metodama&nbsp;njihove korekcije.&nbsp; Predstavljene razvijene metode su brze, efikasne i jednostavne, &scaron;to je naročito važno u slučaju radijacionog akcidenta, kada je potrebno brzo odrediti sadržaj radionuklida u&nbsp; uzorcima vode, a njihova validnost je pokazana u okviru međunarodnih<br />i međulaboratorijskih interkomparacija.</p> / <p>Dissertation involves optimization of detector AB&nbsp;&nbsp; system&nbsp; Quantulus 1220^TM for development of methods for determination of individual radionuclides ³H, ²²²Rn and ⁹⁰Sr, as well as gross alpha/beta activity in waters. Presented experiments had purpose of calibration of the system,&nbsp; investigation&nbsp; of&nbsp; relevant parameters&nbsp; influence&nbsp; on&nbsp; activity&nbsp; measurements&nbsp; of alpha and beta emitters, as well as&nbsp; setting the optimum values of&nbsp; these parameters. Special attention&nbsp; was devoted to&nbsp; PSA&nbsp; discriminator value&nbsp; setting, i.e. adjusting the pulse shape analyzer level at optimum value for an optimal separation of alpha from beta events, as well as testing the effects of quenching in the samples and methods for quench&nbsp; correction. Presented developed methods are fast, efficient and simple, which is especially important in the case of a radiation accident, when there is a need to quickly determine the content of radionuclides in water samples, and their validity has been demonstrated within the framework of international and inter-laboratory&nbsp; ntercomparison measurements.</p>

O aminociclopiraclor é o primeiro herbicida sintetizado do grupo químico ácido pirimidinocarboxílico, pertence à classe das auxinas sintéticas, atua em um amplo espectro de plantas daninhas, e está em fase de registro junto a ANVISA. A literatura sobre o aminociclopiraclor ainda é limitada, mas sabe-se que suas principais vantagens são o amplo espectro de controle de plantas daninhas, elevada eficácia em baixas doses de aplicação, e baixa toxicidade a organismos não alvo. Estudos como degradação, sorção - dessorção e lixiviação de herbicidas em diferentes tipos de solos são indispensáveis para revelar a dinâmica do seu comportamento no solo promovendo subsídios para evitar efeitos prejudiciais ao ambiente e as culturas subsequentes. O presente trabalho teve como objetivo a avaliação da dinâmica do herbicida aminociclopiraclor através de ensaios de degradação e mineralização, sorção-dessorção e lixiviação em três solos brasileiros: Latossolo Vermelho distrófico (LVd - textura arenosa), Plintossolo Pétrico concrecionário (FFc - textura argilosa) e Latossolo Vermelho eutrófico (LVe - textura muito argilosa). Os estudos foram realizados no Laboratório de Ecotoxicologia do CENA/USP seguindo as normas da \"Organisation For Economic Co-operation and Development\" (OECD). As taxas de mineralização do aminociclopiraclor nos solos avaliados foram inferiores a 10%, e seguem a seguinte ordem: FFc < LVd < LVe. A concentração extraível do aminociclopiraclor foi reduzida em 37% após 126 dias, indicando a tendência à formação de resíduos ligados. O sistema de eluição utilizado na técnica de cromatografia em camada delgada não foi adequado para separar e qualificar a presença de metabólitos extraíveis. O modelo de Freundlich apresentou ajuste adequado para a sorção e dessorção do aminociclopiraclor, com coeficientes de correlação superiores a 0,99 para os três solos avaliados. Os coeficientes de sorção variaram entre 0,37 e 1,34 enquanto os de dessorção variaram entre 3,62 a 5,36. Os coeficientes de sorção apresentam correlação positiva significativa com os teores de argila, o mesmo comportamento não foi verificado em relação ao pH. Nos solos de textura argilosa (FFc e LVe), o aminociclopiraclor apresentou médias de lixiviação inferiores a 1%, e no solo de textura arenosa (LVd) superior a 3%. As concentrações do herbicida na primeira camada do solo (0-5 cm) apresentaram correlação positiva significativa com os teores de argila e capacidade de troca catiônica, o mesmo não foi observado em relação a matéria orgânica / The aminocyclopyrachlor is the first herbicide of the chemical group pyrimidinecarboxylic acid, belongs to the class of synthetic auxin, acts in a broad spectrum of weeds and is under registration at ANVISA. The literature on the aminocyclopyrachlor is still limited, but it is known that its main advantages are the broad spectrum of weed control, high efficacy at low application rates, and low toxicity to non-target organisms. Studies such as degradation, sorption-desorption and leaching of herbicides in different types of soils are essential to reveal the dynamics of its behavior in the soil promoting subsidies to avoid adverse environmental effects and the subsequent cultures. This study aimed to evaluate the dynamics of herbicide aminociclopiraclor by testing degradation and mineralization, sorption-desorption and leaching in three Brazilian soils: Latossolo Vermelho distrofico (LVd - sandy texture), Plintossolo Petrico concrecionãrio (FFc - clay texture) and Latossolo Vermelho eutrofico (LVe - clay texture). The studies were conducted at the Laboratory of Ecotoxicology CENA/USP, following the rules of the Organisation For Economic Co-operation and Development (OECD). Mineralization rates in the aminocyclopyrachlor evaluated soils were lower than 10%, and follow the following order: FFc <LVd <LVe. The concentration of extractable aminocyclopyrachlor was reduced by 37% after 126 days, indicating the tendency to formation of bound residues. The system elution technique used in thin layer chromatography was inadequate to separate and qualify the presence of extractable metabolites. The Freundlich model showed an adequate fit for the sorption and desorption of aminocyclopyrachlor, with correlation coefficients higher than 0.99 for the three test soils. The sorption coefficients ranged from 0.37 to 1.34 while the desorption ranged from 3.62 to 5.36. The sorption coefficients showed a significant positive correlation with the clay, the same behavior was not observed in relation to pH. In clay soils (FFc and LVe), the aminocyclopyrachlor presented averages less than 1% leaching, and sandy soil (LVd) exceeding 3%. The concentrations of the herbicide in the topsoil (0-5 cm) showed significant positive correlation with clay content and cation exchange capacity, the same was not observed for organic matter

O 90Y tem uma meia-vida de 2,7 dias, decaindo com 99,98% por emissão beta para o estado fundamental do 90Zr. Neste trabalho foram aplicadas duas metodologias para a padronização do 90Y. O método do traçador em um sistema de coincidência de 4&pi;&beta;-&gamma;, onde foi medido o emissor beta puro, misturado com um emissor de beta-gama, que proporciona a eficiência de detecção beta. Para este método, o radionuclídeo 24Na, que decai com meia-vida de 0,623 dia pela emissão beta, com energia beta máxima de 1393 keV, seguido por dois raios gama, foi usado como traçador. A eficiência foi obtida, selecionando-se o pico de absorção total com energia de 1369 keV no canal gama. Alíquotas conhecidas do traçador, previamente padronizadas pelo método de coincidência 4&pi;&beta;-&gamma;, foram misturadas com alíquotas conhecidas de 90Y. A atividade do emissor beta puro foi calculada por meio de um sistema de coincidência por software (SCS) usando discriminação eletrônica para alterar a eficiência de beta. O comportamento da curva de extrapolação foi predito por meio do código Esquema, que utiliza a técnica de Monte Carlo. O outro método usado foi o método CIEMAT/NIST desenvolvido para sistemas de contagem de cintilação líquida. Para este método, utilizou-se uma solução padrão de 3H. O sistema 2100TR TRICARB foi usado para as medições, o qual opera em coincidência com duas fotomultiplicadoras; uma fonte externa, colocada perto do sistema de medição foi usada para determinar o parâmetro quenching. O coquetel utilizado foi o Ultima Gold, a variação do fator de quenching foi obtida pelo uso de nitrometano. As amostras radioativas foram preparadas em frascos de vidro com baixa concentração de potássio. As atividades determinadas pelos dois métodos foram comparadas e os resultados obtidos são concordantes dentro das incertezas experimentais. Por meio deste trabalho, foi possível avaliar o desempenho do método CIEMAT/NIST, que apresenta várias vantagens em relação ao método do traçador, entre elas a facilidade para a preparação das fontes, medidas simples e rápidas sem a necessidade de determinar as curvas de extrapolação. / The 90Y has a half-life of 2.7 days, decaying with 99.98 % by beta emission to the ground state of 90Zr. In this work two methodologies for the standardization of yttrium-90 (90Y) were applied. One was the tracing method performed in a 4&pi;&beta;-&gamma; coincidence system, measuring the pure beta emitter mixed with a beta-gamma emitter, which provides the beta detection efficiency. For this method, the radionuclide 24Na, which decays with half life of 0.623 day by beta particle, with end point energy of 1393 keV followed by two gamma-rays, was used as tracer, the efficiency was obtained by selecting the 1369 keV total energy absorption peak at the gamma channel. Known aliquots of the tracer, previously standardized by 4&pi;&beta;-&gamma; coincidence, were mixed with known aliquots of 90Y. The activity was calculated by means of a Software Coincidence System (SCS) using electronic discrimination for changing the beta efficiency. The behavior of the extrapolation curve was predicted by means of the Esquema code, which uses the Monte Carlo technique. The other was the CIEMAT/NIST method developed for Liquid Scintillation Counting (LSC) systems. For this method, a 3H standard solution was used. A TRICAB 2100TR system was used for the measurements. It operates with two photomultipliers in coincidence and an external source placed near the measurement system is used for determining the quenching parameter. Ultima Gold was the liquid scintillation cocktail. In order to obtain the quenching parameter curve a nitro methane carrier solution was used. The radioactive samples were prepared in glass vials with low potassium concentration. The activities determined by the two methods were compared and they are in agreement within the experimental uncertainties. By means of this work it was possible to evaluate the performance of the CIEMAT/NIST method, which presents several advantages with respect to the tracer method, among them is the facility for the preparation of the sources, simple and fast measurements without the need of determining extrapolation curves.

O 90Y tem uma meia-vida de 2,7 dias, decaindo com 99,98% por emissão beta para o estado fundamental do 90Zr. Neste trabalho foram aplicadas duas metodologias para a padronização do 90Y. O método do traçador em um sistema de coincidência de 4&pi;&beta;-&gamma;, onde foi medido o emissor beta puro, misturado com um emissor de beta-gama, que proporciona a eficiência de detecção beta. Para este método, o radionuclídeo 24Na, que decai com meia-vida de 0,623 dia pela emissão beta, com energia beta máxima de 1393 keV, seguido por dois raios gama, foi usado como traçador. A eficiência foi obtida, selecionando-se o pico de absorção total com energia de 1369 keV no canal gama. Alíquotas conhecidas do traçador, previamente padronizadas pelo método de coincidência 4&pi;&beta;-&gamma;, foram misturadas com alíquotas conhecidas de 90Y. A atividade do emissor beta puro foi calculada por meio de um sistema de coincidência por software (SCS) usando discriminação eletrônica para alterar a eficiência de beta. O comportamento da curva de extrapolação foi predito por meio do código Esquema, que utiliza a técnica de Monte Carlo. O outro método usado foi o método CIEMAT/NIST desenvolvido para sistemas de contagem de cintilação líquida. Para este método, utilizou-se uma solução padrão de 3H. O sistema 2100TR TRICARB foi usado para as medições, o qual opera em coincidência com duas fotomultiplicadoras; uma fonte externa, colocada perto do sistema de medição foi usada para determinar o parâmetro quenching. O coquetel utilizado foi o Ultima Gold, a variação do fator de quenching foi obtida pelo uso de nitrometano. As amostras radioativas foram preparadas em frascos de vidro com baixa concentração de potássio. As atividades determinadas pelos dois métodos foram comparadas e os resultados obtidos são concordantes dentro das incertezas experimentais. Por meio deste trabalho, foi possível avaliar o desempenho do método CIEMAT/NIST, que apresenta várias vantagens em relação ao método do traçador, entre elas a facilidade para a preparação das fontes, medidas simples e rápidas sem a necessidade de determinar as curvas de extrapolação. / The 90Y has a half-life of 2.7 days, decaying with 99.98 % by beta emission to the ground state of 90Zr. In this work two methodologies for the standardization of yttrium-90 (90Y) were applied. One was the tracing method performed in a 4&pi;&beta;-&gamma; coincidence system, measuring the pure beta emitter mixed with a beta-gamma emitter, which provides the beta detection efficiency. For this method, the radionuclide 24Na, which decays with half life of 0.623 day by beta particle, with end point energy of 1393 keV followed by two gamma-rays, was used as tracer, the efficiency was obtained by selecting the 1369 keV total energy absorption peak at the gamma channel. Known aliquots of the tracer, previously standardized by 4&pi;&beta;-&gamma; coincidence, were mixed with known aliquots of 90Y. The activity was calculated by means of a Software Coincidence System (SCS) using electronic discrimination for changing the beta efficiency. The behavior of the extrapolation curve was predicted by means of the Esquema code, which uses the Monte Carlo technique. The other was the CIEMAT/NIST method developed for Liquid Scintillation Counting (LSC) systems. For this method, a 3H standard solution was used. A TRICAB 2100TR system was used for the measurements. It operates with two photomultipliers in coincidence and an external source placed near the measurement system is used for determining the quenching parameter. Ultima Gold was the liquid scintillation cocktail. In order to obtain the quenching parameter curve a nitro methane carrier solution was used. The radioactive samples were prepared in glass vials with low potassium concentration. The activities determined by the two methods were compared and they are in agreement within the experimental uncertainties. By means of this work it was possible to evaluate the performance of the CIEMAT/NIST method, which presents several advantages with respect to the tracer method, among them is the facility for the preparation of the sources, simple and fast measurements without the need of determining extrapolation curves.

Cancer is the leading cause of death in Canada. Many cancer treatments are using chemotherapy, surgery and radiotherapy. In radiotherapy, photons are the most used ionizing radiation, however alpha particles have higher radiobiological impact which increases the efficiency of patient treatment delivery. Alpha Tau Medical Ltd. (Tel Aviv, Israël) has developed a new brachytherapy method using radioactive seeds. The seeds called DaRT, for Diffusing alpha emitters Radiation Therapy, are composed of 224-Ra atoms which come from 228-Th generator. Currently, these seeds are characterized by an alpha-spectrometer and Geiger-Muller counter or well chamber for quality control. This project offers a new characterization of DaRT seeds using liquid scintillation. Liquid scintillation allows alpha and beta particles detection with the help of liquid cocktail and employing a scintillation counter. The characterization with liquid scintillation allows establishing and quantifying 228-Th trace contamination on the DaRT seeds. Also, it provides a method for seed quality control before they are used on patients by estimating their activity from spectrums established with the liquid scintillation counter. The spectrums obtained also give the possibility of dose estimation using either mass or mass stopping power in water. The results of the dose are compared to expected values from the literature and to simulations. / Le cancer est la première cause de mortalité au Canada. De nombreuses techniques de traitement du cancer existent utilisant la chimiothérapie, la chirurgie et la radiothérapie. En radiothérapie, les photons sont les rayonnements ionisants les plus fréquemment utilisés, cependant les particules alpha présentent des propriétés radiobiologiques intéressantes augmentant l'efficacité des résultats du traitement prodigué au patient. Une nouvelle technique de curiethérapie ayant recourt à des grains a été développée par Alpha Tau Medical Ltd.(Tel Aviv, Israël). Pour ce faire les grains appelés DaRT, pour Radiothérapie par émetteurs-alpha diffusant, sont constitués d'atomes 224-Ra issu d'un processus de fabrication à l'aide d'un générateur de 228-Th. Ces grains sont actuellement caractérisés par spectromètre-alpha et compteur Geiger-Muller ou chambre à puit dans le cas du contrôle de qualité. Ce projet vise à proposer une nouvelle caractérisation des grains DaRT en recourant à la scintillation liquide. La scintillation liquide permet la détection des particules alpha et beta à l'aide de liquide scintillant et d'un compteur de scintillation. La caractérisation des grains avec la scintillation liquide permet d'établir et de quantifier la présence de trace de contamination de 228-Th. Cette technique de mesure de la radioactivité donne aussi la possibilité de réaliser le contrôle de qualité des grains avant son utilisation sur les patients en évaluant l'activité de ces derniers à partir des spectres obtenus par le compteur de scintillation liquide. Les spectres obtenus offrent la réalisation d'une estimation de la dose soit par la masse soit par le pouvoir d'arrêt massique des alpha dans l'eau. Les résultats de la dose sont comparés à des valeurs attendues de la littérature et de simulation.

The aim of the research study was to evaluate the levels of 14C and 3H radionuclides in Hartbeespoort Dam water and to determine if these radionuclides are within regulatory concerns. Water samples from Hartbeespoort Dam were prepared using the Sample Oxidiser Method and measurements of selected radionuclides were done using Liquid Scintillation Counter Quantulus 1220. The results evaluated suggest that water from Hartbeespoort Dam contains levels of 14C and 3H radionuclides that are within regulatory limits. The highest average concentration for 14C measured was 3.77E+01 (+/-2.47E-01) Bq/L, whereas the highest average concentration measured for 3H was 2.74E+01 (+/- 2.30E-01) Bq/L. The observations made regarding the impacts of climate on the 14C radionuclide were that, the concentration levels were higher during winter season when there was a rain than during rainy seasons. Tritium results showed that the climate conditions did not have any significant impacts on the concentration levels. When the concentrations of these radionuclides are above regulatory levels (14C is 100 Bq/L and 3H is10000 Bq/L), their impacts may cause harm to public`s health and the environment. Therefore, Necsa as a nuclear facility owner and National Nuclear Regulator (NNR) as a regulator are responsible for ensuring the public protection from radioactive effluents that contain not just 3H and 14C, but any radionuclide which may cause harm to public`s health. / Environmental Sciences / M. Sc. (Environmental Science)

Dans l’analyse des émetteurs alpha et beta dans l’eau par scintillation liquide, la problématique de la discrimination des rayonnements se pose afin d’atteindre les limites de détection souhaitées. Dans le cas rare ou les énergies permettent une discrimination, nous avons mis en place un protocole d’analyse simultanée tritium/alpha sur des frottis. A l’aide d’une méthode a trois fenêtres il permet d’atteindre les limites de détection de 0,4 Bq/cm2 en tritium et de 0,04 Bq/cm2 en alpha.De façon générale, aucune distinction entre les spectres n’est possible et un ajustement du fond sous le pic alpha ne permet pas d’atteindre les limites de détection définies par les normes. Cependant le processus physique de scintillation permet une distinction des rayonnements, phénomène utilise par certains appareils, ceux-ci proposent donc le réglage par l’utilisateur d’un paramètre discriminant seuil. Nous avons développé un protocole de réglage permettant de reconstituer les spectres alpha et beta discrimines au mieux, rendant accessible une limite de détection de 0,03 Bq/L en alpha.Nous avons par ailleurs développé une approche innovante utilisant un détecteur en coïncidence dont les photomultiplicateurs sont connectes directement a une carte numérique d’acquisition. Chaque impulsion numérisée est ensuite traitée selon plusieurs critères simultanément, à la place des deux habituels. Aucun ne permet a lui seul d’obtenir une discrimination selon un seuil unique, mais la distribution des évènements dans chaque spectre est différente : un fenêtrage des évènements alpha permet d’atteindre une limite de détection de 0,2 Bq/L, quatre fois moindre que par une discrimination en énergie seule. / Analysis of water for alpha and beta emitters by liquid scintillation suffers from poor discrimination between the emissions and prevents reaching the lowest detection limits. In the rare cases where well separated energies permit discrimination, we can use a three-window protocol for simultaneous analysis of tritium and alphas of swipes that yields detection limits of 0.4 Bq/cm2 for tritium and 0.04 Bq/cm2 for alphas. In the general case, no distinction between the two radiations is possible. An adjustment of the background under the alpha peak does not allow reaching detection limits defined by the norms. However the physical process of scintillation offers users of certain models of apparatus to adjust a discrimination threshold that will separate the emissions. We have developed a protocol that reconstitutes spectra using independent settings that gives a detection limit for alphas of 0.03 Bq/L. We have also developed an innovative approach using a scintillation counter with its photomultipliers plugged directly into a fast analog-to-digital acquisition converter. Then each digitized pulse is simultaneously processed according to several criteria, instead of the usual two. No impulsion can be discriminated on the basis of a single threshold but the distribution of events in each spectrum is different: a window setting on the alphas permits attaining a detection limit of 0.2 Bq/L for alphas, four times lower than with a selection on energy alone.

The design of biomaterials, historically initiated and developed by physicians and engineers, in the last decades has slowly shifted toward a more biochemical based approach. For the replacement, repair and regeneration of tissues scientists are now focusing on materials that stimulate specific biological response at the molecular level. These biomaterials have already shown interesting applications in cell proliferation, differentiation, and extracellular matrix production and organization when the material modifications are designed to elicit specific interactions with cell integrins. In the present work we propose the application of this strategy for the development of blood-compatible materials. We first identified, in the coagulation cascade a key enzyme that constitute a valuable biological target for the development of anti-thrombogenic compounds. Piperazinyl-amide derivatives of N-alfa-(3-trifluoromethyl-benzenesulfonyl)-L-arginine were synthesized as graftable thrombin inhibitors. These inhibitors provided a spacer arm for surface grafting and a fluorine tag for XPS (X-ray photoelectron spectroscopy) detection. The possible disturbance of biological activity due to a variable spacer-arm fixed on the N-4 piperazinyl position was evaluated in vitro against human alfa-thrombin, in silico by molecular modelling and via X-ray diffraction study. Selected inhibitors, having inhibition potency in the mM range, were grafted on polyesters surface via wet chemistry and photochemical activation treatments. Wet chemistry surface grafting was performed by specific hydroxyl chain-ends activation and resulted in bioactive molecules fixation of 20-300pmol/cm2. The photochemical grafting was performed using a molecular clip providing an aromatic azide, for nitrene insertion into a polymer, and an activated ester for grafting of tag compounds. This grafting technique resulted in a dramatic increase in fixed bioactive signals (up to nmol/cm2). The material blood-compatibilization induced by the surface fixation of the inhibitors, was measured by a static blood clot weight measurement test. The wet chemistry grafting technique resulted in moderate blood-compatibilization while by the photochemical grafting method important decrease in surface blood clot formation was observed. In the latter case, the blood response to material contact was found to be strongly affected by the polyester surface photo-degradation induced by the activation treatment.

The design of biomaterials, historically initiated and developed by physicians and engineers, in the last decades has slowly shifted toward a more biochemical based approach. For the replacement, repair and regeneration of tissues scientists are now focusing on materials that stimulate specific biological response at the molecular level. These biomaterials have already shown interesting applications in cell proliferation, differentiation, and extracellular matrix production and organization when the material modifications are designed to elicit specific interactions with cell integrins. In the present work we propose the application of this strategy for the development of blood-compatible materials. We first identified, in the coagulation cascade a key enzyme that constitute a valuable biological target for the development of anti-thrombogenic compounds. Piperazinyl-amide derivatives of N-alfa-(3-trifluoromethyl-benzenesulfonyl)-L-arginine were synthesized as graftable thrombin inhibitors. These inhibitors provided a spacer arm for surface grafting and a fluorine tag for XPS (X-ray photoelectron spectroscopy) detection. The possible disturbance of biological activity due to a variable spacer-arm fixed on the N-4 piperazinyl position was evaluated in vitro against human alfa-thrombin, in silico by molecular modelling and via X-ray diffraction study. Selected inhibitors, having inhibition potency in the mM range, were grafted on polyesters surface via wet chemistry and photochemical activation treatments. Wet chemistry surface grafting was performed by specific hydroxyl chain-ends activation and resulted in bioactive molecules fixation of 20-300pmol/cm2. The photochemical grafting was performed using a molecular clip providing an aromatic azide, for nitrene insertion into a polymer, and an activated ester for grafting of tag compounds. This grafting technique resulted in a dramatic increase in fixed bioactive signals (up to nmol/cm2). The material blood-compatibilization induced by the surface fixation of the inhibitors, was measured by a static blood clot weight measurement test. The wet chemistry grafting technique resulted in moderate blood-compatibilization while by the photochemical grafting method important decrease in surface blood clot formation was observed. In the latter case, the blood response to material contact was found to be strongly affected by the polyester surface photo-degradation induced by the activation treatment.