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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.
11

Evolução cromossômica em Cassidinae sensu lato (Coleoptera, Polyphaga, Chrysomelidae)

Julio, Milena de [UNESP] 27 February 2009 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:22:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-02-27Bitstream added on 2014-06-13T20:10:16Z : No. of bitstreams: 1 julio_m_me_rcla.pdf: 410641 bytes, checksum: 5821353ab69f004e70a5c9c055e996e8 (MD5) / Das subfamílias de Chrysomelidae, Cassidinae sensu lato (s.l.), formada por 6.000 espécies e 43 tribos, possui aproximadamente 100 espécies analisadas citogeneticamente e a maioria delas apresentou 2n=18=16+Xyp, o qual é menor que aquele considerado basal para os Polyphaga, 2n=20=18+Xyp. No entanto, alguns grupos de espécies demonstraram manutenção do número diplóide basal e outros, aumento desse número; algumas espécies do último grupo também exibiram variação em relação ao tipo de sistema cromossômico sexual (SCS). Considerando a revisão taxonômica recentemente realizada para as espécies de Cassidinae s.l., a existência de relação filogenética para algumas espécies dessa subfamília, a alta diversidade de espécies desse grupo registrada para a região Neotropical e o baixo número de espécies que tiveram seus cromossomos estudados, o presente trabalho teve como objetivo verificar os mecanismos envolvidos na evolução cariotípica dessa subfamília através do estudo de sete espécies da fauna brasileira e da revisão dos dados citogenéticos. Os espécimes foram coletados em Avaré e Rio Claro, SP, Nonoai, RS, e Ponta Grossa, PR. As preparações cromossômicas obtidas de embrião e testículos de machos adultos foram coradas com solução de Giemsa. As espécies Agroiconota inedita (2n=42=40+Xyp), Charidotella (sensu stricto) immaculata (2n=22=20+Xyp), Charidotella (sensu stricto) sexpunctata (2n=22=20+Xyp), e Stolas chalybaea (2n=24=22+Xyp) revelaram número diplóide maior do que aquele estabelecido como basal para os Polyphaga e cromossomos com dois braços. Os cariótipos de Cteisella confusa, Deloyala cruciata, e Metriona elatior mostraram a fórmula cromossômica 2n=18=16+Xyp, considerada modal para os Cassidinae s.l., e cromossomos com dois braços. As sete espécies apresentaram cromossomos sexuais facilmente identificáveis por serem... / Among the subfamilies of Chrysomelidae, Cassidinae sensu lato (s.l.) , formed by 6 000 species and 43 tribes, possesses approximately 100 species cytogenetically analyzed and most of them presented 2n=18=16+Xyp, which was smaller than 2n=20=18+Xyp considered basal for Polyphaga. However, some groups of species presented maintenance of the basal diploid number and others showed increase of this number; certain species of the latter group also exhibited variation in the sex chromosome system (SCS). Considering the recent taxonomic revision accomplished for the Cassidinae s.l. species, the existence of phylogenetic relationship for some species of this subfamily, the high diversity of species of this group in the Neotropical region, and the low number of Cassidinae s.l. species karyotyped so far, the aim of the present work was to verify the main mechanisms involved in the karyotype evolution of this subfamily through the study of seven species of the Brazilian fauna and the overview of the cytogenetic data. The individuals were collected in Avare and Rio Claro, SP, Nonoai, RS, and Ponta Grossa, PRo The chromosomal preparations obtained from embryo and testes of adult males were stained with Giemsa solution. The species Agroiconota inedita (2n=42=40+Xyp), Charidotella (sensu stricto) immaculata (2n=22=20+Xyp), Charidotella (sensu stricto) sexpunctata (2n=22=20+Xyp), and Stolas chalybaea (2n=24=22+Xyp) revealed diploid number higher than that established as basal for Polyphaga and biarmed chromosomes. The karyotype of Gteisella confusa, Deloyala cruciata, and Metriona elatior showed the chromosomal formulae 2n=18=16+Xyp considered modal for Cassidinae s.l. and biarmed chromosome. The seven species exhibited easily identified sex chromosomes due to their smallest size in the complement. The analysis of meiotic cells of all the species showed pachytenes with a positively heteropycnotic block... (Complete abstract click electronic access below)
12

Síntese, caracterização e estudo termoanalítico dos succinatos de alguns metais de transição bivalentes no estado sólido

Caires, Flávio Junior [UNESP] 18 January 2011 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:29:05Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-01-18Bitstream added on 2014-06-13T19:17:16Z : No. of bitstreams: 1 caires_fj_me_araiq.pdf: 493700 bytes, checksum: 3407a17ff8fb345606e061ffb146a15f (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Esse trabalho descreve a síntese e caracterização dos succinatos de metais de transição bivalentes, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), no estado sólido. Inicialmente prepararam-se os carbonatos dos respectivos íons metálicos adicionando-se lentamente e sob agitação solução saturada de hidrogeno carbonato de sódio à solução de cloreto (Mn, Co, Ni, Zn) ou sulfato (Fe, Cu), até precipitação completa dos íons metálicos. Os succinatos foram obtidos fazendo-se reagir os carbonatos dos íons metálicos com solução de ácido succínico. Os compostos sintetizados foram estudados empregando termogravimetria e análise térmica diferencial simultânea (TG-DTA), termogravimetria derivada (DTG), calorimetria exploratória diferencial (DSC), difratometria de raios X pelo método do pó, espectroscopia no infravermelho, termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR) e complexometria. Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, modos de coordenação etc. Também foi possível identificar os produtos liberados durante o aquecimento. Os resíduos finais foram Mn3O4, Fe2O3, Co3O4, NiO, CuO e ZnO / In this work, the synthesis and characterization of bivalent transition metal ion succinates in the solid state, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), are described. Firstly, the respective metal ion carbonates were prepared by slow addition of sodium hydrogen carbonate saturate solution to the chloride (Mn, Co, Ni, Zn) or sulphate (Fe, Cu) solution under continuous magnetic stirring until complete precipitation of the metal ions. The succinates were obtained by reacting carbonate of the metal ions with succinic acid solution. The synthesized compounds were characterized by simultaneous thermogravimetry and differential thermal analysis (TGDTA), Thermogravimetry derivative (DTG), differential scanning calorimetry (DSC), Xray powder diffractometry, infrared spectroscopy, thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR) and complexometry. The results provided information about the thermal behavior, crystallinity, modes of coordination etc. It was also possible to identify the products evolved during heating. The final residues were Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO
13

Atypical Opioid Interactions – Development of Selective Mu-Delta Heterodimer Antagonists, Clinical Opioids at Non-Mu Pain Targets and Endogenous Biased Signaling

Olson, Keith Mathew, Olson, Keith Mathew January 2017 (has links)
Most clinical opioids produce analgesia through the Mu Opioid Receptor (MOR) providing the only effective treatment for chronic pain patients. These studies explore three pre-clinical strategies to improve MOR analgesia and minimize side effects: 1) compounds that target G-protein Coupled Receptors (GPCRs) heterodimers, such as heterodimerization between the Delta Opioid Receptor (DOR) and MOR (MDOR); 2) multi-functional compounds that target multiple receptor systems for synergistic effects, such as a MOR agonist and a the serotonin reuptake transporter (SERT) inhibitor; or 3) biased agonists that preferentially activate one signaling pathway associated with analgesia over another associated with side effects at the same receptor. First, several indirect lines of evidence indicate the MOR-DOR heterodimer (MDOR) can regulate MOR opioid tolerance and withdrawal. However, studying MDOR remains difficult because no selective MDOR antagonists are available. To address this need, we created a novel series of bivalent MDOR antagonists by connecting a low affinity MOR antagonist (H-Tyr-Pro-Phe-D1Nal-NH2) to a moderate affinity DOR (H- Tyr-Tic-OH) antagonist with variable length polyamide spacers (15-41 atoms). In vitro radioligand binding and [35S]-GTPγS coupling assays in MOR, DOR, and MDOR expressing cell lines show bivalent ligands produce a clear length dependence in MDOR but not MOR or DOR cell lines. The lead compound – D24M with a 24-atom spacer – displayed high potency (IC50MDOR = 0.84 nM) with 91-fold selectivity for MDOR:DOR and 1,000-fold MDOR:MOR selectivity. Second, clinicians have long appreciated subtle but distinct differences in analgesia and side effects of MOR opioids. A variety of non-MOR targets including DOR, Kappa Opioid Receptor (KOR), the Cannabinoid Receptor-1 (CB1), the Sigma-1 Receptor (σ1R), the Dopamine- (DAT), Serotonin- (SERT) and Norepinephrine- Reuptake Transporters (NET) induce analgesia and/or modulate MOR mediated side effects. To determine if different opioid profiles arise from non-MOR interactions, we evaluated the binding and function of nine clinical analgesics at the nine aforementioned targets revealing several clinical opioids contain previously unidentified affinity’s or activity’s. Hydrocodone displayed low affinity at the MOR (KI = 1800 nM) and only ~2 fold less affinity at the σ1R (KI = 4000 nM). Second buprenorphine promoted monoamine influx at DAT, SERT and NET with EC50 > 1,000 nM. These novel interactions suggest the nuanced differences of clinical opioids may arise from previously unappreciated off-target effects. Future studies will assess whether these in vitro results predict hydrocodone and buprenorphine activity in vivo. Finally, the unique function of the numerous endogenous opioid peptides at a given receptor remains unclear. How endogenous ligands interact with ORs produces obvious drug design consequences. These studies show two endogenous Dynorphin analogues – Dynorphin A and Dynorphin B – differentially regulate two ubiquitous signaling modules – βarrestin2 and Gαi/o– at the DOR. Dynorphin A and Dynorphin B swap potency rank orders for β-arrestin2 recruitment and [35S]-GTPγS signaling, indicating two distinct signaling platforms are formed. Dynorphin A but not Dynorphin B treatment simulated AC super activation, while Dynoprhin B internalized DOR better than Dynorphin A. These in vitro assays suggest endogenous Dynorphin analogues differentially regulate signals at the DOR in vitro. Future work includes further characterizing signaling differences in vitro and testing these changes in vivo.
14

Vagueness, presupposition and truth-value judgements / Le Vague, la présupposition et les valeurs de jugements de vérité

Zehr, Jérémy 18 December 2014 (has links)
Cette thèse vise à rendre compte conjointement des jugements de valeurs de vérité non-bivalents, c'est-à-dire des jugements ne correspondant ni à « Vrai » ni à « Faux », déclenchés par des phrases présuppositionnelles (telles que 1 en contexte où Oscar n'est pas français), vagues (telles que 2 en contexte où Oscar est de taille moyenne) ou encore hybrides (telles que 3 en contexte où l'interlocuteur est de taille moyenne).1. Oscar a réalisé que tu es français.2. Oscar est vieux.3. Oscar a réalisé que tu es vieux.Sur la base de systèmes logiques définissant trois valeurs de vérité (vrai, faux et autre) proposés dans la littérature sur le vague tout comme dans la littérature sur la présupposition, j'élabore dans un premier temps un système à cinq valeurs de vérité ordonnées, qui définit ainsi trois paliers intermédiaires entre le vrai et le faux.Suite à l'obtention de résultats expérimentaux incompatibles avec les prédictions de ce système, je propose dans un deuxième temps un système à quatre valeurs de vérité non ordonnées, compatible avec les résultats et qui place cette fois le vague et la présupposition sur des dimensions distinctes. Une expérience menée avec Paul Égré établit par ailleurs que les locuteurs rejettent systématiquement des descriptions contradictoires comme « vieux et jeune », mais qu'ils peuvent accepter des descriptions contradictoires comme "ni vieux ni jeune", "ni veux ni pas vieux" et "vieux et pas vieux". Ces résultats confortent l'idée qu'une phrase vague comme 1 peut être jugée "Ni vraie ni fausse" mais aussi "Vraie et fausse", et nous permettent de discriminer entre deux approches concurrentes de l'antonymie adjectivale. / The aim of my thesis is to give a uniform account of non-bivalent truth-value judgments induced by presuppositional expressions and by vague expression (namely judgments other than "True" or "False"). For example, a presuppositional sentence like 1 below is typically judged neither true nor false in a context where Oscar is not French, and a vague sentence like 2 is also reported as neither true or nor false in a context where Oscar is of an average height. The same holds of a hybrid sentence like 3, combining a vague adjective and a presuppositional expression, in a context where the interlocutor is of an average height:1. Oscar has realized that you are French.2. Oscar is old.3. Oscar has realized that you are old. Abstract:Drawing on systems defining three logical values (true, false and other) and discussed both in the literature on vagueness and in the literature on presupposition, I propose a system with five totally ordered values, thereby defining three intermediate levels between true and false.After collecting experimental data conflicting with the predictions of this system, I propose a system with four values which is compatible with the experimental results and where the four values are partially ordered along a dimension specific to vagueness and along a dimension specific to presupposition.To get further insights about truth-value judgments specific to vagueness, I conducted another set of experiments (in collaboration with Paul Égré), showing that speakers systematically reject contradictory descriptions of the form "old and young" but that they can accept contradictory descriptions of the form "neither old nor young", "neither old nor not old" and "old and not old". These results echo the idea that vague sentences like 1 can be judged "Neither true nor false" but also "True and false", and allow us to discriminate between two competing theories of adjectival antonyms.
15

Changes of bivalent chromatin coincide with increased expression of developmental genes in cancer

Bernhart, Stephan H., Kretzmer, Helene, Holdt, Lesca M., Jühling, Frank, Ammerpohl, Ole, Bergmann, Anke K., Northoff, Bernd H., Doose, Gero, Siebert, Reiner, Stadler, Peter F., Hoffmann, Steve January 2016 (has links)
Bivalent (poised or paused) chromatin comprises activating and repressing histone modifications at the same location. This combination of epigenetic marks at promoter or enhancer regions keeps genes expressed at low levels but poised for rapid activation. Typically, DNA at bivalent promoters is only lowly methylated in normal cells, but frequently shows elevated methylation levels in cancer samples. Here, we developed a universal classifier built from chromatin data that can identify cancer samples solely from hypermethylation of bivalent chromatin. Tested on over 7,000 DNA methylation data sets from several cancer types, it reaches an AUC of 0.92. Although higher levels of DNA methylation are often associated with transcriptional silencing, counter-intuitive positive statistical dependencies between DNA methylation and expression levels have been recently reported for two cancer types. Here, we re-analyze combined expression and DNA methylation data sets, comprising over 5,000 samples, and demonstrate that the conjunction of hypermethylation of bivalent chromatin and up-regulation of the corresponding genes is a general phenomenon in cancer. This up-regulation affects many developmental genes and transcription factors, including dozens of homeobox genes and other genes implicated in cancer. Thus, we reason that the disturbance of bivalent chromatin may be intimately linked to tumorigenesis.
16

Decreased JMJD3 expression in mesenchymal stem cells contributes to longterm suppression of osteoblast differentiation in multiple myeloma

Zhao, Wei 05 April 2018 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Multiple myeloma (MM) is the most frequent cancer to involve the skeleton, with over 80% of myeloma patients developing lytic bone disease (MMBD). Importantly, MM-associated bone lesions rarely heal even when patients are in complete remission. Bone marrow stromal cells (BMSCs) isolated from MM patients have a distinct genetic profile and an impaired osteoblast (OB) differentiation capacity when compared to BMSCs from healthy donors. Utilizing an in vivo model of MMBD and patient samples, we showed that BMSCs from tumor-bearing bones failed to differentiate into OBs weeks after removal of MM cells. Both Runx2 and Osterix, the master transcription factors for OB differentiation, remained suppressed in these BMSCs. However, the molecular mechanisms for MM-induced long-term OB suppression are poorly understood. We characterized both Runx2 and Osterix promoters in murine pre-osteoblast MC4 cells by chromatin immunoprecipitation (ChIP). The transcriptional start sites (TSSs) of Runx2 and Osterix in untreated MC4 cells were co-occupied by transcriptionally active histone 3 lysine 4 tri-methylation (H3K4me3) and transcriptionally repressive histone 3 lysine 27 tri-methylation (H3K27me3), termed the “bivalent domain”. These bivalent domains became transcriptionally silent with increasing H3K27me3 levels when MC4 cells were co-cultured with MM cells or treated with TNF-α, an inflammatory cytokine increased in MM bone marrow microenvironment. The increasing H3K27me3 levels induced by MM cells or TNF-α were associated with the downregulation of the H3K27 demethylase JMJD3 in MC4 cells and murine BMSCs. Knockdown of JMJD3 in MC4 cells was sufficient to inhibit OB differentiation. Further, ectopic overexpression of JMJD3 in MC4 cells partially rescued the suppression of osteoblast differentiation induced by TNFa. We also found that pre-incubation of MC4 cells with the NF-kB inhibitor quinazoline (QNZ) before TNF-a treatment prevented the downregulation of JMJD3. In agreement with our in vitro findings, BMSCs from MM patients had persistently decreased JMJD3 expression compared to healthy BMSCs. Our findings together demonstrate that decreased JMJD3 expression in BMSCs contributes to the long-term OB suppression in MMBD by remodeling histone landscapes at the Runx2 and Osterix TSSs. Thus, developing strategies to restore JMJD3 expression in BMSCs should increase bone formation and possibly decrease tumor burden in MM.
17

Molecular, Biochemical, and Toxicological Evaluation of Anticholinesterases for control of the Malaria Mosquito, Anopheles gambiae

Mutunga, James Mutuku 26 May 2011 (has links)
Pyrethroids are the only class of insecticides approved by the World Health Organization (WHO) for use in insecticide treated nets (ITNs), the first line of malaria vector control. Widespread resistance development to pyrethroids undermines current control efforts, and hence an urgent need for alternative chemistries. I report the evaluation of pharmacological differences between insect and vertebrate acetylcholinesterase (AChE) as well as selectivity and toxicity testing of new carbamate insecticides on Anopheles gambiae, the African malaria mosquito. AChE gorge pharmacology data revealed differences between insect and vertebrate AChE that can be exploited in the design of a bivalent insecticide. Toxicokinetic analysis showed that metabolic detoxication and cuticular penetration affect toxicity of carbamates in a manner dependent on the chemical structure. Structure activity relationships of side-chain branched N-methylcarbamates emphasized the importance of structural complementarity of ligands to the AChE catalytic active site and the substrate, acetylcholine. Monovalent pyrazoles and acetophenone oxime carbamates were toxic to both susceptible and carbamate-resistant mosquitoes carrying a G119S mutation within the catalytic site. A bivalent phthalimide-pyrazole carbamate and sulfenylated phenyl N-methyl carbamates were highly toxic when topically applied onto insect but less toxic by treated filter paper assays. In vitro evaluation of a molecular mosquito-selectivity model using AChE peripheral site ligands confirmed that selectivity of PRC 472 was due to presence of I70 in mosquito, which is Y70 in human AChE. The findings presented here are important steps in the on-going search of a mosquito-selective and resistance mitigating carbamate insecticide for control of malaria mosquitoes. / Ph. D.
18

Conception et synthèse d’hétérocycles azotés et de dérivés stéroïdiens, modulateurs potentiels de transporteurs ABC (glycoprotéine-P) / Design and synthesis of azaheterocycles and steroidal bivalent ligands as potential inhibitors of ABC membrane transporters (P-glycoprotein)

Zeinyeh, Waël 17 December 2010 (has links)
La multichimiorésistance est caractérisée par une résistance simultanée à des agents chimiothérapeutiques de structures diverses, induite notamment par l’efflux des substances actives hors des cellules. Les transporteurs ABC (ATP-Binding Cassette) sont des protéines transmembranaires impliquées dans cet efflux et qui participent à l’échec du traitement de certains cancers. Par ailleurs, ce mécanisme d’efflux a également été évoqué dans le cadre de la résistance de certains microorganismes aux antimicrobiens. Dans cette étude, nous avons conçu et synthétisé des dérivés susceptibles d’inhiber certains transporteurs ABC, en particulier, la glycoprotéine-P (Pgp) impliquée dans la multichimiorésistance des tumeurs humaines, et CpABC3, rencontré chez le parasite Cryptosporidium parvum. Dans un premier temps, nous avons synthétisé trois dérivés de type 4-alkyl-imidazo[4,5-b]pyridin-7-one, hétérocycles destinés à se fixer sur le site à ATP des transporteurs ABC. L’activité de ces composés a été évaluée vis-à-vis d’un fragment recombinant (H6-NBD1) de CpABC3, et un de ceux-ci a montré une liaison (faible) à ce fragment. Nous avons ensuite préparé dix-sept dérivés bivalents susceptibles d’inhiber la Pgp, constitués d’une molécule d’adénine (ciblant le site à ATP) reliée à la progestérone (ciblant le site aux stéroïdes) par un bras de géométrie variable. Ces dérivés ont été testés sur des lignées cellulaires K562/R7 surexprimant la Pgp, et un de ceux-ci a montré une activité supérieure à celle de la progestérone. Enfin, nous avons mis au point une synthèse de chaînes de type oligocyclohexylidène, qui sont de bons candidats pour constituer des bras espaceurs rigides / Multi-drug resistance (MDR) is characterized by a simultaneous resistance to a wide range of structurally unrelated chemotherapeutic agents, partly caused by the efflux of active compounds out of the cell. ABC transporters (ATP-Binding Cassette) are transmembrane proteins implicated in this efflux, and thus, they contribute to the failure of some cancer treatments. Furthermore, this mechanism was evoked in some microorganism resistances to antimicrobial agents. In this study, we designed and synthesized potential inhibitors of ABC transporters, especially P-glycoprotein (Pgp) implicated in human tumors multi-drug resistance, and CpABC3, a transporter found in a human parasite, Cryptosporidium parvum. First, we synthesized three 4-alkyl-imidazo[4,5-b]pyridin-7-one derivatives, targeting ATP-binding site of ABC transporters. Their biological activities were evaluated toward a recombinant fragment of the CpABC3 transporter (H6-NBD1 fragment). One of these compounds showed a weak-binding to this fragment. Next, we prepared seventeen progesterone-adenine hybrids as potential bivalent ligands which may bind simultaneously to the ATP-binding site and the steroid-binding region. We chose to synthesize derivatives with rather short-length linkers with different conformational flexibilities. These bivalent compounds were tested on K562/R7 human leukemic cells overexpressing Pgp. One of them has showed a better activity than progesterone. Finally, we optimized the synthesis of oligocyclohexylidene chains, which are good candidates to constitute rigid linkers
19

Síntese, caracterização e estudo termoanalítico dos succinatos de alguns metais de transição bivalentes no estado sólido /

Caires, Flávio Junior. January 2011 (has links)
Orientador: Massao Ionashiro / Banca: João Olímpio Tognolli / Banca: Eder Tadeu Gomes Cavalheiro / Resumo: Esse trabalho descreve a síntese e caracterização dos succinatos de metais de transição bivalentes, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), no estado sólido. Inicialmente prepararam-se os carbonatos dos respectivos íons metálicos adicionando-se lentamente e sob agitação solução saturada de hidrogeno carbonato de sódio à solução de cloreto (Mn, Co, Ni, Zn) ou sulfato (Fe, Cu), até precipitação completa dos íons metálicos. Os succinatos foram obtidos fazendo-se reagir os carbonatos dos íons metálicos com solução de ácido succínico. Os compostos sintetizados foram estudados empregando termogravimetria e análise térmica diferencial simultânea (TG-DTA), termogravimetria derivada (DTG), calorimetria exploratória diferencial (DSC), difratometria de raios X pelo método do pó, espectroscopia no infravermelho, termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR) e complexometria. Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, modos de coordenação etc. Também foi possível identificar os produtos liberados durante o aquecimento. Os resíduos finais foram Mn3O4, Fe2O3, Co3O4, NiO, CuO e ZnO / Abstract: In this work, the synthesis and characterization of bivalent transition metal ion succinates in the solid state, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), are described. Firstly, the respective metal ion carbonates were prepared by slow addition of sodium hydrogen carbonate saturate solution to the chloride (Mn, Co, Ni, Zn) or sulphate (Fe, Cu) solution under continuous magnetic stirring until complete precipitation of the metal ions. The succinates were obtained by reacting carbonate of the metal ions with succinic acid solution. The synthesized compounds were characterized by simultaneous thermogravimetry and differential thermal analysis (TGDTA), Thermogravimetry derivative (DTG), differential scanning calorimetry (DSC), Xray powder diffractometry, infrared spectroscopy, thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR) and complexometry. The results provided information about the thermal behavior, crystallinity, modes of coordination etc. It was also possible to identify the products evolved during heating. The final residues were Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO / Mestre
20

Investigação das propriedades fotofísicas do Morin complexado com cátions de magnésio bivalente e cério trivalente / Investigation of photophysical properties of the Morin complexed with cations of bivalent magnesium and trivalent cerium

Arandas, Anderson Marcelino de 25 February 2015 (has links)
As propriedades fotofísicas dos complexos morin-Mg2+ e morin-Ce3+, foram investigadas em solução metanólica, em filmes finos de polímeros e em nanozéolitas por técnicas de fluorescência. A associação do metal ao flavonoide ocorre no sítio da carbonila do anel pirona nas razões estequiométricas de 1:1 e 1:2 (magnésio: morin), e esta associação favorece no aumento considerável da intensidade de fluorescência devido à inibição da transferência intramolecular do próton no estado excitado. Os resultados revelaram que os espectros de emissão do complexo morin-Mg2+ sofreram um pequeno deslocamento hipsocrômico. Os decaimentos de fluorescência do sistema Morin-Mg2+ são triexponenciais para o complexos Morin-Mg2+ formados com tempo de vida máximo de 3 ns. O complexo morin-Ce3+ é pouco fluorescente e a complexação com o metal leva a supressão de fluorescência devido a sua natureza paramagnética. A estequiometria aparente dominante é de um 1:1 e o decaimento possui um componente de tempo de vida longo de 4-5 ns. Na comparação das propriedades de fluorescência do morin-Mg2+ com o indicador magnesium green verificamos que ambos são bons indicadores fluorescentes para a microscopia de fluorescência podendo esses complexos serem usados na detecção de Mg2+ em nanozeólita e outros sistemas / The photophysical properties of the molecular complexes of morin with Mg2+ and Ce3+ cations in methanol solution as well as in thin polymeric films and nanozeolytes have been investigated by using fluorescence spectroscopy and microscopy. The association of morin with Mg2+ occurs at the (4)-carbonyl group of the pyrone ring at 1:1 and 1:2 stoichiometric ratio. The complexes have shown an increase of the emission quantum yield by precluding the excited state deactivation though the intramolecular proton transfer process. The fluorescence decays of the complexes are non exponential due to the presence of more than one emission species and the average decay time found was about 3 ns. On the other hand, the addition of Ce3+ to morin solution resulted in fluorescence quenching ascribed to 1:1 non emissive complex due to the paramagnetic nature of the metal cation. The fluorescence properties of morin-Mg2+ complex have been compared with the standard fluorescence indicator magnesium green. The results pointed out that morin-Mg2+ may be used as an alternative low coast indicator of Mg2+ in homogenous as well as in microheterogeneous media.

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