Material Synthesis and Characterization on Low-Dimensional Cobaltates

In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO 4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO 4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (:&thetas;: ∼ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn't vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab -plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.

Avaliação de compatibilidade entre pasta de cimento e fluido de perfuração não-aquoso utilizados em poços petrolíferos

Compatibility testing between a drilling fluid and a cement slurry is one of the steps before an operation of cementing oil wells. This test allows us to evaluate the main effects that contamination of these two fluids may cause the technological properties of a cement paste. The interactions between cement paste and drilling fluid, because its different chemical compositions, may affect the cement hydration reactions, damaging the cementing operation. Thus, we carried out the study of the compatibility of non-aqueous drilling fluid and a cement slurry additives. The preparation procedures of the non-aqueous drilling fluid, the cement paste and completion of compatibility testing were performed as set out by the oil industry standards. In the compatibility test is evaluated rheological properties, thickening time, stability and compressive strength of cement pastes. We also conducted analyzes of scanning electron microscopy and X-ray diffraction of the mixture obtained by the compatibility test to determine the microstructural changes in cement pastes. The compatibility test showed no visual changes in the properties of the cement paste, as phase separation. However, after the addition of nonaqueous drilling fluid to cement slurry there was an increased amount of plastic viscosity, the yield point and gel strength. Among the major causative factors can include: chemical reaction of the components present in the non-aqueous drilling fluid as the primary emulsifier, wetting agent and paraffin oil, with the chemical constituents of the cement. There was a reduction in the compressive strength of the cement paste after mixing with this drilling fluid. Thickening test showed that the oil wetting agent and high salinity of the non-aqueous fluid have accelerating action of the handle of the cement paste time. The stability of the cement paste is impaired to the extent that there is increased contamination of the cement slurry with the nonaqueous fluid. The X-ray diffraction identified the formation of portlandite and calcium silicate in contaminated samples. The scanning electron microscopy confirmed the development of the identified structures in the X-ray diffraction and also found the presence of wells in the cured cement paste. The latter, formed by the emulsion stability of the drilling fluid in the cement paste, corroborate the reduction of mechanical strength. The oil wetting agent component of the non-aqueous drilling fluid, the modified cement hydration processes, mainly affecting the setting time.

A compreensão de reação química como um sistema complexo a partir da discussão dos erros e dificuldades de aprendizagem de estudantes do ensino médio

The study of chemical reactions is among the most important contents to the understanding of Chemistry discipline in basic education. However, there are still few studies about chemical reactions as a complex system because, generally, this content is presented in textbooks, taught and even researched in a fragmented form. The thesis here presented aims to investigate, identify and characterize the mistakes and learning difficulties of the students about chemical reactions as a complex system, using for that purpose the analysis of the answers of 126 exams of candidates for the bachelor’s degree in Chemistry Teaching on the entrance exam for the Federal University of Rio Grande do Norte (UFRN). The mistakes and learning difficulties about the parameters ΔG°, Kp, Ea and of the calculation of the amount of substance in a chemical reaction have been identified, as well as the levels of development of the ability to interpret the chemical reaction as a system. The main theoretical source of this study is structured based on the mistakes and learning difficulties (NÚÑEZ, RAMALHO, 2012), of the chemical reactions as complex systems (NÚÑEZ, 1994; RESHETOVA, 1988; SANDERSON, 1968). As methodology, it was prioritized the analysis of the answers to the exams and the interview with the teachers. The results showed typical mistakes in the study of this subject, especially low levels and skill development. No student was able to integrate the different aspects in the systemic understanding of the chemical reaction. From the interviews with Chemistry teachers from High School, it was determined the reasons the teachers assign to those mistakes and learning difficulties. The interviews revealed that the teachers do not work in the perspective of integration of the contents which leads the students to present difficulties and make mistakes related to the content previously mentioned. The study presents a proposal for the organization of the contents of Chemistry discipline for High School as a possibility of a dialectic systemic integration of contents, understanding that this systematic vision, leads to important contributions to the development of the theoretical thinking of the students. We can mention as one of the conclusions of this study, the fact that the non-systemic organization of contents do not favor this kind of thinking in students.

Necessary conditions for the emergence of homochirality via autocatalytic self-replication

We analyze a recent proposal for spontaneous mirror symmetry breaking based on the coupling of first-order enantioselective autocatalysis and direct production of the enantiomers that invokes a critical role for intrinsic reaction noise. For isolated systems, the racemic state is the unique stable outcome for both stochastic and deterministic dynamics when the system is in compliance with the constraints dictated by the thermodynamics of chemical reaction processes. In open systems, the racemic outcome also results for both stochastic and deterministic dynamics when driving the auto-catalysis unidirectionally by external reagents. Nonracemic states can result in the latter only if the reverse reactions are strictly zero: these are kinetically controlled outcomes for small populations and volumes, and can be simulated by stochastic dynamics. However, the stability of the thermodynamic limit proves that the racemic outcome is the unique stable state for strictly irreversible externally driven autocatalysis. These findings contradict the suggestion that the inhibition requirement of the Frank autocatalytic model for the emergence of homochirality may be relaxed in a noise-induced mechanism.

Spic'ing into Existence: Epitaph, Epithet, and the Ethnopoetic Imagination

Quién Es, Quién Somos? Spic’ing into Existence claims a four-fold close-reading: first, analysis of texts: from theoretical meditations to (prison) memoir and film. Second, a half dozen central figures appear, largely Latinx and black American. They cut across a score of registers, socio-economics, ideological reservations, but all are, as Carl Carlton sang, poetry in motion. Writers, poets, theologians, pathologists, artists, comedians, actors, students whose vocation is invocation, the inner surge of their calling. Third, the manuscript draws from a series of historical moments—from radical liberation of the late 60s, to contemporary student activism. Finally, this body of work is movement, in all its social, gestural, and kinesthetic viscera. From this last heading, we peel away layers of what I call the ethnopoet, the fascia undoing that reveals its bio-political anatomy, dressing its bare life with kinship speech. First, the social revolutions of the Civil Rights, Black Power, abolitionism, the Black Panthers and Young Lords, boycotts and jarring artistic performances. These events are superficial not in vain sense, but key epicenters of underground murmurings, the workings of a cunning assailant. She robs not lavish estates, but another day to breathe. Gesturally, as perhaps the interlocutor, lies this author, interspersing his own diatribes to conjure her presence. The final branch is admittedly the most intangible. Kinesthetically, we map the nimbleness, footwork lígera of what I call the ethnopoet. Ethnopoet is no mere aggregate of ethnicity and poetry, but like chemical reaction, the descriptor for its behavior under certain pressures, temperatures, and elements. Elusive and resisting confinement, and therefore definition, the ethnopoet is a shapeshifting figure of how racialized bodies [people of color] respond to hegemonic powers. She is, at bottom, however, a native translator, the plural-lensed subject whose loyalty is only to the imagination of a different world, one whose survival is not contingent upon her exploitation. The native translator’s constant re-calibrations of oppressive power apparatuses seem taxing at best, and near-impossible, at worst. To effectively navigate through these polarized loci, she must identify ideologies that in turn seek “affective liberatory sances” in relation to the dominant social order (43). In a kind of performative contradiction, she must marshall the knowledge necessary to “break with ideology” while speaking within it. Chicana Studies scholar, Chela Sandoval, describes this dual movement as “meta-ideologizing”: the appropriation of hegemonic ideological forms in order to transform them (82). Nuestros padres se subieron encima de La Bestia, y por eso somos pasageros a ese tren. Y ya, dentro su pansa, tenemos que ser vigilantes cuando plantamos las bombas. In Methodology of the Oppressed, Sandoval schematizes this oppositional consciousness around five principle categories: “equal rights,” “revolutionary,” “supremacist,” “separatist,” and “differential.” Taken by themselves, the first four modes appear mutually exclusive, incapable of occupying the same plane, until a fifth pillar emerges. Cinematographic in nature, differential consciousness, as Sandoval defines it, is “a kinetic motion that maneuvers, poetically transfigures, and orchestrates while demanding alienation, perversion, and reformation in both spectators and practitioners” (44). For Sandoval, then, differential consciousness is a methodology that privileges an incredible sense mobility, one reaching artistic sensibilities. Our fourth and final analytic of movement serves an apt example of this dual meaning. Lexically speaking, ‘movement’ may be regarded as a political mobilization of aggrieved populations (through sustained efforts), or the process of moving objects (people or otherwise) from one location to another. Praxis-wise, it is both action and ideal, content and form. Thus, an ethnic poetics must be regarded less as a series of stanzas, shortened lyric, or even arrangement of language, but as a lens through which peripheralized peoples kaleidecope ideological positions in an “original, eccentric, and queer sight” (43). Taking note of the advantages of postponing identifications, the thesis stands its ground on the term ethnopoet. Its abstraction is not dewey-eyed philosophy, but an anticipation of poetic justice, of what’s to come from callused hands. This thesis is divided into 7.5 chapters. The first maps out the ethnopoet’s cartographies of struggle. By revisiting that alleged Tío Tomas, Richard Rodriguez, we unearth the tensions that negatively, deny citizenship to one silo, but on the flipside, engender manifold ways of seeing, hearing, and moving . The second, through George Jackson’s prison memoirs, pans out from this ethnography of power, groping for an apparatus that feigns an impervious prestige: ‘the aesthetic regime of coercion.’ In half-way cut, the thesis sidesteps to spic into existence, formally announcing, through Aime Cesaire, myself, and Pedro Pietri, the poeticization of trauma. Such uplift denies New Age transcendence of self, but a rehearsal of our entrapment in these mortal envelopes. Thirdly, conscious of the bleeding ethnic body, we cut open the incipient corpse to observe her pathologist. Her native autopsies offer the ethnic body’s posthumous recognition, the ethnopoetics ability to speak for and through the dead. Chapter five examines prolific black artists—Beyonce and Kendrick Lamar—to elide the circumvention of their consumption via invoking radical black hi/her-stories, ones fragmenting the black body. Sixth, the paper compares the Black Power Salute of the 1968 Mexico City Olympics to Duke’s Mi Gente Boycott of their Latino Student Recruitment Weekend. Both wielded “silent gestures,” that shrewdly interfered with white noise of numbed negligence. Finally, ‘taking the mask off’ that are her functionalities, the CODA expounds on ethnopoet’s interiority, particularly after the rapid re-calibration of her politics. Through a rerun of El Chavo del Ocho, one of Mexican television’s most cherished shows, we tune into the heart-breaking indigence of barrio residents, only to marvel at the power of humor to, as Friday’s John Witherspoon put it, “fight another day.” This thesis is the tip of my tongue. Y por una vez, déjala que cante.

A Molecular-scale Programmable Stochastic Process Based On Resonance Energy Transfer Networks: Modeling And Applications

While molecular and cellular processes are often modeled as stochastic processes, such as Brownian motion, chemical reaction networks and gene regulatory networks, there are few attempts to program a molecular-scale process to physically implement stochastic processes. DNA has been used as a substrate for programming molecular interactions, but its applications are restricted to deterministic functions and unfavorable properties such as slow processing, thermal annealing, aqueous solvents and difficult readout limit them to proof-of-concept purposes. To date, whether there exists a molecular process that can be programmed to implement stochastic processes for practical applications remains unknown.

In this dissertation, a fully specified Resonance Energy Transfer (RET) network between chromophores is accurately fabricated via DNA self-assembly, and the exciton dynamics in the RET network physically implement a stochastic process, specifically a continuous-time Markov chain (CTMC), which has a direct mapping to the physical geometry of the chromophore network. Excited by a light source, a RET network generates random samples in the temporal domain in the form of fluorescence photons which can be detected by a photon detector. The intrinsic sampling distribution of a RET network is derived as a phase-type distribution configured by its CTMC model. The conclusion is that the exciton dynamics in a RET network implement a general and important class of stochastic processes that can be directly and accurately programmed and used for practical applications of photonics and optoelectronics. Different approaches to using RET networks exist with vast potential applications. As an entropy source that can directly generate samples from virtually arbitrary distributions, RET networks can benefit applications that rely on generating random samples such as 1) fluorescent taggants and 2) stochastic computing.

By using RET networks between chromophores to implement fluorescent taggants with temporally coded signatures, the taggant design is not constrained by resolvable dyes and has a significantly larger coding capacity than spectrally or lifetime coded fluorescent taggants. Meanwhile, the taggant detection process becomes highly efficient, and the Maximum Likelihood Estimation (MLE) based taggant identification guarantees high accuracy even with only a few hundred detected photons.

Meanwhile, RET-based sampling units (RSU) can be constructed to accelerate probabilistic algorithms for wide applications in machine learning and data analytics. Because probabilistic algorithms often rely on iteratively sampling from parameterized distributions, they can be inefficient in practice on the deterministic hardware traditional computers use, especially for high-dimensional and complex problems. As an efficient universal sampling unit, the proposed RSU can be integrated into a processor / GPU as specialized functional units or organized as a discrete accelerator to bring substantial speedups and power savings.

Développement et caractérisation de nouveaux nanocomposites polymères électriquement conductueurs pour plaques bipolaires de piles à combustible à membrane échangeuse de protons, PEMFC

Face à la diminution des ressources énergétiques et à l’augmentation de la pollution des énergies fossiles, de très nombreuses recherches sont actuellement menées pour produire de l’énergie propre et durable et pour réduire l’utilisation des sources d’énergies fossiles caractérisées par leur production intrinsèque des gaz à effet de serre. La pile à combustible à membrane échangeuse de protons (PEMFC) est une technologie qui prend de plus en plus d’ampleur pour produire l’énergie qui s’inscrit dans un contexte de développement durable. La PEMFC est un dispositif électrochimique qui fonctionne selon le principe inverse de l’électrolyse de l’eau. Elle convertit l’énergie de la réaction chimique entre l’hydrogène et l’oxygène (ou l’air) en puissance électrique, chaleur et eau; son seul rejet dans l’atmosphère est de la vapeur d’eau. Une pile de type PEMFC est constituée d’un empilement Électrode-Membrane-Électrode (EME) où la membrane consiste en un électrolyte polymère solide séparant les deux électrodes (l’anode et la cathode). Cet ensemble est intégré entre deux plaques bipolaires (BP) qui permettent de collecter le courant électrique et de distribuer les gaz grâce à des chemins de circulation gravés sur chacune de ses deux faces. La plupart des recherches focalisent sur la PEMFC afin d’améliorer ses performances électriques et sa durabilité et aussi de réduire son coût de production. Ces recherches portent sur le développement et la caractérisation des divers éléments de ce type de pile; y compris les éléments les plus coûteux et les plus massifs, tels que les plaques bipolaires. La conception de ces plaques doit tenir compte de plusieurs paramètres : elles doivent posséder une bonne perméabilité aux gaz et doivent combiner les propriétés de résistance mécanique, de stabilité chimique et thermique ainsi qu’une conductivité électrique élevée. Elles doivent aussi permettre d’évacuer adéquatement la chaleur générée dans le cœur de la cellule. Les plaques bipolaires métalliques sont pénalisées par leur faible résistance à la corrosion et celles en graphite sont fragiles et leur coût de fabrication est élevé (dû aux phases d’usinage des canaux de cheminement des gaz). C’est pourquoi de nombreuses recherches sont orientées vers le développement d’un nouveau concept de plaques bipolaires. La voie la plus prometteuse est de remplacer les matériaux métalliques et le graphite par des composites à matrice polymère. Les plaques bipolaires composites apparaissent attrayantes en raison de leur facilité de mise en œuvre et leur faible coût de production mais nécessitent une amélioration de leurs propriétés électriques et mécaniques, d’où l’objectif principal de cette thèse dans laquelle on propose: i) un matériau nanocomposite développé par extrusion bi-vis qui est à base de polymères chargés d’additifs solides conducteurs, incluant des nanotubes de carbone. ii) fabriquer un prototype de plaque bipolaire à partir de ces matériaux en utilisant le procédé de compression à chaud avec un refroidissement contrôlé. Dans ce projet, deux polymères thermoplastiques ont été utilisés, le polyfluorure de vinylidène (PVDF) et le polyéthylène téréphtalate (PET). Les charges électriquement conductrices sélectionnées sont: le noir de carbone, le graphite et les nanotubes de carbones. La combinaison de ces charges conductrices a été aussi étudiée visant à obtenir des formulations optimisées. La conductivité électrique à travers l’épaisseur des échantillons développés ainsi que leurs propriétés mécaniques ont été soigneusement caractérisées. Les résultats ont montré que non seulement la combinaison entre les charges conductrices influence les propriétés électriques et mécaniques des prototypes développés, mais aussi la distribution de ces charges (qui de son côté dépend de leur nature, leur taille et leurs propriétés de surface), avait aidé à améliorer les propriétés visées. Il a été observé que le traitement de surface des nanotubes de carbone avait aidé à l’amélioration de la conductivité électrique et la résistance mécanique des prototypes. Le taux de cristallinité généré durant le procédé de moulage par compression des prototypes de plaques bipolaires ainsi que la cinétique de cristallisation jouent un rôle important pour l’optimisation des propriétés électriques et mécaniques visées.

Óleo de carpa (cyprinus carpio): obtenção, refino e produção de concentração de ácidos graxos poliinsaturados

O objetivo do presente trabalho foi analisar as características e os perfis lipídicos dos óleos brutos e refinados de rejeitos de carpa comum (Cyprinus carpio), obtidos através dos processos de ensilagem ácida e termomecânico de farinha de pescado. Também foram realizados o estudo da reação de alcoólise química do óleo de carpa e obtenção de concentrados de concentrados de ácidos graxos poliinsaturados (PUFAs), através da reação de complexação com uréia. O rendimento obtido em óleo bruto para ambos os processos foi em torno de 85% em relação ao óleo presente nas vísceras de carpa. Os óleos brutos obtidos através do processo de ensilagem e do processo termomecânico apresentaram diferenças significantivas (P < 0,05) para ácidos graxos livres, índice de peróxido, valor do ácido tiobarbitúrico e cor Lovibond. Entretanto, os óleos refinados obtidos por ambos os processos não apresentaram diferença significativa para a cor Lovibond, ácidos graxos livres e valores do ácido tiobarbitúrico. Os principais ácidos graxos identificados nos óleos bruto, branqueado e refinado de vísceras de carpa foram oléico, palmítico, palmitoléico, linoléico e linolênico constituindo aproximadamente 69,6% dos ácidos graxo totais do óleo refinado. A relação ω3/ω6 foi de aproximadamente 1,05 para o óleo refinado. Assim, o óleo refinado das vísceras de carpa pode ser considerado uma rica fonte de ácidos graxos essenciais do grupo ω3 e ω6. No estudo da reação de alcoólise química e obtenção dos concentrados de ácidos graxos poliinsaturados, foi realizada a comparação de três tratamentos para reação de alcoólise variando-se a concentração molar óleo:álcool (1:21, 1:27 e 1:39). Os tratamentos apresentaram diferenças significativas para as respostas rendimento em massa de ácidos graxos livres e índice de acidez. O maior rendimento para a reação de alcoólise foi utilizando a concentração molar de 1:39 (óleo:álcool). Na fração não complexada com uréia obteve-se aumento percentual de ácidos graxos insaturados e poliinsaturados de 31,9%, redução de saturados de 75%, e aumento do conteúdo dos ácidos graxos eicosapentaenóico e docosahexaenóico (EPA+DHA) de 85,3%. A fração não complexada com uréia pode ser considerada uma rica fonte de ácidos graxos poliinsaturados e insaturados com um total de 88,9% desses ácidos graxos.

Compreensão da reação de precipitação do iodeto de chumbo entre os níveis de análise macro e micro no ensino da química

O estudo apresentado teve como objetivos planificar e implementar e analisar uma proposta didática alternativa para a abordagem dos níveis macroscópico, simbólico e sub-microscópico, indispensáveis para a compreensão das reações químicas, salientando-se o facto de não se explorar, nos manuais e na prática, todo o potencial de uma reação química muito usual. A proposta utiliza uma diferente abordagem da tradicional reação de precipitação do iodeto de chumbo, centrada em questões-problema: “Ocorreu uma reação química?” e “Será possível dissolver o precipitado?”. A metodologia foi qualitativa e centrou-se na investigação-ação colaborativa. Perante as questões problema, os alunos fizeram previsões, sugeriram e realizaram procedimentos experimentais de carácter investigativo para as testar e fundamentaram as respostas através da comunicação oral e da elaboração de esquemas pictóricos (livremente), estes últimos, para ilustrar o nível sub-microscópico. Analisaram-se conjuntamente os esquemas e os dados da observação direta. Os resultados evidenciam que os alunos: identificam a ocorrência da reação química sensorialmente (visualização do aparecimento de uma substância colorida após a junção de duas soluções incolores - nível macroscópico), representam a reação química utilizando a simbologia química (nível simbólico) mas apresentam algumas dificuldades na interpretação sub-microscópica.

Conditions for observing IR chemiluminescence and the role of condensation in metal oxidation reactions

Infrared chemiluminescence (IRCL) studies of cw metal oxidation reactions wherein metal atoms entrained in a carrier gas were mixed with an oxidizer by means of a nozzle system are described. One goal of the work was to determine the vibrational distribution of the product molecule produced by the chemical reaction. In order to observe IRCL it was important to operate the system at the appropriate P-T point in the phase diagram of both the metal and metal salt, otherwise rapid condensation quenched any IRCL that was present. If the nucleation rate was greater 1010 3 than ~ cm-sec-I, then only "black body" radiation could be seen from the reaction. Most of the studies were on the Li/I2 system which is unique in that the phase diagrams of Li and LiI in the P-T ranges of interest are almost identical. This property permitted a relatively easy control with respect to condensation and the measurement of IRCL in the 10-28 um range for the excited LiI molecule.

In vitro studies of drug transformations: application to forensic toxicology

The forensic toxicologist faces challenges in the detection of drugs and poisons in biological samples due to transformations which occur both during life and after death. For example, changes can result from drug metabolism during life or from the use of formalin solution for post mortem embalming purposes. The former requires the identification of drug metabolites and the latter the identification of chemical reaction products in order to know which substances had been administered. The work described in this thesis was aimed at providing ways of tackling these challenges and was divided into two parts. Part 1 investigated the use of in vitro drug metabolism by human liver microsomes (HLM) to obtain information on drug metabolites and Part 2 investigated the chemical reactions of drugs and a carbamate pesticide with formalin solution and formalin-blood. The initial aim of part I was to develop an in vitro metabolism method using HLM, based on a literature review of previous studies of this type. MDMA was chosen as a model compound to develop the HLM method because its metabolism was known and standards of its metabolites were commercially available. In addition, a sensitive and selective method was developed for the identification and quantitation of hydrophilic phase I drug metabolites using LC/MS/MS with a conventional reverse-phase (C18) column. In order to obtain suitable retention factors for polar drug metabolites on this column, acetyl derivatives were evaluated for converting the metabolites to more lipophilic compounds and an optimal separation system was developed. Acetate derivatives were found to be stable in the HPLC mobile phase and to provide good chromatographic separation of the target analytes. In vitro metabolism of MDMA and, subsequently, of other drugs involved incubation of 4 µg drug substance in pH 7.4 buffer with an NADPH generating system (NGS) at 37oC for 90 min with addition of more NGS after 30 min. The reaction was stopped at 90 min by the addition of acetonitrile before extraction of the metabolites. Acetate derivatives of MDMA metabolites were identified by LC/MS/MS using multiple reaction monitoring (MRM). Three phase I metabolites (both major and minor metabolites) of MDMA were detected in HLM samples. 3,4-dihydroxy-methamphetamine and 4-hydroxy-3-methoxymethamphetamine were found to be major metabolites of MDMA whereas 3,4-methylenedioxyamphetamine was found to be a minor metabolite. Subsequently, ten MDMA positive urines were analysed to compare the metabolite patterns with those produced by HLM. An LC/MS method for MDMA and its metabolites in urine samples was developed and validated. The method demonstrated good linearity, accuracy and precision and insignificant matrix effects, with limits of quantitation of 0.025 µg/ml. Moreover, derivatives of MDMA and its metabolites were quantified in all 10 positive human urine samples. The urine metabolite pattern was found to be similar to that from HLM. The second aim of Part 1 was to use the HLM system to study the metabolism of some new psychoactive substances, whose misuse worldwide has necessitated the development of analytical methods for these drugs in biological specimens. Methylone and butylone were selected as representative cathinones and para-methoxyamphetamine (PMA) was chosen as a representative ring-substituted amphetamine, because of the involvement of these drugs in recent drug-related deaths, because of a relative lack of information on their metabolism, and because reference standards of their metabolites were not commercially available. An LC/MS/MS method for the analysis of methylone, butylone, PMA and their metabolites was developed. Three phase I metabolites of methylone and butylone were detected in HLM samples. Ketone reduction to β-OH metabolites and demethylenation to dihydroxy-metabolites were found to be major phase I metabolic pathways of butylone and methylone whereas N-demethylation to nor-methylone and nor-butylone were found to be minor pathways. Also, demethylation to para-hydroxyamphetamine was found to be a major phase I metabolic pathway of PMA whereas β-hydroxylation to β-OH-PMA was found to be a minor pathway. Formaldehyde is used for embalming, to reduce decomposition and preserve cadavers, especially in tropical countries such as Thailand. Drugs present in the body can be exposed to formaldehyde resulting in decreasing concentrations of the original compounds and production of new substances. The aim of part II of the study was to evaluate the in vitro reactions of formaldehyde with selected drug groups including amphetamines (amphetamine, methamphetamine and MDMA), benzodiazepines (alprazolam and diazepam), opiates (morphine, hydromorphone, codeine and hydrocodone) and with a carbamate insecticide (carbosulfan). The study would identify degradation products to serve as markers for the parent compounds when these were no longer detectable. Drugs standards were spiked in 10% formalin solution and 10% formalin blood. Water and whole blood without formalin were used for controls. Samples were analysed by LC/MS/MS at different times from the start, over periods of up to 30 days. Amphetamine, methamphetamine and MDMA were found to rapidly convert to methamphetamine, DMA and MDDMA respectively, in both formalin solution and formalin blood, confirming the Eschweiler-Clarke reaction between amine-containing compounds and formaldehyde. Alprazolam was found to be unstable whereas diazepam was found to be stable in both formalin solution and water. Both were found to hydrolyse in formalin solution and to give open-ring alprazolam and open-ring diazepam. Other alprazolam conversion products attached to paraformaldehyde were detected in both formalin solution and formalin blood. Morphine and codeine were found to be more stable than hydromorphone and hydrocodone in formalin solution. Conversion products of hydromorphone and hydrocodone attached to paraformaldehyde were tentatively identified in formalin solution. Moreover, hydrocodone and hydromorphone rapidly decreased within 24 h in formalin blood and could not be detected after 7 days. Carbosulfan was found to be unstable in formalin solution and was rapidly hydrolysed within 24 h, whereas in water it was stable up to 48 h. Carbofuran was the major degradation product, plus smaller amounts of other products, 3-ketocarbofuran and 3-hydrocarbofuran. By contrast, carbosulfan slowly hydrolysed in formalin-blood and was still detected after 15 days. It was concluded that HLM provide a useful tool for human drug metabolism studies when ethical considerations preclude their controlled administration to humans. The use of chemical derivatisation for hydrophilic compounds such as polar drug metabolites for analysis by LC/MS/MS with a conventional C18 column is effective and inexpensive, and suitable for routine use in the identification and quantitation of drugs and their metabolites. The detection of parent drugs and their metabolites or conversion and decomposition products is potentially very useful for the interpretation of cases in forensic toxicology, especially when the original compounds cannot be observed.

The structural and mechanical integrity of historic wood

Little is known about historic wood as it ages naturally. Instead, most studies focus on biological decay, as it is often assumed that wood remains otherwise stable with age. This PhD project was organised by Historic Scotland and the University of Glasgow to investigate the natural chemical and physical aging of wood. The natural aging of wood was a concern for Historic Scotland as traditional timber replacement is the standard form of repair used in wooden cultural heritage; replacing rotten timber with new timber of the same species. The project was set up to look at what differences could exist both chemically and physically between old and new wood, which could put unforeseen stress on the joint between them. Through Historic Scotland it was possible to work with genuine historic wood from two species, Oak and Scots pine, both from the 1500’s, rather than relying on artificial aging. Artificial aging of wood is still a debated topic, with consideration given to whether it is truly mimicking the aging process or just damaging the wood cells. The chemical stability of wood was investigated using Fourier-transform infrared (FTIR) microscopy, as well as wet chemistry methods including a test for soluble sugars from the possible breakdown of the wood polymers. The physical properties assessed included using a tensile testing machine to uncover possible differences in mechanical properties. An environmental chamber was used to test the reaction to moisture of wood of different ages, as moisture is the most damaging aspect of the environment to wooden cultural objects. The project uncovered several differences, both physical and chemical, between the modern and historic wood which could affect the success of traditional ‘like for like’ repairs. Both oak and pine lost acetyl groups, over historic time, from their hemicellulose polymers. This chemical reaction releases acetic acid, which had no effect on the historic oak but was associated with reduced stiffness in historic pine, probably due to degradation of the hemicellulose polymers by acid hydrolysis. The stiffness of historic oak and pine was also reduced by decay. Visible pest decay led to loss of wood density but there was evidence that fungal decay, extending beyond what was visible, degraded the S2 layer of the pine cell walls, reducing the stiffness of the wood by depleting the cellulose microfibrils most aligned with the grain. Fungal decay of polysaccharides in pine wood left behind sugars that attracted increased levels of moisture. The degradation of essential polymers in the wood structure due to age had different impacts on the two species of wood, and raised questions concerning both the mechanism of aging of wood and the ways in which traditional repairs are implemented, especially in Scots pine. These repairs need to be done with more care and precision, especially in choosing new timber to match the old. Within this project a quantitative method of measuring the microfibril angle (MFA) of wood using polarised Fourier transform infrared (FTIR) microscopy has been developed, allowing the MFA of both new and historic pine to be measured. This provides some of the information needed for a more specific match when selecting replacement timbers for historic buildings.

Estudo da viabilidade do sistema LZAS para uso como selante de PaCOS

Cells the solid oxide fuel are systems capable to directly convert energy of a chemical reaction into electric energy in clean, quiet way and if its components in the solid state differentiate of excessively the techniques for having all. Its more common geometric configurations are: the tubular one and to glide. Geometry to glide beyond the usual components (anode, cathode and electrolyte) needs interconnect and sealant. E the search for materials adjusted for these components is currently the biggest challenge found for the production of the cells. The sealants need to present chemical stability in high temperatures, to provoke electric isolation, to have coefficient of compatible thermal expansion with the excessively component ones. For presenting these characteristics the glass-ceramics materials are recommended for the application. In this work the study of the partial substitution of the ZrO2 for the Al2O3 in system LZS became it aiming at the formation of system LZAS, this with the addition of natural spodumene with 10, 20 and 30% in mass. The compositions had been casting to a temperature of 1500°C and later quickly cooled with the objective to continue amorphous. Each composition was worn out for attainment of a dust with average diameter of approximately 3μm and characterized by the techniques of DRX, FRX, MEV, dilatometric analysis and particle size analysis. Later the samples had been conformed and treated thermally with temperatures in the interval between 700-1000 °C, with platform of 10 minutes and 1 hour. The analyses for the treated samples had been: dilatometric analysis, DRX, FRX, electrical conductivity and tack. The results point with respect to the viability of the use of system LZAS for use as sealant a time that had presented good results as isolating electric, they had adhered to a material with similar α of the components of a SOFC and had presented steady crystalline phases

Degradación bacteriana de cianuro y compuestos nitrogenados tóxicos

La ruta de asimilación de cianuro en P. pseudoalcaligenes CECT5344 transcurre a través de un nitrilo formado por la reacción química del cianuro con el oxalacetato, siendo este último acumulado como consecuencia de la acción conjunta de una malato:quinona oxidoreductasa (MQO) y la oxidasa terminal resistente a cianuro (CioAB) (Luque-Almagro et al., 2011b). Los nitrilos pueden ser convertidos en amonio por la acción de una nitrilasa o un sistema nitrilo hidratasa/amidasa. Con el objetivo de elucidar la ruta de asimilación de cianuro en P. pseudoalcalígenes CECT5344, se ha analizado el proteoma de este microorganismo en condiciones cianotróficas frente a nitrato como fuente de nitrógeno como control. En este estudio se identificaron proteínas relacionadas con la ruta de asimilación de cianuro en la estirpe CECT5344, que aparecían inducidas por cianuro, como NitB y NitG, cuyos genes se encuentran localizados en la agrupación génica nit1C. Además de NitB y NitG, de función desconocida, la agrupación génica nit1C codifica un regulador transcripcional del tipo Fis dependiente de σ54 (NitA), una nitrilasa (NitC), una proteína que pertenece a la superfamilia S-adenosilmetionina (NitD), un miembro de la superfamilia N-aciltransferasa (NitE), un polipéptido de la familia AIRS/GARS (NitF) y una oxidorreductasa dependiente de NADH (NitH). Un análisis transcripcional mediante RT-PCR determinó que los genes nitBCDEFGH se cotranscriben, mientras que el gen regulador nitA se transcribe de forma divergente. Además, resultados obtenidos por RT-PCR confirman que la expresión de los genes nitBCDEFGH está inducida por cianuro y reprimida por amonio. La relación entre el cianuro y el grupo de genes nit1C queda patente por el fenotipo de los mutantes deficientes nitA, nitB y nitC, incapaces de usar complejos cianuro-metálicos o 2-hidroxinitrilos como única fuente de nitrógeno. Todos estos datos indican que la nitrilasa NitC, junto con la proteína NitB, utilizan de forma específica determinados nitrilos alifáticos como sustrato, entre los que se encuentran el formado durante la asimilación de cianuro (Estepa et al., 2012). Además, entre las proteínas inducidas por cianuro se identificaron una dihidropicolinato sintasa (DapA), una fosfoserina transaminasa (SerC) y una proteína de función desconocida (Orf1), las tres codificadas por genes del operón cio, una cianasa (CynS), la proteína S6 de la subunidad ribosomal 30S (RpsF), una superóxido dismutasa (SodB), la ferritina (Dps), una oxidorreductasa (Fpr) y un factor de elongación P (EF-P). Una vez identificadas, estas proteínas se han analizado funcionalmente y se han localizado en el genoma de P. pseudoalcaligenes CECT5344 los genes correspondientes, así como los genes adyacentes. La inducción de estas proteínas en condiciones cianotróficas sugiere que el metabolismo del cianuro incluye, además de la resistencia y asimilación de este tóxico, otros procesos biológicos relacionados con el metabolismo del cianato y de algunos aminoácidos, el estrés oxidativo y la homeostasis de hierro, entre otros. Por otra parte, el conocimiento en profundidad y la interpretación de la secuencia génica de P. pseudoalcaligenes CECT5344, así como el análisis comparativo frente a organismos no cianotrofos ha permitido entender algunos de los mecanismos implicados en la resistencia y asimilación de cianuro, lo que permitiría conducir a la posterior mejora del proceso de biodegradación de cianuro. Además, el estudio del genoma de la estirpe CECT5344 permitirá explorar la capacidad de este organismo para ser utilizado en procesos de biorremediación de residuos cianurados en los que se encuentran metales y otros tóxicos (Luque-Almagro et al., 2013; Wibberg et al., 2014). En este trabajo se muestran y discuten los resultados de la secuenciación del genoma de P. pseudoalcaligenes, así como el estudio del análisis filogenético y evolutivo de la cepa, estableciéndose de esta manera relaciones con otras especies en base a los genomas secuenciados de las mismas, entre las que destaca P. mendocina ymp relacionada con P. pseudoalcaligenes CECT5344. El estudio de las características del genoma de P. pseudoalcaligenes CECT5344 ha sido completado con un análisis comparativo frente a los genomas de otras especies de Pseudomonas, encontrándose así semejanzas y diferencias en cuanto a la distribución génica funcional. Por último, se muestra un análisis del genoma de P. pseudoalcaligenes CECT5344 en relación con los genes implicados probablemente en los procesos de asimilación de cianuro y residuos cianurados, tales como los codificantes de nitrilasas y aquellos implicados en la resistencia a cianuro como los constituyentes del operón cio que codifican la oxidasa terminal insensible a cianuro. Finalmente, se discute la presencia de genes implicados posiblemente en otros procesos con una alto potencial biotecnológico, tales como la producción de bioplásticos y la biodegradación de diversos contaminantes.