976 resultados para Osmotic dehydration


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The most widespread rock associations in the Western Block of North China Craton are khondalites distributed mainly in Jining, Liangcheng and Datong. A large quantitiy of garnet-bearing granites are contained in the khondalites. A great deal of research has been carried out on them by previous researchers. Studies of these garnet-bearing granites consist essentially of structural characteristics, petrography and geochemistry, and finally geochronological determinations. Summing up these researches, it will not be difficult to see that all of these authors have regarded these large numbers of garnets (up to 20%) contained in granites as crystallized products from magmas, but they have not proved this from petrological perspective. Theoretically, there are possibly three kinds of petrogenesis as to these garnets. The first one is that they have been transferred to the granites from khondalites by melt when anatexis happened to khondalites, and they, in essence, are residual metamorphic garnets; The second one is that when the khondalites were being melted, these garnets were produced from biotite dehydration melting, and the newly formed garnets intruded together with the melt and eventually molded the garnet-bearing granites. Garnets of this possible kind either showed independent crystals, or garnets from khondalites took place secondary growth under favorable temperature and pressure conditions for their crystallization; The last possibility is that these garnets were crystallized from magmas in which suitable pressure, temperature and composition were available. These garnets, generally, should be fine-grained. The aim of this study is, through examining the mineral chemistry of the garnets and the whole rock chemistry, to ascertain under which kind of mechanism, in the world, did these garnets form? Besides, we try to calculate the temperatures under which khondalites began melting and reactions of the garnets and the cooled melts happened by garnet-biotite thermometry. The whole rock chemistry analyses of the garnet-bearing granites tell us that all the samples are strongly peraluminous (A/CNK greater than 1.1) on the A/NK vs. A/CNK plot. On the SiO2-K2O plot, the granites are mainly constrained to be high-K calc-alkaline and calc-alkaline series, consistent with previous researches. On the ACF((Al2O3-Na2O-K2O)-FeO(T)-CaO) discrimination plot, all the six garnet-bearing granite samples drop into the area of S-type granites. The relationship between CaO/Na2O and SiO2 shows that the overwhelming majority of garnet-bearing granites have a CaO/Na2O value over 0.3, revealing that they probably come from metagreywacke precursors or mediate-felsic orthogeneisses compositionally similar to them. Detailed EPMA analyses conducted on the garnets contained in the garnet-bearing granites show that all the garnets are dominated by almandine and pyrope, which occupy 92-96% (Weight Percentage) of each garnet analyzed, typical of granulite facies. Their chemical composition is entirely different from those crystallized in magmas, but extremely similar to those of typical granulite facies metapelites in khondalites and typical granulites, indicating all the garnets to be metamorphogenic. In addition, REEs distribution patterns of the garnets are totally different from typical biotite granites and peraluminous granites. In other words, both LREE and HREE of our garnets are evidently lower than those from these two kinds of rocks. Moreover, compared to the REE pattern of the garnets from typical amphibolites, LREE content of our garnets is obviously higher and HREE content is a little lower. However, REE patterns of our garnets are completely in harmony with those of garnets from typical granulites. So, the REE patterns of garnets, again, prove that all the garnets we studied are metamorphogenic. Biotites appear in two forms, being as inclusions in the garnet and as selvages immediately adjacent to the garnet, respectively. Two reactions and their corresponding temperatures, with the help of petrography and Garnet-Biotite geothermometers, could be obtained, which are Bt+ Pl+ Qtz→Kfs+ Opx+ Grt+ melt as positive reaction and Kfs+ Grt+ melt→Bt+ Pl+ Qtz as reverse reaction, respectively. Summing up the discussion above, we declare that the garnet-bearing granites distributed in the Western Block of North China Craton are the mixture of melts and restites resulted from biotite dehydration melting. The garnets contained in the restites are the products from biotite dehydration melting and restites from the khondalites, respectively.

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In recent years seismic tomography has become a powerful tool for studying the three-dimensional crust and mantle structure. In this study, we collected a large number of regional and teleseismic travel-time data and used seismic tomography method to study the relationship between earthquake occurrence and crustal heterogeneity for the 1992 Landers earthquake, heterogeneity and evolution of lithosphere under North China Craton and Southern California, and deep structure and origin of the Changbai intraplate volcano in Northeast China. Our results show a correlation between the seismic rupture zone and crustal heterogeneity. The distribution of the Landers aftershocks is cluster-like and separated or terminated in areas where low-velocity anomalies exist.Most of the large earthquakes with magnitudes >4.0 occurred in or around areas with high P-wave velocity.The possibility is that high-velocity areas are brittle and strong parts which can sustain seismogenic stress,and so can generate earthquakes. Our tomographic images show a very heterogeneous structure in the crust and upper mantle beneath Southern California. Three major anomalies in the upper mantle are revealed clearly beneath the southern Sierra Nevada, Transverse Ranges and Salton Trough. We consider that the high-velocity anomaly beneath the Transverse Ranges was formed through asymmetrical two-side convergence of subcrustal lithosphere and sinking to asthenosphere. Formation of the dense crust root and “drip structure” caused the high-velocity anomaly under the southern Sierra Nevada. The Salton Trough low is the response to the lithospheric extension when the Pacific plate was rifted away from the North American Plate. The tomograpic images beneath the North China Craton show that there exist different lithospheric structures under the different blocks. Complex, prominent low-velocity and high-velocity anomalies are imaged beneath the North China Basin, Trans-North China Orogen (TNCO), and Ordos Block which correspond to rifted, orogenic and cratonic lithospheres, respectively. The thickness of the three-type lithospheres is about 70, 90 and >250 km, respectively. Our results suggest that lithospheric thinning under the eastern part of North China Craton is due to long-term replacement and chemical and thermal erosion of the ancient lithosphere by the hot asthenosphere. The remains of ancient lithosphere exist either in the present upper mantle or have sunk into the mantle transition zone. Our tomographic result of the Changbai volcanic area suggests that the origin of the Changbai volcano is related to the deep dehydration of the subducted Pacific slab and corner flow in the big mantle wedge (BMW) above the stagnant Pacific slab.

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The continental mantle geochemical characteristics and crust-mantle evolution in the west of Yangtze Plate was discussed through the study of some within-plate basic-ultrabasic rocks from Lower Proterozoic to Later Paleozoic in this paper. In the Lower Proterozoic, the plate subduction between the pre-Tethys Proterozoic Ocean Plate and paleo-Yangtze Plate induced some basic volcanic formed in the island arc-back arc surrounding, which were represented by Ailaoshan Group-Dibadu Formation-Dahongshan Group, and there existed EM I component in the mantle source. The Middle Proterozoic Caiziyuan peridotite was formed in the epicontinental basin at the ocean-land boundary or within-continent rift basin. Its mantle source could be metasomatized by the dehydration fluid of subducted plate, and much initial radioactive ~(143)Nd was added to the source. In the Later Proterozoic, some rifts at the epicontinent or within-continent was formed due to the pre-Tethys oceanic plate subduction, and within-plate hot-spot Dahongshan diabase came into being. The whole-rock isochronal age of diabase is 1066±110Ma, and its mantle source was enriched Nd isotope and trace element which was related to the primary volatile component from asthenosphere and mantle plume. Its mantle source was included "FOZO" component representing mantle plume. The layer ultramafic rocks located at the Panxi Rift in the Middle-Later Paleozoic were resulted from different period and source. The early ultramafic indicated the incipient action of Panxi Rift, which is residue of continental lithospheric partial melting. Its mantle source involved subducted material and had distinct EM II component. The Emeishan basalt in the Later Paleozoic was typical continental flood basalt and its source also contained EM II component. The subduction of paleo-Tethys Ocean Plate provided essential dynamic condition for the large-scale opening of Panxi Rift, while the mantle plume supplied much material for Emeishan basalt. However, the plume was contaminated by the metasomatized continental mantle lithosphere in its upwelling process, which resulted in the Sr isotopic and incompatible elemental enrichment, and the Nd isotope kept down the weak-depleted character of mantle plume. The magmatic history in the west of Yangtze Plate is the tectonic process between pre-Tethys, paleo-Tethys Oceanic Plate and Yangtze Plate in a long history. Due to the subduction of oceanic plate, the crustal source material took part in the crust-mantle evolution widely. the continental mantle lithosphere in the west of Yangtze Plate was metasomatized by the fluid released by the subducted plate and the primary volatile from deeper mantle, and the mantle source include obvious enriched component.

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In recent years, chimney structure has been proved one of important indicators and a useful guide to major petroleum fields exploration through their exploration history both at home and abroad. Chimney structure, which has been called "gas chimney" or "seismic chimney", is the special fluid-filled fracture swarm, which results from the boiling of active thermal fluid caused by abruptly decreasing of high pressure and high temperature in sedimentary layers of upper lithosphere. Chimney structure is well developed in continental shelf basin of East China Sea, which indicates the great perspectives of petroleum resources there. However, the chimney structure also complicated the petroleum accumulation. So the study of chimney structure on its formation, its effect on occurrence and distribution of petroleum fields is very important not only on theoretical, but also on its applied research. It is for the first time to make a clear definition of chimney structure in this paper, and the existence and practical meaning of chimney structure are illustrated. Firstly, on the viewpoint of exploration, this will amplify exploration area or field, not only in marine, but also on continent. Secondly, this is very important to step-by-step exploration and development of petroleum fields with overpressure. Thirdly, this will provide reference for the study on complex petroleum system with multi-sources, commingled sources and accumulation, multi-stage accumulations, and multi-suits petroleum system in the overlay basin. Fourthly, when the thermal fluid enters the oceanic shallow layer, it can help form gas hydrate under favorable low-temperature and high-pressure conditions. Meanwhile, the thermal fluid with its particular component and thermal content will affect the physical, chemical and ecological environments, which will help solving the problem of global resources and environment. Beginning from the regional tectonic evolution characteristics, this paper discussed the tectonic evolution history of the Taibei depression, then made an dynamical analysis of the tectonic-sedimentary evolution during the Mesozoic and Cenozoic for the East China Sea basin. A numerical model of the tectonic-thermal evolution of the basin via the Basin-Mod technique was carried out and the subsidence-buried history and thermal history of the Taibei depression were inverse calculated: it had undergone a early rapid rift and sag, then three times of uplift and erosion, and finally depressed and been buried. The Taibei depression contains a huge thick clastic sedimentary rock of marine facies, transitional facies and continental facies on the complex basement of ante-Jurassic. It is a part of the back-arc rifting basins occurred during the Mesozoic and Cenozoic. The author analyzed the diagenesis and thermal fluid evolution of this area via the observation of cathodoluminescence, scanning electron microscope and thin section, taking advantage of the evidences of magma activities, paleo-geothermics and structural movement, the author concluded that there were at least three tectonic-thermal events and three epochs of thermal-fluid activities; and the three epochs of thermal-fluid activities were directly relative to the first two tectonic-thermal events and were controlled by the generation and expulsion of hydrocarbon in the source rock simultaneously. Based on these, this paper established the corresponding model between the tectonic-thermal events and the thermal-fluid evolution of the Taibei Depression, which becomes the base for the study on the chimney structures. According to the analyses of the gas-isotope, LAM spectrum component of fluid inclusion, geneses of CO_2 components and geneses of hydrocarbon gases, the author preliminarily verified four sources of the thermal fluid in the Taibei Depression: ① dehydration of mud shale compaction, ② expulsion of hydrocarbon in the source rock; ③ CO_2 gas hydro-thermal decomposition of carbonatite; ④magma-derived thermal fluid including the mantle magma water and volatile components (such as H_2O, CO_2, H_2S, SO_2, N_2 and He etc.). On the basis of the vitrinite reflectance (Ro), homogenization temperature of fluid inclusion, interval transit time of major well-logging, mud density of the wells, measured pressure data and the results of previous studies, this paper analyzed the characteristics of the geothermal fields and geo-pressure fields for the various parts in this area, and discussed the transversal distribution of fluid pressure. The Taibei depression on the whole underwent a temperature-loss process from hot basin to cold basin; and locally high thermal anomalies occurred on the regional background of moderate thermal structure. The seal was primarily formed during the middle and late Paleocene. The overpressured system was formed during the middle and late Eocene. The formation of overpressured system in Lishui Sag underwent such an evolutionary process as "form-weaken-strengthen-weaken". Namely, it was formed during the middle and late Eocene, then was weakened in the Oligocene, even partly broken, then strengthened after the Miocene, and finally weakened. The existence of the thermal fluid rich in volatile gas is a physical foundation for the boiling of the fluid, and sharply pressure depletion was the major cause for the boiling of the fluid, which suggests that there exists the condition for thermal fluid to boil. According to the results of the photoelastic simulation and similarity physical experiments, the geological condition and the formation mechanism of chimnestructures are summarized: well compartment is the prerequisite for chimney formation; the boiling of active thermal fluid is the original physical condition for chimney formation; The local place with low stress by tension fault is easy for chimney formation; The way that thermal fluid migrates is one of the important factors which control the types of chimney structures. Based on where the thermal fluid come from and geometrical characteristics of the chimney structures, this paper classified the genetic types of chimney structures, and concluded that there existed three types and six subtypes chimney structures: organic chimney structures generated by the hydrocarbon-bearing thermal fluid in middle-shallow layers, inorganic and commingling-genetic chimney structures generated by thermal fluid in middle-deep layers. According to the seismic profiles interpretations, well logging response analysis and mineralogical and petrological characteristics in the study area, the author summarized the comprehensive identification marks for chimney structures. Especially the horizon velocity analysis method that is established in this paper and takes advantage of interval velocity anomaly is a semi-quantitative and reliable method of chimney structure s identification. It was pointed out in this paper that the occurrence of the chimney structures in the Taibei depression made the mechanism of accumulation complicated. The author provided proof of episodic accumulation of hydrocarbon in this area: The organic component in the boiling inclusion is the trail of petroleum migration, showing the causality between the boiling of thermal fluid and the chimney structures, meanwhile showing the paroxysmal accumulation is an important petroleum accumulation model. Based on the evolutionary characteristics of various types of chimney structures, this paper discussed their relationships with the migration-accumulation of petroleum respectively. At the same time, the author summarized the accumulating-dynamical models associated with chimney structures. The author analyzed such accumulation mechanisms as the facies state, direction, power of petroleum migration, the conditions of trap, the accumulation, leakage and reservation of petroleum, and the distribution rule of petroleum. The author also provides explanation for such practical problems the existence of a lot of mantle-derived CO_2, and its heterogeneous distribution on plane. By study on and recognition for chimney structure, the existence and distribution of much mantle-derived CO_2 found in this area are explained. Caused by tectonic thermal activities, the deep magma with much CO_2-bearing thermal fluid migrate upward along deep fault and chimney structures, which makes two wells within relatively short distance different gas composition, such as in well LF-1 and well LS36-1-1. Meanwhile, the author predicted the distribution of petroleum accumulation belt in middle-shallow layer for this area, pointed out the three favorable exploration areas in future, and provided the scientific and deciding references for future study on the commingling-genetic accumulation of petroleum in middle-deep layer and the new energy-gas hydrate.

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As the largest and highest plateau on the Earth, the Tibetan Plateau has been a key location for understanding the processes of mountain building and plateau formation during India-Asia continent-continent collision. As the front-end of the collision, the geological structure of eastern Tibetan Plateau is very complex. It is ideal as a natural laboratory for investigating the formation and evolution of the Tibetan Plateau. Institute of Geophysics, Chinese Academy of Sciences (CAS) carried out MT survey from XiaZayii to Qingshuihe in the east part of the plateau in 1998. After error analysis and distortion analysis, the Non-linear Conjugate Gradient inversion(NLCG), Rapid Relaxation Inversin (RRI) and 2D OCCAM Inversion algorithms were used to invert the data. The three models obtained from 3 algorithms provided similar electrical structure and the NLCG model fit the observed data better than the other two models. According to the analysis of skin depth, the exploration depth of MT in Tibet is much more shallow than in stable continent. For example, the Schmucker depth at period 100s is less than 50km in Tibet, but more than 100km in Canadian Shield. There is a high conductivity layer at the depth of several kilometers beneath middle Qiangtang terrane, and almost 30 kilometers beneath northern Qiangtang terrane. The sensitivity analysis of the data predicates that the depth and resistivity of the crustal high conductivity layer are reliable. The MT results provide a high conductivity layer at 20~40km depth, where the seismic data show a low velocity zone. The experiments show that the rock will dehydrate and partially melt in the relative temperature and pressure. Fluids originated from dehydration and partial melting will seriously change rheological characteristics of rock. Therefore, This layer with low velocity and high conductivity layer in the crust is a weak layer. There is a low velocity path at the depth of 90-110 km beneath southeastern Tibetan Plateau and adjacent areas from seismology results. The analysis on the temperature and rheological property of the lithosphere show that the low velocity path is also weak. GPS measurements and the numerical simulation of the crust-mantle deformation show that the movement rate is different for different terranes. The regional strike derived from decomposition analysis for different frequency band and seismic anisotropy indicate that the crust and upper mantle move separately instead of as a whole. There are material flow in the eastern and southeastern Tibetan Plateau. Therefore, the faults, the crustal and upper mantle weak layers are three different boundaries for relatively movement. Those results support the "two layer wedge plates" geodynamic model on Tibetan formation and evolution.

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泥质岩是地球上广泛分布的一种表壳沉积岩石,与上地壳平均化学组成接近,是俯冲带沉积物的典型代表。本文以赣北双桥山群泥质板岩为主要研究对象,对泥质岩(KFMASH体系)进行了热力学计算、高压差热(HP-DTA)和榴辉岩相温压条件下变质脱水作用的实验研究。研究结果表明,俯冲沉积物在冷、热俯冲带其变质脱水作用的深度范围分别是95~155 km 和48~84 km。泥质岩经历了一个区域进变质作用过程。该过程可以被分为三个阶段:① 绿泥石变质脱水阶段;② 角闪石、白云母变质脱水阶段;③ 黑云母变质脱水阶段。在各阶段中,随含水矿物的变质脱水作用不断进行,流体被逐渐从体系中释放出来。最后以黑云母的消失为标志,指示了泥质岩体系变质脱水作用的结束。在俯冲带深部温度压力条件下,泥质岩所释放出的流体以富集Cu、Pb、Nd、Ba等流体活动性元素为主要特征。俯冲带沉积物(岩)在进入到俯冲带深部前,受海水浸染而富集Cl,这导致其在俯冲带深部变质脱水过程中,所释放出的流体中富集Cu、Pb、Rb、Sr、Cs、La、Ba、Ce、Pr、Nd、Sm、Eu等微量元素。而未受到海水浸染或浸染程度较弱俯冲带沉积物,在俯冲带变质脱水过程中所释放出的变质流体中,上述微量元素的富集程度则相对较弱。

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基性岩类的(脱水)部分熔融实验是研究地球内部中酸性岩浆(熔体)形成的重要实验方法,自二十世纪70年代以来越来越受到地质学家的高度重视。华北北缘广泛分布的中生代埃达克质岩石的成因,十几年来引起国内外学者的激烈争论,至今仍没有定论。近年来的研究表明张家口地区同时出露的古老太古宙中基性下地壳岩石、中生代中酸性埃达克质岩浆岩以及汉诺坝基性麻粒岩包体等可能反映了源岩和熔融产物的综合信息,这为我们运用实验岩石学手段研究华北北缘埃达克质岩石成因提供了非常理想的条件。 本文在1.5-2.0GPa,800-1000℃条件下,对采自华北北缘的斜长角闪岩同时进行了块状与粉末状两种样品的部分熔融实验研究,利用电子探针对各实验产物进行了主量元素分析以及利用LA-ICP-MS对部分熔体进行了微量元素测试,进而比较了相同条件下块状和粉末状样品的熔融特征,并对比了实验获得的熔体与华北北缘中生代埃达克质岩石的地球化学特征,同时也将实验获得的残留体与汉诺坝基性麻粒岩包体进行了比较。获得以下主要认识: (1)相同的温度、压力和恒温时间条件下块状样品的熔融温度比粉末样品的更低。在1.5-2.0GPa,800℃时块状斜长角闪岩样品已经发生部分融融,而相同条件下粉末样品中没有观察到熔体,粉末样品的部分熔融发生在850℃左右。在850-1000℃温度范围内,相同条件下块状样品的熔体含量比粉末样品的熔体含量高出5-17vol.%,即相同条件下块状样品比粉末样品的熔融程度更高,说明块状样品更容易达到可以分凝形成岩浆的临界熔体分数(CMF),这可能暗示着自然界中的岩浆形成可能比以往通过粉末实验结果推测的更容易发生。此外,在较高的温度条件下(950-1000℃),块状样品与粉末样品的熔体在主量和微量元素上都具有大致相同的地球化学特征,可以认为二者在在岩石学应用上是等效的。 (2)1.5GPa下实验获得的熔体为花岗质-花岗闪长质熔体,850-1000℃熔体的主-微量元素的地球化学特征与华北北缘中生代埃达克质岩石的整体特征具有很好的相似性,并与实验原岩产地张家口地区的三个典型中酸性埃达克质岩体的地球化学特征类似。可以认为实验的斜长角闪岩在1.5GPa下部分熔融能够形成华北北缘中生代埃达克质岩石。2.0GPa下的实验熔体为花岗质-奥长花岗质成分,其主量和微量元素特征均与华北北缘埃达克质岩石存在较大的差别,说明该压力下不能够形成华北北缘埃达克质岩石。 (3)实验残留相主要组成为Hb+Cpx+Gt±Pl,相当于麻粒岩相或榴辉岩相的矿物组合。与汉诺坝基性麻粒岩包体的典型矿物组合Cpx+Opx+Pl存在较大差别,在化学成分上,残留相比麻粒岩包体也整体上富Fe、Al,而贫Mg、Ca。综合来看汉诺坝基性麻粒岩包体可能是多种源岩在相对低压的条件下经过多期部分熔融综合作用的结果,本次实验的原岩及条件难以完全解释其复杂的成因。 另外,针对实验熔体和华北北缘埃达克质岩石之间的一些差异,不排除可能同时存在其他与之类似的源岩,成分上具有相对富Mg、Ca而贫Fe、Al,以及不同程度的Th、U、Zr、Hf富集等特征,与斜长角闪岩一起部分熔融,共同形成中生代华北北缘的中酸性埃达克质岩石。

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Inexpensive and permanently modified poly(methyl methacrylate)(PMMA) microchips were fabricated by an injection-molding process. A novel sealing method for plastic microchips at room temperature was introduced. Run-to-run and chip-to-chip reproducibility was good, with relative standard deviation values between 1-3% for the run-to-run and less than 2.1% for the chip-to-chip comparisons. Acrylonitrile-butadiene-styrene (ABS) was used as an additive in PMMA substrates. The proportions of PMMA and ABS were optimized. ABS may be considered as a modifier, which obviously improved some characteristics of the microchip, such as the hydrophilicity and the electro-osmotic flow (EOF). The detection limit of Rhodamine 6G dye for the modified microchip on the home-made microchip analyzer showed a dramatic 100-fold improvement over that for the unmodified PMMA chip. A detection limit of the order of 10(-20) mole has been achieved for each injected phiX-174/HaeIII DNA fragment with the baseline separation between 271 and 281 bp, and fast separation of 11 DNA restriction fragments within 180 seconds. Analysis of a PCR product from the tobacco ACT gene was performed on the modified microchip as an application example.

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A highly active and selective K-Pd/MnOx-ZrO2-ZnO catalyst for the one-step synthesis of 2-pentanone from ethanol is described. The possible reaction pathways for ethanol reaction over K-Pd/MnOx-ZrO2-ZnO catalyst were investigated by means of TPSR, CO2- and NH3-TPD techniques. The reactions were performed in a fixed bed continuous flow reactor. Complete conversion with high selectivity for 2-pentanone, was observed under 370 similar to 390degreesC, 2 similar to 4 MPa, GHSV = 8000 similar to 10,000 h(-1) and LHSV < 1.25 h(-1) conditions. Ethanol reactions over K-Pd/MnOx-ZrO2-ZnO catalyst showed that the catalyst could catalyze dehydrogenation. aldol. dehydration and hydrogenation reactions. Both acidic and basic properties are found on the surface of K-Pd/MnOx-ZrO2-ZnO catalyst, whose multifunctionality with the combination of basic, acid and metal sites may be responsible for the efficiency of the K-PdMnOx-ZrO2-ZnO catalyst. (C) 2004 Elsevier B.V. All rights reserved.

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The High Grade Metamorphic Complex (HGMC) of Variscan basement of north Sardinia is characterized by the widespread of migmatites. This study is focused on two localities of NE Sardinia (Porto Ottiolu and Punta Sirenella) where ortho- and para-derivates migmatites outcrop. A geological and structural survey was carried out, leading to the realization of a geological schematic map of Punta Sirenella area. Several samples of different rocks were collected for petrographic, micro-structural minero-chemical and geochemical analyses. In the Porto Ottiolu area three main deformation phases have been identified; D1, characterized by tight folds with sub-horizontal axes, rarely preserved in paragneisses; D2, that produce a pervasive foliation oriented N100° 45°SW marked by biotite and sillimanite blastesis and locally transposed by shear zone oriented N170°; D3, late deformation phase caused symmetric folds with sub-horizontal axes with no axial plane schistosity. Leucosomes form pods and layers along S2 schistosity but also leucosomes along shear zones have been observed. In the Punta Sirenella area, three main deformation phases have been identified; D1, is manifested by the transposition of centimeter-sized leucosomes and is rarely observed in paragneisses were produce open folds with sub-vertical axes; D2, NW-SE oriented on whose XY plane three mineralogical lineation (quartz+plagioclase, fibrolite+quarz and muscovite) lie; D3, a ductile-brittle deformation phase that produce a mylonitc S3 foliation that locally become the most evident schistosity in the field oriented N140° steeply dipping toward NE. In both areas, leucosomes of sedimentary-derived migmatites are generally trondhjemitic pointing out for a H2O fluxed melting reaction, but also granitic leucosomes have been found, produced by muscovite dehydration melting. Leucosomes of migmatitic orthogneiss instead, have granitic compositions. Migmatization started early, during the compressional and crustal thickening (sin-D1, pre-D2) and was still active during exhumation stage. For each studied outcrop of migmatite pseudosections for the average mesosome composition have been calculated; these pseudosections have been used to model the P-T conditions of anatexis on the basis of the melt volume (%) of melt, Si/Al and Na/K molar ratios, modal content of garnet and Si content in metamorphic white mica. Further pseudosections have been calculated for the average composition of leucosomes in order to define the P-T conditions of the end of the crystallization through intersection of solidus curve and isopleths of Si content in white mica and/or XMg ratio in biotite. Thermodynamic modeling on ortho- and sedimentary-derived migmatites of Punta Sirenella yield P-T conditions of 1.1-1.3 GPa - 670-740°C for migmatitic event and 0.75-0.90 GPa - 660-730°C for the end of crystallization. These conditions are fit well with previous studies on adjacent rocks. Modeling of Porto Ottiolu ortho- and sedimentary-derived migmatites yield P-T conditions of 0.85-1.05 GPa - 690-730°C for migmatitic event and 0.35-0.55 GPa - 630-690°C strongly affected by re-equilibration during exhumation, expecially for crystallization conditions. Geochemical analyses of samples belonging to Porto Ottiolu and Punta Sirenella orthogneisses show a strong link with those of other orthogneisses outcropping in NE Sardinia (for instance, Lode-Mamone and Golfo Aranci) that are considered the intrusive counterparts of middle-Ordovician metavolcanics rocks outcropping in the Nappe Zone. Thus, the studied ortogneiss bodies, even lacking radiometric data, can be considered as belonging to the same magmatic cycle.

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Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

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Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

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The ability of the Gram-positive foodborne pathogen Listeria monocytogenes to survive and grow in environments of elevated osmolarity can be attributed, at least in part, to the accumulation of a restricted range of low molecular mass solutes compatible with cellular function. Accumulated to high internal concentrations in hyper-saline environments, compatible solutes, either transported into the cell or synthesized de novo, play a dual role: helping to stabilize protein structure and function while also counterbalancing external osmotic strength, thus preventing water loss from the cell and plasmolysis. While previous physiological investigations identified glycine betaine, carnitine, and proline as the principal compatible solutes in the listerial osmostress response, genetic alanysis of the uptake/synthesis systems governing the accumulation of these compounds has, until now, remained largely unexplored. Representing the first genetic analysis of compatible solute accumulation in L. monocytogenes, this thesis describes the molecular characterization of BetL; a highly specific secondary glycine betaine transport system, OpuC; a multicomponent carnitine/glycine betaine transporter, and finally proBA; a two-gene operon encoding the first two enzymes of the listerial proline piosynthesis pathway. In addition to their role in osmotolerance, the potential of each system in contributing to listerial pathogenesis was investigated. While mutations in each gene cluster exhibited dramatic reductions in listerial osmotolerance, OpuC- mutants were additionally shown to exhibit reduced virulence when admisistered via the oral route. This represents the first direct link between the salt stress response and virulence in L. monocytogenes.

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The ability to adapt to and respond to increases in external osmolarity is an important characteristic that enables bacteria to survive and proliferate in different environmental niches. When challenged with increased osmolarity, due to sodium chloride (NaCl) for example, bacteria elicit a phased response; firstly via uptake of potassium (K+), which is known as the primary response. This primary response is followed by the secondary response which is characterised by the synthesis or uptake of compatible solutes (osmoprotectants). The overall osmotic stress response is much broader however, involving many diverse cellular systems and processes. These ancillary mechanisms are arguably more interesting and give a more complete view of the osmotic stress response. The aim of this thesis was to identify novel genetic loci from the human gut microbiota that confer increased tolerance to osmotic stress using a functional metagenomic approach. Functional metagenomics is a powerful tool that enables the identification of novel genes from as yet uncultured bacteria from diverse environments through cloning, heterologous expression and phenotypic identification of a desired trait. Functional metagenomics does not rely on any previous sequence information to known genes and can therefore enable the discovery of completely novel genes and assign functions to new or known genes. Using a functional metagenomic approach, we have assigned a novel function to previously annotated genes; murB, mazG and galE, as well as a putative brp/blh family beta-carotene 15,15’-monooxygenase. Finally, we report the identification of a completely novel salt tolerance determinant with no current known homologues in the databases. Overall the genes identified originate from diverse taxonomic and phylogenetic groups commonly found in the human gastrointestinal (GI) tract, such as Collinsella and Eggerthella, Akkermansia and Bacteroides from the phyla Actinobacteria, Verrucomicrobia and Bacteroidetes, respectively. In addition, a number of the genes appear to have been acquired via lateral gene transfer and/or encoded on a prophage. To our knowledge, this thesis represents the first investigation to identify novel genes from the human gut microbiota involved in the bacterial osmotic stress response.

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Geiparvarin is a natural product which contains both a 3(2H)-furanone and a coumarin moiety in its structure. The aim of this project was to investigate the use of Pd(0)-mediated C–C bondforming reactions to produce structurally modified geiparvarins. Chapter 1 consists of a review of the relevant literature, including that pertaining to the syntheses of selected naturally occurring 3(2H)-furanones. The known syntheses of geiparvarin and closely related analogues are examined, along with the documented biological activity of these compounds. The synthetic routes which allow access to 4-substituted-3(2H)-furanones are also described. Chapter 2 describes in detail the synthesis of a variety of novel structurally modified geiparvarins by two complementary routes, both approaches utilising Pd(0)-mediated crosscoupling reactions, and discusses the characterisation of these compounds. The preparation of 5-ethyl-3(2H)-furanones is described, as is their incorporation into geiparvarin and the corresponding 5″-alkylgeiparvarin analogues via formation and dehydration of intermediate alcohols. Halogenation of 5-ethyl-3(2H)-furanones and the corresponding geiparvarin derivatives is discussed, along with further reactions of the resulting halides. Preparation of 3″-arylgeiparvarins involving both Suzuki–Miyura and Stille reactions, using the appropriate intermediate iodides and bromides, is described. The application of Stille and Heck conditions to give 3″-ethenylgeiparvarin analogues and Sonogashira conditions to produce 3″-ethynylgeiparvarin analogues, using the relevant intermediate iodides, is also extensively outlined. Chapter 3 contains all of the experimental data and details of the synthetic methods employed for the compounds prepared during the course of this research. All novel compounds prepared were fully characterised using NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis; the details of which are included.