Färgning av polyester (PET) sker i temperaturer omkring 130℃ och som en följd av den höga värmen migrerar oligomerer ut ur PET-fibern. Dessa oligomerer skapar därefter problem i form av vita fällningar och avlagringar, som leder till en reducering av maskinernas effektivitet, samt försämring av materialets utseende. En vanligt förekommande metod för att begränsa problemet är att tillsätta hjälpkemikalier i färgbadet. Novozymes A/S hävdar att genomförda studier med PET-garn och enzymet cutinase NS59038 har visat en minskning av det vita damm som kan ses på garnet i samband med migration av oligomerer. Eftersom enorma mängder PET produceras globalt varje år skulle endast en liten minskning av mängden kemikalier innebära en stor skillnad. Kemikalier som ersätts med andra kemikalier kan ifrågasättas om det är en bra metod eller om det bestrider syftet. Ur ett hållbarhetsperspektiv kan enzymer ses som ett bättre alternativ eftersom de enligt Jajpura (2017) är biologiskt hållbara, formar sällan någon biprodukt och dess reaktion kräver oftast mildare förhållanden. Hjälpkemikalien Sera Con P-NSI används av Ludvig Svensson AB som färgar garn av den flamskyddade polyesterfibern Trevira CS. Syftet med projektet har därmed varit att undersöka om enzymet cutinase NS59038 är ett alternativ till hjälpkemikalien Sera Con P-NSI, för att reducera de problem som uppstår med oligomerer i färgningsprocessen med Trevira CS. Garnets egenskaper har jämförts genom visuell analys med mikroskop, viktförändring, reflektionsspektrofotometer och dragprovning. Metoder som använts i syfte att detektera oligomerer har varit FTIR, UV-vis spektrofotometer och svart svavelfilterpapper. Utifrån genomförda analyser av garnets vikt, styrka, färgupptagning och visuell bedömning har det inte kunnat konstateras att cutinase NS59038 skulle vara ett alternativ till Sera Con P-NSI. Resultat från analysmetoderna visade skillnader i medelvärde, men inget samband mellan val av färgrecept och garnets egenskap har detekterats. De olika färgningsförsöken visade inte någon förekomst av fällningar/avlagringar som med använda testmetoder har kunnat bekräftas som oligomerer. Resultaten bedömdes därmed inte som tillräckliga för att konstatera om cutinase NS59038 påverkar garnets kvalitet i jämförelse med hjälpkemikalien Sera Con P-NSI. / In the dyeing process of polyester (PET) the temperature goes up to around 130℃ and as a result oligomers migrate out of the PET fiber. These oligomers create problems as white precipitates that deposits on the material and the inside of machines. This leads to a reduction in machine efficiency, as well as a change of material appearance. One common method for limiting the problem is to add help chemicals in conjunction with the dyeing process. According to results from previous studies, Novozymes A/S claims that the enzyme cutinase NS59038 has reduced the white dust on the yarn of polyester. Based on the enormous quantity of PET that are produced every year, even a small reduction of the chemicals that are used would mean a huge difference. Chemicals that replace other chemicals can be questioned whether or not it can be seen as an alternative or if it disputes the purpose. From a sustainable point of view enzymes could according to Jajpura (2017) be seen as a better alternative because they are biodegradable, their reaction seldom form any byproduct and often requires less energy. The help chemical Sera Con P-NSI is used by Ludvig Svensson AB and is added to the dye bath in the dyeing process of the specific polyester Trevira CS (a flame retardant polyester fiber). The purpose of the project has thus been to investigate whether the enzyme cutinase NS59038 is an alternative to the help chemical Sera Con P-NSI, to reduce the problems with oligomers in the dyeing process of Trevira CS. The properties of the yarn have been compared by visual analysis with microscope, weight change, measurement of the color change with spectrophotometer and tensile strength. Methods used to detect oligomers have been FTIR, UV-vis spectrophotometer and black sulfur filter paper. Based on the analysis of the weight of the yarn, strength, color uptake and visual assessment, it can not be established that cutinase NS59038 would be an alternative to Sera Con P-NSI. Results from the analysis methods show differences in the mean, but no connection between the choice of dye recipe and the properties of the yarn can be detected. None of the precipitates that was predicted to arise on the surface of the yarn was ever detected. The results are therefore not considered sufficient to determine whether cutinase NS59038 affects the quality of the yarn compared to the help chemical Sera Con P-NSI.

Die off-axis Elektronenholografie im Transmissionselektronenmikroskop (TEM) erlaubt die quantitative Rekonstruktion der komplexen Objektaustrittswelle mit atomarer Auflösung. Die Auswertung der Phase dieser Welle ermöglicht die Unterscheidung der Atomsorten bzw. das Zählen der Atome in Projektionsrichtung sowie die Bestimmung von Atompositionen. Damit ist ein TEM über die einfache Abbildung hinaus ein sehr leistungsstarkes Messgerät zur quantitativen Analyse kleinster Strukturen bis hin zur atomaren Skala. Die Prozedur von der Aufnahme eines hochaufgelösten Elektronenhologramms über die Rekonstruktion bis zur bildfehlerkorrigierten Objektwelle ist jedoch sehr umfangreich und teils sehr anfällig für Artefakte. Diese Arbeit zeigt unter kritischer Betrachtung der einzelnen Einflüsse, wie dieser Weg zu beschreiten ist, um schlussendlich zu einer artefaktfreien, interpretierbaren Objektwelle zu gelangen. Im letzten Jahrzehnt haben Bildfehler-Korrektoren die höchstauflösende Transmissions-elektronenmikroskopie auf instrumenteller Seite revolutioniert. Auch die off-axis Holografie kann eine ganze Reihe von Vorteilen aus diesem elektronenoptischen Zusatzsystem ziehen. Neben der Analyse dieser einzelnen Verbesserungen, insbesondere der Phasensignalauflösung, wird gezeigt, wie es das Cs-korrigierte TEM zu optimieren gilt, um schließlich bestmögliche Ergebnisse für quantitative Objektanalyse zu erzielen. Zwei Anwendungsbeispiele zeigen experimentelle Ergebnisse der Elektronenholografie mit Cs-korrigierten Mikroskopen. Bei der Analyse ferroelektrischer Nanoschichten erweisen sich die einzigartigen Möglichkeiten der holografischen Auswertung im Zusammenspiel mit der nunmehr hervorragenden Signalauflösung als äußerst nützlich, um die ferroelektrische Polarisation zu ermitteln. Die Objektwellenrekonstruktion der Korngrenze in einer Goldfolie demonstriert weitere Verbesserungen für die Holografie, wenn zusätzlich eine neuartige Elektronenquelle mit höherem Richtstrahlwert zum Einsatz kommt. Einzelne Goldatome werden mit einem Signal-Rausch-Verhältnis von ca. 10 in Amplitude und Phase messbar. / Off-axis electron holography in a transmission electron microscope (TEM) allows reconstructing the complex object exit-wave quantitatively with atomic resolution. Analyzing the phase shift of this wave gives access to the atomic species and enables counting the number of atoms in projection direction as well as determining atom positions. Therefore, a TEM is a very powerful measuring device for quantitative analysis of smallest structures down to the atomic scale beyond simple microscopic imaging. The procedure of the recording of a high-resolution electron hologram, its reconstruction, and after numerical aberration correction finally ending up with the object-exit wave, is quite comprehensive and partially susceptible to artifacts. This work shows how to manage this procedure in order to obtain an interpretable object exit-wave, which is free of artifacts. In instrumentation within the last decade aberration correctors have revolutionized high-resolution electron microscopy. Also off-axis holography can benefit from this electron optical add-on module. Besides the exploration of each improvement, in particular the phase detection limit, this work demonstrates, how to optimize the Cs-corrected TEM in order to get best possible results for quantitative object analysis. Two application examples show experimental results of electron holography with Cs-corrected microscopes. For the investigation of ferroelectric nanolayers, the unique possibilities of the holographic evaluation together with the strongly improved signal resolution turn out to be very useful when determining the ferroelectric polarization. The object wave reconstruction of the grain boundary in a gold film demonstrates further improvements for holography, when additionally using a new electron gun with improved brightness. Single gold atoms become measurable with a signal-noise-ratio of about 10 in amplitude and phase.

Problematisering: Företag står inför utmaningar som handlar om att inkludera hållbarhetsbegreppets tre dimensioner: det ekonomiska, sociala och miljömässiga ansvaret. Påtryckningar ökar från samhällets olika intressenter, som sätter press på att företag och företagsledare agerar ansvarsfullt. Hållbarhet är idag en aktuell och relevant fråga som företag, styrelser och ledare på något sätt får ta i beaktning på grund av dessa påtryckningar från samhället. Relationen mellan ledarskap och hållbarhet är, enligt oss, en samhällsaktuell fråga för företag. Det finns idag omfattande forskning kring ledarskap och en hel del forskning om hållbarhet. Forskningen däremellan är däremot relativt outforskad. Det behövs därför en förståelse för hur denna relation ser ut. Syfte: Syftet med denna studie är att bidra till förståelse av hur relationen mellan ledarskap och hållbarhet ser ut i ett svenskt företag, samt identifiera de aspekter i ledarskapet som kan vara av betydelse för hållbarhet. Metod: För att besvara syftet är denna studie uppbyggd av en pilotstudie och en enfallsstudie av kvalitativ karaktär, där vi har genomfört semistrukturerade intervjuer med fem ledare i ledningsgruppen på Transdev Sverige AB. Studien har en induktiv ansats. Slutsats: Resultatet från denna studie har visat att relationen mellan ledarskap och hållbarhet ser olika ut. Ledningsgruppens kontext och ledarnas ansvarsområden har varit avgörande i beskrivningen av hur relationen ser ut. Kontexten och ansvarsområdena har dessutom varit avgörande för var i hållbarhetsbegreppet ledarna lägger sin tyngdpunkt. Relationen beskrivs vidare utifrån tre identifierade “relationsbyggare”: mål, moral och kunskap. Dessa tre är aspekter som vi anser vara av betydelse för hur relationen ser ut i denna studies specifika kontext. / Background: Due to increasing expectations and demands from different stakeholders, companies are being called upon to take actions to integrate the three dimensions of sustainability; economic, social and environmental. Corporate sustainability is therefore an inevitable topic of discussion among business organisations and top executives. Separately, there is extensive research on the two topics leadership and sustainability. However, the amount of research of the intersection of these two research fields is scarce and fairly unexplored, which makes this an interesting field of study. As a result of the actuality evolving around leadership and sustainability for corporations and the above stated lack of research, there is a need of a deeper understanding of the relationship between leadership and sustainability. Aim: The aim of this study is to understand the relationship between leadership and sustainability, as well as identifying aspects in the leadership that could be of importance regarding sustainability leadership. Methodology: This is a qualitative case study using a hermeneutics perspective of interpretation. The empirical data consist of a pilot study and five semi-structured interviews with top executives at Transdev Sverige AB. The study revolves around the empirical data and is therefore to be considered to have an inductive approach. Conclusion: The findings of the study has shown that the relationship between leadership and sustainability differ. The context of the top management team and the responsibility of the leaders have been vital in the explanation of their relationship. The context and the area of responsibility have additionally been vital in order to identify where in the sustainability spectrum the leader position himself. The relationship is further explained by three identified “relationship builders”; goal, morale and knowledge. We consider that these three aspects are of relevance to understand the relationship between leadership and sustainability within the specific context of this study.

My thesis is divided into two main parts, such as the theoretical and practical part. In theoretical part, I describe brief history of Internal Audit with the special interest on the Czech Republic and Sweden. I mention these two countries as the headquarters of Skanska are found in Sweden and it has a long developed tradition. Then, I concentrate more on IA organization and procedures, IA standards and code of ethics. Furthermore, I concentrate on the methodology used in IA. In practical part, I focus more on a description of IA process at Skanska. I describe the practical background of this company and later on, I have mentioned two practical cases targeted on audit of one loss project and audit of processes such as Accounts payable and Accounts receivable.

En dépit du développement rapide de la médecine, les maladies cardiovasculaires restent la première cause de mortalité dans le monde. En France, chaque année, plus de 50 000 personnes meurent subitement en raison d'arythmies cardiaques. L'identification des patients à risque élevé de décès soudain est toujours un défi. Pour détecter les arythmies cardiaques, actuellement Holter est généralement utilisé pour enregistrer les signaux électrocardiogramme (ECG) à 1~3 dérivations pendant 24h à 72h. Cependant l'utilisation de Holter est limitée parmi la population en raison de son encombrement (pas convivial) et de son coût. Un Holter mono puce portable nommé SoC-Holter qui permet d'enregistrer 1 à 4 dérivations est introduit. Le déploiement d'un réseau de capteurs sans fil exige que chaque SoC-Holter soit peu encombrant et peu cher, et consomme peu d’énergie. Afin de minimiser la consommation d'énergie et le coût du système, la technologie Complementary Metal Oxide Semiconductor (CMOS) (0.35μm) est utilisée pour la première implémentation de SoC-Holter. Puis une nouvelle méthode de détection basée sur Acquisition Comprimée (CS) est introduite pour résoudre les problèmes de consommation d'énergie et de capacité de stockage de SoC-Holter. Le principe premier de cette plate-forme est d'échantillonner les signaux ECG sous la fréquence de Nyquist ‘sub-Nyquist’ et par la suite de classer directement les mesures compressées en états normal et anormal. Minimiser le nombre de fils qui relient les électrodes à la plate-forme peut rendre l’utilisateur de SoC-Holter plus confortable, car deux électrodes sont très proches sur la surface du corps. La différence ECG enregistrée est analysée à l'aide de Vectocardiogramme (VCG). Les résultats expérimentaux montrent qu'une approche intégrée, à faible coût et de faible encombrement (SoC-Holter) est faisable. Le SoC-Holter consomme moins de 10mW en fonctionnement. L'estimation des paramètres du signal acquis est effectuée directement à partir de mesures compressées, éliminant ainsi l'étape de la reconstruction et réduisant la complexité et le volume des calculs. En outre, le système fournit les signaux ECG compressés sans perte d'information, de ce fait il réduit significativement la consommation d'énergie pour l'envoi de message et l’espace de stockage mémoire. L'effet de placement des électrodes est évalué sur la QRS complexe lorsqu'il a enregistré avec deux électrodes adjacentes. La méthode est basée sur l'algorithme de ‘QRS-VCG loop alignment’. La méthode moindre carré est utilisée pour estimer la corrélation entre une boucle VCG observée et une boucle de référence en respectant les transformations de rotation et la synchronisation du temps. Les emplacements d'électrodes les moins sensibles aux interférences sont étudiés. / According to the figures released by World Health Organization (WHO), cardiovascular disease is the number one cause of death in the world. In France every year more than 50,000 people die suddenly due cardiac arrhythmias. Identification of high risk sudden death patients is still a challenge. To detect cardiac arrhythmias, currently Holter is generally used to record 1~4 leads electrocardiogram (ECG) signals during 24h to 72h. However the use of Holter is limited among the population due to its form factor (not user-friendly) and cost. An integrated single chip wearable Holter named SoC-Holter that enables to record 1 to 4 leads ECG is introduced. Deployment of wireless sensor network requires each SoC-Holter with less power consumption, low-cost charging system and less die area.To minimize energy consumption and system cost, Complementary Metal Oxide Semiconductor (CMOS) technology (0.35μm) is used to prototype the first implementation of SoC-Holter. Then a novel method based on Compressed Sensing (CS) technique is introduced for solving the problems of power consumption and storage capacity of SoC-Holter. The main principle underlying this framework is to sample analog signals at sub-Nyquist rate and to classify directly compressed measurement into normal and abnormal state. Minimizing the wire connected electrodes to the platform can make the carrier more comfortable because two electrodes are attached closely on the surface of the body. Recording difference ECG is analyzed using Vectorcardiogram (VCG) theory. Experimental results show that an integrated, low cost, and user-friendly SoC-Holter is feasible. SoC-Holter consumes less than 10mW while the device is operating. It takes advantage of estimating parameters directly from compressed measurements, thereby eliminating the reconstruction stage and reducing the computational complexity on the platform. In addition, the framework provides compressed ECG signals without loss of information, reducing significantly the power consumption for message sending and memory storage space. The effect of electrode placement is evaluated by estimating QRS complex in recorded ECG signals by two adjacent electrodes. The method is based on the QRS-VCG loop alignment algorithm that estimates Least Square (LS) between an observed VCG loop and a reference loop with respect to the transformations of rotation and time synchronization. The electrode location with less sensitive to interference is investigated.

Work includes certification procedures for experimental aeroplanes. Producer must answer individual work for right procedure certification. Office UCL give works and control production procedure aeroplane. Stationery (applications, confirmation, tec.) are part of work and is need make and feed. Part of work is VUT 001 MARABU and technical characteristics aeroplane.

Die off-axis Elektronenholografie im Transmissionselektronenmikroskop (TEM) erlaubt die quantitative Rekonstruktion der komplexen Objektaustrittswelle mit atomarer Auflösung. Die Auswertung der Phase dieser Welle ermöglicht die Unterscheidung der Atomsorten bzw. das Zählen der Atome in Projektionsrichtung sowie die Bestimmung von Atompositionen. Damit ist ein TEM über die einfache Abbildung hinaus ein sehr leistungsstarkes Messgerät zur quantitativen Analyse kleinster Strukturen bis hin zur atomaren Skala. Die Prozedur von der Aufnahme eines hochaufgelösten Elektronenhologramms über die Rekonstruktion bis zur bildfehlerkorrigierten Objektwelle ist jedoch sehr umfangreich und teils sehr anfällig für Artefakte. Diese Arbeit zeigt unter kritischer Betrachtung der einzelnen Einflüsse, wie dieser Weg zu beschreiten ist, um schlussendlich zu einer artefaktfreien, interpretierbaren Objektwelle zu gelangen. Im letzten Jahrzehnt haben Bildfehler-Korrektoren die höchstauflösende Transmissions-elektronenmikroskopie auf instrumenteller Seite revolutioniert. Auch die off-axis Holografie kann eine ganze Reihe von Vorteilen aus diesem elektronenoptischen Zusatzsystem ziehen. Neben der Analyse dieser einzelnen Verbesserungen, insbesondere der Phasensignalauflösung, wird gezeigt, wie es das Cs-korrigierte TEM zu optimieren gilt, um schließlich bestmögliche Ergebnisse für quantitative Objektanalyse zu erzielen. Zwei Anwendungsbeispiele zeigen experimentelle Ergebnisse der Elektronenholografie mit Cs-korrigierten Mikroskopen. Bei der Analyse ferroelektrischer Nanoschichten erweisen sich die einzigartigen Möglichkeiten der holografischen Auswertung im Zusammenspiel mit der nunmehr hervorragenden Signalauflösung als äußerst nützlich, um die ferroelektrische Polarisation zu ermitteln. Die Objektwellenrekonstruktion der Korngrenze in einer Goldfolie demonstriert weitere Verbesserungen für die Holografie, wenn zusätzlich eine neuartige Elektronenquelle mit höherem Richtstrahlwert zum Einsatz kommt. Einzelne Goldatome werden mit einem Signal-Rausch-Verhältnis von ca. 10 in Amplitude und Phase messbar. / Off-axis electron holography in a transmission electron microscope (TEM) allows reconstructing the complex object exit-wave quantitatively with atomic resolution. Analyzing the phase shift of this wave gives access to the atomic species and enables counting the number of atoms in projection direction as well as determining atom positions. Therefore, a TEM is a very powerful measuring device for quantitative analysis of smallest structures down to the atomic scale beyond simple microscopic imaging. The procedure of the recording of a high-resolution electron hologram, its reconstruction, and after numerical aberration correction finally ending up with the object-exit wave, is quite comprehensive and partially susceptible to artifacts. This work shows how to manage this procedure in order to obtain an interpretable object exit-wave, which is free of artifacts. In instrumentation within the last decade aberration correctors have revolutionized high-resolution electron microscopy. Also off-axis holography can benefit from this electron optical add-on module. Besides the exploration of each improvement, in particular the phase detection limit, this work demonstrates, how to optimize the Cs-corrected TEM in order to get best possible results for quantitative object analysis. Two application examples show experimental results of electron holography with Cs-corrected microscopes. For the investigation of ferroelectric nanolayers, the unique possibilities of the holographic evaluation together with the strongly improved signal resolution turn out to be very useful when determining the ferroelectric polarization. The object wave reconstruction of the grain boundary in a gold film demonstrates further improvements for holography, when additionally using a new electron gun with improved brightness. Single gold atoms become measurable with a signal-noise-ratio of about 10 in amplitude and phase.

Das künstliche Radionuklid 137Cs wurde seit über einem halben Jahrhundert in die Natur eingebracht. Sein erstes Erscheinen in Sedimenten der zentraleuropäischen Seen korrespondiert mit den Nuklearwaffentests in den 60er-Jahren des 20. Jahrhunderts. Die stärkste Kontaminierung der europäischen Seen und Flüsse entstand als Folge des radioaktiven Niederschlags nach dem Unfall in Tschernobyl im Frühjahr 1986. In dieser Arbeit wurde das Migrationsverhalten des künstlichen 137Cs im Lago Maggiore und anderen Seen im Alpenvorland als Folge dieses Niederschlags untersucht. Der Lago Maggiore zählt zu den größten Trinkwasserreservoiren südlich der Alpen. Nach dem Unfall in Tschernobyl gingen ungefähr 20 kBq•m-2 des 137Cs auf die Oberfläche des Sees nieder. Im Zeitraum von 2003 bis 2005 wurden Sedimentkerne und Wasserproben an sieben unterschiedlichen Stellen des Lago Maggiore entnommen. Diese Arbeit beschäftigt sich mit Daten über die Verteilung des 137Cs in den Zuflüssen, dem Wasser des Sees, in Schwebstoffen und Bodensedimenten und mit der Assoziierung von 137Cs mit verschiedenen geochemischen Fraktionen. Um den Abfluss des 137Cs aus dem Wassereinzugsgebiet in den Fluss zu modellieren, wurde ein Compartmentmodell verwendet. Zur Modellierung der Aufnahmemenge von 137Cs im Sediment und der vertikalen Verteilung innerhalb dessen wurde ein Diffusions-Konvektions-Modell entwickelt. Dieses Modell berücksichtigt die Aufnahme von Aktivität durch Sedimentation, Fixierung und Rücklösung, retardierte Diffusion, die Verdichtung des Sediments sowie den Einfluss konkurrierender Ionen auf die retardierte Diffusion innerhalb des Sediments. Die Ergebnisse der Parameteroptimierung – im Wesentlichen die Sedimentationsrate und der 137Cs-Verteilungskoeffizient Kd, welcher die Aufnahme der Aktivität in das Sediment determiniert – werden erörtert und mit denen anderer europäischer Seen, die eine ähnliche 137Cs-Deposition, aber unterschiedliche limnologische Eigenschaften aufweisen, verglichen. Zur Beurteilung der Bioverfügbarkeit von 137Cs wurde die 137Cs-Aktivitätskonzentrationen von Fischproben aus dem Lago Maggiore gemessen. Aus bereits existierenden Daten und unseren Messergebnissen wurden 137Cs Fisch-Wasser Konzentrations-Verhältnisse errechnet und mit denen für andere Seen, die von ähnlichen 137Cs-Kontaminationen betroffen sind, verglichen. / Artificial Cs-137 has been introduced into the environment for more than half a century. Its first appearance in central European lake sediments corresponds to the nuclear weapons testing in the 1960s. The largest contamination of European lakes and rivers occurred as a consequence of the fallout after the Chernobyl accident in spring 1986. In this work the migration behaviour of artificial Cs-137 in Lago Maggiore and other pre-alpine lakes as a consequence of these fallouts was studied. Lago Maggiore is one of the largest drinking water reservoirs in the south of the Alps. After the Chernobyl accident roughly 20 kBq•m-2 of 137Cs were deposited onto the lake surface. From 2003 to 2005 bottom sediment cores and water samples were collected at 7 different locations of Lago Maggiore. Data on the 137Cs distribution in tributaries, lake water, suspended matter, bottom sediments, and the 137Cs association to different geochemical fractions are presented in this work. To model the run-off of 137Cs from the watershed into the lake a compartment model was used. For modeling the input of 137Cs into and the vertical distribution within the sediment a diffusion–convection type model was developed. This model takes into account the uptake of activity by sedimentation, fixation and redissolution, retarded diffusion, the influence of competing ions on the retarded diffusion within the sediments, and compaction of sediments. The results of the parameter optimization – mainly the sedimentation rate and the 137Cs distribution coefficient Kd, which determines the uptake of activity into the sediment – are discussed and compared with those of other European lakes characterized by similar 137Cs deposition levels but different limnological properties. To estimate the bioavailability of 137Cs, its activity concentrations in fish samples from Lago Maggiore were measured. Combining the existing data with our measurements, 137Cs fish–water concentration ratios were calculated and compared with those for other lakes which were affected by similar 137Cs contamination.

[pt] No presente trabalho é proposto o desenvolvimento de um método analítico para determinação de S por espectrometria de absorção molecular de alta resolução com fonte contínua e forno de grafite (HR-CS GF MAS). As amostras foram preparadas por dissolução ácida e os padrões de calibração, assemelhados à matriz da amostra dissolvida, contendo sulfato, tioureia ou L-cisteína foram estudados em função de suas diferentes estabilidades térmicas. A técnica de HR-CS GF MAS é uma alternativa interessante para determinação de S, pois apresenta alta resolução espectral que minimiza interferências espectrais, pelo uso de um monocromador de alta resolução que permite a separação das linhas de absorção molecular do analito e da matriz, pelo uso do forno de grafite como fonte de atomização, que permite a separação da matriz e do analito antes da etapa de medida do sinal analítico. Com isso, este trabalho tem por objetivo desenvolver um método analítico para determinação de S em amostras de cabelo por HR-CS GF MAS, a fim de avaliar os níveis deste elemento no organismo e compará-los com os resultados obtidos por ICP OES. As condições escolhidas para temperatura de pirólise e de vaporização foram 1000 graus C e 2400 graus C, respectivamente, utilizando 800 microgramas de W, como modificador permanente, e 15 microgramas e 10 microgramas, respectivamente, de uma mistura de Pd(mais)Mg, como modificador em solução. O valor determinado para a concentração de S no material certificado de referência NCS DC73347a (cabelo humano) está de acordo com o descrito em seu certificado, bem como as concentrações de S determinadas em 14 amostras de cabelo, que estão em concordância com as determinadas por ICP-OES de acordo com teste t-pareado (95 por cento de confiança), o que comprova a boa exatidão do método proposto. / [en] In the presented work it is proposed the development of an analytical method for sulfur determination by high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). The samples were prepared by acid dissolution and the calibration standards containing sulfate, thiourea, L-cysteine were studied as a function of their different thermal stabilities and its capability for matrix matching. The HR-CS GF MAS technique is an interesting alternative for sulfur determination, since its capability to perform an interference-free analysis due to its high resolution monochromator that allows to overcome the spectral overlapping and by the use of the graphite furnace as atomizer which minimizes the matrix effects before the analytical measurement. The aim of this work is to develop an analytical method for sulfur determination in hair samples by HR-CS GF MAS, in order to evaluate the levels of this element in the human body and to compare them with the results obtained by ICP OES. The chosen conditions for pyrolysis and vaporization temperatures were 1000 C degrees and 2400 C degrees, respectively, using 800 micrograms of W as permanent modifier combined with 15 micrograms and 10 micrograms, respectively, of Pd(plus)Mg mixture as modifier in solution. The value determined for S concentration in the certified reference material NSC DC73347a (human hair) was in agreement with those reported in its certificate, as well as sulfur concentrations determined in 14 hair samples, which are in agreement with those determined by ICP-OES according to the t-paired test (95 percent level of confidence), which proves the good accuracy of the proposed method.

Background: The genes coding for human (h) chorionic somatomammotropin (CS), hCS-A and hCS-B, and placental growth hormone (GH-V), hGH-V are located at a single locus on chromosome 17q22-24. Local regulatory (5´ P and 3´ enhancer) sequences and a remote locus control region (LCR) containing a placenta-specific hypersensitive site (HS) IV, have been implicated in the efficient expression of the placental hCS/GH-V genes, in part through gene transfer studies in placental and non-placental tumor cell lines. However, low levels of endogenous expression are reported in placental tumor cells compared to normal term placenta. Thus it was hypothesized that the hCS/GH-V chromatin structure in human choriocarcinoma cells is less accessible to regulatory regions essential for efficient expression due to DNA and/or histone modifications, specifically methylation and acetylation, respectively. Approach: To assess individual hCS-A, hCS-B and hGH-V gene expression in placental and non-placental tumor cells, and assess the effect of increasing “chromatin accessibility” on hCS/GH-V RNA levels by inhibiting DNA methylation and histone deacetylation using 5-aza-2´-deoxycytidine (azadC) and trichostatin A (TSA). Principal Findings: Low levels of hCS-A, hCS-B and hGH-V RNA were detected in placental and non-placental tumor cells compared to term placenta. A significant >5-fold increase in promoter activity was seen in placental but not non-placental cells transfected with hybrid hCS promoter luciferase genes containing 3´-enhancer sequences. Placental JEG-3 cells pretreated with azadC and TSA resulted in a significant >10-fold increase in hCS-A, hCS-B and hGH-V RNA levels compared to TSA treatment alone, however, a modest ~3-fold effect was seen in non-placental MCF-7 cells. By contrast to the effect of pretreatment with azadC, post-treatment with azadC mutes the stimulatory effects of TSA on hCS/GH-V transcripts. The specificity of the response suggests that azadC treatment, and presumably hypomethylation of DNA, results in an increase in response to TSA and histone hyperacetylation at the hGH/CS locus. An assessment of histone H3/H4 hyperacetylation in JEG-3 cells treated with azadC and TSA versus TSA alone revealed significant increases consistent with a more open chromatin structure including the hCS 3´-enhancer sequences and LCR. Conclusions: These observations suggest that accessibility of remote and local regulatory regions required for efficient placental hGH/CS expression can be restricted by DNA methylation and histone acetylation status. This includes restricting access of the hCS 3´-enhancer sequences to available placental enhancer transcription factors. / May 2016