Influence of triazine based pesticide (Sencor 70 WG - active substance metribuzine) was assessed via biochemical and hematological blood profile determination of experimental fish. As experimental fish we used common carp (Cyprinus carpio L.) and rainbow trout (Oncorhynchus mykiss ). Before rating the Sencor 70 WG pesticide influence on biochemical and hematological blood profile we accomplished a preliminary test to determine a concentration range and after that a basic acute toxicity test to determine 96hLC50 value. Both fish samples fingerlings were used for performing the tests. After 96hLC50 determination two groups of experimental fish (aged 1-2 years) were under this concentration and one control group without the substance. The test was processed according to the OECD methodology No. 203. Fish dissection was performed after the test. The increased amount of phlegm of water consistency on the body surface was found out. The fish were of dark colour in contrast with the control group. The ventricle was larger and containing transudate. An outstanding vascular profusion of internal organs in the ventricle was found out. Biochemical profile of the rainbow trout (Oncorhynchus mykiss ) experimental group under 96 hour acute operation of pesticide Sencor 70 WG (89,3mg.kg-1) proved significant lowering (p<0,01) of total proteins (TP), triglycerides (TRIG), aspartate aminotransferase (AST), amonnia (NH3), alcaline phosphatase (ALP) and Ca2+ in the blood plasma in contrast with the control group. Hematological profile of the same group proved significant lowering (p<0,05) of the number of erythrocytes (Er), haematocrit (PCV), and significant increase (p<0,05) of erythrocyte haemoglobin (MCH) value in contrast with the control group. Biochemical profile of the common carp (Cyprinus carpio L.) experimental group under 96 hour acute operation of pesticide Sencor 70 WG (250,2 mg.l-1) proved significant lowering (p<0,01) of total proteins (TP), triglycerides (TRIG), lactate dehydrogenase (LDH), Ca2+ and inorganic phosphate (PHOS) and significant increase (p<0,01) of glukose (GLU) and amonnia (NH3) concentration in the blood plasma in contrast with the control group. Hematological profile of the same group proved significant lowering (p<0,01) of the haematocrit (PCV), erytrocyte haemoglobin (MCH), mean erytrocyte volume (MCV) and number of leukocytes (Leuko) in contrast with the control group.

Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2018-06-21T13:56:35Z No. of bitstreams: 2 Tese - Francielle Queiroz Soares - 2018.pdf: 4062174 bytes, checksum: caec2644f4aa247943bf36592f90e826 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-06-27T11:03:01Z (GMT) No. of bitstreams: 2 Tese - Francielle Queiroz Soares - 2018.pdf: 4062174 bytes, checksum: caec2644f4aa247943bf36592f90e826 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-06-27T11:03:01Z (GMT). No. of bitstreams: 2 Tese - Francielle Queiroz Soares - 2018.pdf: 4062174 bytes, checksum: caec2644f4aa247943bf36592f90e826 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-06-08 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / Monolithic polymers can be defined as continuous porous polymers, synthesized in situ in a mold. These materials have been used in chromatographic applications due to the combination of high surface area with excellent permeability and mass transport properties. In this work, monolithic polymers based on styrene and divinylbenzene were synthesized by thermal initiation via bulk polymerization in the presence of different diluents; and via high internal phase emulsion polymerization in presence and absence of toluene as diluent. The monoliths produced via bulk polymerization, which were synthesized in the presence of binary mixtures tetrahydrofuran/decanol and toluene/decanol as polymerization diluents in the ratio 15:85 (v/v) showed mechanical resistance to be applied as extractive phases. Both formulations produced polymers with macroporous characteristics and the tetrahydrofuran/decanol mixture presented larger channels, resulting in higher permeability, in this way it was used as extraction phase for the technique of preparation of samples based on a device of sorptive extraction of micropipette tip (DPX) applied to the determination of triazines in water samples. Under optimized conditions the absolute recovery for the triazines varied from 28 to 64%. The monoliths produced by high internal phase emulsion polymerization showed macroporosity. We have found that the effect of the solvent is more significant for the increase in surface area and the volume and mean diameter of pores than the effect of the reduction of these by the increase in velocity. With this, the monolith prepared in the presence of toluene at a speed of 3000 rpm obtained a larger surface area and a larger volume and pore diameter, resulting in a higher permeability. The surface of this monolith was modified with polypyrrole, to verify this film on the selectivity of the resulting phase. When submitted to the extraction process using solid phase extraction devices (SPE), the monolith covered with PPY films presented better extraction efficiency and its parameters were optimized for determination of triazines in water samples by the SPE/LC-UV method (SPE/high performance liquid chromatography with UV-vis detection). According to the figures of merit evaluated, the proposed SPE/LC-UV method presented linearity in the concentration range of 0.5-50 ng.mL-1 and absolute recovery of 75 to 105%, with precision demonstrated by the coefficient of variation lower than 15%. The limit of quantification of the method was 0.5 ng.mL-1 for all the analytes. Thus, it was possible to develop new low-cost monolithic phases with chemical and mechanical resistance and physicochemical characteristics suitable for use as extractive phase in the miniaturized technique of preparation of DPX samples, as well as SPE. The developed phases were evaluated for the determination of triazines in water samples with adequate selectivity and sensitivity. Based on the results, the developed phases present themselves as promising alternative to the commercial extractive phases. / Os polímeros monolíticos podem ser definidos como polímeros contínuos altamente porosos, sintetizados in situ em um molde. Esses materiais têm sido empregados em aplicações cromatográficas devido a combinação de alta área superficial com excelentes propriedades de permeabilidade e transporte de massa. Nesse trabalho, polímeros monolíticos a base de estireno e divinilbenzeno foram sintetizados por iniciação térmica, via polimerização em massa na presença de diferentes diluentes; e via polimerização em emulsão de alta fase interna, na presença e na ausência de tolueno como diluente. Os monolitos produzidos via polimerização em massa, que foram sintetizados na presença das misturas binárias tetrahidrofurano/decanol e tolueno/decanol como diluentes de polimerização na proporção 15:85 (v/v) apresentaram resistência mecânica para serem aplicados como fases extratoras. Ambas as formulações produziram polímeros com característica macroporosa e a mistura tetrahidrofurano/decanol apresentou canais maiores, resultando em menor resistência à vazão, desta forma este foi utilizado como fase extratora para técnica de preparo de amostras baseada em dispositivo de extração sortiva em ponteira (DPX) aplicado à determinação de triazinas em amostras de água. Nas condições otimizadas a recuperação absoluta para as triazinas variou de 28 a 64%. Para os monolitos produzidos via polimerização em emulsão de alta fase interna, o efeito do solvente é mais significativo para o aumento da área superficial e do volume e diâmetro médio de poros do que o efeito da redução desses pelo aumento da velocidade de agitação. Com isso o monolito preparado na presença de tolueno na velocidade de 3000 rpm obteve maior área superficial e maior volume e diâmetro de poro, resultando em menor resistência à vazão e sua superfície foi modificada com polipirrol. Quando submetidos ao processo de extração empregando dispositivos de extração em fase sólida (SPE), o monolito recoberto com filmes de PPY, apresentou maior eficiência de extração sendo então seus parâmetros otimizados para determinação de triazinas em amostras de água pelo método SPE/LC-UV (SPE/cromatografia líquida de alta eficiência com detecção UV-vis). Segundo as figuras de mérito avaliadas o método SPE/LC-UV proposto, apresentou linearidade na faixa de concentração de 0,5-50 ng.mL-1 e recuperação absoluta de 75 a 105 %, com precisão demonstrada pelos coeficientes de variação menores que 15%. O limite de quantificação do método foi de 0,5 ng.mL-1 para todos os analitos. Assim sendo, foi possível desenvolver novas fases monolíticas de baixo custo com resistência química e mecânica e características físico-químicas adequadas para emprego como fase extratora em técnica miniaturizada de preparo de amostras DPX, assim como em SPE. As fases desenvolvidas foram avaliadas para determinação de triazinas em amostras de água apresentando seletividade e sensibilidade adequada. Com base nos resultados, as fases desenvolvidas apresentam se como promissora alternativa às fases extratoras comerciais.

Submitted by Cássia Santos (cassia.bcufg@gmail.com) on 2016-10-13T15:45:24Z No. of bitstreams: 2 Tese - Daniela Cristina Vinhal - 2016.pdf: 4607774 bytes, checksum: 60991eb50ad135a43a5bb84902551bba (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2016-10-14T19:58:28Z (GMT) No. of bitstreams: 2 Tese - Daniela Cristina Vinhal - 2016.pdf: 4607774 bytes, checksum: 60991eb50ad135a43a5bb84902551bba (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-10-14T19:58:28Z (GMT). No. of bitstreams: 2 Tese - Daniela Cristina Vinhal - 2016.pdf: 4607774 bytes, checksum: 60991eb50ad135a43a5bb84902551bba (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-09-30 / In Brazil, the estimates for the year 2016 point to approximately 596,000 new cases of skin cancer, being mostly related to exposure to ultraviolet radiation. According to current consensus, such damage can be minimized by prophylactic use of sunscreens. This way, this study proposes the planning, synthesis, structural characterization and toxicological assessment of a new candidate compound to organic sunscreen, LQFM184 (20). The structural planning was based both on molecular similarity in chemical action triazine derivatives (10, 11 and 13), cinnamic (4) and LQFM048 (14), with the starting compound (E)-2-cyano-3-(4-hydroxy-3-methoxyphenyl)acrylamide (18) which was produced from vanillin. In addition, LQFM184 (20) compound has molecular weight 729.65 Daltons and the synthetic route proposal consisted of two stages, 53% overall yield, which were performed under the scope of green chemistry. All the synthesized compounds were characterized by techniques of nuclear magnetic resonance, infrared, mass, ultraviolet and fluorescence. From the spectrophotometric absorption technique it was identified that LQFM184 (20) compound had two peaks of maximum absorption (λmax.) 306 nm in the region of UVB and 344 nm for UVA and molar absorptivity (ε) whose values were above 104 M-1 cm-1. As to the technique of cyclic voltammetry LQFM184 (20) compound was stable considering the applied potential and when under an atmosphere of synthetic air showed a weight loss of ~14% in the range of 250°C, characterized as a stable compound at high temperatures. From the in vitro evaluation by the spectrophotometric method described by Mansur it presented Solar Protection Factor (SPF) equal to 3.69 for the UVB. Moreover, the compound does not promote irritation or serious damage when in contact with rabbit cornea cells SIRC and was classified in category 4 of the GHS system as OECD 423, low toxicity. At the end of this work it is possible to observe that the proposed synthetic route to obtain the LQFM184 (20) compound was effective, given the obtained high yields, laborious and low cost steps as well as promising profile sunscreen. / No Brasil, as estimativas para o ano de 2016 apontam para a ocorrência de, aproximadamente, 596 mil casos novos de câncer de pele, sendo em sua maioria relacionados com a exposição à radiação ultravioleta. Segundo consenso atual, tais danos podem ser minimizados através do uso profilático de protetores solares. Neste sentido, o presente trabalho propôs o planejamento, a síntese, a caracterização estrutural e a avaliação toxicológica de um novo composto candidato a fotoprotetor orgânico, o LQFM184 (20). O planejamento estrutural baseou-se tanto na semelhança molecular quanto na ação química de derivados triazínicos (10, 11 e 13), cinâmicos (4) e do LQFM048 (14), tendo como partida o composto (E)-2-ciano-3-(4-hidroxi-3-metoxifenil)acrilamida (18) que foi produzido a partir da vanilina. O composto LQFM184 (20) apresentou peso molecular de 729,65 Daltons e a rota sintética proposta constituiu-se por três etapas com rendimento global de 53%, das quais foram realizadas sob o âmbito da química verde. Todos os compostos sintetizados foram caracterizados através das técnicas de ressonância magnética nuclear, infravermelho, massas, ultravioleta e fluorescência. O composto LQFM184 (20) apresentou dois picos de absorção máxima (λmáx.), sendo 298 nm na região da UVB e 334 nm na UVA, além de coeficiente de absortividade molar (ε) acima de 104 M-1 cm-1. Quanto à voltametria cíclica o composto LQFM184 (20) manteve-se estável frente aos potenciais aplicados e quando exposto à atmosfera de ar sintético apresentou uma perda de massa de ~14% na faixa de 254°C, caracterizando-o estável sob temperaturas elevadas, visto que seu ponto de fusão ocorre em 147ºC. A partir da avaliação in vitro pelo método espectrofotométrico descrito por Mansur o mesmo apresentou Fator de Proteção Solar (FPS) igual a 3,69 para a UVB. Além disso, o composto não promove irritação ocular ou lesões oculares graves quando em contato com células de córnea de coelho SIRC e foi classificado na categoria 4 do sistema GHS conforme OECD 423, de baixa toxicidade. Ao término deste trabalho podemos observar que a rota sintética proposta para a obtenção do composto LQFM184 (20) se mostrou eficaz, face aos altos rendimentos obtidos, etapas pouco laboriosas e de baixo custo, bem como promissor perfil fotoprotetor.

Orientador: Sarah Arana / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-23T12:36:44Z (GMT). No. of bitstreams: 1 Peterlini_MarianaFrem_M.pdf: 4643636 bytes, checksum: cd0d6e62df40edebf5ce8326f7c80cd0 (MD5) Previous issue date: 2012 / Resumo: A agricultura intensiva no Brasil tem aumentado o risco de contaminação dos recursos hídricos e dos organismos aquáticos por agroquímicos. Esse é o caso da atrazina, detectada em alta frequência em rios e córregos da região. Assim, neste trabalho, o pacu (Piaractus mesopotamicus) foi escolhido como bioindicador por sua importância econômica e ecológica em Bacias do Pantanal. As brânquias e o tegumento foram aqui avaliados como biomarcadores da toxicidade induzida por atrazina, uma vez que estes órgãos se encontram em contato direto com o ambiente aquático. Para avaliar a sensibilidade de alevinos de pacu e determinar a Concentração Letal Média (CL50) à atrazina foram conduzidos experimentos, em duplicata, em sistema estático por 96 horas, com as seguintes concentrações: 0,0; 13,2; 17,6; 22,0; 26,4; 30,8; 35,2; 39,6 mgL-1. A CL50 obtida para a atrazina foi de 28,58 mgL-1 (96h). Foram realizadas análises anatomopatológica, histopatológica qualitativa e semi-quantitativa para brânquias e análises anatomopatológica e histopatológica qualitativa para o epitélio tegumentar. Amostras de brânquia e de pele dorsal e ventral foram fixadas em Bouin e incluídas em parafina. Para o grupo controle não foi registrada qualquer alteração com os métodos empregados. Os alevinos expostos à atrazina apresentaram alterações comportamentais como: escurecimento da pele, boquejamento intenso e distúrbios motores, além disso, nesses aquários houve constante presença de muco na água; e, alterações anatomopatológicas, como: hiperemia na pele, dilatação da região ventral, presença de líquido no estômago e ascite sanguinolenta. Nas brânquias dos grupos tratados foram observadas as seguintes alterações morfológicas: edema e afastamento na região interlamelar, hipertrofia e hiperplasia na região interlamelar, destacamento do epitélio respiratório, hipertrofia de células do epitélio respiratório, congestão, telangiectasia e fusão de lamelas secundárias. Na pele dorsal e ventral dos grupos tratados não se observou alteração histopatológica. As alterações motoras observadas são provavelmente decorrentes do efeito neurotóxico da atrazina. As análises branquiais confirmam o comprometimento respiratório e de osmoregulação nesse órgão, sendo que a análise semi-quantitativa indicou a hipertrofia de células do epitélio respiratório como a lesão mais severa. Finalmente, as brânquias mostraram-se biomarcadores adequados na avaliação dos efeitos tóxicos da atrazina em pacu e o valor da CL50 sugere que a atrazina é levemente tóxica para o pacu, porém pelos demais resultados observados, se infere que só analisar a mortalidade não é o suficiente para determinar o dano causado por agrotóxicos em peixes, assim, recomenda-se o emprego de vários biomarcadores, como por exemplo, análise de vários outros órgãos. Os resultados obtidos reforçam a importância de estudos desta natureza, para embasar medidas ambientais preventivas e reguladoras quanto ao uso desse herbicida / Abstract: The intensive agriculture in Brazil has caused growing increase of pollution risks of hydric resources and the aquatic organisms by agrochemicals. This is the case of atrazine, detected in high frequency in the rivers and streams. Therefore, in this research, the pacu (Piaractus mesopotamicus) was chosen by bioindicator because of its great economic and ecological importance to the water ecosystem of the Pantanal region. The gills and skin were assessed here as biomarkers of induced toxicity by atrazine, considering that these organs are in direct contact with the aquatic environment. To evaluate the sensitivity of pacu fingerlings and determine the Median Lethal Concentration (LC50) by atrazine, experiments were conducted, performed in duplicate, in static system for 96 hours, with the following concentrations: 0.0; 13.2; 17.6; 22.0; 26.4; 30.8; 35.2; 39.6 mgL-1. The LC50 for pacu was 28.58 mgL-1 (96h). Anatomopathological, qualitative histopathological and semiquantitative histopathological analyses were performed for the gills, and anatomopathological and qualitative histopathological analysis were performed for the skin epithelium. Gills and dorsal and ventral skin samples were fixed in Bouin and processed for the inclusion in paraffin. The control group did not register any other alterations with the methods used. The fingerlings exposed to atrazine presented behavioral changes, such as: darkening of the skin, an increase in the frequency of gasping and motor disturbances. Furthermore, these aquariums presented the constant presence of mucus in the water; and, anatomopathological alterations, such as: skin hyperemia, dilation of the ventral region, the presence of liquid in the stomach and bloody ascites. In the gills of treated groups were found the following morphological alterations: edema and spacing in the interlamellar region, hypertrophy and hyperplasia in the interlamellar region, epithelial lifting, hypertrophy of respiratory epithelium cells, congestion, telangiectasis and fusion of the secondary lamellae. For dorsal and ventral skin of treated groups no histological alterations were observed. The motor alterations observed are probably due to the neurotoxic effects of atrazine. The gills analysis confirm respiratory and osmoregulatory compromise in this organ, noting that semi-quantitative analysis indicated the hypertrophy of respiratory epithelium cells as the most severe lesion. Finally, the gills showed adequate biomarkers in the assessment of toxic atrazine effects in pacu and the LC50 value suggests that atrazine is lightly toxic to pacu. However, by other results observed, it is concluded that analyzing the mortality index alone is not enough to determine the damages caused by agrotoxics in fishes, so the use of other biomarkers is recommended, like for instance, analysis some other organs. The results obtained reinforce the importance of research of this nature, in order to establish preventive and regulatory environmental measures regarding the use of this herbicide / Mestrado / Histologia / Mestra em Biologia Celular e Estrutural

Made available in DSpace on 2014-08-20T14:30:16Z (GMT). No. of bitstreams: 1 Dissertacao_Aline Pinheiro_Moraes.pdf: 846337 bytes, checksum: 66b01044077d89e98213868cd5b7582a (MD5) Previous issue date: 2011-04-01 / Candidiasis is the most common fungal infection in denture wearers. The association between Candida and denture base is directly related to the efficiency of this micro-organism to adhere and colonize these surfaces, which is an essential initial step for the development of denture-related stomatitis. Additionally, the use of denture liners has increased, with these materials more prone to microbial adhesion when compared with acrylic resin due to its higher surface roughness. These materials have demonstrated capacity to interact with oral micro-organisms.This important problem is the reason why several attempts have been made to develop biomaterials containing antifungal. Thus, the aim of this study was to investigate the potential antifungal activity of triazine added to acrylic resin and liners used in prosthodontics using microcosms biofilm model with saliva derived from patients with or without candidiasis, verifying its effectiveness in reducing microbial adherence and consequently reduce the incidence of Candida infections. The mechanical properties of the tested materials after the incorporation of triazine were also evaluated. We considered four commercially available materials (a microwave-cured acrylic resin and two soft denture liners and one hard denture liner) to which were added different concentrations of triazine (0; 2.5; 5.0 and 10%). The results indicated that no difference were found among triazine concentrations in acrylic resin flexural strength (p= 0.059). Triazine addition did not result in surface roughness changes, although all denture liners presented higher surface roughness compared with acrylic resin, while in general, SoftConfort presented the highest roughness (p<0.001). In general, 5 and 10% triazine addition resulted in more soluble materials. All materials presented increased water sorption with the addition of triazine (p<0.05), except for CoeSoft, where no change was observed. Candidiasis patient saliva presented higher counts of total micro-organisms (p= 0.0294) and total streptococci (p = 0.0008). Regarding materials, total streptococci, total micro-organisms and Candida counts were higher in CoeSoft (p<0.0001). Candida species counts was the same for both saliva donors (p>0.05). The addition of triazine did not result in decrease of total micro-organisms, total streptococci or Candida species in all materials tested (p>0.05). In conclusion, the addition of triazine to acrylic resin and denture liners in a complex biofilm model did not modify the development of biofilms in both patients with and without candidiasis / A candidíase é a infecção oral fúngica mais comum em usuários de próteses. A associação entre o microrganismo Candida e as bases das próteses está diretamente relacionada à eficiência deste microrganismo em aderir e colonizar estas superfícies, sendo esta a etapa inicial essencial para o desenvolvimento da estomatite induzida por prótese. Associado a isto, o uso de reembasadores para próteses tem aumentado, sendo estes materiais mais propensos à adesão microbiana quando comparados a resina acrílica devido a sua maior rugosidade de superfície. Além disso, estes materiais tem demonstrado capacidade de interagir com microrganismos bucais. Este importante problema tem levado a tentativa de desenvolvimento de diversos materiais contendo agentes antifúngicos. Assim, o objetivo deste estudo foi investigar o potencial antifúngico da triazina adicionada à resina acrílica e reembasadores utilizados em prótese dentária, através de um modelo de biofilme de microcosmos, com salivas derivadas de pacientes com ou sem candidíase, verificando sua efetividade em reduzir a adesão microbiana e, consequentemente, diminuir a incidência de infecções por Candida. Também avaliaram-se as propriedades mecânicas dos materiais testados após a incorporação da triazina. Foram considerados quatro materiais comercialmente disponíveis (uma resina acrílica ativada por energia de micro-ondas, dois reembasadores resilientes e um reembasador permanente), aos quais foram adicionadas diferentes concentrações de triazina (0; 2,5; 5,0 e 10%). Os resultados indicaram que não houve diferença (p = 0,059) entre as concentrações de triazina para a resina acrílica de micro-ondas no teste de resistência à flexão. Em relação a rugosidade de superfície, embora a adição de triazina não tenha levado ao aumento da rugosidade, os reembasadores apresentaram maior rugosidade que a resina acrílica, com o SoftConfort apresentando, em geral, a maior rugosidade (p<0,001). De maneira geral, quando adicionada triazina a 5,0 e 10%, todos os materiais tornaram-se mais solúveis e apresentaram aumento de sorção de água (p<0,05), a exceção do CoeSoft, que não mostrou diferença com a adição do composto químico. Houve diferença entre salivas, sendo que aquela proveniente de individuo com candidíase apresentou maiores contagens de microrganismos totais (p = 0,0294) e estreptococos totais (p = 0,0008). Em relação aos materiais, a contagem de estreptococos, microrganismos totais e espécies de Candida foi maior no CoeSoft (p<0,0001). Entretanto, a contagem de espécies de Candida foi igual entre os doadores (p>0,05). A adição de triazina não resultou em diminuição de microrganismos totais, estreptococos totais ou espécies de Candida em nenhum dos materiais testados (p>0,05). Como conclusão, a adição de triazina a resina acrílica e reembasadores utilizados para confecção de base e reembasamento de próteses em um modelo complexo de biofilme não modificou o desenvolvimento de biofilmes em ambos os pacientes com ou sem candidíase

MSc (Chemistry) / Department of Chemistry / Identification of unique leads represents a significant challenge in drug discovery. This challenge is widely visible in neglected diseases such as tuberculosis, which is an infectious disease caused by bacillus Mycobacterium tuberculosis. The urgent need in search of new biological entities to fight back TB and drug resistant TB is a drive behind this project. Several specific synthetic protocols have been developed using 1,3,5-triazines due to the important biological properties which they display. The chemistry and an extensive spectrum of biological activities of s-triazines have been examined since several decades and this heterocyclic core has received emerging consensus. Hence, the aim of this project was to synthesize novel anti-TB drugs total with the usage of 1,3,5-triazine as a linker between known anti-TB drugs together with different types of amines. A total of 20 compounds were synthesized, 3 compounds were mono-substituted with an average yield of 75 %, 6 compounds were di-substituted with an average yield of 63 % and 11 compounds were tri-substituted with an average yield of 93 %. Out of 10 compounds which were analysed for biological activity 8 of which showed biological activity against M.smegmatis. Furthermore compound 26 which was hybridized with an amine and a known anti-TB drug inhibited better biological activity. In conclusion the influence of cyanuric chloride in combination with pyrrolidine and anti-TB drugs deserves further study. The newly synthesized compounds were characterized by IR, melting point, GC-MS, biological testing, 1H and 13C NMR. / NRF

When a material is adhered onto a specific surface it is relevant to know how to make thematerial stay on the surface. By investigating different primers to use with a triazine-basedadhesive, further improvements to using the adhesive on metals can be achieved. This studyfound that an adhesive of (2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl)tris(ethane-2,1-diyl)tris(3-mercaptopropanoate) (TEMPIC) and 1,3,5-triallyl-1,3,5-triazinane-2,4,6-trione(TATATO) adhered to titanium and stainless steel, two clinically used metal surfaces. Itfurther found that between a phosphonic acid primer, a biomimetic catechol primer and acommercially available silane primer the phosphonic acid primer gave the best adhesion.These results could be because of a higher amount of crosslinking for the phosphonic acidprimer. For further testing increased pH and increased amount as well as increasedhydrolysation time for the catechol and silane primers respectively is suggested. Shearstrength testing was used to determine the adhesion strength. The shear strength testswere done with conditioning in phosphate buffer saline (PBS) solution for 24h beforehand

The amount of boron accumulated in tumor tissue plays an important role regarding the success of the boron neutron capture therapy (BNCT). In this article, we report a modular system, combining readily available starting materials, like glycine, 1,3,5-triazine and the well-known 9-mercapto-1,7-dicarba-closo-dodecaborane(12), as well as alpha-d-galactopyranose for increased hydrophilicity, with a novel boron-rich tris-meta-carboranyl thiol.

Neste trabalho é apresentada a síntese e a caracterização de compostos do tipo 2-(2’- hidroxifenil)benzazóis derivados da 1,3,5-triazina, fluorescentes devido a um mecanismo de transferência protônica intramolecular no estado excitado (TPIEE). Foram preparados quatro novos corantes diclorotriazinil-(hidroxifenil)benzazólicos, que apresentam emissão de fluorescência na região azul-verde do espectro visível e deslocamentos de Stokes compatíveis com substâncias que sofrem o fenômeno da TPIEE. Estas substâncias foram caracterizadas por diversas técnicas espectroscópicas (IR, RMN e HR-MS), enquanto que as análises fotofísicas (absorção no ultravioleta-visível e emissão de fluorescência) foram realizadas em solução e no estado sólido. Os ensaios preliminares realizados indicam a possibilidade de emprego desses corantes como sondas fluorescentes de material celulósico. / The synthesis and characterization of new 2-(2’-hydroxyphenyl)benzazoles derivatives from 1,3,5-triazine, fluorescent due to an excited state intramolecular proton transfer (ESIPT) mechanism, were presented in this work. The four new dichlorotriazinylbenzazole derivatives synthesized present fluorescence emission in the blue-green region of the spectra and Stokes shift compatible with ESIPT compounds. The characterization of the new fluorescent reactive dyes by means of spectroscopic (IR, RMN, UV-Vis and fluorescence) and spectrometric (HRMS) techniques, and the study of the possibilities to dye cellulose fibers were carried out. Fluorescent cellulose fibers were prepared using the dyes and a methodology used in the industry and show no color change when observed in the visible light (white cellulose) and a blue-green fluorescence when irradiated with UV light.

In the first section of the thesis graphitic carbon nitride was for the first time synthesised using the high-temperature condensation of dicyandiamide (DCDA) – a simple molecular precursor – in a eutectic salt melt of lithium chloride and potassium chloride. The extent of condensation, namely next to complete conversion of all reactive end groups, was verified by elemental microanalysis and vibrational spectroscopy. TEM- and SEM-measurements gave detailed insight into the well-defined morphology of these organic crystals, which are not based on 0D or 1D constituents like known molecular or short-chain polymeric crystals but on the packing motif of extended 2D frameworks. The proposed crystal structure of this g-C3N4 species was derived in analogy to graphite by means of extensive powder XRD studies, indexing and refinement. It is based on sheets of hexagonally arranged s-heptazine (C6N7) units that are held together by covalent bonds between C and N atoms. These sheets stack in a graphitic, staggered fashion adopting an AB-motif, as corroborated by powder X-ray diffractometry and high-resolution transmission electron microscopy. This study was contrasted with one of many popular – yet unsuccessful – approaches in the last 30 years of scientific literature to perform the condensation of an extended carbon nitride species through synthesis in the bulk. The second section expands the repertoire of available salt melts introducing the lithium bromide and potassium bromide eutectic as an excellent medium to obtain a new phase of graphitic carbon nitride. The combination of SEM, TEM, PXRD and electron diffraction reveals that the new graphitic carbon nitride phase stacks in an ABA’ motif forming unprecedentedly large crystals. This section seizes the notion of the preceding chapter, that condensation in a eutectic salt melt is the key to obtain a high degree of conversion mainly through a solvatory effect. At the close of this chapter ionothermal synthesis is seen established as a powerful tool to overcome the inherent kinetic problems of solid state reactions such as incomplete polymerisation and condensation in the bulk especially when the temperature requirement of the reaction in question falls into the proverbial “no man’s land” of classical solvents, i.e. above 250 to 300 °C. The following section puts the claim to the test, that the crystalline carbon nitrides obtained from a salt melt are indeed graphitic. A typical property of graphite – namely the accessibility of its interplanar space for guest molecules – is transferred to the graphitic carbon nitride system. Metallic potassium and graphitic carbon nitride are converted to give the potassium intercalation compound, K(C6N8)3 designated according to its stoichiometry and proposed crystal structure. Reaction of the intercalate with aqueous solvents triggers the exfoliation of the graphitic carbon nitride material and – for the first time – enables the access of singular (or multiple) carbon nitride sheets analogous to graphene as seen in the formation of sheets, bundles and scrolls of carbon nitride in TEM imaging. The thus exfoliated sheets form a stable, strongly fluorescent solution in aqueous media, which shows no sign in UV/Vis spectroscopy that the aromaticity of individual sheets was subject to degradation. The final section expands on the mechanism underlying the formation of graphitic carbon nitride by literally expanding the distance between the covalently linked heptazine units which constitute these materials. A close examination of all proposed reaction mechanisms to-date in the light of exhaustive DSC/MS experiments highlights the possibility that the heptazine unit can be formed from smaller molecules, even if some of the designated leaving groups (such as ammonia) are substituted by an element, R, which later on remains linked to the nascent heptazine. Furthermore, it is suggested that the key functional groups in the process are the triazine- (Tz) and the carbonitrile- (CN) group. On the basis of these assumptions, molecular precursors are tailored which encompass all necessary functional groups to form a central heptazine unit of threefold, planar symmetry and then still retain outward functionalities for self-propagated condensation in all three directions. Two model systems based on a para-aryl (ArCNTz) and para-biphenyl (BiPhCNTz) precursors are devised via a facile synthetic procedure and then condensed in an ionothermal process to yield the heptazine based frameworks, HBF-1 and HBF-2. Due to the structural motifs of their molecular precursors, individual sheets of HBF-1 and HBF-2 span cavities of 14.2 Å and 23.0 Å respectively which makes both materials attractive as potential organic zeolites. Crystallographic analysis confirms the formation of ABA’ layered, graphitic systems, and the extent of condensation is confirmed as next-to-perfect by elemental analysis and vibrational spectroscopy. / Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung neuer Allotropen und Nanostrukturen von Karbonitriden und berührt einige ihrer möglichen Anwendungen. Alle gezeigten, ausgedehnten, kovalent verbundenen Karbonitridgerüste wurden in einem ionothermalen Syntheseprozess – einer Hochtemperaturbehandlung in einem eutektischen Salzgemisch als ungewöhnlichem Lösungsmittel – aus einfachen Präkursormolkülen erzeugt. Der Kondensationsmechanismus folgt einer temperaturinduzierten Deaminierung und Bildung einer ausgedehnten, aromatischen Einheit; des dreifach substituierten Heptazines. Die Dissertation folgt vier übergreifenden Themen, beginnend mit der Einleitung in Karbonitridsysteme und der Suche nach einem Material, welches einzig aus Kohlenstoff und Stickstoff aufgebaut ist – einer Suche, die 1834 mit den Beobachtungen Justus von Liebigs „über einige Stickstoffverbindungen“ begann. Der erste Abschnitt zeigt die erfolgreiche Synthese von graphitischem Karbonitrid (g-C3N4); einer Spezies, welche auf Schichten hexagonal angeordneter s-Heptazineinheiten beruht, die durch kovalente Bindungen zwischen C- und N-Atomen zusammengehalten werden, und welche in einer graphitischen, verschobenen Art und Weise gestapelt sind. Der zweite Abschnitt berührt die Vielfalt von Salzschmelzensystemen, die für die Ionothermalsynthese geeignet sind und zeigt auf, dass die bloße Veränderung der Salzschmelze eine andere Kristallphase des graphitischen Karbonitrides ergibt – das g-C3N4-mod2. Im dritten Abschnitt wird vom Graphit bekannte Interkallationschemie auf das g-C3N4 angewendet, um eine Kalliuminterkallationsverbindung des graphitischen Karbonitirdes zu erhalten (K(C6N8)3). Diese Verbindung kann in Analogie zum graphitischen System leicht exfoliiert werden, um Bündel von Karbonitridnanoschichten zu erhalten, und weist darüberhinaus interessante optische Eigenschaften auf. Der vierte und letzte Abschnitt handelt von der Einführung von Aryl- und Biphenylbrücken in das Karbonitridmaterial durch rationale Synthese der Präkursormoleküle. Diese ergeben die heptazinbasierten Frameworks, HBF-1 und HBF-2 – zwei kovalente, organische Gerüste.