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Amaral, Thaeny Costa. "Síntese, caracterização e estudo biológico de compostos de rutênio, platina, paládio e ouro com o ligante dicloridrato de N,N’-bis (tiofenil-2-metil) etano-1,2-diamina." Universidade Federal de Juiz de Fora (UFJF), 2017. https://repositorio.ufjf.br/jspui/handle/ufjf/5506.
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No presente trabalho foram descritas as sínteses e as caracterizações do ligante dicloridrato de N,N'-bis(tiofenil-2-metil)etano-1,2-diamina (BNHred.2HCl), dos seus complexos [RuCl2BNHred(PPh3)2], [PtCl2BNHred] e [PdCl2BNHred] e dos sais [BNHred.2H+][PtCl4] e [BNHred.2H+][Au(CN)2]2-. Os compostos foram caracterizados por análise elementar (C, H, N), técnicas espectroscópicas no IV, Raman e RMN (solução e estado sólido), difração de raios X (DRX) por policristais e cálculos de DFT. Para os complexos [PtCl2BNHred] e [PdCl2BNHred] os resultados obtidos pelas técnicas de caracterização corroboram que a coordenação ocorreu pelos átomos de nitrogênio do grupo NH e por dois íons cloretos formando complexos com estrutura quadrática. O complexo [RuCl2BNHred(PPh3)2] teve sua estrutura determinada por DRX por policristais onde foi encontrada a estrutura com geometria octaédrica, tendo o íon Ru(II) coordenado aos grupos NH, de forma quelato, duas PPh3 e dois íons cloreto. Os sais [BNHred.2H+][PtCl4] e [BNHred.2H+][Au(CN)2]2- também tiveram suas estruturas determinadas por DRX (policristais), onde o sal [BNHred.2H+][Au(CN)2]2- se cristaliza em um sistema cristalino ortorrômbico e grupo espacial Pnn2 e o sal [BNHred.2H+][PtCl4] cristaliza-se no sistema triclínico e grupo espacial P-1. Além desses compostos, também foi sintetizado e caracterizado o ligante dinitrato de N,N'-bis(tiofenil-2metil)etano-1,2-diamina (BNHred.2HNO3), no qual teve a estrutura cristalina determinada por DRX (policristais), pertencendo ao sistema cristalino monoclínico e grupo espacial P21/c. Testes biológicos contra Mycobacterium tuberculosis, de todos os compostos obtidos foram realizados, onde o sal [BNHred.2H+][Au(CN)2]2- apresentou o CIM90 de 2,31 mg/L.
The present work, syntheses and characterizations of the ligand N,N’-bis(tiophenyl-2methyl)ethane-1,2-diamino dichlorydrate (BNHred.2HCl), their [RuCl2BNHred(PPh3)2], [PtCl2BNHred] and [PdCl2BNHred] complexes and their [BNHred.2H+][PtCl4] and [BNHred.2H+][Au(CN)2]2- salts were described. The compounds were analyzed by elementare analysis (C, H and N), IR, Raman and NMR (in solution and solid state) spectroscopies as well by powder X ray diffraction and DFT calculations. The [PtCl2BNHred] and [PdCl2BNHred] complexes should be square planar geometry since ligand is coordinated by nitrogen atoms of the NH groups and the coordination sphere is completed by two chlorine ions. The octahedral [RuCl2BNHred(PPh3)2] complex structure was determined/refined by powder X ray diffraction where the Ru(II) ion is coordinated by ligand in chelate mode, also by two PPh3 molecules and by two chloride ions. The [BNHred.2H+][PtCl4] and [BNHred.2H+][Au(CN)2]2- salt structures were also solved by powder X ray diffraction. [BNHred.2H+][Au(CN)2]2- salt crystallizes in orthorhombic system and space group Pnn2, while the [BNHred.2H+][PtCl4] salt belongs to triclinic system and space group P-1. In addition, the ligand N,N’-bis(tiophenyl-2-methyl)ethane-1,2-diamino dinitrate (BNHred.2HNO3) was also synthetized and fully characterized. The BNHred.2HNO3 structure was obtained by powder X ray diffraction and presents a monoclinic crystalline system and space group P21/c. Biological tests against Mycobacterium tuberculosis of all the obtained compounds have been carried out, where the [BNHred.2H+][Au(CN)2]2- salt has been shown MIC90 at 2.31 mg/L.
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Silva, Silvioney Augusto da. "Síntese, caracterização e avaliação da atividade antituberculose de complexos de prata e zinco com a base de Schiff N,N´-bis(tiofenil-2-metilideno)etano-1,2-diamina." Universidade Federal de Juiz de Fora (UFJF), 2014. https://repositorio.ufjf.br/jspui/handle/ufjf/4321.
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No presente trabalho a base de Schiff, N,N’-bis(tiofenil-2-metilideno)etano1,2-diamina (BNH), foi obtida a partir da reação de condensação entre etilenodiamina (en) e 2-tiofenocarboxaldeído (TCA) usando a proporção molar 1:2 (en:TCA). Dois novos complexos de prata(I) com BNH foram preparados reagindo BNH:AgNO3. Quando a proporção molar de 1:1 (M:L) foi usada, o complexo polimérico [Ag(BNH)NO3]n foi obtido, onde os íons Ag(I) são coordenados por 2 N (grupo imina) de dois ligantes diferentes e um oxigênio do grupo nitrato. Quando a proporção molar de 1:2 (M:L) foi usada um complexo monomérico e quelato - [Ag(BNH)2]NO3 foi obtido. Neste complexo os íons prata(I) são coordenados por 4 N (grupo imina) de dois ligantes. Da mesma forma, complexos de zinco(II) também foram testados, mas as reações entre o BNH e ZnCl2 em 1:1 ou 1:2 (M:L) resultam no mesmo complexo formulado como [Zn(Cl)2(BNH)], onde o BNH se coordena ao íon Zn(II) pelos átomos de N (imina) e dois íons cloro completam a tetracoordenação em torno do íon zinco(II). Os compostos foram caracterizados por análises elementar (C, H, N) e térmica (TG/DTA), técnicas espectroscópicas de IV, Raman, Ressonância Magnética Nuclear e difração de raios X por monocristal e policristais. Além dos dados estruturais, analíticos, e espectroscópicos, foram realizados estudos biológicos. As propriedades antibacterianas e citotóxicos do BNH e de seus três complexos metálicos foram testadas com base na atividade AntiMBT e IC50 utilizando células VERO. Além disso, dois ligantes – N,N’-bis(tiofenil2-metil)-etano-1,2-diamina (obtido pela redução do BNH) e seu derivado cloridrato, foram sintetizados e parcialmente caracterizados. Um sal de ouro(III) também foi obtido e caracterizado por simples reação entre o cloridrato da diamina e o sal K[AuCl4].
In the present work the Schiff base, N,N’-bis(thiophenyl-2-methylidene) ethane-1,2-diamine (BNH), was obtained from condensation reaction between ethylenediamine (en) and 2- thiophenecarboxaldehyde (TCA) using molar ratio1:2 (en:TCA). Two new silver(I) complexes with BNH were prepared by reacting BNH:AgNO3. When 1:1 molar ratio (M:L) was used, the polymeric complex [Ag(BNH)NO3]n is obtained where Ag(I) ions are coordinated by 2 N (imine group) from two different ligands and one oxygen from nitrate group. When 1:2 molar ratio (M:L) is used a monomeric and chelated complex – [Ag(BNH)2]NO3 was obtained. In this complex silver(I) ions are surrounded by 4 N (imine group) from two ligands. In the same way, the zinc(II) complexes were also tested, but the reactions between the BNH and ZnCl2 in 1:1 or 1:2 (M:L) result in the same complex formulated as [Zn(Cl)2(BNH)], where BNH is coordinated to Zn(II) ions by N (imine) and two chlorine ions complete the tetracoordination around zinc(II) ions. The compounds were characterized by elemental (C, H, N) and thermal analyzes (TG/DTA), IR, Raman, and Nuclear Magnetic Resonance spectroscopic techniques and X rays diffraction - monocrystal and powder. Besides the analytical, spectroscopic and structural data, the biological studies were performed. The antibacterial and cytotoxic properties of BNH and its three metal complexes were tested based on the activity Anti-MBT and IC50 using VERO cells. In addition, two ligands – N,N’-bis(thiophenyl-2-methyl)ethane-1,2-diamine (obtained by BNH reduction) and its hydrochloric derivative were synthesized and partially characterized. A gold(III) salt was also obtained and characterized by simple reaction between the diamine‘s hydrochloride and K[AuCl4] salt.
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Mitchell, Preston Lincoln. "The synthesis of novel Câ†2 chiral diamine ligands." Thesis, University of Southampton, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.368126.
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Jones, Marlon D. "CHIRAL 1, 2-DIAMINO GUESTS IN CHAIN REPLACEMENT PEPTIDOMIMETICS: A NEW HELICAL MOTIF." UKnowledge, 2007. http://uknowledge.uky.edu/gradschool_diss/487.
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Peptides are short, sequence and length specific oligomers composed of small amino acid residues. Nature has refined these peptide sequences and their endogenous function through evolution. In addition, peptides have played an important role in medicine, which has lead to further research into developing peptides as lead pharmaceuticals (therapeutic peptides). Unfortunately, therapeutic peptides are inferior as drug candidates due to their low oral bioavailability; immunogenicity and potential to be attacked by peptidases. Fortunately, peptides can be modified by steric constraints, cyclization, and/or replacement of the peptide backbone itself creating a mimic (peptidomimetic) of the original peptide. Peptidomimetics are deliberately designed to have increased protease resistance, reduced immunogenicity and improved bioavailability when compared to the original endogenous peptide. One such peptide, Magainin is a O One such peptide, Magainin is a well-studied, a-helical peptide found in African clawed frogs. This peptide has antibiotic properties (against pathogenic bacteria), which partly arises from the hydrophilic portion of the peptide having basic amino acid side chains periodically disposed on one side of the a-helix. This property of magainin causes its attraction to negatively charged bacteria cell membranes. Unfortunately, as in the case of other antibiotics, pathogenic bacteria have developed effective countermeasures against magainin. We designed a peptidomimetic based on magainin and implemented a plan to determine what type of molecules could be assembled for a magainin mimic. We successfully utilized molecular modeling (Monte Carlo conformational search), as well as results from previous experiments to elucidate what type of molecules, as well as how many molecules would be necessary to create a novel helical-like magainin peptidomimetic. It was discovered that C2 symmetric diamines would be best at generating the helical-like motif and the amino acid lysine to generate the basic side chain. The next step was the successful connection of two C2 symmetric molecules via a urea linkage and then one more connection to a lysine (a-amino group) residue, creating a short sequence of oligoureas (trimers). Finally, attempts to connect the oligoureas trimers were attempted using a solid-phase synthesis approach to generate a functional magainin mimic.
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Blond, Aurélie. "Synthèse orientée vers la diversité de cis-1,3-diamines pipéridiniques et cyclohexaniques : ligands potentiels d’ARN." Thesis, Paris 5, 2014. http://www.theses.fr/2014PA05P617.
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AUJARD, ISABELLE. "Nouvelle synthese de diamines chirales de symetrie c#2. Utilisation des diamines dans des reactions d'oxydation et de reduction." Paris 6, 1996. http://www.theses.fr/1996PA066458.
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La synthese de diamines 1,2 de symetrie c#2 s'effectue le plus souvent par couplage reducteur de l'imine correspondante et conduit generalement au melange equimoleculaire des diastereoisomeres d,1 et meso. Ce dernier est inutilisable en synthese asymetrique. Nous presentons une nouvelle methode de synthese facilement realisable a grande echelle (>200 g) de diamines secondaires chirales issues d'aldehydes aromatiques. Le couplage reducteur a lieu en presence de zinc associe au me#3sicl. Le melange equimoleculaire d,1/meso ainsi obtenu est ensuite isomerise, de facon simple et rapide, en diamine d,1 par le couple li metal/isoprene. Le dedoublement s'effectue avec de l'acide tartrique chiral. Lors de nos recherches sur l'isomerisation, nous avons observe que les aminals de ces diamines pouvaient etre oxydes en monoamides en presence d'alcool (meoh) et d'une quantite catalytique de palladium sur charbon. L'utilisation d'ultrasons permet une reaction douce et rapide. Associees a lialh#4, ces diamines peuvent egalement conduire a la reduction directe de derives d'acides carboxyliques en aldehydes. Les diamines sont utilisees pour modifier le pouvoir reducteur de l'hydrure et pieger sous forme d'aminal l'aldehyde forme in situ. Une hydrolyse acide de ces aminals libere ensuite l'aldehyde attendu
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Sillén, Sara. "Photodegradation study of 3,5-diamino-6-chloro- N-(2-(methylamino)ethyl)pyrazine-2-carboxamide using preparative SFC and LC-MS." Thesis, Uppsala universitet, Institutionen för farmaci, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-301500.
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In this project the photodegradation of 3,5-diamino-6-chloro-N-(2-(methylamino)ethyl)pyrazine-2-carboxamide was studied. A hypothetical degradation pattern for the compound was proposed and the aim of the project was to study the formed secondary photodegradants and to, if possible, structure elucidate some of these compounds. In order to do this, the parent compound was photodegraded in two steps, where a primary photodegradant was isolated using semi-preparative supercritical fluid chromatography (SFC) and then further degraded into the secondary photodegradants. The photodegradation was first carried out in aqueous solution, where the parent compound was irradiated in UV-A light of 300-400 nm. This resulted in a primary photodegradant with a molecular ion of m/z = 227, where the chloride in position 6 of the pyrazine group had been replaced by a hydroxyl group. During the large scale photodegradation, prior to the preparative purification, the yield of primary photodegradant was very low due to the photodegradation being dependent on both sample volume and concentration and due to the primary photodegradant also being unstable in aqueous solution at room temperature. Due to the above mentioned difficulties the parent compound was photodegraded in methanol instead of water in order to avoid the freeze-drying process where a lot of the primary photodegradant was lost. This resulted in a primary photodegradant with a molecular ion of m/z = 241, where the chloride had been replaced by a methoxy group instead of a hydroxyl group. This compound was more stable which allowed workup by rotary evaporation, instead of freeze-drying, before the preparative purification. This primary photodegradant was isolated using semi-preparative SFC on a Viridis® BEH Prep OBD TM column (250 x 30 mm, 5 µm) and a Luna HILIC column (250 x 30 mm, 5 µm) with MeOH/NH3 100/1 v/v as organic modifier. About 1.2 mg material was isolated and further photodegradation tests in ordinary water and 18O-water were conducted. Some secondary photodegradants were observed in LC-MS analyses, and their element compositions were proposed by accurate mass results. Fundamental structures for these compounds were proposed. Further structural investigational analyses are needed for confirmation in the future.
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Llop, Escorihuela Esther. "Structural analysis of eythropoietin glycans." Doctoral thesis, Universitat Pompeu Fabra, 2008. http://hdl.handle.net/10803/7129.
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La eritropoyetina o EPO es una hormona glicoproteica. En los seres humanos adultos, se produce principalmente en el riñón, en respuesta a la reducción de oxígeno en los tejidos (hipoxia tisular). La EPO estimula la eritropoyesis, es decir, estimula a las células madre de la médula ósea para que aumenten la producción de eritrocitos. La molécula de EPO está formada por una cadena peptídica de 165 aminoácidos que contiene dos puentes disulfuro, un O-glicano (Ser-126), y tres N-glicanos (Asn-24, 38, 83). En conjunto, la glicosilación de esta proteína representa aproximadamente el 40% del peso total (29.4 kDa). La EPO sintetizada con tecnología recombinante (rEPO) se administra como fármaco, desde el año 1989, para el tratamiento de anemias, insuficiencia renal, cancer etc. También se ha observado la utilización de rEPO en deportistas con el fin de aumentar el suministro de oxígeno a los tejidos y así incrementar el rendimiento en deportes de resistencia. En el año 2001, se comercializó una "nueva proteína estimuladora de la eritropoyesis" llamada NESP. Esta proteína es un análogo hiperglicosilado de la EPO que posee dos N-glicanos adicionales (Asn-30, 88). El número y composición de los N-glicanos es muy importante para el metabolismo de estas glicoproteínas, ya que el contenido de carbohidratos (número de ácidos siálicos) determina su vida media. Los métodos que se utilizan actualmente para diferenciar la eritropoyetina endógena urinaria (uEPO) de sus análogos recombinantes (rEPO, NESP) están basados en las diferencias que existen entre sus perfiles isoelectroforéticos (IEF). Se cree que estas diferencias provienen de las células y/o especies en las que se expresan estas glicoproteínas. En este estudio, se llevo a cabo la caracterización estructural de diferentes preparaciones de EPO recombinante. Para ello, se utilizaron las técnicas más comunes en el campo de la glicoproteómica además de otras nuevas, desarrolladas para poder analizar los glicanos de muestras procedentes de geles 2-DE. Los perfiles de glicosilación total de cada una de estas glicoproteínas mostraron características estructurales que pueden facilitar la detección de rEPO y NESP en atletas que abusan de estas sustancias. Un ejemplo es la presencia de Neu5Gc únicamente en fármacos que han sido expresados en células CHO. La metodología desarrollada en este trabajo, podría emplearse también, para el control de calidad de estos fármacos y para el diagnóstico de ciertas patologías.Erythropoietin (EPO) is a glycoprotein hormone secreted primarily by adult kidneys in response to tissue hypoxia. It is involved in the maturation and ultimately regulation of the level of red blood cells. The EPO molecule comprises a single polypeptide chain of 165 aminoacids with two disulfide bonds, 1 O-linked (Ser-126), and 3 N-linked (Asn-24, 38, 83) glycans representing about 40% of the total mass (29.4 kDa). The recombinant analogue (rEPO), available since 1989 has found widespread use in the treatment of anaemia, renal failure, cancer etc. Besides, rEPO is illicitly used by athletes to boost the delivery of oxygen to the tissue and enhance performance in endurance sports. In 2001, a novel erythropoiesis-stimulating protein (NESP) was also marketed. NESP possesses two additional N-glycans (Asn-30, 88). The number and composition of the N-glycans is very important in the metabolism of this glycoprotein because the carbohydrate content (sialylation degree) determines its half-life time. Current tests to differentiate between urinary endogenous (uEPO) and its recombinant analogues (rEPO, NESP) are based on differences in their iso-electric focussing (IEF) profiles. Those differences are believed to stem from the cells/species in which they are expressed. In this study, the structural characterisation of different rEPO preparations was conducted using standard techniques in the field and developing new ones to address glycans from 2-DE sample preparations. Overall glycosylation profiling of each glycoprotein revealed structural features that may pave the way to the unambiguous detection of rEPOs and NESP abuse, such as the presence of Neu5Gc in CHO cell derived drugs only, and the developed methodology may be also employed for maintaining pharmaceutical quality control and for diagnosing pathologic conditions.
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Weder, Christoph. "Synthese und Charakterisierung neuer Polyamide mit stabilen nichtlinear optischen Eigenschaften, basierend auf 2',5'-Diamino-4-(dimethylamino)-4'-nitrostilben /." [S.l.] : [s.n.], 1994. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=10749.
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Hing, Sherry Ann Ong 1957. "COPPER DEFICIENCY AND HYPERLIPOPROTEINEMIA INDUCED BY N,N'-BIS-(2-AMINOETHYL)-1,3-PROPANE DIAMINE (2,3,2-TETRAMINE) IN RABBITS (CHELATORS)." Thesis, The University of Arizona, 1986. http://hdl.handle.net/10150/276804.
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Medou, Ovono Cosmas Martial. "Conception, synthèse et évaluation virologique (VIH) de nouveaux composés peptidomimétiques dérivés du synthon 1-thiophenoxy-1,3-diamino-2-hydroxypropane." Aix-Marseille 2, 2000. http://www.theses.fr/2000AIX22025.
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SEDRANI, RICHARD. "Utilisation en synthese asymetrique d'imidazolidines derivees de diamines chirales possedant un axe de symetrie c#2." Paris 6, 1990. http://www.theses.fr/1990PA066318.
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La condensation de diamines chirales possedant un axe de symetrie c#2 avec des aldehydes permet d'acceder a des imidazolidines chirales sans qu'il y ait creation d'un nouveau centre asymetrique au cours de cette etape. Dans un premier temps, l'addition conjuguee d'especes phenylcuivreuses, substituees en ortho par un groupement imidazolidine chiral, sur des enones et des enoates a ete etudiee. Les diastereoselectivites observees ont ete moyennes. L'approche inverse, c'est-a-dire l'addition 1,4-d'organocuprates sur des cinnamates substitues en ortho par un groupement imidazolidine chiral, a permis d'atteindre des stereoselectivites tres elevees (superieures a 90%). Dans certains cas, la presence de trimethylchlorosilane a provoque une inversion du deroulement stereochimique de l'addition conjuguee. L'addition 1,2 d'especes organometalliques sur des monoimidazolidines chirales du phtalaldehyde a egalement ete etudiee. Ces reactions ont permis d'atteindre des stereoselectivites superieures a 90%
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Soares, Chrislaine Oliveira. "Mecanismos moleculares da ação tóxica pró-oxidante de 1,4-diamino-2-butanona, um análogo de putrescina, sobre células de mamíferos e Trypanosoma cruzi." Universidade de São Paulo, 2012. http://www.teses.usp.br/teses/disponiveis/46/46131/tde-04092012-112933/.
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Compostos α-aminocarbonilícos como ácido 5-aminolevulínico (ALA) e aminoacetona (AA) apresentam um grande potencial pró-oxidante, pois sofrem reações de enolização e subseqüente oxidação aeróbica, com a formação de espécies radicalares de oxigênio, íons NH4+ e α-oxoaldeídos potencialmente citotóxicos. A α-aminocetona 1,4-diamino-2-butanona (DAB), um análogo da putrescina, é um agente microbicida de vários parasitas incluindo Trypanosoma cruzi. Acredita-se que o mecanismo de morte desencadeado por DAB nos parasitas seja por meio da inibição competitiva da ornitina descarboxilase (ODC), importante enzima do metabolismo de poliaminas, muito embora tenha sido observado de igual forma danos oxidativos nestes parasitas quando tratados com DAB. O objetivo deste trabalho é esclarecer o mecanismo de oxidação química de DAB e sua ação pró-oxidante à cultura de células de mamíferos (LLC-MK2 e RKO), assim como sua atividade microbicida contra tripomastigotas de Trypanosoma cruzi. Demonstramos aqui que DAB, quimicamente similar ao ALA e AA, sofre reação de oxidação catalisada por íons fosfato, e por íons de metais de transição como Fe(II) e Cu(II), resultando na formação de radicais de oxigênio, H2O2, NH4+, 2-oxo-4-aminobutanal como produto principal da oxidação de DAB e de compostos ciclicos de caracter pirrólico. Danos oxidativos observados em ferritina, apotransferrina e liposomos de cardiolipina e fosfatidilcolina (20:80) contribuem para a nossa hipótese de ação pró-oxidante de DAB. O tratamento de células de mamíferos das linhagens LLC-MK2 (IC50 1,5 mM, tratamento de 24 h) e RKO (IC50 0,3 mM, tratamento de 24 h) com DAB levou à alteração do balanço redox celular, à ativação de resposta antioxidante e ao desencadeamento de morte celular via apoptose e parada de ciclo celular. Em culturas de tripomastigotas de T. cruzi o tratamento com DAB culminou na redução da motilitidade e viabilidade destes parasitas (IC50 0,2 mM, tratamento de 4 h), assim como depleção do conteúdo tiólico acompanhado pelo aumento da atividade de TcSOD. Além do mais, DAB mostrou-se eficiente em limitar a invasão de tripomastigotas às células hospedeiras (LLC-MK2) e reduzir a proliferação de amastigotas intracelulares, contudo fortemente relacionada à necrose das células hospedeiras infectadas, uma vez que são alvos mais susceptíveis de ação oxidativa. Estes resultados suportam nossa hipótese que DAB exerce ação pró-oxidante e contribui deste modo com o mecanismo já descrito de morte celular associada à inibição da biossíntese de poliaminas em vários microorganismos.α-Aminocarbonyl componds such as 5-aminolevunilic acid (ALA) and aminoacetone (AA) have been shown to exhibit pro-oxidant properties. These compounds undergo phosphate-catalyzed enolization in physiological pH and subsequent aerobic oxidation, yielding reactive oxygen species, NH4+ ions and an α-oxoaldehyde highly cytotoxic. The α-aminoketone 1,4-diamino-2-butanone (DAB) is a putrescine analogue and a microbicidal agent to various parasites including Trypanosoma cruzi. The mechanism of DAB toxicity to these parasites is attributed to DAB competitive inhibition of ornithine decarboxylase (ODC), a key enzyme on polyamine biosynthesis, although it has also been shown DAB isto implicated in oxidative damage to these parasites. Our aim is to clarify the mechanism of DAB aerobic oxidation and of its putative pro-oxidant activity to mammalian cell cultures (LLC-MK2 and RKO cell linages) and to Trypanosoma cruzi trypomastigotes. Here we show that, similar to ALA and AA, DAB undergoes aerobic oxidation in presence of phosphate ions and of transition metal ions such as Fe(II) and Cu(II), yielding oxygen radicals, H2O2, NH4+ and 2-oxo-4-aminobutanal accompanied by its condensation cyclic products displaying pyrrolic characteristics. Oxidative alterations to ferritin, apotransferrin and liposomes of cardiolipin and phosphatidylcholine (20:80) were observed under DAB treatment strongly supporting our hypothesis of DAB pro-oxidative activity. DAB treatment of mammalian cultured cells LLC-MK2 (IC50 1.5 mM, 24 h incubation) and RKO (IC50 0.3 mM, 24 h incubation) resulted in redox imbalance, induction of antioxidant response, activation of apoptosis pathway and cell cycle arrest. DAB is shown here to trigger Trypanosoma cruzi trypomastigotes decreased parasite motility and viability (IC50 0.2 mM, 4 h incubation), as well as redox thiol imbalance parallel to increase TcSOD activity. In addition, DAB efficiently hampered host cell (LLC-MK2) invasion by trypomastigotes. In addition, intracellular amastigotes showed to be susceptible to DAB toxicity, although strongly related to necrosis of infected host cells, which are more vulnerable to oxidative stress. Altogether, these data support our hypothesis that oxidative stress contributes to DAB cytotoxicity.
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Lavaud, Lucien. "Des diamino-benzoquinone-diimines aux azacalixphyrines : développement de colorants émergents du proche infrarouge." Thesis, Aix-Marseille, 2018. http://www.theses.fr/2018AIXM0404/document.
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Les colorants organiques du proche infrarouge présentent un intérêt majeur dans différent secteurs technologiques. Les travaux présentés dans cette thèse portent sur le développement de ce type de chromophores à partir d’unités quinones possédant une conjugaison électronique particulière : les 2,5-diamino-1,4-benzoquinone-diimines (DABQDI). De nouvelles DABQDI ont pu être synthétisées et leur utilisation comme ligand a notamment permis d’obtenir des complexes absorbant du domaine visible jusqu’à celui du proche infrarouge. Ces unités DABQDI ont également pu être incorporées au sein de macrocycles, analogues de porphyrines, appelés azacalixphyrines, capables d’absorber la lumière jusqu’à 1000 nmNear infrared dyes play a significant role in various technological sectors. The present PhD manuscript concerns the development of such chromophores built on quinone units that have a particular electronic delocalization: the 2,5-diamino-1,4-benzoquinone-diimines (DABQDI). New DABQDI have been synthesized and their use as ligand can provide complexes absorbing from the visible to the near infrared domain. DABQDI units were also incorporated in macrocycles, analogous of porphyrins, called azacalixphyrins, able to absorb light up to 1000 nm
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Andersson, Gabriella. "Hantering av kemikalier och dess risker i frisörverksamheter." Thesis, Umeå universitet, Institutionen för ekologi, miljö och geovetenskap, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-104960.
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The purpose of this study was to examine the hairdresser’s knowledge about the chemicals they handle in their business and how they were handling the chemicals and the risks that follows. 9 Salons were visited to gather information. The same questions were asked at the salons. A sample of hair color products was photographed to gather information about ingredients and labeling. The conclusions of the study were that hairdressers have good knowledge about the risks related to human health but they need to improve their knowledge when it comes to environmental risks. The deficiencies that were found were that they lack knowledge about the laws concerning the use and distribution of cosmetics products and that not all saloons are handling the hazardous waste and residues from treatments correctly. The risks that could follow are that not enough is done to protect human health and the environmental. To prevent that damage to human health and the environmental occurs they should use more sources that focus on health and environmental to gather information about the risks with the chemicals they are handling, they should also limit the treatments on children and always inform about the risks when they are using products that can cause an allergic reaction. Keywords: Risks hairdressing, cosmetics products, p-phenylenediamine, Toluene-2,5-diamine, ammonia.
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Tranchier, Jean-Philippe. "Utilisation en synthese asymetrique d'imidazolidines derivees du glyoxal et de diamines chirales possedant un axe de symetrie c#2." Paris 6, 1995. http://www.theses.fr/1995PA066219.
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La reaction de condensation entre le glyoxal et les diamines chirales possedant un axe de symetrie c#2 conduit au monoaminal du glyoxal correspondant. A partir de ce dernier, il est possible d'acceder a des synthons chiraux tels que les imines, hydrazones, esters alpha, beta-ethyleniques qui sont des precurseurs d'aldehydes alpha-amines, aldehydes alpha-hydroxyles, de beta-lactames ou encore d'esters d'acides 3-alkylsuccinaldehydiques
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Drezen, Thierry. "Nouveaux oxydes mesoporeux a base de silice modifies par le vanadium et le fer pour la catalyse heterogene. Synthese hydrothermale de nouveaux oxydes de vanadium et de molybdene textures par des diamines : (nh#2(ch#2)#nnh#2) (n 2, 3, 6, 8)." Nantes, 1998. http://www.theses.fr/1998NANT2065.
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A la suite des premiers travaux de kresge et coll. Sur les mesoporeux, si-mcm-41, obtenus par effet template de molecules amphiphiles, nous avons choisi, dans une premiere partie, de preparer des mesoporeux type mcm-41 modifies par le vanadium et le fer pour leur interet potentiel en catalyse d'oxydation heterogene. Les phases ont ete preparees in-situ et par impregnation. De nombreuses techniques de caracterisation : diffraction rx sur poudre, mesures de surface specifique b. E. T. Et de porosite ; spectroscopies ir, raman, rmn (#5#1v, #2#9si, #1h) et mossbauer (#5#7fe) ont permis de preciser le degre d'oxydation du fer et du vanadium, leur geometrie de site et leur repartition au sein du mesoporeux. Des tests catalytiques d'oxydation du toluene par l'eau oxygenee en milieu aqueux sur les phases au fer et d'oxydation deshydrogenante du propane en propene, a faible taux de conversion, effectues a 400c sur les phases au vanadium ont permis de preciser l'effet de dispersion des especes. Dans une seconde partie, des oxydes bronze de vanadium textures par les diamino-hexane et -octane ont ete prepares par voie hydrothermale et caracterises. La structure est formee de clusters v#1#5o#3#6(cl) stabilises par interactions avec les cations alkyldiammonium avec lesquels ils partagent des liaisons hydrogene. L'anion cl est encapsule au centre d'une cage polyoxovanadique. Deux oxydes de molybdene, un bronze et un oxyde non reduit ont ete egalement textures respectivement par l'ethylenediamine et le diaminopropane. Le double role d'agent reducteur et d'espece texturant des diamines a fait l'objet d'une discussion pour les deux systemes hybrides au vanadium et au molybdene.
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Malpeli, Pascal. "Préparation de nouveaux ligands chiraux d'axe C2. Induction asymétrique lors de l'addition de dérivés lithiés sur des composés carbonylés prochiraux." Rouen, 1991. http://www.theses.fr/1991ROUES022.
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De nouvelles diamines chirales d'axe C2 ont été préparées. Tous ces composés possèdent deux groupes amine tertiaire et certains présentent une fonction éther ou amine secondaire. L'addition asymétrique de dérivés organolithiens et d'aldéhydes ou cétones prochiraux a été étudiée en présence de ces diamines comme ligands. Un excès énantiomérique de 65% a été obtenu par réaction du n-butyllithium et du benzaldéhyde en utilisant la bis(méthyl-1 pyrrolidinyl-2 méthyl)amine dans le THF à -110°C
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GOSMINI, ROMAIN. "Syntheses enantioselectives de 1,4-dihydropyridines au moyen de diamines chirales de symetrie d'ordre 2 et leurs utilisations dans l'approche synthetique d'alcaloides indoliques de types indoloquinolizines." Paris 6, 1991. http://www.theses.fr/1991PA066506.
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Aisement preparee par condensation de la 3 pyridine carboxaldehyde et d'une diamine chirale, la 3 pyridine imidazolidine, activee par des chlorures d'acides, a permis d'acceder regio- et diastereoselectivement a des 1,4-dihydropyridines avec de bons rendements chimiques apres additions de derives organometalliques du cuivre. La configuration du centre asymetrique cree a pu etre determinee. Un modele mecanistique a ete postule et rend compte de la faible diastereoselectivite observee lors de l'utilisation d'halogenures d'alkyles comme activateurs. L'utilisation d'halogenures d'alkyles comme activateurs. L'utilisation d'un chlorure d'acide elabore, le chlorure de l'acide indolylacetique a permis l'obtention enantioselective en quatre etapes d'un tetracycle analogue de la vallesiachotamine. Cette methode a ete etendue a l'addition d'equivalents du crotonaldehyde sur la 3-pyridine imidazolidine. Cette addition a procede regio- et diastereoselectivement pour conduire a un intermediaire synthetique de la vallesiachotamine. Consequemment une etude a ete entreprise afin d'introduire, en position quatre de la dihydropyridine, des groupements fonctionnels. L'addition d'un equivalent organometallique de l'acetaldehyde a pu etre realisee
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Mitchell, Judith M. Mitchell Judith M. Mitchell Judith M. "1, new molybdenum catalysts for alkyl olefin epoxidation ; 2, an efficient method for the preparation of N, N-disubstituted 1,2-diamines ; 3, Progress towards the synthesis of pseurotin A /." Diss., Connect to a 24 p. preview or request complete full text in PDF format. Access restricted to UC campuses, 2003. http://wwwlib.umi.com/cr/ucsd/fullcit?p3099549.
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Mathieu, Claire. "Approche intégrée "Spectroscopies électroniques et Calculs ab-initio d' états de c oeur excit és" des modes d'adsorption de l'ammoniac et de diamines sur la surface Si(001)-2 x1." Phd thesis, Université Pierre et Marie Curie - Paris VI, 2009. http://tel.archives-ouvertes.fr/tel-00796706.
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Le greffage chimique et l'assemblage supramoléculaire de mol écules organiques sur les semiconducteurs est une approche intéressante pour la fabrication de dispositifs dans le domaine de l'électronique moléculaire. En particulier, la surface de silicium orient ée (001), reconstruite 2x 1, peut être utilisée comme un gabarit pour greffer des mol écules organiques de façon organisée dans des conditions de ultra haut vide. Cependant, les molécules bifonctionnelles conduisent à des géométries d'adsorption multiples, qu'il est nécessaire de comprendre a fin de pouvoir les contrôler. Les spectroscopies de photo émission et d'absorption X, associées a des calculs DFT de structures électroniques, ont permis de déterminer les modes d'adsorption de l'ammoniac, de l'éthylènediamine, du 1-4 diaminobutane et du N,N,N',N' tétraméthyl éthylènediamine sur la surface Si(001)-2x 1. Dans ce dernier cas, une évolution des modes d'adsorption, en fonction de la dose d'exposition et d'irradiation a également pu être mise en évidence.
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Le, Bihan Yann-VaÏ. "Etude structurale et fonctionnelle de la reconnaissance et de la métabolisation de lésions puriques et pyrimidiques dans l'ADN par la Formamidopyrimidine-ADN glycosylase." Phd thesis, Université d'Orléans, 2009. http://tel.archives-ouvertes.fr/tel-00488816.
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Les oxydations sur les bases nucléiques constituent l'une des sources principale d'apparition de lésions sur l'ADN, qui peuvent être mutagènes ou létales pour les cellules en l'absence de réparation de l'ADN. La Formamidopyrimidine-ADN glycosylase (Fpg), une enzyme procaryote du système de réparation de l'ADN par excision de base (BER), initie la réparation d'un large panel de lésions de ce type via ses activités ADN glycosylase (excision de la base oxydée) et AP lyase (clivage du site abasique par ß,d-élimination). Nous avons réalisé des études fonctionnelles par des techniques biochimiques et structurales par cristallographie des rayons X afin de préciser la spécificité de substrat et le mécanisme catalytique de Fpg. Ainsi, nous avons pu mettre en évidence des déterminants structuraux permettant à cette enzyme d'accommoder des lésions de tailles très différentes dans son site actif, en l'occurrence des résidus 2,6-diamino-4-hydroxy-5-formamidopyrimidine (FapyG) substitués ou non en N7 par des adduits encombrants. D'autre part, nous avons caractérisé structuralement et fonctionnellement la reconnaissance et l'excision par Fpg d'une lésion pyrimidique, la 5-hydroxy-5-méthyle-hydantoïne (Hyd). Ainsi, nous avons montré que cette lésion appariée à une cytosine était un bon substrat pour l'enzyme, et nous avons précisé structuralement le mode de reconnaissance de l'Hyd par Fpg. D'autre part, nous avons mis en évidence un comportement inattendu de l'enzyme sur ce substrat. En l'occurrence, nous avons montré biochimiquement et structuralement qu'un pontage covalent se formait en quantités non négligeables entre Fpg et l'Hyd dans des conditions physiologiques.
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Le, Bihan Yann-Vaï. "Étude structurale et fonctionnelle de la reconnaissance et de la métabolisation de lésions puriques et pyrimidiques dans l'ADN par la Formamidopyrimidine-ADN glycosylase." Phd thesis, Université d'Orléans, 2009. http://tel.archives-ouvertes.fr/tel-00504364.
Full textAbstract:
Les oxydations sur les bases nucléiques constituent l'une des sources principale d'apparition de lésions sur l'ADN, qui peuvent être mutagènes ou létales pour les cellules en l'absence de réparation de l'ADN. La Formamidopyrimidine-ADN glycosylase (Fpg), une enzyme procaryote du système de réparation de l'ADN par excision de base (BER), initie la réparation d'un large panel de lésions de ce type via ses activités ADN glycosylase (excision de la base oxydée) et AP lyase (clivage du site abasique par β,δ-élimination). Nous avons réalisé des études fonctionnelles par des techniques biochimiques et structurales par cristallographie des rayons X afin de préciser la spécificité de substrat et le mécanisme catalytique de Fpg. Ainsi, nous avons pu mettre en évidence des déterminants structuraux permettant à cette enzyme d'accommoder des lésions de tailles très différentes dans son site actif, en l'occurrence des résidus 2,6-diamino-4-hydroxy-5-formamidopyrimidine (FapyG) substitués ou non en N7 par des adduits encombrants. D'autre part, nous avons caractérisé structuralement et fonctionnellement la reconnaissance et l'excision par Fpg d'une lésion pyrimidique, la 5-hydroxy-5-méthyle-hydantoïne (Hyd). Ainsi, nous avons montré que cette lésion appariée à une cytosine était un bon substrat pour l'enzyme, et nous avons précisé structuralement le mode de reconnaissance de l'Hyd par Fpg. D'autre part, nous avons mis en évidence un comportement inattendu de l'enzyme sur ce substrat. En l'occurrence, nous avons montré biochimiquement et structuralement qu'un pontage covalent se formait en quantités non négligeables entre Fpg et l'Hyd dans des conditions physiologiques. Mots clés : Réparation de l'ADN; Réparation par excision de base; Formamidopyrimidine-ADN glycosylase; 2,6- diamino-4-hydroxy-5-formamidopyrimidine; 7,8-dihydro-8-oxo-guanine; 5-hydroxy-5-méthyle-hydantoïne.
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BOUAYAD, ZOHEIR. "Ouverture nucleophile d'aziridines fonctionnalisees par des composes a methylene actif : synthese de pyrrolidones-2 fonctionnalisees." Clermont-Ferrand 2, 1987. http://www.theses.fr/1987CLF2S884.
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Ward, Meryck. "Development of Schiff base electrochemical sensors for the evaluation of polycyclic aromatic hydrocarbons in aqueous medium." University of the Western Cape, 2017. http://hdl.handle.net/11394/5508.
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Philosophiae Doctor - PhDA novel monomer (N,N'-Bis-(1H-pyrrol-2-ylmethylene)-benzene-1,2-diamine-BPPD) was derived from the condensation reaction between o-phenylenediamine and a pyrrole derivative. The monomer was polymerized electrochemically to produce the new polymer material - polymerized(N,N'-Bis-(1H-pyrrol-2-ylmethylene)-benzene-1,2-diamine) PBPPD. This novel polymer material was deposited at the surface of a screen-printed carbon electrode, as a thin film, in the development of chemical sensors for the detection of polycyclic aromatic hydrocarbons (PAHs). The monomer material was characterized in terms of its optical (spectroscopy) and thermal properties. The polymer material was characterized in terms of its surface morphology and its redox electrochemistry. Fourier transform infrared spectroscopy (FTIR) was used to confirm the azomethine bond formation during the condensation reaction of an aldehyde and primary amine derivative.
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Huang, Sung-ben. "Synthesis and oligomerization of Delta, 4-diamino-2-oxo-1(2H)-pyrimidinehexanoic acid." Thesis, 1990. http://hdl.handle.net/1957/37376.
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"INVESTIGATIONS INTO RARE COORDINATION ENVIRONMENTS OF AL, P AND PD SPECIES: SYNTHESIS AND APPLICATIONS." Thesis, 2014. http://hdl.handle.net/10388/ETD-2014-04-1508.
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This research work includes three parts, with the first section describing the synthesis and applications of neutral 3-coordinate aluminum complexes. As demonstrated in this part, aluminum complexes in a 3-coordinate geometry can be formed only with a ring size greater than or equal to a 6-member ring when supported by diamido ligands. It is found that 1,2-diamido ligands designed for 5-member ring formations can accommodate the formation of only 4-coordinate dinuclear species, which show no activity when used as a single component catalyst in the ring-opening polymerization (ROP) of cyclic esters under specified reaction conditions. Three-coordinate neutral (1,4-diamido)AlMe complexes are successfully synthesized, revealing a higher activity in the ROP of cyclic esters than the existing 6-member analogues under the same reaction conditions. A detailed discussion of the structure-reactivity relationship of Al catalysts in the ROP of cyclic esters is presented.
The second part of this thesis project consists of investigations into the applications of 1,4-diamido ligands for the formation of 3-coordinate NHP (N-heterocyclic phosphine) and 2-coordinate NHP+ cations (phosphenium cations). These novel NHP species are the first to be shown in a 7-member ring supported by 1,4-diamido ligands. Various N-substituents in the 1,4-diamido ligands are examined for the formation of a cyclic structure based on their steric hindrance. It is found that a Dipp (2,6-diisopropylphenyl) group is unable to allow for the formation of a 7-member NHP due to its excessive steric bulk. The less bulky mesityl (2,4,6-trimethylphenyl) group at the N-positions in the ligands leads to successful formation of these novel NHPs and NHP+ species. Furthermore, an investigation is carried out to explore their π-accepting property by means of 31P NMR studies. The NHP and NHP+ species synthesized in this project show chemical shifts downfield relative to the existing 5- and 6-member analogues in 31P NMR experiments, suggesting a high potential of 7-member NHPs to be used as π-acceptor ligands. The second section also examined the resulting NHPs and NHP+ species for coordinating to various metals.
The last part of this research work is dedicated to presenting the first example of chelating 3–triNHC (tri-N-heterocyclic carbene) ligands that allow for the formation of (triNHC)Pd(II) complexes in a meridional fashion, wherein the triNHC ligand coordinates to the metal center in a pseudo-meridional fashion. Novel [(triNHC)MePdX]X (X = Cl or acetate) complexes are successfully synthesized, and they display extraordinary stability against air and heat. Low activities of the resulting complexes are found in promoting C-C coupling reactions, possibly due to the low solubility of the resulting complexes in organic solvents. Various attempts to change the N-substituents to groups other than methyls are conducted to improve the solubility of the complexes in organic solvents for higher activities in C-C coupling reactions. The results from these attempted modifications to these complexes are discussed in detail.
All complexes are characterized by standard spectral methods such as mass spectrometry, X-ray crystallography, elemental analysis, 1H NMR, 13C NMR and 31P NMR spectroscopy.
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HUANG, RONG-NAN, and 黃榮南. "Immunoassay of 2-chloro--4,6-diamino-s-triazine(CAAT),the the didealkylated metabolite of chloro-s-triazine herbicides." Thesis, 1992. http://ndltd.ncl.edu.tw/handle/48702125666331142063.
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Jiang, Ming Hong, and 江明鴻. "Synthesis and properties of high performance polymers based on diamines from 2-substituted hydroquinones." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/24582919507572669211.
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Pan, Jing-Yao, and 潘靜瑤. "Synthesis, Spectra and Structures of Quadruply Bonded Complexes Containing Chiral Diamine Ligands and Palladium Complexes Containing 2-Amino Pyridine Lignad." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/94205572571408956011.
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碩士中原大學
化學系
87
This thesis includes two parts. The first part discusses the synthesis, structures and optical activities of quadruple-bonded complexes containing chiral diamine ligands. The second part discusses synthesis and structures of palladium complexes containing amino pyridine ligand. The complexes [Mo2(O2CCF3)2(S,S-dach)2][BF4]2, 1, and [Mo2(O2CCF3)2(R,R-dach)2][BF4]2 , 2 , (dach = 1,2-diamino cyclohexane) were prepared by reactions of [Mo2(O2CCF3)2 (CH3CN)6[BF4]2 with (S,S-dach)and (R,R-dach), respectively, in CH3CN. Their UV-vis and circular dichroism(CD) spectra have been recorded the structures have been determined by X-ray crystallgraphy. Crystal data for 1: space group P2, a = 9.362(1) A, b = 9.622(1) A, c = 18.962(1) A, V = 1710(2) A3, Z = 2, with final residuals R1 = 0.0348, wR2 = 0.0940. Crystal data for 2: space group P2, a = 9.361(1) A, b = 9.624(1) A, c = 18.977(1) A, V = 1710(2) A3, Z = 2, with final residuals R1= 0.0513, wR2 = 0.1314. The metal centers are bridged by the two O2CCF3 groups which are cis to each other and chelated by two dach ligands. The absorption wavelength at 510 nm for both 1 and 2 can be assigned to dxy Rdxy* transitions. The solution CD spectra of these two complexes show two prominent bands at 510 and 405nm and form mirror images of each other. The one-electron static coupling mechanism was invoked to explain the CD spectrum for these complexes. The reaction of Mo2(O2CCR3)2X2(PPh3)2 with one equivalent of (R,R-dach) or (S,S-dach) in THF afforded the complex Mo2(O2CCR3)2X2(S,S-dach) (R = H, X = Cl, 3; R = H, X = Br, 5; R = F, X = Cl, 7, R = F, X = Br, 9) and Mo2(O2CCR3)2X2(R,R-dach) (R = H, X = Cl, 4; R = H, X = Br, 6; R = F, X = Cl, 8, R = F, X = Br, 10) Their UV-vis and CD spectra have been recorded. Reaction of PdCl2 with 2-amino-6-methylpyridine (Hampy)(Hampy = 2-amino-6-methylpyridine) and 2-amino pyridine(Hapy)(Hapy = 2-aminopyridine) afforded the title complexes PdCl2(Hampy)2, and PdCl2(Hapy)2, respectively, which show a pair of nonlinear N-H…Pd(II) interactions. Crystal data for 11: space group Pca21, a = 8.0531(7) A, b = 14.061(1) A, c = 13.284(1) A, V = 1504.3(2) A3, Z = 4, with final residuals R1 = 0.0521, wR2 = 0.1373.
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Guinchard, Xavier. "CHIMIE DES NITRONES :APPLICATIONS EN SYNTHESE ORGANIQUE ET A LA SYNTHESE DE COMPOSES BIO-ACTIFS." Phd thesis, 2006. http://tel.archives-ouvertes.fr/tel-00267072.
Full textAbstract:
La chimie des nitrones est un outil performant en synthèse organique pour accéder à des composés aminés ou N-hydroxyaminés. Très électrophiles, les nitrones peuvent subir facilement des additions nucléophiles conduisant à des N-hydroxylamines. En particulier, la réaction des N-benzylnitrones α-aminées avec des noyaux indoliques permet d'obtenir des N hydroxylamines indoliques β-aminées avec de bons rendements. Celles-ci sont d'excellents intermédiaires-clefs dans la synthèse d'alcaloïdes indoliques bio-actifs d'origine marine comportant le motif 1-(3'-indolyl)-1,2-diaminoéthane tels que le discodermindole, les nortopsentines, les topsentines ou encore les hamacanthines. Nous avons donc développé des voies de synthèse permettant d'obtenir ces alcaloïdes indoliques à partir de N-hydroxylamines indoliques β-aminées. Cependant, la difficulté de déprotection du groupement protecteur benzyle en présence de fonctionnalités chimiques sensibles à l'hydrogénolyse nous a amené à concevoir une nouvelle famille de nitrones protégées par un carbamate de tert-butyle. Celles-ci, après addition nucléophile de réactifs organométalliques, conduisent à des N (Boc) N hydroxylamines dont le groupement protecteur Boc est aisément éliminé en milieu acide. Cette méthode a permis d'accéder à de nouveaux synthons pouvant être facilement valorisés en synthèse organique. Nous avons appliqué cette méthodologie de synthèse à la préparation du zileuton, un composé inhibiteur de la 5-lipoxygénase, ainsi qu'à la préparation de 1,2-diamines indoliques β-aminées, comportant le motif 1-(3'-indolyl)-1,2-diaminoéthane, intermédiaire-clefs dans la synthèse des alcaloïdes indoliques choisis pour cibles.
Nous avons ensuite tenté de préparer des N-sulfinyl nitrones, dont le groupement protecteur électroattracteur chiral pourrait facilement être éliminé en milieu acide et induire de bonnes diastéréosélectivités lors d'additions nucléophiles.
Enfin, nous présentons les activités biologiques de plusieurs composés issus de ce travail. Nous avons évalué leur cytotoxicité, l'activité inhibitrice de la protéine kinase CK2, l'activité antibactérienne sur Staphylococcus aureus et enfin l'activité inhibitrice de la pompe d'efflux NorA de Staphylococcus aureus.