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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
261

Molekulové modelování - struktura a vlastnosti katalyzátorů na bázi karbenů / Molecular modelling - Structure and Properties of carbene-based catalyst

Kulovaná, Eva January 2012 (has links)
Pomocí molekulového modelování je možné předpovídat chování nových látek a napomáhá při jinak obtížné interpretaci experimentálních dat. Cílem práce byla predikce vybraných vlastností polymeračních katalyzátorů na bázi karbenů, predikce jejich struktur a spektrálních charakteristik a studie mechanismu polymerace za otevření kruhu laktidu. K ověření chování karbenů a jejich prekurzorů ve formě chloridů byly studovány vybrané charakteristiky molekuly. Byl proveden výpočet vybraných molekulových orbitalů a elektrostatických map. Následně pomocí počítačových programů byly získány teoretické vazebné délky a úhly vybraných imidazolových a imidazolinových sloučenin, karbenů a jejich možných produktů hydrolýzy. Data strukturně podobných, již charakterizovaných sloučenin, byla získána z CCDC (Cambridge Crystallographic Data Centre) a následně byla konfrontována s vypočítanými daty. Byla změřena infračervená a Ramanova spektra imidazolové soli a infračervené spektrum příslušného karbenu. Tato spektra byla konfrontována s napredikovanými. Pro lepší interpretaci spekter byla spočítána spektra možných produktů hydrolýzy. Následně byl studován mechanismus polymerace za otevření kruhu laktidu. Na základě spočítaných energií stacionárních bodů byl navržen nový mechanismus polymerace.
262

Regulace produkce lipidů a lipidických metabolitů u kvasinek / Regulation of production of lipids and lipid compounds in yeasts

Rapta, Marek January 2015 (has links)
Oleogenic yeasts under appropriate conditions produce and accumulate lipids and lipid-soluble metabolites in high amounts. This attribute is characteristic also for red yeasts that except lipids accumulate also carotenoids – natural pigments used in food industry and dietary supplements. The aim of this diploma thesis was designed as a comparative screening study of production properties of strains Cystofilobasidium capitatum, Rhodotorula glutinis, Sporobolomyces roseus and Sporobolomyces shibatanus. Choosen carbon sources were glucose and glycerol as waste by-product in biofuel industry. The best production properties were found in Cystofilobasidium capitatum and Rhodotorula glutinis. These two strains produced increased amounts of lipids as well as higher amounts of carotenoids. Strains were tested by FTIR spectroscopy that enables high-throughput, uncomplicated and accurate analysis.
263

Étude cinétique et mécanistique des réactions hétérogènes du folpel et du dimethomorphe avec l'ozone et les radicaux OH. Photooxydation homogène des composés morpholiniques avec les radicaux OH. / A kinetic and mechanistic study of the heterogeneous reactions of folpel and dimethomorph with ozone and OH radicals. Homogeneous photooxidation of morpholinic compounds with OH radicals.

El-Rachidi, Mariam 09 May 2012 (has links)
Cette thèse porte sur la détermination des constantes cinétiques de la dégradation hétérogène de pesticide (folpel et diméthomorphe) par l'ozone et les radicaux OH en utilisant un réacteur photo-chimique couplé à un système GC/MS. Le (4-chlorophenyl)(3,4-dimethoxyphenyl)methanone (CPMPM), est identifié par SPME/GC/MS comme produit de dégradation hétérogène du diméthomorphe par les radicaux OH comme par l'ozone. La réactivité hétérogène du CPMPM vis-à-vis de l'ozone et les radicaux OH est également étudiée. Les résultats obtenus montrent que les valeurs des constantes cinétiques varient entre 10-20 et 10-19 cm3.molécules-1.s-1 vis-à-vis de l'ozone, et entre 10-14 et 10-12 cm3.molécules-1.s-1 vis-à-vis des radicaux OH. Ces valeurs impliquent des durées de vie atmosphériques de l'ordre de quelques jours à quelques mois. Par conséquent les composés étudiés sont relativement persistants et peuvent être transportés vers des régions éloignées de leur point d'application.Les spectres UV et la réactivité homogène vis-à-vis des radicaux OH du N-formylmorpholine (NFM), produit gazeux attendu de la dégradation du diméthomorphe, et de deux autres composés gazeux, la morpholine et le N-acétylmorpholine (NAM), ont été déterminés. Les études cinétiques ont été réalisées dans une chambre atmosphérique couplée à un spectromètre IR. Les résultats obtenus montrent que les composés étudiés ne sont pas sensibles à la photolyse dans l'atmosphère et que leur réactivité vis-à-vis des radicaux OH est élevée. En général, les durées de vie atmosphériques de ces composés sont de l'ordre de quelques heures ; ils sont donc non-persistants dans l'atmosphère. / The research study discussed in this thesis concerns the determination of the kinetic rate constants of the heterogeneous degradation of pesticides folpet and dimethomorph by ozone and OH-radicals using the technique of a simulation chamber coupled to a GC/MS analytical system. The study also involves the identification of the degradation products of the analyzed compound in the condensed phase using SPME/GC/MS. The heterogeneous OH and O3-reactivities of the identified degradation product of dimethomorph, (4-chlorophenyl)(3,4-dimethoxyphenyl)methanone (CPMPM), are also evaluated experimentally. The obtained results show that the rate constant values of the analytes are in the order of 10-20-10-19 and 10-14-10-12 cm3.molecule-1.s-1 relative to heterogeneous O3 and OH-oxidation, respectively. Such values implicate tropospheric life-times that vary from a few days to several months, meaning that these compounds are relatively persistent and may be transported to regions far from their point of application.The UV-absorption spectra and homogeneous OH-reactivities of the expected degradation product of dimethomorph in the gas phase, N-formylmorpholine (NFM), and two other gaseous compounds, morpholine and N-acetylmorpholne (NAM) are also studied. The results show that these compounds are not susceptible to photolysis in the atmosphere and that they exhibit strong reactivity towards OH-radicals. Generally speaking, their atmospheric life-times are in the order of a few hours and thus they are non-persistent.
264

Surveillance of c-allocation in microalgal cells

Wagner, Heiko, Jungandreas, Anne, Wilhelm, Christian January 2014 (has links)
When microalgae are exposed to changing environmental conditions, e.g., light-dark cycles or oscillations in nutrient availability (CO2, nitrogen, phosphate or silicate) they respond with metabolic changes in the carbon allocation pattern. Short time regulations in the time range of few seconds to minutes can be mirrored best by mass spectroscopy based metabolomics. However, these snap shots do not reflect the alterations in the carbon flow to the cellular macromolecules like protein, carbohydrate or lipid. In this review it is shown how the combination of FTIR spectroscopy and Chla-in-vivo-fluorescence based electron transport rates can reveal changes in the metabolic flux rates of carbon during a shift of the environmental conditions. The review will demonstrate in which time range FTIR spectroscopy can deliver significant information and how FTIR spectroscopy data can synergistically support metabolome analysis by mass-spectroscopy.
265

Zur Aufnahme und Bindung von Uran(VI) durch die Grünalge Chlorella vulgaris

Vogel, Manja 15 June 2011 (has links)
Uran kann sowohl durch geogene als auch anthropogene Vorgänge in die Umwelt gelangen. Dazu zählen natürliche Uranerzvorkommen und deren Leaching sowie die Auswaschung von Uran aus den Hinterlassenschaften des ehemaligen Uranerzbergbaus. Die Aufklärung des Verhaltens von Uran in der Geo- und Biosphäre ist für eine Risikoabschätzung des Migrationsverhaltens von Radionukliden in der Umwelt notwendig. Algen sind in der Natur weit verbreitet und die wichtigste Organismengruppe in den aquatischen Lebensräumen. Durch ihre ubiquitäre Verbreitung in der Natur ist ihr Einfluss auf das Migrationsverhalten von Uran in der Umwelt von grundlegendem Interesse z.B. um effektive und wirtschaftliche Remediationsstrategien für Wässer zu entwickeln. Außerdem stehen Algen am Beginn der Nahrungskette und spielen eine wirtschaftlich relevante Rolle als Nahrung beziehungsweise Nahrungsergänzungsmittel. Die Möglichkeit des Transfers von algengebundenem Uran entlang der Nahrungskette könnte eine ernsthafte Gesundheitsgefahr für den Menschen darstellen. Das Ziel dieser Arbeit war die quantitative und strukturelle Charakterisierung der Wechselwirkung zwischen Uran(VI) und der Grünalge Chlorella vulgaris im umweltrelevanten Konzentrations- und pH-Wertbereich unter besonderer Berücksichtigung der Stoffwechselaktivität. Die in dieser Arbeit erzielten Ergebnisse der Sorptionsexperimente zeigen deutlich den maßgeblichen Einfluss des Stoffwechselstatus von Chlorella auf die Wechselwirkung mit Uran. So kann in Gegenwart von umweltrelevanten Urankonzentrationen eine Remobilisierung von zuvor passiv gebundenem Uran durch die stoffwechselaktiven Algen erfolgen. Die in Abhängigkeit von der Stoffwechselaktivität, der Urankonzentration und dem pH-Wert mit den Algenzellen gebildeten Uran(VI)-Komplexe wurden strukturell mit Hilfe der spektroskopischen Methoden TRLF-, EXAFS- und ATR-FTIR-Spektroskopie charakterisiert. Mittels TEM konnte Uran in Form von 30-70 nm großen nadelförmigen Ablagerungen in der Zellwand der lebende Algenzellen nachgewiesen werden. Die in dieser Arbeit erhaltenen Ergebnisse leisten einen wichtigen Beitrag zur Vorhersage des Migrationsverhaltens von Uran unter umweltrelevanten Bedingungen und der radiologischen Risikobewertung von geogen und anthropogen auftretendem Uran. / Uranium could be released into the environment from geogenic deposits and from former mining and milling areas by weathering and anthropogenic activities. The elucidation of uranium behavior in geo- and biosphere is necessary for a reliable risk assessment of radionuclide migration in the environment. Algae are widespread in nature and the most important group of organisms in the aquatic habitat. Because of their ubiquitous occurrence in nature the influence of algae on the migration process of uranium in the environment is of fundamental interest e.g. for the development of effective and economical remediation strategies for contaminated waters. Besides, algae are standing at the beginning of the food chain and play an economically relevant role as food and food additive. Therefore the transfer of algae-bound uranium along the food chain could arise to a serious threat to human health. Aim of this work was the quantitative and structural characterization of the interaction between U(VI) and the green alga Chlorella vulgaris in environmental relevant concentration and pH range with special emphasis on metabolic activity. The obtained findings of the sorption experiments in this study demonstrate clearly, the interactions with uranium are heavily influenced by the status of the investigated Chlorella cells. So in presence of environmentally relevant uranium concentrations a remobilization of algal-bound uranium by metabolically active algae occurred. The U(VI)-algae-complexes formed in dependence of cell activity, uranium concentration and pH value were structural characterized by TRLF, EXAFS and ATR-FTIR spectroscopy. With the help of TEM under the given experimental conditions uranium was detected in form of 30-70 nm needle-like deposites in the cell wall of living algae. The obtained results of this study contribute to the prediction of the migration behavior of uranium under environmental conditions, the radiological risk assessment of geogenic and anthropogenic appearing uranium and a reliable estimation of the accumulation of uranium in the food chain.
266

Quantification et étude du transport des polluants dans la troposphère tropicale de l'océan Indien / Quantification and study of the pollutants transportation in the troposphere of the Indian Ocean

Duflot, Valentin 05 November 2011 (has links)
Ces travaux de recherche se sont focalisés sur la zone Océan Indien austral et ont permis d'améliorer les connaissances scientifiques sur la provenance des masses d'air polluées, sur leur distribution spatiale, sur la contribution relative des zones sources à la charge en polluant mesurée, et sur les propriétés optiques des aérosols détectés. La prépondérance de l'influence du transport des masses d'air polluées en provenance d'Afrique Australe et d'Amérique Latine à la concentration en polluant dans le sud-ouest de l'océan Indien a ainsi été démontrée en utilisant des mesures par spectrométrie infrarouge à transformée de Fourier et des modèles de dispersion de panache couplés à des bases de données d'émission. Une voie de transport privilégiée reliant l'Asie du sud-est au sud-ouest de l'océan Indien dans la haute troposphère en Juillet-Août, ainsi que l'apport en CO résultant, ont été identifiés pour la première fois. La variation saisonnière de la concentration en ozone troposphérique dans le sud de l'océan Indien a également été mise en évidence, ainsi que son lien avec les émissions de précurseurs d'ozone provenant des feux de biomasse se produisant en Afrique Australe et en Amérique Latine. L'analyse des données photométriques AERONET a permis d'établir une climatologie des caractéristiques optiques des aérosols à la verticale de la Réunion, qui apparaît comme étant un site relativement propre dont la troposphère est principalement affectée par les aérosols marins tout au long de l'année, et également par les aérosols de feu pendant la saison des feux australe. De plus, des campagnes de mesure avec lidar et photomètre embarqués à bord d'un navire sillonnant l'océan Indien austral a donné accès à l'évaluation de l'extension verticale et des propriétés optiques d'un panache d'aérosols de feux provenant principalement d'Amérique Latine et d'Afrique Australe, mais aussi d'Asie du sud-est. / This thesis focused on the southern Indian Ocean area and contributed to improve our scientific knowledge on the origin of polluted air masses, on their spatial distribution, on the relative contribution of the identified source regions to the measured pollutant loading, and on the optical properties of the encountered aerosols. The potential primary sources for CO throughout the south-western Indian Ocean troposphere are southern Africa and South America. A secondary potential contribution from Southeast Asia and Indonesia-Malaysia was identified in the upper troposphere, especially in July and August. The seasonal variation of tropospheric ozone concentration in the southern Indian Ocean is highlighted, and its link to wintertime long range transport of tropospheric ozone precursors emitted in biomass burning plumes from southern America and Africa is evidenced. The analysis of sun photometer measurements gave access to a climatology of the optical properties of aerosols in Reunion Island, showing this site can be considered as a clean site, mostly influenced by marine aerosols throughout the year, and also by biomass burning aerosols during the southern hemisphere biomass burning season. A unique data set of shipborne measurements has been collected with a dual Rayleigh-Mie lidar and a handheld sun photometer aboard a research vessel crossing the southern Indian Ocean, and the time evolution of the encountered marine and biomass burning aerosols extinction properties and vertical extension are documented.
267

Investigating the Possibilities of Using a Handheld FTIR-Equipment to Characterize Thermal Aging of Rubbers / Undersöka möjligheterna att använda en handhållen FTIR-utrustning för att karakterisera termisk åldring av gummi

Tengbom, Antonia January 2020 (has links)
Element Materials Technology in Linköping is an independent material testing company that performs testing of materials to several big sectors, such as the Swedish Armed Forces and the aerospace industry. There is of great importance to characterize aging of materials to ensure material performance. Element Materials Technology recently invested in a handheld FTIR equipment and it was of interest to see if this equipment might be an additional analysis technique to characterize aging of rubber materials. A nitrile butadiene rubber and two natural rubbers were thermally aged in 50°C and 70°C for six weeks. The hardness of the rubbers increased when the rubbers were thermally aged. The compression set decreased for the aged samples as well as the tensile strength and the elongation at break. An investigation of possible methods for collecting migrated additives on the rubber surface was performed, using two different solvents and a stationary FTIR equipment. More research needs to be performed to exclude the possibility that the solvents affect the material. Universal Attenuated Total Reflectance – Fourier Transform Infrared Spectroscopy, UATR-FTIR onto the rubber surface showed in some cases changes in the spectrums between unaged and aged samples. However, it could not be concluded weather the changes occurred due to migrating additives or due to changes in the backbone polymer. Four interfaces to the handheld FTIR equipment were investigated and an ATR interface gave best results. An analysis method was developed for the handheld FTIR equipment and the spectrums from the handheld FTIR were similar to spectrums from UATR-FTIR (stationary). It could be concluded from Micro Chamber analysis that volatile organic matters were emitted at elevated temperature. Thermogravimetric analysis could detect the relative composition of the rubbers. Further it could be concluded that the mechanical properties were affected by the thermal treatment. This study could however not establish a correlation between FTIR signals and the results seen from the other analysis. The fact that differences could be detected in the FTIR spectrums before and after aging could indicate that the FTIR analysis technique can possibly be used as an analysis method. However, a more thoroughly investigation needs to be performed before using this technique. / Element Materials Technology i Linköping utför materialutredningar åt en mängd olika typer av företag, där en stor sektor är den svenska Försvarsmakten och flygindustrin. Materialutredningar är essentiella för att säkerställa att rätt material används för rätt applikation. Element Materials Technology investerade nyligen i en handhållen FTIR utrustning. Det finns förhoppningar om att den nya utrustningen kan användas som ett komplement för att ålderskarakterisera gummimaterial. Ett nitril-butadien-gummi och två stycken naturgummin var termiskt åldrade i 50°C och 70°C i sex veckor. Hårdheten på provkroppar ökade efter den termiska åldringen. Sättningen, draghållfastheten och töjningen minskade för proverna åldrade i värme. En metod för att samla upp migrerade additiv från gummiytan utvecklades och undersöktes, genom att använda två olika lösningsmedel och en stationär FTIR utrustning. Ytterligare utredningar behöver däremot genomföras för att utesluta ifall de två lösningsmedel påverkar gummimaterialet och inte bara samlar upp additiv från gummiytan. UATR-FTIR visade på skillnader i spektrum mellan icke-åldrade och åldrade gummimaterial. Däremot kunde det inte avgöras om skillnaderna i spektrumen berodde på migration av additiv till gummiytan eller på förändring i huvudpolymeren. Fyra stycken olika tillbehör till den handhållna FTIR utrustningen prövades, där ATR-tillbehöret gav bra spektrum. En analyseringsmetod utvecklades för den handhållna FTIR-utrustningen och spektrum från dessa analyser gav liknande spektrum som spektrum från UATR-FTIR (stationär). Analys med Micro Chamber visade att flyktiga organiska ämnen lämnade gummimaterialet vid förhöjd temperatur. Termogravimetrisk analys, TGA visade förhållandet mellan gummimaterialets komponenter både före och efter åldring. Studien visade också att de mekaniska egenskaperna påverkades av den termiska åldringen. Analysmetoden FTIR kunde detekterad skillnad i spektrum före och efter åldring av gummimaterialen. Studien kunde däremot inte etablera ett samband mellan dessa FTIR-signaler och de övriga analysresultaten. Det kan däremot inte uteslutas att ett sådant samband finns. Ytterligare studier behöver utföras för att undersöka detta.
268

[pt] ANÁLISE POR FTIR DA RADIÓLISE E DO SPUTTERING DE BASES NITROGENADAS IRRADIADAS POR ELÉTRONS DE (KE)V SOB CONDIÇÕES ASTROFÍSICAS / [en] RADIOLYSIS AND SPUTTERING FTIR ANALYSIS OF NITROGENOUS BASES IRRADIATED BY (KE)V ELECTRONS UNDER ASTROPHYSICAL CONDITIONS

VINICIUS PESSANHA REGO 21 June 2022 (has links)
[pt] A origem da vida ainda é uma questão aberta na ciência. Dentre as possíveis respostas, a panspermia é uma alternativa amplamente discutida. Ao investigar esta possibilidade, o desenvolvimento de modelos que descrevam o comportamento de moléculas interagindo com raios cósmicos são de extrema importância. Para esta finalidade, filmes finos de diferentes espessuras de bases nitrogenadas - adenina, citosina, guanina e timina - foram depositados sobre pastilhas de ZnSe para serem irradiados por elétrons de 1,0 e 0,50 keV. A adenina foi irradiada sob diferentes temperaturas. Após cada irradiação parcial, a espectroscopia óptica na região do infravermelho (FTIR) foi usada para monitorar as modificações nas características espectrais. Observou-se que a seção de choque de destruição das bases nitrogenadas irradiadas é aproximadamente 10 elevado a -16 cm quadrados e, para a adenina, este valor aumenta para temperaturas baixas. Com base nos dados obtidos de glicina, o tempo de meia vida de adenina pura processada por vento solar a 1 UA estimado é de cerca de 40 dias. A seção de choque varia muito pouco quando as espessuras dos filmes são aumentadas de 10 para 30 nm, e os valores encontrados para as quatro bases seguem a ordem: citosina, adenina, guanina e timina, respectivamente, da menos para a mais radioresistente. Para melhor compreender o significado dos resultados experimentais, previsões foram obtidas com o algoritmo CASINO-estendido e apresentam bom acordo se radiólise e sputtering são considerados. / [en] The origin of life is still an open question in science. Among the possible answers, panspermia is a widely discussed alternative. To investigate this possibility, the development of models that describe the behavior of molecules interacting with cosmic rays is extremely important. For this purpose, thin films of different thicknesses of nitrogenous bases - adenine, cytosine, guanine, and thymine - were deposited on ZnSe disks to be irradiated by 1.0 and 0.50 keV electrons. Adenine was irradiated under different temperatures. After each partial irradiation, optical spectroscopy in the infrared region (FTIR) was used to monitor changes in spectral characteristics. It is observed that the destruction cross sections of irradiated nitrogenous bases are approximately 10 raised to -16 square cm and, for adenine, this value increases at low temperatures. In comparition to glycine data, the estimated half-life of pure adenine when processed at 1 au by the solar wind is about 100 days. The cross section varies very little when the film thicknesses are increased from 10 to 30 nm, and the bases follow the order: cytosine, adenine, guanine and thymine, respectively, from the least to the most radioresistant. To better analyze the experimental data, they are compared with predictions obtained with the CASINOextended algorithm. They are in good agreement if radiolysis and sputtering are considered.
269

[en] ANALYSIS OF THE IMPACT OF THE USE OF TELEVISION MARKETING CAMPAIGNS ON SUPERMARKET SALES / [pt] RADIÓLISE DA ALANINA POR ELÉTRONS DE 100 A 1000 EV ANALISADA POR ESPECTROSCOPIA NO INFRAVERMELHO

MATHEUS SEIXAS RODRIGUES 07 March 2022 (has links)
[pt] Compostos orgânicos observados em corpos do espaço interplanetário são de particular importância para revelar os processos físico-químicos que podem estar relacionados com a origem da vida. Aminoácidos, como a alanina, devem ter desempenhado um papel crucial neste processo, uma vez que são componentes básicos das proteínas, constituintes essenciais de todos os organismos vivos. Informações sobre a radioresistência deles são essenciais para o desenvolvimento de modelos sobre como as moléculas prebióticas são formadas ou resistem a viagens no Sistema Solar e além. Em particular, a seção de choque de destruição por impacto de elétrons precisa ser conhecida e o processo da radiólise, entendido. O presente estudo visa determinar a dependência da seção de choque de destruição da alanina por impacto de feixe de elétrons com energias na faixa de 100 eV até 1 keV para alvos com espessura entre 10 nm e 1000 nm. A degradação da amostra pelo feixe de elétrons foi monitorada por espectroscopia no infravermelho (FTIR). Além disso, são apresentadas simulações feitas pelo método Monte Carlo para irradiações na alanina com feixes de elétrons de 250 eV até 5 keV. Infere-se pelas simulações do programa CASINO que os parâmetros considerados variam em função de E(1,7). Resultados experimentais indicam que a seção de choque de destruição efetiva diminui exponencialmente com a espessura da amostra até atingir um nível de saturação. A seção de choque de destruição efetiva aumenta com a energia incidente segundo a lei de potência E (1,76). Determinou-se os valores dos A-values para as bandas estudadas, através do método de espectroscopia no infravermelho, e são da ordem de 10(-18) cm(2)/molec. Encontrou-se um acordo qualitativo moderado entre os resultados da modelagem com os dados experimentais. Conclui-se que ele será sensivelmente melhorado se for acrescentado o processo de sputtering à radiólise analisada. / [en] Organic compounds observed in interplanetary space bodies are of particular relevance for revealing the physical-chemical processes that may be related to life s origin. Amino acids, such as alanine, are supposed to have played a crucial role in this process since they are basic components of proteins, essential constituents of all living organisms. Information about their radioresistance is essential for the development of models on how prebiotics molecules are formed or resist travelling in the Solar System and beyond; in particular the destruction cross-section by electron impact needs to be known and the radiolysis process needs to be understood. The current study aims to determine the dependence of alanine destruction cross-section on electron beam impact with energies in the range of 100 eV - 1 keV for thickness targets range of 10 nm - 1000 nm. The sample s degradation by the electron beam was monitored by infrared spectroscopy (FTIR). Moreover, simulations performed by Monte Carlo method for alanine irradiation with electron beam energies from 250 eV up to 5 keV are presented. It is inferred by the CASINO simulations, that the considered parameters vary as a function of E(1.7). Experimental results indicate that the effective destruction cross section decreases exponentially with the sample s thickness until it reaches a saturation level. The effective destruction cross section increases with incident energy according to the power law of E (1.76). The bands A-values were determined by infrared spectroscopy method and are in the order of 10(-18) cm(2)/molec. A moderate qualitative agreement was found between modeling results and the experimental data. It is concluded that it will be significantly improved if the sputtering process is added to the analyzed radiolysis.
270

[pt] EFEITOS INDUZIDOS PELA IRRADIAÇÃO COM ÍONS DE MEV E ELÉTRONS DE KEV EM MATERIAIS PREBIÓTICOS: RADIÓLISE E SPUTTERING / [en] MEV ION AND KEV ELECTRON IRRADIATION EFFECTS ON PREBIOTIC MATERIALS: RADIOLYSIS AND SPUTTERING

CINTIA APARECIDA PIRES DA COSTA 06 December 2021 (has links)
[pt] A presença de aminoácidos em cometas e meteoritos levanta questões sobre como estes foram formados em ambientes cósmicos, bem como de que maneira eles foram capazes de sobreviver no espaço sideral; radioresistência é uma informação essencial para prever meias-vidas e avançar os estudos sobre origens da vida. O principal objetivo deste trabalho é determinar, por meio de espectroscopia no infravermelho, as seções de choque de destruição de aminoácidos comuns expostos à radiação de íons e elétrons energéticos. As forças de banda vibracionais (A-values) e a dependência do espectro infravermelho com a temperatura da amostra (10 – 400 K) foram analisadas. Seções de choque de destruição aparente (sigma)d(ap) e rendimentos de sputtering (Y0) para glicina, valina e fenilalanina irradiadas por H+, He+ e Nq+ íons de MeV e elétrons de keV foram medidos. Encontrou-se: i) uma dependência aproximadamente linear entre a seção de choque de destruição aparente e o poder de freamento eletrônico (Se): (sigma)d(ap) = (sigma)d + Y0 /N0 = a Sen (onde n aproximadamente 1) para projéteis de MeV e para amostras à temperatura ambiente; ii) resultados preliminares de σdap para feixes de nitrogênio multi-carregados; e iii) resultados de seção de choque de destruição de valina irradiada por elétrons de keV, bem como sua dependência com a energia de incidência do feixe, e com a espessura e temperatura da amostra. Como contribuição teórica, o modelo CASINO-estendido foi desenvolvido visando descrever a evolução da degradação de matéria orgânica por projéteis carregados, particularmente por feixes de elétrons. Comparadas aos resultados experimentais, as previsões do modelo subestimam o dano causado pelo feixe de elétrons, evidência de que efeitos de sputtering e provavelmente algumas características da amostra (como a estrutura cristalográfica) devem ser incluídos. Como implicações astrofísicas, meias-vidas para valina e fenilalanina irradiadas por raios cósmicos são estimadas em aproximadamente 10 milhões de anos no meio interestelar; da glicina, se irradiadas por vento solar a uma unidade astronômica do Sol, é aproximadamente 3 dias. Visando simular materiais astrofísicos realistas bombardeados por elétrons de keV, a meia-vida de valina envolta por gelos de água e CO2 e depositada sobre silicato é também prevista. / [en] The presence of amino acids in comets and meteorites raises questions about how they have been formed in cosmic environments, as well as how long they can survive in outer space; radioresistance is essential information to predict half-lives and make advances on the origins of life studies. The main objective of the current work is to determine, via infrared spectrometry, destruction cross sections of common amino acids exposed to energetic ion and electron radiation. Before sample irradiation, valine vibrational band strengths and their infrared spectral dependence on temperature (10 – 400 K) were analyzed. Apparent destruction cross sections (sigma)d(ap) and sputtering yields (Y0) for glycine, valine and phenylalanine, irradiated by MeV H+, He+ and Nq+ ions and keV electrons, were measured. From experimental data: i) an approximately linear dependence between the apparent destruction cross section and the electronic stopping power (Se) is found: (sigma)d(ap) = (sigma)d + Y0 /N0 = a Sen (where n approximately 1) for MeV projectiles and for samples at room temperature; ii) (sigma)d(ap) preliminary results relative to multi-charged nitrogen ion beams are discussed; and iii) destruction cross section of valine irradiated by keV electrons, as well as its dependence on incident beam energy, on sample thickness and on sample temperature are presented. As a theoretical contribution, the evolution of organic matter damage by charged projectiles, particularly for electron beams, the CASINO-extended model was developed. When compared to experimental results, the model predictions underestimate the damage caused by electron beams, evidence that sputtering and probably some sample characteristics (as crystallographic structure) are involved. As astrophysical implications, cosmic ray half-lives for valine and phenylalanine are estimated to be about 10 million years in the interstellar medium; solar wind half-life at 1 au from the Sun is approximately 3 days for glycine. Aiming to simulate realistic astrophysical materials bombarded by keV electrons, the half-life of valine embedded into water and CO2 ices over a silicate substrate is also predicted.

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