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Le travail présenté concerne la synthèse de calixarènes fonctionnalisés par des groupes sulfonates et carboxylates et l'étude détaillée des structures cristallines de leurs complexes moléculaires ou métalliques avec des métaux 3d et 4f. L'une des préoccupations majeures de ce travail concerne la compréhension des assemblages supramoléculaires dans ces systèmes. Le premier chapitre présente des éléments bibliographiques sur les calixarènes, leur histoire, les différentes conformations et les méthodes principales de fonctionnalisation puis la chimie supramoléculaire associée comprenant les complexes moléculaires et métalliques. Le deuxième chapitre est dédié à une série de complexes moléculaires de type hôte-invité formés entre le para-sulfonatocalix[4]arène (SC4) et différentes bipyridine En continuité avec ce travail nous présentons en suite la structure et les propriétés magnétiques d'un complexe métallique constitué d'un SC4 pontant deux entités dinucléaires de phenanthroline [FeIII2(μ-O)(H2O)5(phen)2] par la coordination des groupes sulfonates. Le troisième chapitre est consacré à la chimie de coordination des calixarènes sulfonatés avec les lanthanides. Nous avons mis en évidence trois types de structures cristallines qui sont toutes des polymères de coordination où les ions lanthanides jouent le rôle d'assembleur des calixarènes par la coordination des groupes sulfonates selon trois types de structure (A, B et C). Nous avons obtenu ces trois structures (A, B et C) pour l'ensemble de lanthanide (La, Pr, Nd , Eu, Gd, Tb, Dy, Ho, Yb). Le quatrième chapitre concerne la chimie de coordination des métaux de transition 3d (Co, Mn, Zn, Cu) avec des calixarènes fonctionnalisés par des groupes carboxylates sur leur partie basse. Avec le calixarène dicarboxylate nous avons obtenu une série de complexes isomorphes dans lesquels deux calixarènes sont coordinés à deux centres métalliques pour former des chaînes infinies. Le cinquième chapitre présente les résultats d'un travail exploratoire visant à synthétiser des azacalix[4]arènes, dans le but de complexer des métaux de transition. L'étude RPE des précurseurs a mis en évidence des espèces radicalaires / This work presents the synthesis of calixarenes functionalized with sulfonate and carboxylate groups and the detailed study of the crystal structures of their molecular or metal complexes with 3d and 4f metals ions. One of the major concerns of this work is the understanding of supramolecular assemblies in these systems. The first chapter gives bibliographic elements on the history, the different conformations and the main methods of functionalization of calixarenes and on their supramolecular chemistry comprising molecular and metal complexes. The second chapter is dedicated to a series of molecular complexes of the host-guest type formed between the para-sulfonatocalix[4]arene (SC4) and various bipyridine. In continuation with this work we then present the synthesis, structure and magnetic properties of a metal complex comprising a SC4 bridging by the sulfonate groups two iron(II) dinuclear entities with coordinated phenathroline [FeIII2 (μ-O)(H2O) 5(phen) 2]. The third chapter is devoted to the coordination chemistry of sulfonated calixarenes with lanthanides. We have found three types of crystal structures which are polymers wherein the lanthanide ion function as an assembler of calixarenes by the coordination of the sulfonate groups along three type of structure (A, B and C). We obtained these three structures (A, B and C) for all lanthanide (La, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Yb). The fourth chapter concerns the coordination chemistry of 3d transition metals (Co, Mn, Zn) with calixarenes functionalized with carboxylate groups on lower rim. With calixarene dicarboxylate we got a series of isomorphic complexes in which two calixarenes are coordinated to two metal centers to form infinite chains. The fifth chapter presents the results of an exploratory work to synthesize azacalix[4]arene with the aim to complex transition metals ions. The EPR study of the precursors has evidenced free radical species

La thématique de cette thèse est l'alignement moléculaire. Celui-ci est un sujet très important qui ouvre la voie sur un contrôle beaucoup plus fin de nombreux phénomènes. Ainsi, nous avons développé une nouvelle technique de mesure de l’alignement moléculaire suivant un axe et permettant d’en conserver le signe. Celle-ci est, à l’instar des techniques de mesure de l’alignement moléculaire développées dans l’équipe, basée sur la mesure de variation d’indice de réfraction induite par l’alignement moléculaire. La technique développée ensuite permet également la mesure de l’alignement moléculaire, tout en étant aussi une application de celui-ci puisqu’il permet ici la génération de troisième harmonique. L’alignement moléculaire est également mis en oeuvre dans la dernière étude puisque nous montrons qu’il apporte la résolution nécessaire à l’étude de la thermalisation d’un échantillon moléculaire excité / The thematic of this thesis is molecular alignment. The latter is a very important topic that opens the way toward a much more thin control of many phenomenons. So, we have developed a new measurement technique of the molecular alignment along one axis that permits to preserve the sign of alignment. This one is, like other measurement techniques developed by the team,based on the measurement of the refractive index variation induced by the molecular alignment.The technique developed then also permits the molecular alignment measurement, being also an application of it because it allows the third harmonic generation. In the last study, molecular alignment is implemented to show that it brings the necessary resolution for the study of an excited molecular sample thermalization

In the United States, rapid military mobilization for the world wars marked a turning point in the national need to manage and evaluate manpower. To orchestrate manpower needs for the military, industry, and those relating to familial obligations, Woodrow Wilson's administration created the Selective Service System during the First World War. In categorizing men, local Selective Service boards utilized rapid physical and psychological diagnostic techniques and applied their assessments to current military branch induction standards to pronounce candidates as militarily fit or unfit. From World War I to World War II, the Selective Service System expanded as a bureaucracy but did not adequately address induction issues surrounding rapidly changing standards, racism, and inconsistent testing procedures. These persistent problems with Selective Service prevented the system from becoming truly consistent, fair, or effective. As a result of Selective Service System, War Department, and military branch standards, military rejection and prematurely military discharge rates increased in World War II. Additionally, though Selective Service did not accurately predict who would or would not serve effectively, rejected and prematurely discharged men faced harsh discrimination on the American home front during World War II.

Ce travail de thèse décrit (i) la synthèse de complexes hétérométalliques d’ions 3d et 4f à partir de précuseurs de Mn, Fe et Co, de sels de lanthanides et de ligands organiques et (ii) l'étude de leurs structures et propriétés. 41 complexes polynucléaires ont été synthétisés dans le cadre de ce travail. Les structures moléculaires de tous les composés ont été déterminées par diffraction des rayons X. Les propriétés magnétiques de 22 complexes ont été étudiées, dont quatre montrent une relaxation lente de leur aimantation considérée comme la signature d’un comportement de molécule-aimant. L'activité catalytique du complexe {Mn4Dy6Li2} calciné a aussi été étudiée et s'est avérée efficace pour l'oxydation du monoxyde de carbone. L'étude systématique de complexes isostructuraux de lanthanides a montré que l'incorporation d’ions 4f peut introduire de l’anisotropie magnétique et que l’ion DyIII est généralement le meilleur candidat pour le ciblage de molécules-aimants hétérométalliques 3d- 4f. / This dissertation describes the syntheses of 3d-4f-metal complexes starting from preformed compounds of Mn, Fe and Co, lanthanide salts and organic ligands and also the investigation of their structures and properties. 41 new polynuclear heterometallic metal complexes were synthesised in the course of this work with different interesting properties. The structures of all obtained compounds have been confirmed using X-ray diffraction. The magnetic properties of 22 complexes were studied, of which four show frequency dependent out-of-phase signals as expected for SMMs. The catalytic activity of calcinated {Mn4Dy6Li2} was investigated and proved effective for the oxidation of CO. It was established, that the use of precursors leads to new families of compounds. Moreover the study of isostructural compounds across the lanthanide series showed 1) that the incorporation of 4f ions introduces magnetic anisotropy and 2) DyIII is usually the best candidate for targeting 3d-4f-SMMs.

Με σκοπό τη μελέτη της χημείας ένταξης του υποκαταστάτη δι-2,6-(2-πυριδυλοκαρβονυλο) πυριδίνη (dpcp) με μέταλλα μετάπτωσης 3d, παρασκευάστηκαν οι τετραπυρηνικές πλειάδες [Cu4(N3)2{pyCO(OMe)pyCO(OMe)py}2(MeOH)2](ClO4)∙2MeOH (1∙2MeOH) και [Co4(N3)2(NO3)2{pyCO(OMe)pyCO(OMe)py}2]∙0.5MeOH (2∙0.5MeOH), η εξαπυρηνική πλειάδα [Ni6(CO3)(N3)6{pyCOpyC(O)(OMe)py}3(MeOH)2(H2O)][Ni6(CO3)(N3)6 {pyCOpyC(O)(OMe)py}3(MeOH)3](ClO4)2 (3∙1.8MeOH) και η διπυρηνική πλειάδα [Fe2{pyCO(OMe)py(Η)CO(OMe)py}2(MeO)2](ClO4)2∙(4∙MeOH). Στην συνέχεια μελετήθηκε η χημεία ένταξης του ίδιου υποκαταστάτη με μέταλλα 3d και 4f και παρασκευάστηκαν τα ετερομεταλλικά διπυρηνικά σύμπλοκα [ΜIILnIII{pyCOH(OEt)pyCOH(OEt)py}3](ClO4)2∙EtOH (5-16∙EtOH) με ΜΙΙ = CuΙΙ, CoΙΙ, NiΙΙ, ZnΙΙ, MnΙΙ, FeΙΙ [LnΙΙΙ = GdΙΙΙ (5 - 10), TbΙΙΙ (11 – 16) αντίστοιχα]. Όλα τα σύμπλοκα χαρακτηρίστηκαν κρυσταλλογραφικά, τα σύμπλοκα 4, 10 και 16 χαρακτηρίστηκαν με φασματοσκοπία Mössbauer ενώ τα σύμπλοκα 1 – 10 χαρακτηρίστηκαν μαγνητικά. Πιο συγκεκριμένα, οι μαγνητικές μελέτες των συμπλόκων 1 – 3, 5 και 10 έδειξαν σιδηρομαγνητικές αλληλεπιδράσεις ενώ εκείνες των συμπλόκων 4, 6, 7 και 9 έδειξαν αντισιδηρομαγνητικές αλληλεπιδράσεις. Προκειμένου να μελετηθεί σε βάθος η οικογένεια των βασικών καρβοξυλικών αλάτων του σιδήρου [Fe3O(O2CR)6(H2O)3]A, παρασκευάστηκαν δύο σειρές αυτών των συμπλόκων με R = CCl3, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, (CH2)3Cl, Me, CHMe2, Et και CMe3. Στην πρώτη σειρά συμπλόκων (17 - 28) το αντισταθμιστικό ιόν (Α) είναι ClO4-, ενώ στη δεύτερη (29 - 40) είναι NO3-. Η προσπάθεια απομόνωσης του ανάλογου με R = CF3 ήταν άκαρπη και για τα δύο αντισταθμιστικά ιόντα και οδήγησε σε ένα τετραπυρηνικό σύμπλοκο [Fe4O2(O2CCF3)8(H2O)6] (41) με δομή τύπου «πεταλούδας». Πραγματοποιήθηκαν μετρήσεις Mössbauer σε στερεά δείγματα και για τις δύο σειρές και οι ισομερείς μετατοπίσεις και οι τετραπολικές αλληλεπιδράσεις διαφέρουν μεταξύ 0.51 – 0.54 mms-1 και 0.36 – 0.76 mms-1 αντίστοιχα. Μετρήσεις Mössbauer και σε διαλύματα αυτών έδειξαν τη σταθερότητά τους και σε διάλυμα, με εξαίρεση το σύμπλοκο 29 (R = Cl3C, Α = NO3-) που οδήγησε σε σύμπλοκο τύπου «πεταλούδας». Το υψηλής συμμετρίας σύμπλοκο [Fe3O(O2CPh)6(py)3](ClO4)∙py (42) έχει μελετηθεί στο παρελθόν κρυσταλλογραφικά αλλά και με μετρήσεις ανελαστικής σκέδασης νετρονίων IINS και είχε προταθεί ύπαρξη του μαγνητικού φαινομένου Jahn-Teller σε πολύ χαμηλές θερμοκρασίες. Θέλοντας να εξακριβωθεί εάν η μαγνητική συμμετρία σχετίζεται με την πραγματική, πραγματοποιήθηκαν κρυσταλλογραφικές μετρήσεις μεταβλητής θερμοκρασίας στο εργαστήριο ΒΜ01Α του ESRF. Τα αποτελέσματα των πειραματικών μετρήσεων έδειξαν ότι η πραγματική συμμετρία παραμένει ίδια. Στη συνέχεια από μετρήσεις μαγνητικής επιδεκτικότητας ac, παρατηρήθηκε η ύπαρξη μαγνητικών φαινομένων χαλάρωσης υπό την επίδραση ασθενών μαγνητικών πεδίων. / Seeking to study the coordination chemistry of the ligand di-2, 6-(2-pyridylcarbonyl) pyridine (dpcp) with 3d transition metal ions, the tetranuclear complexes [Cu4(N3)2{pyCO(OMe)pyCO(OMe)py}2(MeOH)2](ClO4)∙2MeOH (1∙2MeOH) and [Co4(N3)2(NO3)2{pyCO(OMe)pyCO(OMe)py}2]∙0.5MeOH (2∙0.5MeOH), the hexanuclear complex [Ni6(CO3)(N3)6{pyCOpyC(O)(OMe)py}3(MeOH)2(H2O)][Ni6(CO3)(N3)6{pyCOpyC(O) (OMe)py}3(MeOH)3](ClO4)2 (3∙1.8MeOH) and the dinuclear complex [Fe2{pyCO(OMe)py(Η)CO(OMe)py}2(MeO)2](ClO4)2∙(4∙MeOH) were synthesized. In addition, in order to study the coordination chemistry of the same ligand with mixed 3d transition metal ions and 4f lanthanide ions, the heterometallic dinuclear complexes [ΜIILnIII{pyCOH(OEt)pyCOH(OEt)py}3] (ClO4)2∙EtOH (5-16∙EtOH) were synthesized, with ΜΙΙ = CuΙΙ, CoΙΙ, NiΙΙ, ZnΙΙ, MnΙΙ, FeΙΙ [LnΙΙΙ = GdΙΙΙ (5 - 10), TbΙΙΙ (11 – 16) respectively]. All complexes were structurally characterized and complexes 4, 10 and 16 were characterized by Mössbauer spectroscopy. Magnetic properties measurements of complexes 1-3, 5 and 10 indicated the existence of ferromagnetic interactions, while those of 4, 6, 7 and 9 indicated the existence of antiferromagnetic interactions. For the in depth study of the family of basic iron (III) carboxylates [Fe3O(O2CR)6(H2O)3]A, two series of complexes were prepared with R = Cl3C, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, Cl(CH2)3, Me, CHMe2, Et and Me3C. For the former series (17 - 28) the counteranion (A-) is ClO4- and for the latter (29 - 40) is NO3-. Attempts to prepare the respective trifluoroacetate (R = CF3) complexes were unsuccessful and the reaction system lead to the tetranuclear “butterfly” complex [Fe4O2(O2CCF3)8(H2O)6] (41), irrespective of whether perchlorates or nitrates were used as counteranions. Mössbauer studies revealed very similar isomer shifts for all complexes in the region of 0.51 – 0.54 mms-1, and variable quadrupole splittings, ranging from 0.36 to 0.76 mms-1. Mössbauer studies of the complexes were carried out in frozen MeCN solutions in order to assess their stability in solution and they proved to be stable in MeCN solutions, except complex 29 (R = Cl3C, Α = NO3-), which dissociated to a butterfly-type complex. The high-symmetry cluster [Fe3O(O2CPh)6(py)3](ClO4)∙py (42) has been structurally characterized and its Inelastic Incoherent Neutron Scattering studies have been reported. These studies suggested the existence of a magnetic Jahn-Teller effect at lower temperatures. Seeking to study if there is any correlation between magnetic and structural symmetry, we undertook variable-temperature crystallographic studies on ESRF BM01A beamline. With the results of these data we concluded that the symmetry of the crystal remained. Moreover, we have discovered that this complex exhibits magnetic relaxation phenomena under weak magnetic fields, observed by ac magnetic susceptometry.

We describe the rare-earth elements using the Hubbard I approximation. We show that the theory reproduces the cohesive properties, like the volume and bulk modulus, and we find an excellent agreement between theory and experiment for the (inverse) photo emission spectra of the valence band. In addition we reproduce the spin and orbital moments of these elements. This licentiate thesis contains an introduction to the cohesive, magnetic and spectral properties of the rare-earth elements, to density functional theory and to density functional theory in combination with dynamical mean-field theory within the Hubbard I approximation. We also focus on some technical details, e.g. the optimal basis used in the electronic structure code and the role of charge self-consistency in properly describing the valence electrons.

La thématique de cette thèse est l'alignement moléculaire. Celui-ci est un sujet très important qui ouvre la voie sur un contrôle beaucoup plus fin de nombreux phénomènes. Ainsi, nous avons développé une nouvelle technique de mesure de l'alignement moléculaire suivant un axe et permettant d'en conserver le signe. Celle-ci est, à l'instar des techniques de mesure de l'alignement moléculaire développées dans l'équipe, basée sur la mesure de variation d'indice de réfraction induite par l'alignement moléculaire. La technique développée ensuite permet également la mesure de l'alignement moléculaire, tout en étant aussi une application de celui-ci puisqu'il permet ici la génération de troisième harmonique. L'alignement moléculaire est également mis en oeuvre dans la dernière étude puisque nous montrons qu'il apporte la résolution nécessaire à l'étude de la thermalisation d'un échantillon moléculaire excité

Made available in DSpace on 2016-05-19T13:08:18Z (GMT). No. of bitstreams: 2 199.pdf: 2457764 bytes, checksum: f3219878be3144c523ae28e85c474b10 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2015 / Fundação Oswaldo Cruz. Centro de Pesquisas Aggeu Magalhães. Recife, PE, Brasil / Os tripanossomatídeos são caracterizados por processos moleculares diferenciados como a transcrição policistrônica e regulação pós-transcricional da expressão gênica. Em mamíferos, a tradução se inicia com a ligação do complexo eIF4F (formado pelos eIF4A, eIF4E e eIF4G) a extremidade 5' dos mRNAs, o que facilita seu reconhecimento pelo ribossomo. A atividade do eIF4F é reforçada pela proteína de ligação a cauda poli-A (PABP), na extremidade 3' dos mRNAs, que interage com o eIF4G. Dois complexos do tipo eIF4F foram identificados em tripanossomatídeos: o primeiro formado pelos EIF4G3, EIF4E4 e EIF4AI com a PABP1; e um outro baseado na interação do EIF4G4 com o EIF4E3 e o EIF4A1. Este trabalho buscou caracterizar as interações entre as subunidades destes complexos e sua associação com PABPs de Leishmania, avaliando o efeito de mutações em motivos específicos. Proteínas recombinantes foram geradas fusionadas a GST e avaliadas quanto a sua habilidade de interagir com parceiros marcados radioativamente em ensaios do tipo pull-down. Para o EIF4G3, mutações individuais em dois resíduos vizinhos (I8A e R9A), afetaram a interação com o EIF4E4 e a mutação de ambos os resíduos equivalentes do EIF4G4 (IL25-26AA) também impediu sua ligação ao EIF4E3, sugerindo um motivo comum para a ligação aos seus parceiros. As proteínas EIF4E3 e EIF4E4 foram avaliadas quanto à capacidade de interagir com a PABP2 e PABP1 respectivamente, e mutações em motivos conservados nas regiões N-terminais dos EIF4E (Boxes A, B e C) aboliram sua interação com os homólogos da PABP. Para identificar que regiões da PABP1 estão relacionadas às interações com o parceiro EIF4E4, foram obtidas proteínas PABP1 mutantes em motivos conservados e observou-se que a mutação no motivo TGM, C-terminal, aboliu sua interação com o EIF4E4. Com estas abordagens conseguiu-se avançar na definição das interações entre as referidas subunidades do eIF4F e PABP, identificando-se diferenças relevantes em relação a outros eucariotos

Made available in DSpace on 2016-05-19T13:08:19Z (GMT). No. of bitstreams: 2 license.txt: 1914 bytes, checksum: 7d48279ffeed55da8dfe2f8e81f3b81f (MD5) 2015moraes-rmn.pdf: 2690273 bytes, checksum: ed5beefae2ad836171467014e6c521e1 (MD5) Previous issue date: 2015 / Fundação Oswaldo Cruz. Centro de Pesquisas Aggeu Magalhães. Recife, PE, Brasil / Os tripanossomatídeos são organismos caracterizados pelo controle póstranscricional da expressão gênica, principalmente em nível de tradução. Na tradução em eucariotos, tem grande destaque o complexo eIF4F, sendo um de seus principais componentes o fator de iniciação da tradução eIF4E. Já foram descritos em tripanossomatídeos seis homólogos para o eIF4E, nomeados EIF4E1 a 6. Em um estudo com Leishmania amazonensis, focado no EIF4E3, percebeu-se que seu perfil de expressão se alterava rapidamente numa curva de crescimento, com este apresentando ao menos duas bandas. As mudanças observadas sugeriam modificações pós-traducionais do tipo fosforilação, algo posteriormente confirmado. Analisando-se a sequência do EIF4E3 de Leishmania, foi possível identificar a presença de possíveis sítios de fosforilação e de ligação a parceiros funcionais como homólogos do eIF4G, outro componente do complexo eIF4F, e da proteína de ligação á cauda poli-A (PABP). No presente estudo foi analisado o perfil de expressão e a capacidade de ligação a parceiros funcionais do EIF4E3 de Leishmania superexpresso em células transfectadas e no qual foram introduzidas mutações em motivos específicos. Os resultados mostraram um perfil de expressão de ao menos três bandas para o EIF4E3 de L. amazonensis e duas para L. infantum, com o sítio S75, presente apenas na primeira, sendo o responsável por esta diferença. Em ensaios de imunoprecipitação, foi identificado um motivo que, quando mutado, aboliu a ligação do EIF4E3 com a PABP3, sugerindo este como o sítio de interação entre os fatores. Com a análise do efeito de mutações no EIF4E3 de L. amazonensis, foi percebido que ao se mutar três motivos implicados na à PABP e o possível sítio de ligação ao EIF4G, sua fosforilação diminuiu drasticamente, sugerindo a necessidade destas interações para que a fosforilação ocorra. Estes resultados indicam um complexo mecanismo de modificações pós-traducionais responsáveis pela regulação do EIF4E3 e contribuem a para a caracterização da sua função em Leishmania