Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2014-08-11T14:46:08Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao River Souza Magalhaes.pdf: 1856967 bytes, checksum: 6da8a950fc3e088ddd4b5b2558c23691 (MD5) / Made available in DSpace on 2014-08-11T14:46:08Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao River Souza Magalhaes.pdf: 1856967 bytes, checksum: 6da8a950fc3e088ddd4b5b2558c23691 (MD5) Previous issue date: 2011-02-25 / This work presents the synthesis of N-[-(4-methylphenyl)]-thiourea, the ligand N-[N'-(2-hydroxyethyll)-(4-methylphenyl)]-guanidine and the copper II complex. The compounds were characterized by infrared spectroscopy,1H NMR and X-ray diffraction. The results of X-ray shows the mode of ligand coordination to the metal ion, in addition to square planar structure, a connection is observed for the trans chromophore CuN2O2. Conformational studies of the molecule the ligand N-[N'-(2-hydroxyethyl)-(4-methylphenyl)]-guanidine and were performed to compare experimental data with calculated data. the computation of ligand molecule N-[N'-(2-hydroxyethyl)-(4-methylphenyl)]-guanidine shows the small energy difference between the threes tautomers, it is not possible to state firmly the most stable. The 1H NMR data show that the solution is more abundant in the tautomer II and III. Calculations of energy transition states for the reaction path. In addition to the calculations of imaginary for the characterization of transition states. / Este trabalho apresenta a síntese da N-[N'-(2-hidroxietil)-(4-metilfenil)]-tioureia, do ligante N-[N'-(2-hidroxietil)-(4-metilfenil)]-guanidina e do complexo de cobre II [Cu(oib)2]. Os compostos foram caracterizados por espectroscopia de infravermelho, RMN de 1H e difração de raios-X. O resultado de DRX mostra o modo de coordenação do ligante ao íon metálico, além da estrutura quadrado planar, é observado uma ligação trans para o cromóforo CuN2O2. Estudos conformacionais da molécula do ligante N-[N'-(2-hidroxietil)-(4-metilfenil)]-guanidina que foram realizados para confrontar dados experimentais com dados calculados. Os cálculos computacionais da molécula do ligante N-[N'-(2-hidroxietil)-(4-metilfenil)]-guanidina mostra uma pequena diferença de energia entre os três tautômeros, não sendo possível afirmar com firmeza o mais estável. Os dados de RMN 1H mostram que o mais abundante em solução é o tautômero II e o III. Cálculos de energia dos estados de transição para o caminho reacional. Além do cálculo das frequências imaginárias para caracterização dos estados de transição.

[pt] No presente trabalho realizou-se a síntese e caracterização de complexos de zinco e cádmio no estado sólido. Foram sintetizados complexos binários e ternários envolvendo os aminoácidos: glicina,ácido aspártico, metionina, cisteína e o tripeptídeo glutationa, os quais formam parte de diversas proteínas que atuam no sistema nervoso central. Embora estudos em solução envolvendo a formação de complexos entre estes metais e aminoácidos tenham sido realizados, há o reconhecimento de que, em diversas doenças neurodegenerativas, ocorre a precipitação de aglomerados sólidos provenientes de proteínas. Isto cria a necessidade de se estudar estes sistemas no estado sólido. Assim, no presente trabalho, foram desenvolvidas rotas de sínteses, que permitem a obtenção destes complexos em condições próximas ao meio biológico. Modelos simples foram sintetizados e caracterizados pelas técnicas de Espectroscopía Infravermelha, Espectroscopía Raman, Análise Termogravimétrica, Análise Elementar e Absorção Atômica. Foi selecionado um composto com cisteína para realizar um estudo espectroscópico detalhado, utilizando cálculos de mecânica quântica, permitindo a atribuição das bandas nos espectros infravermelho e Raman, identificando-se as bandas M-S e M-N de difícil caracterização. A conclusão deste trabalho mostrou que a grande afinidade destes metais (zinco e cádmio) pelo enxofre permite a realização das sínteses mesmo em meio ácido, observando-se uma redução na tendência de precipitação ao passar dos compostos binários, a ternários e à glutationa. Tripeptídeos como a glutationa facilitam a formação de soluções coloidais estáveis, acontecendo a formação de fases sólidas após um grande período de tempo. Assim, um aumento no potencial zeta, permite a formação de uma fase sólida em poucas horas. / [en] In the present work the synthesis and characterization of solid state zinc and cadmium complexes with sulfured amino acids were performed. Binary and ternary complexes, involving glycine, aspartic acid, methionine, cysteine and glutathione tripeptide were synthetized. These compounds form several proteins that act in the central nervous system. Although studies on the formation of complexes between these metals and amino acids in solution, were realized it is a relevant and interesting topic the fact that in several neuro-degenerative illness occur the precipitation of solid agglomerates from proteins. This shows the necessity of study these systems in the solid state. Thus, in the present work, different routes of synthesis were developed in similar conditions to the biological medium. Simple models were synthesized and characterized by Infrared spectroscopy, Raman spectroscopy, Thermogravimetric analysis, Elemental analysis and Atomic absorption spectrometry. These complexes allow the comprehension of the complex molecules which form these systems. A compound with cysteine was chosen to perform a detailed spectroscopic study using quantum mechanical calculation which permitted identification of the the infrared and Raman spectra bands, M-S and M-N which are very difficult to characterize. The conclusion of this work showed that the big affinity of these metals (zinc and cadmium) for sulfur allowed the synthesis in acid medium. It was observed a reduction in the tendency of precipitation when passing binary from binary to ternary compounds and then to glutathione. Tripeptides like glutathione facilitated the formation of stable colloidal solutions, and the formation of solid phases only occurred after a considerable period of time, so, an increase in the zeta potential allows the formation of a solid phase in few hours.

Chemische Synthese und Charakterisierung von Sauerstoff- und Schwefel-Heteroporphyrinen und ihren Mn(II)-, Co(II)-, Cu(II)-, Zn(II)- und Pd(II)-Komplexen. Strukturelle und spektroskopische Beschreibung der Liganden und Komplexe durch Röntgendiffraktometrie, EXAFS, NMR, UVVIS, Fluoreszenzspektroskopie, CV unf MS. Darstellung und Beschreibung dendritischer Heteroporphyrinmoleküle.

No description available.

<p>&nbsp;&nbsp; U ovoj doktorskoj disertaciji opisane su sinteze novih kompleksa prelaznih metala sa piridoksiliden-&nbsp; (PLAG), odnosno saliciliden-aminogvanidinom (SALAG). Dobijeni<br />kompleksi su okarakterisani elementalnom analizom, IR spektrima, konduktometrijskim i magnetnim merenjima, a većina i rendgenskom<br />strukturnom analizom. Osim toga, dobijene su i nove forme ovih &Scaron;ifovih baza, i to u vidu monokristala, čime su omogućena ispitivanja njihovih&nbsp; molekulskih i kristalnih struktura, kao i uporedna analiza sa koordinovanim ligandima.<br />&nbsp; &nbsp; Sa PLAG je sintetisano 7 novi&nbsp; kompleksa Cu(II), a pored toga po prvi put su<br />izolovani mono i bis(ligand) kompleksi Fe(III) i Co(III), mono(ligand) kompleksi&nbsp; V(V), kao&nbsp; i jedan kompleks Zn(II) u kojem ovaj potencijalno tridentatni&nbsp;<em> ONN&nbsp;</em> ligand,&nbsp; u<br />monoprotonovanoj formi,&nbsp; ima ulogu kontra-jona. Sa stanovi&scaron;ta geometrije zajedničko za izolovane komplekse Cu(II) i V(V) je da imaju kvadratno-piramidalnu strukturu, sa izuzetkom jednog kvadratno-planarnog kompleksa Cu(II), dok je u kompleksima Fe(III) i Co(III) nađeno očekivano oktaedarsko okruženje centralnog<br />jona. Pored ovih, sintetisano je i pet novih kompleksa sa SALAG, od kojih su dva<br />kompleksa Cu(II) i kompleks V(V) okarakterisani rendgenskom strukturnom<br />analizom, dok je mikrokristalnim bis(ligand) kompleksima Co(III) i Ni(III) na osnovu<br />fizičko-hemijskih karakteristika predložena odgovarajuća struktura.<br />&nbsp;&nbsp; Zajedničko za obe opisane &Scaron;ifove baze je da se koordinuju na&nbsp;<em> ONN&nbsp; </em>tridentatni način, i to preko atoma kiseonika deprotonovane fenolne grupe i atoma azota azometinske i imino grupe AG fragmeta. Posebno je nagla&scaron;eno da su&nbsp; sa<br />PLAG izolovana dva dimerna kompleksa Cu(II) u kojima je po prvi put nađena tetradentatna koordinacija ovog&nbsp; liganda, u koju je dodatno uključen atom kiseonika hidroksimetil-grupe PL-ostatka. Za razliku od SALAG, koji je u izolovanim kompleksima koordinovan isključivo kao monoanjon, nastao deprotonacijom fenolne<br />OH-grupe, za PLAG je osim ove, potvđena koordinacija u neutralnoj, zwitter-jonskoj, ali i dvostruko deprotonovanoj formi. Zwitter-jonska forma liganda nastaje migracijom atoma vodonika sa fenolnog hidroksila na piridinski atom azota PL-ostatka, dok deprotonacijom piridinskog ili hidrazinskog atoma azota, odnosno oba pomenuta atoma nastaju monoanjon i dianjon helatnog liganda, respektivno.<br />&nbsp;&nbsp; Na kraju, urađena su&nbsp; i ispitivanja antimikrobne aktivnosti odabranih jedinjenja<br />prema predstavnicima grampozitivnih i gramnegativnih bakterija, kao i dve kulture<br />kvasca. Tom prilikom nije utvrđena nikakva inhibitorna aktivnost&nbsp;&nbsp; prema primenjenim<br />bakterijskim sojevima, dok su u slučaju kvasaca izvesno mikrobicidno dejstvo pokazali samo kompleksi Cu(II).</p> / <p>This PhD thesis describes the syntheses of some new transition metal complexes with&nbsp; pyridoxilidene-&nbsp; (PLAG) and salicylideneaminoguanidine (SALAG). Obtained&nbsp; complexes are characterized by&nbsp;&nbsp; elemental analysis, IR&nbsp; spectroscopy,&nbsp; conductometric and magnetic measurements. Besides, the structural analysis of majority of the obtained complexes was performed. Some new forms of these Schiff&nbsp; bases are synthesized in form of single crystals, which made their X-ray analysis as well as comparison with coordinated forms possible.</p><p>With PLAG, 7 new Cu(II) complexes were obtained and for the first time mono and bis(ligand) complexes of Fe(III) and Co(III) as well&nbsp; mono(ligand)&nbsp; complexes&nbsp; of V(V) were isolated. Furthermore,&nbsp; the structure of Zn(II) complex in which PLAG in its monocationic form has a role of counter ion is presented. With the exception of one Cu(II) complex, all reported Cu(II) and V(V) complexes have a square-pyramidal geometry, whilst&nbsp; Fe(III)&nbsp; and Co(III)&nbsp; are situated in octahedral surroundings. Also, five new complexes of Cu(II), Co(III), Ni(II) and V(V) with SALAG were synthesized. In both&nbsp; Cu(II) complexes and V(V) complex the expected coordination mode and geometry were confirmed by X-ray analysis, while octahedral structure of bis(ligand) complexes with Co(III) and Ni(II) was proposed based on results of physico-chemical&nbsp; characterization.</p><p>Both PLAG and SALAG coordinate the metal ion in tridentate&nbsp; ONN&nbsp; manner, through the oxygen atom of deprotonated phenolic group and nitrogen atoms&nbsp; of azomethine and imino groups of AG moiety. It is also emphasized that in two dimeric Cu(II) complexes with PLAG tetradentate coordination mode was found, in which the oxygen atom of hydroxymethyl group of PL residue was additionally involved. Unlike SALAG, which is coordinated as monoanion in all of the examined complexes, PLAG can have one of three degrees of deprotonation. Zwitter-ion of PLAG is formed by migration of H-atom from phenolic oxygen to pyridine nitrogen, while the deprotonation of pyridine or/and hydrazine nitrogen, makes it mono-and dianion, respectively.</p><p>Also, microbiological tests on the selected compounds were preformed. Namely, antimicrobial activity of these compounds against some gram-positive and gram-negative bacteria, as well as some yeast cultures was examined and none of the samples showed antimicrobial activity against bacteria, whilst only Cu(II) complexes showed certain inhibitory effect against yeasts.</p>