Thesis (Ph. D.)--Auburn University. / Abstract. Vita. Includes bibliographical references (p. 116-125).

MOURA NETO, E. Síntese de Nanopartículas da Galactomanana da Fava Danta (Dimorphandra gardneriana) Modificada. 2013. 147 f. Tese (Doutorado em Química) - Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2013. / Submitted by José Jairo Viana de Sousa (jairo@ufc.br) on 2014-11-06T19:20:00Z No. of bitstreams: 1 2013_tese_emneto.pdf: 3560849 bytes, checksum: f5075b3093fdd4812f56ab3de30a2a46 (MD5) / Approved for entry into archive by José Jairo Viana de Sousa(jairo@ufc.br) on 2015-04-23T20:07:49Z (GMT) No. of bitstreams: 1 2013_tese_emneto.pdf: 3560849 bytes, checksum: f5075b3093fdd4812f56ab3de30a2a46 (MD5) / Made available in DSpace on 2015-04-23T20:07:49Z (GMT). No. of bitstreams: 1 2013_tese_emneto.pdf: 3560849 bytes, checksum: f5075b3093fdd4812f56ab3de30a2a46 (MD5) Previous issue date: 2013 / This work aimed the preparation of nanoparticles galactomannan derivatives. The polysaccharide (galactomannan) was from seeds of Dimorphandra gardneriana with yield of 29±3% and mannose/galactose ratio (M:G) of 1.93±0.02. The galactomannan was modified by sulfation raction (FDS), oxidation (FDO) and by acylation with acetic anhydride (FDAc) and proponic (FDPr) and derivates were used in the developmentof nanoparticles by interaction with chitosan by polyelectrolyte complexes, Schiff base formation and by self-assembled. Galactomannan derivatives were characterized by infrared spectroscopy (IR), nuclear magnetic resonance, elemental analysis, gel permeation chromatography and intrinsic viscosity. The degree of substitution for sulfataion reaction were 0.32 and 0.42; the ratio of glycosidic/oxidized units in oxidized derivatives was 10:2; 10:4 and 10:8. The hydrophobic derivatives were confirmed by the appearance of new absorption at 1740 cm-1 in IR, assigned to C=O stretching and water insolubility. Nanoparticles with unimodal profile were obtained on three routes studied. The particles of chitosan and sulfated galactomannan were obtained by complexation polyelectrolytic with diameters ranging from 10±6 to 377±29 nm, polydispersity index from 0.11±0.02 to 0.5±0.1 and zeta potential of –28±2 to 59±4 mV. For chitosan and oxidized galactomannan nanoparticles, obtained by Schiff base, diameters ranging from 8±2 to 20±9 nm, polydispersity index from 0.36±0.04 to 0.57±0.08 and zeta potential of 0.4±0.5 to 14±1 mV were obatined. Hydrophobically modified galactomannan particles were obtained by self-assembled with diameters ranging from 35.3±0.6 to 213±28 nm, polydispersity index from 0.093±0.003 to 0.9±0.1 and zeta potential of –26.3±0.9 to –3±2 mV. The diameter, zeta potential and polydispersity index are influenced by the methodology and derived used, but for all derivatives of galactomannan at least one condition shows nanoparticles compatible for potential use as drug carriers. Factors such as degree of modification, ratio, order of addition and concentration of polysaccharides, pH and addition of drug have influence on size, polydispersity index, zeta potential and solution stability of the particles. / Este trabalho teve como objetivo a preparação de nanopartículas de derivados da galactomanana. O polissacarídeo (galactomanana) foi extraído de sementes da Dimorphandra gardneriana com rendimento de 29±3% e razão manose/ galactose (M:G) de 1,93±0,02. A galactomanana foi modificada por reação de sulfatação (FDS), oxidação (FDO) e por acilação com anidrido acético (FDAc) e com anidrido propiônico (FDPr). Os derivados foram utilizados no desenvolvimento de nanopartículas por interação com a quitosana via complexação polieletrolítica, por formação de base de Schiff, e por auto-organização. Os derivados da galactomanana foram caracterizados por espectroscopia na região do infravermelho (IV), por ressonância magnética nuclear, por análise elementar, por cromatografia de permeação em gel e por viscosidade intrínseca. O grau de substituição para reação de sulfatação foram 0,32 e 0,42. A razão de unidades glicosídicas/unidades oxidadas para os derivados oxidados foram 10:2; 10:4 e 10:8. Os derivados hidrofóbicos foram confirmados pelo aparecimento de uma nova absorção em 1740 cm-1 no IV, atribuída ao estiramento C=O e a insolubilidade em água. Nanopartículas com perfil unimodal foram obtidas nas três rotas estudadas. As partículas de quitosana e galactomanana sulfatada foram obtidas por complexação polieletrolítica com diâmetros variando de 10±6 a 377±29 nm, índice de polidispersividade de 0,11±0,02 a 0,5±0,1 e potencial zeta de –28±2 a 59±4 mV. Para as de quitosana e galactomanana oxidada obtidas via base de Schiff com diâmetros variando de 8±2 a 20±9 nm, índice de polidispersividade de 0,36±0,04 a 0,57±0,08 e potencial zeta de 0,4±0,5 a 14±1 mV. Partículas de galactomanana modificadas hidrofobicamente foram obtidas via auto-organização com diâmetros variando de 35,3±0,6 a 213±28 nm, índice de polidispersividade de 0,093±0,003 a 0,9±0,1 e potencial zeta de –26,3±0,9 a –3±2 mV. O diâmetro, potencial zeta e índice de poidispersividade são influenciados pela metodologia e derivado utilizado, mas para todos os derivados da galactomanana obteve-se, em pelo menos uma condição, nanopartículas compatíveis para um potencial uso como carreadores de fármacos. Fatores como: grau de modificação, razão, ordem de adição e concentração dos polissacarídeos, pH e a adição de fármaco influenciaram no tamanho, índice de polidispersividade, potencial zeta e estabilidade em solução das partículas.

Tese (doutorado)–Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015. / Submitted by Fernanda Percia França (fernandafranca@bce.unb.br) on 2016-02-25T13:09:38Z No. of bitstreams: 1 2015_VinerSousaLima.pdf: 5403184 bytes, checksum: 532a39e9b5bb8d4affbf6c00dd2a9ff9 (MD5) / Approved for entry into archive by Marília Freitas(marilia@bce.unb.br) on 2016-05-26T18:11:41Z (GMT) No. of bitstreams: 1 2015_VinerSousaLima.pdf: 5403184 bytes, checksum: 532a39e9b5bb8d4affbf6c00dd2a9ff9 (MD5) / Made available in DSpace on 2016-05-26T18:11:41Z (GMT). No. of bitstreams: 1 2015_VinerSousaLima.pdf: 5403184 bytes, checksum: 532a39e9b5bb8d4affbf6c00dd2a9ff9 (MD5) / Neste trabalho retratamos a síntese e caracterização de complexos organoestânicos com bases de Schiff derivadas da condensação de aminoácidos com aldeídos e a reatividade destes complexos com carbonilas metálicas objetivando a formação de compostos heterobimetálicos do tipo [RxSn(BS)][M(CO)¬y], onde x = 1, 2, ou 3; BS = base de Schiff derivada de aminoácido; M = Mo, W, ou Re; y = 3, 4 ou 5. Foram utilizadas BSs já conhecidas e uma inédita na síntese dos complexos organoestânicos. Foram testados diversos precursores mono-, di- e triorganoestânicos e foram avaliadas diferentes possibilidades de rotas sintéticas de complexos com BSs, tendo sido obtidos cinco novos compostos puros e que puderam ser bem caracterizados, tanto em estado sólido quanto em solução, derivados do hexabutildiestanoxano, incluindo quatro estruturas resolvidas por difração de raios X em monocristal. A partir do dibutil(dimetóxi)estanano foi obtida uma estrutura por difração de raios X em monocristal de um novo complexo com BS, mas todos os produtos de reações com este precursor são extremamente instáveis à umidade e de difícil caracterização. Não foram isolados produtos puros com os precursores mono-organoestânicos. Foi demonstrada a eficiência da técnica de RMN para determinar a estrutura molecular dos compostos organoestânicos em solução utilizando parâmetros como deslocamento químico na RMN de 1H, 13C e 119Sn; valores de acoplamentos nJ(13C-119Sn); deslocamentos químicos na RMN de 15N em estado sólido versus solução; e HMBC 1H119Sn. As estruturas observadas em estado sólido para os derivados do hexabutildiestanoxano, com o átomo de SnIV pentacoordenado em uma geometria bipiramidal trigonal não são mantidas em solução; em CDCl3 os complexos obtidos existem com o SnIV também pentacoordenado, mas sem o carboxilato em ponte e com uma interação fraca com o nitrogênio imínico dos ligantes. Os estudos de reatividade dos complexos organoestânicos obtidos com carbonilas homolépticas de Mo e W indicam que não há reação, enquanto os estudos com derivados mais reativos [Bu4N][M(CO)5Br] e [M(MeCN)3(CO)3] levam à decomposição dos complexos organoestânicos e respectivos ligantes. Os estudos de reatividade com carbonilas de Re mostraram tendência ainda mais acentuada de decomposição em relação ao Mo e W, mesmo com a carbonila homoléptica de Re e ainda mais acentuada com seus derivados. _______________________________________________________________________________________ ABSTRACT / In this work we present the synthesis and characterization of organotin(IV) complexes with amino acid-derived Schiff bases and studies of reactivity of these complexes with metal carbonyls, aiming to obtain heterobimetallic compounds of general formula [RxSn(SB)][M(CO)-y], where x = 1, 2, or 3; SB = amino acid-derived Schiff base ligands; M = Mo, W, or Re; y = 3, 4 or 5. We studied eight Schiff bases already known and a novel one in the synthesis of the organotin(IV) complexes. Mono- di- and triorganotin(IV) precursors in different synthetic routes to obtain the Schiff base complexes were also studied, and five novel complexes from the precursor hexabutyldistannoxane were prepared in high yields and purity, being thoroughly characterized both in solution and solid state, including four structures resolved by single-crystal x-ray diffraction analysis. From dibutyl(dimethoxy)stannane, one structure was resolved by single-crystal x-ray diffraction, but all products from reactions with this precursor are highly moisture-sensitive and of difficult characterization. No pure products were isolated from the reactions with mono-iorganotin(IV) precursors. The efficiency of the NMR technique to elucidate organotin(IV) complexes structure in solution was widely demonstrated, and parameters such as 1H, 13C and 119Sn chemical shifts, nJ(13C-119Sn) coupling values, 15N NMR chemical shifts in solution and solid state, and 1H119Sn HMBC are discussed. Solid state structures, featuring a penta-coordinated tin(IV) atom in a trigonal bipyramidal geometry with three butyl groups in the equatorial positions and two oxygen atoms from the Schiff bases’ carboxylate occupying the apical positions, are not retained in solution; in CDCl3, the tin(IV) atom is also penta-coordinated, but the carboxylate bridging is lost and there is a interaction with the Schiff base’s imine nitrogen. Reactivity studies of the Schiff base organotin(IV) complexes with the homoleptic carbonyls of Mo and W led to no reaction at all, while reactivity studies with the more active species [Bu4N][M(CO)5Br] and [M(MeCN)3(CO)3] led to the decomposition of organotin(IV) complexes and respective ligands. Reactivity studies of the organotin(IV) complexes with rhenium carbonyls shown an even more severe proneness to decomposition, and organotin(IV) complexes and ligands decompose even with the relatively inert Re2(CO)10.

Doctor of Philosophy / Department of Chemistry / Christopher J. Levy / A series of chiral symmetrical and unsymmetrical acid-functionalized Schiff-base ligands were synthesized by condensation reactions between 3-formyl salicylic acid and the two diamines (1R,2R)-cyclohexyldiamine (CHDA) and (R)-[1,1'-binapthalene]-2,2'-diamine (BINAM). The addition of a weak base (TEA) to these Schiff-bases resulted in the formation of a partially deprotonated ligand while the addition of the strong base NaOMe, resulted in fully deprotonated ligands. Complexations were carried out using metal salts of Fe(II), Co(II), Ni(II), Cu(II), Cu(I) and Zn(II). The partially deprotonated unsymmetrical Schiff-base (CHDA as the backbone), resulted almost exclusively in the formation of double-stranded helices with M helices. The fully deprotonated ligand, on the other hand, formed cubane-type structures with Fe(II), Co(II) and Ni(II) in methanol. Similar cubane-type structures were also obtained after complexation of the symmetrical CHDA-based ligands with Fe(II) and Co(II) using NaOMe in methanol. Reactions involving Cu(II) and Cu(I) salts resulted in either mono-or dinuclear salen complexes, even if the unsymmetrical Schiff-base was used as the starting ligand. This type of ligand conversion is dependent of the metal salt concentration in the reaction. Unsymmetrical Schiff-base ligands have a higher tendency to undergo conversion to their symmetrical salen analogues if the metal salt is added is much excess.

Several Schiff base ligands, N, N‟-(aryl)benzyaldiimine ligands (R-BEN); N, N‟-(aryl)benzyaldiamine dihydrochloride ligands (R-BENH•2HCl); N, N‟-(aryl)benzyaldiamine ligands (R-BENH); N, N‟-bis(cinnamaldiimine) ligands (R-CA2EN) were synthesized for the investigation of the electronic effect of the substituents at para-position of the Schiff base ligands and their copper complexes. The synthesis of Schiff bases was carried out by reacting a series of para-substituted benzyaldehyde, and para-substituted cinnamaldehyde with ethylenediamine. The imine group of Schiff bases, N, N‟-(aryl)benzyaldiimine ligands and N, N‟-bis(cinnamaldiimine)ligands were reduced to corresponding amines with sodium borohydride in methanol These ligands, N, N‟-(aryl)benzyaldiamine ligands (H-BENH), N, N‟-bis(cinnamaldiimine)ligands (CA2EN) were reacted with copper(II) dihalide and copper(I) monohalide ions respectively to form complexes. The ligands and their complexes were analysed using elemental analyses, FT-IR spectroscopy (mid-IR), UV/vis in aprotic and protic solvents,while mass spectrometry, 1H-NMR and 13C-NMR were used to further analyse the ligands. By using substituent parameters, both the single and dual substituent parameters with the spectroscopic data obtained from the spectroscopic techiques mentioned above, it was hoped to monitor and determine whether the electronic effects (resonance or inductive effcets) was predominantly within the Schiff base ligands and copper complexes. The NMR studies with dual substituent parameters suggest that the effects of the substituents are transimitted through the ligands, via resonance effects and that the phenyl group is nonplanar with the azomethine in N, N‟-(aryl)benzyaldiimine ligands. The presence of an extra double bond in Schiff base {(N, N‟-bis(cinnamaldiimine) ligand)} altered the electron density. The UV/vis studies showed that the symmetry of the N, N‟-bis(4-R-benzyl)-1, 2-diaminoethanedihalidecopper(II) complexes were predominantly tetrahedral for both chloro and bromo complexes. The correlation studies from mid-infrared were beneficial in monitoring the effect experienced by N, N‟-(aryl)benzaldiimine ligands, the studies suggest that the inductive effect is more pronounced at the C=N.

No description available.

No description available.

Polystyrene bis(salicylaldehyde)-propylene-1,3-diiminato Cobalt (II) (salen) and Polystyrene bis(acetylacetone)-propylene-1,3-diiminato Cobalt (II) (BAE) were prepared stepwise from polystyrl chloride. The reaction series included substitution of the chloride with a malononitrile carbanion, reduction to a diamine, condensation to form a Schiff base, and complexation with Co(II) acetate to form the active polymeric material. Optimum conditions with regard to time, temperature, reaction ratios, and solvent were determined for each reaction. The ability of the polymer bound cobalt complex to oxidize 3-methyl indole was measure. The BAE catalyst yielded a large amount of the corresponding o-formylaminoacetophenone. However, the exact yield is not known because product could not be separated from the indole. The salen catalyst showed starting material with a small indication of product.

The purpose of this thesis is to examine a potential Mn(II) complex model system and its corresponding oxygenated products. The Schiff base ligands chosen for this study (Figure 3) were of the type believed to be in, the environment of manganese as it exists in the photosynthetic process. The ligand systems employed will be derived from salicylaldehyde and a series of straight-chain diamines and 3,3'-bis (aminopropyl)- amine. / Master of Science

The synthesis and characterization of two new Schiff base copper(II) complexes are reported. These are Cu(acac: 2-amino-l-phenylethanol) and Cu(acac:2-amino-l-butanol). The ligands, derived from acetylacetone and the appropriate aminoalcohol, are dibasic tridentates with 0,N,O donor atoms. The magnetic properties of the complexes were studied at several temperatures between 78 OK and 296 OK. The magnetic moment of Cu(acac:2-amino-l-phenylethanol) varied little with temperature, and that of Cu(acac:2-amino-lbutanol) increased as the temperature was lowered. This is in contrast to the magnetic moment of Cu(acac:ethanolamine), which decreases as the temperature decreases. Molecular weight data, infrared spectra, magnetic data, electronic spectra, and electron spin resonance spectra of both complexes are reported and discussed.