Thesis (Ph. D.)--University of Pennsylvania, 1932. / "Reprinted from the Journal of the American chemical society, vol. 54, no. 9."

Thesis (Ph. D.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 303-328). Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 303-328). Also available online.

In this research, the use of gold nanostructures (AuNS) was explored to evaluate the interaction between molecules and the nanoparticle (NP) surface. In that way, three different projects were developed; one project using fluorescence and two projects using Raman spectroscopy as measuring technique. The fluorescence spectroscopy project used the fluorescence lifetime imaging microscope (FLIM) to evaluate the relative position of the molecules methylene blue (MB) and cucurbit[7]uril (CB) on the gold nanoparticle (AuNP) surface. Although the inclusion complex is favored in solution, it was found that MB forms an exclusion complex with CB, when CB is attached to the AuNP surface. The first project utilizing Raman spectroscopy, specifically surface enhanced Raman scattering (SERS), took advantage of a confined system (a reverse micelle) to evaluate the Raman signal of water molecules in close proximity to the AuNP surface. It was observed that the SERS water signal had a big shift to higher energies compared with the Raman signal of the bulk water; indicating the water molecules in the system are subjected to different bond-stretching energies. The second Raman project studied the modification of two different AuNS (specifically AuNP and gold nanorod -AuNR) with thiols. Different thiols were used to evaluate the kinetics of the modification of the AuNS surface, also the different AuNS presented different ligands on their surface. In general, and considering the difference in the bonding strength of the ligands present on the AuNS surface (by synthesis) and the size of the thiol, at least 2 h are required to modify the complete AuNS surface.

Submitted by Programa de Pós-graduação em Biotecnologia (mebiotec.ufba@gmail.com) on 2017-04-06T12:35:58Z No. of bitstreams: 1 DISSERTACAO EVARISTO FINAL (1).pdf: 3619384 bytes, checksum: ce2f500cb5c5efadf38bd2d0f730d863 (MD5) / Approved for entry into archive by Delba Rosa (delba@ufba.br) on 2017-06-29T14:36:51Z (GMT) No. of bitstreams: 1 DISSERTACAO EVARISTO FINAL (1).pdf: 3619384 bytes, checksum: ce2f500cb5c5efadf38bd2d0f730d863 (MD5) / Made available in DSpace on 2017-06-29T14:36:51Z (GMT). No. of bitstreams: 1 DISSERTACAO EVARISTO FINAL (1).pdf: 3619384 bytes, checksum: ce2f500cb5c5efadf38bd2d0f730d863 (MD5) / CNPq / A leishmaniose é uma doença de grande relevância à saúde pública em que a Leishmania braziliensis é um dos agentes etiológicos. Seu tratamento é realizado através da administração de medicamentos considerados tóxicos às células humanas, caros e ineficientes às diversas espécies de Leishmania, podendo resultar em cepas resistentes e por essas razões, estudos que abordem novas terapias com vista a reduzir os efeitos indesejados são de suma importância. A terapia fotodinâmica (TFD), é uma das técnicas ditas como sendo promissoras no tratamento de inúmeras doenças parasitárias. Portanto, foi proposto este trabalho com o objectivo de avaliar os efeitos da TFD na L. braziliensis, bem como a interação deste parasito com macrófagos J774, utilizando como fotossensibilizador, o azul de metileno na concentração de 12,5 µg/mL associado ao LASER vermelho de baixa potência com λ = 660 nm; 40 mW; 8,4J /cm2. Os testes foram realizados em triplicata, e as amostras foram distribuídas em quatro grupos: Grupo Controle, Grupo Fotossensibilizador, Grupo LASER, Grupo TFD. Como métodos avaliativos da morfologia e ultraestrura das promastigotas face aos efeitos da TFD sobre a Leishmania, foram utilizadas as microscopias eletrônicas de varredura e de transmissão. Para a avaliação da interação, foi utilizada a microscopia ótica. Nela, foram realizadas contagens de macrófagos infetados e não infetados. Como resultado, foi observado que a TFD foi capaz de criar deformações morfológicas e estruturais compatíveis com alterações promovidas por ‘stress’ oxidativo. Após a analise dos ensaios de interação foi observado que a infecção de macrófagos no grupo TFD apresentou taxa de infecção menor que no controle com uma significância de p=0.0339 e p=0.0181 nos períodos respetivos de 24 e 48 horas. Aavaliação estatística foi realizada através do teste ANOVA com pós-teste de Tukey, p <0,05. Assim, conclui-se que a TFD além de ser eficaz em causar danos potencialmente letais à promastigotas de Leishmania braziliensis ela também, é capaz de estimular a resposta do sistema imune, desempenhando um papel sinergístico. / Leishmaniasis is a disease of great importance to public health in what Leishmania braziliensis is one of the etiological agents. The treatment is performed by administering drugs considered toxic to human cells, expensive and inefficient to several species of Leishmania and can result in resistant strains and for these reasons, studies that address new therapies to reduce the unwanted effects are of paramount importance. Photodynamic therapy (PDT) is a technique said to be promising in the treatment of many parasitic diseases. Therefore, we proposed this work aimed to evaluate the effects of PDT in L. braziliensis and the interaction of this parasite with J774 macrophages, using as a photosensitizer, methylene blue at a concentration of 12.5 µg/mL associated with red Low power LASER with λ = 660 nm; 40 mW; 8,4 J/cm2. The tests were performed in triplicate, and the samples were divided into four groups: control Group, photosensitizer Group, LASER Group and TFD Group. As evaluative methods of morphology and structure, promastigotes against the effects of PDT on Leishmania, electronic microscopy scanning and transmission were used. For the evaluation of the interaction, the optical microscope was used. Here, infected macrophage counts were performed and uninfected. As a result, it was found that PDT was able to create morphological and structural deformation compatible with alterations resulting Oxidative stress. After the analysis of the interaction tests was observed that infection of macrophages in the PDT group showed lower infection rate than the control with a significance of p = 0.0339 and p = 0.0181 in the respective periods of 24 and 48 hours. Statistical analysis was performed using ANOVA with Tukey's post-test, p <0.05. Thus, the conclution is that PDT is effective in causing potentially lethal damage to Leishmania braziliensis promastigotes it is able to stimulate the immune system response and plays a synergistic role.

Made available in DSpace on 2014-10-09T12:52:41Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:13Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Orientador: Carlos Augusto Araújo Valadão / Banca: Euripedes Batista Guimarães / Banca: Guilherme de Camargo Ferraz / Banca: Antonio Carlos Alessi / Banca: Rita de Cássia Campebell / Resumo: 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. / Abstract: 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. / Doutor

Made available in DSpace on 2014-10-09T12:52:41Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:13Z (GMT). No. of bitstreams: 0 / Os experimentos de adsorção descontínuos foram realizados para remover azul de metileno de solução aquosa usando zeólitas sintetizadas a partir de cinza leve de carvão como adsorvente. Os estudos foram conduzidos para avaliar os efeitos do tempo de contato, concentração inicial do corante, parâmetros de ativação hidrotérmica, composição da cinza leve, quantidade do adsorvente, pH e temperatura sobre a adsorção. Um tempo de contato de aproximadamente 10 minutos foi suficiente para a adsorção do corante alcançar o equilíbrio. Os dados de equilíbrio foram analisados usando as isotermas de Langmuir e Freundlich e os resultados se ajustaram melhor à equação da isoterma de Freundlich. A eficiência de adsorção estava entre 72 a 98% sob as condições estudadas. O valor da constante de Freundlich para a capacidade de adsorção (KF) do azul de metileno no adsorvente foi 0,738 (mg/g) (L/mg)1/n. Os dados de adsorção foram ajustados aos modelos cinéticos de pseudoprimeira- ordem de Lagergren e pseudo-segunda-ordem e seguiram as cinéticas de pseudosegunda- ordem. As constantes de velocidade foram estimadas em diferentes concentrações iniciais. O mecanismo do processo de adsorção encontrado mostrou-se complexo, consistindo de adsorção superficial e difusão intrapartícula. Os parâmetros termodinâmicos foram avaliados indicando que o processo de adsorção do azul de metileno sobre a zeólita é espontâneo e exotérmico. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

M.Sc. / This study comprises the preparation and characterisation of new azolinylidene- and divinylcarbene complexes of chromium, molybdenum and tungsten, from 1- phenylpyrawle, 1-methylimidazole and 4,4-dimethyl-2,2-thienyloxazoline precursors. The reaction of 1-phenylpyrazolyllithium with (C0) 6M (M Cr, Mo or W) yields after alkylation with CH3S03CF3 in THE the two products (C0)5M[C(OCH3X(ONPhNCHC(H)] and (C0)5M[C(0{CH2}40C113)(aNPhNCH6H)]. A 'H NMR study indicates the existence of two isomers for each of the two tungsten CO'cli•lexes. 1-Methylimidazolyllithiura reacts with (CO)6M (M = Cr, Mo or W) to give the carbene complexes (C0)5MK'N(CH3)CHCH14(C I i 3)] after alkylation with CH3S03CF3, and the imine complexes (C0)5MOCHN(CH3)CH6H] after protonation with SO3CF3. Reaction of 1-methylimidazolyllithium with the anionic salt (C0)5 Cl = Cr or W), followed by alkylation with CH3S03CF3 affords both the mono- and bis(carbene) complexes, (CO)5M[CN(CH3)CHCHN(CH3)] and (C0)41v1[6N(CH3)CHCIRA(CH3)]2. The complex (C0)5W[C(0 {CH2 } 40C113)(t‘NPhNaldH)] reacts with phenylethynthiolate to furnish an anionic organometallic synthon that can either be alkylated or protonated. Protonation leads to two isomeric forms of the metal-coordinated thioaldehyde, (C0)5W4—SHC(Ph)=C(OCH3)(oNPhNCHell), whilst alkylation with various electrophilic reagents produces the metal coordinated dithio-esther (C0)5 W4--S=C [ SCH3] [C(Ph)=C(OCH3)(tNPhNaldH)]. The neutral divinylcarbene complexes (C0)5Cr{cC(a0CH2CMe2N)SC CH} (a) and (C0)5W{cC(COCH2CMe214)SCH9H} (19) are prepared by reaction of (C0)5MCr with the 3-lithiated thienyloxazoline, followed by alkylation with CH3S03CF3 . These complexes are the first examples of coordinated 'divinylcarbenes utilizing the group 6 transition metals, where the carbene carbon shows carbene character. They are also in another sense unique since the nucleopbutlic heteroatom where alkylation occurs, is situated outside the coordinated ring-system, and, therefore, more than two bonds removed fro the carbene carbon atom.

M.Sc. / Please refer to full text to view abstract.