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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.
31

Nucleic acid assembly, polymerization, and ligand binding

Engelhart, Aaron Edward 08 February 2012 (has links)
In the past 30 years, the discovery of capabilities of nucleic acids far beyond their well-known information-bearing capacity has profoundly influenced our understanding of these polymers. The discovery by the Cech and Altman labs that nucleic acids could perform catalytic functions, coupled with the Gold and Szostak groups’ demonstration of the de novo evolution of nucleic acids that bind arbitrary ligands, has resulted in a proliferation of newfound roles for these molecules. Nucleic acids have found utility in both engineered systems, such as aptamer therapeutics, as well as in newly appreciated roles in extant organisms, such as riboswitches. As a result of these discoveries, many have pondered the potential importance of the dual (catalytic and informational) roles of nucleic acids in early evolution. A high-yielding synthetic route for the nonenzymatic polymerization of nucleic acids, based on the aqueous self-assembly of their components, would provide a powerful tool in nucleic acid chemistry, with potential utility in prebiotic and contemporary nucleic acid systems alike – however, such a route remains elusive. In this thesis, I describe several steps towards such a synthetic route. In these systems, a nucleic-acid binding ligand drives the assembly of short DNA and RNA duplexes, promoting the production of long nucleic acid polymers, while suppressing the production of short, cyclic species. Additionally, the use of a reversible covalent linkage allows for the production of long polymers, as well as the incorporation of previously cyclized products into these polymers. I also report several explorations of novel base pairings, nucleic acid-ligand interactions, and nucleic acid-ion interactions that have informed our studies of self-assembling nucleic acid systems.
32

Prebiotic synthesis of nucleic acids

Bean, Heather D. 01 April 2008 (has links)
The origin of the first RNA polymers is central to most current theories regarding the origin of life. However, difficulties associated with the prebiotic formation of RNA have lead many researchers to conclude that simpler polymers, or proto-RNAs, preceded RNA. These earlier polymers would have been replaced by RNA over the course of evolution. A remaining difficulty for this theory is that the de novo synthesis of a feasible proto-RNA has not yet been demonstrated by plausible prebiotic reactions. This thesis focuses on two problems associated with prebiotic proto-RNA synthesis: The formation of nucleosides and the necessity of reversible backbone linkages for error correction in nucleic acid polymers. "The Nucleoside Problem", or the lack of success in forming pyrimidine nucleosides by plausible prebiotic reactions, represents a significant stumbling block to the RNA world hypothesis. Nearly four decades ago Orgel and coworkers demonstrated that the purine nucleosides adenosine and inosine are synthesized by heating and drying their respective bases and ribose in the presence of magnesium, but these reaction conditions do not yield the pyrimidine nucleosides uridine or cytidine from their respective bases. In this thesis a potential solution to The Nucleoside Problem is hypothesized based upon a proposed chemical mechanism for nucleoside formation. This hypothesis is supported by the successful synthesis of 2-pyrimidinone nucleosides by a plausible prebiotic reaction in good yield, demonstrating that pyrimidine nucleosides could have been available in the prebiotic chemical inventory, but that uridine and cytidine were likely not abundant. Reversible backbone linkages are necessary to provide a mechanism for error correction in non-enzymatic template-directed syntheses of proto-RNAs. In this thesis, acetals are explored as low-energy, reversible linkage groups for nucleosides in polymers. The synthesis of glyoxylate-acetal nucleic acids (gaNAs) through simple heating-drying reactions from neutral aqueous solutions is demonstrated, and these linkages are shown to be hydrolytically stable under a considerable range of solution conditions. Computational models demonstrate that the glyoxylate linkage is an excellent electronic and isosteric replacement for phosphate. Molecular dynamics simulations also indicate that a gaNA duplex would have structural properties that closely match a phosphate-linked RNA helix, suggesting the possibility for cross-pairing between gaNAs and RNAs, allowing for sequence transfer and genetic continuity through the evolution from proto-RNAs to RNA. The principles illustrated in this thesis by 2-pyrimidinone nucleoside and gaNA synthesis can be extended to other prebiotic condensation reactions. Factors affecting condensation yield, such as thermodynamics, kinetics, reactant solubility, and salt effects, are summarized herein.
33

Developing complexity using networks of synthetic replicators

Kosikova, Tamara January 2017 (has links)
Molecular recognition plays an essential role in the self-assembly and self-organisation of biological and chemical systems alike—allowing individual components to form complex interconnected networks. Within these systems, the nature of the recognition and reactive processes determines their functional and structural properties, and even small changes in their identity or orientation can exert a dramatic effect on the observed properties. The rapidly developing field of systems chemistry aims to move away from the established paradigm in which molecules are studied in isolation, towards the study of networks of molecules that interact and react with each other. Taking inspiration from complex natural systems, where recognition processes never operate in isolation, systems chemistry aims to study chemical networks with the view to examining the system-level properties that arise from the interactions and reactions between the components within these systems. The work presented in this thesis aims to advance the nascent field of systems chemistry by bringing together small organic molecules that can react and interact together to form interconnected networks, exhibiting complex behaviour, such as self-replication, as a result. Three simple building blocks are used to construct a network of two structurally similar replicators and their kinetic behaviour is probed through a comprehensive kinetic analysis. The selectivity for one of the recognition-mediated reactive processes over another is examined within the network in isolation as well as in a scenario where the network is embedded within a pool of exchanging components. The interconnected, two-replicator network is examined under far-from-equilibrium reaction-diffusion conditions, showing that chemical replicating networks can exhibit signs of selective replication—a complex phenomenon normally associated with biological systems. Finally, a design of a well-characterised replicator is exploited for the construction of a network integrating self-replication with a another recognition-directed process, leading to the formation of a mechanically-interlocked architecture—a [2]rotaxane.
34

Vznik a ukončení nenarozeného života / Birth and termination of unborn life

LUŇÁKOVÁ, Jana January 2011 (has links)
The thesis deals with the problem of the origin of human life and abortion. It focuses on different approaches to the question as to when unborn human life becomes a person, and, consequently, when it should be guaranteed the right to life. The thesis is divided into four main chapters corresponding to four main aspects of the issue of abortion. The first chapter provides information from embryological (biological creation of man) and medical (abortion) perspective. The second chapter deals with the abortion legislation in the Czech Republic (history and current situation). The third chapter examines different ethical questions such as identity of the person, the right to decide about their own body, etc. The last chapter gives an account on person and abortion from the Christian point of view.
35

Um estudo sobre o ensino dos temas “Origem da Vida” e “Evolução Biológica” em dissertações e teses brasileiras (2006 a 2016) / A study on the teaching of “Origin of Life” and “Biological Evolution” in brazilian dissertations and theses.

Zabotti, Kamilla 19 February 2018 (has links)
Submitted by Rosangela Silva (rosangela.silva3@unioeste.br) on 2018-05-23T14:46:05Z No. of bitstreams: 2 Kamilla Zabotti.pdf: 2089112 bytes, checksum: ee20e95dae4d0db862aee5132206694c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-05-23T14:46:05Z (GMT). No. of bitstreams: 2 Kamilla Zabotti.pdf: 2089112 bytes, checksum: ee20e95dae4d0db862aee5132206694c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-02-19 / The integrated understanding of the natural phenomena and biological process occurs thought the evolutionary thought, thus the Biological Evolution is considered the integrating and unifying base of Biological Science. Though the teaching of how life originated and diversified are the object of researches already developed and published in the last decades, some difficulties still remain in teaching these subjects. Taking these considerations into account, the present research is characterized as State of Art and it aims to highlight what is being produced in academic researches, in the form of dissertations and theses, from 2006 to 2016, regarding the teaching of the themes Origin of Life and Biological Evolution. A total of 78 articles were found, being 65 (83%) dissertations and 16 (17%) theses. 86% of these are from Higher Education Institutions (HEIs) of public administrative nature, with emphasis on state and federal universities, and 13% of private HEIs. Around 80% of dissertations and thesis are concentrated in the South-Southeast region. Half of the papers are dissertations on teaching Biological Evolution, and only one thesis investigates the teaching of the Origin of Life. Around 70% of the academic productions identified are intended for research at the secondary level on basic education. The continuing formation of teachers contemplates only 4% of the productions. In relation to the most prevalent issues in the set of dissertations and theses, stand out: Characteristic of Teacher, with 25%, followed by Didactic Resources and Method-Contents with almost 16% each, and History and Philosophy of Science, with 14%. We found three issues that were not well investigated in the researches: Curriculum and Programs, Non-Formal Education and School Organization, which appears as a research field little explored and that requires an investigation on the teaching and learning process of the Origin and Evolution of Life. These results, as well as the researches focused on the analysis of academic production, can contribute to the deployment of more specific proposals of teaching formation and improvements in the teaching-learning of the Origin of Life and Biological Evolution. / A compreensão integrada dos fenômenos naturais e processos biológicos ocorre por meio do pensamento evolutivo, assim, a Evolução Biológica é considerada o eixo integrador e unificador das Ciências Biológicas. Embora o ensino de como a vida se originou e se diversificou sejam objetivos de pesquisas já desenvolvidas e publicadas nas últimas décadas, persistem algumas dificuldades no ensino desses temas. Levando em conta tais observações, a presente pesquisa é caracterizada como Estado da Arte e tem por objetivo evidenciar o que está sendo produzido nas pesquisas acadêmicas, na forma de dissertações e teses, no período de 2006 a 2016, quanto ao ensino dos temas Origem da Vida e Evolução Biológica. No total, foram encontrados 78 trabalhos, sendo 65 (83%) dissertações e 13 (17%) teses. 86% desses trabalhos são de instituições de ensino superior (IES) de natureza administrativa pública, com destaque para as universidades estaduais e federais, e 13% de IES de natureza privada. Em torno de 80% das dissertações e teses estão concentradas no eixo Sul-Sudeste. Metade dos trabalhos são dissertações, acerca do ensino da Evolução Biológica, e somente uma tese investiga exclusivamente o ensino da Origem da Vida. Em torno de 70% das produções encontradas são destinadas a investigações no ensino médio na educação básica. A formação continuada de professores contempla somente 4% das produções. Quanto às problemáticas que mais prevaleceram no conjunto de dissertações e teses, destacam-se: Características do Professor, com 25%, seguida de Recursos Didáticos e Conteúdo-Método, com quase 16% cada, e História e Filosofia da Ciência, com 14%. Identificamos três problemáticas pouco investigadas nas pesquisas: Currículos e Programas, Educação Não-Formal e Organização da Escola, configurando-se como um campo de pesquisa pouco explorado e que carece de investigações acerca dos processos de ensino e aprendizagem da Origem e Evolução da Vida. Os resultados desta pesquisa, bem como a realização de pesquisas dedicadas à análise do conjunto da produção acadêmica, podem contribuir para a implantação de propostas mais específicas na formação de professores e melhorias no ensino e na aprendizagem da Origem da Vida e Evolução Biológica.
36

Nucléotides à l'interface minéral-eau et réactivité des acides aminés en conditions hydrothermales dans le contexte des origines de la vie / Nucleotides at the mineral-water interface and reactivity of amino acids under hydrothermal conditions in the context of the origins of life

Pedreira-Segade, Ulysse 15 September 2017 (has links)
Les découvertes de traces de vie primitive, fossiles et biosignatures, suggèrent que celle-ci serait apparue il y 4,3 à 3,7 milliards d’années. Cette émergence est le résultat d’étapes menant des plus simples molécules organiques aux premières formes de vie unicellulaire.Ce travail de thèse examine l’hypothèse de l’apparition de la vie dans un environnement hydrothermal, dans lequel la pression, les gradients de température et de pH, la diversité des surfaces minérales et l’abondance d’énergie chimique auraient permis l’accumulation et la complexification de la matière organique. Il s’intéresse particulièrement aux étapes de concentration des nucléotides et de polymérisation des acides aminés, respectivement briques élémentaires du matériel génétique et des protéines, inhérentes au vivant.Cette thèse présente d’abord une étude des interactions de surfaces entre nucléotides en solution et minéraux en feuillets en conditions contrôlées de température, de pH et de salinité. Dans une deuxième partie, elle récapitule les résultats obtenus par l’observation in situ de l’effet des conditions hydrothermales et des surfaces minérales sur la polymérisation des acides aminés non activés.Ce travail suggère que les minéraux en feuillets, et plus particulièrement les argiles gonflantes, augmentent la concentration locale en nucléotide de trois ordres de grandeurs au moins en présentant un comportement très dépendant des conditions physicochimiques du milieu. De plus, il reconfirme l’importance de la température dans la polymérisation des acides aminés en solution, mais montre également que la pression et la présence de surfaces minérales ont une influence majeure sur la réactivité de ces molécules. Les environnements hydrothermaux semblent donc favorables à la concentration, la préservation et la complexification de la matière organique, étapes essentielles à l’émergence des propriétés du vivant. / The discovery of traces of primitive life, such as fossils and biosignatures, suggests that life may have appeared some 4.3 to 3.7 billion years ago. This emergence resulted from a chemical evolution with steps leading from simple organic molecules to the first single-celled organisms.This thesis tests the hypothesis of a hydrothermal origin of life. In such geochemical settings, pressure, temperature and pH gradients, mineral surfaces diversity and abundant chemical energy would have favored the accumulation and complexification of organic matter. This work focuses on the concentration of nucleotides and the polymerization of amino acids, which are the building blocks of genetic material and proteins, respectively.The first part of this thesis presents a large study of the interactions between nucleotides in aqueous solutions and phyllosilicates under controlled conditions of temperature, pH and salinity. The second part describes an in situ study of the effects of hydrothermal conditions and mineral surfaces in the polymerization of non-activated amino acids.This work suggests that sheet minerals, and especially swelling clays, increase the local concentration of nucleotides by three orders of magnitude and exhibit an adsorption behavior that is very dependent on the physical and chemical conditions of the environment. Moreover, this work confirms that the polymerization of amino acids in aqueous solutions is sensitive to temperature and it also underlines that pressure and mineral surfaces have a major role on the reactivity of these molecules. Hydrothermal environments thus favor the concentration, preservation and complexification of organic matter. These are crucial steps for the emergence of the properties of life in the chemical evolution.
37

The dynamics of chemically active droplets

Seyboldt, Rabea 16 June 2020 (has links)
In unserem täglichen Leben begegnen wir Tropfen oft in physikalischen Systems, beispielsweise als Öltropfen in Salatsoße. Diese Tropfen sind meist chemisch inaktiv. In biologischen Zellen bilden Proteine und RNA zusammen Tropfen. Zellen sind chemisch aktiv, so dass die Tropfenkomponenten neu gebildet, abgebaut und modifiziert werden können. In dieser Doktorarbeit wird das dynamische Verhalten von chemisch aktiven Tropfen mit analytischen und numerischen Methoden untersucht. Um das dynamische Verhalten von solchen aktiven Tropfen zu untersuchen, benutzen wir ein Minimalmodell mit zwei Komponenten, die zwei Phasen bilden und durch chemische Reaktionen ineinander umgewandelt werden. Die chemischen Reaktionen werden durch das Brechen von Detailed Balance aus dem Gleichgewicht gehalten, so dass die Tropfen chemisch aktiv sind. Wir konzentrieren uns auf den Fall, in dem Tropfenmaterial im Tropfen in die äußere Komponente umgewandelt wird, und in der äußeren Phase erzeugt wird. Wir finden ein vielfältiges dynamisches Phasendiagramm mit Regionen, in denen Tropfen schrumpfen und verschwinden, Regionen, in denen Tropfen eine stabile stationäre Größe besitzen, und Regionen, in denen eine Forminstabilität zu komplexer Tropfen-Dynamik führt. In der letzten Region deformieren sich Tropfen typischenweise prolat, verformen sich zu einer Hantel, und teilen sich in zwei Tochtertropfen, die wieder anwachsen. Dies kann zu Zyklen von Wachstum und Teilung von Tropfen führen, bis die Tropfen das gesamte Volumen füllen. Während spherische Tropfen durch die chemischen Reaktionen entgegen ihrer Oberflächenspannung deformiert werden, können Tropfen- Zylinder und Platten durch chemische Reaktionen stabilisiert werden. Generell ist die Dynamik von Tropfen ein hydrodynamisches Problem, da die Oberflächenspannung von deformierten Tropfen hydrodynamische Flüsse erzeugt. Wir finden, dass chemische Reaktionen entgegen die Oberflächenspannung Arbeit verrichten können, so dass die Tropfenteilung auch unter Berücksichtigung hydrodynamischer Flüsse möglich ist. Diese Doktorarbeit zeigt, dass die Kombination von chemische Reaktionen und Phasenseparation unter Nichtgleichgewichtsbedingungen zu neuem dynamischen Verhalten führen kann. Die Ergebnisse zeigen die Relevanz von chemischen Reaktionen zum Verständnis von Phasenseparation in biologischen Systemen auf, und können bei der Umsetzung der diskutierten Phänomene in experimentellen Systemen helfen. Die Tropfenteilung, die in dieser Doktorarbeit diskutiert wird, erinnert an die Teilung von biologischen Zellen. Davon motiviert schlagen wir vor, dass die Teilung von chemisch aktiven Tropfen ein Mechanismus für die Replikation von Tropfen-artigen Protozellen am Ursprung des Lebens gewesen sein könnte.:1. Introduction 2. Theory of multi-component phase-separating systems with chemical reactions 3. Minimal model for chemically active droplets in two formulations 4. Shape instability of spherical droplets with chemical reactions 5. Dynamical behavior of chemically active droplets 6. Shape instability of droplets with various geometries 7. Role of hydrodynamic flows in chemically driven droplet division 8. Chemically active droplets as a model for protocells at the origin of life 9. Conclusion Appendices / In our everyday environment, we regularly encounter liquid-liquid phase separation in physical systems such as oil droplets in vinegar. These droplets tend to be chemically inert. In biological cells, protein and RNA may together form liquid droplets. Cells are chemically active, so that droplet components can be created, degraded and modified. In this thesis we study the influence of nonequilibrium chemical reactions on the shape dynamics of a droplet theoretically, using analytical and numerical methods. To discuss the dynamical behavior that results from combining phase separation and chemical reactions in sustained nonequilibrium conditions, we introduce a minimal model with only two components that separate into distinct phases. These two components are converted into each other by chemical reactions. The reactions are kept out of equilibrium by breaking of detailed balance, so that the droplet becomes active. We concentrate on the case where the reaction inside the droplet degrades droplet material into the outer component, and where the reaction outside creates new droplet material. We find that chemically active droplets have a rich dynamic phase space, with regions where droplets shrink and vanish, regions where droplets have a stable stationary size, and regions where the flux-driven instability leads to complex dynamic behavior of droplets. In the latter, droplets typically elongate into a dumbbell shape and then split into two symmetrical daughter droplets. These droplets then grow until they have the same size as the initial droplet. This can lead to cycles of growth and division, so that an initial droplet divides until droplets fill the simulation volume. We analyze the stationary spherical state of the droplet, which is created by a balance of the fluxes driven by the chemical reactions. We find that stationary droplets may have a shape instability, which is driven by the continuous fluxes across the droplet interface and which may trigger the division. We also find that while reactions may destabilize spherical droplet shapes despite the surface tension of the droplet, they can have stabilizing effects on cylindrical droplets and droplet plates. Generally, the shape dynamics of droplets is a hydrodynamic problem because surface tension in non-spherical droplets drives hydrodynamic flows that redistribute material and deform the droplet shape. We therefore study the influence of hydrodynamic flows on the shape changes of chemically active droplets. We find that chemical reactions in active droplets can perform work against surface tension and flows, so that the droplet division is possible even in the presence of hydrodynamic flows. The present thesis highlights how the combination of basic physical behaviors – phase separation and chemical reactions – may create novel dynamic behavior under sustained nonequilibrium conditions. The results demonstrate the importance of considering chemical reactions for understanding the dynamics of droplets in biological systems, as well as proposes a minimalist model for experimentalists that are interested in creating a system of dividing droplets. Finally, the division of chemically active droplets is reminiscent of the division of biological cells, and it motivates us to propose that chemically active droplets could have provided a simple mechanism for the self-replication of droplet-like protocells at the origin of life.:1. Introduction 2. Theory of multi-component phase-separating systems with chemical reactions 3. Minimal model for chemically active droplets in two formulations 4. Shape instability of spherical droplets with chemical reactions 5. Dynamical behavior of chemically active droplets 6. Shape instability of droplets with various geometries 7. Role of hydrodynamic flows in chemically driven droplet division 8. Chemically active droplets as a model for protocells at the origin of life 9. Conclusion Appendices
38

[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.
39

The self-assembly of nucleic acid bases on metal and mineral surfaces

Shvarova, Olga Y. January 2011 (has links)
The ability of RNA bases to self-assemble into larger structures is an important research area relevant to the origins of life. In the RNA helix the bases are arranged on a sugar-phosphate carcass but it has been suggested that the initial ordering could form on a flat surface. This thesis is an attempt to establish experimentally whether the complementary RNA bases, adenine and uracil, have the ability to self-assemble into large ordered structures when adsorbed on metal and mineral surfaces. The Au (111) surface was chosen as a preferred substrate as it is flat, relatively free of defects, chemically inert and reconstructs in a characteristic pattern of corrugation lines, which provide a reference for crystallographic directions. Six of the molecular phases shown were observed for the first time with molecular resolution and the possible two-dimensional arrangements of adenine and uracil molecules for these phases are proposed. The pure adenine and pure uracil structures have chiral unit cells and in the case of pure uracil alternating monochiral domains within the polychiral islands are created. Well-ordered intricate uracil-adenine bimolecular networks were also observed. The self-assembly of both uracil and adenine appears to be weakly influenced by the surface crystallography. The (100) surface of the mineral pyrite (FeS₂) was chosen as the alternative substrate as it is the most common face that occurs naturally in pyrite crystals. The experiments show the formation of small adenine and uracil crystals at the terrace edges. Neither uracil nor adenine were observed to form a monolayer on the surface of the terraces. The results of the experiments described in this thesis are very interesting in terms of establishing the possible mechanisms for creating regular chiral molecular networks and provide a useful insight into the role of surfaces in the processes of self-assembly of RNA bases.
40

Energetic processes driving potential peptide protometabolisms at the origin of living systems / Processus énergétiques gouvernant des protométabolismes peptidiques à l’origine des systèmes vivants

Ajram, Ghinwa 29 November 2018 (has links)
La thèse aborde différentes questions de chimie prébiotique dans le contexte de l’origine de la vie par une approche de chimie systémique. La première partie est dédiée à l’étude de processus d’activation chimique important non seulement pour la formation de polymères, mais aussi pour alimenter le système en énergie de manière à le maintenir dans un état éloigné de l’équilibre, un prérequis pour l’auto-organisation. Il a été suggéré que les intermédiaires 5(4H)-oxazolones formés par l’activation de l’extrémité C-terminale des peptides pourrait être impliquée dans l’auto-organisation du vivant. Dans ce but, nous avons évalué la réactivité de réactifs pertinents dans un contexte prébiotique et décrits dans la littérature comme capables d’activer des acides α-aminés. Aucun d’entre eux n’a manifesté une activité satisfaisante pour l’activation C-terminale des peptides, montrant qu’une voie possible pour alimenter un protométabolisme des peptides en énergie n’est pas identifiée à ce jour à l’exception notable des N-carboxyanhydrides (NCA) qui peuvent être formé par des voies prébiotiquement plausibles. Nous avons par ailleurs démontré que les carbodiimides sont aussi efficaces pour l’activation des N-carbamoylamino acides que pour celle du carboxyle terminal des peptides en milieu aqueux dilué. La seconde partie du document expose de nouveaux résultats en faveur d’un processus de coévolution peptides-nucléotides. D’abord, une étude de la réactivité d’agents d’aminoacylation de l’extrémité 3’ de l’ARN est présentée. Ensuite, nous évaluons des co-polymères acides α-aminés-nucléotides liés par des enchaînements phosphoramidate et esters comme partenaires éventuels de l’évolution chimique. La pertinence cinétique de ces structures est démontrée ainsi que des voies chimiques permettant leur formation. / The thesis addresses several issues in prebiotic chemistry in the context of the origins of life through a systems chemistry approach. The first part is devoted to the study of chemical activation processes that are not only important in the formation of polymers, but also to feed the system with energy in order that a far from equilibrium state is maintained, a prerequisite for self-organization. It has been suggested that 5(4H)-oxazolones intermediates formed by C-terminus peptide activation could be involved in self-organization of life. To this aim, we have checked the reactivity of relevant prebiotic reagents previously proposed to activate α-amino acids. None of them led to a satisfactory C-terminus activation of peptides, showing that no general process for feeding a protometabolism of peptides with energy is identified yet, with the notable exception of N-carboxyanhydrides (NCAs) that can be formed through prebiotically relevant pathways. Additionally, we demonstrated that carbodiimides reagents are as efficient in the activation of N-carbamoyl amino acids as in that of the C-terminus of peptides in diluted aqueous media. The second part of the dissertation discloses new results in support of a process of coevolution of peptides and nucleotides. Firstly, a study of non-enzymatic aminoacylation reagents of the 3’-terminus of RNA is presented. Secondly, we assessed co-polymers of α-amino acids and nucleotides bound by phosphoramidate and ester linkages as potential players in chemical evolution. The kinetic relevance of these structures was demonstrated as well as potential chemical processes that allow their formation.

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