Thesis (Ph. D.)--University of Chicago, Dept. of Chemistry, August 2000. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph.D.(Chemistry))--University of Pretoria, 2000. / Includes abstract in English and Afrikaans. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--University of Akron, Dept. of Chemistry, 2005. / "May, 2005." Title from electronic dissertation title page (viewed 09/24/2005). Includes bibliographical references.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2001. / Summaries in Afrikaans and English.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Douglass F. Taber, Dept. of Chemistry and Biochemistry. Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, Dept. of Chemistry, August 1999. / Includes bibliographical references. Also available on the Internet.

Thesis (PhD)--University of Stellenbosch, 2005. / Bibliography. Also available via the Internet.

Thesis (MSc)--University of Stellenbosch, 2005. / Bibliography. Also available via the Internet.

Made available in DSpace on 2014-06-11T19:31:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-07-03Bitstream added on 2014-06-13T20:22:00Z : No. of bitstreams: 1 borges_jhs_dr_jabo.pdf: 283985 bytes, checksum: b9c4395bd3d21e16f86c5a71e29c87e1 (MD5) / A endotoxemia é um distúrbio grave na clínica veterinária, sendo uma das principais causas de mortalidade em equinos.Trabalhos recentes relatam a eficácia do azul de metileno na prevenção dos danos impostos pelo óxido nítrico. Este estudo foi concebido com o fito de avaliar os efeitos do azul de metileno sobre as respostas clínica, celular e bioquímica, na endotoxemia experimental em equinos. Os animais foram divididos em três grupos. LPS+AM recebeu LPS e foi tratado com 3mg/kg de azul de metileno 60 minutos após a indução da endotoxemia; LPS+NaCl também recebeu LPS e foi tratado com 3mg/kg de azul de metileno 255 minutos após a indução da endotoxemia, e NaCl+AM que recebeu NaCl e foi tratado com azul de metileno 60 minutos após a infusão do NaCl. Foram realizados exames clínicos e laboratoriais durante 12 horas em quatro momentos. Observou-se aumento de temperatura, leucopenia e aumento no fibrinogênio nos animais pré-tratados com LPS, a partir do momento 90minutos. Não foi possível afirmar se houve efeito benéfico do azul de metileno sobre a resposta dos equinos frente à endotoxemia experimental. / Endotoxemy is a severe disturb in Veterinary Clinics and one of the most important causes of deaths in equine. Recent papers report the efficiency of methylene blue in preventing the damage caused by nitric oxide. The aim of this work was to study the effects of methylene blue in clinic, cellular and biochemistry responses in experimental endotoxemy of horses. The animals were divided in three groups. The group LPS+AM received LPS and was treated with 3mg/Kg of methylene blue 60 minutes after the induction of endotoxemy; LPS+NaCl also received LPS and was treated with 3mg/Kg of methylene blue 255 minutes after the induction of endotoxemy and NaCl+AM that received NaCl and was treated with methylene blue 60 minutes after NaCl infusion. Clinical and laboratorial exams were done in four moments during 12 hours. There was an increase in temperature levels, leucopenia and increase in fibrinogen in the animals treated with LPS, beginning within 90 minutes. It was not possible to affirm if there was any benefit in the use of methylene blue in inflammatory response of horses with induced endotoxemy.

M.Sc. / This study focussed on two areas of research in the field of organometallic chemistry. The first entails the preparation and characterisation of a number of Fischer-type carbene complexes of the general formula (C0) 5M(OR)(RI) (1 - 4). For the first group M = Cr, Mo or W, R = Et or Me and re = Ph or BiPh. A second, somewhat different group was prepared by deprotonating 4- methylthiazol-2-methyltlfioether, reacting it with M(CO) 6, where M = Cr or W, and neutralising the resulting anion with methyltriflate. Both metals afforded only one product which could be successfully purified and characterised as M(C0),{C(OCH3)(C=C(CH3)N=C(SCH3)S) (6,7). The crystal structure of the tungsten complex was solved by single crystal X-ray techniques. A similar carbene complex preparation was carried out with 5-methylthiophenilyl-2-thiomethylether and M(C0)6, M = Cr or W, as starting reagents. In addition to the expected carbene complexes M(CO)5 (C(OCH3)(CH2SHCH=C(CH3)S)), M = Cr and W (9a, 10a), deprotonation of a ring carbon yielded M(C0) 5{C(OCH3)(6=C(SCH3)SC(CH3)=CH)) M = Cr and W (9b, 10b), whereas unreacted starting material afforded the sulfide W(C0) 54-SC(SCH3)=CHCH=C(CH3) (11). The second part of the thesis describes the preparation of pentacarbonyl thione and iminocomplexes, as well as tricarbonyl imino-, sulphide and dinuclear re-sulphide complexes. 4- Methylthiazoly1-2-thiolate were used for nucleophilic attack on (C0) 5Cr--C(OR)(12. 1) (1 and 4) to yield the thione complex Cr(C0) 54-S=CN(CH3)C(CH3)=CHS (13) upon methylation. Two other products were also obtained from these reactions : Cr(C0) 54-NC=CHSCH=C(CH3) (12) and Cr(CO) 54-N=C(CH3)SCH=C(CH3) (14), which indicates incomplete reaction with sulfur during the formation of the mentioned thiolate. Three beautiful electron ligand systems were produced by reacting 4-methylthiazol-2-disulphide with (CO),W(THF) or Fe2(C0)) . A new "butterfly" bidentately coordinated tricarbonyl tungsten complex, [(C0)3 1/{N(S)SCH(CH3)) 2] (16) was obtained. The crystal structure of this complex shows many similarities to a known complex, (C0)3W(n2-PyS)2 that was prepared from ionic metalcarbonyl precursors. In addition to 16, a thione complex W(C0) 54-SHC(CIi )=CHS (17) also formed from the reaction with (CO) 5M(THF). The reaction between (CO),M(THF) and 4-methylthiazolyi-2-disulphide thus probably involves heterolytic bond cleavage and protonation on the silica gel. The reaction of Fe 2(CO)9 with the same disulphide resulted in the formation of the dinuclear compound Fe2(C0)6(SC=NC(CH3)=CHS)2 (18), possibly via the homolytic splitting of the disulphide bond. The crystal structure of this compound revealed the Fe-Fe-bond and eclipsed configuration, typical of this type of Fe-cluster complex. Finally, two thione complexesM(C0)54—S(SMe)(eHCH(Me)S), (M= Cr and W; 20,21) were found to isomerise in solution to their sulphide analogues of which only the chromium complex Cr(C0)54— SC(Me)=CHCH=C(C(=S)(SMe)) (22) could be characterised.