学位授与大学：京都大学 ; 取得学位: 博士(工学) ; 学位授与年月日: 2007-09-25 ; 学位の種類: 新制・課程博士 ; 学位記番号: 工博第2851号 ; 請求記号: 新制/工/1419 ; 整理番号: 25536 / Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13380号 / 工博第2851号 / 新制||工||1419(附属図書館) / 25536 / UT51-2007-Q781 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 藤井 滋穂, 教授 清水 芳久 / 学位規則第4条第1項該当

Made available in DSpace on 2015-03-26T13:54:43Z (GMT). No. of bitstreams: 1 texto completo.pdf: 192644 bytes, checksum: 534c199cff8e96f18f0df5f1c9e741ac (MD5) Previous issue date: 2008-07-29 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The objective of this work was to evaluate the effects of supplementation with nitrogenous compounds on intake, digestibility, and microbial protein synthesis in cattle under grazing during dry season. Five Holstein x Zebu steers fitted with rumen and abomasums canullae and with average initial live weight (LW) of 236kg, were used. The animals grazed five Brachiaria decumbens Stapf. paddocks and had free access to water and mineral. The experiment was carried out according to a 5 x 5 Latin square design, with five treatments and five experimental periods. The treatments were formed according to supplementation levels of nitrogenous compounds: 0; 0.35; 0.75; 1.05 and 1.40 g of crude protein (CP)/ Kg LW. A mixture of urea, ammonium sulfate and albumin (4.5:0.5:1.0) were used as nitrogen supplement. The daily quantity of supplement was calculated on animals LW at the beginning of each experimental period. The average CP levels in the diet were 7.39, 8.92, 10.98, 12.55 and 13.62% as dry matter (DM) basis, which corresponded to supplementation levels of 0, 0.35, 0.75, 1.05 and 1.40 g CP/kg LW, respectively. Linear- response-plateau (LRP) relationships were observed between intake estimates and diet CP levels (P<0.05). The LRP pattern showed the increase of intake until CP levels close to 9%, as dry matter basis. The estimates became unchangeable from this level. The total and ruminal digestibility coefficients of DM and neutral detergent fiber (NDF) and the diet level of total digestible nutrients presented a positive linear pattern (P<0.10) according to diet CP levels. The rumen pH was not affected by CP levels (P>0.10). The rumen ammonia nitrogen (RAN) concentration was linearly increased by diet CP levels (P<0.01). This variable assumed the value of 8.00 mg/dL of rumen fluid when the intake estimates reached the maximum values (close to 9 % of CP). The urinary excretion of nitrogen, the serum urea nitrogen concentration, the apparent nitrogen balance and the relative nitrogen balance were linearly increased (P<0.01) by diet CP levels. The different CP levels in the diet did not affected (P>0.10) the estimates of abomasums flow of microbial nitrogenous compounds (NMIC) and the efficiency of microbial synthesis. The NMIC and nitrogen intake became identical on 9.46% of CP in the diet. It is recommended the nitrogenous compounds supplementation to raise the CP level of the diet to 9%, as dry matter basis. Under these circumstances, the utilization of low-quality forage by grazing animals would be optimized. / Objetivou-se avaliar os efeitos da suplementação com compostos nitrogenados sobre o consumo, a digestibilidade e a síntese de proteína microbiana em bovinos em pastejo durante o período seco do ano. Foram utilizados cinco novilhos mestiços Holandês x Zebu, com peso vivo (PV) médio inicial de 236kg, fistulados no rúmen e no abomaso, mantidos individualmente em piquetes de Brachiaria decumbens Stapf. (0,34 ha) com livre acesso a água e mistura mineral. O experimento foi estruturado em delineamento em quadrado latino 5 x 5, com cinco tratamentos e cinco períodos experimentais. Os cinco tratamentos avaliados foram definidos de forma a se suplementar os animais com 0; 0,35; 0,75; 1.05; 1.40g de proteína bruta (PB)/kg PV. Como fonte de compostos nitrogenados empregou-se mistura de uréia, sulfato de amônia e albumina, nas proporções 4,5:0,5:1,0, respectivamente. A quantidade de suplemento fornecida foi calculada com base no PV dos animais no início de cada período experimental. Os níveis médios de PB nas dietas foram 7,39, 8,92, 10,98, 12,55 e 13,62%, com base na matéria seca (MS), para níveis de suplementação 0; 0,35; 0,75; 1,05 e 1,40 g PB/kg PV, respectivamente. Verificou-se relação do tipo linear-response-plateau (LRP) (P<0,05) entre as estimativas de consumo e os níveis de PB da dieta. O comportamento do tipo LRP permitiu evidenciar incremento no consumo até níveis próximos a 9% de PB, com base na MS, a partir do qual observou-se estabilidade das estimativas . Os coeficientes de digestibilidade total e ruminal da MS e da fibra em detergente neutro (FDN) e o nível de nutrientes digestíveis totais na dieta apresentam relações lineares (P<0,10) e positivas com os níveis de PV na dieta. Os valores de pH ruminal não foram afetados pelos níveis de PB na dieta (P>0,10). A concentração de nitrogênio amoniacal ruminal (NAR) foi incrementada de forma linear e positiva (P<0,01) em função da elevação dos níveis de PB na dieta, com valor estimado de 8,00 mg NAR/dL de liquido ruminal, equivalente à otimização do consumo voluntário ( 9% PB). A excreção urinária de nitrogênio, a concentração de nitrogênio uréico no soro, o balanço nitrogenado aparente e o balanço nitrogenado relativo foram incrementados linearmente (P<0,01) com níveis de PB na dieta. A variação nos níveis de PB na dieta não afetou (P>0,01) as estimativas de fluxos abomasal de compostos nitrogenados microbianos (NMIC) e de eficiência de síntese microbiana (P> 0,10). O equilíbrio entre NMIC e o consumo de nitrogênio foi obtido sob o nível de 9,46% de PB na dieta. Recomenda-se a inclusão de suplementos na dieta de forma a elevar-se o nível de PB a 9% com base na MS, para que ocorra otimização na utilização de forragem tropical de baixa qualidade sob pastejo.

Le fluor est devenu un élément incontournable en chimie médicinale. Les propriétés physico-chimiques induites par l'incorporation de cet atome dans les composés organiques en font un outil efficace dans la conception de mimes de fonctions chimiques. Les difficultés pour accéder aux composés azotés fluorés permettent d'envisager l'utilisation des milieux superacides et acides fluorants comme alternative de synthèse.Dans la première partie, la réactivité de N-allyl-N-arylbenzènesulfonamides en milieu superacide HF / SbF5 a été étudiée. La non observation de la cyclisation de type Friedel-Craft intramoléculaire initialement envisagée pour ces composés a été expliquée grâce à une étude mécanistique utilisant la RMN basse température in situ. En modifiant les conditions opératoires, la synthèse de N-arylbenzènesulfonamides α-fluorés a pu être développée. Les structures obtenues ont été testées pour l'inhibition des anhydrases carboniques.Dans la seconde partie, une nouvelle réaction d'hydrofluoration d'ynamides dans le milieu HF / pyridine a été développée. Cette stratégie a permis d'obtenir régio- et stéréosélectivement des (E)-α-fluoroènamides originaux. Par analogie avec les fluoroalcènes décrits en tant que mimes d'amides, les α-fluoroènamides sont potentiellement des isostères de la fonction urée. Le biomimétisme de ces structures est discuté grâce aux résultats d'études structurales réalisées par modélisation moléculaire. La réactivité surprenante de structures ortho-substituées en milieu superacide a permis le développement d'une réaction de polycyclisation intramoléculaire d'ynamides, cette nouvelle méthode permettant d'accéder en une étape à des polycycles azotés à haute valeur ajoutée. / During the last decades, fluorine became an essential element in medicinal chemistry. The original physical and chemical properties induced by the incorporation of this atom in organic compounds led to the development of fluorinated compounds as bioisosters in medicinal chemistry. Difficulties to access to fluorinated nitrogen containing compounds by "classical methods" led to the use of superacid as an alternative for their synthesis.In the first part of this work, the reactivity of unsaturated N-arylbenzenesulfonamides in superacidic media HF / SbF5 was studied. Intramolecular cyclisation of Friedel-Craft type expected for these compounds was studied and explored through a mechanistic study based on in situ low temperature NMR experiments. By modifying the operating conditions, the synthesis of α-fluorinated N-arylbenzenesulfonamide compounds was developed. The synthetized structures were then tested for carbonic anhydrase inhibition.In a second part, a new hydrofluorination reaction of ynamides was developed, using fluorhydric acid / pyridine media. This strategy allowed to access regio- and stereoselectively to original (E)-α-fluoroenamides. By analogy with the described fluoroalkenes as peptid bond isosters, α-fluoroenamides could potentially be considered as urea bioisosters. The bioisosterism of these structures was discussed and evaluated by using molecular modelling. The surprising reactivity of ortho-substitued structures in superacid media allowed the development of an intramolecular polycyclisation reaction, offering a one step route to complex nitrogen containing molecular polycyclic motif.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24601号 / 工博第5107号 / 新制||工||1977(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 伊藤 禎彦, 准教授 西村 文武, 教授 越後 信哉 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM