Este estudo caso-controle teve por objetivo comparar as angulações e inclinações dentárias em casos de má oclusão de Classe I pré e pós-tratamento ortodôntico e em casos de oclusão normal. A amostra consistiu nos modelos dentários em gesso de 18 indivíduos com má oclusão de Classe I (3 homens e 15 mulheres; idade 15,12 ± 1,42 anos), tratados com exodontias de primeiros pré-molares e mecânica de deslize por meio da técnica MBT® com ancoragem por mini-implantes. Estes indivíduos foram pareados por idade com outros 18 indivíduos com oclusão normal não tratada (7 homens e 11 mulheres; idade 14,9 ± 1,0 anos). Os modelos dentários em gesso foram escaneados tridimensionalmente e, em seguida, os modelos digitais foram encaminhados para o programa Power Shape-e® (Delcam®, Birminghan, Reino Unido) para mensuração das angulações e inclinações dentárias. O teste t de Student foi empregado para análise dos dados. Os resultados não apontaram diferenças significantes entre os lados direito e esquerdo (p > 0,05). O tratamento da má oclusão de Classe I impôs uma significativa diminuição nas angulações de caninos e segundos molares superiores e um aumento das inclinações vestibulares das coroas de incisivos laterais superiores, segundos pré-molares, primeiros e segundos molares inferiores. Verificou-se que uma maior angulação dos caninos e pré-molares inferiores contribuiu para a caracterização da má oclusão de Classe I, assim como uma redução na angulação dos incisivos laterais superiores. Os casos de má oclusão de Classe I pós-tratamento, em comparação com os indivíduos com oclusão normal, apresentaram significativas diminuições nas angulações de segundos molares, caninos e incisivos laterais superiores e de segundos molares inferiores e aumentos significativos nas angulações de segundos pré-molares, caninos e incisivos inferiores. Houve também redução das inclinações dentárias de primeiros e segundos molares inferiores no grupo tratado. Portanto, as alterações nas angulações e inclinações contribuíram para a correção da má oclusão de Classe I e para a aproximação com os valores do grupo com oclusão normal. / This case-control study aimed at comparing dental angulation and inclination in cases with Class I malocclusion pretreatment and posttreatment and in cases with normal occlusion. The sample consisted of dental plaster models of 18 subjects with Class I malocclusion (3 males and 15 females, aged 15.12 ± 1.42 years), treated by first premolars extractions and sliding mechanics by MBT® technique with miniimplants for anchorage. These individuals were age-matched with 18 patients with untreated normal occlusion (7 men and 11 women, aged 14.9 ± 1.0 years). The dental plaster models were scanned three-dimensionally, and then the digital models were referred to the software Power Shape-e® (Delcam®, Birmingham, UK) for measurement of angulations and inclinations. The Student t test was used for statistical analysis. The results did not show significant differences between the right and left sides (p> 0.05). The treatment of Class I malocclusion imposed a significant decrease in the angulation of upper canines (U3) and second molars (U7) and an increase in the buccal inclination of the crowns of upper lateral incisors (U2), lower second premolars (L5), first (L6) and second molars (L7). It was found that an increase in the angulation of lower canines (L3) and premolars (L4 and L5) contributed to the characterization of the Class I malocclusion, as well as a decrease in the angulation of U2. Posttreatment cases of Class I malocclusion, compared with normal occlusion, showed significant decreases in the angulation of U7, U3, U2 and L7 and significant increases in the angulation of L5, L3 and lower incisors (L1 and L2). There was also a decrease in inclinations of L6 and L7 in the treated group. Therefore, changes in angulations and inclinations contributed to correction of Class I malocclusion.

O Bisfenol A (BPA, acrônimo da língua inglesa - bisphenol A) é uma substância utilizada na fabricação de embalagens alimentícias e resinas odontológicas. Sua toxicidade deve-se ao fato de que, como disruptor endócrino, afeta o sistema reprodutor, cardiovascular, neuro-endócrino e pode apresentar potencial carcinogênico. Em métodos bioanalíticos, o preparo da amostra tem sido requerido para aumentar a seletividade e sensibilidade analítica, através da remoção dos interferentes da amostra biológica e concentração dos analitos, quase sempre presentes em níveis de traços. A microextração em ponteiras (DPX, acrônimo das iniciais em língua inglesa - Disposable Pipette Extraction), baseada no equilíbrio de sorção do soluto com a fase extratora, consiste em uma ponteira padrão de micropipeta modificada, na qual o sorvente está contido livremente entre dois filtros, permitindo rápida extração do analito em diferentes matrizes complexas. Os polímeros de impressão molecular (MIP acrônimo das iniciais em língua inglesa - Molecularly Imprinted Polymer) consistem em uma rede polimérica tridimensional que possui cavidades seletivas para o reconhecimento molecular do analito ou de substâncias de estrutura análoga. Essa rede polimérica é sintetizada ao redor da substância molde (analito), e a cavidade seletiva é formada após a remoção do molde. As vantagens do processo sol-gel para a síntese do MIP são o controle do tamanho e forma das partículas, ajuste da hidrofobicidade e alta estabilidade térmica. No presente trabalho, o MIP foi sintetizado e utilizado como sorvente para a técnica DPX para a determinação de bisfenol A em amostras de urina por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS, acrônimo das iniciais em língua inglesa - Gas Chromatography coupled to Mass Spectrometry). O MIP foi sintetizado pela via sol-gel utilizando aminopropiltrietoxisilano (APTES) como mônomero funcional e tetraetil-orto-silicato (TEOS) como reagente de ligação cruzada. Como molde foram avaliados o BPA para o MIP, e o tetrabromobisfenol A (TBBPA) para o polímero molecularmente impresso com molécula análoga ao analito (DMIP, acrônimo das iniciais em língua inglesa - Dummy Molecularly Imprinted Polymer). Para avaliar a seletividade do MIP, o polímero não impresso (NIP, acrônimo das iniciais em língua inglesa - Non-imprinted Polymer) foi sintetizado seguindo o mesmo procedimento de síntese do MIP com exceção da adição da molécula molde. Apesar de a capacidade de sorção do MIP ser ligeiramente maior, o DMIP foi selecionado como sorvente para minimizar o efeito de memória. O DMIP foi caracterizado por microscopia eletrônica de varredura (MEV) e por espectroscopia vibracional na região do infravermelho por transformada de Fourier (FTIR, acrônico das inicias em língua inglesa - Fourier Transform Infrared). Os parâmetros da técnica DPX, tais como, o tempo de equilíbrio de sorção entre a amostra e o sorvente e condições de dessorção foram otimizadas por técnicas quimiométricas. A robustez do DMIP sintetizado via sol-gel foi comprovada pela reutilização deste sorvente por mais de 100 vezes, sem perda da eficiência da extração. O método desenvolvido DPX/GC-MS apresentou linearidade na faixa de 50 a 500 ng mL-1, precisão com CV (coeficientes de variação) entre 4 e 14% e de exatidão com valores de erro padrão relativo (EPR) de -13,6 a 12,3%. O método de referência utilizando a extração líquido-líquido e GC-MS (LLE/GC-MS), faixa de linearidade de 5 a 50 ng mL-1, foi desenvolvido e validado. Embora o método DPX/GC-MS inovador, quando comparado ao LLE/GC-MS, tenha apresentado maior limite de quantificação, apresentou as seguintes vantagens: simplicidade, rapidez e utilização de menores volumes de amostra e de solventes orgânicos na etapa do preparo da amostra / Bisphenol A (BPA) is widely used in food package and dental resins manufacturing. Its toxicity is due to its endocrine disruptor activity that affects the reproductive, cardiovascular, neurological system and may have carcinogenic potential. In bioanalytical methods the sample preparation has been required to increase the selectivity and analytical sensibility by removing the interfering from the biological matrix and concentration of the analytes that are in trace levels most of the times. The disposable pipette extraction (DPX) is based on sorption equilibrium of the analyte between the sample and the extraction phase. It consists in a pipette that contais the sorbent phase freely between two filters. Then, the extraction of the solute from the complex sample occurs quickly. Molecularly imprinted polymer is a tridimensional polimeric network that has selectivity cavities that can recognize an analyte or a substance with a similar structure. The polimeric network is synthesized around to a template molecule and after removing this template, a selective cavity is formed. The advantages of the sol-gel process for the synthesis of MIP are the control of the size and shape of the particles, hydrophobicity adjustment and high thermal stability. In the present study MIP was synthesized and used as sorbent to DPX method for determination of BPA in urine samples by gas chromatography coupled to mass spectrometry (GC-MS). Sol-gel methodoly was used to synthesize the polymers. Aminopropyltriethoxysilane (APTES) was used as a functional monomer and tetraethyl orthosilicate (TEOS) as crosslinking reagent. BPA and tetrabromobisphenol A (TBBPA) were evaluated as template to the synthesis of MIP and dummy molecularly imprinted polymer (DMIP) which is a molecularly imprinted polymer that uses a template structurally similar to the analyte. The non-imprinted polymer (NIP) was synthesized following the same procedure that MIP, except for the addition of template. It was made to verify the improvement of selectivity and sensibility of molecularly imprinted polymers. Although the sorption capacity of the MIP is slightly larger, DMIP has been selected as a sorbent in order to minimize the memory effect. The DMIP was characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared spectroscopy (FTIR). The parameters of DPX, such as time sorption equilibrium between the sample and the sorbent and desorption conditions were optimized by chemometrics. Robustness of DMIP sinthesized by sol-gel process was evidenciated for the reuse of DMIP for more than a 100 times. The developed method DPX/GC-MS showed linearity on the range from 50 to 500 ng ml-1, precision values with coefficient of variation (CV) betweeen 4 and 14% and accuracy with relative standard deviation values (RSD) from -13.6 to 12.3%. The reference method using liquid- liquid extraction and GC-MS (LLE/GC-MS) was developed and validated, showing linearity from 0.5 to 50 ng mL-1. Althout the innovative method DPX/GC-MS has showed limit of quantification larger than LLE/GC-MS, it presents the following advantages: simplicity, rapidy and utilization of smaller volumes of organic solvents on the sample preparation step

Este estudo caso-controle teve por objetivo comparar as angulações e inclinações dentárias em casos de má oclusão de Classe I pré e pós-tratamento ortodôntico e em casos de oclusão normal. A amostra consistiu nos modelos dentários em gesso de 18 indivíduos com má oclusão de Classe I (3 homens e 15 mulheres; idade 15,12 ± 1,42 anos), tratados com exodontias de primeiros pré-molares e mecânica de deslize por meio da técnica MBT® com ancoragem por mini-implantes. Estes indivíduos foram pareados por idade com outros 18 indivíduos com oclusão normal não tratada (7 homens e 11 mulheres; idade 14,9 ± 1,0 anos). Os modelos dentários em gesso foram escaneados tridimensionalmente e, em seguida, os modelos digitais foram encaminhados para o programa Power Shape-e® (Delcam®, Birminghan, Reino Unido) para mensuração das angulações e inclinações dentárias. O teste t de Student foi empregado para análise dos dados. Os resultados não apontaram diferenças significantes entre os lados direito e esquerdo (p > 0,05). O tratamento da má oclusão de Classe I impôs uma significativa diminuição nas angulações de caninos e segundos molares superiores e um aumento das inclinações vestibulares das coroas de incisivos laterais superiores, segundos pré-molares, primeiros e segundos molares inferiores. Verificou-se que uma maior angulação dos caninos e pré-molares inferiores contribuiu para a caracterização da má oclusão de Classe I, assim como uma redução na angulação dos incisivos laterais superiores. Os casos de má oclusão de Classe I pós-tratamento, em comparação com os indivíduos com oclusão normal, apresentaram significativas diminuições nas angulações de segundos molares, caninos e incisivos laterais superiores e de segundos molares inferiores e aumentos significativos nas angulações de segundos pré-molares, caninos e incisivos inferiores. Houve também redução das inclinações dentárias de primeiros e segundos molares inferiores no grupo tratado. Portanto, as alterações nas angulações e inclinações contribuíram para a correção da má oclusão de Classe I e para a aproximação com os valores do grupo com oclusão normal. / This case-control study aimed at comparing dental angulation and inclination in cases with Class I malocclusion pretreatment and posttreatment and in cases with normal occlusion. The sample consisted of dental plaster models of 18 subjects with Class I malocclusion (3 males and 15 females, aged 15.12 ± 1.42 years), treated by first premolars extractions and sliding mechanics by MBT® technique with miniimplants for anchorage. These individuals were age-matched with 18 patients with untreated normal occlusion (7 men and 11 women, aged 14.9 ± 1.0 years). The dental plaster models were scanned three-dimensionally, and then the digital models were referred to the software Power Shape-e® (Delcam®, Birmingham, UK) for measurement of angulations and inclinations. The Student t test was used for statistical analysis. The results did not show significant differences between the right and left sides (p> 0.05). The treatment of Class I malocclusion imposed a significant decrease in the angulation of upper canines (U3) and second molars (U7) and an increase in the buccal inclination of the crowns of upper lateral incisors (U2), lower second premolars (L5), first (L6) and second molars (L7). It was found that an increase in the angulation of lower canines (L3) and premolars (L4 and L5) contributed to the characterization of the Class I malocclusion, as well as a decrease in the angulation of U2. Posttreatment cases of Class I malocclusion, compared with normal occlusion, showed significant decreases in the angulation of U7, U3, U2 and L7 and significant increases in the angulation of L5, L3 and lower incisors (L1 and L2). There was also a decrease in inclinations of L6 and L7 in the treated group. Therefore, changes in angulations and inclinations contributed to correction of Class I malocclusion.

L'évolution de la législation en matière de valorisation des déchets organiques incite au développement de filières de valorisation, parmi lesquelles le compostage présente un intérêt d'amendement pour les sols, lié notamment à la présence de substances humiques. La matière organique (MO) est une composante importante du sol en raison de son rôle dans les équilibres physiques, chimiques et biologiques, ainsi que par son implication dans le comportement des métaux et métaux traces (MMT). Les objectifs de cette thèse étaient de développer une approche méthodologique afin de caractériser la MO du sol (MOS) et étudier son évolution spatio-temporelle suite à l’apport d’un compost sur une année et 2 profondeurs, et d'approcher son impact sur le comportement des MMT. Une procédure d’extraction séquentielle en 4 étapes (eau, acide, soude, pyrophosphate) a été réalisée afin de fractionner la MOS. Des analyses quantitatives et qualitatives, ont été effectuées sur les extraits. La procédure de fractionnent chimique a permis de distinguer plusieurs catégories de composés organiques (labiles, fulviques et humiques plus ou moins aromatiques). Les analyses quantitatives et les réponses spectrales sur les extraits ont révélé un effet compost essentiellement les trois premiers mois après l’épandage et en été, avec un impact des paramètres climatiques au cours de l'année, mais pas au-delà de 15 cm. Le compost peut apporter au sol une charge supplémentaire en MMT, notamment potentiellement mobilisables, avec un risque de contamination modéré, mais non négligeable lié aux effets potentiels d’accumulation et de concentration sur le long terme. / The evolution of the legislation regarding the valorization of biowaste (green manure) induces the development of valorization chains, among which amending soils with compost is of particular interest, due to the presence of humic substances. Organic matter (OM) is an important component of the soil due to its physical, chemical and biological participation, and its implication in the behaviour of metals and trace metals (MTM).The aims of this thesis were to develop a methodological approach to characterize OM of soil (SOM) and to study its spatiotemporal evolution over one year at two different depths following the addition of compost, and its impact on the behaviour of MTM. A 4-step sequential extraction procedure (water, acid, sodium hydroxide, pyrophosphate) was used to the SOM fractionation. Quantitative and qualitative analysis were applied on extracts. Solubilization kinetics of MTM was also carried out to refine the study of their mobility.The chemical fractionation procedure allowed distinguishing several classes of organic compounds (labile, fulvic and humic with various aromaticity). Quantitative analyzes and spectral responses of the extracts revealed an effect of the compost (organic carbon, metals, aromaticity and molecular weight compounds) essentially during the first three months after spreading and during the summer period, with a climate parameter effect during the year, but not beyond 15 cm of depth. Compost can bring to the soil an additional load of MTM, including potentially mobilized forms, with a moderate, but not negligible risk of contamination, due to the potential effects of accumulation and concentration over the long term.

Plant roots are critical weathering agents in deep soils, yet the impact of resulting mineral transformations on the vast deep soil carbon (C) reservoir are largely unknown. Root-driven weathering of primary minerals may cause the formation of reactive secondary minerals, which protect mineral-organic associations (MOAs) for centuries or millennia. Conversely, root-driven weathering may also transform secondary minerals, potentially enhancing the bioavailability of C previously protected in MOAs. Here we examined the impact of root-driven weathering on MOAs and their capacity to store C over pedogenic time scales. I compared soil that experienced root-driven weathering, resulting in the formation of discrete rhizosphere zones in deep soil horizons (100-160 cm) of the Santa Cruz Marine Terrace chronosequence (65 ka-226 ka), with adjacent soil that experienced no root growth. Using a combination of radiocarbon, mass spectrometry, Mössbauer spectroscopy, and X-ray spectromicroscopy approaches, we characterized MOA transformations in relation to changes in C content, turnover and chemistry across four soils ranging in age (65 ka-226 ka). We found that the onset of root-driven weathering (65-90 ka) increased the amount of C associated with poorly crystalline iron (Fe) and aluminum (Al) phases, particularly highly-disordered nano-goethite. The increase in C coincided with greater overall C concentrations, longer C residence times, and a greater abundance of microbially-derived C. Continued root-driven weathering (137-226 ka) did not significantly change the amount of C associated with crystalline Fe and Al phases, but resulted in a decline in the amount of C associated with poorly crystalline metal phases. This decline in C associated to poorly crystalline phases coincided with a decrease in C concentrations and potential turnover rates, and a shift toward plant-derived C. In contrast, soil not affected by root-driven weathering showed low amounts of C bound to poorly crystalline Fe and Al phases regardless of soil age and, correspondingly, lower C concentrations and estimated residence times. My results demonstrate that root-driven formation and disruption of poorly crystalline Fe and Al phases directly controls both C accrual and loss in deep soil. Hence root impacts on soil C storage are dependent on soil weathering stage, a consideration critical for predictions of the vulnerability of deep soil C to global change.

Ziel: Das Ziel dieser Studie war es den Zusammenhang zwischen Zahnextraktionen und Patientenfaktoren in 3 Deutschen Zahnarztpraxen zu untersuchen. Material & Methoden: In einer retrospektiven Auswertung aller Patientenkarten von 3 deutschen Zahnarztpraxen wurden Extraktionsfälle ab Januar 2007 (Praxis 1), Mai 2010 ( Praxis 2) und Januar 2010 ( Praxis 3 ) auf Extraktionen hin durchsucht, bis in jeder Praxis jeweils 100 Extraktionspatienten gefunden wurden, die die Einschlusskriterien erfüllten. Alle Patienten ohne Extraktionen die innerhalb dieses Zeitraumes behandelt wurden und die die Einschlusskriterien erfüllten, dienten als Kontrollgruppe. Es wurden nur Patienten eingeschlossen (Fall und Kontrollgruppe), von denen die spezifischen Patientendaten zur Verfügung standen. Alle Patientendaten wurden in einem „Case-Report-Form\"-Formular (CRF) erfasst. Die individuellen Parameter der Patienten der Fallgruppe und der Kontrollgruppe wurden verglichen. Mittels schrittweiser logistischer Regressionsanalyse konnten die Faktoren für ein Extraktionsrisiko bestimmt werden. Ergebnisse: Insgesamt wurden 2174 Patientenakten untersucht (Fallgruppe 300; Kontrollgruppe 1874). Die Gesamtsumme der Zähne vor der Extraktionstherapie betrug 54316. In der Fallgruppe wurden insgesamt 459 Zähne extrahiert. Die Patienten der Fallgruppe waren im Schnitt mehr als 6,7 Jahre älter als die Patienten der Kontrollgruppe(52,4/45,7 Jahre (P< 0,001)), sie waren zu einem größeren Anteil männlich. (58/ 52%) ,es gab eine höhere Zahl an Rauchern, es gab vermehrt Patienten mit einer Kalziumkanalblocker Medikation [15/8 % (p<0,001)] und der parodontale Befund festgestellt mittels PSI der Fallgruppe war schlechter als der der Kontrollgruppe [PSI 2,5/1,8 , (p<0,001)]. Das Risiko einer Zahnextraktion im Allgemeinen und in Folge von Parodontalerkrankungen waren assoziiert mit Kalziumkanalblockermedikation, (OR 1,49/1,65) aktivem Rauchen (OR 1,35/1,71), Alter (10Jahre) OR 1,13/1,37 , Praxis Nr.1 (1,48/1,99) und der Anzahl der Sextanten mit dem PSI Code 4 (1,33/1,76) (p<0,001). Schlussfolgerung: Kalziumkanalblockermedikation, aktives Rauchen, Alter, Zahnarzt und die Anzahl der Sextanten mit einem PSI Wert 4 sind Risikoindikatoren für Zahnextraktionen. Nutzen : Kalziumkanalblockermedikation kann das Extraktionsrisiko erhöhen. Zahnverlust zieht in den meisten Fällen Zahnersatz nach sich, welcher in aller Regel aufwändig ist, den Patienten zusätzliche Belastungen abverlangt und die Kosten einer Therapie erhöht. Die Information über die Einnahme von Kalziumkanalblockern ist ein leicht zu erfassender Parameter und könnte als Indikator genutzt werden, um Betreuungsintervalle zu verkürzen. Es muss jedoch noch geprüft werden, ob eine intensivere Betreuung dieser Patienten deren Zahnextraktionsrate tatsächlich verringern kann.

Fyzikálně-chemická povaha hydrofobních domén huminových kyselin byla studována z několika hledisek. K objasnění významu fluorescenčních spekter byly vzorky podrobeny sekvenční frakcionaci, která pomohla k částečnému objasnění vlivu vodorozpustných složek, volných a vázaných lipidů na optické vlastnosti huminových kyselin. Výsledky naznačily, že fluorescenční píky tradičně přiřazované superpozici jednotlivých struktur jsou spíše důsledkem agregačních vlastností huminových molekul tvořících vlivem hydrofobního efektu zdánlivě vysoce aromatické struktury. Dále pak bylo zjištěno, že na optických vlastnostech huminových kyselin mají podíl i molekuly, které nemají primárně fluoroforní nebo chromoforní vlastnosti. Tento pohled je v souladu s teorií supramolekulárního uspořádání huminových kyselin. Dále byly studovány agregace, konformační chování a termodynamická stabilita huminových kyselin pomocí metody vysoce rozlišovací ultrazvukové spektroskopie. Bylo prokázáno, že huminové kyseliny mají schopnost agregovat už od velmi nízkých koncentrací (

Avec l’arrivée des dernières générations de téléphones chiffrés (BlackBerry PGP, iPhone), l’extraction des données par les experts est une tâche de plus en plus complexe et devient un véritable défi notamment après une catastrophe aérienne ou une attaque terroriste. Dans cette thèse, nous avons développé des attaques physiques sur systèmes cryptographiques à des fins d’expertises judiciaires. Une nouvelle technique de re-brasage à basse température des composants électroniques endommagés, utilisant un mélange eutectique 42Sn/58Bi, a été développée. Nous avons exploité les propriétés physico-chimiques de colles polymères et les avons utilisées dans l’extraction de données chiffrées. Une nouvelle technique a été développée pour faciliter l’injection et la modification à haute-fréquence des données. Le prototype permet des analyses en temps réel des échanges processeur-mémoire en attaque par le milieu. Ces deux techniques sont maintenant utilisées dans des dispositifs d’attaques plus complexes de systèmes cryptographiques. Nos travaux nous ont mené à sensibiliser les colles polymères aux attaques laser par pigmentation. Ce processus permet des réparations complexes avec une précision laser de l’ordre de 15 micromètres. Cette technique est utilisable en réparations judiciaires avancées des crypto-processeurs et des mémoires. Ainsi, les techniques développées, mises bout à bout et couplées avec des dispositifs physiques (tomographie 3D aux rayons X, MEB, laser, acide fumant) ont permis de réussir des transplantations judiciaires de systèmes chiffrés en conditions dégradées et appliquées pour la première fois avec succès sur les téléphones BlackBerry chiffrés à l’aide de PGP. / When considering the latest generation of encrypted mobile devices (BlackBerry’s PGP, Apple’s iPhone), data extraction by experts is an increasingly complex task. Forensic analyses even become a real challenge following an air crash or a terrorist attack. In this thesis, we have developed physical attacks on encrypted systems for the purpose of forensic analysis. A new low-temperature re-soldering technique of damaged electronic components, using a 42Sn/58Bi eutectic mixture, has been developed. Then we have exploited the physico-chemical properties of polymer adhesives and have used them for the extraction of encrypted data. A new technique has been developed to facilitate injection and high-frequency data modification. By a man-in-the-middle attack, the prototype allows analysing, in real-time, the data exchanges between the processor and the memory. Both techniques are now used in more complex attacks of cryptographic systems. Our research has led us to successfully sensitise polymer adhesives to laser attacks by pigmentation. This process allowed complex repairs with a laser with 15 micrometres precision and has been used in advanced forensic repair of crypto-processors and memory chips. Finally, the techniques developed in this thesis, put end-to-end and coupled with physical devices (X-ray 3D tomography, laser, SEM, fuming acids), have made it possible to have successful forensic transplants of encrypted systems in degraded conditions. We have successfully applied them, for the first time, on PGP-encrypted BlackBerry mobile phone.

Tesis por compendio / [ES] Esta tesis doctoral pretende aportar conocimientos fundamentales y prácticos sobre la valorización de las algas pardas. Se ha tratado de comprender la relación entre la estructura y funcionalidad de sus polisacáridos y proteínas, considerando sus propiedades funcionales, tecnológicas y bioactivas. Todo ello se ha abordado desde una perspectiva de biorrefinería, enfocada a la economía circular y la sostenibilidad. En primer lugar, se ha llevado a cabo una optimización para la extracción de compuestos valiosos a partir de algas pardas utilizando diversas tecnologías innovadoras. Se investigó un pretratamiento a alta presión de algas pardas (A. nodosum y S. latissima) para extraer alginato y se comparó con el método de extracción convencional. El objetivo era comprender cómo las diferencias iniciales en la composición y estructura de la pared celular de las algas afectaban a la extracción de este polisacárido y a sus propiedades tecnológicas, así como, su capacidad como emulsionante y gelificante. Asimismo, se examinó la extracción de conjugados proteína-polisacárido mediante la aplicación secuencial de varios métodos de extracción, así como sus propiedades funcionales (capacidad de retención de agua y aceite, emulsionante) y bioactivas (actividad antioxidante y capacidad antihipertensiva). En estos estudios se observaron diferencias en la arquitectura de la pared celular de las algas, pertenecientes a distintos órdenes, como Fucales y Laminariales, que influyeron directamente en los compuestos extraídos y en sus propiedades estructurales y tecnológicas. Sin embargo, a pesar de estas diferencias, los resultados mostraron el potencial de los compuestos extraídos como ingredientes en la industria alimentaria y farmacéutica. La segunda sección de esta tesis exploró la valorización de los subproductos generados durante la extracción del alginato. Se realizó un estudio exhaustivo de todas las fracciones y subproductos producidos en este proceso con el objetivo de identificar las fracciones más prometedoras para su valorización. Los resultados mostraron que los residuos sólidos tenían el potencial más significativo debido a su composición fisicoquímica. Por lo tanto, se sugirieron posibles estrategias para valorizar estos residuos, destacando su alto potencial como ingredientes bioactivos, texturizantes o de valor añadido nutricional para aplicaciones alimentarias, de piensos, cosméticos y farmacéuticos. Además, a partir de este trabajo, se investigó la extracción secuencial y combinada por diferentes métodos para recuperar la mayor cantidad posible de proteína intracelular de estos residuos sólidos. Se comprobó que la fracción proteica de los extractos contenía un alto porcentaje de aminoácidos esenciales, adecuadas propiedades funcionales y una interesante actividad antihipertensiva. Finalmente, la tercera parte de esta tesis se centró en la generación de conocimiento a través de la elucidación estructural del alginato. Para ello, se desarrolló un método rápido para determinar la relación M/G del alginato, que mostró valores cercanos al método de referencia (1H NMR), demostrando su precisión. En conjunto, esta tesis doctoral representa un avance significativo en la generación de conocimiento y valorización de la biomasa algal y sus residuos en compuestos de alto valor. Además, estos enfoques son potencialmente aplicables a otras biomasas algales. / [CA] Esta tesi doctoral pretén aportar coneixements fonamentals i pràctics sobre la valorització de les algues marrons. S'ha tractat de comprendre la relació entre l'estructura i funcionalitat dels seus polisacàrids i proteïnes, considerant les seues propietats funcionals, tecnològiques i bioactivas. Tot això s'ha abordat des d'una perspectiva de biorrefinería, enfocada a l'economia circular i la sostenibilitat. En primer lloc, s'ha dut a terme una optimització per a l'extracció de compostos valuosos a partir d'algues marrons utilitzant diverses tecnologies innovadores. Es va investigar un pretractament a alta pressió d'algues marrons (A. nodosum i S. latissima) per a extraure alginat i es va comparar amb el mètode d'extracció convencional. L'objectiu era comprendre com les diferències inicials en la composició i estructura de la paret cel·lular de les algues afectaven l'extracció d'este polisacàrid i a les seues propietats tecnològiques, així com, la seua capacitat com a emulsionant i gelificant. Així mateix, es va examinar l'extracció de conjugats proteïna-polisacàrid mitjançant l'aplicació seqüencial de diversos mètodes d'extracció, així com les seues propietats funcionals (capacitat de retenció d'aigua i oli, emulsionant) i bioactivas (activitat antioxidant i capacitat antihipertensiva). En estos estudis es van observar diferències en l'arquitectura de la paret cel·lular de les algues, pertanyents a diferents ordes, com Fucales i Laminariales, que van influir directament en els compostos extrets i en les seues propietats estructurals i tecnològiques. No obstant això, malgrat estes diferències, els resultats van mostrar el potencial dels compostos extrets com a ingredients en la indústria alimentària i farmacèutica. La segona secció d'esta tesi va explorar la valorització dels subproductes generats durant l'extracció de l'alginat. Es va realitzar un estudi exhaustiu de totes les fraccions i subproductes produïts en este procés amb l'objectiu d'identificar les fraccions més prometedores per a la seua valorització. Els resultats van mostrar que els residus sòlids tenien el potencial més significatiu a causa de la seua composició fisicoquímica. Per tant, es van suggerir possibles estratègies per a valorar estos residus, destacant el seu alt potencial com a ingredients *bioactivos, texturitzants o de valor afegit nutricional per a aplicacions alimentàries, de pinsos, cosmètics i farmacèutics. A més, a partir d'este treball, es va investigar l'extracció seqüencial i combinada per diferents mètodes per a recuperar la major quantitat possible de proteïna intracel·lular d'estos residus sòlids. Es va comprovar que la fracció proteica dels extractes contenia un alt percentatge d'aminoàcids essencials, adequades propietats funcionals i una interessant activitat antihipertensiva. Finalment, la tercera part d'esta tesi es va centrar en la generació de coneixement a través de l'elucidació estructural de l'alginat. Per a això, es va desenvolupar un mètode ràpid per a determinar la relació M/G de l'alginat, que va mostrar valors pròxims al mètode de referència (1H NMR), demostrant la seua precisió. En conjunt, esta tesi doctoral representa un avanç significatiu en la generació de coneixement i valorització de la biomassa algal i els seus residus en compostos d'alt valor. A més, estos enfocaments són potencialment aplicables a altres biomasses algals. / [EN] This doctoral thesis aims to provide fundamental and practical knowledge on the valorization of brown seaweeds. It has sought to understand the relationship between the structure and functionality of their polysaccharides and proteins, considering their functional, technological and bioactive properties. All this has been approached from a biorefinery perspective, focused on circular economy and sustainability. First, an optimization for extracting valuable compounds from brown seaweeds was carried out using various innovative technologies. A high-pressure pre-treatment of brown seaweeds (Ascophyllum nodosum and Saccharina latissima) to extract alginate was investigated and compared with the conventional extraction method. The purpose was to understand how initial differences in algal cell wall composition and structure affected the extraction of this polysaccharide and its technological properties, such as its ability as emulsifier and gelling agent. Likewise, the extraction of protein-polysaccharide conjugates was examined by sequential application of several extraction methods, as well as their functional properties (water, oil retention activity and emulsifying capacity) and bioactive properties (antioxidant activity and antihypertensive capacity). In these studies, differences were observed in the cell wall architecture of the algae, belonging to different orders, such as Fucales and Laminariales, which directly influenced the extracted compounds and their structural and technological properties. However, despite these differences, the results showed the potential of the extracted compounds as ingredients in the food and pharmaceutical industries. The second section of this thesis explored the valorization of by-products generated during alginate extraction. An exhaustive study of all the fractions and by-products produced in this process was carried out to identify the most promising fractions for valorization. The results showed that solid wastes had the most significant potential due to their physicochemical composition. Therefore, possible strategies to valorize these wastes were suggested, highlighting their high potential as bioactive, texturizing, or nutritional value-added ingredients for food, feed, cosmetic, and pharmaceutical applications. Besides, from this work, sequential and combined extraction by different methods was investigated to recover as much intracellular protein as possible from these solid wastes. It was found that the protein fraction of the extracts contained a high percentage of essential amino acids, adequate functional properties, and an interesting antihypertensive activity. Finally, the third part of this thesis focused on generating knowledge through the structural elucidation of alginate. For this purpose, a rapid method was developed to determine the M/G ratio of alginate, which showed values close to the reference method (1H NMR), demonstrating its accuracy. Overall, this PhD thesis represents a significant advance in generating knowledge and valorizing algal biomass and its residues into high-value compounds. Furthermore, these approaches are potentially applicable to other algal biomasses. / The authors wish to acknowledge funds from the grants PID2022- 138328OB-C21 and CEX2021-001189-S funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” and the project CIRCALGAE (Horizon Europe) under grant agreement 101060607. H. Bojorges acknowledges financial support from the Generalitat Valenciana for the award of a Santiago Grisolía grant (GRISOLIAP/2019/007). The authors acknowledge funds from the project PID2020-117744RJ-I00 and the project CIRCALGAE (Horizon Europe) under grant agreement 101060607. Additionally, the Accreditation as Center of Excellence Severo Ochoa CEX2021-001189-S funded by MCIN/AEI / 10.13039/501100011033 is also fully acknowledged. H. Bojorges expresses gratitude for the financial assistance provided by the Generalitat Valenciana in the form of a Santiago Grisolía grant (GRISOLIAP/2019/007) / Bojorges Gutiérrez, H. (2024). Biorefinery of the relevant brown algae Saccharina latissima and Ascophylum nodosum towards novel, sustainable and functional ingredients [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/211317 / Compendio

The acidification has been a known problem in Sweden for several decades. Sulphurous compounds, spread from the British Isles and the European continent led to a decrease in the pH-value of the rain that fell over Sweden. Since the acidification was discovered in the 1960s, active measures against the sulphurous deposition have been undertaken. The sulphurous deposition has decreased by 90 %, and the problem was for some time considered under control, until recently when a new era of the acidification may have started. Due to the increased demand of renewable energy, and Sweden’s potential to use biomass instead of fossil fuels, whole tree harvesting has been more utilized. Studies indicate that the forest soils are depleted in base cations in a faster rate when whole tree harvesting is performed compared to regular stem harvesting. Mass balance calculations and simulations indicate that an increased bio uptake of base cations due to whole tree harvesting leads to an increased biological acidification. However, although many studies agree that the impact of the whole tree harvest on the base cation supply of the soils is significant, long running Swedish experiments indicate that the difference between whole tree harvesting and regular stem harvesting diminishes over time. After a 40 year period, the difference in base cation supply between whole tree harvested soils and stem harvested soils are small. The reason for this could be different processes that reallocate base cations from different pools, which are not usually studied. The aim has been to investigate and evaluate different chemical extraction methods (Aqua Regia, HCl, EDTA, BaCl2, NH4OAc and water) capability to extract the base cations calcium, potassium, magnesium and sodium from four different Swedish forest soils and what this means for our understanding of how much base cations a soil contains. The extractions indicated that there is a statistical significant difference between the methods ability to extract base cations. Generally Aqua Regia was the most potent method, followed by HCl, EDTA, BaCl2, NH4OAc and water in decreasing order of effectiveness to extract the base cations. Linear correlations were found between EDTA, BaCl2 and NH4OAc. The internationally widely used method NH4OAc was considered to be at risk of underestimating the amount of base cations in the soil. / Försurningsproblematiken har länge varit ett känt problem i Sverige. Svavelhaltiga föroreningar som spreds från de brittiska öarna och den europeiska kontinenten ledde till att pH-värdet i regnet som föll över Sverige sjönk. Sedan upptäckten på 60-talet har aktiva åtgärder vidtagits mot utsläppen vilket har lett till en minskning av de försurande föroreningarna med 90 %. På grund av den stora utsläppsreduktionen som skett ansågs försurningsproblematiken vara under kontroll, tills nyligen då en ny etapp av för- surningen kan ha påbörjats. På grund av den ökande efterfrågan av förnyelsebar energi, i kombination med Sveriges stora skogstillgångar, har helträdsskörd av träd blivit alltmer nyttjad. Studier visar att markens baskatjonförråd utarmas i större utsträckning av helträdsskörd, då även grenar, rötter och toppar tas om hand jämfört med vanlig stamskörd då endast stammen tas med från skogen. Massbalanssimuleringar antyder att ett ökat bioupptag av baskatjoner på grund av helträdsskörd leder till en ökad biologisk försurning. Trots att många studier är överens om helträdsskördens inverkan på markens innehåll av baskatjoner visar lång- liggande försök i Sverige att skillnaderna mellan uttag av hela träd och stamved minskar med tiden. Efter en period på 40 år återstår endast små skillnader mellan avverknings- metoderna. Orsakerna till varför mätningarna och massbalansberäkningarna och simuleringarna inte stämmer överens kan vara många, t.ex. att det finns processer som kan omfördela baskatjoner från de som vanligtvis studeras. Syftet har varit att undersöka och utvärdera olika kemiska extraktionsmetoders (Aqua Regia, HCl, EDTA, BaCl2, NH4OAc och vatten) förmåga att extrahera baskatjonerna kalcium, kalium, magnesium och natrium från fyra olika skogsjordar i Sverige och vad resultaten betyder för vår uppfattning av mängden baskatjoner i marken. Extraktionerna visade att en statistiskt signifikant skillnad fanns mellan metodernas förmåga att extrahera de olika baskatjonerna. Generellt var Aqua Regia den metod som extraherade den största mängden baskatjoner, HCl, EDTA, BaCl2, NH4OAc och vatten följde i fallande ordning efter förmåga att extrahera baskatjonerna. Linjära korrelationer mellan EDTA, BaCl2 och NH4OAc upptäcktes. Den internationellt ofta använda metodiken för att extrahera baskatjoner, NH4OAc, ansågs riskera att underskatta mängden baskatjoner i marken.