西藏产雪莲花的化学成分研究

本学位论文报道了作为传统藏药材广泛使用的西藏产雪莲花化学成分的研究。论文由五章组成，第一章是三种西藏产雪莲花的化学成分的系统分离纯化和结构鉴定；第二章为西藏产雪莲花化学成分的液-质及串联质谱联用分析；第三章提出了以HPLC和TLC为检测方法的雪莲花药材质量标准草案；第四章给出了对西藏产雪莲花挥发油化学成分的气-质联用分析结果；第五章概述了雪莲花的化学成分及药理研究进展。 第一章包括三个部分。第一部分报道了绵头雪莲花(Saussurea laniceps Hand.-Mazz.)全草乙醇提取物化学成分的分离鉴定。采用正相硅胶柱层析及凝胶柱层析等分离方法，从西藏产绵头雪莲花的乙醇提取物中共分离鉴定出15个化合物。其中11个化合物为首次从该植物中分离得到，当中2个化合物系在凤毛菊属植物中首次发现。第二部分报道了水母雪莲花(Saussurea medusa Maxim.)全草乙醇提取物的化学成分。采用正、反相硅胶柱层析及凝胶柱层析等分离方法，共分离鉴定出15个化合物，其中1个为新化合物，另有4个化合物为首次从该植物中分离得到。新化合物结构通过质谱和一维及二维核磁共振等波谱解析方法及碱水解反应确定为巴豆酰基-高车前苷(M-7)。第三部分报道了三指雪莲花 (Saussurea tridactyla Sch.-Bip. ex Hook. f.)全草乙醇提取物的化学成分。采用正相硅胶柱层析及凝胶柱层析等分离方法，共分离鉴定出7个化合物，其中1个化合物为首次从该植物中分离得到。 第二章也包括三个部分。首先是采用液-质联用(HPLC-DAD-ESI-MSn)分析方法，对7个西藏不同产地的三指雪莲花化学成分进行了分析，通过与标准品的 UV和MS数据比较，共鉴定出14个峰，并对其中8个共有成分进行了定量测定。其次是关于八种西藏产雪莲花化学成分的液-质联用(HPLC-DAD-ESI-MSn)分析，通过与标准品的UV和MS数据比较，共鉴定出15个峰，并对其中8个共有成分进行了定量检测。最后通过对八种西藏产雪莲花主要化学成分的多级串联质谱(ESI-MSn)分析，快速、灵敏地鉴定出10个黄酮和3个香豆素化学成分。 第三章同样包括三个部分。首先是以绵头雪莲花中主要香豆素成分东莨菪素和伞形花内酯为对照品，通过TLC定性检测和HPLC含量测定，草拟出较严谨的药材质量标准。其次是将绵头雪莲花、三指雪莲花和雪兔子作为一个药材看待，草拟了以东莨菪素和伞形花内酯的TLC检测为指标的药材质量标准。最后是针对水母雪莲花，以主要黄酮成分芹菜素-7-O-b-D-葡萄糖苷为对照品作TLC检测，并草拟出该药材的质量标准草案。 第四章报道了西藏产雪莲花挥发油的化学成分分析。采用传统水蒸气蒸馏法分别从八种雪莲花全草中提取挥发油，利用气相色谱-质谱联用技术分别从水母雪莲花、绵头雪莲花、槲叶雪莲花、云状雪兔子、拉萨雪兔子、小果雪兔子、雪兔子和三指雪莲花中分别鉴定出83、83、56、34、21、20、24和20个化学成分，分别占其挥发油总量的70.7%、76.0%、82.2%、55.4%、49.7%、70.4 %、76.2%和 76.7%。 第五章为综述，总结和概括了雪莲花的化学和药理研究进展。 The dissertation reports the investigation of the chemical constituents of the genus Saussurea. Quite a lot of species in this genus are traditional Tibetan medicinal plants, and hence have been widely used in traditional Tibetan medicine. This dissertation consisted of five chapters. The first chapter is on the chemical constituents of three Saussurea plants. The second section is about the analysis of chemical constituents of Saussurea plants using HPLC-MS and ESI-MS/MS. In the third chapter, we proposed quality-control standards for the Genus Saussurea based on TLC (thin layer chromatography) and HPLC. The fourth chapter is about chemical compositions of the essential oil from the whole plant of Saussurea plants. The last chapter reviews the research progress of the Genus Saussurea. The first chapter consists of three parts. The first part is about chemical constituents of ethanol extracts from whole plant of Saussurea laniceps Hand.-Mazz. Fifteen compounds were isolated by column chromatography on normal phase silica gel and Sephadex LH-20. Among them, eleven compounds were isolated from this plant for the first time, and two compounds were isolated from Genus Saussurea for the first time. The second part is about chemical constituents of ethanol extracts from whole plant of Saussurea medusa Maxim. Fifteen compounds were isolated by column chromatography on normal phase, reversed phase silica gel and Sephadex LH-20. Five of them were isolated from this plant for the first time, and there is one new flavonoid glucoside which was identified as 6″-O-crotonoyl-homoplantaginin (M-7) based on the evidence of one- and two-dimensional nuclear magnetic resonance, mass spectrometry analysis, and alkaline hydrolysis reaction. The last part is about chemical constituents of ethanol extracts from whole plant of Saussurea tridactyla Sch.-Bip. ex Hook. f.. Seven compounds were isolated by column chromatography on normal phase silica gel and Sephadex LH-20. There is one compound which was isolated from this plant for the first time. The second chapter consists of three parts. In the first part, we analyzed the chemical constituents of S. tridactyla collected from seven different places in Tibet using HPLC-DAD-ESI-MSn. Fourteen peaks in the HPLC were identified by comparison of UV and MS spectra with those of authentic compounds, among which eight common peaks were quantified. In the second part, we analyzed the chemical constituents of eight Saussurea species using HPLC-DAD-ESI-MSn method. Fifteen peaks in the HPLC were identified by comparison of UV and MS spectra with those of authentic compounds and eight main peaks of them were quantified. In the last part, we analyzed the chemical compounds of the above eight Saussurea plants directly by ESI-MS/MS. Thirteen major compounds, including 10 flavonoids and 3 coumarins were easily rapidly identified. The third chapter consists of three parts. In the first part, we proposed a comparative high quality-control standard for S. laniceps, based on quality detection by TLC and quantity analysis by HPLC using two major compounds (umbelliferone and scopoletin) as standard compounds. In the second part, in viewing S. laniceps, S. tridactyla and S. gossypiphora as the members of one family of medicinal herbs, we suggested a quality-control standard based on the TLC detection of the two major compounds (umbelliferone and scopoletin). In the last part, we proposed a quality-control standard for S. medusa based on the TLC detection of its major component (apigenin 7-O-glucoside). The four chapter analyzed the chemical constituents of essential oil of eight Saussurea species. The essential oils were extracted from the whole plants of these samples with water stream distillation. By GC-MS analysis, we identified eighty-three compounds from S. medusa, eighty-three from S. laniceps, fifty-six from S. quercifolia, thirty-four from S. aster, twenty-one from S. kingii, twenty from S. simpsoniana, twenty-four from S. gossypiphora, and twenty from S. tridactyla respetively, which accounted for 70.7%, 76.0%, 82.2%, 55.4%, 49.7%, 70.4 %, 76.2% and 76.7% of the total essential oil, respectively. The last chapter reviews the research progress of the Genus Saussurea.

几种植物药材的色谱－质谱联用分析

本论文由四章组成，第一、二、三章为实验论文，分别报道了中药羌活、菊花、全缘叶绿绒蒿的化学成分的高效液相色谱(HPLC)和液相色谱-质谱(LC-MS)联用分析以及挥发油的气相色谱-质谱(GC-MS)联用分析。第四章概述了重要藏药材化学成分的研究进展。 第一章首先对28批不同产地的羌活药材进行了HPLC分析，建立了羌活的指纹图谱。结果表明，不同产地羌活的化学成分基本相似，但是各组分在含量上存在较大差异。其次，对羌活的主要化学组分包括紫花前胡苷、紫花前胡素、6'-O-反式阿魏酸紫花前胡苷、茴香酸对羟基苯乙酯、羌活醇和异欧前胡素进行了定量分析。此外，针对同一产地不同采集时间的羌活挥发油进行系统分析，结果表明它们的化学成分基本相似，主要含有a－蒎烯、b－蒎烯、柠檬烯和龙脑乙酸酯等，只是各组分含量有所变化，这说明采集药材时要注意采集时间。 第二章分别报道了不同产地不同品种菊花非挥发性成分的液相色谱－二极管阵列检测－串联质谱(LC-PDA-MSn)分析和挥发性成分的气相色谱－质谱(GC-MS)联用分析比较。首先通过液相色谱－质谱－串联质谱对各色谱峰进行定性分析，通过与标准品对照，以及UV和MSn提供的结构信息，结合文献报道共鉴定了11个化学成分，包括绿原酸和10个黄酮化合物，并比较了不同品种菊花的化学成分相同之处和不同之处。另外，对七种不同品种不同产地的菊花挥发性成分通过GC-MS分析表明其主要挥发性成分为单萜类、倍半萜类化合物，共有成分樟脑、龙脑和龙脑乙酸酯等，各成分在不同挥发油中的含量变化明显。 第三章为藏药全缘叶绿绒蒿不同部位挥发油成分的气相色谱－质谱(GC-MS)联用分析，比较其挥发油化学成分及其含量变化的异同点。研究结果表明，全缘叶绿绒蒿花精油的化学成分明显多于全草部位，且两者主要成分有较大的差别。 第四章综述了青藏高原重要藏药材化学成分的研究进展。分别对藏药的资源特色和110多种常用重要藏药材的化学成分的研究情况以及藏药未来发展思路进行了阐述，以期对相关的研究提供一些信息。 This dissertation consists of four parts. The first part reports studies on the fingerprint of Notopterygium incisum and N. forbesii by HPLC-PDA-MSn, and on the constitutents of essential oil by GC-MS. The second part elaborates the chemical constitutents of Chrysanthemum L. by LC-MS and GC-MS analysis. The third part reports the chemical compositions of the essential oil from the different parts of Meconopsis integrifolia. The fourth part reviews on the progress of the studies on the chemical constitutents in Tibetan medicines. The first chapter is about HPLC analysis of a traditional Chinese herbal medicine Qiang-huo (Notopterygium incisum and N. forbesii ). Firstly, based on analyzing and contrasting the relative retention time and relative paek area in chromatographic fingerprint, the HPLC chromatographic fingerprint of Notopterygium incisum was established, which can used as a scientific basement for the quality evalution of this herb. Secondly, quantitative analysis were performed on the main chemical constitutents of Notopterygium incisum and N. forbesii including nodakenin, nodakenetin, 6’-O-trans-feruloylnodakenin, p-hydroxypenethylanisate, notopterol and isoimperatorin. The results indicated that the contents were variable related to different growth regions. Lastly, the essential oil of Notopterygium incisum collected in different harvest times is analyzed by GC-MS. The second chapter is about HPLC-MS and GC-MS analysis of several species of Chrysanthemum L. Firstly, eleven compounds including chlorogenic acid and ten flavone compounds were identified in the methanol extract of Chrysanthemum morifolium Ramat. from different regions by HPLC-MS analysis. Secondly, the essential oil of seven different species of Chrysanthemum L.were extracted by steam distillation, and its compositions were isolated and identified by GC-MS. The main active constitutents such as camphor, borneol and bornyl acetate were detected, but the relative content varied notably. The third chapter is about GC-MS analysis of the essential oil from different parts of Meconopsis integrifolia. It indicated great difference of the chemical compositions of their oil in the flowers and residual overground part. The last chapter is a review of the research progress of the Tibetan medicines, which includes their features and their main chemical constitutents.

Surface-appropriate lipophobicity - Application in isobutene oligomerization over Teflon-modified silica-supported 12-silicotungstic acid

A series of silica-supported 12-silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by an impregnation method. The surface properties of the catalysts were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, infrared (IR) spectroscopy, NH3-TPD and the Drop Shape Analysis (DSA). SEM results combined with energy-dispersive X-ray (EDX) measurements of HSiW/SiO2-Teflon revealed that F-compound (Teflon) is effectively coated on the catalyst surface. The contact angles for water and oil of 50 wt% HSiW/SiO2 and HSiW/SiO2-Teflon indicate that HSiW/SiO2-Teflon catalyst enhances not only the surface hydrophobicity but also the surface lipophobicity by means of the addition of Teflon. Silica-supported 12-silicotungstic acid modified with Teflon exhibits higher C-8(=) selectivity and longer lifetime than that of silica-supported 12-silicotungstic acid in isobutene oligomerization. Thus, surface-appropriate lipophobicity of catalysts may be effective for decreasing the interaction between coke precursors and the catalyst surface and for removing deposited coke more easily.

陡坡带砂砾岩体油气成藏模式研究——以东营凹陷西北部陡坡带为例

Based on the study of sequence stratigraphy, modern sedimentary, basin analysis, and petroleum system in abrupt slop of depression, this paper builds sedimentary system and model, sandy bodies distribution, and pool-forming mechanism of subtle trap. There are some conclusions and views as follows. By a lot of well logging and seismic analysis, the author founded up the sequence stratigraphic of the abrupt slope, systematically illustrated the abrupt slope constructive framework, and pointed out that there was a special characteristics which was that south-north could be divided to several fault block and east-west could be carved up groove and the bridge in studying area. Based all these, the author divided the studying area to 3 fault block zone in which because of the groove became the basement rock channel down which ancient rivers breathed into the lake, the alluvial fan or fan delta were formed. In the paper, the author illustrated the depositional system and depositional model of abrupt slope zone, and distinguished 16 kinds of lithofacies and 3 kinds of depositional systems which were the alluvial fan and fan-delta system, lake system and the turbidite fan or turbidity current deposition. It is first time to expound completely the genetic pattern and distributing rule of the abrupt slope sandy-conglomeratic fan bodies. The abrupt slope sandy-conglomeratic fan bodies distribute around the heaves showing itself circularity shape. In studying area, the sandy-conglomeratic fan bodies mainly distribute up the southern slope of Binxian heave and Chenjiazhuang heave. There mainly are these sandy-conglomeratic fan body colony which distributes at a wide rage including the alluvial fan, sub-water fluvial and the turbidite fan or the other turbidity current deposition in the I fault block of the Wangzhuang area. In the II fault block there are fan-delta front and sub-water fluvial. And in the Binnan area, there mainly are those the alluvial fan (down the basement rock channel) and the sandy-conglomeratic fan body which formed as narrowband sub-water fluvial (the position of bridge of a nose) in the I fault block, the fan-delta front sandy-conglomeratic fan body in the H fault block and the fan-delta front and the turbidity current deposition sandy-conglomeratic fan body in the m fault block. Based on the reservoir outstanding characteristics of complex classic composition and the low texture maturity, the author comparted the reservoir micro-structure of the Sha-III and Sha-IV member to 4 types including the viscous crude cementation type, the pad cementation type, the calcite pore-funds type and the complex filling type, and hereby synthetically evaluated 4 types sandy- conglomeratic fan body reservoir. In the west-north abrupt slope zone of Dongying Depression, the crude oil source is belonging to the Sha-III and Sha-IV member, the deep oil of Lijin oilfield respectively come from the Sha-III and Sha-IV member, which belongs to the autogeny and original deposition type; and the more crude oil producing by Sha-IV member was migrated to the Wangzhuan area and Zhengjia area. The crude oil of Binnan oil-field and Shanjiasi oil-field belongs to mixed genetic. It is the first time to illustrate systematically the genetic of the viscous crude that largely being in the studying area, which are that the dissipation of the light component after pool-forming, the biological gradation action and the bath-oxidation action, these oil accumulation belonging to the secondary viscous crude accumulation. It is also the first time to compart the studying area to 5 pool-forming dynamical system that have the characteristic including the common pressure and abnormal pressure system, the self-fountain and other-fountain system and the closing and half-closing system etc. The 5 dynamical systems reciprocally interconnected via the disappearance or merger of the Ethology and the fluid pressure compartment zone, the fault and the unconformity surface, hereby formed duplicated pattern oil-gas collecting zone. Three oil-gas pool-forming pattern were founded, which included the self-fountain side-direction migrated collecting pattern, the self-fountain side-direction ladder-shape pool-forming pattern and the other-fountain pressure releasing zone migrated collecting pattern. A series of systemic sandy-conglomeratic fan bodies oil-gas predicting theory and method was founded, based on the groove-fan corresponding relation to confirm the favorable aim area, according as the characteristic of seismic-facies to identify qualitatively the sandy-conglomeratic fan bodies or its scale, used the temporal and frequency analysis technique to score the interior structure of the sandy- conglomeratic fan bodies, applied for coherent-data system analysis technology to describe the boundary of the sandy-conglomeratic fan bodies, and utilized the well logging restriction inversion technique to trace quantificational and forecast the sandy-conglomeratic fan bodies. Applied this technique, totally 15 beneficial sandy-conglomeratic fan bodies were predicted, in studying area the exploration was preferably guided, and the larger economic benefit and social benefit was acquired.

东营凹陷中央隆起带次生油藏成藏机制和预测

It is the key project of SINOPEC at ninth five years period with a lot of work and very difficult, which the main object are the study of pool-forming mechanism, distribution rule and pool-forming model of complex secondary pool at Dongying formation in high mature exploration area, and building theories and methods of research, description and prediction of secondary fault block pool. This paper apply comprehensively with various theories, method and techniques of geology, seismic, well log, reservoir engineering, meanwhile apply with computer means, then adopt combination of quality and quantitative to develop studies of pool-forming mechanism, model and pool prediction of fault block pool. On the based of stretch, strike-slip, reversal structure theories, integrated the geometry, kinematics, and dynamics of structure, it is show that the structure framework, the structure evolve, formation mechanism of central uplift belt of Dongying depression and control to formation and distribute of secondary complex fault block pool. The opening and sealing properties, sealing mechanism and sealing models of pool-controlling fault are shown by using quality, direction of normal stress, relations between interface and rock of two sides of fault and shale smear factor (SSF), as well as the juxtaposition of fault motion stage and hydrocarbon migration, etc. The sealing history of controlling fault, formation mechanism and distribute the regulation are established by combining together with bury history, structure evolve history, fault growth history stress field evolve history, which can be guide exploration and production oil field. It were bring up for the first time the dynamics mechanism of Dongying central uplift which were the result of compound tress field of stretch, strike-slip and reversal, companion with reversal drag structure, arcogenesis of paste and salt beds. The dual function of migration and sealing of fault were demonstrated in the research area. The ability of migration and sealing oil of pool-controlling fault is controlled by those factors of style of fault combination, activity regulation and intensity of fault at the period of oil migration. The four kinds of sealing model of pool-controlling fault were established in the research area, which the sealing mechanism of fault and distribution regulation of oil in time and space. The sealing ability of fault were controlled by quality, direction of normal stress, relations between interface and rock of two sides of fault and shale smear factor (SSF), as well as the juxtaposition of fault motion stage and hydrocarbon migration, etc. The fuzzy judge of fault sealing is the base of prediction of secondary pool. The pool-forming model of secondary was established in the research area, which the main factors are ability migration and sealing. The transform zone of fault, inner of arc fault and the compound area of multi fault are enrichment region of secondary pool of Dongying formation, which are confirm by exploration with economic performance and social performance.

板北断块油藏储层均质特征与剩余油分布研究

With the growing development and perfection of reservoir describing technology, its research achievements have played an increasingly important role in old oilfields in recent years. Reservoir description quantitatively describes, characterizes and predicts every kind of reservoir characters in 3D space. The paper takes Banbei block reservoir as an object, studies the reservoir characters and residual oil distributing characteristics of gravity flow genetic reservoir, and definitudes potential adjustment direction of reservoir development. Main achievements are gained as follows. Through fine correlation of strati graphic sequence, the classification of layers and single sands of main payzones in Banbei block is ascertained, the classifying methods of sedimentary unit in gravity flow reservoir characterized with picked cyclical marker bed are formed. On the basis of comprehensive logging evaluation, depositional characters of Banbei block are studied, and classifying methods of sedimentary microfacies in gravity flow reservoir are described. The sedimentary background of main oil layers in Banbei block is open lake with shallow water, and belongs to lacustrine underwater gravity flow- lacustrine phase depositional system. Main microfacies types are underwater water course^ water course side-wing, underwater floodplain, between two water courses, and lacustrine mud, etc. Reservoir sands mainly are underwater water course sands. Influenced by distributing characters of gravity flow underwater water course, sand shapes in plane mainly are stripe, finger-shape, tongue-shape. Sand distribution shows obvious split property. Sands overlap each other. According to comprehensive analysis of lithologic data, logging parameters, and dynamic production data, the researching threads and methods of reservoir heterogeneous characters are perfected. The depositional characters of gravity flow underwater water course in Banbei block determine its high reservoir heterogeneity. Macroscopic heterogeneity is studied in many aspects such as the scale of layers, the scale of single sands, in-situ scale, the distribution of interlayer types, the interlayer scale, and heterogeneity in plane. Thus, heterogeneous characters of reservoir are thoroughly analyzed. Through microscopic research of reservoir, the types of porous structure and related parameters are determined. According to the analysis of dynamic production data, the reaction and inner influential factors of reservoir heterogeneity in waterflood development are further revealed. Started with the concept and classifying methods of flow unit, clustering classification which can better meet the requirements of production is formed. The flow unit of Banbei block can be classified into four types. According to comprehensive evaluation, the first and second type of flow unit have better percolating capability and reserving capability. Research thread of 3D model-building and reservoir numerical simulation combined as an integral is adopted. The types and characters of residual oil distribution are determined. Residual oil of Banbei block mainly distributes in the boundary of sands, near the faults, areas with non-perfect injection-production well pattern , undeveloped sands, vertically poor developed layers. On the basis of comprehensive reservoir study, the threads and methods of improving development effect towards reservoir with high water cut, high recovery percent, serious heterogeneity are ascertained. The whole waterflood development effect of Banbei block reservoir is good. Although its water cut and recovery percent is relatively high, there is still some potential to develop. According to depositional characters of gravity flow and actual production situation? effective means of further improving development level are as follows. We should drill new wells in every kind of areas abounding with residual oil, implement comprehensive measures such as increasing liquid discharge, cyclic waterflood, changing fluid direction when injection-production well pattern is perfected, improve water quality, enhance displacement efficiency in flooding.

Natural substances and high pressure processing to preserve sea bass

Esta tese teve como objectivo estudar estratégias de conservação de pescado fresco, recorrendo ao uso de extractos e óleos essenciais de plantas e do processamento por alta pressão (HPP), usando filetes de robalo como um caso de estudo modelo. Relativamente aos extractos e óleos essenciais, avaliaram-se as suas propriedades antibacterianas e antioxidantes. Os extractos aquosos quente de poejo e de orégão e o óleo essencial de cravinho apresentaram a maior actividade antioxidante. Os óleos essenciais foram mais eficientes do que os extractos para inibir o crescimento das estirpes bacterianas testadas, tendo-se observado os menores valores de concentração mínima inibitória nos óleos essenciais de orégão, citronela, alho e orégão Espanhol. De seguida, estudou-se o efeito dos óleos essenciais de orégão Espanhol e de limão na conservação de filetes de robalo fresco tendo em conta critérios microbiológicos, químicos, físicos e sensoriais. A aplicação do óleo essencial de orégão Espanhol aumentou o tempo de vida útil dos filetes sob o ponto de vista bacteriano, mas não em termos sensoriais. A combinação dos óleos essenciais de orégão Espanhol e de limão melhorou o efeito antioxidante e reduziu a intensidade do odor e a sua eficácia em relação às Enterobacteriaceae, comparando com o tratamento com óleo essencial de orégão Espanhol per se. No sentido de reduzir o odor conferido pelos óleos essenciais realizou-se um estudo de conservação para avaliar o efeito de películas com óleos essenciais (citronela, alho e tomilho) em filetes de robalo, recorrendo a uma teste de desafio bacteriano. As películas sem óleos essenciais aumentaram o tempo de vida útil sob o ponto de vista bacteriano, mas este efeito não foi observado com a incorporação dos óleos essenciais nas películas. Em relação ao HPP, testaram-se diversas condições (nível de pressão, tempo de pressurização e taxa de pressurização) e avaliaram-se os efeitos na actividade enzimática, na qualidade global e na conservação de filetes de robalo fresco. Em geral, o aumento do nível de pressão e do tempo de pressurização diminuiu a actividade da fosfatase ácida e das enzimas proteolíticas, a carga bacteriana e a capacidade de retenção de água, enquanto que os filetes ficaram mais brancos. O HPP revelou potencial para o desenvolvimento de novos produtos: mais brancos, não translúcidos, mais firmes e com maior tempo de frescura e estabilidade microbiológica. Em conclusão, os óleos essenciais e o HPP têm potencial para conservar pescado fresco, devido aos seus efeitos na qualidade bacteriana. Ainda assim, mais esforços devem ser feitos no sentido de reduzir a transferência de odor dos óleos essenciais para o pescado e os efeitos do HPP no aspecto do pescado e na oxidação lipídica.

Caractérisation de stratégies stimulant l’immunité cellulaire par l’étude de la présentation antigénique d’une nanoparticule vaccinale et du blocage d’un mécanisme d’immunosuppression

Il existe plusieurs défis au développement d’une thérapie visant à stimuler l’immunité cellulaire. Dans la prévention contre certains virus et en immunothérapie du cancer, l’induction de lymphocytes T spécifiques est cependant primordiale. Dans la première partie de l’étude, nous avons porté notre attention sur la compréhension de la présentation croisée par le complexe majeur d’histocompatibilité de classe I (CMH I) médiée par des particules pseudo-virales (VLP) composées de la protéine de surface de potexvirus à laquelle nous avons ajouté un épitope de la protéine M1 du virus de l’influenza ou un épitope de la protéine gp100 du mélanome. Cette VLP se caractérise par sa capacité à stimuler, sans l’aide d’adjuvant, le système immunitaire et de présenter de façon croisée l’épitope inséré dans sa protéine de surface et ce, indépendamment de l’activité du protéasome. Nous avons, tout d’abord, comparé les propriétés de présentation antigénique croisée des VLP formées du virus de la mosaïque de la malva (MaMV) à celles des VLP du virus de la mosaïque de la papaye (PapMV). Les résultats confirment que ces propriétés sont partagées par plusieurs membres de la famille des potexvirus malgré des divergences de séquences (Hanafi et al. Vaccine 2010). De plus, nous avons procédé à des expériences pour préciser le mécanisme menant à la présentation de l’épitope inséré dans les VLP de PapMV. Les résultats nous confirment une voie vacuolaire dépendante de l’activité de la cathepsine S et de l’acidification des lysosomes pour l’apprêtement antigénique. L’induction de l’autophagie par les VLP semble également nécessaire à la présentation croisée par les VLP de PapMV. Nous avons donc établi un nouveau mécanisme de présentation croisée vacuolaire dépendant de l’autophagie (Hanafi et al. soumis Autophagy). En second lieu, en immunothérapie du cancer, il est aussi important de contrôler les mécanismes d’évasion immunitaire mis en branle par la tumeur. Nous avons spécifiquement étudié l’enzyme immunosuppressive indoleamine 2,3-dioxygénase (IDO) (revue de la littérature dans les tumeurs humaines; Hanafi et al. Clin. Can. Res 2011) et son inhibition dans les cellules tumorales. Pour ce faire, nous avons tenté d’inhiber son expression par la fludarabine, agent chimiothérapeutique précédemment étudié pour son activité inhibitrice de l’activation de STAT1 (signal transducers and activators of transcription 1). Étonnamment, nos résultats ont montré l’inhibition d’IDO dans les cellules tumorales par la fludarabine, indépendamment de l’inhibition de la phosphorylation de STAT1. Nous avons démontré que le mécanisme d’action dépendait plutôt de l’induction de la dégradation d’IDO par le protéasome (Hanafi et al. PlosOne 2014). Les travaux présentés dans cette thèse ont donc portés autant sur la compréhension d’une nouvelle plateforme de vaccination pouvant médier l’activation de lymphocytes T CD8+ cytotoxiques et sur le contrôle d’une immunosuppression établie par les cellules tumorales pour évader au système immunitaire. Ces deux grandes stratégies sont à considérer en immunothérapie du cancer et la combinaison avec d’autres thérapies déjà existantes pourra permettre une meilleure réponse clinique.

Avaliação de produtos naturais no controle de biofilmes formados em sistema dinâmico

The biofilms microbial forms of association are responsible for generating, accelerating and / or induce the process of corrosion. The damage generated in the petroleum industry for this type of corrosion is significatives, representing major investment for your control. The aim of this study was to evaluate such tests antibiograms the effects of extracts of Jatropha curcas and essential oil of Lippia gracilis Schauer on microrganisms isolated from water samples and, thereafter, select the most effective natural product for further evaluation of biofilms formed in dynamic system. Extracts of J. curcas were not efficient on the complete inhibition of microbial growth in tests type antibiogram, and essential oil of L. gracilis Schauer most effective and determined for the other tests. A standard concentration of essential oil of 20 μL was chosen and established for the evaluation of the biofilms and the rate of corrosion. The biocide effect was determined by microbial counts of five types of microorganisms: aerobic bacteria, precipitating iron, total anaerobic, sulphate reducers (BRS) and fungi. The rate of corrosion was measured by loss of mass. Molecular identification and scanning electron microscopy (SEM) were performed. The data showed reduction to zero of the most probable number (MPN) of bacteria precipitating iron and BRS from 115 and 113 minutes of contact, respectively. There was also inhibited in fungi, reducing to zero the rate of colony-forming units (CFU) from 74 minutes of exposure. However, for aerobic and anaerobic bacteria there was no significant difference in the time of exposure to the essential oil, remaining constant. The rate of corrosion was also influenced by the presence of oil. The essential oil of L. gracilis was shown to be potentially effective

Licenciamento ambiental em postos de revenda de combustíveis à luz dos princípios constitucionais de defesas do meio ambiente: o caso do município de Natal/RN

This study approaches the question of the administrative procedure of the environmental licensing of ranks of fuel resale, taking as basis a study case of the reality of the City of Natal/RN (Brazil). For in such a way, it was done a retrospect on the evolution of the system of road transport in Brazil, having started to briefly analyze the urbanization process that if after accented in the capitals of the Brazilian States the decade of 1950, relating these subjects with the growth of the sector of fuel resale. After that, it was transferred boarding of the defense of the national environment to the light of ambient principles constitutional. In the sequence, a boarding on the ambient guardianship in the Federal Constitution of 1988 was made, treating basically specifies and on the national urban politics and the national politics of the environment, with its instruments. In the sequence, it was transferred the analysis of the abilities and attributions of the National Advice of the Environment (CONAMA) and its Resolutions, for then only enter in the most important part of this work: an analysis of the environmental licensing of ranks of fuel resale, in the reality of the City of Natal/RN. Before this specific boarding, it was proceeded specifically a survey and communication from the applicable norms to such establishments (Resolutions of the CONAMA and norms of the ABNT), for after that carrying through an geo-ambient characterization of the City of Natal/RN. Finally, a reflection was made on the possibility of magnifying of the state activity, in terms of guarantees for the responsible members for the environmental policy and of administrative efficiency, through the idea of the ambient regulation. For the accomplishment of this study, it was proceeded research in diverse sources such as books, magazines, sites of the Internet, periodicals, thesis and dissertations, among others material, beyond visits the agencies that direct or indirectly act with the ambient defense and as fuel resale, such as Secretariat of Environment and Urbanism of the City of Natal (SEMURB), Institute of Economic Development and Environment of RN (IDEMA), Brazilian Institute of the Environment and the Natural resources You renewed, Executive Management of RN (IBAMA/RN), Public prosecutor's office of the Environment of Natal (Public prosecution service of the RN), National Agency of Oil (ANP) and Union of the Retailing of Derivatives of Oil of the RN, among others. To the end, satiated regulation is observed that although on the substance of the ambient licensing in ranks of fuel resale, also with federal, state and municipal norms, the municipal Public Power is very far from the fulfilment of its institutional functions, in the question environmental policy of these establishments, a time that few are the permitted ranks of resale in the city of Natal/RN

Trajetória dos assentamentos rurais financiados pelo crédito fundiário no estado do Rio Grande do Norte: uma análise da experiência do assentamento da fazenda Paz no município de Maxaranguape/RN

The market-assisted land reform (RAAM) has been constituted as an alternative of agrarian reform funded by the Programa Nacional do Crédito Fundiário (PNCF). It is a policy of acquisition, distribution and use of Earth ideologically disseminated and funded by the World Bank in the context of productive insertion of landless workers. Accordingly, this study seeks to analyze the trajectory of rural settlements financed by this policy, seeking to understand what factors promote or limit the process of rural development of those settlements. To do so, take as a reference case study of the Assentamento da Fazenda Paz, in the municipality of Maxaranguape in the State of Rio Grande do Norte. From the methodological point of view, bibliographical and documentary research were used, in addition to visits to the settlement and semi-structured interviews with the settlers, trade union leaders, consultants and technicians linked to the project. Assuming the reports of respondents, initially constructs the hypothesis that informal and formal institutions present in the Assentamento da Fazenda Paz were unable to effectively coordinate the actions of the agents. The results obtained showed the existence of a very complex undertaking, with a total area of 607 hectares and 80 families settled, endowed with good quality water and irrigation infrastructure, with assets of approximately R$ 5 million reais. Experience experienced by the settlers understood the development of complex systems of production and marketing of fruits and vegetables, with an emphasis on the cultivation of papaya in an area of 45 hectares based on modern irrigation system and extensive use of technology. Collective management of production, marketing, revenue and costs stood out as a major challenge for the settlers and their representative organisations, i.e. the Community Association and the cooperative. From this observation it was possible to identify two moments on the trajectory of the project: the first, between 2007-2011, considered by respondents as successful, in which the integration of public policies and abundant input of revenue from the commercialization of the fruits da Paz, mainly through the sale of papaya and pineapple in national and international markets, allowed an average remuneration of R$ 800.00 reais to R$ 1,000 reais seated/monthIn addition to the production of vegetables and other types of products for sale and consumption; the second, from 2012, characterized as a failure, due to the discontinuity of the cultivation, production and marketing of fruits based on the collective bargaining model deployed. Important factors explain the discontinuity of the project, including the model of agriculture implemented, difficulties related to the management of production, marketing and finance the venture, in addition to the breach of trust between the Board of the cooperative and the associates and the distancing of the governmental organizations more directly responsible for the project. It is therefore concluded that we must to rethink rural development as a multidimensional phenomenon, requiring a broad engagement between State and society under the foundations of a territorial development contract

Parâmetros biológicos e tabela de vida de Tetranychus urticae (Acari: Tetranychidae) em cultivares de mamão

Este trabalho foi realizado para avaliar o desenvolvimento e reprodução de Tetranychus urticae em cultivares comerciais de mamão Carica papaya. Foram utilizadas cultivares do grupo Formosa (Tainung 01 e Calimosa) e do grupo Solo (Golden e Sunrise). Para iniciar o bioensaio, foi transferida uma fêmea fertilizada por disco de folha (n=50 repetições) e retirado após um período de 12h, sendo avaliada a cada 12h, registrando-se o período de incubação, duração do estágio de imaturo, longevidade e fecundidade dos adultos e viabilidade desses estágios. Os resultados indicaram que as cultivares de mamão Tainung 01, Calimosa, Sunrise e Golden são bons hospedeiros para T. urticae. O parâmetro viabilidade não sofreu influência das cultivares em todas as fases de desenvolvimento avaliadas, apresentando valores superiores a 90%. Não houve diferença estatística entre as cultivares nos parâmetros: período de pre-oviposição e viabilidade dos ovos. A cultivar Tainung 01 apresentou menor potencial hospedeiro, embora houvesse menor duração nos estágios de ovo, larva, protoninfa e ovo-adulto. Nos parâmetros de tabela de vida e fertilidade, apresentou menores valores de Ro, r m e λ e maior valor de Td. Entre as cultivares, o Sunrise apresentou um elevado potencial hospedeiro para T. urticae, pois essa cultivar proporcionou a maior produção de ovos por fêmea, maior longevidade das fêmeas, bem como a maior taxa de reprodução (maior Ro, r m e λ e menor valor de Td).

Avaliação de fungicidas no controle de Asperisporium caricae na cultura do mamoeiro

Dentre as doenças fúngicas do mamoeiro, a varíola (Asperisporium caricae) é umas das doenças mais importantes. Os objetivos deste trabalho foram avaliar a eficácia de fungicidas no controle da varíola em folhas e frutos do mamoeiro. O experimento foi conduzido em área comercial, no município de Taquarintiga - SP, em delineamento de blocos casualizados, com cinco tratamentos e quatro repetições. Os tratamentos foram tebuconazol + trifloxistrobina (0,06 L.100L-1 de água), piraclostrobina (0,04 L.100L-1 de água), difenoconazol (0,03 L.100L-1 de água), azoxistrobina (128 g.ha-1) e a testemunha. Foram realizadas três avaliações, nas quais foram avaliadas a severidade da varíola através de escala diagramática, nas folhas e nos frutos de três plantas previamente marcadas. Os dados registrados foram submetidos à análise de variância pelo teste F, e as médias, comparadas pelo teste de Scott-Knott (p<0,05). Os fungicidas tebuconazol+trifloxistrobina, piraclostrobina, difenoconazol e azoxistrobina foram eficientes no controle da varíola.

Adubação nitrogenada em cobertura e substratos na produção de mudas de mamoeiro 'Formosa'

Objetivando-se avaliar a produção de mudas de mamoeiro em diferentes substratos com adubações de nitrogênio em cobertura, conduziu-se um experimento em viveiro de formação de mudas no pomar da Universidade Federal de Lavras (UFLA), Minas Gerais. Foram testadas cinco doses de nitrogênio 0; 400; 800; 1600 e 3200 mg de N dm-3 de substrato, aplicados cinco vezes, sendo que em cada aplicação foram adicionados aos sacos de polietileno (capacidade de 500 mL) 20 mL de solução contendo o N e duas composições de substratos: A (composto orgânico + areia + solo na proporção de 1:1:3 em volume) e B (Plantmax® + areia + solo na proporção de 1:1:3 em volume). Foi utilizado o delineamento experimental em blocos ao acaso em esquema fatorial 5 x 2, com 4 repetições e cinco plantas por parcela. Após 150 dias da semeadura avaliaram-se as seguintes variáveis: comprimento da parte aérea (cm); comprimento de raiz (cm), número de folha/muda, matéria seca da parte aérea, da raiz e total (g/planta). Verificou-se que dosagem de até 1.800 mg de N dm-3 em cobertura, foram as que proporcionaram melhor qualidade na formação das mudas. em relação aos substratos verificou-se que o substrato B (Plantmax® + areia + solo na proporção de 1:1:3 em volume) foi o que promoveu os melhores resultados na produção das mudas do mamoeiro 'Formosa'.

Sazonalidade dos ductos secretores e óleo essencial de Foeniculum vulgare var. vulgare Mill. (Apiaceae)

Este trabalho teve como objetivo analisar os ductos secretores e o óleo essencial das folhas de Foeniculum vulgare em diferentes épocas do ano. Para esta finalidade, foram realizados estudos de caracterização anatômica, bem como anatomia comparada dos ductos secretores e testes histoquímicos das folhas. O óleo essencial foi obtido de folhas e frutos, por hidrodestilação em aparelho de Clevenger e analisados quantitativamente e qualitativamente por cromatografia em fase gasosa acoplada ao espectrômetro de massa, realizando-se análises seguidas de três réplicas para folhas coletadas durante o inverno e primavera, e frutos no verão. Os resultados encontrados para os ductos secretores de óleo corresponderam à redução do teor de óleo essencial nas folhas coletadas no final da primavera. O componente majoritário do óleo essencial de folhas e frutos foi o trans-anetol, durante todas as estações do ano. Portanto, evidenciou-se que os ductos secretores e teor de óleo essencial estão relacionados, bem como os constituintes químicos também estão sujeitos a sazonalidade, conforme o estágio fenológico da planta.