Made available in DSpace on 2016-08-12T19:15:24Z (GMT). No. of bitstreams: 1 CarlosHFN_DISSERT.pdf: 959875 bytes, checksum: f9cbf07f6dcf1050e5d484e8edd9d637 (MD5) Previous issue date: 2012-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The states of Rio Grande do Norte and Ceará are the main producers of melons from Brazil. They account for about 90% of national production, which makes the growth of melon Cucumis melo L. one of the main segments of agribusiness in these states. Despite the high technology used for the cultivation of this vegetable crop, this crop has suffered serious damage due to attack of the leafminer Liriomyza sativae (Diptera: Agromyzidae). The control method used by manufacturers to control this pest is basically the use of chemical insecticide, however, the exclusive use of this method has not been satisfactory for suppressing the population of insect biological control and using the parasitoid Opius sp. (Hymenoptera: Braconidae) has been shown to be a promising technique for controlling this pest in melon. Thus, this study aimed to estimate the number of parasitoids to be released in the field and evaluate the effect of insecticides on it, under field conditions. Among the ratios evaluated the proportion of 1:10 (one every ten parasitoid larvae) was the one with the highest rate of emergence of parasitoid 33.13%. Among the insecticides evaluated in the first trial, was observed at all doses of Neem Oil that the rate of emergence of the parasitoid Opius sp. was not different from control, whereas treatment with the lowest Abamectin rate was verified emergency 2.24%, differing from all other treatments. In the second experiment, we observed that treatment with the active Deltamethrin was the highest rate of reduction in population of the parasitoid Opius sp. (71.4%), followed by Abamectin and Cartap Hydrochloride (50.5 and 14.4% respectively) / Os estados do Rio Grande do Norte e Ceará são os principais produtores de melão do Brasil. São responsáveis por cerca de 90% da produção nacional, o que faz do cultivo do meloeiro Cucumis melo L. um dos principais segmentos da cadeia do agronegócio nesses estados. Apesar da alta tecnologia empregada para o cultivo desta olerícola, essa cultura vem sofrendo sérios danos devido ao ataque da mosca minadora Liriomyza sativae (Diptera: Agromyzidae). O método de controle utilizado pelos produtores para o controle desta praga é basicamente o uso de inseticida químico, no entanto, o uso exclusivo deste método não tem sido satisfatório para supressão da população desse inseto, e o controle biológico através da utilização do parasitoide Opius sp. (Hymenoptera: Braconidae) tem se mostrado uma técnica promissora no controle dessa praga na cultura do meloeiro. Sendo assim, o presente trabalho teve como objetivo, estimar o número de parasitoides a serem liberado em campo e avaliar o efeito de inseticidas sobre o mesmo, em condições de campo. Dentre as proporções avaliadas a proporção de 1:10 (um parasitoide a cada dez larvas vivas) foi a que apresentou a maior taxa de emergência deste parasitoide 33,13%. Dentre os inseticidas avaliados no primeiro ensaio, foi verificado em todas as dosagens do Oléo de Neem que a taxa de emergência do parasitoide Opius sp. não diferiu da testemunha, enquanto que no tratamento com a Abamectina foi verificado a menor taxa de emergência 2,24%, diferindo de todos os outros tratamentos. No segundo ensaio, foi observado que no tratamento com o ativo Deltametrina ocorreu a maior taxa de redução na população do parasitoide Opius sp. (71,4%), seguido da Abamectina e do Cloridrato de Cartape (50,5 e 14,4%, respectivamente)

Made available in DSpace on 2016-08-12T19:18:45Z (GMT). No. of bitstreams: 1 CarlosHFN_DISSERT.pdf: 959875 bytes, checksum: f9cbf07f6dcf1050e5d484e8edd9d637 (MD5) Previous issue date: 2012-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The states of Rio Grande do Norte and Ceará are the main producers of melons from Brazil. They account for about 90% of national production, which makes the growth of melon Cucumis melo L. one of the main segments of agribusiness in these states. Despite the high technology used for the cultivation of this vegetable crop, this crop has suffered serious damage due to attack of the leafminer Liriomyza sativae (Diptera: Agromyzidae). The control method used by manufacturers to control this pest is basically the use of chemical insecticide, however, the exclusive use of this method has not been satisfactory for suppressing the population of insect biological control and using the parasitoid Opius sp. (Hymenoptera: Braconidae) has been shown to be a promising technique for controlling this pest in melon. Thus, this study aimed to estimate the number of parasitoids to be released in the field and evaluate the effect of insecticides on it, under field conditions. Among the ratios evaluated the proportion of 1:10 (one every ten parasitoid larvae) was the one with the highest rate of emergence of parasitoid 33.13%. Among the insecticides evaluated in the first trial, was observed at all doses of Neem Oil that the rate of emergence of the parasitoid Opius sp. was not different from control, whereas treatment with the lowest Abamectin rate was verified emergency 2.24%, differing from all other treatments. In the second experiment, we observed that treatment with the active Deltamethrin was the highest rate of reduction in population of the parasitoid Opius sp. (71.4%), followed by Abamectin and Cartap Hydrochloride (50.5 and 14.4% respectively) / Os estados do Rio Grande do Norte e Ceará são os principais produtores de melão do Brasil. São responsáveis por cerca de 90% da produção nacional, o que faz do cultivo do meloeiro Cucumis melo L. um dos principais segmentos da cadeia do agronegócio nesses estados. Apesar da alta tecnologia empregada para o cultivo desta olerícola, essa cultura vem sofrendo sérios danos devido ao ataque da mosca minadora Liriomyza sativae (Diptera: Agromyzidae). O método de controle utilizado pelos produtores para o controle desta praga é basicamente o uso de inseticida químico, no entanto, o uso exclusivo deste método não tem sido satisfatório para supressão da população desse inseto, e o controle biológico através da utilização do parasitoide Opius sp. (Hymenoptera: Braconidae) tem se mostrado uma técnica promissora no controle dessa praga na cultura do meloeiro. Sendo assim, o presente trabalho teve como objetivo, estimar o número de parasitoides a serem liberado em campo e avaliar o efeito de inseticidas sobre o mesmo, em condições de campo. Dentre as proporções avaliadas a proporção de 1:10 (um parasitoide a cada dez larvas vivas) foi a que apresentou a maior taxa de emergência deste parasitoide 33,13%. Dentre os inseticidas avaliados no primeiro ensaio, foi verificado em todas as dosagens do Oléo de Neem que a taxa de emergência do parasitoide Opius sp. não diferiu da testemunha, enquanto que no tratamento com a Abamectina foi verificado a menor taxa de emergência 2,24%, diferindo de todos os outros tratamentos. No segundo ensaio, foi observado que no tratamento com o ativo Deltametrina ocorreu a maior taxa de redução na população do parasitoide Opius sp. (71,4%), seguido da Abamectina e do Cloridrato de Cartape (50,5 e 14,4%, respectivamente)

Made available in DSpace on 2016-08-12T19:18:52Z (GMT). No. of bitstreams: 1 FranciscoELS_DISSERT.pdf: 593076 bytes, checksum: e225bf4fa3857eb2f3da5c8dcc0be47d (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The melon (Cucumis melo L.) is one of the main cucurbits grown in northeastern Brazil. Among the main obstacles to the production of melon, the leafminer Liriomyza sativae (Diptera: Agromyzidae) stands out as one of the main pests. Since the discovery of natural enemies Opius scabriventris (Hymenoptera: Braconidae) and Neochrysocharis sp. (Hymenoptera: Eulophidae) in melon production areas RN and CE, increased the prospects of the use of biological control in this region. However, information on the preferred instar and competition among parasitoids Opius scabriventris and Neochrysocharis sp. still are scarce. Furthermore, the conservation of these parasitoids in agrosystem is of fundamental importance to the MIP, therefore, it is necessary to know the action of plant protection products on O. scabriventris and Neochrysocharis sp. Therefore, the objective of this study was to define the preferred instar O. scabriventris and Neochrysocharis sp., Evaluate the competition between these two species and the toxicity of insecticides used in melon crop on these two parasitoids in laboratory conditions. To determine the preferred instar were exposed leafminer larvae first, second and third instar for the two species of parasitoids. The competition studies were to assess the simultaneous parasitism O. scabriventris x Neochrysocharis sp. in proportions of 1x1, 2x1, 1x2 for the second and third larval instar L. sativae. The toxicity of insecticides to parasitoids were evaluated in bioassays through contact of parasitoids with freshly contaminated surface. The treatments were: abamectin, clorantraniliprole, cyromazine, espinetoram, spinosad and distilled water (control). Later, with the parasitoids that survived the tests of toxicity were evaluated sublethal effects of pesticides that caused lower mortality on the parasitism capacity. Regarding prefered instar tests, O. scabriventris preferably parasitized second instar larvae, while Neochrysocharis sp. preferred third instar larvae. Regarding competition assays, it was found that parasitoids O. scabriventris and Neochrysocharis sp. competed for larvae second and third instar L. sativae. Regarding toxicity tests, the abamectin, espinetoram and spinosad were the most toxic to the parasitoid O. scabriventris and Neochrysocharis sp. The clorantraniliprole and cyromazine insecticide caused reduction in parasitism capacity of O. scabriventris / O meloeiro (Cucumis melo L.) é uma das principais cucurbitáceas cultivadas na região Nordeste do Brasil. Dentre os principais entraves à produção do meloeiro, a mosca minadora Liriomyza sativae (Diptera: Agromyzidae) se destaca como uma das principais pragas. Desde a constatação dos inimigos naturais Opius scabriventris (Hymenoptera: Braconidae) e Neochrysocharis sp. (Hymenoptera: Eulophidae) em áreas de produção de melão do RN e CE, cresceram as perspectivas da utilização do controle biológico nessa região. No entanto, informações sobre o instar preferencial e a competição entre os parasitoides Opius scabriventris e Neochrysocharis sp. são escassas. Além disso, a conservação desses parasitoides no agrossistema é de fundamental importância para o MIP, sendo assim, é necessário conhecer a ação dos produtos fitossanitários sobre O. scabriventris e Neochrysocharis sp. Portanto, o objetivo do presente trabalho foi definir o instar preferencial de O. scabriventris e Neochrysocharis sp., avaliar a competição entre essas duas espécies e a toxidade de inseticidas utilizados na cultura do meloeiro sobre esses dois parasitoides em condições de laboratório. Para determinar o instar preferencial, foram expostas larvas de mosca minadora de primeiro, segundo e terceiro instar para as duas espécies de parasitoides. Os estudos de competição consistiram em avaliar o parasitismo simultâneo de O. scabriventris x Neochrysocharis sp. nas proporções de 1x1, 2x1, 1x2 para larvas de segundo e terceiro instar de L. sativae. A toxicidade dos inseticidas aos parasitoides foram avaliados em ensaios biológicos por meio do contato dos parasitoides com superfície recém-contaminada. Os tratamentos foram: abamectina, clorantraniliprole, ciromazina, espinetoram, espinosade e água destilada (Testemunha). Posteriormente, com os parasitoides que sobreviveram aos ensaios de toxicidade, foram avaliados os efeitos subletais dos inseticidas que ocasionaram menor mortalidade sobre a capacidade de parasitismo. Quanto aos ensaios de ínstar preferencial, O. scabriventris parasitou preferencialmente larvas de segundo instar, enquanto que Neochrysocharis sp. preferiu larvas de terceiro instar. Em relação aos ensaios de competição, verificou-se que os parasitoides O. scabriventris e Neochrysocharis sp. competiram por larvas segundo e terceiro instar de L. sativae. Em relação aos ensaios de toxicidade, os inseticidas abamectina, espinetoram e espinosade foram os mais tóxicos aos parasitoides O. scabriventris e Neochrysocharis sp. Os inseticidas clorantraniliprole e ciromazina ocasionaram redução na capacidade de parasitismo de O. scabriventris

Submitted by AMANDA APARECIDA FERNANDES LEMES null (amanda.aflemes@gmail.com) on 2017-11-09T11:32:59Z No. of bitstreams: 1 Dissertação_Amanda_Aparecida_Fernandes_Lemes.pdf: 1634439 bytes, checksum: 3da6c1a6b018e117ef6f8d99907d3496 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-11-21T14:03:34Z (GMT) No. of bitstreams: 1 lemes_aaf_me_jabo.pdf: 1634439 bytes, checksum: 3da6c1a6b018e117ef6f8d99907d3496 (MD5) / Made available in DSpace on 2017-11-21T14:03:34Z (GMT). No. of bitstreams: 1 lemes_aaf_me_jabo.pdf: 1634439 bytes, checksum: 3da6c1a6b018e117ef6f8d99907d3496 (MD5) Previous issue date: 2017-10-09 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Um dos principais problemas para o cultivo de brássicas é o dano causado pela traça-das-crucíferas, Plutella xylostella (Linnaeus, 1758) (Lepidoptera: Plutellidae), o que implica na aplicação de grandes volumes de agrotóxicos. Diversos inseticidas são empregados no controle de P. xylostella. Indoxacarbe foi o primeiro inseticida bloqueador de canais de sódio comercializado, com mecanismo de ação diferente do DDT e dos piretroides, apresentando várias vantagens, como baixa toxicidade aos organismos benéficos. Porém, aplicações frequentes de inseticidas para controle de P. xylostella, combinado com fatores biológicos da praga, podem favorecer a seleção de indivíduos resistentes. Até o momento, P. xylostella desenvolveu níveis de resistência a 95 ingredientes ativos, existindo na literatura mais de 55 relatos de resistência para o indoxacarbe, em sete países de diferentes continentes, inclusive no Brasil. Nesse sentido, este estudo objetivou determinar os efeitos subletais e residuais do indoxacarbe em duas populações de P. xylostella, sendo uma coletada no campo e outra de laboratório (suscetível), avaliando e comparando a toxicidade desse inseticida em diferentes concentrações e analisando o comportamento destas duas populações e assim formar uma base teórica para melhorar o manejo desta praga. Foram realizados bioensaios com duas populações (PC- de campo e PL- de laboratório-suscetível) de P. xylostella com o inseticida indoxacarbe na dose comercial (100mg.L-1), avaliando os efeitos residuais do produto 1, 3, 7, 14 e 21 dias após a aplicação. Também foi estimada a CL50 e avaliados os efeitos subletais desse produto aplicado e avaliado após 48 h utilizando-se as concentrações subletais de CL5 (0,37 e 1,01 mg.L-1), CL15 (0,87 e 2,06 mg.L-1) e CL25 (1,44 e 3,16 mg.L-1) para as populações PL e PC, analisando-se algumas características biológicas das populações. A dose comercial de indoxacarbe pulverizada em plantas de couve matou todas as larvas com 1 dia e 3 dias após a aplicação. Os bioensaios de imersão foliar mostraram que o indoxacarbe apresentou alto nível de toxicidade para as lagartas de P. xylostella e os valores de CL50 foram de 3,7 e 6,9 mg.L-1 para a população suscetível e de campo, respectivamente. Os efeitos subletais foram indicados por menor sobrevivência larval e pupal e diminuição das taxas de sobrevivência da prole, devido ao efeito crônico do inseticida para ambas as populações. Houve também um aumento no consumo foliar e diminuição na sobrevivência de adultos na população suscetível e diminuição da fecundidade na população de campo. Os valores médios das taxas reprodutiva líquida (R0), intrínseca de aumento (rm) e de crescimento finito (Λ) foram significativamente menores nos tratamentos do que no grupo controle para ambas as populações. Houve diferença significativa entre as respostas das duas populações. O indoxacarbe mostrou-se eficaz contra P. xylostella, sendo que suas concentrações subletais influem negativamente nas características biológicas do inseto. / The main problem for brassica crops is the damage caused by the diamondback moth, Plutella xylostella, which has led to the application of large volumes of pesticides. Several insecticides are employed in the control of P. xylostella. Indoxacarbe was the first commercially available sodium channel blocker insecticide, with a different mechanism of action than DDTs and pyrethroids, has several advantages, such as low toxicity to beneficial organisms. However, frequent applications of these insecticides to control P. xylostella, combined with biological factors of the pest are favoring the selection of resistant individuals. So far P. xylostella has developed levels of resistance to 95 active ingredients and there are in the literature more than 55 reports of resistance to indoxacarb in seven countries on different continents, including Brazil. In this sense, the objective was to determine the residual and sublethal effects of indoxacarb in two populations of P. xylostella, one collected in the field and the other in the laboratory (susceptible), evaluating and comparing the toxicity of this insecticide in different concentrations and analyzing the behavior of these two populations and thus form a theoretical basis to improve the management of this pest. Bioassays were performed with two populations (PC- field and PL- laboratory) of P. xylostella with the insecticide in commercial dose indoxacarb (100 mg.L-1), evaluating the effects of residual products 1, 3, 7, 14 and 21 days after spray. LC50 was also estimated and the sublethal effects of this product applied and evaluated after 48 h were evaluated using the sublethal concentrations of LC5 (0.37 and 1.01 mg.L-1), LC15 (0.87 and 2.06 mg. L-1) and LC25 (1.44 and 3.16 mg.L-1) for PL and PC populations by analyzing some biological characteristics of the individuals. The commercial dose of indoxacarb sprayed on cabbage plants killed all larvae up to 1 day and 3 days after spray. Leaf-dip bioassays showed that indoxacarb showed a high level of toxicity against P. xylostella larvae and the 48 h LC50 values were 3.7 and 6.9 mg.L-1 for the susceptible and field population, respectively. The sublethal effects were indicated by lower larval and pupal survival and decrease in offspring survival rates, due to the chronic effect of the insecticide for both populations. There was also an increase in foliar consumption and a decrease in adult survival in the susceptible population and decrease in fecundity in the field population. The mean values of net reproductive rate (R0), intrinsic rate of increase (rm), finite rate of increase (Λ) were significantly lower in the treatments than in the control group for both populations. There were significant differences between the responses of the two populations. The indoxacarb was effective against P. xylostella and its sublethal concentrations negatively influence the biological characteristics of the insect. / CNPq: 134536/2015-0

O Brasil é o maior produtor de cana-de-açúcar (Saccharum officinarum L.) do mundo e a cultura continua em expansão na safra 2014/15. A expansão das áreas de plantio de cana-de-açúcar e o sistema de colheita mecanizada de cana crua tem levado ao aumento proporcional de inúmeras pragas da cultura, destacando-se o bicudo da cana, Sphenophorus levis, considerado praga primária e limitante da cultura. Inicialmente, essa espécie foi considerada restrita a região de Piracicaba, mas desde 2010 foi encontrada nos estados de São Paulo, Minas Gerais, Paraná, Mato Grosso do Sul, Mato Grosso e Goiás. Suas larvas abrem galerias nos rizomas, causando danos diretos nos tecidos dos colmos, sobretudo nas épocas mais secas do ano, o que ocasiona a morte das touceiras, falhas na rebrota, além de promover danos indiretos, como o aumento do número de plantas invasoras que competem com a cultura. Os métodos químico, mecânico, cultural e biológico já foram testados até o momento, no entanto, o sucesso no seu controle ainda não foi obtido e a população dessa praga continua crescendo e se tornando mais constante nos canaviais pelo Brasil. Dessa forma, estudar estratégias para a melhoria do manejo de S. levis é fundamental para o estabelecimento de métodos de controle eficientes no contexto do MIP. Diante disso, objetivou-se com esse trabalho: 1) Determinar a distribuição espacial e a flutuação populacional de S. levis; 2) Testar o manejo da palha pós-colheita nas linhas de plantio na ocorrência de S. levis e; 3) Avaliar a eficácia da aplicação de Beauveria bassiana na população de S. levis. Em relação à flutuação populacional de S. levis foi observada uma elevação linear da última quinzena de outubro para a primeira de novembro, com queda subsequente e, aumento populacional maior à partir da última quinzena de dezembro. O pico populacional se deu no mês de março, seguido por uma rápida redução a partir de abril. A proporção de fêmeas foi similar a de machos em todos os tratamentos. Os dados sugerem que não houve efeito dos tratamentos na distribuição de adultos do bicudo. Os resultados da flutuação populacional, da distribuição de frequência e distribuição espacial se complementam, pois, em hipótese, a distribuição dos adultos está diretamente relacionada com a flutuação populacional, uma vez que em altas densidades a distribuição foi agregada. Além disso, as estratégias de afastamento da palha da linha de plantio não interferiram nos níveis de infestação de S. levis, quando comparado ao tratamento que não houve manejo da palha e, essa tática utilizada conjuntamente à aplicação de B. bassiana também não influenciou na densidade populacional de adultos de S. levis no período avaliado. Diante disso, concluiu-se que a distribuição de S. levis em cana-de-açúcar apresenta o padrão agregado em altas densidades populacionais; o manejo da palha entre as linhas de cana-de-açúcar não reduz a densidade populacional de S. levis em locais com elevado histórico de infestação e, são necessários mais estudos para ajustar a dose de B. bassiana adequada e eficaz no controle de S. levis. / Brazil is the world\'s largest sugarcane producer and the cultivated area continues to expand in 2014/2015 season. This expansion, along with the mechanical harvesting of green sugarcane leads to a proportional increase in the number of crop pests, especially the sugarcane weevil, Sphenophorus levis, considered a primary and limiting pest in this crop. Initially, this species was restricted to the Piracicaba region, however, since 2010 it has been found in several regions of São Paulo State, and also in other states in the country, such as Minas Gerais, Paraná, Mato Grosso do Sul, Mato Grosso and Goiás. The larvae penetrate the basal part of the plants and the rhizomes, building irregular galleries and causing damage to stem tissues, mainly in the driest season, leading to the death of clumps, failures in regrowth and, consequently, indirect damage due to the increase in the incidence of invasive plants that compete with the crop. Chemical, mechanical, cultural and biological methods have already been tested, however, the success in pest control has not yet been achieved and the population of S. levis continues to grow, becoming more constant in Brazilian sugarcane fields. Thus, the study of strategies to enhance the management of S. levis is essential to adopt effective control methods in the IPM framework. In this sense, this study aims to: 1) Determine the spatial distribution and population dynamics of S. levis; 2) Evaluate the postharvest management of straw on planting rows in occurrence of S. levis and; 3) Evaluate the efficacy of B. bassiana application in the S. levis population in sugarcane. Concerning population dynamics of S. levis, it was observed a linear increase beginning in the last quarter of October until November, with a subsequent decrease and, a highest population increase was observed in the last half of December. The population peak occurred in March, followed by a fast decline in early April. The proportion of females to males was similar in all treatments. The data suggest that there was no effect of treatments on the distribution of adult weevils. The results of population dynamics, frequency distribution and spatial distribution are complementary, because, hypothetically, the distribution of adults is directly related to population dynamics, since at high densities the distribution was aggregated. In addition, strategies for straw management in the planting row did not affect the infestation levels of S. levis and this procedure along with the addition of B. bassiana did not influence population density of adults during the study period. Hence, it is concluded that the distribution of S. levis in sugarcane exhibits an aggregated pattern at high population densities. Straw management between the cane rows does not reduce population density of S. levis in areas with high historical infestation. Therefore, further studies are needed to adjust the appropriate and effective concentration of B. bassiana in the control of S. levis.

Orientadores: Adriana Vitorino Rossi, Regina Buffon / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T19:48:13Z (GMT). No. of bitstreams: 1 Manzoor_Suryyia_D.pdf: 4523839 bytes, checksum: 9aa2a7bc8376699193b0d5e83f0ec0f5 (MD5) Previous issue date: 2013 / Resumo: Este trabalho envolveu um estudo elaborado da técnica de impressão molecular para síntese, caracterização e avaliação de materiais impressos molecularmente (MIMs) para fluconazol (FLU), cafeína (CAF) e antocianinas (ACYs). O polímero de impressão molecular para FLU (FLUMIP) foi sintetizado utilizando-se ácido metacrílico (monômero funcional), etilenoglicoldimetacrilato (EGDMA) (agente reticulador) e acetonitrila em polimerização térmica. O FLUMIP foi caracterizado e aplicado como sorvente em cartuchos de extração em fase sólida (SPE). Sua capacidade de interação seletiva com o analito foi avaliada, obtendo-se alta afinidade para FLU, em comparação com análogos estruturais, com limite de detecção menor que 1,63X10 mmol/L com cromatografia de ultra alta eficiência acoplada com espectrometria de massas. Este MIP foi usado em cartuchos de SPE para extrair o analito de medicamento em cápsula, com recuperação de 91±10 % (n=9). Outro MIM obtido foi uma sílica organicamente modificada (ORMOSIL) para extração de CAF, a partir da reação de metacrilato de 3- (trimetoxisilil) propila e acetato de vinila, seguindo-se condensação e hidrólise com tetraetilortosilicato usando CAF como molécula modelo. Este ORMOLSIL foi caracterizado e testado quanto à sua eficácia de extrair CAF de amostras de café, com recuperação de 88±5 % (n=9); ele atuou como grupo seletivo com alta porcentagem de recuperação para teofilina (77 %) e teobromina (82 %). Limites de detecção e quantificação 5,14x10 e 1,71x10 mmol/L respectivamente foram obtidos com cromatografia líquida de alta eficiência. Também foi sintetizado um MIP usando rutina molécula modelo (RUTMIP), acrilamida (monômero funcional), EGDMA (agente reticulador) e tetraidrofurano por polimerização em bulk. Embora tenha sido alcançada impressão bem sucedida de rutina, confirmada pela comparação de afinidade de RUTMIP em aplicação de SPE (12 vezes maior que afinidade do polímero não impresso), não se alcançou a seletividade esperada para ACYs utilizando o RUTMIP / Abstract: This work involves an elaborative study of molecularly imprinting technique. Keeping in view its robustness and selectivity, this technique was applied for the synthesis of molecularly imprinted materials for the extraction of fluconazole (FLU), caffeine (CAF) and anthocyanins (ACYs). Molecularly imprinted polymer (MIP) for FLU (FLUMIP) was synthesized using methacrylic acid (functional monomer), ethyleneglycoldimethacrylate (crosslinker) and acetonitrile through thermal polymerization. The FLUMIP was characterized and applied as sorbent in solid phase extraction (SPE) cartridges. It was then evaluated for its ability to selectively interact with the analyte and presented an apparent affinity for FLU, which was confirmed by comparing it with structural analogues. The application of ultra high performance liquid chromatography with spectrometer mass detection, allowed a limit of detection 1.63x10 mmol/L. Furthermore, the SPE procedure was applied to extract FLU from medicine samples with recovery of 91±10 % (n=9). An organically modified silica (ORMOSIL) for CAF was also synthesized by reacting vinyl acetate and 3- (trimethoxysilyl) propyl methacrylate, followed by the condensation and hydrolysis with tetraethyl orthosilicate, using CAF as template molecule. The ORMOSIL was characterized and tested for its efficiency to extract the analyte from coffee samples and the percentage recovery of 88±5 % (n=9) was obtained. The cross reactivity studies for theophylline and theobromine showed high recovery (77 % and 82% respectively). The limit of detection and quantification, 5.14x10 and 1.71x10 mmol/L respectively, were achieved using high performance liquid chromatography. Also, a MIP for ACYs (RUTMIP) was synthesized using rutin (template molecule), EGDMA (cross linker) and tetrahydrofuran by the bulk polymerization method. A successful imprinting of rutin was attained. This can be confirmed by the high affinity of rutin for MIP (12 times greater than non imprinted polymer) during SPE procedure; however, the RUTMIP was not efficient enough to selectively extract ACYs from vegetal extracts / Doutorado / Doutora em Ciências

The thesis focuses on the process of production of castings in the company ŽĎAS, a.s. and its methods for implementing customer's requirements. The goal was to create a Work Flow diagram of technical preparation of production based on the company's internal directives. The next step was to compare it with the actual situation represented by a case job and to make a conclusion. The customer's requirements for the case production order included increased level of control and purchasing weld-on parts. The incorporation process for these requirements was not described by the original Work Flow and was the subject of its new revision. For its better practical application the Study contains business and organizational structures of ŽĎAS, a.s.

Les polymères à empreintes moléculaires (MIP) sont des matériaux synthétiques capables de mimer les anticorps biologiques. En effet, ils possèdent deux des principales caractéristiques de ces derniers, à savoir : la capacité de reconnaître et de se lier spécifiquement à des molécules cibles. De plus, leur synthèse facile, leur bas coût de production, leur haute spécificité et stabilité par rapport aux anticorps naturels font des MIP une alternative intéressante. En effet, les propriétés de reconnaissance moléculaire des MIP permettent d'envisager leur utilisation dans une vaste gamme d’applications. Ils sont ainsi largement exploités dans les sciences séparatives pour l'analyse d'échantillons environnementaux ou agro-alimentaires, ou comme élément de reconnaissance dans des biocapteurs. Récemment, des applications de ces matériaux dans les domaines biologiques et biomédicaux ont émergé comme pour la détection, l'extraction et l"élimination de molécules indésirables dans l'organisme, la vectorisation ou l'administration contrôlée des médicaments. Dans nos recherches, nous avons développé des MIP dégradables par voie biochimique ou enzymatique, ayant une application potentielle en tant que système de libération contrôlé de molécules. En général, les MIPs sont synthétisés par polymérisation radicalaire libre en utilisant une formulation composée de monomères fonctionnels, d'agents de réticulation, et d'une molécule cible servant à réaliser l'empreinte moléculaire. Dans ce travail de thèse, nous avons utilisé pour la synthèse de MIP dégradable des agents de réticulation clivables contenant, soit une fonction chimique dégradable par voie chimique ou enzymatique (ponts disulfures et phosphatediester), soit un disaccharide issus d'agro-ressources et pouvant être naturellement hydrolysé par des enzymes. En présence d'un réactif spécifique (agent réducteur ou enzyme), les liaisons dites "sensibles" aux réactifs chimiques ou enzymatiques peuvent être clivées, ce qui entraîne une dégradation de la matrice polymérique. Le polymère perdra alors sa capacité de reconnaissance et de liaison à la molécule cible et permettra la libération de celle-ci. Nous pensons donc, que les nouveaux MIP dégradables pourraient avoir un énorme potentiel comme vecteurs "intelligents" dans des applications médicales tels que les systèmes de libération contrôlée de médicament. Finalement, nous avons étudié la dégradation par des microorganismes de la structure de base de ce type de polymères, en utilisant comme modèles des chaines linéaires et réticulées. / Molecularly imprinted polymers (MIPs) are biomimetic synthetic receptors that possess two of the most important features of biological antibodies – the ability to recognize and bind specific target molecules. Owing to their easier preparation, lower cost, higher specifity and stability compared to antibodies, they have the potential to be widely applied for environemental and food analysis. Recently, MIPs also emerged in the biochemical field as diagnostic tools, chemicals traps to remove undesirable substance from the body, or drug delivery systems, where usually the combination of biocompatibility and degradability after its use is desirable. Here, we developed biochemically or enzymatically degradable MIPs, which have potential applications as activation-modulated drug delivery systems. In general, MIPs are prepared by radical polymerization of functional monomers and cross-linkers in the presence of a target molecule acting as template. Degradable MIPs were synthesized using cleavable cross-linkers containing a degradable group (disulfide bond or phosphate ester bond) or derived from a natural disaccharide. In the presence of a cleaving reagent (reducing agent or enzyme), the chemo or enzyme-sensitive bond could be cleaved, resulting in the degradation of the polymer matrix. The degraded polymers looses the binding sites structure resulting in the loss of recognition and binding capacity towards the target molecules, and thus in the release of bound molecules. These degradable MIPs provide new opportunities as “smart” vectors for controlled delivery of active molecules in biomedical applications. Finally, the biodegradation of the polymer backbone by bacteria was investigated.

No description available.

For over a century, the railway system has been gradually designed and adapted to serve the corresponding demands under variations of given budgets. However, recent developments indicate that the railway systems of many European countries gradually come to their limits, as the national infrastructure managers declare an increasing share of their network tracks as congested. Consequently, the capabilities of each railway system are getting more into focus, to adequately serve the recent intention of shifting more demand to rail to encounter climate change. The system’s capacity is thereby of particular interest, i. e. whether the system already has the ability to serve increasing traffic loads by leveraging existing reserves, or otherwise needs significant extensions to serve the increasing demand. We thus need to quantify the current capacity of the railway system to identify its current capabilities and to deduct corresponding measures to leverage capacity reserves and relieve saturated network parts. Only the appropriate measure selection, i.e. deciding where to apply traffic reorganization and optimization or infrastructural extensions and restructuring, allows to achieve the goal of shifting more demand to rail under limited resource constraints. The main contributions of this thesis are in the design, optimization and application of a network capacity assessment approach for large-scale railway networks, which incorporates the perspectives of infrastructure, operations and demand by using the number of trains per time window and scheduled waiting times as capacity metric. Hence, this thesis provides a new definition of network capacity, and develops petri net (PN)-based capacity assessment models for railway networks with the use of mixed integer program (MIP) and row generation. The capacity is then determined by assessing the maximum utilization and the scheduled waiting times of the railway network with respect to infrastructure, railway operations and demand. We first introduce the definition of railway network capacity, which extends the concept of railway capacity from stations and corridors to entire networks. This new utilization-based and demand-centric definition of practical railway network capacity defines railway network capacity as the maximum number of departing trains in the network over a given time period, regarding the given infrastructure, operations and demand. This definition allows to accurately determine the interplay of infrastructure, operations and demand, with a combined measure of traffic flow and scheduled waiting times. In the context of this new definition on network capacity, different assessment approaches for the capacity of railway stations, corridors and networks are reviewed with regard to their spatial scope, the used approach and the applied capacity metric. Second we propose the railway network utilization model (RNUM), which extends an existing PN based approach from single line to entire network operations. This model builds upon individual lines, which are then connected to more complex structures. The analysis of the maximum utilization is based on the network’s elementary circuits. Furthermore, token modifications are introduced to characterize relevant process circuits and introduce interline separation places to model and assess complex networks. By additionally considering rolling stock circulations and imposed train orders, the utilization is determined for given operation scenarios of a line system, which operates at heterogeneous frequencies. The resulting timetable independent approach allows to fully characterize the utilization of the network. To assess the network capacity, an enumeration-based railway network capacity (RNC) framework is further introduced, which evaluates the maximum utilization over diverse operation scenarios to represent possible network demands. The resulting train flows as well as the average scheduled waiting times per train, the capacity and the corresponding network effects were finally quantified and determined in network-specific macroscopic fundamental diagram for the railway network (MFD-R). Third, we introduce the railway network utilization MIP model (MIP-RNUM) to determine the optimal capacity utilization by combining PNs with mathematical linear programming. The presented model is enabled to simultaneously assess different train locations and line orders to provide the network’s utilization, capacity-optimal train locations and line orders for given operation scenarios. The MIP-RNUM is further improved to provide the demand-centered capacity utilization, by incorporating extended demand structures, which capture the demanded flows and magnitudes as fixed proportions of trains per line. The additional incorporation of local routing and thus optimal line orders in the utilization assessment, extend the model further to provide the optimal and demand-centered capacity utilization without the correspondingly required enumeration of different line orders. The resulting fully extended MIP-RNUM comprehensively captures the interplay of infrastructure, railway operations and demand; and the resulting effects on the network capacity. Fourth, we propose the row generation MIP-RNUM (MIP-RNUM-RG) to assess the capacity of large-scale instances. The proposed approach tackles the computationally intensive enumeration of the network’s cycles of the RNUM by applying lazy-constraint generation i.e. iteratively adding violated constraints of previous solutions to the problem in a row generating manner. To assess the solution quality of intermediate solutions during the capacity assessment of large instances, a lower-bound method is presented, which combines a higher order max-plus system and a binary search algorithm. The lower-bound method allows to check the feasibility of a given solution and to quantify the optimality gap of the current results while solving the MIP-RNUM-RG. In summary, this thesis provides multiple scientific contributions to efficiently assess the capacity of complex railway networks by developing several assessment models and frameworks. By integrating the different perspectives of infrastructure, operations and demand, this thesis supports network design towards the development of demand-centric railway systems. Regarding the intended growth of the railway demand in the near future, this thesis can guide practitioners to assess the capabilities of our present railway systems and derive the necessary actions to transform them into the transport systems of our future. / Das Eisenbahnsystem wurde über ein Jahrhundert lang entworfen und angepasst, um die jeweilige Nachfrage unter einem sich verändernden Budget zu bedienen. Aktuelle Entwicklungen zeigen jedoch, dass die Eisenbahnsysteme vieler europäischer Länder allmählich an ihre Grenzen stoßen. Zeitgleich geraten die Fähigkeiten eines jeden Eisenbahnsystems in den Fokus, mit denen zur Begegnung des Klimawandels mehr Verkehr auf die Schiene verlagert werden kann. Die Systemkapazität ist dabei von besonderem Interesse, d. h. ob das System bereits in der Lage ist, wachsende Verkehrsmengen durch die Nutzung existierender Reserven zu bewältigen, oder ob es zur Bedienung der steigenden Nachfrage einen deutlichen Ausbau braucht. Aus diesem Grund muss die Kapazität des Eisenbahnsystems bewertet werden, um damit seine aktuellen Möglichkeiten zu identifizieren und durch entsprechend abgeleitete Maßnahmen Kapazitätsreserven nutzbar zu machen und saturierte Netzteile zu entlasten. Der wesentliche Beitrag dieser Arbeit liegt im Entwurf, der Erweiterung und Anwendung eines Ansatzes zur Untersuchung der Netzwerkkapazität für großräumige Eisenbahnnetze unter Einbeziehung der Einflussfaktoren Infrastruktur, Betrieb und Nachfrage. Als Kapazitätsmetrik kommen dabei die Zugzahlen pro Zeiteinheit und die planmäßigen Wartezeiten zum Einsatz. Diese Arbeit entwirft dafür eine neue Definition der Netzwerkkapazität und entwickelt anschließend Petri-Netz (PN) basierte Untersuchungsmodelle für die Eisenbahnnetzkapazität unter Nutzung von gemischt-ganzzahliger Programmierung und Zeilengenerierung (eng. row generation). Durch die Analyse der maximalen Kapazitätsausnutzung und der planmäßigen Wartezeiten im Netz wird die Kapazität unter Berücksichtigung der Einflussfaktoren bestimmt. Zuerst wird die Definition der Eisenbahnnetzwerkkapazität eingeführt, die das Konzept der Eisenbahnkapazität von Bahnhöfen und Streckenkorridoren auf Netzwerke erweitert. Diese neue, auf Kapazitätsausnutzung basierende, nachfragezentrierte Definition der praktischen Eisenbahnnetzwerkkapazität definiert die Netzkapazität als die maximale Anzahl der im Netzwerk abfahrenden Züge innerhalb eines gegebenen Zeitintervalls, unter Berücksichtigung der gegebenen Einflussfaktoren. Im Kontext dieser neuen Definition werden verschiedene, existierende Untersuchungsansätze für die Kapazität von Eisenbahnknoten, Streckenkorridoren und Netzwerken rezensiert. Die Ansätze werden insbesondere hinsichtlich ihres räumlichen Umfangs, des angewendeten Verfahrens und der jeweils genutzten Kapazitätsmetrik verglichen. Als Zweites wird das Eisenbahnnetzwerkausnutzungsmodell (eng. railway network utilization model – RNUM) präsentiert, das einen existierenden PN-Ansatz von einer einzelnen Linie auf Netzwerke erweitert. Dieses Modell setzt sich aus einzelnen Linien zusammen, die zu komplexeren Strukturen zusammengesetzt werden. Die Analyse der maximalen Kapazitätsausnutzung basiert auf den Elementarkreisen des entstehenden Netzwerks. Durch die zusätzliche Berücksichtigung von Fahrzeugumläufen und vorgegebenen Zugfolgen wird die Kapazitätsausnutzung für gegebene Betriebsszenarien eines Liniensystems bestimmt, in welchem die Linien mit heterogenen Taktzeiten verkehren. Der resultierende, fahrplanunabhängige Ansatz erlaubt die vollständige Charakterisierung der maximalen Kapazitätsausnutzung unter Berücksichtigung diverser Betriebsszenarien. Die resultierenden Zugverkehrsströme und die mittleren planmäßigen Wartezeiten pro Zug, die ermittelte Kapazität und die zugehörigen Netzwerkeffekte werden schließlich in einem netzwerkspezifischen makroskopischen Fundamentaldiagram für Eisenbahnnetzwerke (MFD-R) bestimmt. Als Drittes wird das Eisenbahnnetzwerkausnutzungs-MIP-modell (MIP-RNUM) eingeführt, um die optimale Kapazitätsausnutzung durch eine Kombination von PN und linearer Programmierung zu bestimmen. Das eingeführte Modell kann simultan verschiedene Zugpositionen und Zugfolgen berücksichtigen, um auf deren Grundlage die Netzwerkausnutzung, kapazitätsoptimale Zugpositionen und -folgen für gegebene Betriebsszenarien zu untersuchen. Im Folgenden wird das MIP-RNUM erweitert, um die nachfragezentrierte Kapazitätsausnutzung zu erfassen. Die zusätzliche Berücksichtigung von variablen Fahrwegen in Knoten und den zugehörigen optimalen Zugfolgen in der Ausnutzungsuntersuchung ergänzen das Modell zusätzlich, um die optimale und nachfragezentrierte Kapazitätsausnutzung ohne die bisher benötigte Enumeration der Zugfolgen zu ermitteln. Das resultierende erweiterte MIP-RNUM erfasst das Zusammenspiel von Infrastruktur, Eisenbahnbetrieb und Nachfrage und deren umfassende Auswirkungen auf die Netzwerkkapazität. Zuletzt wird das zeilengenerierende MIP-RNUM (MIP-RNUM-RG) vorgestellt, um auch die Kapazität großräumiger Instanzen untersuchen zu können. Der vorgestellte Ansatz begegnet der rechenzeitintensiven Enumeration der Elementarkreise des RNUM mit einer sog. lazy constraint generation, d. h. der iterativen, zeilengenerierenden Ergänzung verletzter Nebenbedingungen zum Problem. Um bei der Untersuchung großräumiger Instanzen die Lösungsqualität der jeweiligen Zwischenergebnisse beurteilen zu können, wird eine untere Schranke vorgestellt, die ein max-plus System höherer Ordnung mit einem binären Suchalgorithmus kombiniert. Diese untere Schranke ermöglicht die Zulässigkeitsprüfung einer gegebenen Lösung und darüber hinaus die Quantifizierung der Optimalitätslücke der aktuellen Ergebnisse. Damit stellt diese Arbeit verschiedene wissenschaftliche Beiträge in Form unterschiedlicher Untersuchungsmodelle und -methoden bereit, um die Kapazität komplexer Eisenbahnnetzwerke zu untersuchen. Dabei werden die verschiedenen infrastrukturellen, betrieblichen und nachfragespezifischen Perspektiven integriert betrachtet, um die nachfragezentrierte Netzentwicklung von Eisenbahnsystemen zu unterstützen. Unter Berücksichtigung des Wachstums der Eisenbahnnachfrage in naher Zukunft kann diese Arbeit so Planer*innen helfen, die Fähigkeiten unserer gegenwärtigen Eisenbahnsysteme zu untersuchen und daraus die nötigen Handlungsalternativen abzuleiten, um die Verkehrssysteme unserer Zukunft zu entwickeln.